JP6375467B2 - Adhesive, adhesive film, adhesive tape, and film substrate - Google Patents

Description

  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.

  When an integrated circuit (IC) or a flexible printed circuit board (FPC) is connected to a semiconductor element substrate (such as a TFT substrate), thermocompression bonding is usually performed using an anisotropic conductive film (ACF). When performing such thermocompression bonding, 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).

  However, since thermocompression bonding with an anisotropic conductive film (ACF) is performed at a high temperature, the fluidity of the adhesive on the adhesive tape is increased by heat. For example, the adhesive is greatly distorted during bump compression of an integrated circuit (IC). As a result, there is a problem in that the substrate of the semiconductor element is also distorted, resulting in poor connection.

JP 2012-015441 A

  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.

  In one embodiment, the adhesive force is 5N or more.

In one embodiment, the storage elastic modulus G ′ at 160 ° C. is 5 × 10 ⁵ Pa or more.

  In one embodiment, the pressure-sensitive adhesive of the present invention has a crosslinked structure.

  In one embodiment, 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.

  In one embodiment, the total content of the isocyanate-based crosslinking agent and the epoxy-based 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.

  In one embodiment, content of the said isocyanate type crosslinking agent in the said adhesive composition is 2 weight part-20 weight part with respect to 100 weight part of said acrylic polymers (A).

  In one embodiment, content of the said epoxy-type crosslinking agent in the said adhesive composition is 0.3 weight part-10 weight part with respect to 100 weight part of said acrylic polymers (A).

  In one embodiment, 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.

  In one embodiment, 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.

  In one embodiment, the pressure-sensitive adhesive of the present invention is formed from a pressure-sensitive adhesive composition containing a urethane polymer and an acrylic monomer.

  In one embodiment, the urethane polymer includes a (meth) acryloyl group-terminated urethane 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 μm or less.

  In one embodiment, the adhesive force is 5N or more.

  In one embodiment, the thickness is 15 μm or less.

  In one embodiment, 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 pressure-sensitive adhesive film of the present invention.

  According to the present invention, it is possible to provide 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. According to the present invention, it is possible to provide an adhesive film having sufficient adhesive force and less distortion at high temperature, to provide an adhesive tape having such an adhesive film, and a film having such an adhesive film. A substrate can be provided.

  When there is an expression “mass” in the present specification, it may be read as “weight” which is conventionally commonly used as a unit of weight, and conversely, the expression “weight” in the present specification. May be read as “mass”, which is commonly used as an SI system unit indicating weight.

  In the present specification, the expression “(meth) acryl” means “acryl and / or methacryl”, and the expression “(meth) acrylate” means “acrylate and / or methacrylate”. Means “allyl and / or methallyl”, and “(meth) acrolein” means “acrolein and / or methacrole”. It means "rain".

<< 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.

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. ) Can suppress the distortion of the pressure-sensitive adhesive and the accompanying distortion of the substrate of the semiconductor element even when the bump bonding of the integrated circuit (IC) is performed at a high temperature, thereby reducing the connection failure. . A method for measuring the storage elastic modulus G ′ at 160 ° C. will be described later.

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. When the pressure-sensitive adhesive of the present invention has a cross-linked structure, the pressure-sensitive adhesive of the present invention has more sufficient adhesive force and less strain at high temperatures.

<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

  In Embodiment A, the content of the acrylic polymer (A) in the pressure-sensitive adhesive composition is preferably 50 wt% to 99.9 wt%, more preferably 70 wt% to 99 wt%, Preferably they are 75 weight%-95 weight%, Especially preferably, they are 80 weight%-93 weight%, Most preferably, they are 85 weight%-90 weight%. When 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.

  In Embodiment A, 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.

  In the embodiment A, 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 400,000-1.5 million, Most preferably, it is 500,000-1.2 million.

  In the embodiment A, 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. , N-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, ( Hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, Decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylic acid Decyl, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate And (meth) acrylic acid alkyl esters having a linear or branched alkyl group having 1 to 20 carbon atoms, such as nonadecyl (meth) acrylate and eicosyl (meth) acrylate. As the (meth) acrylic acid alkyl ester having a linear or branched alkyl group, methyl (meth) acrylate, 2- (meth) acrylic acid 2- Ethyl hexyl is mentioned.

  Only one (meth) acrylic acid alkyl ester having a linear or branched alkyl group may be used, or two or more types may be used.

  Examples of the polar group-containing monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 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, and acid anhydrides thereof (for example, maleic anhydride, anhydrous Such as itaconic acid Carboxyl group-containing monomer anhydride-containing monomer) and the like; 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 preferably mentioned in that 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.

