Ida, Shunya (Nara City, JA)
Hosokawa, Kenjiro (Osaka, JA)
Hasegawa, Hiroyoshi (Osaka, JA)
Nakanishi, Seinosuke (Osaka, JA)
Kajino, Katsura (Osaka, JA)
Ueda, Keizo (Ashiya City, JA)

05/111252

10/30/1973

02/01/1971

Download PDF 3769060       PDF help

Click for automatic bibliography generation

Kanegafuchi Boseki Kabushiki Kaisha (Tokyo, JA)

428/196

428/922, 427/210, 428/921, 427/170, 428/920, 427/160, 428/907

D06M23/00; D06M23/16; B44D1/16

117/37R,68,44,68.5,139.5A,138.5

3620797	IMPREGNATION OF A NONWOVEN FABRIC	November 1971	Feitlowitz
3521638	FABRICS HAVING WATER SOLUBLE DISCRETE AREAS AND METHODS OF MAKING	July 1970	Parrish
3617188	SOIL RELEASE FABRICS AND METHOD FOR PRODUCING SAME	November 1971	Snyder
3615745	ANTIMICROBIAL COATINGS AND METHOD USING DIIODOMETHYL SULFONES	October 1971	Crovetti
3127281		March 1964	Meyer
3437508	STRUCTURAL PANEL AND METHOD OF PRODUCTION	April 1969	Gorski
3553005		January 1971	Moragne

Leavitt, Alfred L.

Esposito M. F.

What is claimed is

1. A processed cloth or film having deposited or absorbed thereon a plurality of different processing agents which modify different chemical or physical properties of the untreated cloth or film so that a plurality of said properties are altered, said agents being selected from the group consisting of shrink proofing agent, antipilling agent, water repelling agent, elastic agent, hygroscopic agent, antistatic agent, stain proofing agent, antiflaming agent, antifusing agent, softening agent, ultraviolet absorbing agent, crease proofing agent, water absorbing agent, heat resisting agent, soil releasing agent, oil repelling agent, moth proofing agent, dust proofing agent, mildew proofing agent and delustering agent, one of said agents being applied on substantially uniformly distributed small portions of the surface or surfaces of said cloth or film and the remainder of said cloth or film being free of said one agent, the remainder of said cloth or film having at least one additional agent applied thereon, with at least parts of each agent being uncovered by the other agents so that all the agents are present in amounts effective individually to modify said properties of said cloth or film.

2. A processed cloth or film according to claim 1, in which at least one of the agents is deposited on the cloth or film in spaced-apart, elongated linear zones having a width of not more than about 2 cm.

3. A processed cloth or film according to claim 1, in which at least one of the agents is deposited on the cloth or film in discrete, spaced-apart, spot-like zones having an area of not more than 4 cm².

4. A processed cloth or film according to claim 1, in which said agents are deposited on at least 20 percent of the surface area of the cloth.

5. A processed cloth or film according to claim 1, in which said agents are applied to the same surface of the cloth or film so that said agents do not overlap each other.

6. A processed cloth or film according to claim 1, in which the agents are deposited on the cloth or film in regularly repeating patterns of zones covering portions of said cloth or film.

7. A processed cloth or film according to claim 1, in which the agents are applied to opposite surfaces of the cloth or film.

8. A processed cloth or film according to claim 7, in which both of the agents are applied in the form of zones covering portions of said opposite surfaces of the cloth or film.

9. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers, one of the processing agents is a crease proofing agent and the other agent is a water absorbing agent.

10. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers and natural fibers, one of the processing agents is a crease proofing agent and the other agent is a water absorbing agent.

11. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers, one of the processing agents is a crease proofing agent and the other agent is a stain proofing agent.

12. A processed cloth as claimed in claim 1, wherein said cloth consists of natural fibers, one of the processing agents is a crease proofing agent and the other agent is a stain proofing agent.

13. A processed cloth as claimed in claim 1, wherein said cloth material consists of synthetic fibers and natural fibers, one of the processing agents is a crease proofing agent and the other agent is a stain proofing agent.

14. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers, one of the processing agents is a crease proofing agent and the other agent is an antistatic agent.

15. A processed cloth as claimed in claim 1, wherein said cloth material consists of synthetic fibers and natural fibers, one of the processing agents is a crease proofing agent and the other agent is an antistatic agent.

16. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers, one of the processing agents is an elastic agent and the other agent is a water absorbing agent.

17. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers, one of the processing agents is an elastic agent and the other agent is a stain proofing agent.

18. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers, one of the processing agents is an elastic agent and the other agent is an antistatic agent.

19. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers, one of the processing agents is an antifusing agent and the other agent is a stain proofing agent.

20. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers and natural fibers, one of the processing agents is an antifusing agent and the other agent is a stain proofing agent.

21. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers, one of the processing agents is an antipilling agent and the other agent is a stain proofing agent.

22. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers and natural fibers, one of the processing agents is an antipilling agent and the other agent is a stain proofing agent.

23. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers, one of the processing agents is a stain proofing agent and the other agent is a soil releasing agent.

24. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers and natural fibers, one of the processing agents is a stain proofing agent and the other agent is a soil releasing agent.

25. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers, one of the processing agents is an antifusing agent and the other agent is a softening agent.

26. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers and natural fibers, one of the processing agents is an antifusing agent and the other agent is a softening agent.

27. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers, one of the processing agents is an antiflaming agent and the other agent is a ultraviolet absorbing agent.

28. A processed cloth as claimed in claim 1, wherein said cloth consists of natural fibers, one of the processing agents is an antiflaming agent and the other agent is an ultraviolet absorbing agent.

29. A processed cloth as claimed in claim 1, wherein said cloth material consists of synthetic fibers and natural fibers, one of the processing agents is an antiflaming agent and the other agent is an ultraviolet absorbing agent.

30. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers, one of the processing agents is a stain proofing agent and the other agent is an antistatic agent.

31. A processed cloth as claimed in claim 1, wherein said cloth material consists of synthetic fibers and natural fibers, one of the processing agents is a stain proofing agent and the other agent is an antistatic agent.

32. A processed cloth as claimed in claim 1, wherein said cloth consists of natural fibers, one of the processing agents is a shrink proofing agent and the other agent is a mildew proofing agent.

33. A processed cloth as claimed in claim 1, wherein said cloth consists of natural fibers and synthetic fibers, one of the processing agents is a shrink proofing agent and the other agent is a mildew proofing agent.

34. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers, one of the processing agents is a crease proofing agent and the other agent is an antistatic agent.

35. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers and natural fibers, one of the processing agents is a crease proofing agent and the other agent is an antistatic agent.

36. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers, in which a crease proofing agent is fixed in the cloth in the form of a layer between and spaced from the upper and lower surfaces of the cloth, one of the processing agents is an antistatic agent and the other agent is a stain proofing agent.

37. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers and natural fibers, in which a crease proofing agent is fixed in the cloth in the form of a layer between and spaced from the upper and lower surfaces of the cloth, one of the processing agents is an antistatic agent and the other agent is a stain proofing agent.

38. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers, one of the processing agents is a crease proofing agent and the other agents are an antistatic agent and a water absorbing agent.

39. A processed cloth as claimed in claim 1, wherein said cloth consists of synthetic fibers and natural fibers, one of the processing agents is a crease proofing agent and the other agents are an antistatic agent and a water absorbing agent.

40. A processed cloth as claimed in claim 1, wherein two processing agents having different functions are distributed and fixed in a layer between and spaced from the opposite surfaces of the cloth.

41. A processed cloth as claimed in claim 1, wherein two or more processing agents are fixed together on the cloth.

42. A method of producing a processed cloth or film, which comprises applying one processing agent to a large number of substantially uniformly distributed, small portions of the surface or surfaces of the cloth or film and leaving the remainder of said surface or surfaces free of said one processing agent, applying a second processing agent different from said one processing agent to other portions of the remainder of said surface or surfaces, so that parts of both agents are uncovered by the other agent, and fixing the agents on the cloth or film, said agents being selected from the group consisting of shrink proofing agent, antipilling agent, water repelling agent, elastic agent, hygroscopic agent, antistatic agent, stain proofing agent, antiflaming agent, antifusing agent, softening agent, ultraviolet absorbing agent, crease proofing agent, water absorbing agent, heat resisting agent, soil releasing agent, oil repelling agent, moth proofing agent, dust proofing agent, mildew proofing agent and delustering agent.

43. A method according to claim 42, in which the agents are applied to the same surface of the cloth or film so that said agents do not overlap each other.

44. A method according to claim 42, in which at least said one agent is applied by roll printing same on the cloth or film so that the pattern of said portions repeats regularly.

45. A method according to claim 42, in which said agents are applied to opposite surfaces of the cloth or film so that neither agent penetrates through the cloth or film.

The present invention relates to cloths whose physical and chemical properties are modified by a plurality of processing agents and a method of producing the same.

The term "cloths" used herein means various materials for clothings and industry and the like, for example, woven fabrics, knitted goods, unwoven fabrics, sheets, felts, bats, carpets, films, laminated cloths, etc.

Heretofore, the means for applying a plurality of processing agents on a cloth include treating the cloth with a bath containing a mixture of a plurality of processing agents or treating the cloth serially with separate baths containing different processing agents but in both cases, both the surfaces of the cloth are throughout processed uniformly with a bath, because the treating bath has a permeability into the cloth. Accordingly, for example, if an antistatic processing and a processing for providing elasticity are applied simultaneously on a cloth, such as knitted goods or woven fabrics composed of a synthetic fiber, any one of the antistatic agents provided with a hygroscopic function and the elastic agents provided with a water repellent function covers the other agent and hence both effects are mutually eliminated or reduced and it is impossible to develop both the properties simultaneously and efficiently.

Recently, the technic for processing cloths has been highly developed and various processing agents for supplementing the defects of cloths and modifying the properties thereof have been proposed and used practically, but the processing agents other than the above embodiment, in many cases, can not be used together, because of functions of these processing agents are opposite and are in contention with each other or one of the processing agents is covered with the other agent or a chemical reaction occurs between the processing agents, whereby the functions decrease mutually or there is no common solvent for both the processing agents. Accordingly an effective process by which various processing agents are used together simultaneously according to the desired application to provide the plural effect thereof on cloths, has not been discovered.

The inventors have made various investigations to solve such previous problems and accomplished the present invention.

The object of the present invention is to provide novel processed cloths developing each of the effects of different processing agents plurally and efficiently, which cloths have been treated with a plurality of processing agents having different functions.

Namely, the specific processed cloth of the present invention is characterized in that a large number of small zones distributed substantially uniformly on the cloth surface or the whole of one surface of the cloth is treated with a processing agent and at least one part of a portion other than said treated zones or the whole of the other surface of the cloth is treated with a second processing agent having a function different from the first processing agent.

In general it has been considered in the processing of a cloth that it is conventional to coat a processing agent over all of both the surfaces and that such a means is absolutely necessary in order to develop the effect of the processing agent. However, the inventors have found that most processing agents, although they depend upon the degree of function and the deposited amount, need not always necessarily be deposited uniformly over all of both the surfaces of a cloth and that if a processing agent of one plurality of processing agents is deposited on a large number of small zones uniformly distributed on a surface of the cloth or over all of one surface of the cloth and the other processing agents are deposited on a large number of small zones other than the above described small zones, which are also uniformly distributed on the cloth surface, or when the other processing agent is one kind, if said processing agent is deposited over all of the surface opposite to the surface treated with the first processing agent, the desired properties can be satisfactorily developed on the whole of the cloth and that in some cases, undesirable actions provided by the processing agents are restrained. For example, if the antistatic processing is effected locally, the object can be fully attained and in an extreme case, even when only the periphery of the cloth is processed, a desired antistatic cloth can be obtained. Furthermore, if a silicone processing is made throughout the surface of the cloth in order to improve the elastic property of the cloth and to provide crease proofness, the cloth loses its hygroscopicity, while if such a processing agent is applied so as to be deposited on a large number of distributed small zones, the cloth can be provided with the crease resistance while maintaining the hygroscopicity or vapor permeability.

If a crease proofing agent, such as tetraoxane and an antistatic agent and an antiflaming agent are applied according to the present invention, the effects of the treatments owing to each processing agent, that is, the crease resistance and wash wear property due to tetraoxane, the antistatic property due to the antistatic agent and the flame resisting property due to the antiflaming agent can be provided on knitted goods and woven fabrics.

The present invention has been accomplished by utilizing these facts skillfully. The method of producing the above described specific processed cloth comprises:

1. applying one processing agent for a cloth on a large number of small zones substantially uniformly distributed on the surface of cloth or over all of one surface of the cloth,

2. applying at least one processing agents other than the above described processing agent on at least a part of the cloth surface including the portion other than the above described zones or over all of another surface of the cloth and

3. fixing the above described applied agents on the cloth.

The method of the present invention will be explained practically hereinafter.

Firstly, a processing agent for a cloth is deposited on a large number of small zones substantially uniformly distributed on a surface of a cloth or over all of one surface of the cloth. In the case of depositing the processing agent on a large number of small zones, the processing agent is deposited on a proper pattern uniformly distributed on the cloth surface, for example, point-like, spot-like, parallel line-like, stripe-like, mosaic-like, mesh-like pattern and the like. In this case, one processing agent is usually used alone but if the processing agents have no interference and hindrance between one another, two or more processing agents may be used together.

Then, if necessary, a treatment for fixing the applied agent to the cloth, for example drying, heating and the like is effected or such a treatment is not effected, after which another processing agent having a function different from the above described processing agent is applied on the spaces between the above described patterns or over all of another surface of the cloth. Then, the cloth, in which these processing agents are applied on the small zones, such as mosaic-like, alternating stripe-like pattern and the like or in which each of both the whole surfaces is coated with different processing agents respectively, is subjected to a treatment for fixing the processing agent.

The deposited state of two processing agents in the small zone type may be any of the following. Namely both the boundaries in the deposited zones may be in contact with each other or be spaced somewhat or be overlapped to some extent but non-overlapped portions of at least one of the processing agents must be distributed uniformly. Furthermore, when using processing agents not interferring with each other, one of the agents may be arranged in the small zones and the other agent may be applied on the whole surface. The order of the step for applying one of the processing agent on the small zones and the step for applying the other processing agent on the whole surface is not limited. The processing agents to be applied are not limited to two kinds and may be used optionally in a number of more than two depending upon the object.

The embodiments of patterns when the processing agents are deposited on the cloth in the small zones will be explained with respect to the drawings.

FIG. 1 shows the state where different processing agents are deposited on a stripe-like small zone 1 and the remaining zone 2 respectively. In this embodiment, both the zones are arranged so that the edges of both the zones are in contact with each other. The stripes may be longitudinal stripes, transverse stripes or inclined stripes along the longitudinal direction of the cloth but in order to distribute these small zones uniformly throughout the cloth surface, it is desirable that the width and distance of every stripes are substantially equal respectively;

FIG. 2 shows the state wherein both the small zones 1 and 2 are spot-like and the zones are spaced from each other and arranged uniformly. The shapes of the spots may be selected optionally in square, circular and the other forms;

FIG. 3 shows an embodiment wherein the small zone 1 is arranged in a spot-like or dot-like form and in the remainder 2 another processing agent is distributed in point-like form;

FIG. 4 shows the state wherein small zones 1, 2 and 3 deposited different processing agents respectively are distributed uniformly and regularly; and

FIG. 5 shows an embodiment wherein the small zone 1 and the small zone 2 are partially overlapped at the zone 3. Even in this case, each processing agent has non-overlapped portions uniformly distributed.

