WO2019167712A1 - 両面粘着シート、及びその用途 - Google Patents
両面粘着シート、及びその用途 Download PDFInfo
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- WO2019167712A1 WO2019167712A1 PCT/JP2019/005981 JP2019005981W WO2019167712A1 WO 2019167712 A1 WO2019167712 A1 WO 2019167712A1 JP 2019005981 W JP2019005981 W JP 2019005981W WO 2019167712 A1 WO2019167712 A1 WO 2019167712A1
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- sensitive adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
- C08L93/04—Rosin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Definitions
- the present invention relates to a double-sided pressure-sensitive adhesive sheet, a method for producing the same, and a use thereof.
- adhesive sheets have been widely used for fixing components of OA equipment and electronic equipment.
- OA equipment and electronic equipment are becoming lighter, thinner, and smaller, and the pressure-sensitive adhesive sheets used for fixing these parts are also required to be thin.
- the adhesive sheet becomes weaker as the adhesive sheet becomes thinner, but a thinner and stronger adhesive sheet is required in the market.
- due to a decrease in strength due to the lighter and thinner parts there is also a problem of component destruction at the time of re-attachment, and there is a demand for a tape that is suitable for re-attachment with strong adhesion.
- Patent Document 1 discloses a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer on at least one surface of a base material.
- a pressure-sensitive adhesive tape having a% compressive strength of 300 kPa or less, a total thickness of 250 ⁇ m or less, and a probe tack of 2.0 N / cm 2 or more is described.
- Patent Document 2 discloses a double-sided pressure-sensitive adhesive sheet for fixing a member constituting a portable electronic device, and an acrylic polymer containing 9-30% by mass of a structural unit derived from a polar monomer as a base polymer. There is described a double-sided pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer, wherein the acrylic pressure-sensitive adhesive layer has a thickness of 280 ⁇ m or more.
- Patent Document 1 and Patent Document 2 are thin films, but does not mention the property of strong adhesion and re-sticking.
- This invention is made
- the present inventors have found that the adhesive strength is strong and the adhesion progress is suppressed and reapplying is imparted, and the above problem can be solved.
- a pressure-sensitive adhesive comprising a pressure-sensitive adhesive composition containing 100 parts by weight of a (meth) acrylic copolymer, 40 to 70 parts by weight of a tackifier resin, and 0.01 to 5 parts by weight of a crosslinking agent.
- the adhesive strength A in the measurement after adhering the adhesive surface of the adhesive layer to a SUS plate and leaving it in a 25 ° C./50% RH environment for 20 minutes is 1000 to 1600 g / 25 mm.
- the double-sided pressure-sensitive adhesive sheet according to [2] wherein the content of the styrene-based tackifying resin is greater than the content of the rosin-based tackifying resin.
- the double-sided pressure-sensitive adhesive sheet of the present invention has a strong adhesive force despite being a thin film, and is imparted with appropriateness by re-adhesion while suppressing adhesion progress. Therefore, the double-sided pressure-sensitive adhesive sheet of the present invention can contribute to miniaturization of electronic equipment, and when used for electronic parts, the parts are firmly connected to each other, and if reattachment is required, they are peeled off from the parts without breaking. be able to.
- the double-sided pressure-sensitive adhesive sheet of the present invention comprises a pressure-sensitive adhesive composition containing 100 parts by weight of a (meth) acrylic copolymer, 40 to 70 parts by weight of a tackifier resin, and 0.01 to 5 parts by weight of a crosslinking agent.
- the double-sided PSA sheet is 12 ⁇ m and satisfies the following conditions (i) and (ii).
- the adhesive strength A in the measurement after adhering the adhesive surface of the adhesive layer to a SUS plate and leaving it in a 25 ° C./50% RH environment for 20 minutes is 1000 to 1600 g / 25 mm.
- (Meth) acrylic copolymer is a monomer in which at least one of the monomers constituting the monomer has a (meth) acryloyl group, such as (meth) acrylate It means a copolymer obtained by polymerizing a monomer having a (meth) acryloyl group and a monomer component copolymerizable therewith.
- a monomer component which forms a (meth) acrylic-type copolymer the below-mentioned (meth) acrylate and the crosslinkable group containing monomer copolymerizable with this can be mentioned, for example.
- (meth) acryl means to include both “acryl” and “methacryl”
- “(meth) acrylate” includes both “acrylate” and “methacrylate”.
- “(Meth) acryloyl” means to include both “acryloyl” and “methacryloyl”.
- alkyl (meth) acrylate alkyl (meth) acrylate, alicyclic (meth) acrylate, aryl (meth) acrylate, aralkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, alkoxy polyalkylene glycol mono (meth) acrylate, Aryloxyalkyl (meth) acrylate is mentioned.
- alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate
- alicyclic (meth) acrylate examples include cycloalkyl (meth) acrylate such as cyclohexyl (meth) acrylate and 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate. It is done.
- Examples of the aryl (meth) acrylate include phenyl (meth) acrylate, and examples of the aralkyl (meth) acrylate include benzyl (meth) acrylate.
- alkoxyalkyl (meth) acrylate examples include methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl ( And (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate.
- alkoxypolyalkylene glycol mono (meth) acrylate examples include methoxydiethylene glycol mono (meth) acrylate, methoxydipropylene glycol mono (meth) acrylate, ethoxytriethylene glycol mono (meth) acrylate, ethoxydiethylene glycol mono (meth) acrylate, And methoxytriethylene glycol mono (meth) acrylate.
- aryloxyalkyl (meth) acrylates examples include phenoxymethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-tolyloxyethyl (meth) acrylate, xylyloxymethyl (meth) acrylate, and naphthyloxymethyl. (Meth) acrylate is mentioned.
- (Meth) acrylate may be used alone or in combination of two or more.
- the amount of (meth) acrylate used is preferably 65% by mass or more, more preferably 70% by mass or more, and further preferably 75%. ⁇ 99% by mass.