  Examples of the nitrogen-containing monomer 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 heterocycles and N-vinyl groups (nitrogen-containing heterocycle-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 monomers) (for example, (meth) a A nitrogen-containing heterocyclic ring-containing monomer such as liloylmorpholine; an amino group-containing monomer such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; acrylonitrile and methacrylate Cyano group-containing monomers such as nitrile; imide group-containing monomers such as cyclohexylmaleimide and isopropylmaleimide; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; and the like. The nitrogen-containing monomer is preferably N-vinyl-2-pyrrolidone from the viewpoint that the effects of the present invention can be further exhibited.

  Examples of other copolymerizable monomers include polyfunctional monomers. Examples of 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. Di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, allyl 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;

  Other copolymerizable monomers may be only one type or two or more types.

  In Embodiment A, 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. In terms of obtaining, it is preferably 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. % By weight.

  In the embodiment A, 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 in that the effect of the present invention can be further expressed. More preferably 10 to 45% by weight, still more preferably 15 to 40% by weight, and particularly preferably 20 to 35% by weight.

  In the embodiment A, a hydroxyl group-containing monomer (2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate) is used as the polar group-containing monomer in that the effect of the present invention can be further exhibited. , (Meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid 6-hydroxyhexyl, vinyl alcohol, allyl alcohol, etc.). When 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. In terms of expression, 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.

  In the embodiment A, 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. Specifically, the content ratio of the carboxyl group-containing monomer in the total amount of the 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% by weight to 2% by weight, and particularly preferably 0% by weight to 0.5% by weight.

  In the embodiment A, the acrylic polymer (A) is obtained by polymerizing the monomer component by any appropriate polymerization method as long as the effects of the present invention are not impaired. Examples of 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. Among these, the solution polymerization method and the active energy ray polymerization method are preferable in terms of productivity.

  Examples of the solvent used when 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.

  In the embodiment A, when the monomer component is polymerized, 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.

  Examples of the photopolymerization initiator include a benzoin ether photopolymerization initiator, an acetophenone photopolymerization initiator, an α-ketol photopolymerization initiator, an aromatic sulfonyl chloride photopolymerization initiator, and a photoactive oxime photopolymerization initiator. Agents, benzoin photopolymerization initiators, benzyl photopolymerization initiators, benzophenone photopolymerization initiators, ketal photopolymerization initiators, and thioxanthone photopolymerization initiators.

  As a usage-amount of a photoinitiator, Preferably it is 0.01 weight%-0.2 weight% with respect to the monomer component whole quantity which forms acrylic polymer (A), for example, More preferably, it is 0.05. % By weight to 0.15% by weight.

  Examples of the thermal polymerization initiator include azo initiators, peroxide polymerization initiators (eg, dibenzoyl peroxide, tert-butyl permaleate), redox polymerization initiators, and the like. Among these, azo initiators disclosed in JP-A No. 2002-69411 are preferable.

  For example, in the case of an azo initiator, the amount of the thermal polymerization initiator used is preferably 0.05% to 0.5% by weight with respect to the total amount of monomer components forming the acrylic polymer (A). More preferably, it is 0.1% by weight to 0.3% by weight.

  In Embodiment A, the pressure-sensitive adhesive composition contains an isocyanate-based crosslinking agent and / or an epoxy-based crosslinking agent. When 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.

  In Embodiment A, the total content of the isocyanate-based crosslinking agent and the epoxy-based 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% by weight to 25% by weight, further preferably 0.5% by weight to 23% by weight, particularly preferably 1% by weight 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.

  In Embodiment A, 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.

  In the embodiment A, 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.

  Examples of the isocyanate crosslinking agent (polyfunctional isocyanate compound) include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 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. Examples of the isocyanate crosslinking agent 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”).

  As the 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. Examples of the epoxy-based crosslinking agent 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.

  In Embodiment A, 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.

  In Embodiment A, as a method for 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. For example, 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. Form an adhesive. In order to apply the pressure-sensitive adhesive composition, for example, 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. Can be mentioned.

  In Embodiment A, when the pressure-sensitive adhesive of the present invention is formed on a substrate, the thickness of the resulting pressure-sensitive adhesive layer (pressure-sensitive adhesive layer) can be appropriately set according to the purpose. The thickness is preferably 1 μm to 500 μm, more preferably 5 μm to 300 μm, still more preferably 10 μm to 200 μm, and particularly preferably 15 μm to 100 μm, and most preferably 20 μm to 50 μm.

<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.

  In Embodiment B, 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 still more preferably. 30 to 80% by weight, particularly preferably 35 to 75% by weight, and most preferably 40 to 70% by weight. When 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.

  In Embodiment B, 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.

  In the embodiment B, 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, in that the effect of the present invention can be expressed more. More preferably, it is 400,000-1.5 million, Most preferably, it is 500,000-1.2 million.

  In the embodiment B, the acrylic polymer (B) is preferably a (meth) acrylic acid alkyl ester having a glass transition temperature (Tg) of −20 ° C. or less when a homopolymer is used, and the acrylic polymer (B). The acrylic polymer preferably contains 80% by weight or more based on the total amount of the monomer components forming the. By adopting such a polymer as the acrylic polymer (B), it is possible to provide a pressure-sensitive adhesive having a sufficient adhesive force and less distortion at a high temperature.

