WO2018016416A1 - Pressure-sensitive adhesive, pressure-sensitive adhesive film, pressure-sensitive adhesive tapes, and film substrates - Google Patents
Pressure-sensitive adhesive, pressure-sensitive adhesive film, pressure-sensitive adhesive tapes, and film substrates Download PDFInfo
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- WO2018016416A1 WO2018016416A1 PCT/JP2017/025564 JP2017025564W WO2018016416A1 WO 2018016416 A1 WO2018016416 A1 WO 2018016416A1 JP 2017025564 W JP2017025564 W JP 2017025564W WO 2018016416 A1 WO2018016416 A1 WO 2018016416A1
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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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
- 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
- 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
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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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
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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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
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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 an adhesive.
- the present invention also relates to an adhesive tape having the adhesive of the present invention.
- the present invention further relates to a film substrate having the pressure-sensitive adhesive of the present invention.
- the present invention relates to an adhesive film.
- the present invention also relates to an adhesive tape having the adhesive film of the present invention.
- the present invention further relates to a film substrate having the pressure-sensitive adhesive film of the present invention.
- thermocompression bonding is usually performed with an anisotropic conductive film (ACF).
- ACF anisotropic conductive film
- an adhesive tape may be bonded in advance to the back side of the substrate of the semiconductor element to be reinforced (Patent Document 1).
- thermocompression bonding with an anisotropic conductive film is performed at a high temperature, the fluidity of the adhesive on the adhesive tape is increased by heat.
- the adhesive is greatly distorted during bump compression of an integrated circuit (IC).
- IC integrated circuit
- An object of the present invention is to provide a pressure-sensitive adhesive having sufficient adhesive force and low distortion at high temperature, to provide a pressure-sensitive adhesive tape having such a pressure-sensitive adhesive, and a film having such a pressure-sensitive adhesive It is to provide a substrate.
- An object of the present invention is to provide a pressure-sensitive adhesive film having sufficient adhesive force and less distortion at high temperature, to provide a pressure-sensitive adhesive tape having such a pressure-sensitive adhesive film, and a film having such a pressure-sensitive adhesive film It is to provide a substrate.
- the pressure-sensitive adhesive of the present invention is The adhesive force to the surface of the polyimide film is 1N or more,
- the storage elastic modulus G ′ at 160 ° C. is 1 ⁇ 10 5 Pa or more.
- the adhesive force is 5N or more.
- the storage elastic modulus G ′ at 160 ° C. is 5 ⁇ 10 5 Pa or more.
- the pressure-sensitive adhesive of the present invention has a crosslinked structure.
- the pressure-sensitive adhesive of the present invention is formed from a pressure-sensitive adhesive composition containing an acrylic polymer (A) and an isocyanate-based crosslinking agent and / or an epoxy-based crosslinking agent.
- the total content of the isocyanate crosslinking agent and the epoxy crosslinking agent in the pressure-sensitive adhesive composition is 0.1 parts by weight to 100 parts by weight of the acrylic polymer (A). 30 parts by weight.
- the content of the isocyanate crosslinking agent in the pressure-sensitive adhesive composition is 2 to 20 parts by weight with respect to 100 parts by weight of the acrylic polymer (A).
- the content of the epoxy crosslinking agent in the pressure-sensitive adhesive composition is 0.3 to 10 parts by weight with respect to 100 parts by weight of the acrylic polymer (A).
- the pressure-sensitive adhesive of the present invention is formed from a pressure-sensitive adhesive composition containing an acrylic polymer (B) and an ultraviolet curable oligomer.
- the ultraviolet curable oligomer is at least one selected from an ultraviolet curable urethane oligomer, an ultraviolet curable acrylic oligomer, and an ultraviolet curable urethane acrylic oligomer.
- the pressure-sensitive adhesive of the present invention is formed from a pressure-sensitive adhesive composition containing a urethane polymer and an acrylic monomer.
- the urethane-based polymer includes a (meth) acryloyl group-terminated urethane-based polymer.
- the pressure-sensitive adhesive tape of the present invention has the pressure-sensitive adhesive of the present invention.
- the film substrate of the present invention has the pressure-sensitive adhesive of the present invention.
- the adhesive film of the present invention is The adhesive force to the surface of the polyimide film is 1N or more,
- the storage elastic modulus G ′ at 160 ° C. is 1 ⁇ 10 4 Pa or more,
- the thickness is 20 ⁇ m or less.
- the adhesive force is 5N or more.
- the thickness is 15 ⁇ m or less.
- the pressure-sensitive adhesive film of the present invention is formed from a pressure-sensitive adhesive composition containing an acrylic polymer.
- the pressure-sensitive adhesive tape of the present invention has the pressure-sensitive adhesive film of the present invention.
- the film substrate of the present invention has the adhesive film of the present invention.
- a pressure-sensitive adhesive having sufficient adhesive force and less distortion at high temperature to provide a pressure-sensitive adhesive tape having such a pressure-sensitive adhesive, and a film having such a pressure-sensitive adhesive.
- a substrate can be provided.
- a substrate can be provided.
- weight which is conventionally commonly used as a unit of weight
- weight which is commonly used as an SI system unit indicating weight
- (meth) acryl means “acryl and / or methacryl”
- the expression “(meth) acrylate” means “acrylate and / or methacrylate”.
- “(meth) acrolein” means “acrolein and / or methacrole”. It means "rain”.
- the pressure-sensitive adhesive of the present invention has an adhesive strength to the surface of the polyimide film of 1N or more, preferably 3N or more, more preferably 5N or more, further preferably 7N or more, and particularly preferably 9N or more. . If the adhesive force of the pressure-sensitive adhesive of the present invention to the surface of the polyimide film is within the above range, the pressure-sensitive adhesive of the present invention has sufficient adhesive force, for example, on the back side of the substrate of the semiconductor element for strong reinforcement. Can be bonded with high reliability. The measuring method of the adhesive force with respect to the surface of a polyimide film is mentioned later.
- the adhesive of the present invention has a storage elastic modulus G ′ at 160 ° C. of 1 ⁇ 10 5 Pa or more, preferably 2 ⁇ 10 5 Pa or more, more preferably 3 ⁇ 10 5 Pa or more, and further preferably Is 4 ⁇ 10 5 Pa or more, particularly preferably 5 ⁇ 10 5 Pa or more. If the storage elastic modulus G ′ at 160 ° C. of the pressure-sensitive adhesive of the present invention is within the above range, the pressure-sensitive adhesive of the present invention is less distorted at a high temperature. For example, an anisotropic conductive film (ACF) is formed on a substrate of a semiconductor element.
- ACF anisotropic conductive film
- the adhesive of the present invention has a storage elastic modulus G ′ at 25 ° C. of preferably 5 ⁇ 10 4 Pa or more, more preferably 7 ⁇ 10 4 Pa or more, and further preferably 1 ⁇ 10 5 Pa or more. Yes, particularly preferably 5 ⁇ 10 5 Pa or more.
- the upper limit of the storage elastic modulus G ′ at 25 ° C. of the pressure-sensitive adhesive of the present invention is preferably 1 ⁇ 10 8 Pa or less. If the storage elastic modulus G ′ at 25 ° C. of the pressure-sensitive adhesive of the present invention is within the above range, it can be bonded to an adherend at room temperature or a heat roll, and deformation is reduced even when pressure is applied, and reinforcement is achieved. It may be possible to easily use it as a tape for use. A method for measuring the storage elastic modulus G ′ at 25 ° C. will be described later.
- the pressure-sensitive adhesive of the present invention preferably has a crosslinked structure.
- the pressure-sensitive adhesive of the present invention has more sufficient adhesive force and less strain at high temperatures.
- Embodiment A One embodiment (sometimes referred to as embodiment A) of the pressure-sensitive adhesive of the present invention is formed from a pressure-sensitive adhesive composition comprising an acrylic polymer (A) and an isocyanate-based crosslinking agent and / or an epoxy-based crosslinking agent.
- the content of the acrylic polymer (A) in the pressure-sensitive adhesive composition is preferably 50% by weight to 99.9% by weight, more preferably 70% by weight to 99% by weight, The amount is preferably 75% to 95% by weight, particularly preferably 80% to 93% by weight, and most preferably 85% to 90% by weight.
- the content ratio of the acrylic polymer (A) in the pressure-sensitive adhesive composition is within the above range, it is possible to provide a pressure-sensitive adhesive having more sufficient adhesive force and less distortion at high temperature. Only one type of acrylic polymer (A) may be used, or two or more types may be used.
- the acrylic polymer (A) is a polymer formed from a monomer component that essentially contains an acrylic monomer. That is, the acrylic polymer (A) is a polymer having a structural unit derived from an acrylic monomer as an essential monomer structural unit.
- the weight average molecular weight of the acrylic polymer (A) is preferably 200,000 to 2,500,000, more preferably 300,000 to 1,800,000, from the viewpoint that the effects of the present invention can be expressed more. More preferably, it is 400,000 to 1,500,000, particularly preferably 500,000 to 1,200,000.
- the acrylic polymer (A) is preferably a polymer formed from a monomer component that essentially includes a (meth) acrylic acid alkyl ester having a linear or branched alkyl group and a polar group-containing monomer. It is.
- the monomer component may contain other copolymerizable monomers.
- Examples of the (meth) acrylic acid alkyl ester having a linear or branched alkyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate.
- the (meth) acrylic acid alkyl ester having a linear or branched alkyl group may be only one kind or two or more kinds.
- polar group-containing monomers examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and vinyl.
- Hydroxyl group-containing monomers such as alcohol and allyl alcohol; nitrogen-containing monomers; epoxy group-containing monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; sulfonic acid group-containing monomers such as sodium vinyl sulfonate Phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate; (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, acid anhydrides thereof (for example, maleic anhydride, anhydrous Itaconic acid, etc.
- Carboxyl group-containing monomers such as acid anhydride-containing monomer); and the like.
- the polar group-containing monomer is preferably a hydroxyl group-containing monomer or a nitrogen-containing monomer from the viewpoint that the effects of the present invention can be further exhibited.
- As the hydroxyl group (hydroxyl group) -containing monomer 2-hydroxyethyl (meth) acrylate is preferable because the effects of the present invention can be further exhibited.
- Only one type of polar group-containing monomer may be used, or two or more types may be used.
- nitrogen-containing monomer examples include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N Amide group-containing monomers such as hydroxyethyl (meth) acrylamide; monomers having nitrogen-containing heterocyclic and N-vinyl groups (nitrogen-containing heterocyclic-containing vinyl monomers) (for example, N-vinyl-2-pyrrolidone, N-vinyl) -2-piperidone, N-vinyl-2-caprolactam, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, etc.) and nitrogen-containing heterocycles and monomers having (meth) acryloyl groups (containing nitrogen-containing heterocycles) (Meth) acrylic monomer) (for example, (meth) Nitrogen-containing heterocycle-containing monomers
- copolymerizable monomers include, for example, polyfunctional monomers.
- the multifunctional monomer include hexanediol di (meth) acrylate, butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and neopentyl glycol.
- examples include (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, and urethane acrylate.
- Examples of other copolymerizable monomers other than polyfunctional monomers include (meth) acrylic acid esters having an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
- (Meth) acrylic acid esters having aromatic hydrocarbon groups such as phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate; vinyl esters such as vinyl acetate and vinyl propionate; styrene, vinyl Aromatic vinyl compounds such as toluene; olefins or dienes such as ethylene, butadiene, isoprene and isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride;
- copolymerizable monomers may be only one type or two or more types.
- the content ratio of the alkyl (meth) acrylate having a linear or branched alkyl group in the total amount of the monomer components forming the acrylic polymer (A) exhibits the effect of the present invention more.
- it is preferably 50% by weight to 95% by weight, more preferably 55% by weight to 90% by weight, still more preferably 60% by weight to 85% by weight, and particularly preferably 65% by weight to 80% by weight. % By weight.
- the content ratio of the polar group-containing monomer in the total amount of the monomer components forming the acrylic polymer (A) is preferably 5% by weight to 50% by weight from the viewpoint that the effects of the present invention can be further expressed. More preferably 10 to 45% by weight, still more preferably 15 to 40% by weight, particularly preferably 20 to 35% by weight.
- a hydroxyl group-containing monomer (2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate) is used as the polar group-containing monomer in that the effects of the present invention can be further exhibited.
- the hydroxyl group (hydroxyl group) -containing monomer is essential as the polar group-containing monomer, the content ratio of the hydroxyl group (hydroxyl group) -containing monomer in the total amount of monomer components forming the acrylic polymer (A) is more effective than the effect of the present invention.
- it is preferably 10% to 25% by weight, more preferably 10% to 24% by weight, still more preferably 11% to 23% by weight, and particularly preferably 12% by weight. ⁇ 22% by weight.
- a carboxyl group-containing monomer (particularly (meth) acrylic acid) is not used or is used in a small amount in that it can exhibit the effects of the present invention more and suppress corrosion of metals and the like. It is preferable to do.
- the content ratio of the carboxyl group-containing monomer in the total amount of monomer components forming the acrylic polymer (A) is preferably 0% by weight to 5% by weight, more preferably 0% by weight to 3% by weight. More preferably, it is 0 to 2% by weight, and particularly preferably 0 to 0.5% by weight.
- the acrylic polymer (A) is obtained by polymerizing the monomer component by any appropriate polymerization method within a range not impairing the effects of the present invention.
- the polymerization method for obtaining the acrylic polymer (A) include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a polymerization method (active energy ray polymerization method) by active energy ray irradiation.
- the solution polymerization method and the active energy ray polymerization method are preferable in terms of productivity.
- Examples of the solvent used in the case of adopting the solution polymerization method include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; and aliphatics such as n-hexane and n-heptane.
- Organic solvents such as hydrocarbons; cycloaliphatic hydrocarbons such as cyclohexane and methylcyclohexane; ketones such as methyl ethyl ketone and methyl isobutyl ketone;
- One type of solvent may be sufficient and 2 or more types may be sufficient as it.
- a polymerization initiator such as a photopolymerization initiator or a thermal polymerization initiator is preferably used depending on the type of the polymerization reaction. In addition, only 1 type may be sufficient as a polymerization initiator, and 2 or more types may be sufficient as it.
- the photopolymerization initiator examples include a benzoin ether photopolymerization initiator, an acetophenone photopolymerization initiator, an ⁇ -ketol photopolymerization initiator, an aromatic sulfonyl chloride photopolymerization initiator, and a photoactive oxime photopolymerization initiator.
- the amount of the photopolymerization initiator used is, for example, preferably 0.01% to 0.2% by weight, more preferably 0.05%, based on the total amount of monomer components forming the acrylic polymer (A). % By weight to 0.15% by weight.
- thermal polymerization initiators examples include azo initiators, peroxide polymerization initiators (eg, dibenzoyl peroxide, tert-butyl permaleate), redox polymerization initiators, and the like.
- azo initiators eg, dibenzoyl peroxide, tert-butyl permaleate
- redox polymerization initiators e.g., redox polymerization initiators, and the like.
- the azo initiators disclosed in JP-A-2002-69411 are preferable.
- the amount of the thermal polymerization initiator used is preferably 0.05% by weight to 0.5% by weight with respect to the total amount of the monomer components forming the acrylic polymer (A). More preferably, it is 0.1 wt% to 0.3 wt%.
- the pressure-sensitive adhesive composition contains an isocyanate-based crosslinking agent and / or an epoxy-based crosslinking agent.
- the pressure-sensitive adhesive composition contains an isocyanate-based crosslinking agent and / or an epoxy-based crosslinking agent, it is possible to provide a pressure-sensitive adhesive having sufficient adhesive force and less distortion at high temperatures. Only one type of isocyanate crosslinking agent may be used, or two or more types may be used. Only one type of epoxy-based crosslinking agent may be used, or two or more types may be used.
- the total content of the isocyanate crosslinking agent and the epoxy crosslinking agent in the pressure-sensitive adhesive composition is preferably 0.1% by weight to 30% by weight with respect to 100% by weight of the acrylic polymer (A). %, More preferably 0.2% to 25% by weight, still more preferably 0.5% to 23% by weight, particularly preferably 1% to 20% by weight, most preferably 5 to 18% by weight. If the total content of the isocyanate-based crosslinking agent and the epoxy-based crosslinking agent in the pressure-sensitive adhesive composition is within the above range with respect to 100% by weight of the acrylic polymer (A), the adhesive composition has a more sufficient adhesive force, An adhesive having less distortion at high temperature can be provided.
- the content of the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition is preferably 2% by weight to 20% by weight, more preferably 3% by weight with respect to 100% by weight of the acrylic polymer (A). % To 19% by weight, more preferably 5% to 17% by weight, particularly preferably 6% to 15% by weight, and most preferably 7% to 13% by weight. If the content of the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition is within the above range with respect to 100% by weight of the acrylic polymer (A), the adhesive composition has more sufficient adhesive force and less distortion at high temperatures. Adhesive can be provided.
- the content of the epoxy crosslinking agent in the pressure-sensitive adhesive composition is preferably 0.3% by weight to 10% by weight, more preferably 100% by weight with respect to the acrylic polymer (A). 0.5 to 9% by weight, more preferably 0.7 to 8% by weight, particularly preferably 1 to 7% by weight, most preferably 2 to 6% by weight. It is. If the content of the epoxy crosslinking agent in the pressure-sensitive adhesive composition is within the above range with respect to 100% by weight of the acrylic polymer (A), the adhesive composition has more sufficient adhesive force and less distortion at high temperatures. Adhesive can be provided.
- isocyanate crosslinking agent polyfunctional isocyanate compound
- examples of the isocyanate crosslinking agent include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, Cycloaliphatic polyisocyanates such as cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, And aromatic polyisocyanates such as xylylene diisocyanate.
- isocyanate crosslinking agent examples include trimethylolpropane / tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate L”), trimethylolpropane / hexamethylene diisocyanate adduct (Japan Polyurethane Industry Co., Ltd.) ), Trade names “Coronate HL” and “Coronate HX”), and trimethylolpropane / xylylene diisocyanate adduct (manufactured by Mitsui Chemicals, trade name “Takenate D110N”).
- an epoxy-based crosslinking agent for example, an epoxy-based resin having two or more epoxy groups in the molecule is used, and specifically, diglycidylaniline, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane. N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, etc. It is done.
- epoxy-based crosslinking agent examples include “Tetrad C” manufactured by Mitsubishi Gas Chemical Co., Ltd., “Adeka Resin EPU Series” and “Adeka Resin EPR Series” manufactured by ADEKA Co., Ltd., “Celoxide” manufactured by Daicel Co., Ltd. and the like. The commercial item of is also mentioned.
- the pressure-sensitive adhesive composition may include other cross-linking agents, cross-linking accelerators, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), if necessary.
- Additives such as anti-aging agents, fillers, colorants (such as pigments and dyes), UV absorbers, antioxidants, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, etc. It may be contained in any appropriate amount as long as the effect is not impaired. Only one kind of such an additive may be used, or two or more kinds thereof may be used.
- Embodiment A as a method of forming the pressure-sensitive adhesive of the present invention from the pressure-sensitive adhesive composition, any appropriate method can be adopted as long as the effects of the present invention are not impaired.
- the pressure-sensitive adhesive composition is applied on any appropriate base material (for example, a PET base material), and is subjected to a crosslinking reaction by heating with an oven or the like, followed by further drying or the like as necessary.
- any appropriate coating method can be used.
- Examples of such a coating method include a coating method using a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater.
- a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater.