The means for distributing and depositing the processing agents on the cloth in these patterns may be effected by printing or spraying the processing agent liquid or a solution of a processing agent or a dispersion of the agent in a proper solvent or a paste of a processing agent mixed with a sizing agent is printed or sprayed in a given pattern and then evaporating, removing or extracting the solvent or the sizing agent.

When one of the processing agents is applied throughout the surface as mentioned above, the conventional immersing process, the process for coating the whole surface or a vapor phase treating process and the like may be naturally adopted. Furthermore, the object can be attained by dispersing and depositing microcapsules containing sealed therein a processing agent on the cloth surface uniformly and breaking the capsules by the action of pressure, heating and the like.

Such operations for applying the processing agents are generally carried out by repeating the operations for each of the processing agents employed. When repeating the printings, it is desirable to arrange the succeeding patterns in the spaces of the preceding patterns but when the permeability of the cloth is high, the processing agent may penetrate and extend from the succeedingly applied zones and overlap with the preceding zones. Accordingly, when the overlapped zones where the effects are reduced by the action of contention and hindrance of mutual processing agents, are formed, it is desired that each area of the applied zones is made small as much as possible to reduce the overlapped portions, or that a processing for restraining the permeability is previously applied to the cloth or a process for printing a paste is adopted. In order to carry out the removal of solvent rapidly, it is effective to apply the processing agent on a heated cloth.

Moreover, for promoting the rapid penetration or depositing of the processing agent into the interior of the cloth, the following means are carried out optionally, if necessary. Namely, an assistant, such as a surface active agent is used together with the processing agent or the cloth to be treated is subjected to a preliminary treatment by means of such an assistant. Alternatively, when the cloth is a film composed of an organic synthetic thermoplastic polymer, the film is previously subjected to a surface active treatment, such as corona discharge treatment and the like.

When combining the treatment with the spray treatment, the printing treatment with the immersing treatment or the printing treatment with the vapor phase treatment, that is when overlapping of both the processing agents are is carried out, it is essential to select both the processing agents so as not to reduce the effect of the processing agents to be printed by the processing agent to be sprayed, immersed or vapor phase treated. In addition, the object of the present invention can be accomplished by combining two spraying treatments.

When using the micro-capsule process, several processing agents can be applied on the cloth surface in small zones where these agents are distributed alternately and substantially uniformly by contacting the cloth with a system containing a mixture of different microcapsules a one step operation, therefore such a process is very convenient.

The above described small zones in which the processing agents are deposited should be distributed substantially uniformly over the whole surface of the cloth and a preferred result can be obtained. The smaller the areas of the small zones and the larger the number of such zones, the better is the result. In the line-like or the stripe-like pattern, the width is at most about 2 cm, preferably at most about 1 cm and in the case of the spot-like pattern, the area of one small zone is not more than about 4 cm ² , preferably not more than about 1 cm ² . When the area is too large, it is difficult to develop the plural effects harmonized uniformly over the whole cloth and local unevenness of texture and appearance and the like is noticeable and this can not attain the object of the present invention.

Then, the processing agents applied on the cloth are subjected to an appropriate fixing treatment. The setting treatment includes generally drying at room temperature or at an elevated temperature, aging, baking, steaming, extraction with a solvent, fixing by a reaction with another chemical and the like, but it is selected properly depending upon the properties of the processing agents deposited on the cloth. If it is possible to carry out the fixing treatment commonly for various deposited processing agents, it is preferred to effect the fixing step at the same time after finished the steps for applying the processing agents.

In addition, it is effective to effect the fixing treatment each time a processing agent is applied, particularly in the case when the manners of the fixing treatment are different or there is a risk that a plurality of processing agents may cause undesirable interferences by carrying out continuously the steps for applying said processing agents.

As the apparatus for carrying out the above described processes, well known textile printing machines, such as roller printing machine, screen printing machine and the like, printing machines, such as relief printing, intaglio printing, and the like, a well known spraying device, saturation bath, ager type vapor phase treating device and the like may be used depending upon the object.

The processing agents applicable to the present invention are treating agents, which can be deposited or adsorbed on the cloths to give or modify the particular chemical or physical properties and, for example, shrink proofing agent, antipilling agent, water repelling agent, elastic agent, hygroscopic agent, antistatic agent, stain proofing agent, antiflaming agent, antifusing agent, softening agent, ultraviolet absorbing agent, crease proofing agent, water absorbing agent, heat resisting agent, soil releasing (SR) agent oil repelling agent, moth proofing agent, dust proofing agent, mildew proofing agent, delustering agent and the like may be mentioned.

In the present invention, when these processing agents are applied only on one surface of the cloth, there is no problem in the permeability into the cloth, while when both the surfaces of the cloth are applied with the processing agent, it is preferable to select the processing agent having a very low permeability or no permeability into the cloth.

The above described various processing agents can provide the inherent effect to the cloth alone respectively but when these processing agents are used together and applied on knitted goods and woven fabrics, the applied processing agents interfere with one another in the conventional processes as described above and it is difficult to develop the inherent treating effects brought about by the respective processing agents together, while according to the present invention when such a plurality of processing agents are used, the effects of these agents can be developed most efficiently.

The shrink proofing agents include the reaction products of phosphorus pentachloride with carboxyl group of ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/itaconic acid copolymer, ethylene/methylhydrogen maleate copolymer, ethylene/maleic acid copolymer, ethylene/acrylic acid/methyl methacrylate copolymer, ethylene/methacrylic acid/ethyl acrylate copolymer, ethylene/itaconic acid/methyl methacrylate copolymer, ethylene/methylhydrogen maleate/ethyl acrylate copolymer, ethylene/methacrylic acid/vinyl acetate copolymer, ethylene/acrylic acid/vinyl formate copolymer, ethylene/propylene/acrylic acid copolymer, ethylene/styrene/acrylic acid copolymer, ethylene/methacrylic acid/acrylonitrile copolymer, ethylene/fumaric acid/vinyl methyl ether copolymer, ethylene/vinyl chloride/acrylic acid copolymer, ethylene/vinylidene chloride/acrylic acid copolymer, ethylene/vinyl fluoride/methacrylic acid copolymer, ethylene/chlorotrifluoroethylene/methacrylic acid copolymer, polyethylene/acrylic acid graft copolymer, polyethylene/methacrylic acid graft copolymer, polyethylene/propylene acrylate graft copolymer, polyethylene/butene-1/methacrylic acid graft copolymer, polyethylene/vinyl acetate/methacrylic acid graft copolymer, polypropylene/acrylic acid graft copolymer, polypropylene/methacrylic acid graft copolymer, polybutene/acrylic acid graft copolymer, poly-3-methylbutene/acrylic acid graft copolymer, and polyethylene/acrylic acid/methyl acrylate graft copolymer and particularly the reaction products containing at least 0.1 mol% of acid chloride group are preferable.

As the ultraviolet absorbing agents, 2-hydroxy-4-octoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, sodium salt of 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and di-p-n-nonylphenol isophthalate are frequently used.

As the water repellent agents, use may be made of dialkyl-polysiloxanediol, alkylhydrogen polysiloxane, alkylpyridium halide, Werner type metal complex, the other long chain aliphatic derivatives and the like and particularly alkylhydrogen polysiloxane is used in many cases. The most preferable one is methylhydrogen polysiloxane having a viscosity of less than 100 centistokes.

As the antistatic agents, use may be made of, for example anionic, cationic, amphoteric or non-ionic compounds. The antistatic agents having a durability, as the anionic antistatic agents are, for example, ammonium polyacrylate, alkali metal salts of copolymer of styrene/vinylacetate/methyl methacrylate with maleic anhydride (or ethylene oxide addition product), carboxylic acid compounds, such as Werner type complex prepared from chromium chloride and 1,2,3,4-butane-tetracarboxylic acid, polyester derivatives, such as esters of styrene/maleic anhydride copolymer with polyethylene glycol or polyhydric alcohol, copolymer of higher fatty acid bis (hydroxyalkyl) amide with maleic anhydride and the like, sulfonic acid derivatives, such as polyvinylsulfonic acid, polystyrenesulfonic acid, polyvinyltoluenesulfonic acid or copolymer of methyl methacrylate with ethylenesulfonic acid, copolymer of acrylic amide with ethylenesulfonic acid and the like, phosphorus compounds, such as polymer of diallyl-2-cyanoethylphosphonate, polymer of dimethylvinylphosphonate, etc.

As the above described cationic antistatic agents, use may be made of quaternary ammonium salt obtained by reacting diethylaminoethylmethacrylate with dimethyl sulfate, acrylate derivatives, such as triacryloylhexahydrotriazine derivative, acrylic amide derivatives, such as a polymer of acrylic amide, methylene urea, a polymer of melamine-monomethyleneacrylic amide, a polymer of acrylic amide-propylbutyloxymethyl morpholinium chloride, vinyl ether derivatives, such as polyvinyl-2-chloroethyl ether pyridinium salt, a polymer of unsaturated ureide ether from aminoethyl vinyl ether and isocyanate, a quaternary ammonium salt of copolymer of vinyl cyclohexyl ether and diethylaminovinyl ether, vinyl nitrogen derivatives, such as a quaternary salt of polymer or copolymer of vinylpyridine, a quaternary salt of poly-2-vinylpyridine and p-toluenesulfonic acid, polyamine resins, such as polyethyleneglycol polyamine and the like.

As the non-ionic antistatic agents, use may be made of acrylates, such as a copolymer of polyethylene glycol ester and acrylic amide, ethylene oxide derivatives, such as a reaction product of melamine, formaldehyde and ethylene oxide, an addition product of phenol resin and ethylene oxide, an addition product of cellulose and ethylene oxide, a reaction product of polyethylene glycol and chlorohydrin, a copolymer of dimethyl terephthalate with ethylene glycol and polyethylene glycol, use of combination of tolylene-diisocyanate and polyethylene glycol, use of combination of polyacetal from polyethylene glycol and dimethylol urea, polyester of polyethylene glycol with maleic acid and itaconic acid, use of combination of polyethylene glycol and 1,3,5-triacryloyl-hexahydro-S-triazine, amide compounds, such as N-methoxymethylated polyamide, N,N'-dimethyl-N,N'-bishydroxymethyladipic amide.

The amphoteric antistatic agents include alanine type, imidazoline type, carboxylic acid type, dicarboxylic acid type, diamine type, betaine type and sulfobetaine type.

The cationic antistatic agents are preferable in view of the effect and antiwashing property.

As the softening agents, mention may be made of anionic agents, such as long chain alkyl sulphates, cationic agents, such as long chain alkyl quaternary ammonium salts, betaine type of amphoteric agents and the like.

The stain proofing agents applicable to the present invention include polymers having the general formula ##SPC1##

wherein RF represents a linear or branched perfluoroalkyl group having three to 21 carbon atoms, R' represents an alkyl group having one to 17 carbon atoms, R ² represents hydrogen or methyl group and m and n represent 1 to 10;

polymers having the general formula ##SPC2##

wherein RF' represents a linear or branched perfluoroalkyl group, m' represents 2 to 10 and R ³ represents hydrogen or methyl group;

polymers having the general formula

RF ² CH=CHCH ₂ OOCCR ⁴ =CH ₂

wherein RF ² represents a linear or branched perfluoroalkyl group having one to 20 carbon atoms and R ⁴ represents hydrogen or methyl group;

polymers having the general formula ##SPC3##

wherein RF ³ represents a linear or branched perfluoroalkyl group having three to 21 carbon atoms, R ⁵ represents an alkyl group having one to 17 carbon atoms, R ⁶ represents hydrogen or methyl group and m ² and n' represents 1 to 10;

polymers having the general formula ##SPC4##

wherein RF ⁴ represents a linear or branched perfluoroalkyl group having three to 18 carbon atoms, m ³ represents 0 to 16 and R ⁷ represents hydrogen or methyl group;

polymers having the general formula ##SPC5##

wherein RF ⁵ represents a linear or branched perfluoroalkyl group having one to 18 carbon atoms, R ⁸ represents an alkyl group haivng one to six carbon atoms and R ⁹ represents hydrogen or methyl group;

polymers having the general formula ##SPC6##

wherein RF ⁶ represents a linear or branched perfluoroalkyl group having one to 18 carbon atoms, R ¹⁰ and R" represent alkyl group having one to six carbon atoms and R ¹² represents hydrogen or methyl group and A represents --(CH ₂ ) _a --, in which a represents 0 to 4;

polymers having the general formula ##SPC7##

wherein RF ⁷ represents a linear or branched perfluoroalkyl group having three to 18 carbon atoms, n ² represents an alkyl group having zero to 16 carbon atoms and R ¹³ represents hydrogen or methyl group; and

polymers having the general formula ##SPC8##

wherein RF ⁸ represents a linear or branched perfluoroalkyl group having three to 21 carbon atoms, m ³ represents an alkyl group having zero to five carbon atoms, R ¹⁴ and R ¹⁵ represent alkyl groups having one to 19 carbon atoms, B represents ##SPC9##

or [RF ⁹ ]--A'--Z, wherein [RF ⁹ ] is a linear or branched perfluoroalkyl group having three to 20 carbon atoms, A' is --O-- or --S-- and Z is a triazine or pyridine ring.

The soil releasing agents include, for example a reaction product of poly-(N-methylperfluorooctane-sulfon amide-ethyl) acetate-ethylperfluorooctanoate and polyethyleneimine, a copolymer having polyoxyethylene group, which is obtained by copolymerizing dimethyl terephthalate, ethylene glycol and polyethylene glycol, a copolymer having polyoxyethylene group, which is obtained by copolymerizing dimethyl terephthalate, 1,4-bis-hydroxymethylcyclohexane and poly (oxyethylene) glycol.

As the other stain proofing agents, there are inorganic processing agents, such as alumina sol, silica sol and the like and they are used in an amount of 0.1 to 10 percent by weight based on the fibers, preferably 0.4 to 3 percent by weight.

As the oil repelling agents, use may be made of mainly low molecular substances or polymers containing fluorine atom and further the substances having soil releasing property may be used.

As the fluorine-containing compounds, for example mention may be made of the above described stain proofing agents.

The soil releasing agents include, for example a reaction product of poly-(N-methyl-perfluorooctanesulfonamide-ethyl) acetate, ethyl-perfluorooctanoate and polyethyleneimine, and a copolymer having polyoxyethylene group, which is obtained by copolymerizing dimethyl terephthalate, ethylene glycol and polyethylene glycol.

The dust proofing agents include, for example in organic agents, such as alumina sol, silica sol and the like.

As the antiflaming agents, use may be made of mainly compounds containing phosphorus or halogen, for example 2,3-dibromopropyl phosphate, trisdichloropropyl phosphate, 1,2,3,4 -tetrabromoethane, tetrakis-hydroxy-dimethyl phosphonium chloride, tris-2-chloroethyl phosphate, tris-aziridinyl-phosphin oxide, bis-B-chloroethyl phosphate, dialkyl phosphate carboxymethylolamide, dimethylol phosphono-propylene monomethylol amide, chloroparaffin, diammonium hydrogen phosphate, ammonium sulfamate, ammonium phosphate, borax and boric acid.

