KR20120045998A - Adhesive composition - Google Patents

Abstract

PURPOSE: An adhesive composition is provided to have long pot life, thereby having excellent workability, to obtain usable adhesion within 10 minutes after finishing adhesion process, and to have excellent workability. CONSTITUTION: An adhesive composition comprises: 100.0 parts by weight of (meth)acrylic copolymer of which weight average molecular weight is 100,000-2,000,000 g/mol; 0.1-1 parts by weight of a peroxide crosslinking agent; and 0.05-5 parts by weight of a carbodiimide crosslinking agent. The adhesive composition additionally comprises an isocyanate crosslinking agent and/or an imidazole compound in chemical formula 1. In chemical formula 1, R^1, R^2 and R^3 is respectively hydrogen, halogen, or a substituted or unsubstituted C1-10 linear or branched alkyl group.

Description

Adhesive composition {ADHESIVE COMPOSITION}

The present invention relates to an adhesive composition. More specifically, the present invention relates to a pressure-sensitive adhesive composition that has a long pot life, is excellent in workability, and reaches a practical adhesive performance in a short aging time after adhesion processing.

In recent years, the use of flat panel displays (FPDs), such as liquid crystal display (LCD), plasma display (PDP), and organic electroluminescent (EL) devices, has been expanded. Thereby, improvement of the workability | operativity and productivity of the adhesive used for FPD is calculated | required.

Patent Document 1 discloses an adhesive composition for an optical member comprising an acrylic polymer, a peroxide, and a silane coupling agent. By mix | blending a peroxide and a silane coupling agent with an acrylic polymer, the adhesive composition of patent document 1 exhibits high durability which does not produce peeling (peeling) and foaming under high temperature, high humidity, and also ages after a coating, drying, and a crosslinking process. There is an advantage of exhibiting excellent productivity that does not require.

[Prior Art Literature]

(Patent Document 1) JP2005-307034 A

However, when examining the adhesive layer formed from the adhesive composition of the said patent document 1, although it can shorten compared with the conventional aging (aging) period, after adhesive processing, at least 0.5 until it reaches practical adhesive performance. Specific aging (maturation) time, called work, is necessary, and in view of productivity, further shortening was still desired.

This invention is made | formed in view of the said situation, Comprising: It aims to provide the adhesive composition which is excellent in workability | operativity by long pot life, and also reaches practical adhesive performance in a short aging time, and excellent in productivity.

The present inventors earnestly researched in order to solve the said problem. As a result, the adhesive composition which a (meth) acryl copolymer, a peroxide crosslinking agent, and a carbodiimide crosslinking agent are contained in a specific composition has a long pot life, and is excellent in workability, and is immediately after adhesion processing (within 10 minutes after completion of an adhesion process). The practical adhesive performance was reached, and the productivity improved significantly, and the present invention was completed.

That is, this invention is 100 mass parts of (meth) acryl copolymers (A) whose weight average molecular weights are 100,000-2 million g / mol; It is an adhesive composition containing 0.1-1 mass part of peroxide crosslinking agents (B) and 0.05-5 mass part of carbodiimide crosslinking agents (C) with respect to 100 mass parts of said (meth) acryl copolymers (A).

The pressure-sensitive adhesive composition of the present invention has a long pot life, is excellent in workability, and reaches a practical adhesive performance immediately after adhesion processing (within 10 minutes after completion of the adhesion processing), and productivity is greatly improved. Therefore, the adhesive composition of this invention is effective for adhesion | attachment of various to-be-adhered bodies, and the adhesive layer formed from the adhesive composition of this invention can especially be used suitably as an adhesive layer of an optical member, a surface protection film, and an adhesive sheet.

This invention is 0-9 mass parts carboxyl group-containing monomer (a-1), 0-9 mass parts hydroxy group containing (meth) acrylic monomer (a-2), and 99.9-82 mass parts (meth) acrylic acid ester monomer (However, the total amount of the carboxyl group-containing monomer (a-1) and the hydroxy group-containing (meth) acrylic monomer (a-2) consisting of (a-3) is not 0 parts by mass, and the carboxyl group-containing monomer (a- 1), the total amount of the hydroxy group-containing (meth) acrylic monomer (a-2) and the (meth) acrylic acid ester monomer (a-3) is 100 parts by mass) and contains a monomer component, and the weight average molecular weight is 100,000 to 200 100 parts by mass of (meth) acrylic copolymer (A) which is 10,000 g / mol; It is providing the adhesive composition containing 0.1-1 mass part of peroxide crosslinking agents (B) and 0.05-5 mass part of carbodiimide crosslinking agents (C) with respect to 100 mass parts of said (meth) acryl copolymers (A).

The adhesive composition of this invention contains a peroxide crosslinking agent and a carbodiimide crosslinking agent as a crosslinking agent. By using a peroxide crosslinking agent and a carbodiimide crosslinking agent together as a crosslinking agent, a pot life is long without affecting adhesive physical property, and practical adhesive performance is reached immediately after adhesive processing (within 10 minutes after completion of an adhesive processing), and workability And the pressure-sensitive adhesive composition in which the productivity is all greatly improved. For this reason, when the adhesive composition of this invention is used, it can be applied as various uses, such as the adhesive for optical members, the adhesive for surface protection films, and the adhesive for adhesive sheets which do not require a aging process.

Moreover, the adhesive layer formed using the adhesive composition of this invention has adhesiveness suitable for an optical member, adhesiveness to a base material, and furthermore, metal corrosion inhibitory prevention, light leakage resistance, durability, and adherend contamination resistance Excellent low temperature stability and rework.

In addition, the pressure-sensitive adhesive layer formed by using the pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive for a surface protection film, and has an appropriate adhesive force and adhesion to a base material, and is also excellent in metal corrosion inhibition / prevention resistance, adherend contamination, low temperature stability, and transparency. In addition, it suppresses and prevents foaming under high temperature and high pressure conditions (at the time of autoclave treatment).

In addition, the pressure-sensitive adhesive layer formed by using the pressure-sensitive adhesive composition of the present invention has an appropriate adhesive force and adhesiveness to a base material as an adhesive for pressure-sensitive adhesive sheet, and furthermore, metal corrosion inhibition and prevention, adherend contamination resistance, low temperature stability, transparency Excellent in heat resistance and heat and moisture resistance.

Hereinafter, each component of the adhesive composition of this invention is demonstrated in detail. In addition, in this specification, "(meth) acrylate" is a generic term of acrylate and methacrylate. Similarly, the compound containing (meth), such as (meth) acrylic acid, is also a general term for the compound which has "meta" in a name, and the compound which does not have "meta". For this reason, "(meth) acryl" includes both acryl and methacryl. "(Meth) acrylate" includes both acrylate and methacrylate. "(Meth) acrylic acid" includes both acrylic acid and methacrylic acid.

(A) (meth) acrylic copolymer

The (meth) acryl copolymer (hereinafter also referred to as "component (A)") used in the present invention is a carboxyl group-containing monomer (a-1) 0 to 9 parts by mass, and a hydroxy group-containing (meth) acryl monomer ( a-2) The monomer component which consists of 0-9 mass parts and 99.9-82 mass parts of (meth) acrylic acid ester monomers (a-3) is included. In addition, the total amount of a carboxyl group-containing monomer (a-1) and a hydroxyl group containing (meth) acryl monomer (a-2) is not 0 mass part. In addition, the total amount of a carboxyl group-containing monomer (a-1), a hydroxyl group containing (meth) acryl monomer (a-2), and a (meth) acrylic acid ester monomer (a-3) is 100 mass parts. And the weight average molecular weight of the said (meth) acryl copolymer is 100,000-2 million g / mol.

(a-1) Carboxyl group-containing monomer

The carboxyl group-containing monomer (henceforth also called "component (a-1)") which concerns on this invention is an unsaturated monomer which has at least 1 carboxyl group in a molecule | numerator. Specific examples of the carboxyl group-containing monomer include, but are not limited to, the following: (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, crotonic acid, itaconic acid, itaconic anhydride, myristoleic acid, palmi Toleic acid, oleic acid, etc. are mentioned. These may be used independently or may be used in combination of 2 or more type.

Among these, (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, crotonic acid, itaconic acid and itaconic anhydride are preferable, and (meth) acrylic acid is more preferable.

In this invention, the usage-amount of a carboxyl group-containing monomer is 0-9 mass parts. When the amount of use exceeds 9 parts by mass, the carboxyl group in the copolymer (A) becomes excessive, and the crosslinking point generated by the reaction between the carboxyl group and the carbodiimide crosslinking agent (C) becomes excessive, so that the flexibility of the pressure-sensitive adhesive composition of the present invention is lowered. The light leakage resistance and the durability of the pressure-sensitive adhesive layer decrease.

(a-2) hydroxy group-containing (meth) acrylic monomer

The hydroxyl group containing (meth) acryl monomer (henceforth a "component (a-2)") which concerns on this invention is an acryl monomer which has a hydroxyl group in a molecule | numerator. Specific examples of the hydroxy group-containing (meth) acryl monomer include, but are not limited to, the following: 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,6-hexanediol Mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, tri Methylolethane di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4- Hydroxycyclohexyl (meth) acrylate, N-2-hydroxyethyl (meth) acrylamide, cyclohexanedimethanol monoacrylate, and the like, and alkylglycidyl ether and allyl Rayisi there may be mentioned ether, articles rayisi dill (meth) containing articles, such as group-rayisi acrylate compound and a (meth) compounds and the like obtained by the addition reaction of acrylic acid. These may be used independently or may be used in combination of 2 or more type.

Among these, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, N-2-hydroxyethyl (meth) acrylamide, and cyclohexane dimethanol monoacrylate are preferable, and 2 -Hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and N-2-hydroxyethyl (meth) acrylamide are more preferable.

The usage-amount of the hydroxyl group containing acrylic monomer is 0-9 mass parts. When the amount of use exceeds 9 parts by mass, the hydroxy group in the copolymer (A) becomes excessive and the crosslinking point generated by the reaction between the hydroxy group and the carbodiimide crosslinking agent (C) becomes excessive, so that the flexibility of the pressure-sensitive adhesive composition of the present invention The light leakage resistance and durability of the pressure-sensitive adhesive layer decreases.

(a-3) (meth) acrylic acid ester monomer

A (meth) acrylic acid ester monomer (henceforth a "component (a-3)" is ester of (meth) acrylic acid which does not have a hydroxyl group in a molecule | numerator. Although it does not restrict | limit to the following as a specific example of a (meth) acrylic acid ester monomer, Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (Meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n -Octyl (meth) acrylate, tert-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, Stearyl (meth) acrylate, isostearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, dodecyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclo Heck (Meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, butoxymethyl (meth) acrylate , 3-methoxybutyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 4-butylphenyl (Meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene oxide monoalkyl ether (Meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate, trifluoroethyl (meth) acrylate, pentadecafluorooxyethyl (meth) acrylate , 2-chloroethyl (meth) acrylic The rate, 2, 3- dibromo propyl (meth) acrylate, tribromophenyl (meth) acrylate, etc. are mentioned. These may be used independently or may be used in combination of 2 or more type.

Among these, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Methyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are more preferable.

The usage-amount of the (meth) acrylic acid ester monomer (a-3) is 99.9-82 mass parts.

The manufacturing method of a (meth) acryl copolymer (A) is not specifically limited, Conventionally, such as solution polymerization method, emulsion polymerization method, suspension polymerization method, reverse phase suspension polymerization method, thin film polymerization method, spray polymerization method using a polymerization initiator, etc. Known methods can be used. As a polymerization control method, adiabatic polymerization method, temperature controlled polymerization method, isothermal polymerization method, etc. are mentioned. Moreover, in addition to the method of starting superposition | polymerization with a polymerization initiator, the method of irradiating radiation, an electron beam, an ultraviolet-ray, etc., and initiating superposition | polymerization can also be employ | adopted. Among these, the solution polymerization method using a polymerization initiator is preferable because molecular weight can be easily adjusted and impurities can be reduced. For example, using ethyl acetate, toluene, methyl ethyl ketone, or the like as a solvent, the polymerization initiator is preferably added at 0.01 to 0.50 parts by mass to 100 parts by mass of the total amount of the monomers, for example, under a nitrogen atmosphere. It is obtained by making it react for 3 to 10 hours at 60-90 degreeC of reaction temperature. As said polymerization initiator, For example, Azo compounds, such as azobisisobutyronitrile (AIBN), 2,2'- azobis (2-methyl-butyronitrile), azobiscyano valeric acid; tert-butylperoxy pivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, di-tert-butylperoxide, cumene hydroperoxide, benzoyl peroxide, tert-butylhydride Organic peroxides such as loperoxide; Inorganic peroxides, such as hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate, are mentioned. These may be used independently or may be used together 2 or more types.

As needed, the other monomer copolymerizable with the said component (a-1)-(a-3) can be used. The other monomers are not particularly limited, and specific examples thereof include acrylic monomers having epoxy groups such as glycidyl (meth) acrylate and methylglycidyl (meth) acrylate; Amino groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, N-tert-butylaminoethyl (meth) acrylate, and methacryloxyethyltrimethylammonium chloride (meth) acrylate Having an acrylic monomer; Acrylic monomer which has amide groups, such as (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N, N-methylene bis (meth) acrylamide; Acrylic monomer which has phosphoric acid groups, such as 2-methacryloyloxyethyl diphenyl phosphate (meth) acrylate, a trimethacryloyloxy ethyl phosphate (meth) acrylate, and a triacryloyloxyethyl phosphate (meth) acrylate ; Acrylic monomers having sulfonic acid groups such as sodium sulfopropyl (meth) acrylate, sodium 2-sulfoethyl (meth) acrylate and sodium 2-acrylamide-2-methylpropane sodium sulfonate; Acrylic monomers having urethane groups such as urethane (meth) acrylates; acryl vinyl monomers having a phenyl group such as p-tert-butylphenyl (meth) acrylate and o-biphenyl (meth) acrylate; 2-acetoacetoxyethyl (meth) acrylate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (-methoxyethyl) silane, vinyltriacetylsilane, methacryloyloxypropyltrimethoxysilane, etc. Vinyl monomers having a silane group of; Styrene, chloro styrene, -methyl styrene, vinyltoluene, vinyl chloride, vinyl acetate, vinyl propionate, acrylonitrile, vinylpyridine, and the like. These other monomers may be used independently or may be used in combination of 2 or more type.