- a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater.
- the thickness of the resulting pressure-sensitive adhesive layer can be appropriately set according to the purpose.
- the thickness is preferably 1 ⁇ m to 500 ⁇ m, more preferably 5 ⁇ m to 300 ⁇ m, even more preferably 10 ⁇ m to 200 ⁇ m, and particularly preferably 15 ⁇ m to 200 ⁇ m from the viewpoint that the effects of the present invention can be further exhibited. 100 ⁇ m, most preferably 20 ⁇ m to 50 ⁇ m.
- the content of the acrylic polymer (B) in the pressure-sensitive adhesive composition is preferably 20% by weight to 90% by weight, more preferably 25% by weight to 85% by weight, and further preferably It is 30% to 80% by weight, particularly preferably 35% to 75% by weight, and most preferably 40% to 70% by weight.
- the content ratio of the acrylic polymer (B) in the pressure-sensitive adhesive composition is within the above range, it is possible to provide a pressure-sensitive adhesive having more sufficient adhesive force and less distortion at high temperatures. Only one type of acrylic polymer (B) may be used, or two or more types may be used.
- the acrylic polymer (B) is a polymer formed from a monomer component that essentially contains an acrylic monomer. That is, the acrylic polymer (B) is a polymer having a structural unit derived from an acrylic monomer as an essential monomer structural unit.
- the weight average molecular weight of the acrylic polymer (B) is preferably 200,000 to 2,500,000, more preferably 300,000 to 1,800,000, from the viewpoint that the effects of the present invention can be expressed more. More preferably, it is 400,000 to 1,500,000, particularly preferably 500,000 to 1,200,000.
- the acrylic polymer (B) is preferably a (meth) acrylic acid alkyl ester having a glass transition temperature (Tg) of ⁇ 20 ° C. or lower when a homopolymer is used.
- the acrylic polymer preferably contains 80% by weight or more based on the total amount of the monomer components forming the.
- Glass transition temperature (Tg) when homopolymerized means “glass transition temperature (Tg) of homopolymer of monomer”, and only a certain monomer (sometimes referred to as “monomer X”). It means the glass transition temperature (Tg) of a polymer formed as a monomer component.
- the numerical values listed in Table 1 are listed, and the glass transition temperature (Tg) of homopolymers not listed in Table 1 is, for example, “Polymer Handbook” (3rd edition, John Wiley & Sons, Inc.). , 1989) may be used.
- this homopolymer solution is cast-coated on a release liner and dried to prepare a test sample (sheet-like homopolymer) having a thickness of about 2 mm. Then, about 1 mg to 2 mg of this test sample was weighed into an aluminum open cell, and a temperature-modulated DSC (trade name “Q-2000”, manufactured by TA Instruments Inc.) was used to measure 50 ml / min of nitrogen. The homopolymer's Reversing Heat Flow (specific heat component) behavior is obtained at a heating rate of 5 ° C./min in an atmosphere.
- the temperature at the point where the curve of the part intersects is the glass transition temperature (Tg) when the homopolymer is formed.
- Examples of the (meth) acrylic acid alkyl ester having a glass transition temperature of ⁇ 20 ° C. or less when made into a homopolymer include (meth) acrylic acid alkyl esters shown in Table 1.
- “(meth) acrylic acid alkyl ester” indicates “acrylic acid alkyl ester and / or methacrylic acid alkyl ester”.
- the (meth) acrylic acid alkyl ester having a glass transition temperature of ⁇ 20 ° C. or lower when homopolymer is used may be only one kind or two or more kinds.
- the (meth) acrylic acid alkyl ester having a glass transition temperature of ⁇ 20 ° C. or less when made into a homopolymer is preferably a glass transition temperature when made into a homopolymer, from the viewpoint that the effects of the present invention can be further exhibited.
- the (meth) acrylic acid alkyl ester having a glass transition temperature of ⁇ 20 ° C. or lower when made into a homopolymer is preferably n-butyl acrylate, from the viewpoint that the effects of the present invention can be more manifested.
- 2-ethylhexyl acrylate and lauryl acrylate is preferably n-butyl acrylate, from the viewpoint that the effects of the present invention can be more manifested.
- the acrylic polymer (B) contains a (meth) acrylic acid alkyl ester having a glass transition temperature (Tg) of ⁇ 20 ° C. or less when it is a homopolymer based on the total amount of monomer components forming the acrylic polymer (B).
- the ratio is preferably 80% by weight or more, more preferably 83% by weight or more, still more preferably 87% by weight or more, and particularly preferably 90% by weight or more.
- the upper limit of the content is preferably 100% by weight or less, more preferably 98% by weight or less, still more preferably 96% by weight or less, and particularly preferably 95% by weight or less. If the said content rate exists in the said range, it can provide the adhesive which has more sufficient adhesive force and there are few distortions at high temperature.
- the acrylic polymer (B) is the above (meth) acrylic as a monomer component for forming the polymer, from the viewpoint of enabling tuning of characteristics, proper use according to the purpose, and imparting functions as necessary.
- a copolymerizable monomer may be included together with the acid alkyl ester. In addition, only 1 type may be sufficient as a copolymerizable monomer and 2 or more types may be sufficient as it.
- Examples of the copolymerizable monomer include polar group-containing monomers.
- the monomer component forming the acrylic polymer (B) includes the polar group-containing monomer, it is possible to provide a pressure-sensitive adhesive having a sufficient adhesive force and less distortion at a high temperature.
- Examples of the polar group-containing monomer include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and acid anhydrides thereof (for example, acid anhydride groups such as maleic anhydride and itaconic anhydride).
- Carboxyl group-containing monomers such as (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, Hydroxyl group-containing monomers such as vinyl alcohol and allyl alcohol; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxy Methyl (meth) acrylamide, An amide group-containing monomer such as hydroxyethyl (meth) acrylamide; an amino group-containing monomer such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate; ) Epoxy group-containing monomers such as gly
- the polar group-containing monomer is preferably a carboxyl group-containing monomer or a hydroxyl group-containing monomer, more preferably acrylic acid, 4-hydroxybutyl acrylate, acrylic acid 2 or the like, from the viewpoint that the effects of the present invention can be further exhibited.
- -Hydroxyethyl is preferably a carboxyl group-containing monomer or a hydroxyl group-containing monomer, more preferably acrylic acid, 4-hydroxybutyl acrylate, acrylic acid 2 or the like, from the viewpoint that the effects of the present invention can be further exhibited.
- the content ratio of the polar group-containing monomer in the total amount of the monomer components forming the acrylic polymer (B) is preferably 1% by weight to 20% by weight, more preferably, from the viewpoint that the effects of the present invention can be expressed more. 1% to 15% by weight.
- examples of the copolymerizable monomer include a polyfunctional monomer.
- a polyfunctional monomer means a monomer having two or more ethylenically unsaturated groups in one molecule.
- examples of the ethylenically unsaturated group include radical polymerizable functional groups such as a vinyl group, a propenyl group, an isopropenyl group, a vinyl ether group (vinyloxy group), and an allyl ether group (allyloxy group).
- multifunctional monomer examples include hexanediol di (meth) acrylate, butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and neopentyl glycol.
- examples of the copolymerizable monomer include (meth) acrylic acid alkoxyalkyl esters.
- (meth) acrylic acid alkoxyalkyl esters include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and (meth) acrylic acid 3- Examples include methoxypropyl, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 4-ethoxybutyl (meth) acrylate, and the like. Only one (meth) acrylic acid alkoxyalkyl ester may be used, or two or more types may be used.
- examples of the copolymerizable monomer include (meth) acrylic acid esters having an alicyclic hydrocarbon group such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate; phenyl ( (Meth) acrylates having an aromatic hydrocarbon group such as meth) acrylate, phenoxyethyl (meth) acrylate, and benzyl (meth) acrylate; the above (meth) acrylic acid alkyl esters and the above (meth) acrylic acid alkoxyalkyl esters , Polar group-containing monomers, and (meth) acrylic acid esters other than the polyfunctional monomers; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyltoluene; ethylene and butadiene Vinyl ethers such as vinyl alkyl ethers; isoprene, o
- the acrylic polymer (B) is obtained by polymerizing the monomer component by any appropriate polymerization method within a range not impairing the effects of the present invention.
- the polymerization method for obtaining the acrylic polymer (B) include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a polymerization method by active energy ray irradiation (active energy ray polymerization method).
- active energy ray polymerization method active energy ray polymerization method.
- the solution polymerization method and the active energy ray polymerization method are preferable, and the solution polymerization method is more preferable.
- Examples of the solvent used in the case of adopting the solution polymerization method include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; and aliphatics such as n-hexane and n-heptane.
- Organic solvents such as hydrocarbons; cycloaliphatic hydrocarbons such as cyclohexane and methylcyclohexane; ketones such as methyl ethyl ketone and methyl isobutyl ketone;
- One type of solvent may be sufficient and 2 or more types may be sufficient as it.
- a polymerization initiator such as a photopolymerization initiator or a thermal polymerization initiator may be used depending on the type of the polymerization reaction. In addition, only 1 type may be sufficient as a polymerization initiator, and 2 or more types may be sufficient as it.
- the photopolymerization initiator examples include a benzoin ether photopolymerization initiator, an acetophenone photopolymerization initiator, an ⁇ -ketol photopolymerization initiator, an aromatic sulfonyl chloride photopolymerization initiator, and a photoactive oxime photopolymerization initiator.
- the amount of the photopolymerization initiator used is, for example, preferably 0.01% by weight to 0.2% by weight, more preferably 0.05% by weight based on the total amount of monomer components forming the acrylic polymer (B). % By weight to 0.15% by weight.
- thermal polymerization initiators examples include azo initiators, peroxide polymerization initiators (eg, dibenzoyl peroxide, tert-butyl permaleate), redox polymerization initiators, and the like.
- azo initiators eg, dibenzoyl peroxide, tert-butyl permaleate
- redox polymerization initiators e.g., redox polymerization initiators, and the like.
- the azo initiators disclosed in JP-A-2002-69411 are preferable.
- the amount of the thermal polymerization initiator used is preferably 0.05 wt% to 0.5 wt% with respect to the total amount of monomer components forming the acrylic polymer (B). More preferably, it is 0.1 wt% to 0.3 wt%.
- the pressure-sensitive adhesive composition contains an ultraviolet curable oligomer.
- the pressure-sensitive adhesive composition contains an ultraviolet curable oligomer, it is possible to provide a pressure-sensitive adhesive having sufficient adhesive force and less distortion at high temperatures. Only one type of ultraviolet curable oligomer may be used, or two or more types may be used.
- the content of the ultraviolet curable oligomer in the pressure-sensitive adhesive composition is preferably 10% by weight to 300% by weight, more preferably 20% by weight with respect to 100% by weight of the acrylic polymer (B). % To 150% by weight, more preferably 30% to 120% by weight, particularly preferably 35% to 110% by weight, and most preferably 40% to 105% by weight. If the content of the ultraviolet curable oligomer in the pressure-sensitive adhesive composition is within the above range with respect to 100% by weight of the acrylic polymer (B), the adhesive composition has more sufficient adhesive force and less distortion at high temperatures. Adhesive can be provided.
- UV curable oligomers have a polymerizable ethylenically unsaturated double bond, and include aromatic urethane oligomers, aliphatic urethane oligomers, epoxy acrylate oligomers, polyester acrylate oligomers, and other special oligomers.
- ultraviolet curable oligomer examples include, for example, commercial products such as UV-2000B, UV-2750B, UV-3000B, UV-3010B, UV-3200B, UV-3300B, and UV-3700B manufactured by Nippon Kasei Gosei Co., Ltd.
- the pressure-sensitive adhesive composition includes a cross-linking agent, a cross-linking accelerator, a silane coupling agent, a tackifying resin (such as a rosin derivative, a polyterpene resin, a petroleum resin, and an oil-soluble phenol) as necessary.
- Additives such as additives, fillers, colorants (such as pigments and dyes), ultraviolet absorbers, antioxidants, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, etc. It may be contained in any appropriate amount as long as it is not impaired. Only one kind of such an additive may be used, or two or more kinds thereof may be used.
- Embodiment B as a method of forming the pressure-sensitive adhesive of the present invention from the pressure-sensitive adhesive composition, any appropriate method can be adopted as long as the effects of the present invention are not impaired.
- the pressure-sensitive adhesive composition is applied on any appropriate base material (for example, PET base material, etc.), heated by an oven or the like to undergo a crosslinking reaction, further dried, etc. as necessary, and further subjected to ultraviolet rays. It is cured by irradiation or the like to form the pressure-sensitive adhesive of the present invention.
- any appropriate coating method can be used.
- Examples of such a coating method include a coating method using a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater.
- a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater.
- a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater.
- the thickness of the resulting pressure-sensitive adhesive layer can be appropriately set according to the purpose.
- the thickness is preferably 1 ⁇ m to 500 ⁇ m, more preferably 5 ⁇ m to 300 ⁇ m, even more preferably 10 ⁇ m to 200 ⁇ m, and particularly preferably 15 ⁇ m to 200 ⁇ m from the viewpoint that the effects of the present invention can be further exhibited. 100 ⁇ m, most preferably 20 ⁇ m to 50 ⁇ m.
- Embodiment C Yet another embodiment (sometimes referred to as embodiment C) of the pressure-sensitive adhesive of the present invention is formed from a pressure-sensitive adhesive composition comprising a urethane-based polymer and an acrylic monomer.
- the content of the urethane-based polymer in the pressure-sensitive adhesive composition is preferably 10% by weight to 90% by weight, more preferably 20% by weight to 80% by weight, and still more preferably 30% by weight. Is 75% by weight, particularly preferably 35% by weight to 70% by weight, and most preferably 40% by weight to 65% by weight. If the content rate of the urethane type polymer in an adhesive composition exists in the said range, it can provide the adhesive which has more sufficient adhesive force and there are few distortions at high temperature. Only one type of urethane polymer in the pressure-sensitive adhesive composition may be used, or two or more types may be used.
- the content of the acrylic monomer in the pressure-sensitive adhesive composition is preferably 20% by weight to 80% by weight, more preferably 30% by weight to 75% by weight, and particularly preferably 35% by weight. ⁇ 70 wt%, most preferably 40 wt% to 65 wt%. If the content ratio of the acrylic monomer in the pressure-sensitive adhesive composition is within the above range, it is possible to provide a pressure-sensitive adhesive having more sufficient adhesive force and less distortion at high temperature.
- the acrylic monomer in the pressure-sensitive adhesive composition may be only one type or two or more types.
- the urethane polymer is preferably obtained using a reaction between a polyol compound and a polyisocyanate compound. That is, the urethane polymer can be obtained by using a raw material containing a polyol compound and a polyisocyanate compound and using a reaction between the polyol compound and the polyisocyanate compound. Only one kind of polyol compound may be used, or two or more kinds may be used. Only one polyisocyanate compound may be used, or two or more polyisocyanate compounds may be used.
- the reaction between the polyol compound and the polyisocyanate compound can be performed by any suitable method that can be employed in the production of the urethane-based polymer.
- the urethane-based polymer is obtained, for example, by mixing and stirring a polyol compound and a polyisocyanate compound, and the polyisocyanate compound is added so that the isocyanate group becomes excessive with respect to the hydroxyl group in the polyol compound. It is preferable.
- an organic solvent having no active hydrogen that can react with an isocyanate group eg, ethyl acetate, methyl ethyl ketone, chloroform, etc.
- a catalyst eg, tin chloride, organotin compound, etc.
- an organic base such as a tertiary amine compound; an organic acid such as acetic acid and acrylic acid; etc.
- the ratio of the polyisocyanate compound and the polyol compound is equivalent to NCO / OH, preferably 0.1 to 2.0, more preferably 0.3 to 1.8. More preferably, it is 0.5 to 1.5, and particularly preferably 0.8 to 1.3.
- NCO / OH ratio is within the above range, a pressure-sensitive adhesive having a sufficient adhesive force and less distortion at high temperatures can be provided.
- the molecular weight of the urethane-based polymer can be appropriately set according to the purpose.
- the molecular weight of the urethane polymer is such that the number average molecular weight (Mn) is preferably 5000 or more, more preferably 10,000 or more, from the viewpoint that the effects of the present invention can be expressed more.
- a polyol compound having a melting point and / or freezing point of 15 ° C. to 75 ° C. is preferably selected as the polyol compound.
- examples of such a polyol compound include a polyol compound having a crystal component, and exhibits crystallization and melting behavior due to temperature change.
- the melting point and / or freezing point of the polyol compound can be confirmed by a manufacturer's catalog, MSDS (Product Safety Data Sheet) or the like.
- melting point and “freezing point” can be similarly treated as physical property values that define a specific polyol compound, and when only one physical property value is described in a catalog or the like, the values are What is necessary is just to employ
- examples of the polyol compound include polyester polyols (polycondensates of divalent alcohols and divalent basic acids such as adipic acid, azelaic acid, and sepatic acid), polyether polyols (ethylene oxide, And the like obtained by addition polymerization of tetrahydrofuran, etc.), polyacrylate polyol, polycarbonate polyol, polyolefin polyol, polybutadiene polyol and hydrogenated product, polyisoprene polyol and hydrogenated product, phenolic polyol, epoxy polyol, caprolactone polyol, polysulfone polyol Etc.
- examples of the polyol compound include copolymer polyols such as polyester / polyether polyols.
- the polyol compound preferably includes polyester polyol, polyether polyol, and polycarbonate diol.
- polyester polyol examples include, for example, a trade name “Nipporan 4002” which is polyethylene adipate glycol, a trade name “Nipporan 4009” which is polybutylene adipate glycol, and a trade name “Nipporan 164” which is polyhexamethylene adipate glycol. (Nippon Polyurethane Co., Ltd.) is commercially available.
- polyether polyol examples include, for example, trade names “PTMG1000” (melting point (Tm): 17 ° C.) and “PTMG1300” (melting point (Tm): 18 ° C.) which are polytetramethylene ether glycol (PTMG).
- PTMG1500 melting point (Tm): 18 ° C.
- PTMG1800 melting point (Tm): 20 ° C.
- PTMG2000 melting point (Tm): 20 ° C.
- PTMG3000 melting point (Tm): 21 ° C) (above, manufactured by Diachemical Co., Ltd.) and the like are commercially available.
- polycarbonate diol specifically, for example, the trade name “Nipporan 981” (melting point (Tm): 42 ° C.) (manufactured by Nippon Polyurethane Co., Ltd.), which is 1,6-hexamethylene carbonate glycol, is commercially available. Is possible.
- examples of the polyisocyanate compound include hexamethylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylene diisocyanate, xylylene diene.
- the polyisocyanate compound is preferably a hydrogenated xylylene diisocyanate.
- the urethane-based polymer preferably includes a (meth) acryloyl group-terminated urethane-based polymer.
- the (meth) acryloyl group-terminated urethane polymer is a compound having two or more acryloyl groups or methacryloyl groups in one molecule and having a urethane bond as a repeating structural unit.
- the content ratio of the (meth) acryloyl group-terminated urethane polymer in the urethane polymer is preferably 50% by weight to 100% by weight. More preferably 70% to 100% by weight, still more preferably 90% to 100% by weight, particularly preferably 95% to 100% by weight, and most preferably substantially 100% by weight. %.
- the (meth) acryloyl group-terminated urethane polymer is preferably obtained by reacting a hydroxyl group-containing acrylic monomer with a polyurethane prepolymer obtained by a reaction between a polyol compound and a polyisocyanate compound.