  “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. Specifically, 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. Moreover, what is necessary is just to employ | adopt the value obtained by the following measuring methods for the glass transition temperature (Tg) of the homopolymer which is not described in the said literature etc. That is, in a reactor equipped with a thermometer, a stirrer, a nitrogen introducing tube and a reflux condenser, 100 parts by weight of monomer X, 0.2 parts by weight of 2,2′-azobisisobutyronitrile, and ethyl acetate as a polymerization solvent Add 200 parts by weight and stir for 1 hour while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature is raised to 63 ° C. and the reaction is carried out for 10 hours. Next, the mixture is cooled to room temperature to obtain a homopolymer solution having a solid concentration of 33% by weight. Next, 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 in an aluminum open cell, and using a temperature modulation DSC (trade name “Q-2000”, manufactured by T.A. Instruments Inc.), nitrogen of 50 ml / min. The reversing heat flow (specific heat component) behavior of the homopolymer is obtained at a heating rate of 5 ° C./min in an atmosphere. Referring to JIS-K-7121, the low temperature side baseline of the obtained Reversing Heat Flow and the straight line that is equidistant from the straight line extending the high temperature side base line, and the stepwise change of the glass transition 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 lower when a homopolymer is used include (meth) acrylic acid alkyl esters shown in Table 1. In this specification, “(meth) acrylic acid alkyl ester” indicates “acrylic acid alkyl ester and / or methacrylic acid alkyl ester”. In addition, only 1 type may be sufficient as the (meth) acrylic-acid alkylester whose glass transition temperature when it is set as a homopolymer is -20 degrees C or less, and 2 or more types may be sufficient as it.

  As the (meth) acrylic acid alkyl ester having a glass transition temperature of −20 ° C. or less when made as a homopolymer, the glass transition temperature when made as a homopolymer is preferable in that the effect of the present invention can be further expressed. Is a (meth) acrylic acid alkyl ester having a temperature of −30 ° C. or lower, and more preferably a (meth) acrylic acid alkyl ester having a glass transition temperature of −40 ° C. or lower when a homopolymer is used.

  Specifically, 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 in that the effect of the present invention can be more expressed. , 2-ethylhexyl acrylate, and lauryl acrylate.

  In acrylic polymer (B), the content of (meth) acrylic acid alkyl ester having a glass transition temperature (Tg) of -20 ° C. or lower when homopolymer is used with respect to the total amount of monomer components forming 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.

  In the embodiment B, 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. When 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 monomer such as (containing monomer); 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, N Amide group-containing monomers such as hydroxyethyl (meth) acrylamide; Amino group-containing monomers such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; Epoxy group-containing monomers such as glycidyl acrylate and methyl glycidyl (meth) acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; N-vinyl-2-pyrrolidone, (meth) acryloylmorpholine, N-vinylpiperidone, N- Heterocycle-containing vinyl monomers such as vinyl piperazine, N-vinyl pyrrole, N-vinyl imidazole, vinyl pyridine, vinyl pyrimidine, vinyl oxazole; sulfonic acid group-containing monomers such as sodium vinyl sulfonate; 2-hydride Phosphoric acid group-containing monomer such as carboxymethyl ethyl acryloyl phosphate; and the like; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; cyclohexyl maleimide, imide group-containing monomers such as isopropyl maleimide. Only one type of polar group-containing monomer may be used, or two or more types may be used.

  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, or acrylic acid 2 in that the effects of the present invention can be further expressed. -Hydroxyethyl.

  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.

  In Embodiment B, 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).

  Examples of 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. Di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, allyl Examples include (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, and urethane acrylate. Only one type of polyfunctional monomer may be used, or two or more types may be used.

  In Embodiment B, examples of the copolymerizable monomer also include (meth) acrylic acid alkoxyalkyl esters. Examples of the (meth) acrylic acid alkoxyalkyl ester 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.

  In Embodiment B, 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 (Meth) acrylic acid esters other than the above-mentioned polar group-containing monomers and polyfunctional monomers; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyltoluene; ethylene, butadiene, Vinyl ethers such as vinyl alkyl ethers; isoprene, olefins or dienes such as isobutylene vinyl chloride; glass transition temperature when formed into a homopolymer exceeds -20 ° C. (meth) acrylic acid alkyl ester; and the like. These may be only one kind or two or more kinds.

  In Embodiment B, 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. Examples of 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). Among these, from the viewpoint of productivity, 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 when 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.

  In the embodiment B, when the monomer component is polymerized, 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.

  Examples of the photopolymerization initiator include a benzoin ether photopolymerization initiator, an acetophenone photopolymerization initiator, an α-ketol photopolymerization initiator, an aromatic sulfonyl chloride photopolymerization initiator, and a photoactive oxime photopolymerization initiator. Agents, benzoin photopolymerization initiators, benzyl photopolymerization initiators, benzophenone photopolymerization initiators, ketal photopolymerization initiators, and thioxanthone photopolymerization initiators.