Among these other monomers, (meth) acrylamide, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate and vinyl acetate are preferable, and (meth) ) Acrylamide and vinyl acetate are more preferred.

It is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of total amounts of components (a-1)-(a-3), and, as for the usage-amount when using another monomer, it is more preferable that it is 0.2-5 mass parts, It is more preferable that it is 3 mass parts.

The weight average molecular weight (Mw) of the (meth) acryl copolymer (A) obtained by copolymerizing each said component is 100,000-2 million g / mol. If the weight average molecular weight is less than 100,000 g / mol, heat resistance is insufficient. On the other hand, when a weight average molecular weight exceeds 2 million g / mol, adhesiveness is low and adhesiveness falls. In addition, in this specification, the weight average molecular weight shall employ | adopt the polystyrene conversion value measured by the method as described in an Example.

 In addition, the sum total of the usage-amount of the said component (a-1) and a component (a-2) is not 0 mass part. That is, it means that at least one of the structural unit derived from component (a-1) and the structural unit derived from component (a-2) is necessarily contained in 0 of (meth) acryl copolymer (A). And the total amount of component (a-1), component (a-2), and component (a-3) shall be 100 mass parts.

The said component (A) may be used independently, or may be used in combination of 2 or more type of polymer.

(B) peroxide crosslinking agent

The adhesive composition of this invention contains a peroxide crosslinking agent (henceforth a "component (B)" in addition to the said component (A). Radicals generate | occur | produce by heating, a peroxide crosslinking agent performs hydrogen extraction of a (meth) acryl copolymer, radicals generate | occur | produce in a (meth) acryl copolymer, and the part reacts, and forms a crosslinked structure.

The peroxide crosslinking agent used in the present invention is not particularly limited. Specifically, for example, di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate, t-butylperoxy Neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutyl peroxy- 2-ethylhexanoate, di (4-methylbenzoyl) peroxide, benzoyl peroxide, t-butyl peroxy butyrate, etc. are mentioned.

Among these, in consideration of the crosslinking reaction efficiency, di (4-t-butylcyclohexyl) peroxydicarbonate, dilauroyl peroxide and benzoyl peroxide are preferable, and di (4-t-butylcyclohexyl) peroxycarbonate And benzoyl peroxide are more preferable.

The compounding quantity of a component (B) is 0.1-1 mass part with respect to 100 mass parts of components (A), More preferably, it is 0.2-0.8 mass part. If it is in this range, an appropriate crosslinked structure can be formed and further excellent heat resistance can be achieved. If the compounding quantity of the said peroxide crosslinking agent (B) is less than 0.1 mass part, sufficient crosslinked structure cannot be formed and heat resistance will fall. On the other hand, when it exceeds 1 mass part, a crosslinking reaction will advance too much and adhesive force will fall, and it will be impossible to follow shrinkage of a polarizing plate with time, and light leakage resistance and durability will fall.

The said component (B) may be used independently, or may be used in combination of 2 or more type.

(C) carbodiimide crosslinking agent

In addition to the said component (A) and (B), the adhesive composition of this invention contains a carbodiimide crosslinking agent (henceforth a "component (C)"). A carbodiimide crosslinking agent reacts and couple | bonds with the hydroxyl group and / or carboxyl group in the said (meth) acryl copolymer (A), and forms a crosslinked structure.

The carbodiimide crosslinking agent (C) used in the present invention is not particularly limited. Specifically, for example, a compound having two or more carbodiimide groups (-N = C = N-) in a molecule is preferably used, and it is possible to use known polycarbodiimide.

Moreover, as a carbodiimide compound, the high molecular weight polycarbodiimide produced | generated by decarbonation condensation reaction of diisocyanate in presence of a carbodiimide-ized catalyst can also be used.

As such a compound, what carried out the decarboxylation condensation reaction of the following diisocyanate is mentioned.

As diisocyanate, 4,4'- diphenylmethane diisocyanate, 3,3'- dimethoxy-4,4'- diphenylmethane diisocyanate, 3,3'-di Methyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylether diisocyanate, 3,3'-dimethyl-4,4'-diphenylether diisocyanate 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, One or a mixture of two or more of 4,4'-dicyclohexylmethane diisocyanate, tetramethylxylene diisocyanate can be used.

Examples of the carbodiimidation catalyst include 1-phenyl-2-phosphorene-1-oxide, 3-methyl-2-phosphorene-1-oxide, 1-ethyl-3-methyl-2-phosphorene-1-oxide, Phosphorene oxides, such as 1-ethyl-2-phosphorene-1-oxide or these 3-phosphorene isomers, can be used.

Such high molecular weight polycarbodiimide may be synthesized or a commercial item may be used. As a commercial item of the component (C), the carbodilite (trademark) series which is a Nisshinbo Chemical Co., Ltd. product is mentioned, for example. Among them, carbodilite (registered trademark) V-01, V-03, V-05, V-07, and V-09 are preferable because they are excellent in compatibility with an organic solvent.

The said component (C) may be used independently, or may be used in combination of 2 or more type.

The compounding quantity of a component (C) is 0.05-5 mass parts with respect to 100 mass parts of components (A). If it is in this range, an appropriate crosslinked structure can be formed, and excellent heat resistance can be further achieved. In addition, the crosslinking effect of a peroxide crosslinking agent can be promoted. For this reason, the adhesive composition of this invention can exhibit practical adhesive performance immediately after adhesive processing (within 10 minutes after completion of an adhesion process), and can improve productivity significantly. When the compounding quantity of the said carbodiimide crosslinking agent (C) is less than 0.05 mass part, sufficient crosslinked structure cannot be formed and heat resistance falls. In addition, a specific aging (aging) time is required until the practical adhesion performance is reached after the adhesion processing without sufficiently promoting the crosslinking effect of the peroxide crosslinking agent. On the other hand, when it exceeds 5 mass parts, a crosslinking reaction will advance too much and adhesive force will fall, and it will be impossible to follow shrinkage of a polarizing plate with time, and light leakage resistance and durability will fall.

(D) isocyanate crosslinking agent

In addition to the said component (A), (B), and (C), the adhesive composition of this invention may also contain an isocyanate crosslinking agent (D) (henceforth a "component (D)"). By adding an isocyanate crosslinking agent (D), the durability of the adhesive layer obtained can be improved more.

Component (D) used in the present invention is not particularly limited. Specifically, triallyl isocyanate, dimer acid diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diiso, for example Cyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4 '-MDI), 1,4-phenylene diisocyanate, xylylene diisocyanate (XDI), tetramethylxylidene diisocyanate (TMXDI), tolidine diisocyanate (TODI ) And aromatic diisocyanates such as 1,5-naphthalene diisocyanate (NDI); Aliphatic diisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate methyl (NBDI) Ryu; Alicyclic diisocyanates such as transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H6-XDI (hydrogenated XDI), H12-MDI (hydrogenated MDI) Nates; Carbodiimide-modified diisocyanates of the diisocyanates; Or these isocyanurate modified diisocyanates etc. are mentioned. Moreover, the adduct of the said isocyanate compound and polyol compounds, such as a trimethylol propane, the beret body and the isocyanurate body of these isocyanate compounds can also be used suitably.

The said component (D) may be synthesize | combined, and a commercial item may be used. As a commercial item of a component (C), for example, Coronate (trademark) L, Coronate (trademark) HL, Coronate (registered trademark) 2030, Coronate (registered trademark) 2031 (above, Nippon Polyurethane Co., Ltd.) Product), Takeate (registered trademark) D-102, Takeate (registered trademark) D-110N, Takeate (registered trademark) D-200, Takenate (registered trademark) D-202 (above, Mitsui Kagaku Co., Ltd.) Duranate (trademark) 24A-100, Duranate (trademark) TPA-100, Duranate (trademark) TKA-100, Duranate (trademark) P301-75E, Duranate (trademark) E402-90T, Duranate (Trademark) E405-80T, a duranate (trademark) TSE-100, a duranate (trademark) D-101, a duranate (trademark) D-201 (above, Asahi Kasei Chemical Co., Ltd.), etc. are mentioned.

Among these components (D), Coronate (registered trademark) L, Coronate (registered trademark) HL, Takenate (registered trademark) D110N, Duranate (trademark) 24A-100, and Duranate (trademark) TPA-100 are preferable. And, coronate (L) L and duranate (trademark) 24A-100 are more preferable.

The said component (D) may be used independently, or may be used in combination of 2 or more type.

It is preferable that the usage-amount when using a component (D) is 0.05-5 mass parts with respect to 100 mass parts of components (A). If it is this range, the adhesive composition of this invention can have favorable durability. The said compounding quantity becomes like this. More preferably, it is 0.07-4 mass parts, More preferably, it is 0.1-3 mass parts.

(E) imidazole compound

The adhesive composition of this invention may also contain an imidazole compound (henceforth a "component (E)") in addition to the said component (A)-(C) and if necessary the said component (D). The imidazole compound is considered to play a role of, for example, a crosslinking (curing) accelerator for the carbodiimide crosslinking agent (C), and the pressure-sensitive adhesive of the present invention using a carbodiimide crosslinking agent (C) and an imidazole compound (E) in combination The composition reaches practical adhesive properties in a short aging time, and is excellent in productivity.

The imidazole compound used in the present invention is represented by the following formula (1).

[Formula 1]

In said Formula (1), R <^1> , R <^2> and R <^3> are respectively independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1-C10 linear or branched alkyl group.

As an example of the said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned, for example.

As an example of a C1-C10 linear or branched alkyl group, For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- butyl group , n-pentyl group, iso-amyl group, tert-pentyl group, neopentyl group, n-hexyl group, 3-methylpentan-2-yl group, 3-methylpentan-3-yl group, 4-methylpentyl group, 4 -Methylpentan-2-yl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 3,3-dimethylbutan-2-yl group, n-heptyl group, 1-methylhexyl group, 3 -Methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 1- (n-propyl) butyl group, 1,1-dimethylpentyl group, 1,4-dimethylpentyl group , 1,1-diethylpropyl group, 1,3,3-trimethylbutyl group, 1-ethyl-2,2-dimethylpropyl group, n-octyl group, 2-ethylhexyl group, 2-methylhexane- 2-yl group, 2,4-dimethylpentan-3-yl group, 1,1-dimethylpentan-1-yl group, 2,2-dimethylhexane-3-yl group, 2,3-dimethylhexane-2- Diary, 2,5-dimethylhexane-2-yl group, 2,5-di Butylhexane-3-yl group, 3,4-dimethylhexane-3-yl group, 3,5-dimethylhexane-3-yl group, 1-methylheptyl group, 2-methylheptyl group, 5-methylheptyl group, 2 -Methylheptan-2-yl group, 3-methylheptan-3-yl group, 4-methylheptan-3-yl group, 4-methylheptan-4-yl group, 1-ethylhexyl group, 2-ethylhexyl group, 1-propyl Pentyl group, 2-propylpentyl group, 1,1-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 1-ethyl-1-methylpentyl group, 1-ethyl- 4-methylpentyl group, 1,1,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 1-isopropyl-1,2-dimethylpropyl group, 1,1,3,3- Tetramethylbutyl group, n-nonyl group, 1-methyloctyl group, 6-methyloctyl group, 1-ethylheptyl group, 1- (n-butyl) pentyl group, 4-methyl-1- (n-propyl) phene Tilyl group, 1,5,5-trimethylhexyl group, 1,1,5-trimethylhexyl group, 2-methyloctan-3-yl group, n-decyl group, 1-methylnonyl group, 1-ethyloctyl group, 1- (n-butyl) hexyl group, 1,1-dimethyloctyl group, 3,7-dimethyloctyl group, etc. are mentioned.

The alkyl group may be substituted with another substituent. As an example of a substituent, For example, Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom; Alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group; Aryl groups such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, and phenanthryl group; Alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; Aryloxy groups such as phenoxy group and p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group and phenoxycarbonyl group; Acyloxy groups such as acetoxy group, propionyloxy group, methacryloyloxy group and benzoyloxy group; Acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group; Alkylamino groups such as methylamino group and cyclohexylamino group; Dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group, and piperidino group; In addition to arylamino groups, such as a phenylamino group and p-tolylamino group, a hydroxyl group, a carboxy group, a formyl group, an amino group, a nitro group, a cyano group, a trifluoromethyl group, a trichloromethyl group, etc. are mentioned.

As specific examples of the imidazole compound, for example, imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 1-ethylimidazole, 2-ethylimidazole 4-ethylimidazole, 1-propylimidazole, 2-propylimidazole, 4-propylimidazole, 1-butylimidazole, 2-butylimidazole, 4-butylimidazole, 1-pentylimidazole, 2-pentylimidazole, 4-pentylimidazole, 1-hexylimidazole, 2-hexylimidazole, 4-hexylimidazole, 1-heptylimidazole, 2 -Heptylimidazole, 4-heptylimidazole, 1-octylimidazole, 2-octylimidazole, 4-octylimidazole, 1-nonylimidazole, 2-nonylimidazole, 4- Nonylimidazole, 1-decylimidazole, 2-decylimidazole, 4-decylimidazole, 1,2-dimethylimidazole, 1,2-diethylimidazole, 1-ethyl- 2-methylimidazole, 2-ethyl-4-methylimidazole, 1,4-dimethylimidazole, 1,5-dimethylimidazole, 1,2,4-trimethylimidazole, To 1,4-dimethyl-2- Imidazol, imidazol-2-fluoro, and the like can be mentioned imidazole-4-fluorophenyl, 2-feeders imidazole, 4 feeders imidazole, 2-iodo-imidazole, 4-iodo-imidazole.