- an organic solvent having no active hydrogen that can react with an isocyanate group eg, ethyl acetate, methyl ethyl ketone, chloroform, etc.
- a catalyst eg, tin chloride, organic tin compound, etc.
- the reaction can also be carried out by adding metal catalysts; organic bases such as tertiary amine compounds; organic acids such as acetic acid and acrylic acid;
- hydroxyl group-containing acrylic monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, Examples include 2-hydroxy-3-phenyloxypropyl (meth) acrylate, neoventyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, and pentaerythritol tri (meth) acrylate. Only one type of hydroxyl group-containing acrylic monomer may be used, or two or more types may be used.
- the amount of the hydroxyl group-containing acrylic monomer used is preferably 0.1% by weight to 10% by weight and more preferably 0.1% by weight to 5% by weight with respect to the polyurethane prepolymer.
- the ratio of the polyurethane prepolymer to the hydroxyl group-containing acrylic monomer is preferably added so that the hydroxyl groups in the hydroxyl group-containing acrylic monomer are equivalent to the isocyanate residue of the polyurethane prepolymer.
- polyol compound: hydroxyl group-containing acrylic monomer 1: 0.1 to 1: 0.4.
- the pressure-sensitive adhesive composition contains an acrylic monomer.
- the acrylic monomer preferably includes a (meth) acrylic monomer having an amide group.
- the content ratio of the (meth) acrylic monomer having an amide group in the total amount of the acrylic monomer is preferably 5% by weight. It is ⁇ 99% by weight, more preferably 15% by weight to 97% by weight, and further preferably 25% by weight to 95% by weight.
- the content ratio of the (meth) acrylic monomer having an amide group is within the above range, it is possible to provide a pressure-sensitive adhesive having more sufficient adhesive force and less distortion at high temperature.
- (meth) acrylic monomers having an amide group examples include N-methylol (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, and N- (1,1-dimethyl).
- (meth) acrylamide mono-substituted (meth) acrylamide such as N, N-dimethylaminopropyl (meth) acrylamide; N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N, N-diallyl (meth) acrylamide, N, N-di-isopropyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide, N, N-disubstituted amines such as N, N-ethylmethyl (meth) acrylamide N- (meth) acryloylpyrrolidone; N- (meth) acryloylpiperidine; N- (meth) acryloylpyrrolidine; N- (meth) acryloylaziridine;
- the acrylic monomer may contain any appropriate other acrylic monomer as long as the effects of the present invention are not impaired.
- Such other acrylic monomers may be only one type or two or more types.
- examples of such other acrylic monomers include (meth) acrylic monomers; polyfunctional monomers such as hexanediol diacrylate, trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate.
- Such other acrylic monomer is preferably a (meth) acrylic monomer.
- (meth) acrylic monomers examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, and (meth) acrylic.
- (meth) acrylic monomers preferably include butyl (meth) acrylate, isobornyl (meth) acrylate, and (meth) acrylic acid.
- the content of butyl (meth) acrylate in the total amount of the acrylic monomer is preferably 1% by weight to 90% by weight, more preferably 5% by weight to 60% by weight, and still more preferably. It is 10% by weight to 40% by weight, and particularly preferably 15% by weight to 30% by weight.
- the content ratio of butyl (meth) acrylate in the total amount of the acrylic monomer is within the above range, it is possible to provide a pressure-sensitive adhesive having more sufficient adhesive force and less distortion at high temperature.
- the content ratio of isobornyl (meth) acrylate in the total amount of the acrylic monomer is preferably 1% by weight to 90% by weight, more preferably 5% by weight to 60% by weight, and still more preferably It is 10% by weight to 40% by weight, and particularly preferably 15% by weight to 30% by weight.
- the content ratio of isobornyl (meth) acrylate in the total amount of the acrylic monomer is within the above range, it is possible to provide a pressure-sensitive adhesive having sufficient adhesive force and less distortion at high temperature.
- the content ratio of (meth) acrylic acid in the total amount of the acrylic monomer is preferably 1% by weight to 90% by weight, more preferably 2% by weight to 65% by weight, and still more preferably 3%. % By weight to 40% by weight, particularly preferably 4% by weight to 25% by weight.
- the content ratio of (meth) acrylic acid in the total amount of the acrylic monomer is within the above range, it is possible to provide a pressure-sensitive adhesive having more sufficient adhesive force and less distortion at high temperature.
- the pressure-sensitive adhesive composition includes a crosslinking agent, a crosslinking accelerator, a silane coupling agent, a tackifying resin (such as a rosin derivative, a polyterpene resin, a petroleum resin, and an oil-soluble phenol), and anti-aging as necessary.
- Additives such as additives, fillers, colorants (such as pigments and dyes), ultraviolet absorbers, antioxidants, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, etc. It may be contained in any appropriate amount as long as it is not impaired. Only one kind of such an additive may be used, or two or more kinds thereof may be used.
- any appropriate method can be adopted as long as the effects of the present invention are not impaired.
- a urethane polymer is formed in the presence of an acrylic monomer
- a photopolymerization initiator is further added to a mixture containing the urethane polymer and the vinyl monomer, It is applied on an appropriate substrate (for example, a PET substrate), and any appropriate active energy ray ( ⁇ ray, ⁇ ray, ⁇ ray, neutron ray, electron beam, etc. depending on the type of photopolymerization initiator, etc.
- reaction conditions when irradiating active energy rays any appropriate conditions that can be generally adopted as polymerization by irradiation with active energy rays can be adopted.
- a hydroxyl group-containing acrylic monomer when used in forming the urethane polymer, a polyol compound and a polyisocyanate compound are reacted in the presence of the acrylic monomer component to form a polyurethane prepolymer. Later, a hydroxyl group-containing acrylic monomer is added to react with the polyurethane prepolymer, a photopolymerization initiator is further added to the resulting mixture, and it is applied onto any suitable substrate (eg, a PET substrate).
- a photopolymerization initiator is further added to the resulting mixture, and it is applied onto any suitable substrate (eg, a PET substrate).
- any appropriate active energy ray ( ⁇ ray, ⁇ ray, ⁇ ray, neutron ray, electron beam, ultraviolet ray, visible light, etc.) can be cured and cured.
- the pressure-sensitive adhesive of the invention can be formed.
- any appropriate conditions that can be generally adopted as polymerization by irradiation with active energy rays can be adopted.
- Embodiment C specifically, for example, after dissolving a polyol compound in an acrylic monomer component, a polyisocyanate compound is added to react with the polyol compound, viscosity adjustment and the like are performed, and the resulting mixture is obtained.
- the pressure-sensitive adhesive of the present invention can be formed by coating on any appropriate base material (for example, PET base material) and then curing by ultraviolet irradiation or the like. Further, after curing, the cured product may be peeled off from the base material and used as the pressure-sensitive adhesive of the present invention.
- any appropriate coating method can be used.
- a coating method using a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater.
- a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater.
- any appropriate substrate for example, PET substrate
- any appropriate base material that has been subjected to a peeling treatment may be placed.
- any appropriate solvent may be added for viscosity adjustment.
- a solvent include ethyl acetate, toluene, chloroform, dimethylformamide and the like.
- photopolymerization initiator Only one type of photopolymerization initiator may be used, or two or more types may be used.
- any appropriate amount usually used for photopolymerization can be adopted.
- the thickness of the resulting pressure-sensitive adhesive layer can be appropriately set according to the purpose.
- the thickness is preferably 1 ⁇ m to 500 ⁇ m, more preferably 5 ⁇ m to 300 ⁇ m, even more preferably 10 ⁇ m to 200 ⁇ m, and particularly preferably 15 ⁇ m to 200 ⁇ m from the viewpoint that the effects of the present invention can be further exhibited. 100 ⁇ m, most preferably 20 ⁇ m to 50 ⁇ m.
- the urethane polymer when the urethane polymer includes a (meth) acryloyl group-terminated urethane polymer, the (meth) acryloyl group is polymerized with the vinyl group by polymerizing a vinyl monomer in the presence of the urethane polymer. In some cases, a vinyl polymer bonded to the (meth) acryloyl group-terminated urethane polymer is obtained.
- Adhesive film In the pressure-sensitive adhesive film of the present invention, the adhesive force to the surface of the polyimide film is 1N or more, preferably 3N or more, more preferably 5N or more, still more preferably 7N or more, and particularly preferably 9N or more. . If the adhesive force of the adhesive film of the present invention with respect to the surface of the polyimide film is within the above range, the adhesive film of the present invention has sufficient adhesive force, for example, strong on the back side of the semiconductor element substrate for reinforcement. Can be bonded with high reliability. The measuring method of the adhesive force with respect to the surface of a polyimide film is mentioned later.
- the adhesive film of the present invention has a storage elastic modulus G ′ at 160 ° C. of 1 ⁇ 10 4 Pa or more, preferably 1.5 ⁇ 10 4 Pa or more, more preferably 2 ⁇ 10 4 Pa or more, More preferably, it is 2.3 ⁇ 10 4 Pa or more, and particularly preferably 2.4 ⁇ 10 4 Pa or more. If the storage elastic modulus G ′ at 160 ° C. of the pressure-sensitive adhesive film of the present invention is within the above range, the pressure-sensitive adhesive film of the present invention is less distorted at high temperatures. For example, an anisotropic conductive film (ACF) is applied to a substrate of a semiconductor element.
- ACF anisotropic conductive film
- the adhesive film of the present invention has a storage elastic modulus G ′ at 25 ° C. of preferably 5 ⁇ 10 4 Pa or more, more preferably 7 ⁇ 10 4 Pa or more, and further preferably 1 ⁇ 10 5 Pa or more. Yes, particularly preferably 5 ⁇ 10 5 Pa or more.
- the upper limit of the storage modulus G 'at 25 ° C. of the adhesive of the present invention is preferably 1 ⁇ 10 8 Pa or less. If the storage elastic modulus G ′ at 25 ° C. of the pressure-sensitive adhesive of the present invention is within the above range, it can be bonded to an adherend at room temperature or a heat roll, and deformation is reduced even when pressure is applied, and reinforcement is achieved. It may be possible to easily use it as a tape for use. A method for measuring the storage elastic modulus G ′ at 25 ° C. will be described later.
- the pressure-sensitive adhesive film of the present invention has a thickness of 20 ⁇ m or less, preferably 18 ⁇ m or less, more preferably 15 ⁇ m or less, further preferably 13 ⁇ m or less, particularly preferably 12 ⁇ m or less, and most preferably 10 ⁇ m or less. It is.
- the lower limit of the thickness of the pressure-sensitive adhesive film of the present invention is preferably 3 ⁇ m or more. If the thickness of the pressure-sensitive adhesive film of the present invention is within the above range, the pressure-sensitive adhesive film of the present invention is less distorted at high temperatures.
- an integrated circuit IC is formed on a substrate of a semiconductor element by an anisotropic conductive film (ACF).
- the distortion of the adhesive film can be suppressed, the distortion of the substrate of the semiconductor element associated therewith can also be suppressed, and the connection failure can be reduced.
- a method for measuring the thickness of the adhesive film will be described later.
- the pressure-sensitive adhesive film of the present invention preferably has a crosslinked structure.
- the pressure-sensitive adhesive film of the present invention has a cross-linked structure, the pressure-sensitive adhesive film of the present invention has a sufficient adhesive force and is less distorted at high temperatures.
- the pressure-sensitive adhesive film of the present invention is within a range that does not impair the effects of the present invention, so long as the three requirements of adhesive strength to the surface of the polyimide film, storage elastic modulus G ′ at 160 ° C., and thickness are within the above ranges. It can be formed from an adhesive composition.
- Examples of such a pressure-sensitive adhesive composition include a pressure-sensitive adhesive composition containing an acrylic polymer and a pressure-sensitive adhesive composition containing a urethane-based polymer.
- An acrylic polymer is a polymer formed from a monomer component that essentially contains an acrylic monomer. That is, the acrylic polymer is a polymer having a structural unit derived from an acrylic monomer as an essential monomer structural unit.
- any suitable acrylic can be used as long as the three requirements of the adhesive strength to the surface of the polyimide film, the storage elastic modulus G ′ at 160 ° C., and the thickness are within the above ranges as long as the effects of the present invention are not impaired.
- System polymers can be employed.
- Examples of the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive film of the present invention include the following pressure-sensitive adhesive composition containing an acrylic polymer (A), pressure-sensitive adhesive composition containing an acrylic polymer (B), and a urethane-based polymer.
- the adhesive composition containing is mentioned.
- the content of the acrylic polymer (A) in the pressure-sensitive adhesive composition is preferably 50% by weight to 99.9% by weight, more preferably 70%. % By weight to 99% by weight, more preferably 75% by weight to 95% by weight, particularly preferably 80% by weight to 93% by weight, and most preferably 85% by weight to 90% by weight. If the content rate of the acrylic polymer (A) in an adhesive composition exists in the said range, it can provide an adhesive film which has more sufficient adhesive force and there are few distortions at high temperature. Only one type of acrylic polymer (A) may be used, or two or more types may be used.
- the acrylic polymer (A) is a polymer formed from a monomer component that essentially contains an acrylic monomer. That is, the acrylic polymer (A) is a polymer having a structural unit derived from an acrylic monomer as an essential monomer structural unit.
- the weight average molecular weight of the acrylic polymer (A) is preferably 200,000 to 2,500,000, more preferably 300,000 to 1,800,000, and even more preferably 400,000, from the viewpoint that the effects of the present invention can be expressed more. ⁇ 1.5 million, particularly preferably 500,000 to 1,200,000.
- the acrylic polymer (A) is preferably a polymer formed from a monomer component that essentially includes a (meth) acrylic acid alkyl ester having a linear or branched alkyl group and a polar group-containing monomer.
- the monomer component may contain other copolymerizable monomers.
- the content ratio of the (meth) acrylic acid alkyl ester having a linear or branched alkyl group is preferable in that the effect of the present invention can be expressed more. Is 50% to 95% by weight, more preferably 55% to 90% by weight, still more preferably 60% to 85% by weight, and particularly preferably 65% to 80% by weight.
- the content ratio of the polar group-containing monomer in the total amount of the monomer components forming the acrylic polymer (A) is preferably 5% by weight to 50% by weight, more preferably, from the viewpoint that the effect of the present invention can be expressed more. It is 10% by weight to 45% by weight, more preferably 15% by weight to 40% by weight, and particularly preferably 20% by weight to 35% by weight.
- a hydroxyl group-containing monomer (2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic acid) as a polar group-containing monomer in that the effects of the present invention can be further exhibited.
- the hydroxyl group (hydroxyl group) -containing monomer is essential as the polar group-containing monomer, the content ratio of the hydroxyl group (hydroxyl group) -containing monomer in the total amount of monomer components forming the acrylic polymer (A) is more effective than the effect of the present invention.
- it is preferably 10% to 25% by weight, more preferably 10% to 24% by weight, still more preferably 11% to 23% by weight, and particularly preferably 12% by weight. ⁇ 22% by weight.
- carboxyl group-containing monomers are preferably not used or even if used.
- the content ratio of the carboxyl group-containing monomer in the total amount of monomer components forming the acrylic polymer (A) is preferably 0% by weight to 5% by weight, more preferably 0% by weight to 3% by weight. More preferably, it is 0 to 2% by weight, and particularly preferably 0 to 0.5% by weight.
- the pressure-sensitive adhesive composition containing the acrylic polymer (A) may contain a crosslinking agent.
- a crosslinking agent any appropriate crosslinking agent can be adopted as long as the effects of the present invention are not impaired.
- Such a crosslinking agent is preferably an isocyanate crosslinking agent.
- the pressure-sensitive adhesive composition containing the acrylic polymer (A) contains an isocyanate-based crosslinking agent, it is possible to provide a pressure-sensitive adhesive film having more sufficient adhesive force and less distortion at high temperatures. Only one type of isocyanate crosslinking agent may be used, or two or more types may be used.
- the content of the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition is preferably 100% by weight of the acrylic polymer (A). 0.1 wt% to 50 wt%, more preferably 2 wt% to 40 wt%, further preferably 5 wt% to 30 wt%, and particularly preferably 7 wt% to 20 wt%. Most preferably, it is 9 to 18% by weight. If the content of the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition is within the above range with respect to 100% by weight of the acrylic polymer (A), the adhesive composition has more sufficient adhesive force and less distortion at high temperatures. An adhesive film can be provided.
- isocyanate-based crosslinking agent polyfunctional isocyanate compound
- any appropriate method can be adopted as long as the effects of the present invention are not impaired.
- a pressure-sensitive adhesive composition containing an acrylic polymer (A) is applied on any appropriate base material (for example, PET base material), and is subjected to a crosslinking reaction by heating with an oven or the like. Drying etc. are performed and the adhesive film of this invention is formed.
- any appropriate coating method can be used.
- Examples of such a coating method include a coating method using a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater.
- a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater.
- a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater.
- the content of the acrylic polymer (B) in the pressure-sensitive adhesive composition is 20% by weight to 90% by weight, more preferably 25% by weight to 85% by weight. %, More preferably 30% to 80% by weight, particularly preferably 35% to 75% by weight, and most preferably 40% to 70% by weight. If the content rate of the acrylic polymer (B) in an adhesive composition exists in the said range, it can provide an adhesive film which has more sufficient adhesive force and there are few distortions at high temperature. Only one type of acrylic polymer (B) may be used, or two or more types may be used.
- the acrylic polymer (B) is a polymer formed from a monomer component that essentially contains an acrylic monomer. That is, the acrylic polymer (B) is a polymer having a structural unit derived from an acrylic monomer as an essential monomer structural unit.
- the weight average molecular weight of the acrylic polymer (B) is preferably 200,000 to 2,500,000, more preferably 300,000 to 1,800,000, and even more preferably 400,000, from the viewpoint that the effects of the present invention can be expressed more. ⁇ 1.5 million, particularly preferably 500,000 to 1,200,000.
- the acrylic polymer (B) is preferably a monomer component that forms an acrylic polymer (B) with a (meth) acrylic acid alkyl ester having a glass transition temperature (Tg) of ⁇ 20 ° C. or lower when it is a homopolymer.
- the acrylic polymer preferably contains 80% by weight or more based on the total amount. For such an acrylic polymer, the above item ⁇ 1-2.
- the description in embodiment B> may be incorporated.
- the acrylic polymer (B) contains a (meth) acrylic acid alkyl ester having a glass transition temperature (Tg) of ⁇ 20 ° C. or less when it is a homopolymer based on the total amount of monomer components forming the acrylic polymer (B).
- the ratio is preferably 80% by weight or more, more preferably 83% by weight or more, still more preferably 87% by weight or more, and particularly preferably 90% by weight or more.
- the upper limit of the content is preferably 100% by weight or less, more preferably 98% by weight or less, still more preferably 96% by weight or less, and particularly preferably 95% by weight or less. If the said content rate exists in the said range, it can have a sufficient adhesive force and can provide the adhesive film with few distortions at high temperature.
- the acrylic polymer (B) can be obtained by polymerizing the monomer component by any appropriate polymerization method as long as the effects of the present invention are not impaired.
- the polymerization method of the acrylic polymer (B) the above item ⁇ 1-2.
- the description in embodiment B> may be incorporated.
- the pressure-sensitive adhesive composition containing the acrylic polymer (B) may contain an ultraviolet curable oligomer.
- the pressure-sensitive adhesive composition containing the acrylic polymer (B) contains the ultraviolet curable oligomer, it is possible to provide a pressure-sensitive adhesive film having a sufficient adhesive force and less distortion at a high temperature. Only one type of ultraviolet curable oligomer may be used, or two or more types may be used.