  As a usage-amount of a photoinitiator, Preferably it is 0.01 weight%-0.2 weight% with respect to the monomer component whole quantity which forms an acryl-type polymer (B), More preferably, it is 0.05. % By weight to 0.15% by weight.

  Examples of the thermal polymerization initiator include azo initiators, peroxide polymerization initiators (eg, dibenzoyl peroxide, tert-butyl permaleate), redox polymerization initiators, and the like. Among these, azo initiators disclosed in JP-A No. 2002-69411 are preferable.

  For example, in the case of an azo initiator, 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 (B). More preferably, it is 0.1% by weight to 0.3% by weight.

  In Embodiment B, the pressure-sensitive adhesive composition contains an ultraviolet curable oligomer. When 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.

  In Embodiment B, 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.

  The ultraviolet curable oligomer has a polymerizable ethylenically unsaturated double bond, and includes an aromatic urethane oligomer, an aliphatic urethane oligomer, an epoxy acrylate oligomer, a polyester acrylate oligomer, and other special oligomers.

  Specific examples of the UV curable oligomer include, for example, UV-2000B, UV-2750B, UV-3000B, UV-3010B, UV-3200B, UV-3300B, and UV-3700B manufactured by Nippon Kasei Gosei Co., Ltd. , UV-6640B, UV-8630B, UV-7000B, UV-7610B, UV-1700B, UV-7630B, UV-6300B, UV-6640B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV -7630B, UV-7640B, UV-7650B, UT-5449, UT-5454; CN902, CN902J75, CN929, CN940, CN944, CN944B85, CN959, CN961E75, CN961H81, CN96 manufactured by Sartomer , CN963, CN963A80, CN963B80, CN963E75, CN963E80, CN963J85, CN964, CN965, CN965A80, CN966, CN966A80, CN966B85, CN966H90, CN966J75, CN968, CN969, CN970, CN970A60, CN970E60, CN971, CN971A80, CN971J75, CN972, CN973, CN973A80 CN973H85, CN973J75, CN975, CN977, CN977C70, CN978, CN980, CN981, CN981A75, CN981B88, CN982, CN982A75, CN982B88, CN982E98, CN983, CN98C, CN983, CN98C 986, CN989, CN991, CN992, CN994, CN996, CN997, CN999, CN9001, CN9002, CN9004, CN9005, CN9006, CN9007, CN9008, CN9009, CN9010, C9011, CN9013, C9018, C9019, C9090 CN9029, CN9030, CN9060, CN9165, CN9167, CN9178, CN9290, CN9782, CN9783, CN9788, CN9873; EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL200E ECRYL8301, EBECRYL8804, EBECRYL8807, EBECRYL9260, KRM7735, KRM8296, KRM8452, EBECRYL4858, EBECRYL8402, EBECRYL9270, EBECRYL8311, EBECRYL871;

  In the embodiment B, 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.

  In Embodiment B, any appropriate method can be adopted as a method for forming the pressure-sensitive adhesive of the present invention from the pressure-sensitive adhesive composition as long as the effects of the present invention are not impaired. For example, 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. In order to apply the pressure-sensitive adhesive composition, for example, 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. Can be mentioned.

  In Embodiment B, when the pressure-sensitive adhesive of the present invention is formed on a substrate, the thickness of the resulting pressure-sensitive adhesive layer (pressure-sensitive adhesive layer) can be appropriately set according to the purpose. The thickness is preferably 1 μm to 500 μm, more preferably 5 μm to 300 μm, still more preferably 10 μm to 200 μm, and particularly preferably 15 μm to 100 μm, and most preferably 20 μm to 50 μm.

<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.

  In Embodiment C, 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. It is -75 weight%, Most preferably, it is 35 weight%-70 weight%, Most preferably, it is 40 weight%-65 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.

  In Embodiment C, 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. It is -70 weight%, Most preferably, it is 40 weight%-65 weight%. 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.

  In embodiment C, the urethane-based 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.

  In embodiment C, 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. In this reaction, if necessary, an organic solvent having no active hydrogen that can react with an isocyanate group (eg, ethyl acetate, methyl ethyl ketone, chloroform, etc.) and a catalyst (eg, tin chloride, organotin compound, etc.) And an organic base such as a tertiary amine compound; an organic acid such as acetic acid and acrylic acid; etc.).

  In Embodiment C, the ratio between the polyisocyanate compound and the polyol compound is an equivalent ratio, preferably 0.1 to 2.0, more preferably 0.3 to 1.8 as NCO / OH. More preferably, it is 0.5 to 1.5, and particularly preferably 0.8 to 1.3. When the 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.

  In Embodiment C, the molecular weight of the urethane-based polymer can be appropriately set depending on 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.

  In Embodiment C, 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. In the present invention, 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. In the present invention, “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 | adopt and when selecting a specific polyol compound, it is not necessary to confirm the physical-property value of both "melting point" and "freezing point".