- Such an embodiment is preferable from the viewpoint of the adhesive strength of the obtained pressure-sensitive adhesive layer and the suppression of adhesion progress.
- crosslinkable group-containing monomer examples include a carboxyl group-containing monomer and a hydroxyl group-containing monomer.
- carboxyl group-containing monomer examples include (meth) acrylic acid, ⁇ -carboxyethyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, crotonic acid, maleic acid, and fumaric acid.
- hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2- Examples include hydroxy-3-phenoxypropyl (meth) acrylate.
- the crosslinkable group-containing monomer may be used alone or in combination of two or more.
- the amount of the crosslinkable group-containing monomer is preferably 0.1 to 15% by mass, more preferably 0.5 to 10%. % By mass, more preferably 1 to 8% by mass.
- an appropriate crosslinked structure can be formed by the reaction between the (meth) acrylic copolymer and a crosslinking agent described later.
- the monomer component may further contain other monomers other than the (meth) acrylate and the crosslinkable group-containing monomer.
- Examples of other monomers include amino group-containing monomers, amide group-containing monomers, glycidyl group-containing monomers, vinyl group-containing monomers, and polymerizable macromonomers.
- Examples of amino group-containing monomers include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate;
- examples of amide group-containing monomers include (meth) acrylamide, N-methyl (meth) acrylamide, N -Ethyl (meth) acrylamide;
- Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether;
- Examples of the vinyl group-containing monomer include vinyl acetate. , Ethylene, propylene, isobutylene, vinyl chloride, styrene, ⁇ -methylstyrene, butadiene, isoprene, and chloroprene.
- the polymerizable macromonomer for example, a macromonomer whose main chain constituent monomer is methyl methacrylate (product name: 45% AA-6 (AA-6S), AA-6; manufactured by Toagosei Co., Ltd.), main chain constituent monomer Is a macromonomer (product name: AB-6; manufactured by Toagosei Co., Ltd.) whose main chain is a copolymer of styrene / acrylonitrile (product name: AN-6S; manufactured by Toagosei Co., Ltd.) Can be mentioned.
- a macromonomer whose main chain constituent monomer is methyl methacrylate product name: 45% AA-6 (AA-6S), AA-6; manufactured by Toagosei Co., Ltd.
- main chain constituent monomer Is a macromonomer (product name: AB-6; manufactured by Toagosei Co., Ltd.) whose main chain is a copolymer of s
- the amount of other monomers used is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass. It is as follows.
- the weight average molecular weight (Mw) measured by the gel permeation chromatography (GPC) method of the (meth) acrylic copolymer is not particularly limited, but is preferably 100,000 to 1,500,000, more preferably 20 It is 10,000 to 1,200,000, more preferably 300,000 to 1,000,000.
- the molecular weight distribution (Mw / Mn) of the (meth) acrylic copolymer is preferably 20 or less, more preferably 1.5 to 18, and still more preferably 1.8 to 15.
- the glass transition temperature (Tg) of the (meth) acrylic copolymer is preferably less than 0 ° C., more preferably ⁇ 80 to ⁇ 10 ° C., and further preferably ⁇ 70 to ⁇ 20 ° C.
- the Tg of the (meth) acrylic copolymer can be obtained from the Fox equation, and the Tg of the homopolymer formed from each monomer in the Fox equation was described in Polymer Handbook Fourth Edition (Wiley-Interscience 2003). A value can be adopted.
- the (meth) acrylic copolymer can be produced by copolymerizing the above monomer components, and may be any of a random copolymer, a block copolymer, and a graft copolymer.
- the (meth) acrylic copolymer can be produced by, for example, a conventionally known polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, a suspension polymerization method, and among these, the solution polymerization method is preferable. .
- a monomer component, a polymerization initiator and, if necessary, other components such as a chain transfer agent and a polymerization solvent are charged in a reaction vessel, and the reaction start temperature is set to 40 to 100 ° C.
- the reaction system is maintained at a temperature of 50 to 90 ° C. for 2 to 20 hours.
- the reaction is carried out in an inert gas atmosphere such as nitrogen gas.
- at least one selected from a monomer component, a polymerization initiator, a chain transfer agent, and a polymerization solvent may be added during the polymerization reaction.
- polymerization initiator examples include thermal polymerization initiators such as azo initiators and peroxide polymerization initiators.
- examples of the azo initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2- Cyclopropylpropionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbohydrate) Nitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′- Azobis (N, N'-dimethyleneisobutylamidine), 2,2'-azobis [2-methyl-N- (2-hydroxy
- peroxide polymerization initiators examples include t-butyl hydroperoxide, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, and di-i-propyl peroxide.
- the polymerization initiator may be used alone or in combination of two or more.
- the amount of the polymerization initiator used is usually 0.001 to 5 parts by mass, preferably 0.005 to 3 parts by mass with respect to a total of 100 parts by mass of the monomer components. It is.
- polymerization solvent examples include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and n-octane; cyclopentane, cyclohexane, cycloheptane, cyclo Alicyclic hydrocarbons such as octane; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, diphenyl ether; chloroform, carbon tetrachloride, 1,2- Halogenated hydrocarbons such as dichloroethane and chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl acetate and methyl propionat
- the pressure-sensitive adhesive composition used for the double-sided pressure-sensitive adhesive sheet of the present invention contains a tackifier resin.
- the tackifier resin is not particularly limited as long as it is a material that can impart tackiness to the pressure-sensitive adhesive composition.
- examples of the tackifying resin include styrene tackifying resins, rosin tackifying resins such as rosin ester resins, terpene tackifying resins such as terpene phenol resins, and alicyclic saturated hydrocarbon resins.
- the styrenic tackifier resin contained in the pressure-sensitive adhesive composition is not particularly limited.
- Examples of the styrene-based tackifier resin include styrene-based and substituted styrene-based petroleum resins.