- the content of the ultraviolet curable oligomer in the pressure-sensitive adhesive composition containing the acrylic polymer (B) is preferably 10% by weight to 300% by weight, more preferably 100% by weight with respect to the acrylic polymer (B). It is 20 to 150% by weight, more preferably 30 to 120% by weight, particularly preferably 35 to 110% by weight, and most preferably 40 to 105% by weight. If the content of the ultraviolet curable oligomer in the pressure-sensitive adhesive composition containing the acrylic polymer (B) is within the above range with respect to 100% by weight of the acrylic polymer (B), the adhesive composition has a more sufficient adhesive force, An adhesive film with less distortion at high temperature can be provided.
- UV curable oligomers For UV curable oligomers, the above item ⁇ 1-2.
- the description in embodiment B> may be incorporated.
- the pressure-sensitive adhesive composition containing the acrylic polymer (B), a crosslinking agent, a crosslinking accelerator, a silane coupling agent, a tackifying resin (rosin derivative, polyterpene resin, petroleum resin, oil-soluble phenol, etc.), if necessary, Additives such as anti-aging agents, fillers, colorants (such as pigments and dyes), UV absorbers, antioxidants, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, etc. It may be contained in any appropriate amount as long as the effect is not impaired. Only one kind of such an additive may be used, or two or more kinds thereof may be used.
- any appropriate method can be adopted as long as the effects of the present invention are not impaired.
- a pressure-sensitive adhesive composition containing an acrylic polymer (B) is applied on any appropriate base material (for example, a PET base material), and is subjected to a crosslinking reaction by heating with an oven or the like. Drying and the like, and further curing by ultraviolet irradiation or the like to form the adhesive film of the present invention.
- any appropriate coating method can be used.
- Examples of such a coating method include a coating method using a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater.
- a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater.
- a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater.
- the content of the urethane polymer in the pressure-sensitive adhesive composition is preferably 10% by weight to 90% by weight, more preferably 20% by weight to 80% by weight. More preferably, it is 30 wt% to 75 wt%, particularly preferably 35 wt% to 70 wt%, and most preferably 40 wt% to 65 wt%. If the content ratio of the urethane-based polymer in the pressure-sensitive adhesive composition containing the urethane-based polymer is within the above range, it is possible to provide a pressure-sensitive adhesive film having more sufficient adhesive force and less distortion at high temperature. . As for the urethane type polymer in the adhesive composition containing a urethane type polymer, only 1 type may be sufficient and 2 or more types may be sufficient.
- the urethane polymer is preferably obtained using a reaction between a polyol compound and a polyisocyanate compound. That is, the urethane polymer can be obtained by using a raw material containing a polyol compound and a polyisocyanate compound and using a reaction between the polyol compound and the polyisocyanate compound. Only one kind of polyol compound may be used, or two or more kinds may be used. Only one polyisocyanate compound may be used, or two or more polyisocyanate compounds may be used.
- the reaction between the polyol compound and the polyisocyanate compound can be performed by any suitable method that can be employed in the production of the urethane-based polymer.
- the urethane-based polymer is obtained, for example, by mixing and stirring a polyol compound and a polyisocyanate compound, and the polyisocyanate compound is added so that the isocyanate group becomes excessive with respect to the hydroxyl group in the polyol compound. It is preferable.
- an organic solvent having no active hydrogen that can react with an isocyanate group eg, ethyl acetate, methyl ethyl ketone, chloroform, etc.
- a catalyst eg, tin chloride, organotin compound, etc.
- an organic base such as a tertiary amine compound; an organic acid such as acetic acid and acrylic acid; etc.
- the ratio of the polyisocyanate compound and the polyol compound is an equivalent ratio, and is preferably 0.1 to 2.0, more preferably 0.3 to 1.8, and still more preferably 0 as NCO / OH. 0.5 to 1.5, particularly preferably 0.8 to 1.3. If the ratio of NCO / OH is within the above range, an adhesive film having more sufficient adhesive force and less distortion at high temperature can be provided.
- the molecular weight of the urethane-based polymer can be appropriately set according to the purpose.
- the molecular weight of the urethane polymer is such that the number average molecular weight (Mn) is preferably 5000 or more, more preferably 10,000 or more, from the viewpoint that the effects of the present invention can be expressed more.
- the urethane polymer preferably contains a (meth) acryloyl group-terminated urethane polymer.
- the (meth) acryloyl group-terminated urethane polymer is a compound having two or more acryloyl groups or methacryloyl groups in one molecule and having a urethane bond as a repeating structural unit.
- the content of the (meth) acryloyl group-terminated urethane polymer in the urethane polymer is preferably 50% by weight to 100% by weight, more preferably Is 70% to 100% by weight, more preferably 90% to 100% by weight, particularly preferably 95% to 100% by weight, and most preferably substantially 100% by weight.
- the (meth) acryloyl group-terminated urethane polymer is preferably obtained by reacting a hydroxyl group-containing acrylic monomer with a polyurethane prepolymer obtained by a reaction between a polyol compound and a polyisocyanate compound.
- an organic solvent having no active hydrogen that can react with an isocyanate group eg, ethyl acetate, methyl ethyl ketone, chloroform, etc.
- a catalyst eg, tin chloride, organic tin compound, etc.
- the reaction can also be carried out by adding metal catalysts; organic bases such as tertiary amine compounds; organic acids such as acetic acid and acrylic acid;
- the ratio of the polyurethane prepolymer to the hydroxyl group-containing acrylic monomer is preferably added so that the hydroxyl groups in the hydroxyl group-containing acrylic monomer are equivalent to the isocyanate residue of the polyurethane prepolymer.
- polyol compound: hydroxyl group-containing acrylic monomer 1: 0.1 to 1: 0.4.
- the pressure-sensitive adhesive composition containing a urethane polymer may contain an acrylic monomer.
- the content of the acrylic monomer in the pressure-sensitive adhesive composition containing a urethane polymer is preferably 20% by weight to 80% by weight, and more preferably Is 30% to 75% by weight, particularly preferably 35% to 70% by weight, and most preferably 40% to 65% by weight. If the content ratio of the acrylic monomer in the pressure-sensitive adhesive composition containing the urethane polymer is within the above range, it is possible to provide a pressure-sensitive adhesive film having sufficient adhesive force and less distortion at high temperature. .
- the acrylic monomer in the pressure-sensitive adhesive composition containing a urethane polymer may be only one type or two or more types.
- the acrylic monomer preferably includes a (meth) acrylic monomer having an amide group.
- the content ratio of the (meth) acrylic monomer having an amide group in the total amount of the acrylic monomer is preferably 5 wt% to 99 wt%. More preferably 15 to 97% by weight, still more preferably 25 to 95% by weight. If the content ratio of the (meth) acrylic monomer having an amide group is within the above range, it is possible to provide a pressure-sensitive adhesive film having more sufficient adhesive force and less distortion at high temperature.
- the acrylic monomer may contain any appropriate other acrylic monomer as long as the effects of the present invention are not impaired. Such other acrylic monomers may be only one type or two or more types. For such other acrylic monomers, the above item ⁇ 1-3. The description in embodiment C> may be incorporated.
- the content ratio of butyl (meth) acrylate in the total amount of the acrylic monomer is preferably 1% by weight to 90% by weight, more preferably 5% by weight to 60% by weight, and still more preferably 10% by weight to 40% by weight. % By weight, particularly preferably 15% by weight to 30% by weight.
- the content ratio of butyl (meth) acrylate in the total amount of the acrylic monomer is within the above range, it is possible to provide an adhesive film having more sufficient adhesive force and less distortion at high temperature.
- the content ratio of isobornyl (meth) acrylate in the total amount of the acrylic monomer is preferably 1% by weight to 90% by weight, more preferably 5% by weight to 60% by weight, and further preferably 10% by weight to 40% by weight. % By weight, particularly preferably 15% by weight to 30% by weight.
- the content ratio of (meth) acrylic acid in the total amount of the acrylic monomer is preferably 1% by weight to 90% by weight, more preferably 2% by weight to 65% by weight, and further preferably 3% by weight to 40% by weight. %, Particularly preferably 4 to 25% by weight.
- the content ratio of (meth) acrylic acid in the total amount of the acrylic monomer is within the above range, it is possible to provide an adhesive film having more sufficient adhesive force and less distortion at high temperature.
- additives such as additives, fillers, colorants (such as pigments and dyes), ultraviolet absorbers, antioxidants, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, etc. It may be contained in any appropriate amount as long as it is not impaired. Only one kind of such an additive may be used, or two or more kinds thereof may be used.
- any appropriate method can be adopted as long as the effects of the present invention are not impaired.
- a urethane polymer is formed in the presence of an acrylic monomer
- a photopolymerization initiator is further added to a mixture containing the urethane polymer and the vinyl monomer, It is applied on an appropriate substrate (for example, a PET substrate), and any appropriate active energy ray ( ⁇ ray, ⁇ ray, ⁇ ray, neutron ray, electron beam, etc. depending on the type of photopolymerization initiator, etc.
- reaction conditions when irradiating active energy rays any appropriate conditions that can be generally adopted as polymerization by irradiation with active energy rays can be adopted.
- a polyurethane prepolymer is formed by reacting a polyol compound and a polyisocyanate compound in the presence of the acrylic monomer component, and then a hydroxyl group-containing acrylic monomer is formed.
- a system monomer is added to react with the polyurethane prepolymer, a photopolymerization initiator is further added to the resulting mixture, and the mixture is applied on any appropriate substrate (for example, a PET substrate).
- the adhesive film of the present invention is cured by irradiating with any appropriate active energy ray ( ⁇ ray, ⁇ ray, ⁇ ray, neutron ray, electron beam, ultraviolet ray, visible light, etc.) depending on the type of Can be formed.
- any appropriate active energy ray ⁇ ray, ⁇ ray, ⁇ ray, neutron ray, electron beam, ultraviolet ray, visible light, etc.
- any appropriate conditions that can be generally adopted as polymerization by irradiation with active energy rays can be adopted.
- the adhesive film of the present invention can be formed by curing by ultraviolet irradiation or the like. Further, after curing, the cured product may be peeled off from the substrate to form the pressure-sensitive adhesive film of the present invention.
- any appropriate coating method can be used.
- a coating method using a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater.
- a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, and a direct coater.
- any appropriate base material for example, PET base material
- any appropriate base material for example, PET base material
- any appropriate solvent may be added for viscosity adjustment.
- a solvent include ethyl acetate, toluene, chloroform, dimethylformamide and the like.
- photopolymerization initiator Only one type of photopolymerization initiator may be used, or two or more types may be used.
- any appropriate amount usually used for photopolymerization can be adopted.
- the urethane polymer contains a (meth) acryloyl group-terminated urethane polymer
- the (meth) acryloyl group is polymerized with the vinyl group by polymerizing a vinyl monomer in the presence of the urethane polymer, )
- a vinyl polymer combined with an acryloyl group-terminated urethane polymer may be obtained.
- the pressure-sensitive adhesive tape of the present invention has the pressure-sensitive adhesive or pressure-sensitive adhesive film of the present invention.
- the pressure-sensitive adhesive tape of the present invention has the pressure-sensitive adhesive or pressure-sensitive adhesive film of the present invention as a pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive tape of the present invention may have only one pressure-sensitive adhesive layer, or may have two or more layers.
- the pressure-sensitive adhesive tape of the present invention may have a base material.
- a base material for example, Polyester resins such as polyethylene terephthalate (PET), acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate, triacetyl cellulose (TAC), polysulfone, polyarylate, polyimide, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene And base materials formed from plastic materials such as ethylene-propylene copolymers and cyclic olefin polymers.
- PET polyethylene terephthalate
- acrylic resins such as polymethyl methacrylate (PMMA)
- PMMA polymethyl methacrylate
- TAC triacetyl cellulose
- polysulfone polyarylate
- polyimide polyimide
- polyvinyl chloride polyvinyl acetate
- polyethylene polypropylene
- base materials formed from plastic materials such as ethylene-propylene copolymers and cyclic o
- One embodiment of the pressure-sensitive adhesive tape of the present invention is a form having a single pressure-sensitive adhesive layer on a single-layer base material.
- the thickness of the substrate can be appropriately set according to the purpose.
- the thickness is preferably 1 ⁇ m to 500 ⁇ m, more preferably 5 ⁇ m to 300 ⁇ m, even more preferably 10 ⁇ m to 200 ⁇ m, and particularly preferably 15 ⁇ m to 200 ⁇ m from the viewpoint that the effects of the present invention can be further exhibited. 100 ⁇ m, most preferably 20 ⁇ m to 50 ⁇ m.
- the substrate surface may be subjected to known and conventional surface treatments such as physical treatment such as corona discharge treatment and plasma treatment, and chemical treatment such as undercoat treatment.
- the film substrate of the present invention has the pressure-sensitive adhesive or pressure-sensitive adhesive film of the present invention.
- the film substrate according to the present invention is a film in which a conductive metal layer such as copper is laminated or subjected to wiring processing on one side or both sides of a heat-resistant insulating film, or a wiring pattern of a metal layer by etching using a photolithography technique or the like.
- Film or field effect transistor formed film sometimes referred to as FPC, etc., is a flexible substrate, has flexibility, and can be repeatedly deformed with weak force. Yes, even when deformed, it has the characteristic of maintaining its electrical characteristics.
- FPC field effect transistor formed film
- it is a plate-like or film-like component that constitutes an electronic circuit by fixing a large number of electronic components such as integrated circuits, resistors, capacitors, etc. on the surface and connecting the components by wiring.
- test and evaluation method in an Example etc. are as follows. Note that “parts” means “parts by weight” unless otherwise noted, and “%” means “% by weight” unless otherwise noted.
- the storage elastic modulus G ′ at 25 ° C. and 160 ° C. was prepared by applying the pressure-sensitive adhesive composition to the separator film instead of the PET film substrate in Examples and Comparative Examples, and by the predetermined method of each Example and Comparative Example.
- the separator was peeled from the pressure-sensitive adhesive layer, and only the pressure-sensitive adhesive layer was laminated to produce a laminate of a pressure-sensitive adhesive layer having a thickness of about 1.5 mm, which was used as a measurement sample.
- the measurement sample was measured at a heating rate of 5 ° C./min in the range of ⁇ 70 to 200 ° C. in a shear mode with a frequency of 1 Hz using “Advanced Rheometric Expansion System (ARES)” manufactured by Rheometric Scientific. .
- AWS Advanced Rheometric Expansion System
- a peel test was performed using a tensile tester (trade name “TCM-1kNB”, manufactured by Minebea Co., Ltd.), and the adhesive force to the polyimide film was measured. The average load at that time was defined as the adhesive force to the polyimide film. The measurement was performed in an atmosphere of 23 ° C. and 50% RH under conditions of a peeling angle of 180 ° and a tensile speed of 300 mm / min.
- Adhesive tape is attached to the lower surface of a polyimide film (Kapton 50EN, manufactured by Toray DuPont Co., Ltd.) having a thickness of 12.5 ⁇ , and an iron plate having a width of 2 mm, a length of 20 mm, and a thickness of 1 mm is placed on the upper surface of the polyimide film.
- a pressure was applied at 160 ° C. for 5 seconds to an iron plate placed on the polyimide film so that a pressure of 30 MPa was applied to the polyimide film (Shinto Kogyo Co., Ltd., CYPT-10).
- the cross section of the polyimide film on which the pressure-sensitive adhesive tape was applied with an iron plate was cut, and it was observed whether the pressure-sensitive adhesive tape was deformed by heat and pressure applied thereto.
- the case where there was almost no deformation of the pressure-sensitive adhesive was indicated as ⁇ , the case where there was a deformation but slight, ⁇ , and the case where the deformation was large as x.
- Example 1 2-ethylhexyl acrylate (2EHA) as a monomer component: 63 parts by weight, N-vinyl-2-pyrrolidone (NVP): 15 parts by weight, methyl methacrylate (MMA): 9 parts by weight, 2-hydroxyethyl acrylate ( (HEA): 13 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 0.2 part by weight, and ethyl acetate as a polymerization solvent: 133 parts by weight were put into a separable flask. The mixture was stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 65 ° C.
- acrylic polymer (1) having a solid content concentration of 30% by weight. It was.
- the weight average molecular weight of the acrylic polymer (1) was 800,000.
- an isocyanate-based crosslinking agent (trade name “Takenate D110N”, manufactured by Mitsui Chemicals, Inc.) is added to the acrylic polymer (1) solution with respect to 100 parts by weight of the acrylic polymer (1) (solid content).
- a silane coupling agent ( ⁇ -glycidoxypropyltrimethoxysilane, trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.) is added in an amount of 100 parts by weight of an acrylic polymer (solid content).
- the adhesive composition (1) was prepared by mixing this.
- the pressure-sensitive adhesive composition (1) was applied to one surface of a PET substrate (“Lumirror S10” (thickness 75 ⁇ m, manufactured by Toray Industries, Inc.)), and an application layer was formed on the PET substrate.
- a PET substrate (“Lumirror S10” (thickness 75 ⁇ m, manufactured by Toray Industries, Inc.)
- an application layer was formed on the PET substrate.
- the coating layer on the PET base material is put into an oven, the coating layer is dried at 130 ° C. for 3 minutes, and a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer having a thickness of 25 ⁇ m on one surface of the PET base material (1) was obtained.
- Table 2 The results are shown in Table 2.
- Example 2 2-ethylhexyl acrylate (2EHA) as a monomer component: 63 parts by weight, N-vinyl-2-pyrrolidone (NVP): 15 parts by weight, methyl methacrylate (MMA): 9 parts by weight, 2-hydroxyethyl acrylate ( (HEA): 13 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 0.2 part by weight, and ethyl acetate as a polymerization solvent: 133 parts by weight were put into a separable flask. The mixture was stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 65 ° C.
- NDP N-vinyl-2-pyrrolidone
- MMA methyl methacrylate
- HOA 2-hydroxyethyl acrylate
- 2,2′-azobisisobutyronitrile as a polymerization initiator
- acrylic polymer (2) having a solid content concentration of 30% by weight. It was.
- the weight average molecular weight of the acrylic polymer (2) was 800,000.
- an isocyanate-based crosslinking agent (trade name “Takenate D110N”, manufactured by Mitsui Chemicals, Inc.) is added to the acrylic polymer (2) solution with respect to 100 parts by weight of the acrylic polymer (2) (solid content).
- a silane coupling agent ( ⁇ -glycidoxypropyltrimethoxysilane, trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 100 parts by weight of an acrylic polymer (solid content).
- the adhesive composition (2) was prepared by mixing this.
- the pressure-sensitive adhesive composition (2) was applied to one surface of a PET substrate (thickness 75 ⁇ m), and an application layer was formed on the PET substrate.
- the coating layer on the PET base material was put into an oven, the coating layer was dried at 130 ° C. for 3 minutes, and a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer having a thickness of 25 ⁇ m on one surface of the PET base material ( 2) was obtained.
- Table 2 The results are shown in Table 2.
- Example 3 N-butyl acrylate (BA) as a monomer component: 95 parts by weight, acrylic acid (AA): 5 parts by weight, and ethyl acetate as a polymerization solvent: 185.7 parts by weight are charged into a separable flask, and nitrogen is added. The mixture was stirred for 1 hour while introducing gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 63 ° C. and reacted for 10 hours, and toluene was added to obtain a solution of an acrylic polymer (3) having a solid content concentration of 25% by weight. The weight average molecular weight of the acrylic polymer (3) was 600,000.