Among these imidazole compounds, a compound in which at least one of R ¹ , R ^2, and R ³ is a C 1-10 linear or branched alkyl group is preferable from the viewpoint of productivity and price, and 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-butylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole are more preferable.

It is preferable that the compounding quantity of a component (E) is 0.005-0.2 mass part with respect to 100 mass parts of components (A). If it is this range, sufficient hardening promoting effect can be achieved, it can mature in a short time after crosslinking, and sufficient adhesive force can be achieved. The said compounding quantity becomes like this. More preferably, it is 0.007-0.2 mass part, More preferably, it is 0.01-0.2 mass part, Especially preferably, it is 0.01-0.15 mass part.

The said component (E) may be used independently and may be used in combination of 2 or more type. Moreover, the said component (E) may use a commercial item, and may use a synthetic product.

Moreover, the adhesive composition of this invention may contain a silane coupling agent (henceforth a "component (F)") in addition to the said component. By using a silane coupling agent, reactivity can be improved and the mechanical strength and adhesive force of a crosslinked material can be improved. Such a silane coupling agent is not particularly limited. Specifically, for example, methyl trimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, ethyltrimethoxysilane, diethyldiethoxysilane, n- Butyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, vinyltrichlorosilane, vinyl Trimethoxysilane, vinyltriethoxysilane, vinyl tris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-metha Krilloxypropylmethyldiethoxy Silane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl- γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis- (3- [triethoxysilyl] Propyl) tetrasulfide, (gamma) -isocyanatopropyl triethoxysilane, etc. are mentioned. Moreover, the silane coupling agent which has functional groups, such as an epoxy group (glycidoxy group), an amino group, a mercapto group, and a (meth) acryloyl group, the silane coupling agent containing the functional group reactive with these functional groups, another coupling agent, poly The compound which has a hydrolyzable silyl group obtained by making isocyanate etc. react with arbitrary functional groups at arbitrary ratios can also be used.

Moreover, as a component (F), you may use a silane coupling agent oligomer. The silane coupling agent oligomer condenses at least two silane compounds having at least an alkoxy group to form a -Si-O-Si-structure, at least one alkoxy group is bonded to the silicon atom, and has an organic functional group in the molecule. Compound.

As an organic functional group, a vinyl group, an epoxy group, a styryl group, a (meth) acryloyl group, a methacryloxy group, an acryloxy group, an amino group, a ureido group, a chloropropyl group, a mercapto group, a polysulfide group etc. are mentioned, for example. Can be. Among these, an epoxy group, a mercapto group, and a (meth) acryloyl group are preferable, and an epoxy group and a mercapto group are preferable in order to make both the improvement of durability of the adhesive layer obtained, and the realization of low adhesiveness compatible.

As the silane coupling agent oligomer, a dimer having 2 silicon atoms in one molecule may be used, up to about 100 silicon atoms in one molecule, that is, having an average degree of polymerization of 2 to 100. When the average degree of polymerization increases, the viscosity of the silane coupling agent oligomer increases, which may result in a paste form or a solid form, and thus becomes difficult to handle. Therefore, the average degree of polymerization is preferably 2 to 80, more preferably 3 to 50.

The organic functional group contained in a silane coupling agent oligomer is normally couple | bonded with the silicon atom via the appropriate coupling group. As the linking group, a divalent hydrocarbon group having an aromatic ring such as an alkylene group such as methylene group, ethylene group, trimethylene group, hexamethylene group, decamethylene group and methylphenylethyl group, methoxymethyl group, methoxyethyl group, methoxy And divalent aliphatic groups having an oxygen atom such as a propyl group. In addition, when an organic functional group is an epoxy group, the functional group may be formed between two adjacent carbon atoms which comprise a ring.

The silane coupling agent oligomer may be, for example, a co-oligomer obtained by partially cohydrolytic polycondensation of the silane compound and tetraalkoxysilane represented by the following formula (2).

[Formula 2]

In said Formula (2), R <^4> and R <^5> represents an alkyl group or a phenyl group each independently, X represents the organic group which has a mercapto group, an epoxy group, or a (meth) acryloyloxy group, Y represents an alkyl group, an alkoxy group, and a phenyl group , Phenoxy group, aralkyl group or aralkyloxy group.

In the above formula, the alkyl group represented by R ⁴ and R ⁵ is, for example, 1 to 10 carbon atoms. In particular, compounds in which R ⁴ and R ⁵ are each independently a methyl group or an ethyl group are appropriately used.

As a specific example of the organic functional group represented by X, for example, a mercaptomethyl group, 3-mercaptopropyl group, 6-mercaptohexyl group, 10-mercaptodecyl group, 2- (4-mercaptomethylphenyl) ethyl group, glycish Doxymethyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, acryloyloxymethyl group, 3-acryloyloxypropyl group, methacryloyloxymethyl group, 3-methacryl Royloxypropyl group etc. are mentioned.

The alkyl group and the alkoxy group represented by Y are preferably 1 to 10 carbon atoms, and the aralkyl and aralkyloxy groups are preferably 7 to 10 carbon atoms.

As a specific example of the functional group containing silane compound represented by the said Formula (2), For example, mercaptomethyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 2- (4 -Mercaptomethylphenyl) ethyltrimethoxysilane, 6-mercaptohexyltrimethoxysilane, 10-mercaptodecyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldie Methoxysilane, glycidoxymethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxy Silane, acryloyloxymethyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, methacryloyloxymethyltrimethoxysilane, 3-metha Chryloyloxypropyltrimethoxysilane, 3 -Methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltributoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxy Silane, 3-methacryloyloxypropylmethyl diethoxysilane, etc. are mentioned.

In the tetraalkoxy silane which is partially cohydrolyzed polycondensation with the functional group containing silane compound represented by the said Formula (2), C1-C10 is preferable for the four alkoxy groups couple | bonded with a silicon atom. The four alkoxy groups couple | bonded with the silicon atom may be the same all, and the other alkoxy group may couple | bond with the silicon atom. From the point of easiness of manufacture or acquisition, the compound in which the same alkoxy group couple | bonds with the silicon atom is preferable, Specifically, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc. are mentioned. Can be.

When the silane coupling agent oligomer is formed by partial cohydrolysis polycondensation of the functional group-containing silane compound represented by the above formula (2) with tetraalkoxysilane, -OR ⁴ and-which are bonded to the silicon atom in the above formula (2) A silanol group formed by partially hydrolyzing an alkoxysilyl group or a phenoxysilyl group of OR ⁵ and a silanol group formed by partially hydrolyzing an alkoxysilyl group in a tetraalkoxy silane condensed to form a silane coupling agent oligomer. . Such an oligomer is preferable because the pressure-sensitive adhesive composition tends to be difficult to scatter in the coating and drying step of the pressure-sensitive adhesive.

When the silane coupling agent oligomer which can be used in this invention is represented by the combination of monomers, the following are mentioned, for example.

As the mercaptomethyl group-containing oligomer, mercaptomethyltrimethoxysilane-tetramethoxysilane cooligomer, mercaptomethyltrimethoxysilane-tetraethoxysilane cooligomer, mercaptomethyltriethoxysilane-tetramethoxysilane Co oligomer, mercaptomethyl triethoxysilane- tetraethoxysilane co oligomer, etc. are mentioned.

As the mercaptopropyl group-containing oligomer, 3-mercaptopropyltrimethoxysilane-tetramethoxysilane cooligomer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane cooligomer, 3-mercaptopropyltrie And methoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer, and the like.

As a glycidoxy methyl group containing oligomer, it is glycidoxy methyl trimethoxysilane-tetramethoxysilane copolymer, glycidoxy methyl trimethoxysilane-tetraethoxysilane co oligomer, glycidoxy methyl triethoxysilane- Tetramethoxysilane co oligomer, glycidoxy methyl triethoxysilane- tetraethoxysilane co oligomer, etc. are mentioned.

As a glycidoxy propyl group containing co-oligomer, 3-glycidoxy propyl trimethoxysilane-tetramethoxysilane co oligomer, 3-glycidoxy propyl trimethoxysilane-tetraethoxysilane co-oligomer, 3-glycidoxy Doxypropyl triethoxysilane- tetramethoxysilane co oligomer, 3-glycidoxy propyl triethoxysilane- tetraethoxysilane co oligomer, etc. are mentioned.

As the methacryloyloxypropyl group-containing oligomer, 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane -Tetramethoxysilane cooligomer, 3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane cooligomer, 3-acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane cooligomer, 3- Acryloyloxypropyl group containing co-oligomers, such as acryloyloxypropylmethyl diethoxysilane- tetraethoxysilane co oligomer, 3-methacryloyloxypropyl trimethoxysilane- Trimethoxysilane Co-Oligomer, 3-Methacryloyloxypropyltrimethoxysilane-Tetraethoxysilane Co-Oligomer, 3-Methacryloyloxypropyltriethoxysilane-Tetramethoxysilane Co-Oligomer, 3-Meta Chryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxy Silane-tetraethoxysilane cooligomer, 3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane cooligomer, 3-methacryloyloxypropylmethyldiethoxysilane-tetraethoxysilane cooligomer Etc. can be mentioned.

The said silane coupling agent may synthesize | combine or may use a commercial item. As a commercial item of a silane coupling agent, it is KBM-303, KBM-403, KBE-402, KBE-403, KBE-502, KBE-503, KBM-5103, KBM-573, KBM-802, KBM-803, for example. , KBE-846, KBE-9007 (above, Shin-Etsu Chemical Co., Ltd. product); X-41-1805, a silane coupling agent oligomer having a mercapto group, a methoxy group and an ethoxy group, X-41-1810, a silane coupling agent oligomer having a mercapto group, a methyl group and a methoxy group, an epoxy group having a methoxy group and an ethoxy group X-41-1053 which is an silane coupling agent oligomer, X-41-1058 which is a silicone silane coupling agent which has an epoxy group, a methyl group, and a methoxy group etc. (all are brand names, all are Shin-Etsu Chemical Co., Ltd. product) are mentioned.

 Among these silane coupling agents, KBM-303, KBM-403, KBE-402, KBE-403, KBM-5103, KBM-573, KBM-802, KBM-803, KBE-846, KBE-9007, X-41- 1805 and X-41-1810 are preferable, and KBM-403 and X-41-1810 are more preferable. In addition, the said silane coupling agent may be used independently, and may be used in combination of 2 or more type.

In the present invention, the amount of the silane coupling agent used is not particularly limited. Specifically, the amount of use when the silane coupling agent (F) is used is preferably 0.03 to 1 part by mass, more preferably 0.05 to 0.5 part by mass, even more preferably based on 100 parts by mass of the component (A). Is 0.1-0.3 mass parts. If it exists in this range, the outstanding heat resistance and adhesiveness can be exhibited.

The pressure-sensitive adhesive composition of the present invention, in addition to the silane coupling agent or in place of the silane coupling agent, curing accelerators, ionic liquids, lithium salts, inorganic fillers, softeners, antioxidants, antioxidants, stabilizers, tackifying resins, modified Resins (polyol resins, phenol resins, acrylic resins, polyester resins, polyolefin resins, epoxy resins, epoxidized polybutadiene resins, etc.), leveling agents, antifoaming agents, plasticizers, dyes, pigments (colored pigments, extender pigments, etc.), Additives such as treatment agents, sunscreens, fluorescent brighteners, dispersants, thermal stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, lubricants and solvents may be included. Among these, as a hardening accelerator, a dibutyltin dilaurate, JCS-50 (made by Johoku Chemical Co., Ltd.), formate TK-1 (made by Mitsui Chemical Co., Ltd.), etc. are mentioned, for example. As the ionic liquid, for example, phosphonium ions, pyridinium ions, pyrrolidinium ions, imidazolium ions, guanidinium ions, ammonium ions, isoronium ions, thiuronium ions, piperidinium ions, As cationic components such as pyrazolium ions and sulfonium ions, and anion components, halogen ions, nitrate ions, sulfate ions, phosphate ions, perchlorate ions, thiocyanate ions, thiosulfate ions, sulfite ions, tetrafluoroborate ions, The substance which has an anion component, such as a hexafluoro phosphate ion, a formate ion, an oxalic acid ion, an acetate ion, a trifluoroacetic acid ion, an alkylsulfonic acid ion, is mentioned. As the antioxidant, for example, dibutyl hydroxytoluene (BHT), Irganox (registered trademark) 1010, Irganox (registered trademark) 1035FF, Irganox (registered trademark) 565 (both BASF Japan Co., Ltd.) Products). As tackifying resin, rosin, such as rosin acid, polymeric rosin acid, and rosin acid ester, terpene resin, terpene phenol resin, aromatic hydrocarbon resin, aliphatic saturated hydrocarbon resin, petroleum resin, etc. are mentioned, for example. Although the usage-amount of an additive in the case of using the said additive is not restrict | limited, For example, it is 0.1-20 mass parts with respect to 100 mass parts of total amounts of the said component (A)-(C).

The pressure-sensitive adhesive composition of the present invention is stirred so as to be a uniform mixture by mixing each component described above in a batch, sequentially mixing each component, or mixing any of a plurality of components and then mixing the remaining components. It can manufacture by doing. More specifically, if necessary, it can be prepared by heating to a temperature of, for example, 20-40 ° C, and stirring, for example, for 5 minutes to 5 hours until homogeneous with a stirrer or the like.