- styrene-based tackifying resin examples include, for example, FMR-0150, FTR-0100, FTR-2120, FTR-2140, FTR-6100, FTR-6110, FTR-6125, FTR-7100, FTR-8100, and FTR. -8120.
- the above products are manufactured by Mitsui Chemicals.
- YS resin SX-100 manufactured by Yasuhara Chemical Co., Ltd. is also included.
- the rosin tackifying resin contained in the pressure sensitive adhesive composition is not particularly limited, but a rosin ester tackifying resin is usually used.
- rosin ester resin examples include, for example, Superester A75, Superester A100, Superester A115, Superester A125, Pine Crystal KE-100, Pine Crystal KE-311, Pine Crystal KE-359, Pine Crystal KE- 604, ester gum AT, ester gum H, ester gum HP, Pencel D-125, Pencel D-135, and Pencel D-160.
- the above products are manufactured by Arakawa Chemical Industries, Ltd.
- Harrier Star TF Harrier Star S, Haritac 8LJA, Haritac ER95, Haritac SE10, Haritac PH, Haritac F85, Haritac F105, Haritac FK100, Haritac PCJ can be mentioned.
- the above products are manufactured by Harima Kasei Co., Ltd.
- terpene tackifying resin examples include YS resin PX800, YS resin PX1000, YS resin PX1150, YS resin PX1250, YS polystar U115, YS polyster U130, YS polystar UH115, YS polystar T80, YS polystar T100, YS polystar T115, YS polyster T130, YS polyster T145, and YS polyster T160.
- the above products are manufactured by Yasuhara Chemical Co., Ltd.
- Tamanoru 803L, Tamanoru 901 made by Arakawa Chemical Co., Ltd. are also mentioned.
- alicyclic saturated hydrocarbon resin examples include Archon P-90, Archon P-100, Archon P-115, Archon P-125, Archon P-135, Archon M-90, Archon M-100, Archon M- 115.
- the above products are manufactured by Arakawa Chemical Industries, Ltd.
- the tackifier resin may be used alone or in combination of two or more, but preferably contains at least one of a styrene-based tackifier resin and a rosin-based tackifier resin. It is more preferable to use an imparting resin and a rosin tackifying resin in combination.
- the tackifier resin is contained in an amount of preferably 40 to 70 parts by mass, more preferably 45 to 65 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer. If it is 40 parts by mass or more, a predetermined pressure-sensitive adhesive layer strength can be obtained, so that physical properties such as adhesive strength can be expressed. If it is 70 parts by mass or less, the uniformity of the pressure-sensitive adhesive component is maintained.
- the composition of the pressure-sensitive adhesive composition may be adjusted so that the total of the tackifying resins falls within the above range.
- the content of the styrene-based tackifying resin when the styrene-based tackifying resin and the rosin-based tackifying resin are used in combination is not particularly limited, but with respect to 100 parts by mass of the (meth) acrylic copolymer,
- the amount is preferably 20 to 38 parts by mass, more preferably 23 to 35 parts by mass, and still more preferably 27 to 35 parts by mass. If it is 20 parts by mass or more, component destruction at the time of reattachment can be suppressed, and if it is 38 parts by mass or less, a relatively incompatible styrene-based tackifying resin is uniformly dissolved in the pressure-sensitive adhesive composition. Moreover, the dullness of the adhesive layer which consists of an obtained adhesive composition can be prevented.
- the content of the rosin-based tackifying resin is not particularly limited, but is preferably 18 to 32 parts by mass, more preferably 20 to 30 parts per 100 parts by mass of the (meth) acrylic copolymer. Part by mass, more preferably 26-30 parts by mass. If it is 18 parts by mass or more, it can be strongly tacky, and if it is 32 parts by mass or less, it is possible to suppress component destruction during reattachment.
- the content of the styrene-based tackifying resin with respect to the content of the rosin-based tackifying resin is not particularly limited, but the content of the styrene-based tackifying resin is larger than the content of the rosin-based tackifying resin. It is preferable. If there are more styrene type tackifying resins than rosin type tackifying resin, it will become easy to maintain the relationship of the following adhesive force B / adhesive force A, maintaining strong adhesive force.
- the crosslinking agent contained in the pressure-sensitive adhesive composition has reactivity with the crosslinkable group possessed by the (meth) acrylic copolymer.
- crosslinking agent examples include isocyanate compounds, epoxy compounds, and metal chelate compounds.
- an isocyanate compound having 2 or more isocyanate groups in one molecule is usually used, preferably 2 to 8, and more preferably 3 to 6.
- the number of isocyanate groups is within the above range, it is preferable from the viewpoint of the crosslinking reaction efficiency between the (meth) acrylic copolymer and the isocyanate compound and the flexibility of the pressure-sensitive adhesive layer.
- diisocyanate compound having 2 isocyanate groups in one molecule examples include aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate.
- Aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, 2,2,4-trimethyl
- aliphatic diisocyanates having 4 to 30 carbon atoms such as -1,6-hexamethylene diisocyanate.
- alicyclic diisocyanate examples include 7 to 30 carbon atoms such as isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylene diisocyanate.
- Diisocyanate is mentioned.
- aromatic diisocyanate examples include aromatic diisocyanates having 8 to 30 carbon atoms such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenyl ether diisocyanate, diphenylmethane diisocyanate, and diphenylpropane diisocyanate.
- isocyanate compound having 3 or more isocyanate groups in one molecule examples include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. Specific examples include 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, and 4,4 ', 4 "-triphenylmethane triisocyanate.
- Examples of the isocyanate compound include multimers (for example, dimers or trimers, biurets, and isocyanurates) and derivatives (for example, polyhydric alcohols) of the above isocyanate compounds having 2 or 3 isocyanate groups. Addition reaction product with two or more diisocyanate compounds) and polymer.
