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[0001] The present invention relates to a heat-peelable pressure-sensitive adhesive sheet which can be efficiently made easily peelable from an adherend by short-term heating at any time when required.
[0002] Heat-peelable pressure-sensitive adhesive sheets comprising a substrate and formed thereon a pressure-sensitive adhesive layer containing a foaming agent or expanding agent, e.g., heat-expandable microspheres, have conventionally been known (see, for example, JP-B-50-13878, JP-B-51-24534, JP-A-56-61468, JP-A-56-61469, and JP-A-60-252681; the terms “JP-B” and “JP-A” as used herein mean an “examined Japanese patent publication” and an “unexamined published Japanese patent application”, respectively). These heat-peelable pressure-sensitive adhesive sheets combine adhesiveness and peelability after use. This kind of pressure-sensitive adhesive sheet is characterized in that the adhesive force thereof is lowered by thermally foaming or expanding the foaming agent or expanding agent and, as a result, the adhesive sheet can be easily peeled from the adherend. Due to this characteristic, these pressure-sensitive adhesive sheets are used as a means for temporary fixation in the production of electronic parts and as labels to be recycled, etc.
[0003] With the recent trend toward capacity increase and size reduction in hard disks for use as a storage device in personal computers and the like, recording/reproducing magnetic heads of the type having a high areal recording density have come to be employed. At present, GMR (giant magnetoresistive) heads are coming to be mainly used. Although heat-peelable pressure-sensitive adhesive sheets are used for temporary fixation also in the production of such GMR heads, there has been the following problem. Since the GMR heads have poor resistance to static electricity, electrostatic breakage occurs due to static electricity generated in the head production process, resulting in an impaired yield of products.
[0004] Accordingly, an object of the invention is to provide a heat-peelable pressure-sensitive adhesive sheet which, even when used for temporarily fixing electronic parts having poor resistance to static electricity, such as magnetic heads, is effective in preventing the yield of such electronic parts from being reduced by electrostatic breakage, while ensuring its functions of adhesiveness before heating and peelability after heating.
[0005] The present inventors made intensive investigations in order to accomplish the object described above. As a result, they have found that the electrostatic breakage of electronic parts can be prevented when a heat-expandable pressure-sensitive adhesive layer is regulated so as to have a surface resistivity not higher than a specific value. The invention has been completed based on this finding.
[0006] The invention provides a heat-peelable pressure-sensitive adhesive sheet comprising a substrate and formed on at least one side thereof a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres, wherein the heat-expandable pressure-sensitive adhesive layer has a surface resistivity of 10
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[0011] [Description of the Reference Numerals]
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[0018] The invention will be explained below in detail by reference to the accompanying drawings according to need. In the drawings, like members or parts are designated by like numerals.
[0019] The embodiment shown in
[0020] The substrate
[0021] The substrate
[0022] The poorly bondable substrate is used as the substrate for a substrate-peelable pressure-sensitive adhesive sheet, in which the substrate and the layer overlying the same can be easily peeled from each other. This substrate-peelable pressure-sensitive adhesive sheet can, for example, be used in the following manner. The pressure-sensitive adhesive sheet is applied to an adherend a, and the substrate is then peeled off to leave the heat-expandable pressure-sensitive adhesive layer on the adherend a. Thereafter, another adherend b is adherend to this heat-expandable pressure-sensitive adhesive layer. Namely, the substrate-peelable pressure-sensitive adhesive sheet can be used as an adhesive for temporary fixation. In this case, when the adherend state is desired to be ended, the adhesive layer is heated, whereby the adherends a and b can be easily separated from each other. On the other hand, the strongly bondable substrate is used as the substrate for a substrate-fixed pressure-sensitive adhesive sheet, wherein the substrate is strongly bonded to the layer overlying the same. Such a substrate-fixed pressure-sensitive adhesive sheet can be adhered to an adherend at a predetermined adhesive force. When the adhered state of this adhesive sheet is desired to be ended, the adhesive sheet is heated, whereby it can be easily peeled or separated from the adherend.