- Example 4 In a reaction vessel equipped with a condenser, a thermometer and a stirrer, N, N-dimethylacrylamide (DMAA) 36.18 parts by weight, acrylic acid (AA) 18.08 parts by weight, and butyl acrylate (BA).
- DMAA N, N-dimethylacrylamide
- AA acrylic acid
- BA butyl acrylate
- HXDI hydrogenated xylylene diisocyanate
- the obtained pressure-sensitive adhesive composition (4) was applied on a 75 ⁇ m thick PET film so that the thickness after curing was 25 ⁇ m.
- the peeled PET separator was stacked and coated, and then the coated PET separator surface was cured by irradiating with ultraviolet light (illuminance 5 mW / cm 2 , light amount 1200 mJ / cm 2 ) using a black light.
- a pressure-sensitive adhesive tape (4) having a PET separator subjected to a release treatment was obtained. The results are shown in Table 2.
- dibutyltin dilaurate IV (manufactured by Wako Pure Chemical Industries, Ltd.): 0.0272 parts by weight was added and stirred at 40 ° C. for 20 hours in an air atmosphere to obtain a solution of an acrylic polymer (C1).
- an isocyanate crosslinking agent (trade name “Takenate D110N”, manufactured by Mitsui Chemicals, Inc.) is added to the acrylic polymer (1) solution with respect to 100 parts by weight of the acrylic polymer (C1) (solid content).
- 2-benzyl-2- (dimethylamino) -4-morpholinobutylphenone (trade name “Irgacure 369”, manufactured by BASF) is acrylic as a photopolymerization initiator.
- N-butyl acrylate (BA) as a monomer component: 95 parts by weight, acrylic acid (AA): 5 parts by weight, and ethyl acetate as a polymerization solvent: 185.7 parts by weight are charged into a separable flask, and nitrogen is added. The mixture was stirred for 1 hour while introducing gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 63 ° C. and reacted for 10 hours, and toluene was added to obtain an acrylic polymer solution having a solid content concentration of 25% by weight. The acrylic polymer in the acrylic polymer solution had a weight average molecular weight of 600,000.
- cyclohexyl methacrylate as a monomer component [glass transition temperature of homopolymer (polycyclohexyl methacrylate): 66 ° C.]: 95 parts by weight, acrylic acid: 5 parts by weight, ⁇ -methylstyrene dimer as a chain transfer agent: 10 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 10 parts by weight, and toluene as a polymerization solvent: 120 parts by weight are charged into a separable flask, and nitrogen gas is introduced. The mixture was stirred for 1 hour. After removing oxygen in the polymerization system in this way, the temperature was raised to 85 ° C.
- an acrylic oligomer solution having a solid content concentration of 50% by weight.
- the weight average molecular weight of the acrylic oligomer in the acrylic oligomer solution was 4000.
- a silane coupling agent ⁇ -glycidoxypropyltrimethoxysilane, trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.
- KBM403 ⁇ -glycidoxypropyltrimethoxysilane
- KBM403 trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.
- a crosslinking agent epoxy crosslinking agent, trade name “TETRAD-C”, manufactured by Mitsubishi Gas Chemical Co., Ltd.
- the acrylic oligomer solution is added so as to be 0.075 parts by weight in terms of solid content with respect to parts by weight, and the acrylic oligomer solution is further converted into an acrylic oligomer in terms of solid content with respect to 100 parts by weight of the acrylic polymer (solid content).
- the pressure-sensitive adhesive composition (C2) was prepared by adding the mixture so that the amount was 25 parts by weight, and mixing this.
- the pressure-sensitive adhesive composition (C2) was applied to one surface of a PET substrate (thickness 75 ⁇ m), and an application layer was formed on the PET substrate. Next, what formed the coating layer on the PET base material is put into an oven, the coating layer is dried at 130 ° C. for 3 minutes, and a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer having a thickness of 25 ⁇ m on one surface of the PET base material (C2) was obtained.
- Table 2 The results are shown in Table 2.
- an isocyanate crosslinking agent (trade name “Takenate D110N”, manufactured by Mitsui Chemicals, Inc.) is 1.1 weight in terms of solid content with respect to 100 parts by weight of the acrylic polymer (solid content).
- the silane coupling agent ( ⁇ -glycidoxypropyltrimethoxysilane, trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 100 parts by weight of the acrylic polymer (solid content). It added so that it might become 0.15 weight part in conversion of solid content, and this was mixed, and the adhesive composition (C3) was prepared.
- the pressure-sensitive adhesive composition (C3) was applied to one surface of a PET substrate (thickness 75 ⁇ m), and an application layer was formed on the PET substrate. Next, what formed the coating layer on the PET base material is put into an oven, the coating layer is dried at 130 ° C. for 3 minutes, and a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer having a thickness of 25 ⁇ m on one surface of the PET base material (C3) was obtained. The results are shown in Table 2.
- Example 5 2-ethylhexyl acrylate (2EHA) as a monomer component: 63 parts by weight, N-vinyl-2-pyrrolidone (NVP): 15 parts by weight, methyl methacrylate (MMA): 9 parts by weight, 2-hydroxyethyl acrylate ( (HEA): 13 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 0.2 part by weight, and ethyl acetate as a polymerization solvent: 133 parts by weight were put into a separable flask. The mixture was stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 65 ° C.
- NDP N-vinyl-2-pyrrolidone
- MMA methyl methacrylate
- HOA 2-hydroxyethyl acrylate
- ethyl acetate as a polymerization solvent
- an isocyanate-based crosslinking agent (trade name “Takenate D110N”, manufactured by Mitsui Chemicals, Inc.) is added to the acrylic polymer (5) solution with respect to 100 parts by weight of the acrylic polymer (5) (solid content).
- a silane coupling agent ( ⁇ -glycidoxypropyltrimethoxysilane, trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.) is added in an amount of 100 parts by weight of an acrylic polymer (solid content). It added so that it might become 0.5 weight part in conversion of solid content with respect to a part, and the adhesive composition (5) was prepared by mixing this.
- the pressure-sensitive adhesive composition (5) was applied to one surface of a PET substrate (“Lumirror S10” (thickness 75 ⁇ m, manufactured by Toray Industries, Inc.)), and an application layer was formed on the PET substrate. Next, what formed the coating layer on the PET substrate is put into an oven, the coating layer is dried at 130 ° C. for 3 minutes, and a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer having a thickness of 10 ⁇ m on one surface of the PET substrate. (5) was obtained. The results are shown in Table 3.
- Example 6 The same procedure as in Example 5 was performed except that the pressure-sensitive adhesive composition (5) was applied so as to obtain a pressure-sensitive adhesive tape (6) having a pressure-sensitive adhesive film (pressure-sensitive adhesive layer) having a thickness of 15 ⁇ m. The results are shown in Table 3.
- Example 7 N-butyl acrylate (BA) as a monomer component: 95 parts by weight, acrylic acid (AA): 5 parts by weight, and ethyl acetate as a polymerization solvent: 185.7 parts by weight are charged into a separable flask, and nitrogen is added. The mixture was stirred for 1 hour while introducing gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 63 ° C. and reacted for 10 hours, and toluene was added to obtain an acrylic polymer solution having a solid content concentration of 25% by weight. The acrylic polymer in the acrylic polymer solution had a weight average molecular weight of 600,000.
- cyclohexyl methacrylate as a monomer component [glass transition temperature of homopolymer (polycyclohexyl methacrylate): 66 ° C.]: 95 parts by weight, acrylic acid: 5 parts by weight, ⁇ -methylstyrene dimer as a chain transfer agent: 10 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 10 parts by weight, and toluene as a polymerization solvent: 120 parts by weight are charged into a separable flask, and nitrogen gas is introduced. The mixture was stirred for 1 hour. After removing oxygen in the polymerization system in this way, the temperature was raised to 85 ° C.
- an acrylic oligomer solution having a solid content concentration of 50% by weight.
- the weight average molecular weight of the acrylic oligomer in the acrylic oligomer solution was 4000.
- a silane coupling agent ⁇ -glycidoxypropyltrimethoxysilane, trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.
- KBM403 ⁇ -glycidoxypropyltrimethoxysilane
- KBM403 trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.
- a crosslinking agent epoxy crosslinking agent, trade name “TETRAD-C”, manufactured by Mitsubishi Gas Chemical Co., Ltd.
- the acrylic oligomer solution is added so as to be 0.075 parts by weight in terms of solid content with respect to parts by weight, and the acrylic oligomer solution is further converted into an acrylic oligomer in terms of solid content with respect to 100 parts by weight of the acrylic polymer (solid content).
- the pressure-sensitive adhesive composition (7) was prepared by adding the mixture so that the amount was 25 parts by weight, and mixing them.
- the pressure-sensitive adhesive composition (7) was applied to one surface of a PET substrate (thickness 75 ⁇ m), and an application layer was formed on the PET substrate. Next, the coating layer formed on the PET substrate is put into an oven, the coating layer is dried at 130 ° C. for 3 minutes, and a 10 ⁇ m thick adhesive film (adhesive layer) is formed on one surface of the PET substrate.
- An adhesive tape (7) having the following was obtained. The results are shown in Table 3.
- Example 8 2-ethylhexyl acrylate (2EHA) as a monomer component: 63 parts by weight, N-vinyl-2-pyrrolidone (NVP): 15 parts by weight, methyl methacrylate (MMA): 9 parts by weight, 2-hydroxyethyl acrylate (HEA): 13 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 0.2 part by weight, and 133 parts by weight of ethyl acetate as a polymerization solvent were put into a separable flask, The mixture was stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 65 ° C.
- NDP N-vinyl-2-pyrrolidone
- MMA methyl methacrylate
- HEA 2-hydroxyethyl acrylate
- 2,2′-azobisisobutyronitrile as a polymerization initiator
- an isocyanate crosslinking agent (trade name “Takenate D110N”, manufactured by Mitsui Chemicals, Inc.) is 1.1 weight in terms of solid content with respect to 100 parts by weight of the acrylic polymer (solid content).
- the silane coupling agent ( ⁇ -glycidoxypropyltrimethoxysilane, trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 100 parts by weight of the acrylic polymer (solid content).
- the adhesive composition (8) was prepared.
- the pressure-sensitive adhesive composition (8) was applied to one surface of a PET substrate (thickness 75 ⁇ m), and an application layer was formed on the PET substrate.
- the coating layer formed on the PET substrate is put into an oven, the coating layer is dried at 130 ° C. for 3 minutes, and a 10 ⁇ m thick adhesive film (adhesive layer) is formed on one surface of the PET substrate.
- An adhesive tape (8) having the following was obtained. The results are shown in Table 3.
- Example 4 The same procedure as in Example 5 was performed except that the pressure-sensitive adhesive composition (5) was applied so as to obtain a pressure-sensitive adhesive tape (C4) having a pressure-sensitive adhesive film (pressure-sensitive adhesive layer) having a thickness of 25 ⁇ m. The results are shown in Table 3.
- Example 5 It carried out similarly to Example 7 except having apply
- the results are shown in Table 3.
- Example 6 The same procedure as in Example 8 was performed except that the adhesive composition (8) was applied so as to obtain an adhesive tape (C6) having an adhesive film (adhesive layer) having a thickness of 25 ⁇ m. The results are shown in Table 3.
- the pressure-sensitive adhesive or pressure-sensitive adhesive tape of the present invention has a sufficient adhesive force and has little distortion at high temperatures. For this reason, it can utilize for the adhesive tape etc. which are bonded together to the board
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Abstract
Description
ポリイミドフィルムの表面に対する接着力が1N以上であり、
160℃における貯蔵弾性率G’が1×105Pa以上である。 The pressure-sensitive adhesive of the present invention is
The adhesive force to the surface of the polyimide film is 1N or more,
The storage elastic modulus G ′ at 160 ° C. is 1 × 10 5 Pa or more.
ポリイミドフィルムの表面に対する接着力が1N以上であり、
160℃における貯蔵弾性率G’が1×104Pa以上であり、
厚みが20μm以下である。 The adhesive film of the present invention is
The adhesive force to the surface of the polyimide film is 1N or more,
The storage elastic modulus G ′ at 160 ° C. is 1 × 10 4 Pa or more,
The thickness is 20 μm or less.
本発明の粘着剤は、ポリイミドフィルムの表面に対する接着力が1N以上であり、好ましくは3N以上であり、より好ましくは5N以上であり、さらに好ましくは7N以上であり、特に好ましくは9N以上である。本発明の粘着剤のポリイミドフィルムの表面に対する接着力が上記範囲内にあれば、本発明の粘着剤は、十分な接着力を有し、例えば、半導体素子の基板の裏側に補強のために強固に信頼性良く貼り合せることが可能となる。ポリイミドフィルムの表面に対する接着力の測定方法については後述する。 << 1. Adhesive >>
The pressure-sensitive adhesive of the present invention has an adhesive strength to the surface of the polyimide film of 1N or more, preferably 3N or more, more preferably 5N or more, further preferably 7N or more, and particularly preferably 9N or more. . If the adhesive force of the pressure-sensitive adhesive of the present invention to the surface of the polyimide film is within the above range, the pressure-sensitive adhesive of the present invention has sufficient adhesive force, for example, on the back side of the substrate of the semiconductor element for strong reinforcement. Can be bonded with high reliability. The measuring method of the adhesive force with respect to the surface of a polyimide film is mentioned later.
本発明の粘着剤の一つの実施形態(実施形態Aと称することがある)は、アクリル系ポリマー(A)、およびイソシアネート系架橋剤および/またはエポキシ系架橋剤を含む粘着剤組成物から形成される。 <1-1. Embodiment A>
One embodiment (sometimes referred to as embodiment A) of the pressure-sensitive adhesive of the present invention is formed from a pressure-sensitive adhesive composition comprising an acrylic polymer (A) and an isocyanate-based crosslinking agent and / or an epoxy-based crosslinking agent. The
本発明の粘着剤の別の一つの実施形態(実施形態Bと称することがある)は、アクリル系ポリマー(B)および紫外線硬化型オリゴマーを含む粘着剤組成物から形成される。 <1-2. Embodiment B>
Another embodiment (sometimes referred to as Embodiment B) of the pressure-sensitive adhesive of the present invention is formed from a pressure-sensitive adhesive composition containing an acrylic polymer (B) and an ultraviolet curable oligomer.
本発明の粘着剤のさらに別の一つの実施形態(実施形態Cと称することがある)は、ウレタン系ポリマーおよびアクリル系モノマーを含む粘着剤組成物から形成される。 <1-3. Embodiment C>
Yet another embodiment (sometimes referred to as embodiment C) of the pressure-sensitive adhesive of the present invention is formed from a pressure-sensitive adhesive composition comprising a urethane-based polymer and an acrylic monomer.
本発明の粘着フィルムは、ポリイミドフィルムの表面に対する接着力が1N以上であり、好ましくは3N以上であり、より好ましくは5N以上であり、さらに好ましくは7N以上であり、特に好ましくは9N以上である。本発明の粘着フィルムのポリイミドフィルムの表面に対する接着力が上記範囲内にあれば、本発明の粘着フィルムは、十分な接着力を有し、例えば、半導体素子の基板の裏側に補強のために強固に信頼性良く貼り合せることが可能となる。ポリイミドフィルムの表面に対する接着力の測定方法については後述する。 ≪2. Adhesive film >>
In the pressure-sensitive adhesive film of the present invention, the adhesive force to the surface of the polyimide film is 1N or more, preferably 3N or more, more preferably 5N or more, still more preferably 7N or more, and particularly preferably 9N or more. . If the adhesive force of the adhesive film of the present invention with respect to the surface of the polyimide film is within the above range, the adhesive film of the present invention has sufficient adhesive force, for example, strong on the back side of the semiconductor element substrate for reinforcement. Can be bonded with high reliability. The measuring method of the adhesive force with respect to the surface of a polyimide film is mentioned later.
アクリル系ポリマー(A)を含む粘着剤組成物においては、粘着剤組成物中のアクリル系ポリマー(A)の含有割合は、好ましくは50重量%~99.9重量%であり、より好ましくは70重量%~99重量%であり、さらに好ましくは75重量%~95重量%であり、特に好ましくは80重量%~93重量%であり、最も好ましくは85重量%~90重量%である。粘着剤組成物中のアクリル系ポリマー(A)の含有割合が上記範囲内にあれば、より十分な接着力を有し、高温での歪みがより少ない、粘着フィルムを提供することができる。アクリル系ポリマー(A)は、1種のみであってもよいし、2種以上であってもよい。 <2-1. Pressure-sensitive adhesive composition containing acrylic polymer (A)>
In the pressure-sensitive adhesive composition containing the acrylic polymer (A), the content of the acrylic polymer (A) in the pressure-sensitive adhesive composition is preferably 50% by weight to 99.9% by weight, more preferably 70%. % By weight to 99% by weight, more preferably 75% by weight to 95% by weight, particularly preferably 80% by weight to 93% by weight, and most preferably 85% by weight to 90% by weight. If the content rate of the acrylic polymer (A) in an adhesive composition exists in the said range, it can provide an adhesive film which has more sufficient adhesive force and there are few distortions at high temperature. Only one type of acrylic polymer (A) may be used, or two or more types may be used.
アクリルポリマー(B)を含む粘着剤組成物においては、粘着剤組成物中のアクリル系ポリマー(B)の含有割合は、20重量%~90重量%であり、より好ましくは25重量%~85重量%であり、さらに好ましくは30重量%~80重量%であり、特に好ましくは35重量%~75重量%であり、最も好ましくは40重量%~70重量%である。粘着剤組成物中のアクリル系ポリマー(B)の含有割合が上記範囲内にあれば、より十分な接着力を有し、高温での歪みがより少ない、粘着フィルムを提供することができる。アクリル系ポリマー(B)は、1種のみであってもよいし、2種以上であってもよい。 <2-2. Pressure-sensitive adhesive composition containing acrylic polymer (B)>
In the pressure-sensitive adhesive composition containing the acrylic polymer (B), the content of the acrylic polymer (B) in the pressure-sensitive adhesive composition is 20% by weight to 90% by weight, more preferably 25% by weight to 85% by weight. %, More preferably 30% to 80% by weight, particularly preferably 35% to 75% by weight, and most preferably 40% to 70% by weight. If the content rate of the acrylic polymer (B) in an adhesive composition exists in the said range, it can provide an adhesive film which has more sufficient adhesive force and there are few distortions at high temperature. Only one type of acrylic polymer (B) may be used, or two or more types may be used.
ウレタン系ポリマーを含む粘着剤組成物においては、粘着剤組成物中のウレタン系ポリマーの含有割合は、好ましくは10重量%~90重量%であり、より好ましくは20重量%~80重量%であり、さらに好ましくは30重量%~75重量%であり、特に好ましくは35重量%~70重量%であり、最も好ましくは40重量%~65重量%である。ウレタン系ポリマーを含む粘着剤組成物中のウレタン系ポリマーの含有割合が上記範囲内にあれば、より十分な接着力を有し、高温での歪みがより少ない、粘着フィルムを提供することができる。ウレタン系ポリマーを含む粘着剤組成物中のウレタン系ポリマーは、1種のみであっても良いし、2種以上であってもよい。 <2-3. Adhesive Composition Containing Urethane Polymer>
In the pressure-sensitive adhesive composition containing a urethane polymer, the content of the urethane polymer in the pressure-sensitive adhesive composition is preferably 10% by weight to 90% by weight, more preferably 20% by weight to 80% by weight. More preferably, it is 30 wt% to 75 wt%, particularly preferably 35 wt% to 70 wt%, and most preferably 40 wt% to 65 wt%. If the content ratio of the urethane-based polymer in the pressure-sensitive adhesive composition containing the urethane-based polymer is within the above range, it is possible to provide a pressure-sensitive adhesive film having more sufficient adhesive force and less distortion at high temperature. . As for the urethane type polymer in the adhesive composition containing a urethane type polymer, only 1 type may be sufficient and 2 or more types may be sufficient.