  In the embodiment C, 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.

  In embodiment C, the polyol compound preferably includes polyester polyol, polyether polyol, and polycarbonate diol.

  Specific examples of the polyester polyol 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.

  Specific examples of the polyether polyol 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.

  Specifically, as the polycarbonate diol, 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.

  In the embodiment C, examples of the polyisocyanate compound include hexamethylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylene diisocyanate, xylylene diene. Isocyanate, naphthalene diisocyanate, trimethylhexamethylene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, cyclohexylene diisocyanate, methylenebis (4-phenylmethane) diisocyanate, hexamethylene diisocyanate, Dimer acid diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, triphenyl methyl Emissions triisocyanate, tri (isocyanatophenyl) triphosphate and the like.

  In embodiment C, the polyisocyanate compound preferably includes hydrogenated xylylene diisocyanate.

  In Embodiment C, 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.

  In Embodiment C, when the urethane polymer includes a (meth) acryloyl group-terminated urethane polymer, 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, 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. In this reaction, if necessary, an organic solvent having no active hydrogen that can react with an isocyanate group (eg, ethyl acetate, methyl ethyl ketone, chloroform, etc.) and 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;

  Examples of the hydroxyl group-containing acrylic monomer 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 and 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. Specifically, with respect to the polyol compound blended in the production of the polyurethane prepolymer, the molar ratio is preferably, polyol compound: hydroxyl group-containing acrylic monomer = 1: 0.08 to 1: 0.5, and more Preferably, polyol compound: hydroxyl group-containing acrylic monomer = 1: 0.1 to 1: 0.4. When the ratio of the polyol compound and the hydroxyl group-containing acrylic monomer is within the above range, it is possible to provide a pressure-sensitive adhesive having a sufficient adhesive force and less distortion at a high temperature.

  In Embodiment C, the pressure-sensitive adhesive composition includes an acrylic monomer.

  In Embodiment C, the acrylic monomer preferably includes a (meth) acrylic monomer having an amide group.

  In Embodiment C, when the acrylic monomer contains 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 weight%, More preferably, it is 15 weight%-97 weight%, More preferably, it is 25 weight%-95 weight%. When 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.

  Examples of the (meth) acrylic monomer having an amide group include N-methylol (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, and N- (1,1-dimethyl). -3-oxobutyl) (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 acrylics such as N, N-ethylmethyl (meth) acrylamide Amide; N- (meth) acryloylmorpholine; N- (meth) acryloylpyrrolidone; N- (meth) acryloylpiperidine; N- (meth) acryloylpyrrolidine; N- (meth) acryloylaziridine; dimethylaminoethyl acrylate; It is done. The (meth) acrylic monomer having an amide group may be only one kind or two or more kinds.

  In Embodiment C, 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.

  Examples of (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, and (meth) acrylic. Hexyl acid, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) (Meth) acrylic acid esters such as isobornyl acrylate, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, Contains carboxyl groups such as itaconic acid Nomers; acid anhydride monomers such as maleic anhydride and itaconic anhydride; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl Hydroxyl group-containing monomers such as alcohol; tertiary amino group-containing monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate; epoxy group-containing monomers such as glycidyl methacrylate; Sulfonic acid group-containing monomers such as (meth) acrylamide-2-methylpropane sulfonic acid and sulfopropyl (meth) acrylate; Phosphoric acid-containing monomers such as 2-hydroxyethyl (meth) acryloyl phosphate; N- (meth) acryloyl Succinimide monomers such as ximethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide; cyanoacrylate monomers such as (meth) acrylonitrile; Can be mentioned.

  In Embodiment C, (meth) acrylic monomers preferably include butyl (meth) acrylate, isobornyl (meth) acrylate, and (meth) acrylic acid.

  In Embodiment C, 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. It is 10 to 40% by weight, particularly preferably 15 to 30% by weight. When 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.

  In Embodiment C, 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 to 40% by weight, particularly preferably 15 to 30% by weight. When 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.

  In Embodiment C, 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 even more preferably 3%. % By weight to 40% by weight, particularly preferably 4% by weight to 25% by weight. When 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.

  In Embodiment C, 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.

  In Embodiment C, as a method for 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. As such a method, preferably, 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 (α ray, β ray, γ ray, neutron ray, electron beam, etc. depending on the type of photopolymerization initiator, etc. It can be formed by being cured by irradiation with ultraviolet rays, visible light, or the like. As the 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.

  In embodiment C, when a hydroxyl group-containing acrylic monomer is 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). Depending on the type of photopolymerization initiator, etc., any appropriate active energy ray (α ray, β ray, γ 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. As the 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.

  In 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 to form the pressure-sensitive adhesive of the present invention.

  In order to apply the pressure-sensitive adhesive composition, for example, 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. Can be mentioned.