[0023] The rubber-like organic elastic layer
[0024] From the standpoint of imparting those functions, the rubber-like organic elastic layer
[0025] Examples of the synthetic rubber or synthetic resin having rubber elasticity include synthetic rubbers such as nitrile, diene, and acrylic rubbers; thermoplastic elastomers such as polyolefins and polyesters; and synthetic resins having rubber elasticity, such as ethylene/vinyl acetate copolymers, polyurethanes, polybutadiene, and flexible poly(vinyl chloride). Even polymers which are intrinsically rigid, such as poly (vinyl chloride), can be made to have rubber elasticity by incorporating a plasticizer, softener, or the like thereinto. Such compositions can also be used as a material for constituting the rubber-like organic elastic layer. Furthermore, pressure-sensitive adhesive materials, such as, e.g., the pressure-sensitive adhesive constituting the heat-expandable pressure-sensitive adhesive layer
[0026] The rubber-like organic elastic layer
[0027] An appropriate method can be used for forming the rubber-like organic elastic layer
[0028] The rubber-like organic elastic layer
[0029] The heat-expandable pressure-sensitive adhesive layer
[0030] The pressure-sensitive adhesive is preferably one which restrains, in the lowest possible degree, the foaming and/or expansion of the heat-expandable microspheres during heating. Examples thereof include known pressure-sensitive adhesives such as rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, vinyl alkyl ether-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, polyamide-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, styrene/diene block copolymer-based pressure-sensitive adhesives, and pressure-sensitive adhesives having improved creep characteristics obtained by incorporating a hot melt resin having a melting point of about 200° C. or lower into these pressure-sensitive adhesives. Such pressure-sensitive adhesives can be used alone or in combination of two or more thereof (see, for example, JP-A-56-61468, JP-A-61-174857, JP-A-63-17981, and JP-A-56-13040). The pressure-sensitive adhesive may contain appropriate additives besides the pressure-sensitive adhesive ingredient (base polymer). Examples of the additives include crosslinking agents (e.g., polyisocyanates and melamine alkyl ethers), tackifiers (e.g., resins which are solid, semi-solid, or liquid at ordinary temperature, such as rosin derivative resins, polyterpene resins, petroleum resins, and oil-soluble phenol resins), plasticizers, fillers, and antioxidants.
[0031] Examples of pressure-sensitive adhesives generally used include rubber-based pressure-sensitive adhesives containing natural rubber or any of various synthetic rubbers as the base polymer; and acrylic pressure-sensitive adhesives containing as the base polymer an acrylic polymer (homopolymer or copolymer) formed from one or more monomers selected from alkyl (meth)acrylates (e.g., C
[0032] The acrylic polymer may contain units derived from one or more other monomers copolymerizable with the alkyl (meth)acrylates so as to be improved in cohesive force, heat resistance, crosslinkability, or other properties according to need. Examples of such monomers include carboxyl-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; acid anhydride monomers such as maleic anhydride and itaconic anhydride; hydroxyl-containing monomers such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl)methyl methacrylate; sulfo-containing monomers such as styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate, and (meth)acryloyloxynaphthalenesulfonic acid; (N-substituted) amide monomers such as (meth) acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, and N-methylolpropane (meth) acrylamide; aminoalkyl (meth) acrylate monomers such as aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth)acrylate; alkoxyalkyl (meth)acrylate monomers such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide; itaconimide monomers such as N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, and N-laurylitaconimide; succinimide monomers such as N-(meth) acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, and N-(meth)acryloyl-8-oxyoctamethylenesuccinimide; vinyl monomers such as vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine, N-vinylcarboxamides, styrene, α-methylstyrene, and N-vinylcaprolactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy-containing acrylic monomers such as glycidyl (meth)acrylate; glycol acrylate monomers such as polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, and methoxypolypropylene glycol (meth) acrylate; acrylate monomers having a heterocycle, one or more halogen or silicon atoms, or the like, such as tetrahydrofurfuryl (meth)acrylate, fluorinated (meth)acrylates, and silicone (meth)acrylates; polyfunctional monomers such as hexanediol (meth)acrylate, (poly) ethylene glycol di(meth) acrylate, (poly) propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy acrylates, polyester acrylates, and urethane acrylates; olefin monomers such as isoprene, butadiene, and isobutylene; and vinyl ether monomers such as vinyl ether. These monomers can be used alone or in combination of two or more thereof.
[0033] From the standpoint of a balance between moderate adhesive force before heat treatment and a decrease in adhesive force through heat treatment, a preferred pressure-sensitive adhesive is one which comprises as the base polymer a polymer having a dynamic modulus of elasticity of 50,000 to 10,000,000 dyn/cm
[0034] The heat-expandable microspheres are not particularly limited as long as they are microcapsules obtained by encapsulating a substance which readily gasifies and expands upon heating, such as isobutane, propane, or pentane, in elastic shells. In many cases, the shells are made of a hot-melt material or a material which is broken by thermal expansion. Examples of the shell-forming material include vinylidene chloride/acrylonitrile copolymers, poly(vinyl alcohol), poly(vinyl butyral), poly(methyl methacrylate), polyacrylonitrile, poly (vinylidene chloride),and polysulfones. The heat-expandable microspheres can be produced by a conventional method such as coacervation or interfacial polymerization. A commercial product of heat-expandable microspheres, e.g., MICROSPHERE (trade name; manufactured by Matsumoto Yushi Seiyaku K. K.), is also usable.