The viscosity of the pressure-sensitive adhesive composition of the present invention is not particularly limited. However, in consideration of ease of coating, ease of control of the film thickness of the pressure-sensitive adhesive layer formed of the composition, and the like, the viscosity immediately after the mixing at 25 ° C. (within 10 minutes after mixing the respective components for a predetermined time) is preferable. It is 300? 7000m㎩s. For example, when using as an adhesive of an optical member, the viscosity immediately after mixing | blending at 25 degreeC (within 10 minutes after mixing each component for predetermined time), More preferably, it is 2000-6000 mPa * s, More preferably, Is 2500? 5000m㎩? S. For example, when using as an adhesive of a surface protection film, the viscosity immediately after mix | blending in 25 degreeC (within 10 minutes after mixing each component for predetermined time), More preferably, it is 350-5000 mPa * s, More preferably It is 400–4000m㎩s. For example, when using as an adhesive of an adhesive sheet, the viscosity just after mixing | blending in 25 degreeC (within 10 minutes after mixing each component for predetermined time) becomes like this. More preferably, it is 350-6800 mPa * s, More preferably, Is 400-6500 m²? S. In addition, in this specification, a viscosity shall employ | adopt the value measured by the method as described in the Example mentioned later.

The adhesive composition of this invention suppresses excessive viscosity rise and gelation of the adhesive composition after composition preparation, and has the outstanding pot life.

The pot life can be evaluated by comparing the viscosity of the composition immediately after preparing the pressure-sensitive adhesive composition with the viscosity of the composition 12 hours after the preparation. That is, it is preferable that the composition after 12 hours pass after preparation does not gelatinize, and it is more preferable that the viscosity of the composition after 12 hours pass after preparation is a raise within 50% with respect to the viscosity of the composition immediately after preparing an adhesive composition. Do. If it is such range, it will become the adhesive composition which has the outstanding workability.

In addition, in this specification, "immediately after" after "preparing an adhesive composition" at the time of defining the said viscosity means within 10 minutes. That is, "the viscosity of the composition immediately after preparing an adhesive composition" means the viscosity measured within 10 minutes after completion | finish of preparation of an adhesive composition (mixing each component for predetermined time).

The pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition of the present invention is obtained by crosslinking the above pressure-sensitive adhesive composition. In that case, although crosslinking of an adhesive composition is generally performed after application | coating of an adhesive composition, it is also possible to transfer the adhesive layer which consists of an adhesive composition after crosslinking to a base material etc .. The crosslinking of the pressure-sensitive adhesive composition is usually performed for 1 to 5 minutes under conditions of a temperature of 70 to 140 ° C.

The pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition of the present invention reaches practical adhesive performance in a short period of time immediately after crosslinking (adhesive processing) (no aging step). The practical adhesion performance of the said adhesive layer is the gel fraction of the adhesive layer immediately after bridge | crosslinking (adhesion process), and the gel powder of the adhesive layer after leaving for 7 days in 23 degreeC and 50% RH atmosphere after the said bridge | crosslinking (adhesion process). It can evaluate by comparing. That is, the gel fraction after being left for 7 days is preferably a gel fraction ± 15% immediately after crosslinking (adhesive processing), more preferably a gel fraction ± 10% immediately after crosslinking (adhesive processing), and crosslinking (adhesive processing). It is still more preferable that it is gel fraction +/- 5% immediately after), and it is especially preferable that it is gel fraction +/- 3% immediately after bridge | crosslinking (adhesion process). If it is such range, it will become the adhesive composition which productivity improved significantly. The said gel fraction shall employ | adopt the value measured by the method as described in the Example mentioned later.

In addition, in this specification, "immediately" immediately after "crosslinking (adhesion process)" at the time of defining the said gel fraction means within 10 minutes. That is, the "gel fraction of the adhesive layer immediately after crosslinking (adhesion process)" means the gel fraction measured within 10 minutes after adhesion processing (drying (crosslinking) of the adhesion layer at a predetermined temperature for a predetermined time). Similarly, "immediately after the polarizing plate preparation with an adhesive layer" means within 10 minutes after adhesive processing (drying (crosslinking) the application layer of the solution of an adhesive composition for a predetermined time, and forming an adhesive layer), It means to produce a sample for measurement in time.

The adhesive composition of this invention can be used for adhesion of various base materials. As a base material which can be used here, glass, a plastic film, paper, metal foil, etc. are mentioned. As glass, general inorganic glass is mentioned. Examples of the plastic in the plastic film include polyvinyl chloride resin, polyvinylidene chloride, cellulose resin, acrylic resin, cycloolefin resin, amorphous polyolefin resin, polyethylene, polypropylene, polystyrene, ABS resin, Polyamide, polyester, polycarbonate, polyurethane, polyvinyl alcohol, ethylene-vinyl acetate copolymer, chlorinated polypropylene, and the like. The amorphous polyolefin resin usually has a polymerized unit of a cyclic polyolefin such as norbornene or a polycyclic norbornene monomer, and may be a copolymer of a cyclic olefin and a linear cyclic olefin. Examples of commercially available amorphous polyolefin resins include trade names ATON (ARTON) of JSR Corporation, ZEONEX (registered trademark) of Nihon Xeon Corporation, ZEONOR (registered trademark), APO of Mitsui Kagaku Co., Ltd., and Apel (registered trademark). . In order to form amorphous polyolefin resin into a film and to form a film, well-known methods, such as a solvent casting method and a melt-extrusion method, can be used suitably. Examples of the paper include imitation paper, fine paper, kraft paper, art coated paper, caster coated paper, white rolled paper, parchment paper, water resistant paper, glassine paper, corrugated paper, and the like. As metal foil, aluminum foil etc. are mentioned, for example.

Therefore, this invention also provides the optical member, the surface protection film, and the adhesive sheet provided with the adhesive layer formed from the adhesive composition of this invention.

Hereinafter, although these uses are demonstrated in detail, the use of the adhesive composition of this invention is not limited to these uses at all.

<Optical member>

The pressure-sensitive adhesive composition of the present invention may be used by directly applying on one side or both sides of the optical member to form an adhesive layer. You may be. That is, this invention provides the optical member provided with the adhesive layer formed from the adhesive composition of this invention.

As an optical member of this invention, a polarizing plate, a retardation plate, the optical film for plasma displays, the conductive film for touch panels, etc. are mentioned preferably, for example. Among these, the adhesive composition of this invention is excellent in the adhesiveness of a polarizing plate and glass. Of course, this invention is not limited to the said form, It is also possible to use for the adhesion of another member.

When using the adhesive composition of this invention for the adhesive layer of an optical member, the component (A) contained in a composition contains 0-9 mass parts carboxyl group-containing monomer (a-1) and 0-1.8 mass parts hydroxyl group content ( It is preferable to contain the monomer component which consists of a meta) acryl monomer (a-2) and 99.9-8.2 mass parts of (meth) acrylic acid ester monomers (a-3), and a weight average molecular weight is 1 million-2 million g / mol. It is preferable.

In addition, the sum total of the usage-amount of the said component (a-1) and a component (a-2) is not 0 mass part. That is, it means that at least one of the structural unit derived from a component (a-1) and the structural unit derived from a component (a-2) is necessarily contained in the (meth) acryl copolymer (A). And the total amount of a component (a-1), a component (a-2), and a component (a-3) shall be 100 mass parts.

The usage-amount of the component (a-1) in the component (A) in an optical member use is 0 mass part (that is, it does not contain (a-1) component), or contains (a-1) component. In this case, it is more preferable that it is 0.1-9 mass parts, and it is still more preferable that it is 0.2-9 mass parts. In addition, the usage-amount of the component (a-2) in the component (A) in an optical member use is 0 mass part (that is, contains no (a-2) component), or (a-2) component. When it contains, it is more preferable that it is 0.05-1.8 mass parts, and it is still more preferable that it is 0.1-1.8 mass parts. Moreover, as for the usage-amount of the component (a-3) in the component (A) in an optical member use, it is more preferable that it is 99.9-90 mass parts, and it is still more preferable that it is 99.9-91 mass parts.

It is preferable that it is 0.05-10 mass parts, and, as for the sum total of the usage-amount of the component (a-1) in the component (A) and the usage-amount of the component (a-2) in an optical member use, it is more preferable that it is 0.1-9 mass parts. .

As for the weight average molecular weight of the component (A) in an optical member use, it is more preferable that it is 1 million-1.8 million g / mol, and it is still more preferable that it is 1.1 million-1.7 million g / mol.

Moreover, it is preferable that it is 0.15-0.9 mass part with respect to 100 mass parts of components (A), and, as for content of the component (B) in the adhesive composition for optical member uses, it is more preferable that it is 0.2-0.8 mass part. Moreover, it is preferable that it is 0.05-4 mass parts with respect to 100 mass parts of components (A), and, as for content of a component (C), it is more preferable that it is 0.05-3 mass parts. If it is such a range, as an adhesive composition for optical members, a pot life is long, it is excellent in workability, reaches | attains practical adhesive performance immediately after adhesive processing (crosslinking) process, and productivity improves significantly.

Moreover, it is preferable that it is 0.07-3 mass parts with respect to 100 mass parts of components (A), and, as for the usage-amount of the component (D) when using an isocyanate crosslinking agent as a component (D), it is more preferable that it is 0.1-2 mass parts. desirable.

It is preferable that it is 0.007-0.18 mass part with respect to 100 mass parts of component (A), and, as for the usage-amount of the component (E) when using an imidazole compound as a component (E), it is more preferable that it is 0.01-0.1 mass part.

In addition, in this use, it is preferable to contain a silane coupling agent (F) in a composition. Since the preferable specific example of a silane coupling agent (F), the preferable range of usage-amount, etc. are the same as the above, description is abbreviate | omitted here.

Coating of the adhesive composition for optical member use is not specifically limited, For example, a natural coater, a knife belt coater, a floating knife, a knife over roll, a knife on blanket, a spray, a dip, a kiss roll, a squeeze roll, a reverse roll, air Various coating methods using devices, such as a blade, a curtain flow coater, a doctor blade, a wire bar, a die coater, a coma coater, a baker applicator, and a gravure coater, are mentioned. Moreover, what is necessary is just to select the coating thickness (thickness after drying) of the adhesive composition at the time of using for an optical member according to the base material to be used, and a use, Preferably it is 5-35 micrometers, More preferably, it is 15-30 micrometers.

When using the adhesive composition of this invention for an optical member, it is preferable that the gel fraction of the adhesive layer in 23 degreeC and 50% RH atmosphere immediately after crosslinking (adhesion process) is 50 to 95%, and is 60 to 92%. It is more preferable, and it is still more preferable that it is 70 to 90%. If it is such a range, a punching process and a slit processing can be promptly performed as an optical member provided with an adhesive layer. In order to set a gel fraction as mentioned above, what is necessary is just to select conditions suitably, such as adjusting the monomer composition of component (A), the addition amount of component (B), and component (C) to the said range.

In the optical member of the present invention, the adhesive force of the pressure-sensitive adhesive layer formed on the optical member is preferably about 0.5 to 9 (N / 25 mm), and more preferably about 1 to 6 (N / 25 mm). If it is the adhesive force of this range, it may be advantageous to rework property. In addition, in this specification, an "adhesive force" is calculated | required by measuring according to the adhesive tape and the adhesive sheet test method of JISZ0237 (2000), More specifically, it measures according to the method described in the following Example.

The pressure-sensitive adhesive composition of the present invention used for the optical member has a long pot life, is excellent in workability, exhibits practical adhesive performance (in particular, an appropriate gel fraction) immediately after crosslinking (adhesive processing), and greatly improves productivity. In addition, the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition of the present invention used for the optical member has a suitable adhesive force and adhesiveness to the substrate for the optical member, and furthermore, metal corrosion inhibitory resistance, light leakage resistance, durability, adherend contamination resistance Excellent low temperature stability and rework.

<Surface protection film>

The adhesive composition of this invention can be used suitably also for a surface protection film, especially the surface protection film for optical members. That is, this invention provides the surface protection film provided with the adhesive layer formed from the adhesive composition of this invention.

It does not specifically limit as a protective film, A well-known protective film can be used similarly. For example, a film such as polyethylene terephthalate (PET), polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyester, polyvinyl chloride, polycarbonate, polyamide, polystyrene, or a composite film thereof Although it can use, polyethylene terephthalate is especially preferable. In addition, the protective film can use what has a thickness of 15-50 micrometers, for example.

Moreover, formation of the adhesive layer to a protective film is a method which apply | coats the adhesive composition of this invention directly to a protective film, and apply | coated and formed the adhesive composition of this invention to another base material (for example, a peeling liner etc.) once. Can be carried out by a method of transferring the same.

The surface protection film of this invention can be used for the use which protects the optical member adhering to flat display panels, such as a liquid crystal display panel and a plasma display panel. As an optical member, a polarizing plate, a phase difference plate, a brightness improving plate, an anti-glare sheet, etc. are included, for example. The optical member may be a laminate of two or more optical materials such as a laminate of a polarizing plate and a retardation plate, a laminate of a retardation plate, a laminate of a polarizing plate and a brightness enhancement plate, or an antiglare sheet. In addition, the surface protection film of the present invention can be used not only when the optical member is distributed alone, but also when the optical member is distributed in a state where the optical member is attached to the flat display panel.

When using the adhesive composition of this invention for the adhesive layer of a surface protection film, the component (A) contained in a composition contains 0-0.5 mass part carboxyl group-containing monomer (a-1) and 0.6-9 mass parts hydroxyl group content. It is preferable to contain the monomer component which consists of a (meth) acryl monomer (a-2) and 99.4-90.5 mass parts of (meth) acrylic acid ester monomers (a-3), and a weight average molecular weight is 100,000-1 million g / mol Is preferably. In addition, the total amount of a component (a-1), a component (a-2), and a component (a-3) shall be 100 mass parts.