- Examples of the polyhydric alcohol in the derivative include trivalent or higher alcohols such as trimethylolpropane, glycerin and pentaerythritol as low molecular weight polyhydric alcohols; high molecular weight polyhydric alcohols such as polyether polyols, Examples include polyester polyol, acrylic polyol, polybutadiene polyol, and polyisoprene polyol.
- isocyanate compounds include diphenylmethane diisocyanate trimer, polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate or tolylene diisocyanate biuret or isocyanurate, trimethylolpropane and tolylene diisocyanate or xylylene diisocyanate.
- Reaction product for example, a trimolecular adduct of tolylene diisocyanate or xylylene diisocyanate
- reaction product of trimethylolpropane and hexamethylene diisocyanate for example, a trimolecular adduct of hexamethylene diisocyanate
- polyether polyisocyanate for example, a polyether polyisocyanate
- Polyester polyisocyanate is mentioned.
- xylylene diisocyanate and hexamethylene diisocyanate cross-linking agents are preferable from the viewpoint of difficult yellowing, and tolylene diisocyanate cross-linking agents are preferable from the viewpoint of stress relaxation.
- the xylylene diisocyanate crosslinking agent include xylylene diisocyanate and its multimers, derivatives and polymers;
- examples of the hexamethylene diisocyanate crosslinking agent include hexamethylene diisocyanate and its multimers, derivatives and polymers.
- tolylene diisocyanate crosslinking agents include tolylene diisocyanate and its multimers, derivatives and polymers.
- Examples of the epoxy compound include compounds having two or more epoxy groups in the molecule.
- ethylene glycol diglycidyl ether polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexane.
- an alkoxide, acetylacetone, ethyl acetoacetate or the like is coordinated to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium.
- a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium.
- Compounds. Specific examples include aluminum isopropylate, aluminum secondary butyrate, aluminum ethyl acetoacetate / diisopropylate, aluminum trisethyl acetoacetate, and aluminum trisacetylacetonate.
- the crosslinking agent may be used alone or in combination of two or more.
- the crosslinking agent is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, and still more preferably 100 parts by weight of the (meth) acrylic copolymer. 1 to 2.5 parts by mass. With such an embodiment, excellent adhesive properties can be realized.
- the pressure-sensitive adhesive composition used for the double-sided pressure-sensitive adhesive sheet of the present invention contains various additives such as a silane coupling agent, an organopolysiloxane compound, a pigment, a flame retardant, a plasticizer, an antistatic agent, a lubricant, and a filler. Also good.
- content of an additive is not specifically limited, It should be content of the range which does not inhibit the characteristic of the adhesive composition used for the double-sided adhesive sheet and double-sided adhesive sheet of this invention.
- the pressure-sensitive adhesive composition used for the double-sided pressure-sensitive adhesive sheet of the present invention may contain an organic solvent in order to adjust coatability.
- an organic solvent the polymerization solvent demonstrated in the column of the manufacturing conditions of a (meth) acrylic-type copolymer is mentioned, for example.
- the content of the organic solvent in the pressure-sensitive adhesive composition is usually 30 to 90% by mass, preferably 40 to 90% by mass.
- the pressure-sensitive adhesive composition used for the double-sided pressure-sensitive adhesive sheet of the present invention comprises 40 to 65 parts by weight of a tackifier resin and 0.01 to 5 parts by weight of a crosslinking agent with respect to 100 parts by weight of a (meth) acrylic copolymer. And can be prepared by mixing them.
- the pressure-sensitive adhesive composition may contain other components.
- the double-sided pressure-sensitive adhesive sheet of the present invention is composed of a core material and pressure-sensitive adhesive layers (first pressure-sensitive adhesive layer and second pressure-sensitive adhesive layer) formed on both surfaces of the core material. Therefore, the double-sided pressure-sensitive adhesive sheet of the present invention has a structure of at least three layers. Moreover, the peeling film may be affixed on the surface which is not in contact with the core material in the said adhesive layer.
- the double-sided pressure-sensitive adhesive sheet of the present invention includes a core material.
- the core material used in the double-sided pressure-sensitive adhesive sheet of the present invention has a thickness of 1 to 12 ⁇ m. If it is 1 ⁇ m or more, an appropriate sheet strength can be obtained, and if it is 12 ⁇ m or less, adhesion progress can be suppressed.
- plastic films such as ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), polyamide (nylon), polyimide, and polyvinyl chloride (PVC).
- the core material include glass, paper, and nonwoven fabric.
- the core material is preferably PET from the viewpoint of strength and ease of handling.
- a core material in which a black color material such as a black pigment or a white color material such as a white pigment is dispersedly contained may be used.
- the pressure-sensitive adhesive layer provided on both surfaces of the core material can be formed from a pressure-sensitive adhesive composition.
- the pressure-sensitive adhesive layers on both surfaces of the core material may be the same as or different from each other.
- One pressure-sensitive adhesive layer has a thickness of 1 to 12 ⁇ m. If it is 1 ⁇ m or more, a double-sided pressure-sensitive adhesive sheet having an appropriate adhesive strength can be obtained, and if it is 12 ⁇ m or less, adhesion progress can be suppressed.
- the gel fraction of the pressure-sensitive adhesive layer is preferably 10 to 98% by mass, more preferably 20 to 90% by mass, and still more preferably 30 to 85% by mass from the viewpoints of cohesive strength, adhesive strength described later, and appropriate reattachment. %.
- the double-sided pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive force A of 1000 to 1600 g / 25 mm after measurement after sticking the pressure-sensitive adhesive surface of a pressure-sensitive adhesive layer on a SUS plate and leaving it in a 25 ° C./50% RH environment for 20 minutes.
- a pressure-sensitive adhesive force A 1000 to 1600 g / 25 mm after measurement after sticking the pressure-sensitive adhesive surface of a pressure-sensitive adhesive layer on a SUS plate and leaving it in a 25 ° C./50% RH environment for 20 minutes.