  In embodiment C, in order to avoid polymerization inhibition by oxygen when forming the pressure-sensitive adhesive of the present invention, on the pressure-sensitive adhesive composition applied on any suitable substrate (for example, PET substrate), Furthermore, any appropriate base material that has been subjected to a peeling treatment may be placed.

  In Embodiment C, when forming the pressure-sensitive adhesive of the present invention, any appropriate solvent may be added for viscosity adjustment. Examples of such a solvent include ethyl acetate, toluene, chloroform, dimethylformamide and the like.

  Only one type of photopolymerization initiator may be used, or two or more types may be used.

  As a usage-amount of a photoinitiator, the arbitrary appropriate quantity normally used for photopolymerization can be employ | adopted.

  In Embodiment C, when the pressure-sensitive adhesive of the present invention is formed on a substrate, the thickness of the resulting pressure-sensitive adhesive layer (pressure-sensitive adhesive layer) can be appropriately set according to the purpose. The thickness is preferably 1 μm to 500 μm, more preferably 5 μm to 300 μm, still more preferably 10 μm to 200 μm, and particularly preferably 15 μm to 100 μm, and most preferably 20 μm to 50 μm.

  In Embodiment C, 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.

≪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.

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. ), Even when bump bonding of an integrated circuit (IC) is performed at a high temperature, 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 storage elastic modulus G ′ at 160 ° C. will be described later.

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 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 film of the present invention has a thickness of 20 μm or less, preferably 18 μm or less, more preferably 15 μm or less, further preferably 13 μm or less, particularly preferably 12 μm or less, and most preferably 10 μm or less. It is. The lower limit of the thickness of the pressure-sensitive adhesive film of the present invention is preferably 3 μm 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. For example, an integrated circuit (IC) is formed on a substrate of a semiconductor element by an anisotropic conductive film (ACF). Even when the bump pressure bonding is performed at a high temperature, 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. When 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 polymer.

  The 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.

  As an acrylic polymer, 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.

<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, and 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, in that the effect of the present invention can be further expressed. ˜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.

  For the (meth) acrylic acid alkyl ester having a linear or branched alkyl group, the above item <1-1. The description in embodiment A> may be incorporated.

  For the polar group-containing monomer, the above item <1-1. The description in embodiment A> may be incorporated.

  For other copolymerizable monomers, the above item <1-1. The description in embodiment A> may be incorporated.

  In the total amount of the monomer components forming the acrylic polymer (A), 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.

  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 expressed. 4-hydroxybutyl, 6-hydroxyhexyl (meth) acrylate, vinyl alcohol, allyl alcohol, and the like) are preferably included. When 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. In terms of expression, 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.

  It is preferable that the carboxyl group-containing monomer (especially (meth) acrylic acid) is not used or is used in a small amount even if it is used, in that the effect of the present invention can be further expressed and the corrosion of metals and the like is suppressed. Specifically, the content ratio of the carboxyl group-containing monomer in the total amount of the 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% by weight to 2% by weight, and particularly preferably 0% by weight to 0.5% by weight.

  Regarding the polymerization method of the acrylic polymer (A), the above item <1-1. The description in embodiment A> may be incorporated.

  The pressure-sensitive adhesive composition containing the acrylic polymer (A) may contain a crosslinking agent. As such 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. When 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.

  When the pressure-sensitive adhesive composition containing the acrylic polymer (A) contains an isocyanate-based crosslinking agent, 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 to 50% by weight, more preferably 2 to 40% by weight, still more preferably 5 to 30% by weight, particularly preferably 7 to 20% by weight. 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.

  For the isocyanate-based crosslinking agent (polyfunctional isocyanate compound), the above item <1-1. The description in embodiment A> may be incorporated.

  For the pressure-sensitive adhesive composition containing the acrylic polymer (A), if necessary, other cross-linking agents, cross-linking accelerators, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.) ), Anti-aging agents, fillers, colorants (pigments, dyes, etc.), UV absorbers, antioxidants, chain transfer agents, plasticizers, softeners, surfactants, antistatic agents, and other additives. It may be contained in any appropriate amount as long as the effects of the invention are not impaired. Only one kind of such an additive may be used, or two or more kinds thereof may be used.

  As a method of forming the pressure-sensitive adhesive film of the present invention from the pressure-sensitive adhesive composition containing the acrylic polymer (A), any appropriate method can be adopted as long as the effects of the present invention are not impaired. For example, 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. In order to apply the pressure-sensitive adhesive composition, for example, 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. Can be mentioned.

<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, and 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 a homopolymer is used. The acrylic polymer preferably contains 80% by weight or more based on the total amount. About such an acrylic polymer, the above-mentioned item <1-2. The description in embodiment B> may be incorporated.

  In acrylic polymer (B), the content of (meth) acrylic acid alkyl ester having a glass transition temperature (Tg) of -20 ° C. or lower when homopolymer is used with respect to the total amount of monomer components forming 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.