As the antifusing agents, organopolysiloxane is effective and the above described dialkyl-polysiloxanediol and alkyl hydrogen polysiloxane are mainly used.

As the crease proofing agents, use may be made of urea derivatives, triazine derivatives, triazone derivatives, dihydrazide derivatives, hydrazine derivatives, alkylcarbamate derivatives, acetal derivatives, organic silicone series prepolymers, and polyurethane prepolymers. As the urea derivatives, dimethylol compounds are used in many cases, for example dimethylol urea, dimethylol-ethylene urea, dimethylolpropylene urea, and dimethylol-dihydroxyethylene urea. The triazine derivatives include trimethylolmelamine and hexamethylolmelamine. The triazone derivatives include dimethyloltriazone. The hydrazide derivatives include methylolated product of dihydrazide. The hydrazine derivatives include dimethylolated product of symmetric hydrazine. The alkyl carbamate derivatives include dimethylolmethylcarbamate, dimethylolethylcarbamate, dimethylolpropylcarbamate, and dimethylolbutylcarbamate. As the organic silicone prepolymer, dialkylpolysiloxane diols are used in many cases, for example dimethylpolysiloxane diol and diethylpolysiloxane diol having a viscosity of at least 100 centistokes, preferably at least 2,000 centistrokes. As the polyurethane prepolymers, the prepolymers having a high polymerization degree of a viscosity of at least 1,000 centistokes, preferably at least 3,000 centistokes are used.

Furthermore, as the crease proofing agents, tetraoxane of methylol derivatives can be preferably used. Tetraoxane is a tetramer of aldehyde and even if it is fixed on knitted goods or woven fabrics alone, the crease proofing property or the wash wear property can be provided on the cloths.

The water absorbing agents or moisture absorbing agents are mainly polyester compounds and polyamide compounds containing a hydrating group and include relatively low molecular weight carboxylic acid and sulfonic acid derivatives. The polyester compounds are mainly a copolymer containing hydrating polyoxyalkylene group, which is a copolymer of polyoxyalkylene glycol having an avarage molecular weight of 300 to 6,000, particularly poly (oxyethylene) glycol or alkoxypoly (oxyalkylene) glycol, particularly methoxyl poly (oxyethylene) glycol with dimethyl terephthalate and ethylene glycol, for example a copolymer of dimethyl terephthalate, ethylene glycol, and polyoxyethylene glycol and a copolymer of dimethyl terephthalate, ethylene glycol and methoxy-poly (oxyethylene) glycol. As the polyamide compounds, use may be made of mainly N-methoxymethyl-polyhexamethylene adipamide and the addition product of a lactam or a derivative thereof with polyalkylene glycol is particularly preferable and an addition product of caprolactam oligomer having a polymerization degree of at most 5 with 2 to 50 mole of alkylene oxide having at most four carbon atoms is the most excellent in the treating effect and durability.

The elastic agents include polyorganosiloxane prepolymers or urethane prepolymers. As the polyorganosiloxane prepolymers, use may be made of polyorganosiloxane diols and alkyl hydrogen polysiloxanes.

The polyorganosiloxane diols are shown by the general formula

HO -- (SiRR'O) _n -- H

and have a viscosity of 1,000 to 100,000 centistokes of 15 percent trichlene solution at 25°C and have OH group at the end and R and R' may be the same or different and show alkyl, aryl, --CH=CH ₂ , --CH ₂ --CH ₂ --CF ₃ , --NCO, --OH, --OCH ₃ , etc. and the alkyl group has one to four carbon atoms. Dialkyl polysiloxane diol, diphenyl polysiloxane diol and alkyl phenyl polysiloxane diol are most frequently used and particularly dimethyl polysiloxane diol is the most preferable. The viscosity of polyorganosiloxane diol is 1,000 to 100,000 centistokes, preferably 5,000 to 50,000 centistokes. The alkyl hydrogen polysiloxane is somewhat poor in view of the elasticity of the formed film as compared with polyorganosiloxane diol but is advantageous in view of the water repellent property. The alkyl groups in alkyl hydrogen polysiloxane include methyl, ethyl, propyl and butyl groups but methyl hydrogen polysiloxane is the most preferable. The viscosity is preferred to be at most 1,000 centistokes, preferably 5 to 50 centistokes.

The polyurethane prepolymers to be used in the present invention have urethane bonds or urea bonds in the molecular chain and have isocyanate group in the end and such prepolymers can be produced by reacting a compound having active hydrogen with a compound having isocyanate group.

The organic diisocyanates to be used for the production of the prepolymers include 1,5-naphthalene diisocyanate, 4,4'-diphenyl methane diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, methylene bis (4-phenyl isocyanate), m-phenylene diisocyanate, p-phenylene diisocyanate, diphenylmethane-3,3'-dimentyl-4,4'-diisocyanate, xylene diisocyanate, cyclohexylene diisocyanate, 1,6-hexamethylene diisocyanate, dimethyl diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, methylcyclohexylene diisocyanate and the like. The active hydrogen compounds to be used for the formation of long chain segments are mainly diols and triols having a linear structure and also include polyols. As the triols, for example glycerin-propylene oxide adduct is used. As the diols, polyalkylene oxide glycols, such as poly-1,2propylene oxide glycol, polyethylene oxide glycol, ethylene oxide/propylene oxide copolymer glycol are preferable. The molecular weight of the diols is preferred to be at most 5,000. The prepolymers are preferred to be high molecular weight and 3,000 to 50,000, more preferably 10,000 to 25,000 and the isocyanate group is 1 to 3 percent, preferably 1.5 to 2.5 percent.

According to the present invention, it is possible to use polyorganosiloxane prepolymer and urethane prepolymer together. In this case, the isocyanate group in the polyurethane prepolymer and the hydroxyl group in the polyorganosiloxane diol form a block copolymer through the polyaddition reaction and the thus treated cloth is low in the waxy touch and has a feeling enriched in weight feeling and thickness as compared with the case when the urethane polymer of silicone polymer is used alone. The above described conditions concerning the urethane prepolymer are preferable for the formation of the block copolymer and the ratio of the mixture is preferred to be from 10:2 to 2:10.

In the present invention, an addition of a catalyst is preferable in order to carry out the hardening of the prepolymer under a practical industrial condition and in the case of polyorganosiloxane prepolymer, the use of catalyst is necessary. Dibutyltin dilaurate, dibutyltin octanoate, dibutyltin diethyl hexonate, chelate tin and the like are preferable but the catalyst is not limited thereto. They are used within the range of 1 to 30 percent by weight, preferably 3 to 10 percent by weight based on polyorganosiloxane prepolymer alone or in admixture. According to the present invention, a primer may be used together with the above catalyst in order to deposit the formed polymer on the fibers. The primers are, for example silane isocyanate, alkoxysilane, silane acetate, vinylthrichlorosilane, vinyl-tris (β-methoxyethoxy) silane, β-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyl-trimethoxysilane, γ-methacrylo-propyl-methoxysilane and the like. They are used in an amount of not more than 15 percent by weight based on polyorganosiloxane prepolymer.

The amount of polyorganosiloxane prepolymer and urethane prepolymer to be used in the present invention is 0.1 to 10 percent by weight, preferably 0.2 to 3 percent by weight based on the fibers. The amount of less than 0.1 percent by weight can not attain the satisfactory effect and the amount of more than 10 percent by weight is not preferable in the texture of the finished base cloth.

As the soil releasing agents, use may be made of carboxymethyl cellulose, hydroxyethyl cellulose, starch, water soluble polyvinyl alcohol, a block copolymer of polyethylene glycol and polyethylene terephthalate, a reaction product of an amino resin and polyethylene glycol, a reaction product of polyamide and polyethylene glycol, an acrylate/acrylic acid copolymer, an acrylate/methylol acrylic amide copolymer and acrylic acid/acrylic amide copolymer.

As the antipilling agents, use may be made of polyurethane compounds having a high polymerization degree, for example the above described elastic processing urethane prepolymer, reactive acrylate resins, butadiene latex and the like.

As the moth proofing agents and mildew proofing agents, use may be made of pentachlorophenol, sodium salt of pentachlorophenol, metal salts of naphthenic acid, cetyl pyridium bromide, dimethylbenzyl ammonium phosphate, trimethylcetyl ammonium pentachlorophosphate, tributyltin phthalate mercuric chloride, phenyl mercuric chloride, phenyl mercuric acetate, phenyl mercuric oleate, phenyl mercuric urea, phenyl mercuric p-toluene-sulfonanilide, phenyl mercuric triethanol ammonium acetate, ethyl mercuric chloride, ethyl mercuric oleate, ethyl mercuric p-toluene sulfonanilide, bistributyltin oxide, tributyltin acetate, tributyltin propionate, tributyltin butyrate, butyl p-oxybenzoate, sodium 3,5,3',5'-tetrachloro-2,2'-dioxytriphenyl methane-2"-sulfonate, disulfobenzoate of pentachlorodioxytriphenyl methane, dichlorodiphenyl, dichlorodiphenyl trichloroethane, sodium 3,5,3',5', 4"-pentachloro-2,2'-dioxytriphenyl methane-2"-sulfonate, 3,4-dichlorobenzene sulfomethylamide, sodium chloro-o-cresolate, 3,3',4'-trichloro-6-(2"-sulfo-4-chloro) phenoxydichloro urea and the like.

It has been usually carried out in dyeing, textile printing, printing and the like to disperse, distribute and fix a dye stuff, pigment and the like on a cloth. However, these procedures intend to obtain multi-color effect or design effect relying upon vision by the agents having different color tones and are fundamentally different from the present invention, in which a plurality of physical and chemical properties are given. Accordingly, the dye stuffs and pigments, which aim only the provision of color and do not bring about the modification of the physical and chemical properties, are not included in the processing agents of the present invention.

An embodiment wherein tetraoxane is used as a crease proofing agent of an example of treating of a cloth in the process of the present invention will be explained hereinafter.

In the process of the present invention, tetraoxane is usually applied on knitted goods or woven fabrics as an aqueous solution. In this case, the concentration of tetraoxane in the aqueous solution is selected variously depending upon the kind of knitted goods or woven fabrics to be treated, the means depositing it on them, the kind of the processing agents other than tetraoxane or with or without the drying treatment after the applying treatment and it is difficult to determine the concentration generally and the concentration is preferred to be 0.05 to 25 percent by weight, more particularly 0.5 to 20 percent by weight, most preferably 2 to 15 percent by weight.

Tetraoxane can be easily dissolved in water at room temperature but the solubility of tetraoxane at room temperature is about 5 to 8 per cent and in hot water, for example at 80°C, it reaches more than 13 percent, so that it is desirable to dissolve tetraoxane in water at a high temperature.

Furthermore, in order to promote the dispersion of tetraoxane in water, it is possible to use a dispersing agent (for example, anionic, cationic or nonionic various surfactants).

If the dispersing agent is used together it is possible to obtain a dispersion having a stable high concentration, for example more than 15 percent by weight of tetraoxane even at room temperature.

When tetraoxane is fixed on knitted goods or woven fabrics according to the present invention, a desirable result can be obtained by existing various catalysts to be used generally in the processing for crease proofing or wash wear, for example ammonium salts, organic amine salts or metal salts (for example, magnesium chloride, zinc nitrate or zinc fluoride etc.) together. The amount of the catalyst used is generally 1/10 to 1/2, preferably 1/4 to 1/25 (weight ratio) based on tetraoxane.

Moreover, according to the present invention, the most effective result can be obtained by applying tetraoxane on knitted goods or woven fabrics together with a sizing agent.

As the above described sizing agents, mention may be made of, for example starch, carboxylmethyl cellulose, polyvinyl alcohol and propylene glycol ester of alginic acid. Propylene glycol ester of alginic acid gives the best result.

However, some of the sizing agents can react with tetraoxane to fix tetraoxane on knitted goods or woven fabrics, but it is difficult to remove the sizing agent by washing and the knitted goods and woven fabrics become rigid, so that it is necessary to take account of the selection of the sizing agent deeply. Among the above described sizing agents, particularly propylene glycol ester of alginic acid, after it is deposited on knitted goods or woven fabrics together with tetraoxane, can be easily removed by washing with water and give an excellent effect resulting from tetraoxane to the cloth without hardening the cloth, so that it is the best sizing agent.

According to the present invention, tetraoxane and the other processing agents are deposited on the respective separate positions of the surface of knitted goods or woven fabrics. The order of the depositing treatment is not particularly defined and after the deposition of tetraoxane, the other processing agents may be deposited or the deposition treatments may be effected in the reverse order. Alternatively, if it is possible to deposit the processing agents in different positions, a plurality of processing agents may be deposited simultaneously in one step.

Tetraoxane can be deposited on knitted goods or woven fabrics in an aqeuous solution but if tetraoxane can be deposited on the given portion of the cloth surface in a desired state, the process is not particularly limited and various depositing processes or printing processes are applicable in relation to the depositing condition or means of the processing agents other than tetraoxane.

When tetraoxane is applied over all of one surface of the cloth, the printing process is convenient in many cases.

The processing agents other than tetraoxane are applied directly or in the solution state suitable for each processing agent on knitted goods or woven fabrics.

Particularly, when tetraoxane and the other processing agents are applied on the same surface of the cloth, unless a fairly broad portion on the surface of the cloth is coated or fixed with the respective processing agent in the conventional processing treatment, the effect can not be attained, while according to the present invention, the same treating effect as brought about by the conventional process can be attained by a small area partially deposited with the processing agent.

For example, when tetraoxane and the other processing agents are fixed so that the processing agents are separated independently in spot-like uniformly on the same surface of the cloth without doubling with each other, the above described treating effect is noticeably shown.

Tetraoxane and the other processing agents in the process of the present invention are fixed so that they occupy at least 20%, preferably at least 40 percent of the surface area of the cloth (the sum of the upper surface and the under surface).

When the deposited surface is less than 20 percent, it is impossible to obtain the treating effect owing to each of the processing agents on the cloth and such an amount is not preferable.

When tetraoxane is deposited on the cloth according to the present invention, it is desirable to select the concentration, viscosity or depositing condition of the solution so as not to penetrate to tetraoxane from the applied surface into the opposite surface. Because when a processing agent other than tetraoxane is applied on the opposite surface to the surface applied with tetraoxane, it is difficult to provide the effect of the processing agent satisfactorily on the cloth.

Tetraoxane may be applied on the upper surface or the under surface of the cloth or on both the surfaces and the processing agents other than tetraoxane also may be applied on the upper surface or the under surface of the cloth or on both the surfaces and such application is variously determined depending upon the kind of processing agent, the depositing state or the depositing means.

Furthermore, when tetraoxane is applied over all of one surface of the cloth, tetraoxane or the other processing agents are partially applied on the other surface.

The amount of tetraoxane deposited is 0.05 to 25 percent by weight, preferably 0.5 to 15 percent by weight based on the cloth. Particularly when tetraoxane is partially deposited, even if the amount is small, the effect can be fully developed.

The apparatuses for applying tetraoxane and the other processing agent on the cloth include, for example rollers textile printing machines, such as relief printing or intaglio printing machine, textile printing machines, such as manual or automatic screen printing machine or paper printing machines, such as relief printing or intaglio printing machine or a mangle.