- the double-sided pressure-sensitive adhesive sheet of the present invention has the pressure-sensitive adhesive force B and the above-mentioned pressure-sensitive adhesive strength B when the pressure-sensitive adhesive layer B is attached to a SUS plate and left to stand in a 25 ° C./50% RH environment for 24 hours.
- the adhesive strength A ratio (adhesive strength B / adhesive strength A) is 1.00 or more and 1.25 or less. About the measurement conditions of adhesive force B, it describes in an Example.
- the adhesive strength B is an adhesive strength measured after being left for 24 hours after sticking, it is usually higher than the adhesive strength A.
- the double-sided pressure-sensitive adhesive sheet of the present invention has an adhesive force B / adhesive force A of 1.00 or more and 1.25 or less, the rate of increase in the adhesive force is not high, and adhesion progress can be suppressed. That is, the double-sided pressure-sensitive adhesive sheet of the present invention has high re-sticking characteristics, and can suppress component destruction due to re-sticking.
- the double-sided PSA sheet of the present invention has a strong adhesive force while being a thin film, and is imparted with appropriateness by suppressing adhesion progress and reapplying, and can be used for various applications.
- a heat dissipation sheet or a light shielding tape can be attached to the target article.
- the heat dissipation sheet and the light shielding tape will be described.
- the heat dissipation sheet can be dissipated to the entire surface of OA equipment and electronic equipment by installing it in a local high temperature part.
- the graphite sheet used for the heat dissipation sheet include a natural graphite sheet obtained by forming natural graphite powder into a sheet, an artificial graphite sheet obtained by heat-treating a polymer film, and the like.
- the polymer film examples include polyimide, polyamide, polyoxadiazole, polybenzothiazole, polybenzobisthiazole, polybenzoxazole, polybenzobisoxazole, polyparaphenylene vinylene, polybenzimidazole, polybenzobisimidazole, poly A film made of thiazole or the like can be mentioned.
- the thickness of the graphite sheet is preferably 10 to 100 ⁇ m, and more preferably 15 to 50 ⁇ m. By setting the thickness of the graphite sheet in the above range, it is suitably used for fixing components of OA equipment and electronic equipment.
- a light-shielding tape can prevent the problem which arises by a leaked light by using for non-self-light-emitting display units, such as a liquid crystal display module unit, and a backlight unit, for example.
- the double-sided pressure-sensitive adhesive sheet of the present invention can be produced as follows.
- the pressure-sensitive adhesive composition is applied to one side of the release film so that the thickness after drying is 1 to 12 ⁇ m, and is usually dried at 60 to 100 ° C. for 1 to 10 minutes to remove the solvent. Thereafter, the obtained pressure-sensitive adhesive layer is bonded to one side of the core material having a thickness of 1 to 12 ⁇ m (referred to as the first surface of the core material).
- the pressure-sensitive adhesive composition is applied on one side of another release film so that the thickness after drying becomes 1 to 12 ⁇ m. Then, the pressure-sensitive adhesive layer obtained by drying at 60 to 100 ° C. for 1 to 10 minutes to remove the solvent is the side where the pressure-sensitive adhesive layer of the core is not bonded (referred to as the second surface of the core).
- a double-sided pressure-sensitive adhesive sheet is produced by pasting together.
- the coating method is not particularly limited, and a conventionally known method can be used.
- Examples of the method for applying the pressure-sensitive adhesive composition include a method using a roll coater, a fountain coater, a lip coater, a knife coater, a die coater, a gravure coater, a reverse coater, a curtain coater, a slit die coater and the like.
- the pressure-sensitive adhesive layer formed on the first surface and the pressure-sensitive adhesive layer formed on the second surface may be the same or different.
- Example 1 Double-sided PSA sheet and production thereof
- the pressure-sensitive adhesive composition was applied to a release film so that the thickness after drying was 5 ⁇ m, dried at 90 ° C. for 3 minutes, and bonded to a PET film (core material) having a thickness of 2 ⁇ m (first surface pressure-sensitive adhesive). Agent layer formation).
- the first surface pressure-sensitive adhesive layer of the PET film is a sheet with a pressure-sensitive adhesive layer that is coated on the release film so that the thickness of the pressure-sensitive adhesive composition after drying is 5 ⁇ m and dried at 90 ° C. for 3 minutes.
- a double-sided pressure-sensitive adhesive sheet (Example 1) was prepared by bonding to the non-bonded side (second surface pressure-sensitive adhesive layer formation).
- Examples 2 to 6 and Comparative Examples 1 to 3 Various double-sided pressure-sensitive adhesive sheets (Examples 2 to 6 and Comparative Examples) were used except that the amount of tackifying resin used and the thicknesses of the core material and the pressure-sensitive adhesive layer were changed as described in Table 1. Examples 1 to 3) were obtained.
- Measurement device HLC-8120GPC (manufactured by Tosoh Corporation) -GPC column configuration: The following five columns (all manufactured by Tosoh Corporation) (1) TSK-GEL HXL-H (guard column) (2) TSK-GEL G7000HXL (3) TSK-GEL GMHXL (4) TSK-GEL GMHXL (5) TSK-GEL G2500HXL ⁇ Sample concentration: diluted with tetrahydrofuran to 1.0 mg / cm 3 ⁇ Mobile phase solvent: tetrahydrofuran ⁇ Flow rate: 1.0 cm 3 / min -Column temperature: 40 ° C
- Adhesive strength A and adhesive strength B Peel off the release film on the first pressure-sensitive adhesive layer side of the double-sided pressure-sensitive adhesive sheet obtained in Examples and Comparative Examples, and bond the entire surface of the exposed pressure-sensitive adhesive layer to a 50 ⁇ m thick PET film, cut into 25 mm ⁇ 150 mm, A test piece was prepared. Next, the peeled film on the second pressure-sensitive adhesive layer side was peeled off, and the pressure-sensitive adhesive layer exposed was bonded to a SUS plate, and the roller having a weight of 2 kg was reciprocated three times and pressed.