The usage-amount of the component (a-1) in the component (A) in surface protection film uses is 0 mass part (that is, it does not contain (a-1) component), or contains (a-1) component. In that case, it is more preferable that it is 0.1-0.5 mass part. Moreover, as for the usage-amount of the component (a-2) in the component (A) in surface protection film uses, it is more preferable that it is 0.7-9 mass parts, and it is still more preferable that it is 1-9 mass parts. Moreover, it is more preferable that the usage-amount of the component (a-3) in the component (A) in surface protection film uses is 99.3-90.6 mass parts.

As for the sum total of the usage-amount of the component (a-1) in the component (A) and the usage-amount of the component (a-2) in a surface protection film use, it is more preferable that it is 0.7-9.4 mass parts, and it is still more that it is 0.8-9.3 mass part. desirable.

As for the weight average molecular weight of component (A) in surface protection film use, it is more preferable that it is 150,000-900,000 g / mol, and it is still more preferable that it is 200,000-850,000 g / mol.

Moreover, it is preferable that it is 0.15-0.9 mass part with respect to 100 mass parts of components (A), and, as for content of the component (B) in the adhesive composition for surface protection film uses, it is more preferable that it is 0.2-0.8 mass part. In addition, it is preferable that content of a component (C) is 0.1-5 mass parts with respect to 100 mass parts of components (A). If it is such a range, as an adhesive composition for surface protection films, a pot life is long, it is excellent in workability, a practical adhesive performance is reached immediately after bridge | crosslinking (adhesion process), and productivity improves significantly.

Moreover, as for the component (D), when using the isocyanate crosslinking agent, it is more preferable that it is 0.07-3 mass parts with respect to 100 mass parts of components (A), and it is 0.1-2.5 mass parts Even more preferred.

It is preferable that it is 0.007-0.18 mass part with respect to 100 mass parts of component (A), and, as for the usage-amount of the component (E) when using an imidazole compound as a component (E), it is more preferable that it is 0.01-0.1 mass part.

In addition, in this use, it is preferable that a silane coupling agent (F) is not contained in an adhesive composition.

The application method of the adhesive composition for surface protection film uses is not specifically limited, A conventionally well-known method can be used. Specifically, natural coater, knife belt coater, floating knife, roll coat, air knife coat, knife over roll, knife on blanket, spray, dip, kiss roll, squeeze roll, reverse roll, air blade, curtain flo coater, doctor blade And various coating methods using devices such as a wire bar, a die coater, a comma coater, a baker applicator, and a gravure coater. Among them, a roll coat, gravure coat, reverse coat, roll brush, spray coat, air knife coat, and die coat method are preferably used. Moreover, the coating thickness (thickness after drying) of the composition formed on a protective film is not specifically limited, It can select suitably according to a desired use. Preferably, the coating thickness (thickness of the adhesive layer: thickness after drying) of the composition formed on a protective film is 3-200 micrometers, More preferably, it is 10-100 micrometers, More preferably, it is 15-50 micrometers.

When using the adhesive composition of this invention for a surface protection film, it is preferable that the gel fraction of the adhesive layer in 23 degreeC and 50% RH atmosphere immediately after crosslinking (adhesion process) is 70 to 100%, and is 80 to 99% Is more preferable, and it is still more preferable that it is 85 to 98%. If it is such a range, a punching process and a slit process can be promptly performed as a surface protection film provided with an adhesive layer. In order to set a gel fraction as mentioned above, what is necessary is just to select conditions suitably, such as adjusting the monomer composition of component (A), the addition amount of component (B), and component (C) to the said range.

In the surface protection film of this invention, about 0.05-0.30 (N / 25mm) is preferable and, as for the adhesive force of the adhesive layer formed in the surface protection film, about 0.09-0.20 (N / 25mm) is more preferable. If it is the adhesive force of this range, it is advantageous for adherend contamination.

The pressure-sensitive adhesive composition of the present invention used for the surface protective film has a long pot life, is excellent in workability, exhibits practical adhesive performance (in particular, an appropriate gel fraction) immediately after crosslinking (adhesive processing), and productivity is greatly improved. In addition, the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition has an appropriate adhesive force and adhesion to a substrate, and is excellent in preventing metal corrosion, preventing corrosion, adherend contamination, low temperature stability, and transparency, and under high temperature and high pressure conditions (autoclave treatment). It suppresses and prevents foaming at the time).

<Adhesive sheet>

The adhesive composition of this invention can also be made into adhesive sheets, such as a sheet form and a tape form, by coating on a base material or a separator, performing a drying (crosslinking) process, and forming an adhesive layer. That is, this invention provides the adhesive sheet provided with the adhesive layer formed from the adhesive composition of this invention.

As a base material of an adhesive sheet, polyester films, such as a polyethylene terephthalate film (PET film), plastic films, such as a polypropylene film and a cellophane film, plastics, such as a polyurethane and ethylene-propylene terpolymer (EPT), and rubber foam Known various leaf members, such as paper and aluminum foil, are used. Depending on the material, the surface of these substrates may be subjected to a background treatment such as corona treatment, plasma treatment, easy formation of an adhesive layer, formation of an antistatic layer, or the like. Moreover, various things, such as the thing which peeled the surface of the plastic film similar to the said base material with peeling agents, such as a silicone type, a fluorine type, and a long-chain alkyl type, and the polypropylene film which did not perform this peeling process can be used for a separator. .

When providing an adhesive layer on a base material, it may be provided in the one surface, and may be set as a single-sided adhesive sheet, and may be provided in both surfaces and may be a double-sided adhesive sheet. When installing on both surfaces, using the adhesive composition of this invention only on one side, it can also be set as a tape from which an adhesive type differs in both surfaces. When forming an adhesive layer on a separator, it can be used as a double-sided adhesive sheet.

When using the adhesive composition of this invention for the adhesive layer of an adhesive sheet, the component (A) contained in a composition is 0-9 mass parts carboxyl group-containing monomer (a-1) and 0-9 mass parts hydroxyl group content ( It is preferable to contain the monomer component which consists of a meta) acryl monomer (a-2) and 99.9-82 mass parts of (meth) acrylic acid ester monomers (a-3), and a weight average molecular weight is 100,000-1 million g / mol It is preferable.

In addition, the sum total of the usage-amount of the said component (a-1) and a component (a-2) is not 0 mass part. That is, it means that at least one of the structural unit derived from a component (a-1) and the structural unit derived from a component (a-2) is necessarily contained in the (meth) acryl copolymer (A). And the total amount of a component (a-1), a component (a-2), and a component (a-3) shall be 100 mass parts.

The usage-amount of the component (a-1) in the component (A) in an adhesive sheet use is 0 mass part (that is, it does not contain (a-1) component), or it may contain (a-1) component. In this case, it is more preferable that it is 0.1-8 mass parts, and it is still more preferable that it is 0.15-7.5 mass parts. In addition, the usage-amount of the component (a-2) in the component (A) in an adhesive sheet use is 0 mass part (that is, it does not contain (a-2) component), or (a-2) component When it contains, it is preferable that it is 0.1-9 mass parts. Moreover, it is more preferable that the usage-amount of the component (a-3) in the component (A) in an adhesive sheet use is 99.3-90.6 mass parts.

As for the sum total of the usage-amount of the component (a-1) in the component (A) and the usage-amount of the component (a-2) in an adhesive sheet use, it is more preferable that it is 0.7-9.4 mass parts, and it is further that it is 0.8-9.3 mass part. desirable.

It is more preferable that it is 150,000-950,000 g / mol, and, as for the weight average molecular weight of the component (A) in an adhesive sheet use, it is still more preferable that it is 200,000-900,000 g / mol.

Moreover, it is preferable that it is 0.15-0.9 mass part with respect to 100 mass parts of components (A), and, as for content of the component (B) in the adhesive composition for adhesive sheets, it is more preferable that it is 0.2-0.8 mass part. Moreover, it is preferable that it is 0.06-4 mass parts with respect to 100 mass parts of components (A), and, as for content of a component (C), it is preferable that it is 0.1-3 mass parts. If it is such a range, as an adhesive composition for surface protection films, a pot life is long, it is excellent in workability, reaches practical adhesive performance immediately after a crosslinking process, and productivity improves significantly.

Moreover, as for the component (D), when using the isocyanate crosslinking agent, it is more preferable that it is 0.07-3 mass parts with respect to 100 mass parts of components (A), and it is 0.1-2 mass parts More preferred.

It is preferable that it is 0.007-0.18 mass part with respect to 100 mass parts of component (A), and, as for the usage-amount of the component (E) when using an imidazole compound as a component (E), it is more preferable that it is 0.01-0.12 mass part.

In addition, in this use, it is preferable that a silane coupling agent (F) is not contained in an adhesive composition.

The coating method of the adhesive composition for adhesive sheet use is not specifically limited, A conventionally well-known method is used. Specifically, natural coater, knife belt coater, floating knife, roll coat, air knife coat, knife over roll, knife on blanket, spray, dip, kiss roll, squeeze roll, reverse roll, air blade, curtain flow coater, doctor blade And various coating methods using devices such as a wire bar, a die coater, a comma coater, a baker applicator, and a gravure coater. Among them, a roll coat, gravure coat, reverse coat, roll brush, spray coat, air knife coat, and die coat method are preferably used. In addition, the coating thickness (thickness after drying) of the composition formed on an adhesive sheet is not specifically limited, It can select suitably according to a desired use. Preferably, the coating thickness (thickness of an adhesive layer: thickness after drying) of the composition formed on an adhesive sheet is 3-200 micrometers, More preferably, it is 5-100 micrometers.

When using the adhesive composition of this invention for an adhesive sheet, it is preferable that the gel fraction of the adhesive layer in the atmosphere of 23 degreeC and 50% RH immediately after crosslinking (adhesion process) is 70-100%, and is 80-99% It is more preferable, and it is still more preferable that it is 85 to 98%. If it is such a range, a punching process and a slit process can be promptly performed as an adhesive sheet provided with an adhesive layer. In order to set the gel fraction as mentioned above, conditions may be suitably selected, such as adjusting the monomer composition of component (A), the addition amount of component (B), and component (C) to the said range.

In the adhesive sheet of this invention, about 0.05-20 (N / 25mm) is preferable and, as for the adhesive force of the adhesive layer formed in the adhesive sheet, about 0.1-15 (N / 25mm) is more preferable. If it is the adhesive force of such a range, it can respond to adhesive sheets, such as the sheet form and tape shape in which various adhesive force is calculated | required.

The adhesive composition of this invention used for an adhesive sheet has long pot life, is excellent in workability, demonstrates practical adhesive performance (especially appropriate gel fraction) immediately after bridge | crosslinking (adhesion process), and productivity improves significantly. Moreover, the adhesive layer obtained from the said adhesive composition has appropriate adhesive force and adhesiveness to a base material, and is excellent in metal corrosion inhibitory prevention property, adherend contamination resistance, low temperature stability, transparency, heat resistance, and heat and moisture resistance.

[ Example ]

This invention is demonstrated in more detail using the following example and a comparative example. However, the technical scope of the present invention is not limited only to the following examples.

In addition, the measurement of the solid content and viscosity of the polymer solution obtained by the synthesis example, the viscosity of an adhesive composition, and the weight average molecular weight of a polymer (A) was performed with the following method.

<Solid content>

About 1 g of polymer solution is precisely weighed into a precisely weighed glass dish. After drying at 105 ° C for 1 hour, the temperature is returned to room temperature, and the mass of the total of the glass plate and the remaining solid content is precisely weighed. Solid content was computed by following formula (1) using X as the total mass of the glass plate and polymer solution before drying the mass of a glass plate, and Y as a total mass of a glass plate and residual solid content.

[Equation 1]

<Viscosity>

The polymer solution or adhesive composition which injected into the glass bottle was temperature-controlled at 25 degreeC, and it measured by the Brookfield viscometer. In addition, the viscosity measurement of the adhesive composition was performed twice in total immediately after preparing the adhesive composition and 12 hours after the preparation of the adhesive composition.

<Weight average molecular weight>

It measured by the measuring method of the following Table 1, measurement conditions.

Equipment: Gel Permeation Chromatograph GPC (Device No. GPC-16) Detector: Differential Refractive Index Detector RI (8020 Type Sensitivity 32, manufactured by Tosso Corporation) UV Absorption Detector UV (Waters 2424, wavelength 215nm, sensitivity 0.2AUFS) Column: Tosso Corporation TSKgel GMHXL (two), G2500HXL (one)
(S / N M0052, M0051, N0010, φ7.8 mm x 30 cm) Solvent: Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) Flow rate: 1.0ml / min Column temperature: 23 ℃ Sample: [Concentration] about 0.2%
[Dissolution] The mixture was stirred gently at room temperature.
[Solubility] Soluble (visually confirmed)
Filtration It filtered on a 0.45 micrometer filter.
Injection volume: 0.200ml
Standard Sample: Monodisperse Polystyrene Data Processing: GPC Data Processing System

Synthesis Example 1

99 parts by mass of n-butyl acrylate (manufactured by Nihon Shokubai Co., Ltd.), 1 part by mass of 2-hydroxyethyl acrylate (manufactured by Nihon Shokubai Co., Ltd.), and 120 parts by mass of ethyl acetate were added to the flask equipped with a reflux machine and a stirrer. It was. Subsequently, it heated to 65 degreeC, carrying out nitrogen substitution, 0.04 mass part of azobisisobutyronitrile (AIBN) was added, and it superposed | polymerized for 6 hours, maintaining 65 degreeC. After completion of the polymerization reaction, 280 parts by mass of ethyl acetate was added and diluted to obtain a solution of a polymer (sample name: A-1). Solid content of the obtained polymer solution was 20 mass%, and the viscosity was 4500 mPa * s. Moreover, the weight average molecular weight of the obtained polymer (A-1) was 1.6 million g / mol.