When tetraoxane solution is printed on the cloth by means of these apparatuses, it is desirable to restrain and penetration of the solution into the under surface of the cloth as far as possible. Accordingly, a better result can be obtained, when the depth of the engraved portion of roll on the roller printing machine is small as far as possible. The permeability of tetraoxane solution into the cloth varies depending upon the fineness of yarns, density, knitted or woven structure and the like and therefore it is impossible to make a general statement but, for example when the cloth to be treated is a thin base cloth, such as a broad, the roullete number in a roller printing machine is at least 30, a gravure printing machine is at least 100 meshes and a screen printing machine is at least 200 meshes. The processing agents other than tetraoxane have no such a limitation. The amount of tetraoxane deposited on the cloth by these printing machines is considerably smaller than the total deposited amount by means of the immersing padding process, and for example is less than half.

However, when the area deposited with the printed processing agent on the cloth is very small or the depth of the roll is extremely small, the amount of the processing agent deposited is considerably small, so that in such a case it is desirable to make the concentration of the processing agent sufficiently high. On the other hand, when the printing is effected by means of various printing machines, a plurality of solutions of processing agents to be deposited on the cloth must be adjusted to a proper viscosity by the content of processing agent, sizing agent and the like in order not to flowout the processing agent from the engraved portion or in order to make the pattern edge of the engraved portion clear.

Thus, according to the present invention, the property of the cloth material can be optionally modified by means of different processing agents without causing interference and hindrance of processing agents with one another and the cloth providing each effect of the processing agent together can be produced. The cloth can be variously processed by a plurality of processing agents, which have never been heretofore used together because of the mutually opposing and contending function or shielding function and further by using a much smaller amount of processing agent as compared with the conventional means for processing the cloth, substantially the same effect can be attained. Accordingly, the present invention is very excellent as the means for processing cloth. In addition, the cloth obtained by the present invention is provided with a plurality of effects of various processing agents, which have never been previously provided together and the cloth has a novel combined plural properties and feeling and the demand field can be widely broadened.

The invention will be explained by the following examples but is not limited thereto.

In the examples, the crease resistance is determined by JIS-L-1079-22B process, the tear strength is determined by Pendulum process, the tensile strength is determined by strip process, the bending resistance is determined by Clerk process and the water repellent property is determined by JIS-L-1079-5,24,2 spray process.

The soil releasing property is determined by measuring the reflection factor of 550 mμby a spectrophotometer (made by HITACHI LTD., EPU-2A type), after treated with the test process for oil stain of Japan Oil Chemical Society.

The water absorbing property is determined by expressing the time necessary until 0.02 cc of potassium permanganate solution dropped on a center portion of a circle having a diameter of 3 cm made in a sample spread and reaches the periphery, by second.

The frictional electrostatic voltage is measured by Rotary static tester (made by KOA SHOKAI) by using a cotton broad cloth of 60 count yarn as a friction member.

The compression elasticity is determined as follows:

The thickness after the piled four sheets of cloths are subjected to a load of 10 g/cm ² for one minute is t, the thickness after the cloths are further subjected to a load of 300 g/cm ² for one minute is t ₁ and the thickness after the said cloths are left to stand under no load for one minute is t ₂ .

Compression degree (%) = [(t - t ₁ )/t ] × 100

Elasticity (%) = [(t ₂ - t ₁ )/(t - t ₁ )] × 100

Pilling test: JIS-L-1076 (1967)-A Method (using ICI type tester).

Oil repellent property: AATCC Test Method 118-1966 T.

Light resistance: Irradiation by a fadometer for 20 hours.

Wash and wear property: The determination was made from 5th class (best) to 1st class (worst) according to small crease grade standard photograph of AATCC TEST METHOD 88A. The washing condition is as follows: A sample of 30 cm × 30 cm was washed with 45 times amount of solution containing 1 g of Zabu (made by KAO SEKKEN K.K.; anionic detergent, Trade Mark) in 1 l of water by means of an automatic reversing washing machine at 40°C for 15 minutes and then washed with water for 15 minutes and taken out from the washing machine and two points in one end were suspended without squeezing and dried at room temperature. This procedure was repeated five times.

Antiflaming property: Test method of the Autonomy Agency of Japan, Law, Article 4, Item 3, No. 5 (practiced on April, 1969).

Mildew proofing property: JIS-L-1006 (1956).

Shrink proofing property: Treated with AATCC type launder-o-meter at 60°C for 20 minutes.

Antifusing property: Time (second) until a bore is made on a sample cloth by the fusion of the fiber, when an ignited incense having a diameter of 1 mm is put on the cloth.

Bending resistance : JIS-L-1079 C Method (Clerk method).

Test method for oil stain: One drop of colored paraffin is fallen on a sample cloth and this cloth is immersed in water and the behavior of the oil drop is observed.

Test method for aqueous stain: One drop of red ink is fallen on a smaple cloth and this is washed and the removal is observed.

Test method for redeposition of wet stain: A sample cloth having 3 inch ² and a flannel having the same area, which has been stained in the following manner are washed together in a launder-o-meter and the redeposition of the stain on the sample is observed.

A process for making the stained cloth:

40 g car's black

20 g tallow

20 g paraffin

4 l trichloroethylene

A flannel is padded with a liquid having the above composition and dried.

Whiteness: The opposite reflection factor against a standard white sheet (magnesium oxide) at 440 mμ by means of a spectrophotometer.

Tear strength : Pendulum process.

Tensile strength : JIS-L-1004, 511-(1) strip method.

Dust proofing property : Natural dust collected through a screen having 250 meshes is added to a cloth of 5 cm × 5 cm in an amount of 10 percent by weight based on the cloth and charged in a glass bottle of 500 cc having a cap together with 10 steel balls having a diameter of 10 mm. The glass bottle is rotated at a rate of 45 revolutions per minute and the sample is taken out after 10 minutes and is treated with a tumbler of 45 revolutions per minute for 5 minutes and the excess dust deposited on the sample is removed and then the sample cloth is compared with the standard white sheet (magnesium oxide) with respect to the whiteness.

Washing condition: 50 times amount of solution containing 1 g of the above described detergent of Zabu is used and the washing is effected by means of an automatic reversing washing machine at 40°C for 15 minutes and then water washing is performed at 40°C for 15 minutes. This procedure is repeated several times.

Example 1

A crease proofing agent solution having the following composition was applied to a nylon tricot cloth to form longitudinal stripes, each having a width of 2 mm and arranged at 2 mm intervals, as shown in FIG. 1 by means of a gravure roll, and the solvent was removed by means of a drier attached to the gravure roll. Then, a hygroscopic agent solution having the following composition was applied to the cloth to form another stripes as not to double on the two kinds of stripes by means of a roll, and dried, after which the cloth was heat treated at 150°C for 3 minutes. The thus obtained cloth had an excellent crease resistance and hygroscopicity as shown in the following Table 1.

(1) Crease proofing agent solution: Organopolysiloxane diol having a polymerization degree of 100 10 parts Dibutyltin dilaurate 0.1 part Perchlene 100 parts (2) Hygroscopic agent solution: Lurotex (made by BASF) 7 parts Water 100 parts

TABLE 1

Crease resistance Hygros- (%) copicity wale course (sec.) Not treated 60 58 35 Present invention 82 75 3 Two-bath method 80 74 ∞ (water is repelled) Note: Two-bath method: After a crease proofing agent was applied to the cloth by a padding method and dried, a hygroscopic agent was applied to the cloth by the same method and dried, after which the cloth was heat treated at 150°C for 3 minutes. The amounts of the crease proofing agent and hygroscopic agent adhered were the same as those in the present invention.

Example 2

An elastic processing agent solution having the following composition was applied to a woven fabric prepared from polyester finished yarns in the form of a spot composed of squares having a dimension of 5 × 5 mm arranged at 3 mm intervals as shown in FIG. 5, and dried in the same manner as described in Example 1. Then, an antistatic agent solution having the following composition was applied to the fabric in the space between the spots after which the cloth was dried and cured at 160°C for 2 minutes.

The thus obtained cloth had an excellent elastic property and antistatic property as shown in the following Table 2.

(1) Antistatic agent solution: AMS-313 (made by Lion Yushi K.K.) 2 parts Perchlene 100 parts (2) Elastic processing agent solution: Organosiloxane diol having a polymerization degree of 800 2 parts Catalyst PC (made by Shinetsu Kagaku K.K.) 0.02 part Catalyst PD (made by Shinetsu Kagaku K.K.) 0.02 part Perchlene 100 parts

TABLE 2

Compression Frictional elasticity (%) charge Compression Elasti- (V) degree city Not treated 10,000 21.9 85.2 Present invention 1,000 23.5 94.0 Conventional method 4,100 22.9 89.8

Example 3

A stain proofing agent solution having the following composition was applied to a cotton/polyester blended yarn fabric in the form of a spot as shown in FIG. 3, and dried. Then a soil releasing agent (SR agent) having the following composition was further applied to the fabric in the form of a spot composed of circles, each having a diameter of 1 mm, by means of a printing roll, and dried at 100°C for 45 seconds, after which the fabric was heat treated at 160°C for 2 minutes.

The thus obtained cloth had an excellent resistance against both oily stain and aqueous stain as shown in the following Table 3.

(1) Stain proofing agent solution: Scotch guard FC-310 (made by Sumitomo-3M K.K.) 10 parts 1,1,1-trichloroethane 100 parts (2) Soil releasing agent solution: Permalose T (made by ICI Ltd.) 15 parts Water 100 parts

TABLE 3

Test for Test for Redeposi- Soil releas- oily aqueous tion of ing property stain stain wet stain (reflectance) (%) Not Oil-drop treated adheres stained stained 10 Oil-drop Present becomes not not invention ball and stained stained 80 does not adhere

Example 4

A softener solution having the following composition was applied to a polyethylene film so as to form longitudinal stripes, each having a width of 2 mm and arranged at 1 mm intervals as shown in FIG. 1 by means of a gravure roll, and dried. Then an antistatic agent solution having the following composition was further applied to spaces between the above obtained stripes of the softener by means of the same roll, and dried at 160°C for 2 minutes.

The thus obtained film had an excellent softness and antistatic property as shown in the following Table 4.

(1) Softener solution: Morin Softener SN (made by 10 parts Morin Kagaku K.K.) Water 100 parts (2) Antistatic agent solution: Sorbitan salt of lauric acid 10 parts Water 100 parts

TABLE 4

Frictional charge Softness (V) Not treated 15,000 poor Present 1,200 good invention One-bath 10,000 good method

Example 5

A crease proofing agent solution having the following composition was applied to the portion 1 of the surface of a scoured and dyed tricot knitted from polyester finished yarns as shown in FIG. 5 by means a gravure roll, and dried by means of a drier attached to the roll. Then, an antistatic agent solution having the following composition was further applied to the portion 2 of the tricot surface so as not to double on the two portions 1 and 2, and dried by the drier. Then, a stain proofing agent solution having the following composition was further applied to the portion 3 of the tricot surface, and dried by the drier. The treated tricot cloth was heat treated at 130°C for 2 minutes.

The thus obtained cloth contained the above described crease proofing agent, antistatic agent and stain proofing agent in amounts of 0.4 percent, 2.0 percent and 3.2 percent as a solid component respectively, and had an excellent crease resistance, antistatic property and stain proofing property as shown in the following Table 5.

(1) Creasing proofing agent solution: Dimethyl-polyoxysiloxane diol (polymerization degree: 1500) 70 parts Stannous octoate 0.7 part Trichloroethylene 30 parts (2) Antistatic agent solution: Copolymer of polyethylene glycol ester and acrylamide 10 parts Water 100 parts (3) Stain proofing agent solution: Scotch guard FC-218 (made by Sumitomo-3M K.K.) 10 parts Acetone 100 parts

TABLE 5

Crease Frictional Oil repell- resistance charge ing property (%) (V) (grade) wale course Not treated 57.1 95.7 7,500 0 Present 77.4 94.7 150 6 invention Control 1 77.5 96.0 5,500 0 Control 2 78.5 96.1 9,000 0

Example 6

A printing bath was made from 75 parts of an emulsion composed of 47 percent of Kerosene, 51 percent of water and 2 percent of polyethylene glycol oleyl ether (H.L.B: 14), 20 parts of ethylene glycol diglycidyl ether and 5 parts of 25 percent aqueous solution of magnesium borofluoride. This printing bath was printed only on one surface of a scoured and bleached broad cloth composed of cotton yarns of 40 counts by means of a gravure roll engraved a pattern of 150 meshes on its entire surface. After the printed cloth was dried by a drier attached to the gravure roll, a dispersion having the following composition was printed on the other surface of the cloth by means of the above described gravure roll. This dispersion was composed of 92.5 parts of the above described emulsion, 5 parts of 50 percent emulsion of an emulsion copolymer (polymerization degree: 300) prepared from vinyl acetate and maleic acid anhydride in a mixing ratio of 1:1, 2 parts of ethylene glycol diglycidyl ether and 0.5 part of 50 percent aqueous solution of zinc borofluoride. The thus treated broad cloth, both surfaces of which were printed, was dried and then heat treated in a dry state at 150°C for 3 minutes. This procedure is the present invention.

As a control, a conventional padding method is shown. The above described broad cloth was immersed in an aqueous solution composed of 3 parts of the above described vinyl acetate/maleic acid anhydride copolymer, 1.2 parts of ethylene glycol diglycidyl ether, 0.3 part of 50 percent aqueous solution of zinc borofluoride and 95.5 parts of water, and the solution was squeezed to 60 percent based on the weight of the cloth by means of a padder. After dried, the cloth was further immersed in an aqueous solution composed of 12 parts of ethylene glycol diglycidyl ether, 3 parts of 50 percent aqueous solution of magnesium borofluoride and 85 parts of water, and the solution was squeezed to 60 percent based on the weight of the cloth. The resulting cloth was dried and heat treated in a dry state at 150°C for 3 minutes.

The obtained result is shown in the following Table 6.

TABLE 6

Crease resistance Soil re- (average of warp Bending Tear leasing and weft) (%) resis- strength property dry wet tance (g) (reflec- state state (mm) tance)(%) Not 50 46 62 1023 24 treated Control 76 76 102 604 39 Present 80 80 75 833 48 invention

As seen from Table 6, the cloth treated with the method of the present invention is excellent in all the properties, and the present invention is suitable for improving both of crease resistance and soil releasing property of cloth.

Example 7

A printing bath was prepared from 77 parts of the emulsion described in Example 6, 18 parts of 1,4-butane diol diglycidyl ether and 5 parts of 25 percent aqueous solution of magnesium borofluoride. This printing bath was printed only on upper surface of a scoured and bleached gaberdine cloth composed of polyester/cotton blended yarns (mix spinning ratio: 65:35) of 45 counts by means of a gravure roll engraved a pattern of 150 meshes on its entire surface. After the printed cloth was dried by means by a drier attached to the gravure roll, a dispersion having the following composition was printed to the under surface of the cloth by means of a gravure roll engraved a pattern of 180 meshes on its entire surface. This dispersion was composed of 88 parts of the above described emulsion, 10 parts of stearoylmethylamide-methylenepyridinium chloride and 2 parts of sodium acetate. The treated cloth, both surfaces of which were effected with different printings, was dried and heat treated in a dry state at 150°C for 3 minutes. The above procedure is the present invention.