- the sample was left in an environment of 25 ° C./50% RH for 20 minutes, and then the end of the test piece was pulled at a speed of 300 mm / min in the direction of 180 ° with respect to the PET film surface, and the adhesive strength A was measured. Further, the adhesive strength B was measured by the same method as the measurement of the adhesive strength A, except that it was left in a 25 ° C./50% RH environment for 24 hours after pressure bonding.
- the double-sided pressure-sensitive adhesive sheets of the examples were all thin films but had high initial adhesive strength and suppressed adhesion progress, indicating that re-paste is good.
- the double-sided pressure-sensitive adhesive sheet of Comparative Example 3 in excess of the above, the adhesion progress could not be suppressed.
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Abstract
Description
[1] (メタ)アクリル系共重合体を100質量部と、粘着付与樹脂を40~70質量部と、架橋剤を0.01~5質量部とを含有する粘着剤組成物からなる粘着剤層を芯材の両面に有する両面粘着シートであって、前記芯材の厚さが1~12μmであり、前記芯材の両面に有する前記粘着剤層の厚さがそれぞれ1~12μmであり、下記の条件(i)、 (ii)を満たすことを特徴とする両面粘着シート。
(i)前記粘着剤層の粘着面をSUS板に貼付し、25℃/50%RH環境下に20分間放置した後の測定における粘着力Aが1000~1600g/25mmである。
(ii)前記粘着剤層の粘着面をSUS板に貼付し、25℃/50%RH環境下に24時間放置した後の測定における粘着力Bとしたときの、粘着力B/粘着力Aの値が1.00以上1.25以下である。
[2] 前記粘着付与樹脂が、スチレン系粘着付与樹脂およびロジン系粘着付与樹脂を含有することを特徴とする前項[1]に記載の両面粘着シート。
[3] 前記スチレン系粘着付与樹脂の含有量が前記ロジン系粘着付与樹脂の含有量よりも多いことを特徴とする前項[2]に記載の両面粘着シート。
[4] 前記スチレン系粘着付与樹脂の含有量が20~35質量部、前記ロジン系粘着付与樹脂の含有量が18~32質量部であることを特徴とする前項[3]に記載の両面粘着シート。
[5] 前記スチレン系粘着付与樹脂の含有量が27~35質量部、前記ロジン系粘着付与樹脂の含有量が26~30質量部であることを特徴とする前項[4]に記載の両面粘着シート。
[6] 放熱シート用の両面粘着シートである、前項[1]乃至[5]のいずれか一項に記載の両面粘着シート。
[7] 遮光テープ用の両面粘着シートである、前項[1]乃至[5]のいずれか一項に記載の両面粘着シート。
(i)前記粘着剤層の粘着面をSUS板に貼付し、25℃/50%RH環境下に20分間放置した後の測定における粘着力Aが1000~1600g/25mmである。
(ii)前記粘着剤層の粘着面をSUS板に貼付し、25℃/50%RH環境下に24時間放置した後の測定における粘着力Bとしたときの、粘着力B/粘着力Aの値が1.00以上1.25以下である。
以下、構成を具体的に説明する。
(メタ)アクリル系共重合体とは、これを構成する単量体のうち少なくとも主成分である単量体の一つが(メタ)アクリロイル基を有する単量体であり、(メタ)アクリレート等の(メタ)アクリロイル基を有するモノマーと、これと共重合性を有するモノマー成分とを重合することにより得られる共重合体を意味する。
(メタ)アクリル系共重合体を形成するモノマー成分としては、例えば、後述の(メタ)アクレートと、これと共重合可能な架橋性基含有モノマーを挙げることができる。
(メタ)アクリル系共重合体は、上記モノマー成分を共重合することにより製造することができ、ランダム共重合体、ブロック共重合体およびグラフト共重合体のいずれでもよい。(メタ)アクリル系共重合体は、例えば、溶液重合法、塊状重合法、乳化重合法、懸濁重合法等の従来公知の重合法により製造することができ、これらの中でも溶液重合法が好ましい。
アゾ系開始剤としては、例えば、2,2’-アゾビスイソブチロニトリル、2,2’-アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)、2,2’-アゾビス(2-シクロプロピルプロピオニトリル)、2,2’-アゾビス(2,4-ジメチルバレロニトリル)、2,2’-アゾビス(2-メチルブチロニトリル)、1,1’-アゾビス(シクロヘキサン-1-カルボニトリル)、2-(カルバモイルアゾ)イソブチロニトリル、2-フェニルアゾ-4-メトキシ-2,4-ジメチルバレロニトリル、2,2’-アゾビス(2-アミジノプロパン)ジヒドロクロリド、2,2’-アゾビス(N,N’-ジメチレンイソブチルアミジン)、2,2’-アゾビス〔2-メチル-N-(2-ヒドロキシエチル)-プロピオンアミド〕、2,2’-アゾビス(イソブチルアミド)ジヒドレート、4,4’-アゾビス(4-シアノペンタン酸)、2,2’-アゾビス(2-シアノプロパノール)、ジメチル-2,2’-アゾビス(2-メチルプロピオネート)等のアゾ化合物が挙げられる。