本発明の粘着テープは、本発明の粘着剤または粘着フィルムを有する。 ≪Adhesive tape≫
The pressure-sensitive adhesive tape of the present invention has the pressure-sensitive adhesive or pressure-sensitive adhesive film of the present invention.
ポリエチレンテレフタレート(PET)等のポリエステル系樹脂、ポリメチルメタクリレート(PMMA)等のアクリル系樹脂、ポリカーボネート、トリアセチルセルロース(TAC)、ポリサルフォン、ポリアリレート、ポリイミド、ポリ塩化ビニル、ポリ酢酸ビニル、ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体、環状オレフィン系ポリマーなどのプラスチック材料から形成される基材が挙げられる。本発明の粘着テープは、基材を、1層のみ有していてもよいし、2層以上有していてもよい。 The pressure-sensitive adhesive tape of the present invention may have a base material. As such a base material, for example,
Polyester resins such as polyethylene terephthalate (PET), acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate, triacetyl cellulose (TAC), polysulfone, polyarylate, polyimide, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene And base materials formed from plastic materials such as ethylene-propylene copolymers and cyclic olefin polymers. The pressure-sensitive adhesive tape of the present invention may have only one layer, or two or more layers.
本発明のフィルム基板は、本発明の粘着剤または粘着フィルムを有する。 ≪Film substrate≫
The film substrate of the present invention has the pressure-sensitive adhesive or pressure-sensitive adhesive film of the present invention.
重量平均分子量は、ゲルパーミエーションクロマトグラフ(GPC)法により測定した。具体的には、GPC測定装置として、商品名「HLC-8120GPC」(東ソー株式会社製)を用いて、下記の条件にて測定し、標準ポリスチレン換算値により算出した。
(分子量測定条件)
・サンプル濃度:約2.0g/L(テトラヒドロフラン溶液)
・サンプル注入量:20μL
・カラム:商品名「TSKgel,SuperAWM-H+superAW4000+superAW2500」(東ソー株式会社製)
・カラムサイズ:各6.0mmI.D.×150mm
・溶離液:テトラヒドロフラン(THF)
・流量:0.4mL/min
・検出器:示差屈折計(RI)
・カラム温度(測定温度):40℃ <Measurement of weight average molecular weight>
The weight average molecular weight was measured by a gel permeation chromatograph (GPC) method. Specifically, using a trade name “HLC-8120GPC” (manufactured by Tosoh Corporation) as a GPC measuring apparatus, the measurement was performed under the following conditions, and the standard polystyrene equivalent was calculated.
(Molecular weight measurement conditions)
Sample concentration: about 2.0 g / L (tetrahydrofuran solution)
Sample injection volume: 20 μL
Column: Product name “TSKgel, SuperAWM-H + superAW4000 + superAW2500” (manufactured by Tosoh Corporation)
Column size: 6.0 mmI. D. × 150mm
・ Eluent: Tetrahydrofuran (THF)
・ Flow rate: 0.4mL / min
・ Detector: Differential refractometer (RI)
Column temperature (measurement temperature): 40 ° C
25℃および160℃における貯蔵弾性率G’は、実施例および比較例でPETフィルム基材の代わりにセパレーターフィルムに粘着剤組成物を塗布し、各実施例および比較例の所定の方法で作成した粘着剤層からセパレータを剥離して、粘着剤層のみを積層して、厚さ約1.5mmの粘着剤層の積層体を作製し、測定サンプルとした。
上記測定サンプルを、Rheometric Scientific社製「Advanced Rheometric Expansion System(ARES)」を用いて、剪断モードで、周波数1Hzの条件で、-70~200℃の範囲で昇温速度5℃/分で測定した。 <Measurement of storage modulus>
The storage elastic modulus G ′ at 25 ° C. and 160 ° C. was prepared by applying the pressure-sensitive adhesive composition to the separator film instead of the PET film substrate in Examples and Comparative Examples, and by the predetermined method of each Example and Comparative Example. The separator was peeled from the pressure-sensitive adhesive layer, and only the pressure-sensitive adhesive layer was laminated to produce a laminate of a pressure-sensitive adhesive layer having a thickness of about 1.5 mm, which was used as a measurement sample.
The measurement sample was measured at a heating rate of 5 ° C./min in the range of −70 to 200 ° C. in a shear mode with a frequency of 1 Hz using “Advanced Rheometric Expansion System (ARES)” manufactured by Rheometric Scientific. .
厚み12.5μのポリイミドフィルム(カプトン50EN、東レ・デュポン株式会社製)を、両面接着テープ(日東電工社製、商品名「No.531」)を介して、SUS304板を、2kgハンドローラーを用いて貼着し、測定用ポリイミドフィルム基板を得た。
次いで、粘着テープより、長さ100mm、幅25mmのテープ片を得た。23℃、50%RH雰囲気下で、テープ片の剥離ライナーを剥離して、測定用ポリイミドフィルム基板に2kgローラーを1往復させることにより圧着して、貼り合わせた。
23℃、50%RHの雰囲気中で30分間放置した後、引張試験機(商品名「TCM-1kNB」、ミネベア社製)を用いて剥離試験を行い、ポリイミドフィルムに対する接着力を測定した。その際の平均荷重をポリイミドフィルムに対する接着力とした。測定は、23℃、50%RHの雰囲気下、剥離角度180°、引張速度300mm/分の条件で行った。 <Measurement of adhesion to polyimide film surface>
Using a 2 kg hand roller, a SUS304 plate with a 12.5 μm thick polyimide film (Kapton 50EN, manufactured by Toray DuPont Co., Ltd.) via a double-sided adhesive tape (manufactured by Nitto Denko Corporation, trade name “No. 531”) And a polyimide film substrate for measurement was obtained.
Next, a tape piece having a length of 100 mm and a width of 25 mm was obtained from the adhesive tape. In an atmosphere of 23 ° C. and 50% RH, the release liner of the tape piece was peeled off, and a 2 kg roller was reciprocated once on the polyimide film substrate for measurement, and bonded together.
After being left in an atmosphere of 23 ° C. and 50% RH for 30 minutes, a peel test was performed using a tensile tester (trade name “TCM-1kNB”, manufactured by Minebea Co., Ltd.), and the adhesive force to the polyimide film was measured. The average load at that time was defined as the adhesive force to the polyimide film. The measurement was performed in an atmosphere of 23 ° C. and 50% RH under conditions of a peeling angle of 180 ° and a tensile speed of 300 mm / min.
厚み12.5μのポリイミドフィルム(カプトン50EN、東レ・デュポン株式会社製)の下面に粘着テープを貼り合せ、ポリイミドフィルムの上面に、幅2mm×長さ20mm×厚み1mmの鉄板を乗せ、ホットプレス機(新東工業株式会社、CYPT-10)で30MPaの圧力がポリイミドフィルムにかかるようにポリイミドフィルムの上に乗せた鉄板に160℃で5秒間圧力を加えた。
鉄板により圧力のかかった部分の粘着テープを貼り合せたポリイミドフィルムの断面を切り、粘着テープの粘着剤が加えられた熱と圧力により変形しているかを観察した。粘着剤の変形がほとんどない場合を○、変形はあるがわずかな場合を△、変形が大きい場合を×とした。 <Evaluation of Deformation of Adhesive at 30 MPa Press at 160 ° C.>
Adhesive tape is attached to the lower surface of a polyimide film (Kapton 50EN, manufactured by Toray DuPont Co., Ltd.) having a thickness of 12.5μ, and an iron plate having a width of 2 mm, a length of 20 mm, and a thickness of 1 mm is placed on the upper surface of the polyimide film. A pressure was applied at 160 ° C. for 5 seconds to an iron plate placed on the polyimide film so that a pressure of 30 MPa was applied to the polyimide film (Shinto Kogyo Co., Ltd., CYPT-10).
The cross section of the polyimide film on which the pressure-sensitive adhesive tape was applied with an iron plate was cut, and it was observed whether the pressure-sensitive adhesive tape was deformed by heat and pressure applied thereto. The case where there was almost no deformation of the pressure-sensitive adhesive was indicated as ◯, the case where there was a deformation but slight, Δ, and the case where the deformation was large as x.
モノマー成分としてのアクリル酸2-エチルヘキシル(2EHA):63重量部、N-ビニル-2-ピロリドン(NVP):15重量部、メタクリル酸メチル(MMA):9重量部、アクリル酸2-ヒドロキシエチル(HEA):13重量部、重合開始剤としての2,2’-アゾビスイソブチロニトリル:0.2重量部、および、重合溶媒としての酢酸エチル:133重量部を、セパラブルフラスコに投入し、窒素ガスを導入しながら1時間撹拌した。このようにして重合系内の酸素を除去した後、65℃に昇温し、10時間反応させ、その後、酢酸エチルを加えて固形分濃度30重量%のアクリル系ポリマー(1)の溶液を得た。アクリル系ポリマー(1)の重量平均分子量は80万であった。
次に、アクリル系ポリマー(1)の溶液に、イソシアネート系架橋剤(商品名「タケネートD110N」、三井化学株式会社製)をアクリル系ポリマー(1)(固形分)100重量部に対して固形分換算で5重量部となるように添加し、シランカップリング剤(γ-グリシドキシプロピルトリメトキシシラン、商品名「KBM403」、信越化学工業株式会社製)をアクリル系ポリマー(固形分)100重量部に対して固形分換算で0.5重量部となるように添加し、これを混合することによって粘着剤組成物(1)を調製した。
PET基材(「ルミラーS10」(厚み75μm、東レ社製))の一方の面に粘着剤組成物(1)を塗布し、PET基材上に塗布層を形成した。次に、PET基材上に塗布層を形成したものをオーブンに投入し、塗布層を130℃で3分間乾燥させ、PET基材の一方の面に、厚み25μmの粘着剤層を有する粘着テープ(1)を得た。
結果を表2に示した。 [Example 1]
2-ethylhexyl acrylate (2EHA) as a monomer component: 63 parts by weight, N-vinyl-2-pyrrolidone (NVP): 15 parts by weight, methyl methacrylate (MMA): 9 parts by weight, 2-hydroxyethyl acrylate ( (HEA): 13 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 0.2 part by weight, and ethyl acetate as a polymerization solvent: 133 parts by weight were put into a separable flask. The mixture was stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 65 ° C. and reacted for 10 hours, and then ethyl acetate was added to obtain a solution of acrylic polymer (1) having a solid content concentration of 30% by weight. It was. The weight average molecular weight of the acrylic polymer (1) was 800,000.
Next, an isocyanate-based crosslinking agent (trade name “Takenate D110N”, manufactured by Mitsui Chemicals, Inc.) is added to the acrylic polymer (1) solution with respect to 100 parts by weight of the acrylic polymer (1) (solid content). A silane coupling agent (γ-glycidoxypropyltrimethoxysilane, trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.) is added in an amount of 100 parts by weight of an acrylic polymer (solid content). It added so that it might become 0.5 weight part in conversion of solid content with respect to a part, and the adhesive composition (1) was prepared by mixing this.
The pressure-sensitive adhesive composition (1) was applied to one surface of a PET substrate (“Lumirror S10” (thickness 75 μm, manufactured by Toray Industries, Inc.)), and an application layer was formed on the PET substrate. Next, what formed the coating layer on the PET base material is put into an oven, the coating layer is dried at 130 ° C. for 3 minutes, and a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer having a thickness of 25 μm on one surface of the PET base material (1) was obtained.
The results are shown in Table 2.
モノマー成分としてのアクリル酸2-エチルヘキシル(2EHA):63重量部、N-ビニル-2-ピロリドン(NVP):15重量部、メタクリル酸メチル(MMA):9重量部、アクリル酸2-ヒドロキシエチル(HEA):13重量部、重合開始剤としての2,2’-アゾビスイソブチロニトリル:0.2重量部、および、重合溶媒としての酢酸エチル:133重量部を、セパラブルフラスコに投入し、窒素ガスを導入しながら1時間撹拌した。このようにして重合系内の酸素を除去した後、65℃に昇温し、10時間反応させ、その後、酢酸エチルを加えて固形分濃度30重量%のアクリル系ポリマー(2)の溶液を得た。アクリル系ポリマー(2)の重量平均分子量は80万であった。
次に、アクリル系ポリマー(2)の溶液に、イソシアネート系架橋剤(商品名「タケネートD110N」、三井化学株式会社製)をアクリル系ポリマー(2)(固形分)100重量部に対して固形分換算で10重量部となるように添加し、シランカップリング剤(γ-グリシドキシプロピルトリメトキシシラン、商品名「KBM403」、信越化学工業株式会社製)をアクリル系ポリマー(固形分)100重量部に対して固形分換算で0.5重量部となるように添加し、これを混合することによって粘着剤組成物(2)を調製した。
PET基材(厚み75μm)の一方の面に粘着剤組成物(2)を塗布し、PET基材上に塗布層を形成した。次に、PET基材上に塗布層を形成したものをオーブンに投入し、塗布層を130℃で3分間乾燥させ、PET基材の一方の面に厚み25μmの粘着剤層を有する粘着テープ(2)を得た。
結果を表2に示した。 [Example 2]
2-ethylhexyl acrylate (2EHA) as a monomer component: 63 parts by weight, N-vinyl-2-pyrrolidone (NVP): 15 parts by weight, methyl methacrylate (MMA): 9 parts by weight, 2-hydroxyethyl acrylate ( (HEA): 13 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 0.2 part by weight, and ethyl acetate as a polymerization solvent: 133 parts by weight were put into a separable flask. The mixture was stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 65 ° C. and reacted for 10 hours, and then ethyl acetate was added to obtain a solution of acrylic polymer (2) having a solid content concentration of 30% by weight. It was. The weight average molecular weight of the acrylic polymer (2) was 800,000.
Next, an isocyanate-based crosslinking agent (trade name “Takenate D110N”, manufactured by Mitsui Chemicals, Inc.) is added to the acrylic polymer (2) solution with respect to 100 parts by weight of the acrylic polymer (2) (solid content). A silane coupling agent (γ-glycidoxypropyltrimethoxysilane, trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 100 parts by weight of an acrylic polymer (solid content). It added so that it might become 0.5 weight part in conversion of solid content with respect to a part, and the adhesive composition (2) was prepared by mixing this.
The pressure-sensitive adhesive composition (2) was applied to one surface of a PET substrate (thickness 75 μm), and an application layer was formed on the PET substrate. Next, what formed the coating layer on the PET base material was put into an oven, the coating layer was dried at 130 ° C. for 3 minutes, and a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer having a thickness of 25 μm on one surface of the PET base material ( 2) was obtained.
The results are shown in Table 2.
モノマー成分としてのアクリル酸n-ブチル(BA):95重量部、アクリル酸(AA):5重量部、および、重合溶媒としての酢酸エチル:185.7重量部をセパラブルフラスコに投入し、窒素ガスを導入しながら1時間撹拌した。このようにして重合系内の酸素を除去した後、63℃に昇温して10時間反応させ、トルエンを加えて固形分濃度25重量%のアクリル系ポリマー(3)の溶液を得た。アクリル系ポリマー(3)の重量平均分子量は60万であった。
次に、アクリル系ポリマー(2)の溶液に、紫光UV-3700B (日本合成化学(株)製)、)をアクリル系ポリマー(3)(固形分)100重量部に対して固形分換算で100重量部となるように添加し、イルガキュア651を3重量部となるように添加し、これを混合することによって粘着剤組成物(3)を調製した。
PET基材(厚み75μm)の一方の面に粘着剤組成物(3)を乾燥後の厚みが25μmになるように塗布した。PET基材上に塗布層を形成したものをオーブンに投入し、塗布層を130℃で3分間乾燥させ、この上に、剥離処理したPETセパレーターを重ねて被覆した後、この被覆したPETセパレーター面にブラックライトを用いて紫外線(照度5mW/cm2、光量1200mJ/cm2)を照射して硬化させ、片面に剥離処理したPETセパレーターを有する粘着テープ(3)を得た。
結果を表2に示した。 Example 3
N-butyl acrylate (BA) as a monomer component: 95 parts by weight, acrylic acid (AA): 5 parts by weight, and ethyl acetate as a polymerization solvent: 185.7 parts by weight are charged into a separable flask, and nitrogen is added. The mixture was stirred for 1 hour while introducing gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 63 ° C. and reacted for 10 hours, and toluene was added to obtain a solution of an acrylic polymer (3) having a solid content concentration of 25% by weight. The weight average molecular weight of the acrylic polymer (3) was 600,000.
Next, in a solution of the acrylic polymer (2), purple light UV-3700B (manufactured by Nippon Synthetic Chemical Co., Ltd.)) is added to 100 parts by weight of the acrylic polymer (3) (solid content) in terms of solid content. It added so that it might become a weight part, Irgacure 651 was added so that it might become 3 weight part, and the adhesive composition (3) was prepared by mixing this.
The pressure-sensitive adhesive composition (3) was applied to one surface of a PET substrate (thickness 75 μm) so that the thickness after drying was 25 μm. A coating layer formed on a PET substrate is placed in an oven, the coating layer is dried at 130 ° C. for 3 minutes, and a release-treated PET separator is overlaid thereon, and then the coated PET separator surface Were cured by irradiating with UV light (illuminance 5 mW / cm 2 , light amount 1200 mJ / cm 2 ) using a black light to obtain a pressure-sensitive adhesive tape (3) having a PET separator peel-treated on one side.
The results are shown in Table 2.