As a control, a conventional padding method is shown. A treating bath was produced from 10 parts of 1,4-butane diol diglycidyl ether, 3 parts of 50 percent aqueous solution of magnesium borofluoride and 82 parts of water. The above described gaberdine cloth was immersed in the bath and the liquid was squeezed to 60 percent based on the weight of the cloth.

Then, the cloth was immersed in a treating solution composed of 6 parts of stearoylmethylamidemethylenepyridinium chloride, 1.5 parts of sodium acetate and 92.5 parts of water, and the solution was squeezed to 60 percent based on the weight of the cloth. Then, the cloth was dried and heat treated in a dry state at 150°C for 3 minutes.

The obtained result is shown in the following Table 7.

TABLE 7

Wash and Water Water absorb- Bend- wear pro- repell- ing property ing perty ing (sec.) resis- (grade) property upper under tance (%) surface surface (mm) Not 2.5 0 26 27 68 treated Control 5.0 70 ∞ ∞ 105 Present 5.0 70 34 ∞ 72 invention

As seen from Table 7 in the treated cloth according to the present invention, the under surface has water absorbing property, but the upper surface has water repelling property. Further, the cloth has an excellent wash wear resistance and a unique cloth.

Example 8

A printing bath was prepared from 75 parts of the emulsion described in Example 6, 20 parts of diglycerol dibutyl ether and 5 parts of 50 percent aqueous solution of zinc borofluoride. This printing bath was printed on the same gabardine cloth as used in Example 7 to form a longitudinal stripe by means of a gravure roll having engraved portions of 1 mm width (150 meshes) and non-engraved portions of 1 mm width, and dried by means of a drier attached to gravure roll. Further, another longitudinal stripe composed of engraved portions of 0.8 mm width (200 meshes) and non-engraved portions of 1.2 mm width was applied to the cloth so as not to double on the two stripes by using 1 percent aqueous solution of distearyl-dimethylammonium chloride. The treated cloth was dried and treated with steam at 120°C for 5 minutes to obtain a result as shown in the following Table 8.

TABLE 8

Crease resistance (average of warp Frictional and weft) (%) charge dry wet (V) state state Not treated 40 50 1650 Present 84 83 50 invention

As seen from Table 8, the cloth treated with the method of the present invention is excellent in the crease resistance and antistatic property.

Example 9

A printing bath was prepared from 75 parts the emulsion as described in Example 6, 20 parts of propylene glycol diglycidyl ether and 5 parts of 25 percent aqueous solution of zinc borofluoride. This printing bath was printed on the upper surface of a broad cloth composed of 40 count yarns by means of a gravure roll having a spotted pattern wherein 100 circles having a diameter of 1 mm were spotted per 400 cm ² . After the printed cloth was dried by means of a roller attached to the gravure roll, a solution composed of 85 parts of the above described emulsion, and 15 parts of aniline salt of hydroxymethanephosphonic acid was printed on the under surface of the printed cloth by means of a gravure roll engraved a pattern of 100 meshes on the entire surface. Then the cloth was dried and heat treated in a dry state at 150°C for 2 minutes. This procedure is the present invention.

As a control, a conventional padding method is shown. The above described broad cloth was immersed in an aqueous solution composed of 12 parts of propylene glycol diglycidyl ether, 3.5 parts of 25 percent aqueous solution of zinc borofluoride and 84.5 parts of water, and the solution was squeezed to 60 percent based on the weight of the cloth by means of a padder. The cloth was dried and heat treated in a dry state at 150°C for 2 minutes. Then, the cloth was further immersed in 9 percent aqueous solution of aniline salt of hydroxymethanephosphonic acid, and the solution was squeezed to 60 percent based on the weight of the cloth by means of a padder and dried.

The obtained result is shown in the following Table 9.

TABLE 9

Crease resistance (average of warp Bending and weft) (%) resistance dry wet (mm) state state Not treated 47 48 65 Control 75 78 115 Present 80 80 69 invention

The broad cloth not treated has no flame resistance, but both of the broad cloths treated with the method of the present invention and with the controlled method have an excellent flame resistance. However, the cloth treated with the controlled method has a rigid texture, while the cloth treated with the method of the present invention has a favourable texture.

Example 10

A first printing bath was prepared from 2 parts of β-(acryloxyethyl)-diethylmethylammonium metasulfate (polymerization degree: 200), 10 parts of water, 1.5 parts of lauryl sulfate and 86.5 parts of the emulsion described in Example 6. This printing bath was printed on one surface of a scoured and bleached polyester/cotton mix spun tasah cloth (mix spinning ratio: 65:35) by means of a first gravure roll having a transverse stripe composed of engraved portions of 0.5 mm width and non-engraved portions of 0.7 mm width and dried by means of an attached drier. Then, a second printing bath composed of 20 parts of diethylene glycol, 5 parts of 2.5 percent aqueous solution of magnesium borofluoride and 75 parts of the above described emulsion was printed on the same surface as described above of the cloth by means of a second gravure roll having a transverse stripe composed of engraved portions of 0.5 mm width and non-engraved portions of 0.7 mm width so as not to double on the two stripes, and dried by means of an attached roll. Further, a third printing bath composed of 10 parts of stearoylmethylamide-methylenepyridinium chloride, 2 parts of sodium acetate and 88 parts of the above described emulsion was printed on the other surface of the above treated cloth, on which the first and second printing baths were not printed, by means of a third printing gravure roll engraved a pattern of 150 meshes on the entire surface, and dried by means of an attached drier. Then, the thus treated cloth was heat treated in a dry state at 150°C for 3 minutes. The thus obtained cloth, which was treated with three processing agents of the antistatic agent, the crease proofing agent and the water repelling agent simultaneously, developed no static electricity, and had a crease resistance. Further, one surface of the cloth had water absorbing property, but the other surface had water repelling property. Consequently, this cloth was a unique finished cloth.

Example 11

An antistatic agent solution having the following composition was applied to the upper surface of a scoured and dyed tricot composed of 40 denier nylon yarns to form longitudinal stripes, each stripe having a width of 1 mm and arranged at 1 mm intervals, as shown in FIG. 1 by means of a gravure roll, and dried by means of an attached drier. Then, a crease proofing agent solution having the following composition was applied to the same surface in the form of a stripe so as not to double on the former and latter stripes and not to penetrate to the under surface, and dried by an attached drier. Further, a water absorbing agent solution having the following composition was applied to the entire under surface of the cloth, and dried. The thus treated cloth was heat treated at 130°C for 3 minutes.

The thus obtained cloth contained the above described antistatic agent, crease proofing and water absorbing agent in amounts of 0.8 percent, 0.4 percent and 0.5 percent as a solid component respectively, and had an excellent antistatic property, crease resistance and water absorbing property as shown in the following Table 10.

(1) Antistatic agent solution: Quaternary ammonium salt of diethylaminoethyl methacrylate and dimethyl sulfate 20 parts Water 80 parts (2) Crease proofing agent solution: Dimethylpolysiloxane (polymeri- zation degree: 1000) 80 parts Dibutyltin dilaurate 0.8 part Trichloroethylene 20 parts (3) Water absorbing agent solution: Compound obtained by the addition reaction of 10 moles of ethylene oxide to 1 mole of caprolactam 3 parts Isobutanol 3 parts Water 100 parts

TABLE 10

Frictional Crease Water ab- charge resistance sorbing (V) (%) property (under wale course surface) (sec.) Not treated 3000 79.7 94.0 120 Present 50 85.4 95.0 10 invention Control 1 40 79.8 94.5 30 Control 2 3200 86.4 95.1 water is repelled Control 3 300 81.1 95.0 1.5 Note: Control 1 : The above described antistatic agent was diluted with water and adhered to the cloth in an amount of 0.8 percent as a solid component by padding. Control 2: The above described crease proofing agent was diluted with water and adhered to the cloth in an amount of 0.4 percent as a solid component by padding. Control 3: The above described water absorbing agent was diluted with water and adhered to the cloth in an amount of 0.5 percent as a solid component by padding.

Example 12

An antistatic agent solution having the following composition was applied to the upper surface of a scoured polyester tricot in the form of longitudinal stripes, each having a width of 10 mm arranged at 1 mm intervals as shown in FIG. 1, by means a gravure roll, and dried by means of an attached drier. A stain proofing agent solution having the following composition was applied to the entire under surface of the treated cloth and dried by means of an attached drier. Then the treated tricot was heat treated at 150°C for 1 minutes. The thus obtained cloth contained the antistatic agent and the stain proofing agent in amounts of 1.0 percent and 4.2 percent as a solid component, respectively, and had an excellent antistatic property and stain proofing property as shown in the following Table 11.

(1) Antistatic agent solution: Quaternary ammonium salt of vinyl cyclohexyl ether and diethylamino vinyl ether 5 parts Water 100 parts (2) Stain proofing agent solution: Scotch guard FC-218 (made by Sumitomo-3M K.K.) 25 parts Acetone 100 parts

TABLE 11

Frictional Oil repelling charge property (V) (grade) Not treated 8500 0 Present 100 6 invention Control 1 80 0 Control 2 1000 7 Note: Control 1: The above described antistatic agent was diluted with water and adhered to the cloth in an amount of 1.0 percent as a solid component by padding. Control 2: The above described stain proofing agent was diluted with water and adhered to the cloth in an amount of 4.0 percent as a solid component by padding.

Example 13

An antiflaming agent solution (A) having the following composition was applied to the upper surface of a lace stitched certain cloth prepared from a fluorescently whitened ground weave of polyethylene terephthalate filaments and a pattern of rayon filaments in the form of spots as shown in FIG. 2 by means of a gravure roll, and dried by means of an attached drier. Then, an ultraviolet absorbing agent solution having the following composition was further applied to the upper surface so as not to double on the two agents, and dried by means of an attached drier. Further, antiflaming agent solution (B) having the following composition was applied to the entire under surface of the cloth, and dried by means of an attached drier. The resulting cloth was heat treated at 120°C for 5 minutes. The thus obtained cloth contained the above described antiflaming agent (A), antiflaming agent (B) and ultraviolet absorbing agent in amounts of 4.1 percent, 2.1 percent and 0.1 percent as a solid component respectively, and had an excellent flame resistance and light resistance as shown in the following Table 12.

(1) Antiflaming agent solution (A): Tris-2,3-dibromopropyl phosphonate 400 parts Perchloroethylene 600 parts (2) Ultraviolet absorbing solution : 2-hydroxy-4-octoxybenzophenone 0.5 part Acetone 100 parts (3) Antiflaming agent solution (B): Tris-chloroethyl phosphate 300 parts Trichloroethylene 700 parts

TABLE 12

Flame resis- Flame resis- Light tance of poly- tance of resis- ester portion rayon portion tance (number of (vertical contacted times flame test) (grade) with fire) Not 1 burned 1 treated completely Present invention 5 6.1 in. 3 Control 15 1 Control 21 burned 3 completely Note: Control 1: The above described antiflaming agent (A) was diluted with perchlene and adhered to the cloth in an amount of 4.2 percent as a solid component by padding. Control 2: The above described ultraviolet absorbing agent was diluted with acetone and adhered to the cloth in an amount of 0.1 percent as a solid component by padding.

Example 14

An antifusing agent solution having the following composition was applied to the entire upper surface of a broad cloth composed of blended yarns of 65 percent of polyester and 35 percent of cotton in the form of spots by means of an gravure roll, and dried by means of an attached drier. Then, a softening agent solution having the following composition was applied to the surface in the form of spots so as not to double on the two agents, and dried by an attached drier. The resulting cloth was heat treated at 150°C for 2 minutes.

The thus obtained cloth contained the above described antifusing agent and softening agent in amounts of 7.0 percent and 3.2 percent as a solid component respectively, and had an excellent fuse resistance and softness as shown in the following Table 13.

(1) Antiflaming agent solution: Dimethylpolysiloxane diol (polymerization degree: 1800) 100 parts Dibutyltin dilaurate 1 part 1,1,1-trichloroethane 20 parts (2) Softening agent solution: Cetylpyrimidium bromide 20 parts Water 100 parts

TABLE 13

Fuse Texture resistance (sec.) Not treated 5 poor Present 30 excellent invention Control 25 poor (rigid, stiff) Note: Control: The above described antifusing agent was printed and adhered to the cloth in an amount of 7.0 percent as a solid component.

Example 15

An antipilling agent solution having the following composition was applied to the upper surface of a scoured and dyed ester/rayon staple mix spun serge in the form of stripes having a 1.5 mm width at 1.5 mm intervals as shown in FIG. 1 by means of a gravure roll, and dried by means of an attached drier. Then, a softening agent solution having the following composition was applied to the surface so as not to double on the two agents, and dried by means of an attached drier. The resulting cloth was heat treated at 120°C for 5 minutes.

The thus obtained cloth contained the above described antipilling agent and softening agent in amounts of 2.5 percent and 2.0 percent as a solid component respectively, and had an excellent anitpilling property and softening as shown in the following Table 14.

(1) Antipilling agent solution: Polyurethane prepolymer (average molecular weight 18,000; NCO content 1.8%) prepared from 6 moles of polypropylene ether glycol (M.W. 2,000), 12 moles of tolylene diiso- cyanate, and 1 mole of polypropylene triol 30 parts Trichloroethylene 100 parts (2) Softening agent solution: DKS Taflon Perma A sol (made by Daiichi Kogyo K.K.; 10 parts polyamine series compound) Water 100 parts

TABLE 14

Antipilling property Texture (grade) Not treated 1 poor Present 4 soft and invention excellent Control 1 5 highly stiff Control 2 2 soft and excellent Note: Control 1: The above described antipilling agent was diluted with water and adhered to the cloth in an amount of 2.5 percent as a solid component by padding. Control 2: The above described softening agent was diluted with water and adhered to the cloth in an amount of 2.0 percent as a solid component by padding.

Example 16

A moth proofing agent solution having the following composition was applied to the entire upper surface of a scoured and dyed serge made of worsted yarns in the form of spots by means of a gravure roll, and dried by means of an attached drier. Then, a shrink proofing agent having the following composition was applied to the entire under surface, and dried by means of an attached drier. The thus treated serge was heat treated at 130°C for 5 minutes.

The thus obtained cloth contained the above described moth proofing agent and shrink proofing agent in amounts of 0.05 percent and 2.0 percent as a solid component respectively, and had an excellent moth proofing property and shrink proofing property as shown in the following Table 15.

(1) Moth proofing agent solution: Pentachlorophenol 0.1 part Methanol 100 parts (2) Shrink proofing agent solution: Zeset T (made by Du Pont Co., 100 parts reactive polyethylene) Perchloroethylene 900 parts

TABLE 15

Shrink proofing Moth proofing property (areal property shrinkage) (%) (moth proof- ing effect) (%) Not treated 12 20 Present invention 6 80

Example 17

An antipilling agent solution having the following composition was applied to the upper surface of a scoured and dyed jersey knitted from polyacrylonitrile spun yarn in the form of spots as shown in FIG. 3 by means of a gravure roll, and dried by means of an attached drier. A stain proofing agent solution having the following composition was further applied to the jersey in the form of spots so as not to double on the spots of the above two processing agents, and dried by means of an attached drier. The resulting cloth was heat treated at 150°C for 1 minute.