[0035] From the standpoint of efficiently lowering the adhesive force of the pressure-sensitive adhesive layer by heat treatment, it is preferred to use heat-expandable microspheres having such a moderate strength that they do not break until the volume expansion ratio thereof reaches at least 5 times, preferably at least 7 times, more preferably at least 10 times.
[0036] The amount of the heat-expandable microspheres to be incorporated can be suitably determined according to the desired expansion ratio of the pressure-sensitive adhesive layer, the desired degree of decrease of the adhesive force thereof, etc. However, the heat-expandable microspheres are incorporated, for example, in an amount of generally 1 to 150 parts by weight, preferably 10 to 130 parts by weight, more preferably 25 to 100 parts by weight, per 100 parts by weight of the base polymer constituting the heat-expandable pressure-sensitive adhesive layer
[0037] In order for the heat-expandable pressure-sensitive adhesive layer in the invention to exhibit satisfactory adhesiveness, the adhesive layer before heating has a center line average surface roughness of preferably 2 μm or less (e.g., about 0.02 to 2 μm), more preferably 0.4 μm or less (e.g., about 0.02 to 0.4 μm) , and a maximum surface roughness of preferably 5 μm or less (e.g., about 0.1 to 5 μm) , more preferably 4 μm or less (e.g., about 0.5 to 4 μm). The center line average surface roughness and maximum surface roughness of the heat-expandable pressure-sensitive adhesive layer before heating can be regulated by suitably selecting the thickness of the heat-expandable pressure-sensitive adhesive layer
[0038] The particle diameter of the heat-expandable microspheres preferably satisfies the relationship (thickness of the heat-expandable pressure-sensitive adhesive layer
[0039] The conductive material to be added to the heat-expandable pressure-sensitive adhesive layer
[0040] In the case where a particulate conductive material, e.g., an inorganic conductive material such as a metal or metal oxide, is added, this conductive material preferably satisfies the relationship (thickness of the heat-expandable pressure-sensitive adhesive layer
[0041] Although the amount of a particulate conductive material to be added is preferably larger from the standpoint of lowering the surface resistivity of the pressure-sensitive adhesive layer, too large amounts thereof result in reduced adhesiveness. Because of this, the particulate conductive material is added, for example, in an amount of preferably 50 to 200 parts by weight, more preferably 70 to 150 parts by weight, per 100 parts by weight of the base polymer constituting the heat-expandable pressure-sensitive adhesive layer
[0042] In the case of using an organic antistatic agent or the like as the conductive material, it is added in an amount of preferably 0.5 to 30 parts by weight, more preferably 1 to 5 parts by weight, per 100 parts by weight of the base polymer constituting the heat-expandable pressure-sensitive adhesive layer
[0043] The heat-expandable pressure-sensitive adhesive layer
[0044] The thickness of the heat-expandable pressure-sensitive adhesive layer
[0045] As the separator
[0046]
[0047] The heat-expandable pressure-sensitive adhesive layer
[0048] The conductive layer
[0049] In each of the embodiments described above, the heat-expandable pressure-sensitive adhesive layer
[0050] Techniques for regulating the surface resistivity of the heat-expandable pressure-sensitive adhesive layer to 10
[0051] Since the heat-expandable pressure-sensitive adhesive layer
[0052] In the case where the heat-peelable pressure-sensitive adhesive sheet which has a rubber-like organic elastic layer interposed between the substrate and the heat-expandable pressure-sensitive adhesive layer is applied to an adherend, the surface of the pressure-sensitive adhesive sheet satisfactorily conforms to the surface shape of the adherend due to the elasticity of the rubber-like organic elastic layer. As a result, a large adhesion area and hence an enhanced adhesive strength can be obtained. When this adhesive sheet is heated for peeling from the adherend, the expansion (volume change) of the heat-expandable layer can be accurately controlled to thereby enable the heat-expandable layer to evenly expand preferentially in the thickness direction. As a result, the adhesive sheet can be more easily peeled off. In addition, even when the particle diameter of the heat-expandable microspheres contained in the heat-expandable pressure-sensitive adhesive layer is slightly too large, the surface roughness attributable to these microspheres is buffered by the rubber-like organic elastic layer. As a result, the heat-expandable pressure-sensitive adhesive layer can have reduced surface roughness.