(Synthesis example 2-19)

In Synthesis Example 1, except that the composition of the monomer component was changed to the composition shown in Table 2 below, the same procedure as in Synthesis Example 1 was performed to obtain the polymers (A-2) to (A-19). A solution was obtained. Moreover, solid content and viscosity of the obtained polymer (A-2)-(A-19) solution, and the weight average molecular weight of the polymer (A-2)-(A-19) were measured. The results are shown in Table 2 below. In addition, in following Table 2, "BA" is butyl acrylate; "MA" is methyl acrylate; "HEA" is 2-hydroxyethyl acrylate; "4HBA" is 4-hydroxybutyl acrylate; "HEAA" is N-2-hydroxyethylacrylamide; "AA" is acrylic acid.

( Example  One)

500 mass parts (100 mass parts as solid content of a polymer) of the polymer (A-1) solution obtained by the said synthesis example 1 which is a polymer (A), and benzoyl peroxide (Sigma-Aldrich Japan Co., Ltd. product, sample name B-) which is a peroxide crosslinking agent (B) 1) 0.2 mass part, 1 mass part of carbodilite (trademark) V-01 (product of Nisshinbo Chemical Co., Ltd., sample name C-1) which is a carbodiimide crosslinking agent (C), and the isocyanate crosslinking agent (D) 1 mass of Nate (registered trademark) L (trimethylolpropane / tolylenediisocyanate trimer adduct, product of Nippon Polyurethane Co., Ltd., sample name D-1) 0.1 mass part and imidazole compound (E) 0.01 parts by mass of imidazole (manufactured by Tokyo Kasei Co., Ltd., sample name E-1) and 0.1 parts by mass of Shin-Etsu Silicone X-41-1810 (manufactured by Shin-Etsu Chemical Co., Ltd., sample name F-1), which is a silane coupling agent (F). 10 minutes mixing at room temperature (25 ℃), the pressure-sensitive adhesive composition is dissolved A solution was obtained.

The solution was applied onto a peeling PET film (Mitsubishi Jushi Co., Ltd., MRF38, thickness: 38 μm) so that the thickness after drying was 25 μm, dried at 130 ° C. for 3 minutes to form an adhesive layer, and then onto the polarizing plate. It attached and the polarizing plate with an adhesive layer was produced.

( Example  2? 10, Comparative example  1? 9)

With the composition ratio as shown in Table 4 and Table 5, except that the polymer, peroxide crosslinking agent, carbodiimide crosslinking agent, isocyanate crosslinking agent, imidazole compound, silane coupling agent and other crosslinking agent synthesized in the above synthesis example were used In the same manner as in Example 1, preparation of the solution in which the pressure-sensitive adhesive composition was dissolved and production of the polarizing plate with pressure-sensitive adhesive layer were performed. Further, peroxide crosslinking agents B-1 and B-2, carbodiimide crosslinking agents C-1, C-2 and C-3, imidazole compounds E-1, E-2, E-3 and E-4, silane coupling agents Details of F-1, F-2, F-3 and F-4, and other crosslinking agent G-1 are as described in Table 3 below.

Peroxide crosslinking agent (B)
B-1: benzoyl peroxide (Sigma Aldrich Japan Co., Ltd. product)
B-2: di (t-butylcyclohexyl) peroxide dicarbonate (manufactured by Sigma Aldrich Japan Co., Ltd.) Carbodiimide crosslinking agent (B)
C-1: Carbodi Light (registered trademark) V-01 (Nisshinbo Chemical Co., Ltd. product)
C-2: Carbodi Light (registered trademark) V-05 (product of Nisshinbo Chemical Co., Ltd.)
C-3: Carbodi Light (registered trademark) V-09 (product of Nisshinbo Chemical Co., Ltd.) Isocyanine art crosslinking agent (D)
D-1: Coronate (registered trademark) L (trimethylolpropane / tolylenediisocyanate trimer adduct, manufactured by Nippon Polyurethane Co., Ltd.) Imidazole compound (E)
E-1: 1-methylimidazole (made by Tokyo Kasei Co., Ltd.)
E-2: 1-butyl amidazole (made by Tokyo Kasei Co., Ltd.)
E-3: 1,2-dimethylimidazole (made by Tokyo Kasei Co., Ltd.)
E-4: 2-ethyl-4-methylimidazole (made by Tokyo Kasei Co., Ltd.)

F-4: 하기 화학식 4로 표시되는 화합물
[화학식 4]

Silane Coupling Agent (F)
F-1: Shin-Etsu Silicone X-41-1810 (Shin-Etsukagaku Kogyo Co., Ltd. product)
F-2: 3-glycidoxypropylmethyldiethoxysilane (Shin-Etsu Chemical Co., Ltd. make, brand name: KBM-403)
F-3: the compound represented by Chemical Formula 3
(3)

F-4: the compound represented by Chemical Formula 4
[Chemical Formula 4]

? Other Crosslinking Agents (G)
G-1: 1,3-bis (N, N- diglycidylaminomethyl) cyclohexane (manufactured by Mitsubishi Chemical Corporation, trade name TETRAD C)

Each performance was evaluated according to the following method about the polarizing plate with the adhesive layer of Examples 1-10 and Comparative Examples 1-9 obtained as mentioned above. The results are shown in Tables 4 and 5 below.

1. Inhibition and prevention of metal corrosion

Immediately after preparation of the polarizing plate having the pressure-sensitive adhesive layer (in each example, the coating layer of the solution in which the pressure-sensitive adhesive composition was dissolved was dried (crosslinked) at 130 ° C. for 3 minutes to form an pressure-sensitive adhesive layer), and then attached to the polarizing plate, The polarizing plate with a layer was produced, and the adhesion layer surface was affixed on aluminum foil, it was left to stand in 60 degreeC and 90% RH atmosphere for 2 days, and the corrosiveness at that time was observed. In addition, in following Table 4 and Table 5, "(circle)" shows no change and "x" shows the thing of whitening, respectively.

2. Light leakage

Immediately after preparation of the polarizing plate having the pressure-sensitive adhesive layer (in each example, the coating layer of the solution in which the pressure-sensitive adhesive composition was dissolved was dried (crosslinked) at 130 ° C. for 3 minutes to form an pressure-sensitive adhesive layer), and then attached to the polarizing plate, 50 degreeC, after manufacturing a polarizing plate with a layer, cutting this polarizing plate into 120 mm (polarizing plate MD direction) x 60 mm, and 120 mm (polarizing plate TD direction) x 60 mm, and superimposing on each surface of a glass plate, respectively. The autoclave process was performed for 20 minutes on 0.49 Mpa (5 kg / cm <2>) conditions. Then, the appearance after leaving to stand for 120 hours and 500 hours in 80 degreeC atmosphere was observed. In Table 4 and Table 5, light leakage was not observed after 120 hours and 500 hours, light leakage was observed after 120 hours, and light leakage was observed after 120 hours. Each of them is shown.

3. Durable

Immediately after preparation of the polarizing plate having the pressure-sensitive adhesive layer (in each example, the coating layer of the solution in which the pressure-sensitive adhesive composition was dissolved was dried (crosslinked) at 130 ° C. for 3 minutes to form an pressure-sensitive adhesive layer), and then attached to the polarizing plate, A polarizing plate with a layer was produced, and the polarizing plate was cut into 120 mm (polarizing plate MD direction) x 60 mm and pasted onto a glass plate, followed by autoclave treatment for 20 minutes under conditions of 50 ° C and 0.49 MPa (5 kg / cm 2). It was. Then, the external appearance after leaving to stand for 120 hours in 100 degreeC atmosphere and 80 degreeC, 90% RH atmosphere was observed. In following Table 4 and Table 5, "(circle)" shows that foaming, lifting, and peeling were not observed, and "x" shows that foaming, lifting, and peeling were observed, respectively.

4. Adhesion

Immediately after preparation of the polarizing plate having the pressure-sensitive adhesive layer (in each example, the coating layer of the solution in which the pressure-sensitive adhesive composition was dissolved was dried (crosslinked) at 130 ° C. for 3 minutes to form an pressure-sensitive adhesive layer), and then attached to the polarizing plate, The polarizing plate with a layer was produced, this polarizing plate was cut | disconnected to 25 mm width, and it stuck to the glass plate, and autoclave-processed for 20 minutes on 50 degreeC and 0.49 Mpa (5 kg / cm <2>) conditions. Using a tensile tester, the adhesive force was measured in accordance with the adhesive tape-adhesive sheet test method described in JIS Z0237 (2000) at a peel angle of 90 ° and a peel rate of 0.3 m / min in an atmosphere of 23 ° C. and 50% RH. It was.

5. Adhesiveness to substrate

4. The adhesion was measured when measuring the adhesive force. In the following Table 4 and Table 5, "(circle)" shows that an adhesive did not come off at all from a base material, and "x" shows that an adhesive peeled from a base material, respectively.

6. Contaminant on adherend

4. The contact angle of the glass plate surface before and behind the measurement of the said 4. adhesive force was measured. In addition, the contact angle was measured according to the wettability test method of the substrate glass surface described in JIS R3257 (1999). In following Table 4 and Table 5, "(circle)" shows the case where the contact angle change of the glass plate surface before and behind an adhesive force measurement is 3 degrees or less, and "x" shows the case where there was a change in the contact angle of the glass plate surface before and after an adhesive force measurement, respectively.

7. Low temperature stability

Immediately after preparation of the polarizing plate having the pressure-sensitive adhesive layer (in each example, the coating layer of the solution in which the pressure-sensitive adhesive composition was dissolved was dried (crosslinked) at 130 ° C. for 3 minutes to form an pressure-sensitive adhesive layer), and then attached to the polarizing plate, The polarizing plate with a layer was produced, cut to 120 mm (polarizing plate MD direction) x 60 mm, and after sticking to a glass plate, the autoclave process was performed for 20 minutes on 50 degreeC and 0.49 Mpa (5 kg / cm <2>) conditions. Then, the external appearance after leaving for 120 hours in -40 degreeC atmosphere was observed. In the following Table 4 and Table 5, "(circle)" shows that foaming, lifting, peeling and recrystallization were not observed, and "x" shows that foaming, lifting, peeling and recrystallization were observed, respectively.

8. Reworkability

4. The peeling state was observed in the measurement of the said 4. adhesive force. In the following Table 4 and Table 5, "(circle)" shows that an interface break was observed, and "x" shows that an adhesive was electrodeposited and / or aggregated break was observed on a glass plate (adhered body), respectively.

9. Gel fraction

Instead of the polarizing plate which has the adhesive layer produced in Examples 1-10 and Comparative Examples 1-9, using the peeling process polyester film, the solution which melt | dissolved the solution in which an adhesive composition is melt | dissolved on the polyester film after peeling process is carried out. The coating layer was coated to have a thickness of 25 μm, and the coating layer was dried (crosslinked) at 130 ° C. for 3 minutes to form an adhesive layer on the exfoliated polyester film, and within 10 minutes (the exfoliated polyester having an adhesive layer). Immediately after film preparation) and after forming the pressure-sensitive adhesive layer (adhesive work), the gel fraction after standing for 7 days in an atmosphere of 23 ° C. and 50% RH was measured. That is, about 0.1 g of the pressure-sensitive adhesive composition was weighed immediately after preparation of the polarizing plate having the pressure-sensitive adhesive layer and after being left to stand at 23 ° C. and 50% RH for 7 days, and the weight W ₁ (g) was measured. This was collected in a sample bottle, and about 30 g of ethyl acetate was added and left to stand for 24 hours. After a predetermined time, the contents of the sample bottle were separated by filtration through a 200 mesh stainless steel wire mesh (weight of the film W ₂ (g)), and the total weight W ₃ of the wire and the residue dried at 90 ° C. for 1 hour (g ) Was measured. The gel fraction was calculated by the following equation (2) from these measurements.

[Equation 2]

Each evaluation result is put together, and is shown in following Table 4 and Table 5. In addition, in following Table 4 and Table 5, the viscosity of "immediately after mixing | blending" which prescribes the viscosity of an adhesive composition is the viscosity measured within 10 minutes after preparation of adhesive composition is complete (mixed each component for predetermined time). Means. In the same manner, in Tables 4 and 5 below, the term “immediately after processing”, which defines the gel fraction of the pressure-sensitive adhesive composition, means that the peeled poly having the pressure-sensitive adhesive layer instead of the polarizing plate having the pressure-sensitive adhesive layer in the above 9. gel fraction. It means the gel fraction measured about the sample immediately after preparation of ester film (within 10 minutes).

Moreover, about the polarizing plate with an adhesive layer of the comparative example 3, in the measurement of said 9. gel fraction, it is said 9. gel except leaving for 0.5 days in 23 degreeC and 50% RH atmosphere after adhesive layer formation (adhesion process) further. The gel fraction was 63% when the method of measuring the fraction was performed and the gel fraction after standing for 0.5 day was measured.

As is apparent from Table 4 and Table 5, the pressure-sensitive adhesive composition (Examples 1 to 10) of the present invention is superior in pot life to the pressure-sensitive adhesive composition (Comparative Examples 1 to 9) outside the scope of the present invention, and is crosslinked. The adhesive layer can then be crosslinked (cured) in a very short period of time (within 10 minutes). From this, it is considered that the pressure-sensitive adhesive composition of the present invention can significantly improve both workability and productivity. In addition, as is apparent from Table 4 and Table 5, the polarizing plates (Examples 1 to 10) using the pressure-sensitive adhesive composition of the present invention are in comparison with the polarizing plates using the pressure-sensitive adhesive composition (Comparative Examples 1 to 9) outside the scope of the present invention. It has excellent light leakage resistance, durability, adhesion to substrate, adherend contamination, low temperature stability and rework resistance.