重合溶媒は1種単独で用いてもよく、2種以上を用いてもよい。
本発明の両面粘着シートに用いられる粘着剤組成物は、粘着付与樹脂を含む。粘着付与樹脂は、粘着剤組成物に、粘着性を付与できる材料であれば特に限定されるものではない。粘着付与樹脂としては、例えば、スチレン系粘着付与樹脂、ロジンエステル系樹脂等のロジン系粘着付与樹脂、テルペンフェノール系樹脂等のテルペン系粘着付与樹脂、脂環族飽和炭化水素樹脂が挙げられる。
粘着剤組成物に含まれるスチレン系粘着付与樹脂は、特に限定されるものではない。スチレン系粘着付与樹脂としては、例えば、スチレン系、置換スチレン系石油樹脂などが挙げられる。
粘着剤組成物に含まれるロジン系粘着付与樹脂は、特に限定されるものではないが、通常ロジンエステル系粘着付与樹脂が用いられる。
テルペン系粘着付与樹脂としては、例えば、YSレジンPX800、YSレジンPX1000、YSレジンPX1150、YSレジンPX1250、YSポリスターU115、YSポリスターU130、YSポリスターUH115、YSポリスターT80、YSポリスターT100、YSポリスターT115、YSポリスターT130、YSポリスターT145、YSポリスターT160が挙げられる。以上の製品は、ヤスハラケミカル株式会社製である。また、タマノル803L、タマノル901(荒川化学工業株式会社製)も挙げられる
脂環族飽和炭化水素樹脂としては、例えば、アルコンP-90、アルコンP-100、アルコンP-115、アルコンP-125、アルコンP-135、アルコンM-90、アルコンM-100、アルコンM-115が挙げられる。以上の製品は、荒川化学工業株式会社製である。
粘着剤組成物に含まれる架橋剤は、(メタ)アクリル系共重合体が有する架橋性基と反応性を有するものである。
本発明の両面粘着シートに用いられる粘着剤組成物は、シランカップリング剤、オルガノポリシロキサン化合物、顔料、難燃剤、可塑剤、帯電防止剤、滑剤、フィラー等の各種添加剤が含まれていてもよい。添加剤の含有量は特に限定されないが、本発明の両面粘着シート及び両面粘着シートに用いられる粘着剤組成物の特性を阻害しない範囲の含有量にするべきである。
本発明の両面粘着シートに用いられる粘着剤組成物は、塗工性を調整するため、有機溶媒を含有してもよい。有機溶媒としては、例えば、(メタ)アクリル系共重合体の製造条件の欄で説明した重合溶媒が挙げられる。粘着剤組成物中の有機溶媒の含有量は、通常30~90質量%、好ましくは40~90質量%である。
本発明の両面粘着シートに用いられる粘着剤組成物は、(メタ)アクリル系共重合体100質量部に対して、粘着付与樹脂を40~65質量部と、架橋剤0.01~5質量部とを含有するものであり、これらを混合することにより調製することができる。なお、粘着剤組成物は、その他の成分を含有してもよい。
本発明の両面粘着シートは、芯材と、芯材の両面に形成された粘着剤層(第一粘着剤層及び第二粘着剤層)から構成される。したがって、本発明の両面粘着シートは少なくとも3層の構造を有している。また、前記粘着剤層における芯材と接していない面には、剥離フィルムが貼付されていてもよい。
本発明の両面粘着シートは、芯材を含む。本発明の両面粘着シートに用いられる芯材は、1~12μmの厚さを有するものである。1μm以上であれば適切なシート強度が得られ、12μm以下であれば接着昂進を抑制できる。
本発明の両面粘着シートを遮光テープとして使用する場合、黒色顔料等の黒色系色材または白色顔料等の白色系色材が分散含有された芯材を用いてもよい。
芯材の両面に設けられる粘着剤層は、粘着剤組成物から形成することができる。芯材の両面の各粘着剤層は、互いに同一であってもよいし、異なっていてもよい。
1つの粘着剤層は、1~12μmの厚さを有するものである。1μm以上であれば適切な粘着力である両面粘着シートが得られ、12μm以下であれば接着昂進を抑制できる。
本発明の両面粘着シートは、粘着剤層の粘着面をSUS板に貼付し、25℃/50%RH環境下に20分間放置した後の測定における粘着力Aが1000~1600g/25mmである特徴を有する。このような特徴を有することにより、初期の粘着力が強い両面粘着シートであることを示す。測定条件の詳細については、実施例に記載する。
本発明の両面粘着シートは、粘着剤層の粘着面をSUS板に貼付し、25℃/50%RH環境下に24時間放置した後の測定における粘着力Bとしたとき、粘着力Bと前記粘着力Aの比(粘着力B/粘着力A)が1.00以上1.25以下である特徴を有する。粘着力Bの測定条件については、実施例に記載する。
本発明の両面粘着シートは、上記したように薄膜でありながら強粘着力であり、かつ接着昂進を抑制し貼直し適正が付与されるものであり、様々な用途に用いることができる。例えば、本発明の両面粘着シートを用いて、放熱シートや遮光テープを対象物品に貼付することができる。以下、放熱シート、遮光テープを説明する。
放熱シートは局所的な高温部に設置することで、熱をOA機器や電子機器の全面に放熱することができる。放熱シートに使用するグラファイトシートは、例えば、天然黒鉛粉末をシート化して得られた天然グラファイトシート、高分子フィルムを熱処理して得られた人工グラファイトシート等が挙げられる。
前記高分子フィルムとして、例えば、ポリイミド、ポリアミド、ポリオキサジアゾール、ポリベンゾチアゾール、ポリベンゾビスチアゾール、ポリベンゾオキサゾール、ポリベンゾビスオキサゾール、ポリパラフェニレンビニレン、ポリベンゾイミダゾール、ポリベンゾビスイミダゾール、ポリチアゾール等からなるフィルムが挙げられる。
グラファイトシートの厚さは、10~100μmであることが好ましく、15~50μmであることがより好ましい。グラファイトシートの厚さを前記範囲とすることで、OA機器や電子機器の部品固定に好適に用いられる。