[0053] The heat-peelable pressure-sensitive adhesive sheet of the invention may be used for permanently bonding an appropriate article as an adherend. However, since the adhesive sheet has the advantages described above, it is suitable for use in applications where an adherend is kept adherent thereto for a given period and this adhered state is desired to be ended after accomplishment of the purpose of adhesion. In particular, the adhesive sheet of the invention is most suitable for use as a temporarily fixing material in the production of magnetic heads, IC chips, and the like, in which application the use of conventional heat-peelable pressure-sensitive adhesive sheets results in a reduced yield due to static breakage.
[0054] Conditions for the heat treatment for facilitating the peeling of the pressure-sensitive adhesive sheet of the invention from an adherend can be suitably selected according to the desired degree of decrease in adhesion area, which depends on the surface state of the adherend, kind of the heat-expandable microspheres, etc., the heat resistance of the substrate and adherend, the heating means to be used, and others. General conditions for the heat treatment include a temperature of from 100 to 250° C. and a heating period of from 1 to 90 seconds (in the case of heating with a hot plate or the like) or from 5 to 15 minutes (in the case of heating in a hot-air drying chamber or the like) . The pressure-sensitive adhesive layer is heated usually under such conditions to expand and/or foam the heat-expandable microspheres contained in the pressure-sensitive adhesive layer. As a result, the pressure-sensitive adhesive layer expands and deforms and, hence, the adhesive force is reduced or lost. The heat treatment can be conducted at a suitable stage according to the purpose of use. In some cases, an infrared lamp or hot water can be used as a heat source.
[0055] According to the heat-peelable pressure-sensitive adhesive sheet of the invention, even when it is used for temporarily fixing electronic parts susceptible to static breakage, such as magnetic heads, it is effective in preventing the yield of such electronic parts from being reduced by electrostatic breakage, while ensuring its functions of adhesiveness before heating and peelability after heating.
[0056] The invention will be described below in greater detail by reference to Examples, but the invention should not be construed as being limited by these Examples. Particle size was measured with laser scattering/diffraction particle size distribution analyzer Model SALD-2000J (manufactured by Shimadzu Corporation).
[0057] Heat-expandable microspheres A (MATSUMOTO MICROSPHERE F-50D; manufactured by Matsumoto Yushi Seiyaku K. K.; average particle diameter, 13.4 μm; maximum particle diameter, 63 μm) were classified with a centrifugal air classifier to obtain classified heat-expandable microspheres B (average particle diameter, 12.3 μm; maximum particle diameter, 42 μm).
[0058] On the other hand, a toluene solution of a pressure-sensitive adhesive composed of a 2-ethylhexyl acrylate/ethyl acrylate/methyl methacrylate copolymer (containing 1 part by weight of a polyurethane crosslinking agent) was applied to a 100 μm thick polyester film in a thickness of 10 μm on a dry basis. The coating was dried to form a rubber-like organic elastic layer.
[0059] A toluene solution containing 100 pars by weight of a pressure-sensitive adhesive composed of a 2-ethylhexyl acrylate/ethyl acrylate/methyl methacrylate copolymer (containing 2 parts by weight of a polyurethane crosslinking agent), 30 parts by weight of the classified heat-expandable microspheres B, and 80 parts by weight of an acicular conductive powder C (trade name; “PASSTRAN 5110S”, manufactured by Mitsui Mining & Smelting Co., Ltd.) was applied to a separator in a thickness of 35 μm on a dry basis. The coating was dried to form a pressure-sensitive adhesive layer. This adhesive layer was adhered to the rubber-like organic elastic layer formed on the polyester film. Thus, an antistatic heat-peelable pressure-sensitive adhesive sheet was obtained.
[0060] The same procedure as in Example 1 was conducted, except that 100 parts by weight of a platy conductive powder D (trade name “PASTRAN 4610”, manufactured by Mitsui Mining & Smelting Co., Ltd.) was used in place of 80 parts by weight of the acicular conductive powder C (trade name; “PASTRAN 5110S”, manufactured by Mitsui Mining & Smelting Co., Ltd.). Thus, an antistatic heat-peelable pressure-sensitive adhesive sheet was obtained.