( Synthetic example  20)

40 parts by mass of n-butyl acrylate (manufactured by Nihon Shokubai Co., Ltd.), 59 parts by mass of 2-ethylhexyl acrylate, 1 part by mass of 2-hydroxyethyl acrylate, and ethyl acetate in a flask equipped with a refluxer and a stirrer Mass part was injected. Subsequently, it heated to 65 degreeC, carrying out nitrogen substitution, 0.1 mass part of azobisisobutyronitrile (AIBN) was added, 0.05 mass part of AIBN was further added after 1 hour, and superposition | polymerization was carried out for 6 hours, maintaining 65 degreeC. 36 mass parts of ethyl acetate were added and diluted after completion | finish of a polymerization reaction, and it cooled to room temperature, and obtained the solution of a polymer (sample name: A-20). Solid content of the obtained polymer solution was 35%, and the viscosity was 3500 mPa * s. In addition, the weight average molecular weight of the obtained polymer (A-20) was 800,000 g / mol.

( Synthetic example  21? 38)

In Synthesis Example 20, the same procedure as in Synthesis Example 20 was carried out except that the composition of the monomer component was changed to the composition shown in Table 6 below to obtain the polymers (A-21) to (A-38). A solution was obtained. Moreover, solid content and viscosity of the obtained polymer (A-20)-(A-38) solution, and the weight average molecular weight of the polymer (A-20)-(A-38) were measured. The results are shown in Table 6 below. In addition, in the following Table 6, "BA" is butyl acrylate; "2EHA" is 2-ethylhexyl acrylate; "HEA" is 2-hydroxyethyl acrylate; "4HBA" is 4-hydroxybutyl acrylate; "HEAA" is N-2-hydroxyethylacrylamide; "AA" is acrylic acid; "AM" is an acrylamide.

( Example  11)

286 mass parts (100 mass parts as solid content of a polymer) of the polymer (A-20) solution obtained by the said Synthesis Example 20 which is a polymer (A), and benzoyl peroxide (Sigma-Aldrich Japan Co., Ltd. product, sample name B-) which is a peroxide crosslinking agent (B) 1) 0.2 parts by mass, carbodiimide (C) carbodilite (registered trademark) V-01 (manufactured by Nisshinbo Chemical Co., Ltd., sample name C-1) 0.5 parts by mass, and dura which is isocyanate crosslinking agent (D) 1-methyl imidazole (Tokaka Seiko), which is 0.5 parts by mass of Nate (trademark) 24A-100 (hexamethylene diisocyanate-buret type, manufactured by Asahi Kasei Chemical Co., Ltd., sample name D-2) and imidazole compound (E) 0.01 parts by mass of Kyokyo Co., Ltd., sample name E-1) was mixed at room temperature (25 ° C) for 10 minutes to obtain a solution in which the pressure-sensitive adhesive composition was dissolved.

The solution was applied onto a peeling PET film (Mitsubishi Jushi Co., Ltd., MRF38, thickness: 38 μm) so that the thickness after drying was 25 μm, dried at 130 ° C. for 3 minutes to form an adhesive layer, and then further adhesion. The surface protection film 1 was produced by sticking the layer side to PET film (The product made by Toray Corporation, brand name Lumirror (trademark) S10 # 25, thickness: 23 micrometers).

( Example  12? 20, Comparative example  10? 18)

Except for using the polymer synthesized in Synthesis Examples 21-38, carbodiimide crosslinking agent, imidazole compound, isocyanate crosslinking agent and other additives in the composition ratio as shown in Table 8 and Table 9 below, In the same manner as in 11, preparation of the solution in which the pressure-sensitive adhesive composition was dissolved and preparation of the surface protection film were carried out to obtain the surface protection films (2) to (10) and the comparative surface protection films (1) to (9). Moreover, peroxide crosslinking agents B-1 and B-2, carbodiimide crosslinking agents C-1 and C-3, isocyanate crosslinking agents D-2 and D-3, imidazole compound E-1, E-2, E- Details of 3 and E-4 and other additives H-1, H-2 and H-3 are as described in Table 7 below.

Peroxide crosslinking agent (B)
B-1: benzoyl peroxide (Sigma Aldrich Japan Co., Ltd. product)
B-2: di (t-butylcyclohexyl) peroxide dicarbonate (manufactured by Sigma Aldrich Japan Co., Ltd.) Carbodiimide crosslinking agent (B)
C-1: Carbodi Light (registered trademark) V-01 (Nisshinbo Chemical Co., Ltd. product)
C-3: Carbodi Light (registered trademark) V-09 (product of Nisshinbo Chemical Co., Ltd.) Isocyanine art crosslinking agent (D)
D-2: hexamethylene diisocyanate? Beret type (Asahi Kasei Chemical Co., Ltd., duranate (trademark) 24A-100)
D-3: hexamethylene diisocyanate isosa inurate (product of Asahi Kasei Chemical Co., Ltd., brand name: Duranate (trademark) TPA-100) Imidazole compound (E)
E-1: 1-methylimidazole (made by Tokyo Kasei Co., Ltd.)
E-2: 1-butyl amidazole (made by Tokyo Kasei Co., Ltd.)
E-3: 1,2-dimethylimidazole (made by Tokyo Kasei Co., Ltd.)
E-4: 2-ethyl-4-methylimidazole (made by Tokyo Kasei Co., Ltd.) ? Other additives (H)
H-1: aluminum trisacetylacetate (Kawaken Fine Chemical Co., Ltd. make, brand name aluminate)
H-2: dibutyltin dilaurate (manufactured by Tokyo Kasei Co., Ltd.)
H-3: Acetyl Acetone (manufactured by Tokyo Kasei Co., Ltd.)

About the surface protection films obtained in Examples 11-20 and Comparative Examples 10-18 obtained as mentioned above, each performance was evaluated in accordance with the following method.

1. Inhibition and prevention of metal corrosion

Immediately after preparation of the surface protective film having the pressure-sensitive adhesive layer (in each example, within 10 minutes after drying (crosslinking) the coating layer of the solution in which the pressure-sensitive adhesive composition was dissolved at 130 ° C. for 3 minutes to form the pressure-sensitive adhesive layer), the pressure-sensitive adhesive layer After attaching cotton to aluminum foil, it was left to stand in 60 degreeC and 90% RH atmosphere for 2 days, and the corrosiveness at that time was observed. In addition, in the following Table 8 and Table 9, "(circle)" shows no change and "x" shows the thing bleached, respectively.

2. Autoclave Aptitude

Immediately after preparation of the surface protective film having an adhesive layer (in each example, within 10 minutes after the coating layer of the solution in which the adhesive composition was dissolved was dried (crosslinked) at 130 ° C. for 3 minutes to form an adhesive layer), the surface protective film Was cut to a width of 25 mm, and the resultant was attached to a polarizing plate, and subjected to autoclave treatment for 20 minutes under conditions of 50 ° C and 0.49 MPa (5 kg / cm 2), and foaming at that time was observed. In addition, in following Table 8 and Table 9, "(circle)" shows the case where foaming is not observed, and "x" shows the case where foaming is observed, respectively.

3. Adhesion

Immediately after preparation of the surface protective film having an adhesive layer (in each example, within 10 minutes after the coating layer of the solution in which the adhesive composition was dissolved was dried (crosslinked) at 130 ° C. for 3 minutes to form an adhesive layer), the surface protective film Was cut to a width of 25 mm, and the resultant was attached to a polarizing plate, and subjected to autoclave treatment for 20 minutes under conditions of 50 ° C and 0.49 MPa (5 kg / cm 2). Using a tensile tester, at 23 ° C and 50% RH in an atmosphere of peeling angle of 180 ° and peeling rate of 0.3 m / min, measurement of adhesive force was performed in accordance with the adhesive tape-adhesive sheet test method described in JIS Z0237 (2000). It was done.

4. Adhesiveness to substrate

In the measurement of the above 3. adhesive force, the adhesion to the protective film (base material) was evaluated. In the following Table 8 and Table 9, "(circle)" shows that an adhesive did not peel at all from a base material, and "x" shows that an adhesive peeled from a base material, respectively.

5. Contaminant on adherend

3. The contact angle of the polarizing plate surface before and behind the measurement of the said 3. adhesive force was measured. In addition, the contact angle was measured according to the wettability test method of the substrate glass surface described in JIS R3257 (1999). In the following Table 8 and Table 9, "(circle)" shows the case where the contact angle change of the polarizing plate surface before and after adhesive force measurement is 3 degrees or less, and "x" shows the case where there was a change in the contact angle of the polarizing plate surface before and after adhesive force measurement, respectively.

6. Low temperature stability

Immediately after preparation of the surface protective film having an adhesive layer (in each example, within 10 minutes after the coating layer of the solution in which the adhesive composition was dissolved was dried (crosslinked) at 130 ° C. for 3 minutes to form an adhesive layer), the surface protective film Was attached to the polarizing plate, and the autoclave process was performed for 20 minutes on 50 degreeC and 0.49 Mpa (5 kg / cm <2>) conditions. Then, the external appearance after leaving for 120 hours in -40 degreeC atmosphere was observed. In Table 8 and Table 9 below, "o" indicates that foaming, lifting, peeling and recrystallization were not observed, and "x" indicates that foaming, lifting, peeling and recrystallization were observed.

7. Transparency of the adhesive layer

Immediately after preparation of the surface protective film having an adhesive layer (in each example, within 10 minutes after the coating layer of the solution in which the adhesive composition was dissolved was dried (crosslinked) at 130 ° C. for 3 minutes to form an adhesive layer), the surface protective film The transparency of the pressure-sensitive adhesive layer was visually confirmed. In addition, in following Table 8 and Table 9, "(circle)" shows the case where transparency is favorable, and "x" shows the case where white turbidity is seen in an adhesive layer, respectively.

8. Gel fraction

Instead of the PET film having the pressure-sensitive adhesive layer produced in Examples 11 to 20 and Comparative Examples 10 to 18, a solution in which the pressure-sensitive adhesive composition was dissolved was dried on a peel-processed polyester film using a peeled polyester film. After apply | coating so that thickness may be set to 25 micrometers, this coating layer was dried (crosslinked) at 130 degreeC for 3 minutes, and the adhesive layer was formed on the peeled-processed polyester film, and within 10 minutes (peel-processed poly with an adhesive layer) Immediately after the preparation of the ester film) and the pressure-sensitive adhesive layer formation (adhesive processing), the gel fraction after standing for 7 days in an atmosphere of 23 ° C. and 50% RH was measured. Namely, about 0.1 g of the pressure-sensitive adhesive composition was weighed immediately after preparation of the peeled-processed polyester film having the pressure-sensitive adhesive layer and after being left to stand at 23 ° C. and 50% RH for 7 days, and the weight W ₁ (g) was measured. This was collected into a sample bottle, and about 30 g of ethyl acetate was added and left to stand for 24 hours. The contents of the sample bottle after a predetermined period of time were separated by filtration through a 200 mesh stainless steel wire mesh (weight of the film W ₂ (g)), and the total weight W ₃ of the wire mesh and the residue dried at 90 ° C. for 1 hour (g ) Was measured. The gel fraction was calculated by the following equation (2) from these measurements.

[Equation 2]

Each evaluation result is put together, and is shown in following Table 8 and Table 9. In addition, in the following Table 8 and Table 9, the viscosity of "immediately after mixing | blending" which prescribes the viscosity of an adhesive composition is the viscosity measured within 10 minutes after preparation of adhesive composition is complete (mixed each component for predetermined time). Means. In the same manner, in Tables 8 and 9 below, the term "immediately after processing" that defines the gel fraction of the pressure-sensitive adhesive composition is immediately after preparation of the peeled polyester film having the pressure-sensitive adhesive layer in the above-mentioned 9.gel fraction (within 10 minutes or less). The gel fraction measured for the sample of).

As is apparent from Table 8 and Table 9, the pressure-sensitive adhesive composition (Examples 11 to 20) of the present invention is excellent in pot life as compared to the pressure-sensitive adhesive composition (Comparative Examples 10 to 18) outside the scope of the present invention, and is crosslinked. The adhesive layer can then be crosslinked (cured) in a very short period of time (within 10 minutes). From this, it is considered that the pressure-sensitive adhesive composition of the present invention can significantly improve both workability and productivity. In addition, as apparent from Table 8 and Table 9, the surface protective film (Examples 11 to 20) using the pressure-sensitive adhesive composition of the present invention is a comparative surface using the pressure-sensitive adhesive composition (Comparative Examples 10 to 18) outside the scope of the present invention. Compared with a protective film, it is excellent in adhesiveness with respect to a base material, adherend contamination, low temperature stability, transparency of an adhesive layer, and autoclave suitability.

( Synthetic example  39)

40 parts by mass of n-butyl acrylate (manufactured by Nihon Shokubai Co., Ltd.), 59 parts by mass of 2-ethylhexyl acrylate, 1 part by mass of 2-hydroxyethyl acrylate, and ethyl acetate in a flask equipped with a refluxer and a stirrer Mass part was injected. Subsequently, it heated to 65 degreeC, carrying out nitrogen substitution, 0.1 mass part of azobisisobutyronitrile (AIBN) was added, 0.05 mass part of AIBN was further added after 1 hour, and superposition | polymerization was carried out for 6 hours, maintaining 65 degreeC. 36 mass parts of ethyl acetate were added and diluted after completion | finish of a polymerization reaction, and it cooled to room temperature, and obtained the solution of a polymer (sample name: A-39). Solid content of the obtained polymer solution was 35%, and the viscosity was 3500 mPa * s. Moreover, the weight average molecular weight of the obtained polymer (A-39) was 800,000 g / mol.