The thus obtained cloth contained the above described antipilling agent and stain proofing agent in amounts of 2.5 percent and 4.0 percent as a solid component respectively, and had an excellent antipilling property and stain proofing property as shown in the following Table 16.

(1) Antipilling agent solution: Polyurethane prepolymer (average molecular weight 20,000; NCO content 1.7 %) prepared from 6 moles of polypropylene ether glycol (M.W. 1,800), 12 moles of hexamethylene diiso- cyanate, and 1 mole of polypropylene triol 10 parts Trichloroethylene 100 parts (2) Stain proofing agent solution: Scotch guard FC-310 20 parts Perchloroethylene 80 parts

TABLE 16

Antipilling Oil repelling property property (grade) (grade) Not treated 1.5 0 Present 4.5 6 invention Control 1 5.0 4 Control 2 2.0 7

Example 18

A stain proofing agent solution having the following composition was applied to the entire upper surface of a scoured and dyed 70 denier nylon taffeta so as not to penetrate to the under surface by means of a gravure roll, and dried by means of an attached drier. An antiflaming agent solution having the following composition was further applied to the entire under surface of the taffeta, and dried by means of an attached drier. Then, the treated taffeta was heat treated at 150°C for 1 minute.

The thus obtained cloth contained the above described stain proofing agent and antiflaming agent in amounts of 3.0 percent and 4.0 percent as a solid component respectively, and had an excellent stain proofing property and flame resistance as shown in the following Table 17.

(1) Stain proofing agent solution: Scotch guard FC-218 22 parts Water 100 parts Isobutanol 2 parts (2) Antiflaming agent solution: Tris-(chloroethyl) phosphate 340 parts Trichloroethylene 660 parts

TABLE 17

Oil repelling Flame resis- property tance (number (grade) of times con- upper under tacted with surface surface fire) Not treated 0 0 1 Present invention 6 4 4 Control 1 6 4 2 Control 2 0 4 4 Note: Control 1: Only the above described stain proofing agent was printed and adhered to the cloth in an amount of 3.0 percent as a solid component. Control 2: Only the above described anti-flaming agent was printed and adhered to the cloth in an amount of 4.0 percent as a solid component.

Example 19

An antiflaming agent solution having the following composition was applied to the entire under surface of a scoured and dyed twill curtain fabric composed 100 percent nylon by means of a gravure roll, and dried by means of an attached drier. An ultraviolet absorbing agent solution having the following composition was further applied to the entire upper surface of the fabric, and dried by means of an attached drier. The thus treated curtain fabric was heat treated at 120°C for 7 minutes.

The thus obtained cloth contained the above described antiflaming agent and ultraviolet absorbing agent in amounts of 5.2 percent and 0.1 percent as a solid component respectively, and had an excellent flame resistance and light resistance as shown in the following Table 18.

(1) Antiflaming agent solution: Tetraquis-hydroxydimethyl- phosphonium chloride 25 parts Ethanol 100 parts (2) Ultraviolet absorbing agent solution: 2,2',4,4'-tetrahydroxybenzo- phenone 0.5 part Methanol 100 parts

TABLE 18

Flame resistance Light (vertical test) resistance remained carbonized (grade) fire(sec.) length (in.) Not treated completely 1 burned Present 0 4.2 3 invention Control 1 0 3.6 1 Control 2 completely 3 burned

Example 20

A water repelling agent solution having the following composition was applied to the entire under surface of a scoured and dyed woven fabric composed of polyester finished yarns by means of an gravure roll, and dried by means of an attached drier. Then an antifusing agent solution having the following composition was applied to the entire upper surface of the woven fabric, and dried by means of an attached drier. The thus treated fabric was heat treated at 150°C for 2 minutes.

The thus obtained cloth contained the above described water repelling agent and antifusing agent in amounts of 3.0 percent and 5.8 percent as a solid component respectively, and had an excellent water repelling property and fuse resistance as shown in the following Table 19.

(1) Water repelling agent solution: Methyl-hydrogen-polysiloxane (viscosity 100 centistokes) 10 parts Perchloroethylene 90 parts (2) Antifusing agent solution: Methyl-hydrogen-polysiloxane diol (polymerization degree 1,500) 90 parts Dibutyltin dioctoate 0.9 part Perchloroethylene 30 parts Butylated melamine 10 parts

TABLE 19

Water repell- Fuse ing property resistance (sec.) Not treated 0 5 Present invention 100 32 Control 1 100 10 Control 2 80 27 Note: Control 1: The above described water repelling agent was diluted with perchlene and adhered to the cloth in an amount of 3.0 percent as a solid component by padding. Control 2: The above described antifusing agent was diluted with perchlene and adhered to the cloth in an amount of 5.8 percent as a solid component by padding.

Example 21

In 60 parts of water was dissolved 4.5 parts of tetraoxane at 40° C, and 1.5 parts of Scourol 400 (made by Kao Sekken K.K.,non-ionic surfactant) was added to the solution. Then, 34 parts of kerosene was gradually added to the solution while stirring vigorously to prepare an emulsion having a viscosity of 430 cps. This emulsion was printed on one surface of a scoured and bleached polyester/cotton mixed spun broad (mix spinning ratio: polyester/cotton=65/35) by means of a gravure roll engraved a pattern of 150 meshes on its entire surface, and dried. Then, an soil releasing agent solution composed of 3 parts of Serogen 7 (made by Daiichi Kogyo K.K.) 1 part of polyethylene glycol diglycidyl ether (polymerization degree of polyethylene glycol: 400), 0.2 part of zinc borofluoride and 96 parts of water was further printed on the other surface of the broad by means of the same roll, and dried. The printed broad was heat treated in a dry state at 150°C for 3 minutes.

The thus treated cloth had a crease resistance and a soil releasing property, and further a soft texture as shown in the following Table 20.

As a control, a conventional one-bath method was effected. The same starting broad cloth was immersed in a solution composed of 4 parts of tetraoxane, 1 part of polyethylene glycol diglycidyl ether, 3 parts of Serogen 7A, 1 part of zinc borofluoride and 91 parts of water, and the solution was squeezed to 60 percent based on the weight of the cloth by means of a padder. After dried, the resulting cloth was heat treated in a dry state. The result is also shown in Table 20.

TABLE 20

Crease Wash and Soil re- resistance wear leasing Bending (%) property property resist- (average of (grade) (reflec- ance warp and weft) tance) (mm) (%) Not treated 76 3.0 42 62 One-bath method 84 4.0 57 118 Present invention 85 4.5 63 77

Example 22

A dispersion composed of 12 parts of tetraoxane, 77 parts of water and 1 part of Noigen ET 120 (made by Daiichi Kogyo K.K.) was heated to 90°C. After the tetraoxane was dissolved, 7 parts of 5 percent aqueous solution of Dacloid HF (made by Kamogawa Kako K.K.) was added to the solution, and the resulting mixture was cooled to room temperature from outside, and added with 3 parts of 50 percent aqueous solution of zinc chloride to obtain an opaque dispersion having a viscosity of 280 cps. The resulting dispersion was printed on a scoured and bleached polyester/cotton mix spun broad (mix spinning ratio of polyester/cotton= 65/35) by the use of a stripe pattern having engraved portions of 2 mm width, each portion being patterned to 160 meshes, and nonengraved portions of 1 mm width by means a gravure roll, and dried. Then, 2 percent aqueous solution of cetyl-trimethylpyridinium chloride was printed on the above printed broad by the use of a stripe pattern having engraved portions of 1 mm width, each portion being patterned to 120 meshes, and non-engraved portions of 2 mm width by means of a gravure roll so as not to double on the two kinds of stripes. After dried, the printed borad was heat treated in a dry state at 150°C for 3 minutes.

The thus obtained cloth had a crease resistance and an antistatic property as shown in the following Table 21.

TABLE 21

Treating Crease resis- Frictional method tance (average charge of warp and weft) (%) (V) Not treated 75 330 Present 90 0 invention

Example 23

A solution of 15 parts of tetraoxane and 4 parts of 50 percent aqueous solution of zinc borofluoride dissolved in dimethylformamide was printed on a woolen tropical suiting by means of a gravure roll engraved a pattern of 200 meshes on its entire surface. After dried, the printed tropical suiting was treated with steam at 130°C for 20 minutes.

The thus treated wool was excellent in the wash and wear property as shown in the following Table 22.

TABLE 22

Crease resist- Wash and Wash and tance (areal wear wear shrinkage) property property (%) (grade) after 5 times washing (grade) Not treated 23 2 1 Present invention 6 5 5

Example 24

A scoured and bleached polyester/cotton mix spun broad was printed by using the following three printing baths and patterns on both surfaces by means of a three color gravure roll.

i. Composition of the first bath and pattern of the first roll:

The first bath is the same as the tetraoxane dispersion in Example 22. The first roll has a transverse linear stripe pattern having engraved portions of 0.5 mm without mesh and non-engraved portions of 0.5 mm width.

ii. Composition of the second bath and pattern of the second roll:

The second bath is a emulsion having the following composition, wherein Permalose T is used as a water absorbing agent.

Permalose T 7 parts Kerosene/water emulsion (viscosity: 3,500 cps) 75 parts Water 18 parts

The second roll has a longitudinal stripe pattern having engraved portions of 1 mm width, each engraved portion being patterned to 120 meshes, and non-engraved portions of 1 mm width.

iii. Composition of the third bath and the pattern of the third roll:

The third bath is a dispersion having the following composition, wherein vinyl acetate/maleic acid anhydride copolymer is used as a soil releasing agent.

Vinyl acetate/maleic acid anhydride copolymer (polymeri- zation degree: 150) 12 parts Glycerin diglycidyl ether 2 parts Zinc borofluoride 0.5 parts Water 85.5 parts

The third roll in engraved to 150 meshes on its entire surface.

Namely, the above described polyester/cotton mix spun broad was printed on its upper surface by using the first bath and roll and the second bath and roll, and was printed on its under surface by using the third bath and roll, after which the printed broad was heat treated in a dry state at 150°C for 3 minutes. The obtained result is shown in the following Table 23.

As seen from Table 23, the thus obtained cloth had an excellent crease resistance, water absorbing property and soil releasing property.

TABLE 23

Crease resistance Water Reflec- (average of warp absorb- tance and weft) (%) ing dry wet property (%) state state (sec.) Not treated 77 67 48 39 Present invention 85 84 9 59

Example 25

A crease proofing agent solution having the following composition was applied to the entire upper surface of a cotton twill fabric cloth (count: warp 36/2 ^S , weft 24/2 ^S ; density: warp 111.5/inch, weft 57/inch; 264.4g/m ² ) so as not to penetrate to the under surface by means of an intaglio roll, and dried at 80°C. Then, a catalyst solution having the following composition was further applied to the under surface of the cloth by means of the above described roll, and dried. The cloth was heat treated at 150°C for 3 minutes, washed with a bath composed 1 g of Scourol 400 (made by Kao Sekken K.K.; non-ionic surfactant), 1 g of soda ash and 1 l of water at 70°C for 30 seconds, and dried. The thus obtained cloth contained the creasing proofing agent resin in an amount of 3.2 as a solid component, which was set only in the middle layer of the cloth, and had an excellent crease resistance, wash and wear property, abrasion resistance, tensile strength and tear strength. Even when this cloth was washed repreatedly, there was no difference between the both surfaces in the whiteness.

(1) Crease proofing agent solution: Dimethyl-dihydroxyethylene urea 15 parts Kerosene viscosity increasing agent 60 parts Bicron K 43 (Softener) (made by Ipposha Yushi K.K.) 2 parts Water 23 parts (2) Catalyst solution: Zinc nitrate 8 parts Kerosene viscosity increasing agent 30 parts Water 62 parts ##SPC10##

Example 26

A crease proofing agent solution having the following composition was applied to the entire upper surface of a mix spun broad cloth (count: warp 45 ^S , weft 45 ^S ; density: warp 141/inch, weft 73/inch; 122.9 g/m ² ) composed of 65 percent of polyethylene terephthalate and 35 percent of cotton so as to penetrate as far as the middle layer of the cloth by means of an intaglio roll, and dried at 80°C for 7 minutes. A catalyst solution having the following composition was applied to the under surface of the cloth by means of the same roll, and dried. The cloth was further heat treated at 140°C for 5 minutes, washed with a bath composed of 1 g of Emal NC (made by Kao Sekken K.K.; anionic surfactant), 1 g of soda ash and 1 l of water at 50°C for 1 minute, and dried.

The thus obtained cloth contained the crease proofing agent resin in an amount of 3.0 percent as a solid component, which was set only in the middle layer, and had an excellent crease resistance, wash and wear property, abrasion resistance, tensile strength and tear strength, and further had substantially the same water absorbing property as that of the untreated cloth. Even when the cloth was washed repeatedly, there was no difference between the both surfaces in the whiteness.

(1) Crease proofing agent solution: Imidazolidone resin (trade mark: Permafresh D.C.) 30 parts 1% aqueous solution of hydroxy- ethyl-cellulose (trade mark: cellosize QP 15,000) 90 parts (2) Catalyst solution: Zinc nitrate catalyst (trade mark: Catalyst F) 2 parts 0.3% aqueous solution of hydroxyethyl-cellulose 98 parts ##SPC11##

Example 27

A catalyst solution having the following composition was applied to the entire upper surface of a mix spun broad cloth (count: warp 45 ^S , weft 45 ^S ; density: warp 141/inch, weft 73/inch, 122.9 g/m ² ) composed of 65 percent of polyethylene terephthalate and 35 percent of cotton so as to penetrate as far as the middle layer of the cloth by means of an intaglio roll, and dried at 100°C for 1 minute. A crease proofing agent solution having the following composition was further applied to the under surface of the cloth so as to penetrate as far as the middle layer by means of a roll having a pattern of longitudinal lines, and dried. The cloth was heat treated at 160°C for 2 minutes, washed with a bath composed of 2 g of Scourol 100 (made by Kao Sekken K.K.; non-ionic surfactant) and 1 l of water at 70°C for 15 seconds, and dried.

The thus obtained cloth contained the crease proofing agent resin in an amount of 3.2 percent as a solid component, which was set in a pattern of lines in the middle layer of the cloth, and had an excellent crease resistance, wash and wear property, abrasion resistance, tensile strength and tear strength, and further had substantially the same excellent water absorbing property as that of untreated cloth. Even when the cloth was washed repeatedly, there was no difference between the both surfaces of the cloth in the whiteness. The obtained result is shown in Table 26.

(1) Catalyst solution: Magnesium chloride 1.2 parts Kerosene viscosity increasing agent 30 parts Water 69 parts (2) Crease proofing agent solution: Dimethylolethyl carbamate 20 parts Kerosene viscosity increasing agent 60 parts Bicron K 43 (softener 2 parts Water 20 parts ##SPC12##

Example 28

A crease proofing agent solution having the following composition was applied to the upper surface of a mix spun broad cloth (density: warp 136/inch, weft 72/inch) made of mix spun monofilaments composed of 65 percent of polyethylene terephthalate and 35 percent of rayon by means of a roll having a pattern of parallel fine lines, the direction of which are parallel to the direction of the warp of the cloth. Then, the catalyst solution was further applied to the under surface of the cloth at an angle 80° against the direction of the warp by means of a roll having a pattern of parallel fine lines. The cloth was dried at 100°C for 20 seconds, heat treated at 170°C for 1 minute, washed with perchloroethylene at 20°C for 5 minutes and dried.