[0061] A quaternary ammonium salt type acrylic copolymer (trade name “BONDHIP-PA 100”, manufactured by Konishi Co., Ltd.) was applied to a surface of a 50 μm thick polyester film in a thickness of 1 μm to impart electrical conductivity to the substrate. Subsequently, a toluene solution of a pressure-sensitive adhesive consisting mainly of a 2-ethylhexyl acrylate/ethyl acrylate/methyl methacrylate copolymer (containing 1 part by weight of a polyurethane crosslinking agent) was applied to the conductivity-imparted side of the substrate in a thickness of 10 μm on a dry basis. The coating was dried to form a rubber-like organic elastic layer.
[0062] A toluene solution containing 100 pars by weight of a pressure-sensitive adhesive composed of a 2-ethylhexyl acrylate/ethyl acrylate/methyl methacrylate copolymer (containing 2 parts by weight of a polyurethane crosslinking agent) and 30 parts by weight of the classified heat-expandable microspheres B was applied to a separator in a thickness of 35 μm on a dry basis. The coating was dried to form a pressure-sensitive adhesive layer. This adhesive layer was adhered to the rubber-like organic elastic layer formed on the polyester film. Thus, an antistatic heat-peelable pressure-sensitive adhesive sheet was obtained.
[0063] A toluene solution containing 100 parts by weight of a pressure-sensitive adhesive composed of a 2-ethylhexyl acrylate/ethyl acrylate/methyl methacrylate (30/70/5 by weight) copolymer (containing 2 parts by weight of a polyurethane crosslinking agent), 30 parts by weight of the classified heat-expandable microspheres B, and 3 parts by weight of a nonionic antistatic agent E (trade name “ELC EA”, manufactured by Kao Corporation) was applied to a 100 μm thick polyester film in a thickness of 45 μm on a dry basis. The coating was dried to obtain an antistatic heat-peelable pressure-sensitive adhesive sheet.
[0064] The same procedure as in Example 1 was conducted, except that the acicular conductive powder C (trade name “PASTRAN 5110S”, manufactured by Mitsui Mining & Smelting Co., Ltd.) was omitted. Thus, a heat-peelable pressure-sensitive adhesive sheet was obtained.
[0065] The surface resistivity of the heat-expandable pressure-sensitive adhesive layer of each of the pressure-sensitive adhesive sheets obtained in the Examples and Comparative Example was determined with high resistivity meter Hiresta UP MCP-HT 450 (manufactured by Mitsubishi Chemical Corp.). For this evaluation, the found value obtained at 1 minute after initiation of voltage application was used. The heat-expandable pressure-sensitive adhesive layer of each pressure-sensitive adhesive sheet before heating was further examined for center line average surface roughness and maximum surface roughness with a non-contact three-dimensional surface roughness meter (manufactured by ZYGO). Furthermore, each pressure-sensitive adhesive sheet was examined for adhesive force in the following manner. The adhesive sheet (20 mm wide) was applied to a 25 μm-thick polyester film (LUMILAR S-10, manufactured by Toray Industries, Inc.) by pressing the polyester film against the heat-expandable pressure-sensitive adhesive layer side of the adhesive sheet by rolling a 2 kg roller forward and backward once on the film. The resulting sample was examined for 180° peel strength (adhesive force) (unit, N/20 mm; the polyester film was peeled off at a rate of 300 mm/min at 23±2° C. and 65±5% RH) before and after heating. The heat treatment was conducted on a 130° C. hot plate for 60 seconds. The results of these evaluations are shown in the Table below.
[0066] Furthermore, the pressure-sensitive adhesive sheets obtained in the Examples and Comparative Example were used for temporary fixing in a GMR head processing step. As a result, when the pressure-sensitive adhesive sheets obtained in the Examples were used, neither static breakage nor adhesion failures, such as undesirable separation of parts from the pressure-sensitive adhesive sheet, occurred and the adhesive sheets could be smoothly peeled off after heating. In contrast, when the pressure-sensitive adhesive sheet obtained in the Comparative Example was used for the temporary fixing of GMR heads, static breakage occurred.
TABLE Center line Surface average Maximum Adhesive force resist- rough- rough- (N/20 mm) ivity ness ness Before After (Ω/□) (μm) (μm) heating heating Example 1 2.23 × 10 0.31 3.50 2.5 ≦0.05 Example 2 3.45 × 10 0.32 3.89 1.9 ≦0.05 Example 3 6.11 × 10 0.12 1.77 3.8 ≦0.05 Example 4 8.81 × 10 0.14 1.92 2.5 ≦0.05 Compara- ≧1.0 × 10 0.49 8.14 3.9 ≦0.05 tive Example 1
[0067] While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent on one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.