冷却管、温度計、および攪拌装置を備えた反応容器に、N,N-ジメチルアクリルアミド(DMAA)を36.18重量部、アクリル酸(AA)を18.08重量部、ブチルアクリレート(BA)を126.56重量部、イソボルニルアクリレート(IBXA)を180.81重量部、ポリオール化合物として、数平均分子量1000のポリ(ヘキサメチレンカーボネート)グリコール(日本ポリウレタン株式会社製、商品名「ニッポラン981」(融点(MSDSに記載):42℃))を278.00重量部投入し、攪拌しながら、ポリイソシアナート化合物として、水添キシリレンジイソシアネート(HXDI、三井化学ポリウレタン株式会社製)を67.48重量部滴下し、65℃で5時間反応させ、ウレタンポリマー-アクリル系モノマー混合物を得た。その後、ヒドロキシエチルアクリレート(HEA)16.14重量部を投入し、65℃で1時間反応することで、アクリロイル基末端ウレタンポリマー-アクリル系モノマー混合物を得た。さらに、光重合開始剤として、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン(BASF製、商品名「イルガキュア651」)を0.15重量部加え、粘着剤組成物(4)を調製した。なお、ポリイソシアナート化合物とポリオール化合物の使用量は、NCO/OH(当量比)=1.25であった。
得られた粘着剤組成物(4)を、厚さ75μmのPETフィルム上に、硬化後の厚みが25μmになるように塗布した。この上に、剥離処理したPETセパレーターを重ねて被覆した後、この被覆したPETセパレーター面にブラックライトを用いて紫外線(照度5mW/cm2、光量1200mJ/cm2)を照射して硬化させ、片面に剥離処理したPETセパレーターを有する粘着テープ(4)を得た。
結果を表2に示した。 Example 4
In a reaction vessel equipped with a condenser, a thermometer and a stirrer, N, N-dimethylacrylamide (DMAA) 36.18 parts by weight, acrylic acid (AA) 18.08 parts by weight, and butyl acrylate (BA). 126.56 parts by weight, isobornyl acrylate (IBXA) 180.81 parts by weight, and a polyol compound, poly (hexamethylene carbonate) glycol having a number average molecular weight of 1000 (manufactured by Nippon Polyurethane Co., Ltd., trade name “Nipporan 981” ( 278.00 parts by weight (melting point (described in MSDS): 42 ° C.)), and while stirring, 67.48 weights of hydrogenated xylylene diisocyanate (HXDI, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) as a polyisocyanate compound. A portion of the solution was dropped and reacted at 65 ° C for 5 hours. It was obtained mer mixture. Thereafter, 16.14 parts by weight of hydroxyethyl acrylate (HEA) was added and reacted at 65 ° C. for 1 hour to obtain an acryloyl group-terminated urethane polymer-acrylic monomer mixture. Further, 0.15 parts by weight of 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF, trade name “Irgacure 651”) was added as a photopolymerization initiator, and an adhesive composition (4) Was prepared. In addition, the usage-amount of the polyisocyanate compound and the polyol compound was NCO / OH (equivalent ratio) = 1.25.
The obtained pressure-sensitive adhesive composition (4) was applied on a 75 μm thick PET film so that the thickness after curing was 25 μm. On this, the peeled PET separator was stacked and coated, and then the coated PET separator surface was cured by irradiating with ultraviolet light (illuminance 5 mW / cm 2 , light amount 1200 mJ / cm 2 ) using a black light. A pressure-sensitive adhesive tape (4) having a PET separator subjected to a release treatment was obtained.
The results are shown in Table 2.
モノマー成分としてのアクリル酸2-エチルヘキシル(2EHA):63重量部、N-ビニル-2-ピロリドン(NVP):15重量部、メタクリル酸メチル(MMA):9重量部、アクリル酸2-ヒドロキシエチル(HEA):13重量部、重合開始剤としての2,2’-アゾビスイソブチロニトリル:0.2重量部、および、重合溶媒としての酢酸エチル:133重量部を、セパラブルフラスコに投入し、窒素ガスを導入しながら1時間撹拌した。このようにして重合系内の酸素を除去した後、65℃に昇温し、10時間反応させ、その後、酢酸エチルを加えて固形分濃度30重量%のアクリル系ポリマーの溶液を得た。
得られたアクリル系ポリマーの溶液を室温まで冷却した。その後、該樹脂溶液に、アクリル系ポリマー100重量部に対して、重合性炭素-炭素二重結合を有する化合物として、2-イソシアナトエチルメタクリレート(昭和電工社製、商品名「カレンズMOI」):5.17重量部を加えた。さらに、ジラウリン酸ジブチルスズIV(和光純薬工業社製):0.0272重量部を添加し、空気雰囲気下、40℃で20時間攪拌し、アクリル系ポリマー(C1)の溶液を得た。
次に、アクリル系ポリマー(1)の溶液に、イソシアネート系架橋剤(商品名「タケネートD110N」、三井化学株式会社製)をアクリル系ポリマー(C1)(固形分)100重量部に対して固形分換算で1重量部となるように添加し、さらに、光重合開始剤として、2-ベンジル-2-(ジメチルアミノ)-4-モルフォリノブチルフェノン(BASF製、商品名「イルガキュア369」)をアクリル系ポリマー(C1)(固形分)100重量部に対して固形分換算で3重量部加え、粘着剤組成物(C1)を調製した。
得られた粘着剤組成物(C1)を、厚さ75μmのPETフィルム上に、乾燥後の厚みが25μmになるように塗布した。PET基材上に塗布層を形成したものをオーブンに投入し、塗布層を130℃で3分間乾燥させ、この上に、剥離処理したPETセパレーターを重ねて被覆した後、この被覆したPETセパレーター面にブラックライトを用いて紫外線(照度5mW/cm2、光量1200mJ/cm2)を照射して硬化させ、片面に剥離処理したPETセパレーターを有する粘着テープ(C1)を得た。
結果を表2に示した。 [Comparative Example 1]
2-ethylhexyl acrylate (2EHA) as a monomer component: 63 parts by weight, N-vinyl-2-pyrrolidone (NVP): 15 parts by weight, methyl methacrylate (MMA): 9 parts by weight, 2-hydroxyethyl acrylate ( (HEA): 13 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 0.2 part by weight, and ethyl acetate as a polymerization solvent: 133 parts by weight were put into a separable flask. The mixture was stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 65 ° C. and reacted for 10 hours, and then ethyl acetate was added to obtain an acrylic polymer solution having a solid content concentration of 30% by weight.
The resulting acrylic polymer solution was cooled to room temperature. Thereafter, in the resin solution, 2-isocyanatoethyl methacrylate (trade name “Karenz MOI” manufactured by Showa Denko KK) as a compound having a polymerizable carbon-carbon double bond with respect to 100 parts by weight of the acrylic polymer: 5.17 parts by weight were added. Further, dibutyltin dilaurate IV (manufactured by Wako Pure Chemical Industries, Ltd.): 0.0272 parts by weight was added and stirred at 40 ° C. for 20 hours in an air atmosphere to obtain a solution of an acrylic polymer (C1).
Next, an isocyanate crosslinking agent (trade name “Takenate D110N”, manufactured by Mitsui Chemicals, Inc.) is added to the acrylic polymer (1) solution with respect to 100 parts by weight of the acrylic polymer (C1) (solid content). Furthermore, 2-benzyl-2- (dimethylamino) -4-morpholinobutylphenone (trade name “Irgacure 369”, manufactured by BASF) is acrylic as a photopolymerization initiator. 3 parts by weight in terms of solid content was added to 100 parts by weight of the polymer (C1) (solid content) to prepare an adhesive composition (C1).
The obtained pressure-sensitive adhesive composition (C1) was applied on a 75 μm thick PET film so that the thickness after drying was 25 μm. A coating layer formed on a PET substrate is placed in an oven, and the coating layer is dried at 130 ° C. for 3 minutes. Were cured by irradiating with UV light (illuminance 5 mW / cm 2 , light amount 1200 mJ / cm 2 ) using a black light to obtain a pressure-sensitive adhesive tape (C1) having a PET separator peeled on one side.
The results are shown in Table 2.
モノマー成分としてのアクリル酸n-ブチル(BA):95重量部、アクリル酸(AA):5重量部、および、重合溶媒としての酢酸エチル:185.7重量部をセパラブルフラスコに投入し、窒素ガスを導入しながら1時間撹拌した。このようにして重合系内の酸素を除去した後、63℃に昇温して10時間反応させ、トルエンを加えて固形分濃度25重量%のアクリル系ポリマー溶液を得た。
なお、上記アクリル系ポリマー溶液中のアクリル系ポリマーの重量平均分子量は60万であった。
次に、モノマー成分としてのメタクリル酸シクロヘキシル[ホモポリマー(ポリメタクリル酸シクロヘキシル)のガラス転移温度:66℃]:95重量部、アクリル酸:5重量部、連鎖移動剤としてのα-メチルスチレンダイマー:10重量部、重合開始剤としての2,2’-アゾビスイソブチロニトリル:10重量部、および、重合溶媒としてのトルエン:120重量部を、セパラブルフラスコに投入し、窒素ガスを導入しながら、1時間攪拌した。このようにして、重合系内の酸素を除去した後、85℃に昇温し、5時間反応させて、固形分濃度50重量%のアクリル系オリゴマー溶液を得た。
なお、上記アクリル系オリゴマー溶液中のアクリル系オリゴマーの重量平均分子量は4000であった。
次に、上記アクリル系ポリマー溶液に、シランカップリング剤(γ-グリシドキシプロピルトリメトキシシラン、商品名「KBM403」、信越化学工業株式会社製)をアクリル系ポリマー(固形分)100重量部に対して固形分換算で0.15重量部となるように添加し、架橋剤(エポキシ系架橋剤、商品名「TETRAD-C」、三菱ガス化学株式会社製)をアクリル系ポリマー(固形分)100重量部に対して固形分換算で0.075重量部となるように添加して、さらに、上記アクリル系オリゴマー溶液をアクリル系ポリマー(固形分)100重量部に対して固形分換算でアクリル系オリゴマーの量が25重量部となるように添加し、これを混合することによって粘着剤組成物(C2)を調製した。
PET基材(厚み75μm)の一方の面に粘着剤組成物(C2)を塗布し、PET基材上に塗布層を形成した。次に、PET基材上に塗布層を形成したものをオーブンに投入し、塗布層を130℃で3分間乾燥させ、PET基材の一方の面に、厚み25μmの粘着剤層を有する粘着テープ(C2)を得た。
結果を表2に示した。 [Comparative Example 2]
N-butyl acrylate (BA) as a monomer component: 95 parts by weight, acrylic acid (AA): 5 parts by weight, and ethyl acetate as a polymerization solvent: 185.7 parts by weight are charged into a separable flask, and nitrogen is added. The mixture was stirred for 1 hour while introducing gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 63 ° C. and reacted for 10 hours, and toluene was added to obtain an acrylic polymer solution having a solid content concentration of 25% by weight.
The acrylic polymer in the acrylic polymer solution had a weight average molecular weight of 600,000.
Next, cyclohexyl methacrylate as a monomer component [glass transition temperature of homopolymer (polycyclohexyl methacrylate): 66 ° C.]: 95 parts by weight, acrylic acid: 5 parts by weight, α-methylstyrene dimer as a chain transfer agent: 10 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 10 parts by weight, and toluene as a polymerization solvent: 120 parts by weight are charged into a separable flask, and nitrogen gas is introduced. The mixture was stirred for 1 hour. After removing oxygen in the polymerization system in this way, the temperature was raised to 85 ° C. and reacted for 5 hours to obtain an acrylic oligomer solution having a solid content concentration of 50% by weight.
The weight average molecular weight of the acrylic oligomer in the acrylic oligomer solution was 4000.
Next, a silane coupling agent (γ-glycidoxypropyltrimethoxysilane, trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 100 parts by weight of the acrylic polymer (solid content) in the acrylic polymer solution. In contrast, 0.15 parts by weight in terms of solid content was added, and a crosslinking agent (epoxy crosslinking agent, trade name “TETRAD-C”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added to an acrylic polymer (solid content) 100. The acrylic oligomer solution is added so as to be 0.075 parts by weight in terms of solid content with respect to parts by weight, and the acrylic oligomer solution is further converted into an acrylic oligomer in terms of solid content with respect to 100 parts by weight of the acrylic polymer (solid content). The pressure-sensitive adhesive composition (C2) was prepared by adding the mixture so that the amount was 25 parts by weight, and mixing this.
The pressure-sensitive adhesive composition (C2) was applied to one surface of a PET substrate (thickness 75 μm), and an application layer was formed on the PET substrate. Next, what formed the coating layer on the PET base material is put into an oven, the coating layer is dried at 130 ° C. for 3 minutes, and a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer having a thickness of 25 μm on one surface of the PET base material (C2) was obtained.
The results are shown in Table 2.
モノマー成分としてのアクリル酸2-エチルヘキシル(2EHA):63重量部、N-ビニル-2-ピロリドン(NVP):15重量部、メタクリル酸メチル(MMA):9重量部、アクリル酸2-ヒドロキシエチル(HEA):13重量部、重合開始剤としての2,2'-アゾビスイソブチロニトリル:0.2重量部、および、重合溶媒としての酢酸エチル133重量部を、セパラブルフラスコに投入し、窒素ガスを導入しながら1時間撹拌した。このようにして重合系内の酸素を除去した後、65℃に昇温し、10時間反応させ、その後、酢酸エチルを加えて固形分濃度30重量%のアクリル系ポリマー溶液を得た。
なお、上記アクリル系ポリマー溶液中のアクリル系ポリマーの重量平均分子量は80万であった。
次に、上記アクリル系ポリマー溶液に、イソシアネート系架橋剤(商品名「タケネートD110N」、三井化学株式会社製)をアクリル系ポリマー(固形分)100重量部に対して固形分換算で1.1重量部となるように添加し、シランカップリング剤(γ-グリシドキシプロピルトリメトキシシラン、商品名「KBM403」、信越化学工業株式会社製)をアクリル系ポリマー(固形分)100重量部に対して固形分換算で0.15重量部となるように添加し、これを混合することによって粘着剤組成物(C3)を調製した。
PET基材(厚み75μm)の一方の面に粘着剤組成物(C3)を塗布し、PET基材上に塗布層を形成した。次に、PET基材上に塗布層を形成したものをオーブンに投入し、塗布層を130℃で3分間乾燥させ、PET基材の一方の面に、厚み25μmの粘着剤層を有する粘着テープ(C3)を得た。
結果を表2に示した。 [Comparative Example 3]
2-ethylhexyl acrylate (2EHA) as a monomer component: 63 parts by weight, N-vinyl-2-pyrrolidone (NVP): 15 parts by weight, methyl methacrylate (MMA): 9 parts by weight, 2-hydroxyethyl acrylate ( HEA): 13 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 0.2 part by weight, and 133 parts by weight of ethyl acetate as a polymerization solvent were put into a separable flask, The mixture was stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 65 ° C. and reacted for 10 hours, and then ethyl acetate was added to obtain an acrylic polymer solution having a solid content concentration of 30% by weight.
In addition, the weight average molecular weight of the acrylic polymer in the acrylic polymer solution was 800,000.
Next, to the acrylic polymer solution, an isocyanate crosslinking agent (trade name “Takenate D110N”, manufactured by Mitsui Chemicals, Inc.) is 1.1 weight in terms of solid content with respect to 100 parts by weight of the acrylic polymer (solid content). The silane coupling agent (γ-glycidoxypropyltrimethoxysilane, trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 100 parts by weight of the acrylic polymer (solid content). It added so that it might become 0.15 weight part in conversion of solid content, and this was mixed, and the adhesive composition (C3) was prepared.
The pressure-sensitive adhesive composition (C3) was applied to one surface of a PET substrate (thickness 75 μm), and an application layer was formed on the PET substrate. Next, what formed the coating layer on the PET base material is put into an oven, the coating layer is dried at 130 ° C. for 3 minutes, and a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer having a thickness of 25 μm on one surface of the PET base material (C3) was obtained.
The results are shown in Table 2.
モノマー成分としてのアクリル酸2-エチルヘキシル(2EHA):63重量部、N-ビニル-2-ピロリドン(NVP):15重量部、メタクリル酸メチル(MMA):9重量部、アクリル酸2-ヒドロキシエチル(HEA):13重量部、重合開始剤としての2,2’-アゾビスイソブチロニトリル:0.2重量部、および、重合溶媒としての酢酸エチル:133重量部を、セパラブルフラスコに投入し、窒素ガスを導入しながら1時間撹拌した。このようにして重合系内の酸素を除去した後、65℃に昇温し、10時間反応させ、その後、酢酸エチルを加えて固形分濃度30重量%のアクリル系ポリマー(5)の溶液を得た。アクリル系ポリマー(5)の重量平均分子量は80万であった。
次に、アクリル系ポリマー(5)の溶液に、イソシアネート系架橋剤(商品名「タケネートD110N」、三井化学株式会社製)をアクリル系ポリマー(5)(固形分)100重量部に対して固形分換算で5重量部となるように添加し、シランカップリング剤(γ-グリシドキシプロピルトリメトキシシラン、商品名「KBM403」、信越化学工業株式会社製)をアクリル系ポリマー(固形分)100重量部に対して固形分換算で0.5重量部となるように添加し、これを混合することによって粘着剤組成物(5)を調製した。
PET基材(「ルミラーS10」(厚み75μm、東レ社製))の一方の面に粘着剤組成物(5)を塗布し、PET基材上に塗布層を形成した。次に、PET基材上に塗布層を形成したものをオーブンに投入し、塗布層を130℃で3分間乾燥させ、PET基材の一方の面に、厚み10μmの粘着剤層を有する粘着テープ(5)を得た。
結果を表3に示した。 Example 5
2-ethylhexyl acrylate (2EHA) as a monomer component: 63 parts by weight, N-vinyl-2-pyrrolidone (NVP): 15 parts by weight, methyl methacrylate (MMA): 9 parts by weight, 2-hydroxyethyl acrylate ( (HEA): 13 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 0.2 part by weight, and ethyl acetate as a polymerization solvent: 133 parts by weight were put into a separable flask. The mixture was stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 65 ° C. and reacted for 10 hours, and then ethyl acetate was added to obtain a solution of an acrylic polymer (5) having a solid content concentration of 30% by weight. It was. The weight average molecular weight of the acrylic polymer (5) was 800,000.
Next, an isocyanate-based crosslinking agent (trade name “Takenate D110N”, manufactured by Mitsui Chemicals, Inc.) is added to the acrylic polymer (5) solution with respect to 100 parts by weight of the acrylic polymer (5) (solid content). A silane coupling agent (γ-glycidoxypropyltrimethoxysilane, trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.) is added in an amount of 100 parts by weight of an acrylic polymer (solid content). It added so that it might become 0.5 weight part in conversion of solid content with respect to a part, and the adhesive composition (5) was prepared by mixing this.
The pressure-sensitive adhesive composition (5) was applied to one surface of a PET substrate (“Lumirror S10” (thickness 75 μm, manufactured by Toray Industries, Inc.)), and an application layer was formed on the PET substrate. Next, what formed the coating layer on the PET substrate is put into an oven, the coating layer is dried at 130 ° C. for 3 minutes, and a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer having a thickness of 10 μm on one surface of the PET substrate. (5) was obtained.
The results are shown in Table 3.
厚み15μmの粘着フィルム(粘着剤層)を有する粘着テープ(6)を得るように粘着剤組成物(5)を塗布した以外は、実施例5と同様に行った。
結果を表3に示した。 Example 6
The same procedure as in Example 5 was performed except that the pressure-sensitive adhesive composition (5) was applied so as to obtain a pressure-sensitive adhesive tape (6) having a pressure-sensitive adhesive film (pressure-sensitive adhesive layer) having a thickness of 15 μm.
The results are shown in Table 3.