The thus obtained cloth contained the crease proofing agent in an amount of 2.8 percent as a solid component, which formed a spotted pattern in the middle layer of the cloth, and had an excellent crease resistance, abrasion resistance, tensile strength, tear strength, and water absorbing property. Even when the cloth was washed repeatedly, there was no difference between the both surfaces of the cloth in the whiteness. The obtained result is shown in Table 27.

(1) Crease proofing agent solution: Dimethyl-polysiloxane diol 2.5 parts n-(dimethoxymethylsilylpropyl)- ethylenediamine (primer) 0.03 part Trichlene 97.5 parts

Viscosity of this solution is 110 centistokes.

(2) Catalyst solution: Dibutyltin dilaurate 0.03 part Trichlene 100 parts ##SPC13##

Example 29

An antistatic agent solution prepared from 15 parts of a cationic antistatic agent of a polymer, which was a polymerization product of quaternary ammonium salt of diethylaminoethyl methacrylate with dimethyl sulfate, and 85 parts of 45 percent aqueous solution of hydroxyethyl-cellulose was applied to one surface of a scoured and dyed cloth of nylon jersey knitted from nylon-6 twist yarns of 70d/18f/2p by means of a gravure roll, and dried at 80°C. Then, water absorbing agent solution composed of 2 g of a reaction product, which was obtained by reacting 31 g of ethylene oxide with 60 g of dimer or trimer of caprolactam, and 1 g of water was further applied to the other surface of the cloth, after which the cloth was heat treated at 130°C for 5 minutes.

The thus obtained cloth contained the above described antistatic agent and water absorbing agentin both the surfaces in amounts of 1 percent and 0.4 percent as a solid component respectively, and both the agents did penetrate from the applied surface to the other surface, and consequently the cloth had an excellent antistatic property and water absorbing property.

The obtained result is shown in the following Table 28.

TABLE 28

Frictional Water absorbing charge (V) property (sec.) before after before after washing washing washing washing Not treated 8500 9200 65 38 Present invention 150 350 5 7 Control 1 140 420 60 45 Control 2 230 5500 5 6 Control 3 145 440 65 58 Control 4 250 5800 5 5

Example 30

An antistatic agent solution composed of 20 g of a cationic antistatic agent prepared by copolymerization of 3 parts of 2-methacryloyloxyethyl-trimethylammonium-methyl sulfate and 1 part of 2,3-dibromopropyl methacrylate, 60 g of a viscosity increasing agent prepared from kerosene and 20 g of water was applied to the under surface of a twill fabric cloth having 2/2 twill texture which was prepared from polyester false twist yarns of 100d/32f/2p, and dried at 100°C. Then, an antipilling agent composed of 10 parts of a prepolymer prepared from 1 mole of polypropylene ether glycol (molecular weight: 2,000), 2 moles of tolylene diisocyanate and 1.6 mole of polypropylene ether triol (molecular weight 4,000) and 90 parts of xylene as a solvent was further applied to the upper surface of the cloth, and the cloth was heat treated at 130°C for 5 minutes.

The thus obtained cloth contained the above described antistatic agent and antipilling agent in amounts of 1 percent and 1.2 percent as a solid component respectively, and both the processing agents did not penetrate from the applied surface to the other surface of the cloth.

The cloth had an excellent antipilling property and antistatic property as shown in Table 29.

TABLE 29

Frictional Antipilling charge (V) property (grade) before after before after washing washing washing washing Not treated 6500 8000 2 1.5 Present invention 180 280 5 4.5 Control 1 170 450 2.5 2 Control 2 7200 8200 5 4 Control 3 185 550 2.5 2 Control 4 7500 8400 4 3 Note: Control 1: The antistatic agent was applied to only one surface of a cloth. Control 2: The antipilling agent was applied to only one surface of a cloth. Control 3: The antistatic agent was applied by padding method. Control 4: The antipilling agent was applied by padding method.

Example 31

An antistatic agent solution composed of 15 g of an oil repelling agent of Scotch guard FC-218 (made by 3M Co., U.S.A.; fluorine series processing agent) having an antistatic property and 85 g of acetone was applied to a cloth of a scoured and dyed polyester jersey knitted from polyester textured yarns of 110d/32f/2p by means of a roll so that 1 percent of the antistatic agent as a solid component was adhered to the cloth, and then an elastic crease proofing agent solution composed of 4.5 g of dimethylpolysiloxane diol (viscosity of 15 percent solution in trichlene: 20,000 centistokes), 0.04 g of dibutyltin dilaurate (as a setting catalyst), 0.04 g of primer of n-(dimethoxy-methyl-silyl-propyl) ethylene-diamine, and 95 g of trichlene was further applied to the other surface of the cloth by means of the same roll so that 2.4 percent of the crease proofing agent as a solid component was adhered, and dried.

Then cloth was heat treated at 150°C for 3 minutes. Both of the antistatic agent and crease proofing agent did not penetrate from the applied surface to the other surface, and the cloth had an excellent antistatic property and crease resistance.

As a control, the antistatic agent or crease proofing agent was applied to a cloth by padding method to produce a treated cloth containing the antistatic agent and crease proofing agent in amounts of 1 percent or 2.4 percent as a solid component respectively.

The properties of the thus obtained cloths were examined to obtain a result as shown in Table 30. ##SPC14##

Example 32

A crease proofing agent solution composed of 15 parts of Permafresh DC (made by Nippon Leichhold K.K. ; imidazoline series resin), 2.2 parts of Catalyst F (zinc nitrate catalyst) and 88.5 parts of 1.5 percent aqueous solution of Celloace 4000 (made by Kyowa Sangyo K.K.; hydroxyethylcellulose) was applied to the upper surface of a scoured, bleached and fluorescently whitened broad cloth made of 1/40 count mix spun yarns composed of 65 percent of polyethylene terephthalate and 35 percent of cotton by means of a knife coater, and dried. Then, an antistatic agent solution composed of 15 parts of a copolyester emulsion (solid component concentration: 30 percent) having polyoxyethylene groups, which was prepared by a copolymerization of 97 parts of dimethyl terephthalate, 31 parts of ethylene glycol and 187.5 parts of polyethylene glycol (molecular weight: 1,500), and 85 parts of water was further applied to the under surface of the cloth by means of a gravure roll, whereby the crease proofing agent and antistatic agent were adhered to the cloth in amounts of 4.2 percent and 1.5 percent as a solid component respectively. The cloth was heat treated at 160°C for 2 minutes.

The thus obtained cloth had an excellent antistatic property and crease resistance as shown in Table 31. Even when oil was adhered to the cloth, the oil was able to be easily removed by washing with water. ##SPC15##

Example 23

An antistatic agent solution composed of 10 parts of copolyester having antistatic property, which was prepared by a copolymerization of 53.7 parts of dimethyl terephthalate, 9.1 parts of dimethyl sodium salt of sulfoisophthalate and 43 parts of ethylene glycol, 40 parts of a viscosity increasing agent prepared from kerosene and 50 parts of water was applied to the under surface of a twill fabric cloth having 2/2 twill texture which was prepared from polyester false twist yarns of 110d/32f/2p, by means of a gravure roll so that the antistatic agent was adhered to the cloth in an amount of 1.5 percent as a solid component, and dried at 80°C. Then, a water repelling agent solution composed of 5 parts of methyl-hydrogen polysiloxane (viscosity: 18 centistokes). 0.04 part of dibutyltin dilaurate (as a catalyst) and 95 parts of trichloroethylene (as a solvent) was further applied to the upper surface in the same manner as described above so that the water repelling agent was adhered to the cloth in an amount of 0.8 percent as a solid component. The cloth was heat treated at 180°C.

Both the processing agents were not penetrated from the applied surface to the other surface, and the cloth had an excellent antistatic property and water repelling property.

As a control, each processing agent was adhered to the starting cloth so that the adhered amount was the same as that of the present invention.

The properties of the thus obtained cloths were examined to obtain a result as shown in Table 32. ##SPC16##

Example 34

A crease proofing agent emulsion having the following composition was applied to one surface of a mix spun broad cloth (density: warp 136/inch, weft 72/inch, weight 134 g/m ² ) made by mix spun monofilaments of 45 counts composed of 65 percent of polyethylene terephthalate and 35 percent of cotton in the form of parallel lines along the warp of the cloth by means of a roll having a pattern of fine lines, and dried at 80°C. After the cloth was backed at 150°C for 2 minutes, a water absorbing agent emulsion having the following composition was further applied to the other surface of the cloth by the same roll as described above, and dried at 80°C. The cloth was heat treated at 150°C for 2 minutes, washed with water and dried.

The thus obtained cloth contained the crease proofing agent resin and water absorbing agent in amounts of 3.2 percent and 0.6 percent as a solid component respectively which were set in the form of alternate stripe in the cross-section of the cloth, and had an excellent water absorbing property, crease resistance and wash and wear property as shown in Table 33. In the cloth, the stripes were not observed by naked eye, and the cloth had an uniform appearance.

1. Crease proofing agent emulsion:

Dimethylol-dihydroxyethyleneurea resin 15 parts Zinc nitrate (catalyst) 8 parts Kerosene viscosity increasing agent 60 parts Bicron K 43 (softener) 2 parts Water 15 parts

2. Water absorbing agent emulsion:

A dispersion of a polyester having a concentration of 3.3 percent in water, which was prepared in the following manner.

5 g of a copolyester, which was obtained by a copolymerization of 500 parts of dimethyl terephthalate, 350 parts of ethylene glycol, 50 parts of diethylene glycol and 850 parts of polyethylene glycol (molecular weight: 6,000), was dissolved in 45 g of tetrahydro-furfryl alcohol, 1 g of sorbitan oleate and 1 g of polyoxyethylene-(15)-sorbitan laurate were added to the solution. The resulting mixture was heated and stirred at 90°C, and added to 100 g of water. ##SPC17##

Example 35

A crease proofing agent solution having the following composition was applied to one surface of a mix spun broad cloth (density: warp 136/inch, weft 72/inch, weight 134 g/m ² ) made of mix spun monofilaments of 45 counts composed of 65 percent polyethylene terephthalate and 35 percent of cotton by means of an intaglio roll having a pattern or small points, and dried at 80°C. After the cloth was heat treated at 150°C for 2 minutes, a water absorbing agent solution having the following composition was applied to the cloth by means of an intaglio roll. The cloth was dried at 80°C, heat treated at 150°C for 2 minutes and washed with water at 60°C.

In the resulting cloth, 3.2 percent of the crease proofing agent as a solid component was set in the form of fine points all over the surface of the cloth, and 2 percent of the water absorbing agent as a solid component was set between the points. The cloth had an excellent crease resistance, water absorbing property and wash and wear property as shown in Table 34.

(1) Crease proofing agent solution: Dimethylolethyl carbamate 20 parts Magnesium chloride (catalyst) 1.2 parts Hydroxyethyl-cellulose (viscosity increasing agent) 0.5 part Water 79 parts

2. Water absorbing agent solution:

5 percent solution of a copolyester in benzyl alcohol, which copolyester was preferred by a copolymerization of

97 parts of dimethyl tetraphthalate,

31 parts of ethyleneglycol, and

58 parts of methoxy-poly (oxyethylene) glycol having a molecular weight of 350. ##SPC18##

Example 36

A crease proofing agent emulsion having the following composition was applied to a cloth of mix spun poplin (viscosity: warp 116/inch, weft 70/inch, weight 113 g/m ² ) made of mix spun monofilaments of 45 counts composed of 65 percent of polyethylene terephthalate and 35 percent of cotton by means of a roll having a lattice pattern, and dried at 80°C. Then a water absorbing agent dispersion having the following composition was further applied to the cloth by means of an intaglio roll, and dried at 80°C. The cloth was heat treated at 150°C for 3 minutes.

In the thus obtained cloth, 3.2 percent of the crease proofing agent as a solid component was adhered on one surface in the form of a lattice pattern, and the water absorbing agent was adhered between the lattices and further adhered all over the other surface. The cloth had an excellent crease resistance and water absorbing property as shown in Table 35.

(1) Crease proofing agent emulsion: Permafresh 183 (made by Sun Chemical Co., U.S.A.; methylolimidazolidone series resin) 20 parts Catalyst X-4 (catalyst) 2 parts Maikon SF (softener) 0.5 part Hydroxyethyl-cellulose (viscosity increasing agent) 74 parts Water

2. Water absorbing agent dispersion:

10 percent dispersion of a copolyester obtained by a copolymerization of 97 parts of dimethyl terephthalate,

51.5 parts of 1,4-bis-hydroxymethyl-cyclohexane, and

220 parts of poly (oxyethylene glycol having a molecular weight of 154. ##SPC19##

Example 37

A crease proofing agent solution having the following composition as applied to the upper surface of a cloth of a half stitched tricot (density: wale 44/inch, course 64/inch) knitted from mix spun yarn composed of 50 percent of nylon-6and 50 percent of cotton by means of an intaglio roll, and then a water absorbing agent solution having the following composition was further applied to the under surface of the cloth by means of the same roll. Then, the cloth was heat treated at 150°C for 5 minutes.

The thus obtained cloth contained 2 percent of the crease proofing agent (as a solid component) adhered to the upper surface of the cloth and 2 percent of the water absorbing agent (as a solid component) adhered mainly to the under surface of the cloth, and had an excellent crease resistance and water absorbing property as shown in Table 36.

The conventional knit wear is often, out of shape by wearing, but in the above obtained cloth, there was no out of shape by wearing.

(1) Crease proofing agent solution: Polyurethane prepolymer(average mole- cular weight: 18,000; NCO content: 1.8%; viscosity: 8,000 centistokes) prepared from 6 moles of polypropylene ether glycol (molecular weight 2,000), 12 moles of tolylene diisocyanate, and 1 mole of polypropylene triol 20 parts Perchloroethylene (solvent) 80 parts

2. Water absorbing agent solution:

A solution obtained by dissolving 1 g of an addition product, which was prepared from 60g of a caprolactam dimer and trimer mixture and 31g of ethylene oxide, in 1 l of water. ##SPC20##

Example 38

A crease proofing agent solution having a viscosity of 40 cps and prepared by dissolving 200 g of a polyurethane prepolymer (average molecular weight: 18,000; HCO content: 1.8 percent; viscosity: 4,500 cs), which was prepared from 6 moles of polypropylene ether glycol (molecular weight: 2,000), 12 moles of tolylene diisocyanate and 6 moles of polypropylene triol, in 800 g of trichloroethylene was applied to the upper surface of a cloth of 40 denier nylon-6 half stitched tricot by means of a gravure roll, and the trichloroethylene was removed by means of an attached drier. Then, a water absorbing agent solution obtained by dissolving 30 g of an addition product of 1 mole of caprolactam and 10 moles of ethylene oxide and 10g of isobutanol in 1,000 g of water was further applied to the under surface of the cloth by means of the same roll, and the water was removed by means of an attached drier. The cloth was heat treated at 150°C for 2 minutes.