遮光テープは、例えば、液晶表示モジュールユニット等の非自発光型表示ユニットと、バックライトユニットとの貼着に用いることで、漏洩光によって生じる問題を防ぐことができる。
本発明の両面粘着シートは、以下のように製造することができる。
剥離フィルムの片面に粘着剤組成物を乾燥後の厚みが1~12μmとなるように塗工し、通常60~100℃で、1~10分乾燥し溶媒を除去する。その後、得られた粘着剤層を厚さ1~12μmの芯材の片面(芯材の第一面とする)に貼り合わせる。
塗工方法は特に限定されるものではなく、従来公知の方法を用いることができる。粘着剤組成物の塗工方法としては、例えば、ロールコーター、ファウンテンコーター、リップコーター、ナイフコーター、ダイコーター、グラビアコーター、リバースコーター、カーテンコーター、スリットダイコーター等を用いる方法が挙げられる。
なお、第一面に形成した粘着剤層と、第二面に形成した粘着剤層とは、同一であっても、異なっていてもよい。
撹拌機、還流冷却器、温度計および窒素導入管を備えた反応装置にn-BA(n-ブチルアクリレート)97質量部、AA(アクリル酸)2質量部、2HEA(2-ヒドロキシエチルアクリレート)1質量部、酢酸エチル80質量部を仕込み、窒素ガスを導入しながら75℃に昇温した。次いで、アゾビスイソブチロニトリル0.3質量部を添加し、フラスコ内の内容物の温度が75~76℃に維持できるように加熱および冷却を繰り返しながら4時間反応を行った。反応終了後、酢酸エチルをさらに20質量部添加することにより、重量平均分子量(Mw)85万の(メタ)アクリル系共重合体を得た。
前記(メタ)アクリル系共重合体の固形分100質量部に対して、スチレン系粘着付与樹脂(FTR-6100:三井化学株式会社製)35質量部、ロジン系粘着付与樹脂(D-135:荒川化学工業株式会社製)30質量部、イソシアネート系架橋剤(L-45:綜研化学株式会社製)1.5質量部(固形分)を混合し、粘着剤組成物を得た。
剥離フィルムに前記粘着剤組成物を乾燥後の厚みが5μmとなるように塗工し、90℃で3分乾燥し、厚さ2μmのPETフィルム(芯材)に貼り合わせた(第一面粘着剤層形成)。さらに、剥離フィルムに前記粘着剤組成物を乾燥後の厚みが5μmとなるように塗工、90℃で3分乾燥させた粘着剤層付きシートを、前記PETフィルムの第一面粘着剤層が貼り合わされていない側に貼り合わせて(第二面粘着剤層形成)、両面粘着シート(実施例1)を作製した。
粘着付与樹脂の使用量、および芯材と粘着剤層の厚みを表1に記載したとおりに変更したこと以外は実施例1と同様に行い、種々の両面粘着シート(実施例2乃至6及び比較例1乃至3)を得た。
実施例1乃至6及び比較例1乃至3において使用した(メタ)アクリル系共重合体の重量平均分子量、粘着力A及び粘着力Bの測定条件を下記する。
(重量平均分子量(Mw))
(メタ)アクリル系共重合体について、ゲルパーミエーションクロマトグラフィー(GPC)法により、下記条件で標準ポリスチレン換算による重量平均分子量(Mw)を求めた。
・測定装置:HLC-8120GPC(東ソー株式会社製)
・GPCカラム構成:以下の5連カラム(すべて東ソー株式会社製)
(1)TSK-GEL HXL-H (ガードカラム)
(2)TSK-GEL G7000HXL
(3)TSK-GEL GMHXL
(4)TSK-GEL GMHXL
(5)TSK-GEL G2500HXL
・サンプル濃度:1.0mg/cm3となるように、テトラヒドロフランで希釈
・移動相溶媒:テトラヒドロフラン
・流量:1.0cm3/min
・カラム温度:40℃
実施例及び比較例で得られた両面粘着シートの第一粘着剤層側の剥離フィルムを剥がし、露出した粘着剤層全面を厚さ50μmのPETフィルムに貼り合せ、25mm×150mmに裁断して、試験片を作成した。次いで、第二粘着剤層側の剥離フィルムを剥がして露出した粘着剤層をSUS板に貼り合せて、重さ2kgのローラーを3往復させて圧着させた。圧着後25℃/50%RH環境下に20分間放置した後、PETフィルム面に対して180°方向に300mm/minの速度で試験片端部を引っぱり、粘着力Aを測定した。
また、圧着後25℃/50%RH環境下に24時間放置したこと以外は粘着力Aの測定と同様の方法で、粘着力Bを測定した。
Claims (7)
- (メタ)アクリル系共重合体を100質量部と、粘着付与樹脂を40~70質量部と、架橋剤を0.01~5質量部とを含有する粘着剤組成物からなる粘着剤層を芯材の両面に有する両面粘着シートであって、前記芯材の厚さが1~12μmであり、前記芯材の両面に有する前記粘着剤層の厚さがそれぞれ1~12μmであり、下記の条件(i)、(ii)を満たすことを特徴とする両面粘着シート。
(i)前記粘着剤層の粘着面をSUS板に貼付し、25℃/50%RH環境下に20分間放置した後の測定における粘着力Aが1000~1600g/25mmである。
(ii)前記粘着剤層の粘着面をSUS板に貼付し、25℃/50%RH環境下に24時間放置した後の測定における粘着力Bとしたときの、粘着力B/粘着力Aの値が1.00以上1.25以下である。 - 前記粘着付与樹脂が、スチレン系粘着付与樹脂およびロジン系粘着付与樹脂を含有することを特徴とする請求項1に記載の両面粘着シート。
- 前記スチレン系粘着付与樹脂の含有量が前記ロジン系粘着付与樹脂の含有量よりも多いことを特徴とする請求項2に記載の両面粘着シート。
- 前記スチレン系粘着付与樹脂の含有量が20~35質量部、前記ロジン系粘着付与樹脂の含有量が18~32質量部であることを特徴とする請求項3に記載の両面粘着シート。
- 前記スチレン系粘着付与樹脂の含有量が27~35質量部、前記ロジン系粘着付与樹脂の含有量が26~30質量部であることを特徴とする請求項4に記載の両面粘着シート。
- 放熱シート用の両面粘着シートである、請求項1乃至5のいずれか一項に記載の両面粘着シート。
- 遮光テープ用の両面粘着シートである、請求項1乃至5のいずれか一項に記載の両面粘着シート。
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