モノマー成分としてのアクリル酸n-ブチル(BA):95重量部、アクリル酸(AA):5重量部、および、重合溶媒としての酢酸エチル:185.7重量部をセパラブルフラスコに投入し、窒素ガスを導入しながら1時間撹拌した。このようにして重合系内の酸素を除去した後、63℃に昇温して10時間反応させ、トルエンを加えて固形分濃度25重量%のアクリル系ポリマー溶液を得た。
なお、上記アクリル系ポリマー溶液中のアクリル系ポリマーの重量平均分子量は60万であった。
次に、モノマー成分としてのメタクリル酸シクロヘキシル[ホモポリマー(ポリメタクリル酸シクロヘキシル)のガラス転移温度:66℃]:95重量部、アクリル酸:5重量部、連鎖移動剤としてのα-メチルスチレンダイマー:10重量部、重合開始剤としての2,2’-アゾビスイソブチロニトリル:10重量部、および、重合溶媒としてのトルエン:120重量部を、セパラブルフラスコに投入し、窒素ガスを導入しながら、1時間攪拌した。このようにして、重合系内の酸素を除去した後、85℃に昇温し、5時間反応させて、固形分濃度50重量%のアクリル系オリゴマー溶液を得た。
なお、上記アクリル系オリゴマー溶液中のアクリル系オリゴマーの重量平均分子量は4000であった。
次に、上記アクリル系ポリマー溶液に、シランカップリング剤(γ-グリシドキシプロピルトリメトキシシラン、商品名「KBM403」、信越化学工業株式会社製)をアクリル系ポリマー(固形分)100重量部に対して固形分換算で0.15重量部となるように添加し、架橋剤(エポキシ系架橋剤、商品名「TETRAD-C」、三菱ガス化学株式会社製)をアクリル系ポリマー(固形分)100重量部に対して固形分換算で0.075重量部となるように添加して、さらに、上記アクリル系オリゴマー溶液をアクリル系ポリマー(固形分)100重量部に対して固形分換算でアクリル系オリゴマーの量が25重量部となるように添加し、これを混合することによって粘着剤組成物(7)を調製した。
PET基材(厚み75μm)の一方の面に粘着剤組成物(7)を塗布し、PET基材上に塗布層を形成した。次に、PET基材上に塗布層を形成したものをオーブンに投入し、塗布層を130℃で3分間乾燥させ、PET基材の一方の面に、厚み10μmの粘着フィルム(粘着剤層)を有する粘着テープ(7)を得た。
結果を表3に示した。 Example 7
N-butyl acrylate (BA) as a monomer component: 95 parts by weight, acrylic acid (AA): 5 parts by weight, and ethyl acetate as a polymerization solvent: 185.7 parts by weight are charged into a separable flask, and nitrogen is added. The mixture was stirred for 1 hour while introducing gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 63 ° C. and reacted for 10 hours, and toluene was added to obtain an acrylic polymer solution having a solid content concentration of 25% by weight.
The acrylic polymer in the acrylic polymer solution had a weight average molecular weight of 600,000.
Next, cyclohexyl methacrylate as a monomer component [glass transition temperature of homopolymer (polycyclohexyl methacrylate): 66 ° C.]: 95 parts by weight, acrylic acid: 5 parts by weight, α-methylstyrene dimer as a chain transfer agent: 10 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 10 parts by weight, and toluene as a polymerization solvent: 120 parts by weight are charged into a separable flask, and nitrogen gas is introduced. The mixture was stirred for 1 hour. After removing oxygen in the polymerization system in this way, the temperature was raised to 85 ° C. and reacted for 5 hours to obtain an acrylic oligomer solution having a solid content concentration of 50% by weight.
The weight average molecular weight of the acrylic oligomer in the acrylic oligomer solution was 4000.
Next, a silane coupling agent (γ-glycidoxypropyltrimethoxysilane, trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 100 parts by weight of the acrylic polymer (solid content) in the acrylic polymer solution. In contrast, 0.15 parts by weight in terms of solid content was added, and a crosslinking agent (epoxy crosslinking agent, trade name “TETRAD-C”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added to an acrylic polymer (solid content) 100. The acrylic oligomer solution is added so as to be 0.075 parts by weight in terms of solid content with respect to parts by weight, and the acrylic oligomer solution is further converted into an acrylic oligomer in terms of solid content with respect to 100 parts by weight of the acrylic polymer (solid content). The pressure-sensitive adhesive composition (7) was prepared by adding the mixture so that the amount was 25 parts by weight, and mixing them.
The pressure-sensitive adhesive composition (7) was applied to one surface of a PET substrate (thickness 75 μm), and an application layer was formed on the PET substrate. Next, the coating layer formed on the PET substrate is put into an oven, the coating layer is dried at 130 ° C. for 3 minutes, and a 10 μm thick adhesive film (adhesive layer) is formed on one surface of the PET substrate. An adhesive tape (7) having the following was obtained.
The results are shown in Table 3.
モノマー成分としてのアクリル酸2-エチルヘキシル(2EHA):63重量部、N-ビニル-2-ピロリドン(NVP):15重量部、メタクリル酸メチル(MMA):9重量部、アクリル酸2-ヒドロキシエチル(HEA):13重量部、重合開始剤としての2,2'-アゾビスイソブチロニトリル:0.2重量部、および、重合溶媒としての酢酸エチル133重量部を、セパラブルフラスコに投入し、窒素ガスを導入しながら1時間撹拌した。このようにして重合系内の酸素を除去した後、65℃に昇温し、10時間反応させ、その後、酢酸エチルを加えて固形分濃度30重量%のアクリル系ポリマー溶液を得た。
なお、上記アクリル系ポリマー溶液中のアクリル系ポリマーの重量平均分子量は80万であった。
次に、上記アクリル系ポリマー溶液に、イソシアネート系架橋剤(商品名「タケネートD110N」、三井化学株式会社製)をアクリル系ポリマー(固形分)100重量部に対して固形分換算で1.1重量部となるように添加し、シランカップリング剤(γ-グリシドキシプロピルトリメトキシシラン、商品名「KBM403」、信越化学工業株式会社製)をアクリル系ポリマー(固形分)100重量部に対して固形分換算で0.15重量部となるように添加し、これを混合することによって粘着剤組成物(8)を調製した。
PET基材(厚み75μm)の一方の面に粘着剤組成物(8)を塗布し、PET基材上に塗布層を形成した。次に、PET基材上に塗布層を形成したものをオーブンに投入し、塗布層を130℃で3分間乾燥させ、PET基材の一方の面に、厚み10μmの粘着フィルム(粘着剤層)を有する粘着テープ(8)を得た。
結果を表3に示した。 Example 8
2-ethylhexyl acrylate (2EHA) as a monomer component: 63 parts by weight, N-vinyl-2-pyrrolidone (NVP): 15 parts by weight, methyl methacrylate (MMA): 9 parts by weight, 2-hydroxyethyl acrylate ( HEA): 13 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 0.2 part by weight, and 133 parts by weight of ethyl acetate as a polymerization solvent were put into a separable flask, The mixture was stirred for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 65 ° C. and reacted for 10 hours, and then ethyl acetate was added to obtain an acrylic polymer solution having a solid content concentration of 30% by weight.
In addition, the weight average molecular weight of the acrylic polymer in the acrylic polymer solution was 800,000.
Next, to the acrylic polymer solution, an isocyanate crosslinking agent (trade name “Takenate D110N”, manufactured by Mitsui Chemicals, Inc.) is 1.1 weight in terms of solid content with respect to 100 parts by weight of the acrylic polymer (solid content). The silane coupling agent (γ-glycidoxypropyltrimethoxysilane, trade name “KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 100 parts by weight of the acrylic polymer (solid content). It added so that it might become 0.15 weight part in conversion of solid content, and this was mixed, and the adhesive composition (8) was prepared.
The pressure-sensitive adhesive composition (8) was applied to one surface of a PET substrate (thickness 75 μm), and an application layer was formed on the PET substrate. Next, the coating layer formed on the PET substrate is put into an oven, the coating layer is dried at 130 ° C. for 3 minutes, and a 10 μm thick adhesive film (adhesive layer) is formed on one surface of the PET substrate. An adhesive tape (8) having the following was obtained.
The results are shown in Table 3.
厚み25μmの粘着フィルム(粘着剤層)を有する粘着テープ(C4)を得るように粘着剤組成物(5)を塗布した以外は、実施例5と同様に行った。
結果を表3に示した。 [Comparative Example 4]
The same procedure as in Example 5 was performed except that the pressure-sensitive adhesive composition (5) was applied so as to obtain a pressure-sensitive adhesive tape (C4) having a pressure-sensitive adhesive film (pressure-sensitive adhesive layer) having a thickness of 25 μm.
The results are shown in Table 3.
厚み25μmの粘着フィルム(粘着剤層)を有する粘着テープ(C5)を得るように粘着剤組成物(7)を塗布した以外は、実施例7と同様に行った。
結果を表3に示した。 [Comparative Example 5]
It carried out similarly to Example 7 except having apply | coated the adhesive composition (7) so that the adhesive tape (C5) which has a 25-micrometer-thick adhesive film (adhesive layer) may be obtained.
The results are shown in Table 3.
厚み25μmの粘着フィルム(粘着剤層)を有する粘着テープ(C6)を得るように粘着剤組成物(8)を塗布した以外は、実施例8と同様に行った。
結果を表3に示した。 [Comparative Example 6]
The same procedure as in Example 8 was performed except that the adhesive composition (8) was applied so as to obtain an adhesive tape (C6) having an adhesive film (adhesive layer) having a thickness of 25 μm.
The results are shown in Table 3.
The pressure-sensitive adhesive or pressure-sensitive adhesive tape of the present invention has a sufficient adhesive force and has little distortion at high temperatures. For this reason, it can utilize for the adhesive tape etc. which are bonded together to the board | substrate etc. of a semiconductor element.
Claims (20)
- ポリイミドフィルムの表面に対する接着力が1N以上であり、
160℃における貯蔵弾性率G’が1×105Pa以上である、
粘着剤。 The adhesive force to the surface of the polyimide film is 1N or more,
The storage elastic modulus G ′ at 160 ° C. is 1 × 10 5 Pa or more.
Adhesive. - 前記接着力が5N以上である、請求項1に記載の粘着剤。 The pressure-sensitive adhesive according to claim 1, wherein the adhesive force is 5 N or more.
- 前記160℃における貯蔵弾性率G’が5×105Pa以上である、請求項1または2に記載の粘着剤。 The pressure-sensitive adhesive according to claim 1, wherein the storage elastic modulus G ′ at 160 ° C. is 5 × 10 5 Pa or more.
- 架橋構造を有する、請求項1から3までのいずれかに記載の粘着剤。 The pressure-sensitive adhesive according to any one of claims 1 to 3, which has a crosslinked structure.
- アクリル系ポリマー(A)、およびイソシアネート系架橋剤および/またはエポキシ系架橋剤を含む粘着剤組成物から形成される、請求項1から4までのいずれかに記載の粘着剤。 The pressure-sensitive adhesive according to any one of claims 1 to 4, wherein the pressure-sensitive adhesive is formed from a pressure-sensitive adhesive composition containing an acrylic polymer (A) and an isocyanate-based crosslinking agent and / or an epoxy-based crosslinking agent.
- 前記粘着剤組成物中の前記イソシアネート系架橋剤とエポキシ系架橋剤の合計の含有量が、前記アクリル系ポリマー(A)100重量部に対して0.1重量部~30重量部である、請求項5に記載の粘着剤。 The total content of the isocyanate crosslinking agent and the epoxy crosslinking agent in the pressure-sensitive adhesive composition is 0.1 to 30 parts by weight with respect to 100 parts by weight of the acrylic polymer (A). Item 6. The pressure-sensitive adhesive according to item 5.
- 前記粘着剤組成物中の前記イソシアネート系架橋剤の含有量が、前記アクリル系ポリマー(A)100重量部に対して2重量部~20重量部である、請求項6に記載の粘着剤。 The pressure-sensitive adhesive according to claim 6, wherein the content of the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition is 2 to 20 parts by weight with respect to 100 parts by weight of the acrylic polymer (A).
- 前記粘着剤組成物中の前記エポキシ系架橋剤の含有量が、前記アクリル系ポリマー(A)100重量部に対して0.3重量部~10重量部である、請求項6に記載の粘着剤。 The pressure-sensitive adhesive according to claim 6, wherein the content of the epoxy-based crosslinking agent in the pressure-sensitive adhesive composition is 0.3 to 10 parts by weight with respect to 100 parts by weight of the acrylic polymer (A). .
- アクリル系ポリマー(B)および紫外線硬化型オリゴマーを含む粘着剤組成物から形成される、請求項1から4までのいずれかに記載の粘着剤。 The pressure-sensitive adhesive according to any one of claims 1 to 4, which is formed from a pressure-sensitive adhesive composition containing an acrylic polymer (B) and an ultraviolet curable oligomer.
- 前記紫外線硬化型オリゴマーが、紫外線硬化型ウレタン系オリゴマー、紫外線硬化型アクリル系オリゴマー、紫外線硬化型ウレタンアクリル系オリゴマーから選ばれる少なくとも1種である、請求項9に記載の粘着剤。 The pressure-sensitive adhesive according to claim 9, wherein the ultraviolet curable oligomer is at least one selected from an ultraviolet curable urethane oligomer, an ultraviolet curable acrylic oligomer, and an ultraviolet curable urethane acrylic oligomer.
- ウレタン系ポリマーおよびアクリル系モノマーを含む粘着剤組成物から形成される、請求項1から4までのいずれかに記載の粘着剤。 The pressure-sensitive adhesive according to any one of claims 1 to 4, which is formed from a pressure-sensitive adhesive composition containing a urethane-based polymer and an acrylic monomer.
- 前記ウレタン系ポリマーが(メタ)アクロイル基末端ウレタン系ポリマーを含む、請求項11に記載の粘着剤。 The pressure-sensitive adhesive according to claim 11, wherein the urethane-based polymer includes a (meth) acryloyl group-terminated urethane-based polymer.
- 請求項1から12までのいずれかに記載の粘着剤を有する、粘着テープ。 A pressure-sensitive adhesive tape comprising the pressure-sensitive adhesive according to any one of claims 1 to 12.
- 請求項1から12までのいずれかに記載の粘着剤を有する、フィルム基板。 A film substrate having the pressure-sensitive adhesive according to any one of claims 1 to 12.
- ポリイミドフィルムの表面に対する接着力が1N以上であり、
160℃における貯蔵弾性率G’が1×104Pa以上であり、
厚みが20μm以下である、
粘着フィルム。 The adhesive force to the surface of the polyimide film is 1N or more,
The storage elastic modulus G ′ at 160 ° C. is 1 × 10 4 Pa or more,
The thickness is 20 μm or less,
Adhesive film. - 前記接着力が5N以上である、請求項15に記載の粘着フィルム。 The pressure-sensitive adhesive film according to claim 15, wherein the adhesive force is 5 N or more.
- 前記厚みが15μm以下である、請求項15または16に記載の粘着フィルム。 The pressure-sensitive adhesive film according to claim 15 or 16, wherein the thickness is 15 µm or less.
- アクリル系ポリマーを含む粘着剤組成物から形成される、請求項15から17までのいずれかに記載の粘着フィルム。 The pressure-sensitive adhesive film according to any one of claims 15 to 17, which is formed from a pressure-sensitive adhesive composition containing an acrylic polymer.
- 請求項15から18までのいずれかに記載の粘着フィルムを有する、粘着テープ。 An adhesive tape comprising the adhesive film according to any one of claims 15 to 18.
- 請求項15から18までのいずれかに記載の粘着フィルムを有する、フィルム基板。
A film substrate comprising the pressure-sensitive adhesive film according to claim 15.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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KR1020187036868A KR102047204B1 (en) | 2016-07-19 | 2017-07-13 | Adhesive, Adhesive Film, Adhesive Tape, and Film Substrate |
CN201780044591.4A CN109476977B (en) | 2016-07-19 | 2017-07-13 | Pressure-sensitive adhesive, pressure-sensitive adhesive film, pressure-sensitive adhesive tape, and film substrate |
SG11201811266XA SG11201811266XA (en) | 2016-07-19 | 2017-07-13 | Pressure-sensitive adhesive, pressure-sensitive adhesive film, pressure-sensitive adhesive tapes, and film substrates |
JP2018512222A JP6375467B2 (en) | 2016-07-19 | 2017-07-13 | Adhesive, adhesive film, adhesive tape, and film substrate |
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JP2016-141196 | 2016-07-19 | ||
JP2016-141197 | 2016-07-19 | ||
JP2016141196 | 2016-07-19 | ||
JP2016141197 | 2016-07-19 |
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PCT/JP2017/025564 WO2018016416A1 (en) | 2016-07-19 | 2017-07-13 | Pressure-sensitive adhesive, pressure-sensitive adhesive film, pressure-sensitive adhesive tapes, and film substrates |
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JP (1) | JP6375467B2 (en) |
KR (1) | KR102047204B1 (en) |
CN (1) | CN109476977B (en) |
SG (1) | SG11201811266XA (en) |
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WO (1) | WO2018016416A1 (en) |
Cited By (1)
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EP3781622B1 (en) * | 2018-04-20 | 2022-10-12 | Basf Se | Adhesive compositions with a gelcontent from crosslinking of keto- or aldehyde groups |
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KR102099071B1 (en) * | 2019-05-09 | 2020-05-18 | 길화소재 주식회사 | Adhesive film for protecting semiconductor wafer and preparation method thereof |
JP2022051105A (en) * | 2020-09-18 | 2022-03-31 | スリーエム イノベイティブ プロパティズ カンパニー | Liquid adhesive, laminate, and method of producing semiconductor chip |
JP2024007852A (en) | 2022-07-06 | 2024-01-19 | 日東電工株式会社 | Optical member having surface protective film, optical laminate, and manufacturing method of optical device |
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JP2002338916A (en) * | 2001-05-22 | 2002-11-27 | Nitto Denko Corp | Adhesive sheet for fixing flexible printed circuit board and method for mounting electronic part on flexible printed circuit board |
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JP4515357B2 (en) * | 2005-01-27 | 2010-07-28 | リンテック株式会社 | Adhesive for polarizing plate, polarizing plate with adhesive and method for producing the same |
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JP2014047254A (en) * | 2012-08-30 | 2014-03-17 | Nitto Denko Corp | Double-sided adhesive sheet, laminate and removal method of plate |
JP6363930B2 (en) * | 2014-10-10 | 2018-07-25 | 日東電工株式会社 | Optical film with adhesive, method for producing the same, and method for producing an image display device |
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2017
- 2017-07-13 SG SG11201811266XA patent/SG11201811266XA/en unknown
- 2017-07-13 KR KR1020187036868A patent/KR102047204B1/en active IP Right Grant
- 2017-07-13 CN CN201780044591.4A patent/CN109476977B/en active Active
- 2017-07-13 WO PCT/JP2017/025564 patent/WO2018016416A1/en active Application Filing
- 2017-07-13 JP JP2018512222A patent/JP6375467B2/en active Active
- 2017-07-19 TW TW106124072A patent/TWI649397B/en active
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JP2002338916A (en) * | 2001-05-22 | 2002-11-27 | Nitto Denko Corp | Adhesive sheet for fixing flexible printed circuit board and method for mounting electronic part on flexible printed circuit board |
JP2008174595A (en) * | 2007-01-16 | 2008-07-31 | Somar Corp | Cooling-and-peeling type self-adhesive composition and cooling-and-peeling type self-adhesive sheet using the same |
JP2010155933A (en) * | 2008-12-26 | 2010-07-15 | Somar Corp | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
WO2016199819A1 (en) * | 2015-06-11 | 2016-12-15 | 三井化学東セロ株式会社 | Electronic-device-protecting film, electronic-device-protecting member, method for manufacturing electronic device, and method for manufacturing package |
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EP3781622B1 (en) * | 2018-04-20 | 2022-10-12 | Basf Se | Adhesive compositions with a gelcontent from crosslinking of keto- or aldehyde groups |
Also Published As
Publication number | Publication date |
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CN109476977A (en) | 2019-03-15 |
JP6375467B2 (en) | 2018-08-15 |
KR20190003791A (en) | 2019-01-09 |
CN109476977B (en) | 2021-04-06 |
JPWO2018016416A1 (en) | 2018-07-19 |
KR102047204B1 (en) | 2019-11-20 |
TWI649397B (en) | 2019-02-01 |
TW201811956A (en) | 2018-04-01 |
SG11201811266XA (en) | 2019-01-30 |
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