The thus obtained cloth contained 3.2 percent of the crease proofing agent as a solid component and 0.5 percent of the water absorbing agent as a solid component, and had an excellent crease resistance and water absorbing property as shown in Table 37. ##SPC21##

Example 39

A crease proofing agent solution having a viscosity of 700 cp and prepared by dissolving 40 g of dimethyl-polysiloxane diol (viscosity of 15 percent solution in trichlene: 15,000 cs), 8 g of methylhydrogen-polysiloxane (viscosity: 18 cs), 0.4 g of vinyltrichlorosilane and 0.4 g of dibutyltin dioctoate in 51.2 g of 1,1,1-trichloroethane was applied to the upper surface of a cloth of 40 denier polyester tricot by means of a gravure roll, and the 1,1,1-trichloroethane was removed by means of an attached drier. Then, a water absorbing agent solution obtained by dissolving 20 g of an emulsion (solid component: 30 percent) of a copolyester having polyoxyethylene groups, which was prepared by a copolymerization of 97 parts of dimethyl terephthalate, 31 parts of ethylene glycol and 187.5 parts of polyethylene glycol (molecular weight: 1,500), in 100g of water was further applied to the under surface of the cloth by means of a gravure roll, and the water was removed by means of an attached drier. The cloth was heat treated at 150°C for 3 minutes.

The thus obtained cloth contained 0.6 percent of the crease proofing agent as a solid component and 1.3 percent of the water absorbing agent as a solid component, and had an excellent crease resistance and water absorbing property. Even when the cloth was washed repeatedly the texture of the cloth was not deteriorated.

TABLE 38

Crease Water absorbing resistance(%) property (sec.) (wale + upper under course) surface surface Not treated 162.1 longer longer than than 180 180 Present 181.6 longer 7 invention than 180 Control 1 180.7 longer longer than than 180 180 Control 2 167.0 7 40 Control 3 189.9 longer longer than than 180 180 Control 4 165.5 7 7 Note: Control 1: The above described crease proofing agent solution was printed to the upper surface of a cloth, and 0.6 percent of the solid component was adhered to the cloth. Control 2: The above described water absorbing agent solution was printed to the under surface of a cloth, and 1.3 percent of the solid component was adhered to the cloth. Control 3: The above described crease proofing agent was diluted with 1,1,1-trichloroethane, and 0.6 percent of the solid component was adhered to a cloth by padding method. Control 4: The above described water absorbing agent was diluted with 1,1,1-trichloroethane, and 1.3 percent of the solid component was adhered to a cloth by padding method.

Example 40

A crease proofing agent solution having a viscosity of 700 cp and prepared by dissolving 20 g of dimethyl-polysiloxane diol (viscosity of 15 percent solution in trichlene at 25°C: 20,000 cs), 5 g of the same polyurethane prepolymer as used in Example 38, 0.2 g of dibutyltin dilaurate (catalyst), 0.2 g of N-(trimethoxypropyl)-ethylenediamine (primer) in 100 g of trichloroethylene was applied to the upper surface of a cloth of 30 denier nylon half-stitched tricot by means of a gravure roll, and the trichloroethylene was removed by means an attached drier. Then, a water absorbing agent solution obtained by dissolving 20 g of an addition product, which was produced from 30 g of a mixture of caprolactam dimer and trimer and 30 g of propylene oxide, in 1,500 g of ethanol was further applied to the under surface of the cloth, and the ethanol was removed by means of an attached drier. The cloth was heat treated at 150°C for 3 minutes.

The thus obtained cloth contained 0.5 percent of the crease proofing agent as a solid component and 0.9 percent of the water absorbing agent as a solid component, and had an excellent crease resistance and water absorbing property as shown in Table 39. ##SPC22##

Example 41

A crease proofing agent solution having the following composition was applied to the entire upper surface of a cloth of cotton twill fabric (count: warp 36/2 ^S , weft 24/a S ; density: warp 111.5/inch, weft 57/inch; 264.4 g/m ² ) so as not to penetrate to the under surface by means of an intaglio roll, and dried at 80°C. Then, a deactivating solution having the following composition was applied to the upper surface of the cloth by means of a roll engraved shallower than the above described roll, and dried. The cloth was heat treated at 150°C for 3 minutes, washed with a bath composed of 1 g of Scourol 400 (made by Kao Sekken K.K.; nonionic surfactant), 1 g of soda ash and 1 l of water at 70°C for 30 seconds, and dried.

The thus obtained cloth contained the crease proofing agent resin in an amount of 3.2 percent as a solid component, which was set only in the middle layer of the cloth, and had an excellent crease resistance, wash and wear property, abrasion resistance, tensile strength and tear strength. Even when the cloth was washed repeatedly, there was no difference between the both surface of the cloth in the whiteness. The result is shown in Table 40.

(1) Crease proofing agent solution: Dimethylol-dihydroxyethylene urea 15 parts Kerosene viscosity improving agent 60 parts Bicron K 43 (softener) 2 parts Zinc nitrate 1.5 parts Water 22 parts (2) Deactivating solution: Soda ash 8 parts Kerosene viscosity improving agent 60 parts Water 32 parts ##SPC23##

Example 42

A crease proofing agent solution having the following composition was applied to one entire surface of a mix spun broad cloth (count: warp 45 S, weft 45 S; density: warp 141/inch, weft 73/inch, 122.9 g/m ² ) composed of 65 percent of polyethylene terephthalate and 35 percent of cotton so as to penetrate as far as the middle layer of the cloth by means of an intaglio roll, and dried at 80°C for 7 minutes. Then, a deactivating solution having the following composition was further applied only superficially to the same surface of the cloth by means of a roll engraved shallower than the above described roll, and dried. The cloth was heat treated at 140°C for 5 minutes, washed with a bath composed of 1 g of Emal NC (made by Kao Sekken K.K.; nonionic surfactant), 1 g of soda ash and 1 l of water at 50°C for 1 minute, and dried.

The thus obtained cloth contained the crease proofing agent resin in an amount of 3.0 percent as a solid component, which was set only in the middle layer of the cloth, and had an excellent crease resistance, wash and wear property, abrasion resistance, tensile strength and tear strength, and further had substantially the same water absorbing property as that of untreated cloth. Even when the cloth was washed repeatedly, there was no difference between the both surface of the cloth in the whiteness. The result is shown in Table 41.

(1) Crease proofing agent solution: Imidazolidone series resin (trade mark: Permafresh DC) 30 parts 1% aqueous solution of hydroxyethyl- cellulose (trade mark: Cellosize QP 15,000) 88 parts Zinc nitrate catalyst (trade mark: Catalyst F) 2 parts (2) Deactivating solution: Potassium carbonate 2 parts 5% aqueous solution of hydroxy- ethyl-cellulose 98 parts ##SPC24##

Example 43

A crease proofing agent solution having the following composition was applied to the entire surface of a mix spun broad cloth (count: warp 45 ^S , weft 45 ^S ; density: warp 141/inch, weft 73/inch, 122.9 g/m ² ) composed of 65 percent of polyethylene terephthalate and 35 percent of cotton so as to penetrate so far as the middle layer of the cloth by means of an intaglio roll, and dried at 100°C for 1 minute. Then, a deactivating solution having the following composition was further applied only superficially to the same surface of the cloth by means of a roll engraved shallower than the above described roll, and dried. The cloth was heat treated at 160°C for 2 minutes, washed with a bath composed of 2 g of Scourol 100 (made by Kao Sekken K.K.; nonionic surfactant) and 1 l of water at 70°C for 15 seconds, and dried.

The thus obtained cloth contained the crease proofing agent resin in an amount of 3.2 percent as a solid component, which was set only in the middle layer of the cloth, and had an excellent crease resistance, wash and wear property, abrasion resistance, tensile strength and tear strength, and further had substantially the same water absorbing property as that of untreated cloth. Even when the cloth was washed repeatedly, there was no difference between the both surface of the cloth in the whiteness. The result is shown in Table 42.

(1) Crease proofing agent solution: Magnesium chloride 2 parts Dimethylolethyl carbamate 20 parts Kerosene viscosity improving agent 60 parts Bicron K 43 (softener) 2 parts Water 18 parts (2) Deactivating solution: Urea 4 parts Kerosene viscosity improving agent 30 parts Water 66 parts ##SPC25##

Example 44

A double jersey (stretched length: 70 mm/50 course) knitted from false twist nylon-6 yarns of 70d/18f/2p was scoured with 30 times amount of a solution containing 1 g of an anionic surfactant and 1 g of soda ash at 70°C to obtain a sample cloth. A crease proofing agent solution having the following composition was applied to one surface of the cloth by means of a gravure roll, and dried at 170°C. Then, a stain proofing agent solution having the following composition was applied to the other surface of the above cloth, and the cloth was heat treated at 170°C for 1 minute.

The thus obtained cloth contained the crease proofing agent and stain proofing agent in amounts of 1.5 percent and 0.4 percent respectively, and had an excellent crease resistance and strain proofing property. The obtained result is shown in the following Table 43.

When the above described two processing agents were applied in reverse order, similar result was obtained.

(1) Crease proofing agent solution: Dimethyl-polysiloxane diol (viscosity of 10% solution in trichlene: 15,000 centistokes) 4 parts Ethyl-hydrogenpolysiloxane (viscosity: 18 centistokes) 0.5 part Dibutyltin dilaurate 0.04 part Trichloroethylene (solvent) 95.5 parts (2) Stain proofing agent solution: ##SPC26## 2.4 parts Acetone 97.6 parts ##SPC27##

Example 45

A crease proofing agent solution having the following composition was applied to one surface of a cloth of scoured and dyed double jersey (stretched length: 65 mm/50 course) knitted from 1100/22f/2p polyester textured yarns by means of a roll. Then a stain proofing agent solution having the following composition was applied to the other surface of the cloth, and the cloth was heat treated at 170°C for 1 minute.

The thus obtained cloth contained the crease proofing agent and stain proofing agent in amounts of 1.4 percent and 0.6 percent as a solid component respectively and had an excellent crease resistance and stain proofing property. The obtained result is shown in Table 44.

(1) Crease proofing agent solution: Dimethylpolysiloxane diol (viscosity of 15% solution in trichlene: 21,000 centistokes) 45 parts Dibutyltin dilaurate 0.04 part N-(dimethoxymethylsilyl-propyl) ethylenediamine (primer) 0.04 part Xylene (solvent) 95 parts (2) Stain proofing agent solution: Polymer prepared by a emulsion polymerization of C ₈ F ₁₇ CH=CH C ₉ H ₁₈ OCOCH=CH ₂ 1.2 parts Polymer of 2-ethylhexyl metha- crylate 1.4 parts Dimethylol-hydroxyethylene urea 1.0 parts 10% aqueous solution of magnesium chloride 1.0 parts Water 98 parts ##SPC28##

Example 46

A crease proofing agent having the following composition was applied to one surface of a scoured and dyed cloth (density: wale 38/inch, course 35/inch) knitted from 44 count wool worsted yarns by means of a gravure roll. Then, a stain proofing agent solution having the following composition was applied to the other surface of the cloth, and the cloth was heat treated at 105°C for 10 minutes.

The thus obtained cloth contained the crease proofing agent and stain proofing agent in amounts of 1.5 percent and 1.2 percent as a solid component respectively, and had an excellent crease resistance and stain proofing property. The obtained result is shown in Table 45.

(1) Crease proofing agent solution: Polyurethane prepolymer having an average molecular weight of 18,000, an NCO content of 1.8% and a viscosity of 4,500 centistokes, which was prepared from 6 moles of polypropylene ether glycol (molecular weight: 2,000), 12 moles of tolylene diisocyanate, and 1 mole of polypropylene triol 10 parts Perchloroethylene (solvent) 90 parts (2) Stain proofing agent solution: Poly (N-perfluro-octanoylamino methacrylamide) 8 parts Benzo trifluoride 1 Hexafluoroxylene 1 (solvent) 92 parts Ethyl acetate 1 ##SPC29##

Example 47

A crease proofing agent solution having the following composition was applied to one surface of a fluorescently whitened broad cloth (density: warp 120/inch, weft 70/inch) made of 40 count mix spun monofilaments composed of 65 percent of polyethylene terephthalate and 35 percent of cotton by means of a roll, and dried at 100°C. Then, a stain proofing agent solution having the following composition was further applied to the other surface of the cloth, and the cloth was heat treated at 150°C for 3 minutes.

The thus obtained cloth contained the crease proofing agent and stain proofing agent in amounts of 1.5 percent and 2 percent as a solid component respectively, and had an excellent crease resistance and stain proofing property, and both the agents did not penetrate to the opposite surface. The obtained result is shown in Table 46.

(1) Crease proofing agent solution: Dimethyl-polysiloxane diol (viscosity of 15% solution in trichlene: 20,000 centistokes) 5 parts Prepolymer used in Example 46 2.5 parts Dibutyltin dilaurate (catalyst) 0.1 part N-(trimethoxypropyl)-ethylene- diamine (primer) 0.1 part Trichloroethylene (solvent) 93 parts (2) Stain proofing agent solution: [CF ₃ (CF ₂ ) ₆ COHN -- CH ₂ O] ₄ Ti This compound was produced by reacting N-methylol compound of fluorinated carboxylic acid amide having the formula of CF ₃ (CF ₂ ) ₆ COHN ₂ OH with titanium tetraoxide in toluene as a solvent 10 parts Benzene (solvent) 90 parts ##SPC30##

Example 48

A crease proofing agent emulsion having the following composition was applied to one surface of the starting cloth used in Example 47 by means of a gravure roll, and dried at 120°C. Then, a stain proofing agent solution having the following composition was further applied to the other surface of the cloth, whereby both the processing agents were adhered in amounts of 2 percent as a solid component.

In the thus obtained cloth, both the processing agents did not penetrate to the opposite surface, and the cloth had an excellent crease resistance and stain proofing property. The obtained result is shown in Table 47.

(1) Crease proofing agent emulsion: Dimethyl-polysiloxane diol (viscosity: 100 centistokes) 5 parts Polyethylene glycol phenyl ether (HLB 17) (emulsion) 7 parts Dibutyltin dilaurate 0.5 part Water 88 parts

The above components were mixed in a mixer to prepare an emulsion.

(2) Stain proofing agent solution: Emulsion polymerization product of ##SPC31## (solid content: 18.7%) 50 parts Acetone (solvent) 50 parts ##SPC32##

Example 49

A crease proofing agent solution having the following composition was applied to one surface of the same starting mix spun broad cloth as used in Example 47 by means of a gravure roll. Then, a stain proofing agent emulsion having the following composition was further applied to the other surface of the cloth, and the cloth was heat treated at 180°C for 30 seconds.

In the thus obtained cloth, both the processing agent did not penetrate to the opposite surface, and the cloth contained the processing agents in amounts of 1.5 percent and 1.6 percent, and had an excellent crease resistance and stain proofing property. The obtained result is shown in Table 48.

(1) Crease proofing agent solution: Polyurethane prepolymer having an average molecular weight of 10,000 and an NCO content of 1.8%, which was prepared from 1 mole of polypropylene glycol ether (molecular weight: 2,000), 2 moles of tolylene diisocyanate, and 1.6 moles of polypropylene ether triol (molecular weight: 4,000) 10 parts Xylene (solvent) 90 parts (2) Stain proofing agent emulsion: Emulsion (solid content: 30%) of polyester having polyoxyethylene groups, which was prepared by a polymerization of 97 parts of dimethyl terephthalate, 31 parts of ethylene glycol, and 187.5 parts of polyethylene glycol (molecular weight: 1,500) 15 parts Water 85 parts ##SPC33##