  Acrylic polymer (B), as a monomer component to form it, from the point of enabling the tuning of properties, proper use according to purpose and imparting the function as necessary, together with the above (meth) acrylic acid alkyl ester, A copolymerizable monomer may be included. In addition, only 1 type may be sufficient as a copolymerizable monomer and 2 or more types may be sufficient as it.

  For the copolymerizable monomer, the above item <1-2. The description in embodiment B> may be incorporated.

  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. Regarding 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. When 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% by weight to 150% by weight, more preferably 30% by weight to 120% by weight, particularly preferably 35% by weight to 110% by weight, and most preferably 40% by weight 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.

  For the ultraviolet curable oligomer, the above item <1-2. The description in embodiment B> may be incorporated.

  In 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.

  As a method for forming the pressure-sensitive adhesive film of the present invention from the pressure-sensitive adhesive composition containing the acrylic polymer (B), any appropriate method can be adopted as long as the effects of the present invention are not impaired. For example, 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 pressure-sensitive adhesive film of the present invention. In order to apply the pressure-sensitive adhesive composition, for example, 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. Can be mentioned.

<2-3. Adhesive Composition Containing Urethane Polymer>
In the pressure-sensitive adhesive composition containing the urethane polymer, 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. More preferably, it 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 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-based 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 appropriate 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. In this reaction, if necessary, an organic solvent having no active hydrogen that can react with an isocyanate group (eg, ethyl acetate, methyl ethyl ketone, chloroform, etc.) and a catalyst (eg, tin chloride, organotin compound, etc.) And 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 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.

  About a polyol compound, the above-mentioned item <1-3. The description in embodiment C> may be incorporated.

  For the polyisocyanate compound, the above item <1-3. The description in embodiment C> may be incorporated.

  The urethane polymer preferably includes 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.

  When the urethane polymer includes a (meth) acryloyl group-terminated urethane polymer, the content ratio of the (meth) acryloyl group-terminated urethane polymer in the urethane polymer is preferably 50% by weight to 100% by weight, and 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. In this reaction, if necessary, an organic solvent having no active hydrogen that can react with an isocyanate group (eg, ethyl acetate, methyl ethyl ketone, chloroform, etc.) and 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;

  Regarding the hydroxyl group-containing acrylic monomer, the above item <1-3. The description in embodiment C> may be incorporated.

  The ratio of the polyurethane prepolymer and 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. Specifically, with respect to the polyol compound blended in the production of the polyurethane prepolymer, the molar ratio is preferably, polyol compound: hydroxyl group-containing acrylic monomer = 1: 0.08 to 1: 0.5, and more Preferably, polyol compound: hydroxyl group-containing acrylic monomer = 1: 0.1 to 1: 0.4. When the ratio between the polyol compound and the hydroxyl group-containing acrylic monomer is within the above range, an adhesive film having more sufficient adhesive force and less distortion at high temperature can be provided.

  The pressure-sensitive adhesive composition containing a urethane polymer may contain an acrylic monomer.

  When the pressure-sensitive adhesive composition containing a urethane polymer contains 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.

  When the acrylic monomer 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 to 99% by weight. 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.

  About the (meth) acrylic-type monomer which has an amide group, the above-mentioned item <1-3. The description in embodiment C> may be incorporated.

  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. When 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 still more preferably 10% by weight to 40% by weight. % By weight, particularly preferably 15% by weight to 30% by weight. When the content ratio of isobornyl (meth) acrylate in the total amount of the acrylic monomer is within the above range, an adhesive film having more sufficient adhesive force and less distortion at high temperature can be provided.

  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. When 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.

  For pressure-sensitive adhesive compositions containing urethane-based polymers, cross-linking agents, cross-linking accelerators, silane coupling agents, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), 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.

  As a method of forming the pressure-sensitive adhesive film of the present invention from a pressure-sensitive adhesive composition containing a urethane-based polymer, any appropriate method can be adopted as long as the effects of the present invention are not impaired. As such a method, preferably, 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 (α ray, β ray, γ ray, neutron ray, electron beam, etc. depending on the type of photopolymerization initiator, etc. It can be formed by being cured by irradiation with ultraviolet rays, visible light, or the like. As the 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.

  When a hydroxyl group-containing acrylic monomer is used to form a urethane-based polymer, 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 (α ray, β ray, γ ray, neutron ray, electron beam, ultraviolet ray, visible light, etc.) depending on the type of Can be formed. As the 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.

  Specifically, for example, after a polyol compound is dissolved in an acrylic monomer component, a polyisocyanate compound is added to react with the polyol compound, viscosity adjustment is performed, and the resulting mixture is subjected to any appropriate mixture. After coating on a base material (for example, PET base material), 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.

  In order to apply the pressure-sensitive adhesive composition containing the urethane-based polymer, for example, 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. Can be mentioned.

  In order to avoid polymerization inhibition due to oxygen when forming the pressure-sensitive adhesive film of the present invention, on the pressure-sensitive adhesive composition containing a urethane-based polymer coated on any appropriate base material (for example, PET base material), Furthermore, any appropriate base material that has been subjected to a peeling treatment may be placed.

  When forming the pressure-sensitive adhesive film of the present invention, any appropriate solvent may be added to adjust the viscosity. Examples of such a solvent include ethyl acetate, toluene, chloroform, dimethylformamide and the like.

  Only one type of photopolymerization initiator may be used, or two or more types may be used.

  As a usage-amount of a photoinitiator, the arbitrary appropriate quantity normally used for photopolymerization can be employ | adopted.

  When 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.

≪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.

  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. 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 , 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.

  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 substrate.

  The thickness of the substrate can be appropriately set according to the purpose. The thickness is preferably 1 μm to 500 μm, more preferably 5 μm to 300 μm, still more preferably 10 μm to 200 μm, and particularly preferably 15 μm to 100 μm, and most preferably 20 μm to 50 μm.

  The surface of the base material 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 undercoating treatment.

≪Film substrate≫
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. Generally, 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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples at all. In addition, the 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.

<Measurement of weight average molecular weight>
The weight average molecular weight was measured by a gel permeation chromatograph (GPC) method. Specifically, as a GPC measurement apparatus, a product name “HLC-8120GPC” (manufactured by Tosoh Corporation) was used, and measurement was performed under the following conditions, and the standard polystyrene conversion value 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

<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 a range of −70 to 200 ° C. in a shear mode with a frequency of 1 Hz using a “Advanced Rheometric Expansion System (ARES)” manufactured by Rheometric Scientific. .

<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 leaving 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.

<Evaluation of Deformation of Adhesive at 30 MPa Press at 160 ° C.>
A 12.5μ thick polyimide film (Kapton 50EN, manufactured by Toray DuPont Co., Ltd.) is bonded with an adhesive tape. The 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.

[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 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 (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.

[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.

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 the acrylic polymer (2) solution, purple light UV-3700B (manufactured by Nippon Synthetic Chemical Co., Ltd.)) is converted to 100 in terms of solid content with respect to 100 parts by weight of the acrylic polymer (3) (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.

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.

[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, 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 in the resin solution: 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). It was added so as to be 1 part by weight in terms of conversion, and 2-benzyl-2- (dimethylamino) -4-morpholinobutylphenone (trade name “Irgacure 369” manufactured by BASF) was 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, 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 (C1) having a PET separator peeled on one side.
The results are shown in Table 2.

[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 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 chain transfer agent: 10 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 10 parts by weight, and 120 parts by weight of toluene as a polymerization solvent are put 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 is added, and a crosslinking agent (epoxy crosslinking agent, trade name “TETRAD-C”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) is 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.

[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.

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 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 (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.

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.

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 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 chain transfer agent: 10 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator: 10 parts by weight, and 120 parts by weight of toluene as a polymerization solvent are put 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 is added, and a crosslinking agent (epoxy crosslinking agent, trade name “TETRAD-C”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) is 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.

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.

[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.

[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.

[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 (4)

An adhesive tape having a base material and an adhesive layer,
The adhesive layer is an adhesive film,
The adhesive film is
(A) formed from an acrylic polymer formed from a monomer component containing a (meth) acrylic acid alkyl ester and a polar group-containing monomer, and an adhesive composition containing an isocyanate-based crosslinking agent and / or an epoxy-based crosslinking agent Adhesive film,
(B) Adhesion containing an acrylic polymer containing 80% by weight or more of a (meth) acrylic acid alkyl ester having a glass transition temperature of −20 ° C. or lower when homopolymer is used with respect to the total amount of monomer components, and an ultraviolet curable oligomer An adhesive film formed from the agent composition,
(C) A pressure-sensitive adhesive film formed from a pressure-sensitive adhesive composition containing a (meth) acryloyl group-terminated urethane polymer, an amide monomer having an amide group, and isobornyl (meth) acrylate,
Either
The adhesive force of the adhesive film to the surface of the polyimide film is 5N or more,
The storage elastic modulus G ′ at 160 ° C. of the pressure-sensitive adhesive film is 1 × 10 ⁴ Pa or more,
The adhesive film has a thickness of 20 μm or less.
Adhesive tape.
In addition, the adhesive force was bonded by bonding the pressure-sensitive adhesive film having a width of 25 mm by reciprocating a 2 kg roller on the surface of the polyimide film in an atmosphere of 23 ° C. and 50% RH. After being left for 30 minutes in an atmosphere of 50% RH, measurement is performed under the conditions of a peeling angle of 180 ° and a tensile speed of 300 mm / min in an atmosphere of 23 ° C. and 50% RH.   The pressure-sensitive adhesive tape according to claim 1, wherein the thickness is 15 μm or less. The pressure-sensitive adhesive tape according to claim 1 or 2 , 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. The pressure-sensitive adhesive tape according to any one of claims 1 to 3 , which is bonded to a substrate of a semiconductor element.