( Synthetic example  40? 57)

In Synthesis Example 39, except that the composition of the monomer component was changed to the composition shown in Table 10 below, the same procedure as in Synthesis Example 39 was performed to obtain the polymers (A-40) to (A-57). A solution was obtained. Moreover, solid content and viscosity of the obtained polymer (A-39)-(A-57) solution, and the weight average molecular weight of the polymer (A-39)-(A-57) were measured. The results are shown in Table 10 below. In addition, in the following Table 10, "BA" is butyl acrylate; "2EHA" is 2-ethylhexyl acrylate; "VAc" is vinyl acetate; "HEA" is 2-hydroxyethyl acrylate; "4HBA" is 4-hydroxybutyl acrylate; "HEAA" is N-2-hydroxyethylacrylamide; "AA" is acrylic acid; "AM" is an acrylamide.

( Example  21)

286 mass parts (100 mass parts as solid content of a polymer) of the polymer (A-39) solution obtained by the said synthesis example 39 which is a polymer (A), and benzoyl peroxide (Sigma-Aldrich Japan Co., Ltd. product, sample name B-) which is a peroxide crosslinking agent (B). 1) 0.2 parts by mass, carbodiimide crosslinking agent (C) Carbodilite (registered trademark) V-01 (manufactured by Nisshinbo Chemical Co., Ltd., sample name C-1) 0.3 parts by mass, Dura is an isocyanate crosslinking agent (D) 1-methyl imidazole (Tokaka Seiko), which is 0.2 part by mass of Nate (trademark) 24A-100 (hexamethylene diisocyanate-buret type, manufactured by Asahi Kasei Chemical Co., Ltd., sample name D-2) and imidazole compound (E) 0.01 parts by mass of Kyokyo Co., Ltd., sample name E-1) was mixed at room temperature (25 ° C) for 10 minutes to obtain a solution in which the pressure-sensitive adhesive composition was dissolved.

After apply | coating this solution so that the thickness after drying may be set to 25 micrometers on peeling PET film (made by Mitsubishi Jushi Co., Ltd., MRF38, thickness: 38 micrometers), it dries at 130 degreeC for 3 minutes, and forms an adhesive layer further, The adhesive sheet 1 was produced by sticking a layer side to PET film (The product made by Toray Corporation, brand name Lumirror (trademark) S10 # 25, thickness: 23 micrometers).

( Example  22-30, Comparative example  19? 27)

Except for using the polymer synthesized in Synthesis Examples 40-57, carbodiimide crosslinking agent, imidazole compound, isocyanate crosslinking agent and other additives in the composition ratio as shown in Table 12 and Table 13, In the same manner as in 21, preparation of the solution in which the pressure-sensitive adhesive composition was dissolved and production of the pressure-sensitive adhesive sheet were performed to obtain pressure-sensitive adhesive sheets (2) to (10) and comparative pressure-sensitive adhesive sheets (1) to (9). Moreover, peroxide crosslinking agents B-1 and B-2, carbodiimide crosslinking agents C-1, C-2 and C-3, isocyanate crosslinking agents D-2 and D-3, imidazole compound E-1, E- The details of 2, E-3 and E-4, and other additives H-1, H-2, H-3 and H-4 are as described in Table 11 below.

Peroxide crosslinking agent (B)
B-1: benzoyl peroxide (Sigma Aldrich Japan Co., Ltd. product)
B-2: di (t-butylcyclohexyl) peroxide dicarbonate (manufactured by Sigma Aldrich Japan Co., Ltd.) Carbodiimide crosslinking agent (B)
C-1: Carbodi Light (registered trademark) V-01 (Nisshinbo Chemical Co., Ltd. product)
C-2: Carbodi Light (registered trademark) V-05 (product of Nisshinbo Chemical Co., Ltd.)
C-3: Carbodi Light (registered trademark) V-09 (product of Nisshinbo Chemical Co., Ltd.) Isocyanine art crosslinking agent (D)
D-2: hexamethylene diisocyanate? Beret type (Asahi Kasei Chemical Co., Ltd., duranate (trademark) 24A-100)
D-3: hexamethylene diisocyanate isosa inurate (product of Asahi Kasei Chemical Co., Ltd., brand name: Duranate (trademark) TPA-100) Imidazole compound (E)
E-1: 1-methylimidazole (made by Tokyo Kasei Co., Ltd.)
E-2: 1-butyl amidazole (made by Tokyo Kasei Co., Ltd.)
E-3: 1,2-dimethylimidazole (made by Tokyo Kasei Co., Ltd.)
E-4: 2-ethyl-4-methylimidazole (made by Tokyo Kasei Co., Ltd.) ? Other additives (H)
H-1: aluminum trisacetylacetate (Kawaken Fine Chemical Co., Ltd. make, brand name aluminate)
H-2: dibutyltin dilaurate (manufactured by Tokyo Kasei Co., Ltd.)
H-3: Acetyl Acetone (manufactured by Tokyo Kasei Co., Ltd.)
H-4: N, N, N ', N'-tetraglycidyl-m-xylene diamine (manufactured by Mitsumi Chemical Co., Ltd., trade name: Tetrad X)

About the adhesive sheets of Examples 21-30 and Comparative Examples 19-27 obtained as mentioned above, each performance was evaluated in accordance with the following method.

1. Inhibition and prevention of metal corrosion

Immediately after preparation of the pressure sensitive adhesive sheet having the pressure sensitive adhesive layer (in each example, within 10 minutes after the coating layer of the solution in which the pressure sensitive adhesive composition was dissolved was dried (crosslinked) at 130 ° C. for 3 minutes to form an pressure sensitive adhesive layer), the pressure sensitive adhesive layer surface After sticking to aluminum foil, it was left to stand for 60 days in the atmosphere of 60 degreeC and 90% RH, and the corrosiveness at that time was observed. In addition, in following Table 12 and Table 13, "(circle)" shows no change and "x" shows the thing bleached, respectively.

2. Adhesion

Immediately after fabrication of the adhesive sheet having the adhesive layer (in each example, within 10 minutes after the coating layer of the solution in which the adhesive composition was dissolved was dried (crosslinked) at 130 ° C. for 3 minutes to form the adhesive layer), the adhesive sheet was 25 It was cut to a width of mm, and pressed to a stainless plate by a method of reciprocating once with a roller of 2 kg, and left for 20 minutes in an atmosphere of 23 ° C. and 50% RH. After that, using a tensile tester, at 23 ° C and 50% RH in an atmosphere of peeling angle of 180 ° and peeling rate of 0.3 m / min, the adhesive force according to the adhesive tape-adhesive sheet test method described in JIS Z0237 (2000). Was measured.

3. Adhesiveness to substrate

At the time of the measurement of the said 2. adhesive force, the adhesiveness with respect to the adhesive sheet (base material) was evaluated. In the following Table 12 and Table 13, "(circle)" shows that an adhesive did not peel at all from a base material, and "x" shows that an adhesive peeled from a base material, respectively.

4. Contaminant on adherend

The contact angle of the polarizing plate surface before and behind the measurement of the said 2. adhesive force was measured. In addition, the contact angle was measured according to the wettability test method of the substrate glass surface described in JIS R3257 (1999). In the following Table 12 and Table 13, "(circle)" shows the case where the contact angle change of the stainless plate surface before and after adhesive force measurement is within 3 degrees, and "x" shows the case where the contact angle of the stainless plate surface before and after the adhesive force measurement changed, respectively. Indicates.

5. Low temperature stability

Immediately after fabrication of the adhesive sheet having the adhesive layer (in each example, within 10 minutes after the coating layer of the solution in which the adhesive composition was dissolved was dried (crosslinked) at 130 ° C. for 3 minutes to form the adhesive layer), the adhesive sheet was stainless The plate was pressed by a method of reciprocating once with a roller of 2 kg, and left for 1 hour in an atmosphere of 23 ° C. and 50% RH. Then, the external appearance after leaving for 120 hours in -40 degreeC atmosphere was observed. In addition, in following Table 12 and Table 13, "(circle)" shows that foaming, lifting, and peeling were not observed, and "x" shows that foaming, lifting, and peeling were observed, respectively.

6. Transparency of the adhesive layer

Immediately after preparation of the pressure sensitive adhesive sheet having the pressure sensitive adhesive layer (in each example, within 10 minutes after drying (crosslinking) the coating layer of the solution in which the pressure sensitive adhesive composition was dissolved at 130 ° C. for 3 minutes to form the pressure sensitive adhesive layer), the pressure sensitive adhesive of the pressure sensitive adhesive sheet The transparency of the layer was visually confirmed. In addition, in following Table 12 and Table 13, "(circle)" shows the case where transparency is favorable, and "x" shows the case where the turbidity is seen in an adhesive layer, respectively.

7. Heat resistance

Immediately after fabrication of the adhesive sheet having the adhesive layer (in each example, within 10 minutes after the coating layer of the solution in which the adhesive composition was dissolved was dried (crosslinked) at 130 ° C. for 3 minutes to form the adhesive layer), the adhesive sheet was stainless The plate was pressed by a method of reciprocating once with a roller of 2 kg, and left for 1 hour in an atmosphere of 23 ° C. and 50% RH. Then, the external appearance after leaving to stand for 500 hours in 80 degreeC atmosphere was observed. In following Table 12 and Table 13, "(circle)" shows that foaming, lifting, and peeling were not observed, and "x" shows that foaming, lifting, and peeling were observed, respectively.

8. Moisture and heat resistance

Immediately after fabrication of the adhesive sheet having the adhesive layer (in each example, within 10 minutes after the coating layer of the solution in which the adhesive composition was dissolved was dried (crosslinked) at 130 ° C. for 3 minutes to form the adhesive layer), the adhesive sheet was stainless The plate was pressed by a method of reciprocating once with a roller of 2 kg, and left for 1 hour in an atmosphere of 23 ° C. and 50% RH. Then, the appearance after leaving for 500 hours at 60 degreeC and 90% RH atmosphere was observed. In following Table 12 and Table 13, "(circle)" shows that foaming, lifting, and peeling were not observed, and "x" shows that foaming, lifting, and peeling were observed, respectively.

9. Gel fraction

Instead of the PET film having the pressure-sensitive adhesive layer produced in Examples 21 to 30 and Comparative Examples 19 to 27, a solution in which the pressure-sensitive adhesive composition was dissolved was dried on a peel-processed polyester film, using a peeled polyester film. After apply | coated so that thickness may be set to 25 micrometers, this coating layer was dried (crosslinked) at 130 degreeC for 3 minutes, and the adhesive layer was formed on the peeled-processed polyester film, and within 10 minutes (peel-processed poly with an adhesive layer) Immediately after preparation of the ester film), and the gel fraction after standing for 7 days in an atmosphere of 23 ° C. and 50% RH after the pressure-sensitive adhesive layer formation (adhesive processing) was measured. Namely, about 0.1 g of the pressure-sensitive adhesive composition was weighed immediately after preparation of the peeled polyester film having the pressure-sensitive adhesive layer and left to stand at 23 ° C. and 50% RH for 7 days, and the weight W ₁ (g) was measured. This was collected into a sample bottle, and about 30 g of ethyl acetate was added and left to stand for 24 hours. The contents of the sample bottle after a predetermined period of time were separated by filtration through a 200 mesh stainless steel wire mesh (weight of the film W ₂ (g)), and the total weight W ₃ of the wire mesh and the residue dried at 90 ° C. for 1 hour (g ) Was measured. The gel fraction was calculated by the following equation (2) from these measurements.

[Equation 2]

Each evaluation result is put together, and is shown in following Table 12 and Table 13. In addition, in the following Table 12 and Table 13, the viscosity of the "immediately after mixing | blending" which prescribes the viscosity of an adhesive composition is the viscosity measured within 10 minutes after preparation of adhesive composition is complete (mixed each component for predetermined time). Means. In the same manner, in Tables 12 and 13 below, the term "immediately after" defining the gel fraction of the pressure-sensitive adhesive composition is immediately after fabrication of the peeled polyester film having the pressure-sensitive adhesive layer in the above-mentioned 9.gel fraction (within 10 minutes or less). The gel fraction measured for the sample of).

As is apparent from Table 12 and Table 13, the pressure-sensitive adhesive composition (Examples 21 to 30) of the present invention is excellent in pot life as compared to the pressure-sensitive adhesive composition (Comparative Examples 19 to 27) outside the scope of the present invention, and crosslinked. After that, the pressure-sensitive adhesive layer can be crosslinked (cured) in a very short period (within 10 minutes). From this, it is considered that the pressure-sensitive adhesive composition of the present invention can significantly improve both workability and productivity. In addition, as apparent from Table 12 and Table 13, the adhesive sheets of Examples 21 to 30 of the present invention, as compared with the adhesive sheets of Comparative Examples 19 to 27, adhesion to the substrate, adherend contamination, low temperature stability, pressure-sensitive adhesive The layer is excellent in transparency, heat resistance and heat and moisture resistance.

Claims (15)

100 parts by mass of the (meth) acryl copolymer (A) having a weight average molecular weight of 100,000 to 2 million g / mol;
0.1-1 mass part of peroxide crosslinking agents (B) with respect to 100 mass parts of said (meth) acryl copolymers (A); And
The adhesive composition containing 0.05-5 mass parts of carbodiimide crosslinking agents (C) with respect to 100 mass parts of said (meth) acryl copolymers (A).

The said (meth) acryl copolymer (A) is 0-9 mass parts carboxyl group-containing monomer (a-1), and 0-9 mass parts hydroxy group containing (meth) acryl monomer (a-2) ) And 99.9 to 82 parts by mass of a (meth) acrylic acid ester monomer (a-3), containing a carboxyl group-containing monomer (a-1) and a hydroxy group-containing (meth) acrylic monomer (a-2) The total amount of and is not 0 parts by mass, and the total amount of the carboxyl group-containing monomer (a-1), the hydroxy group-containing (meth) acrylic monomer (a-2) and the (meth) acrylic acid ester monomer (a-3) is 100 mass. Mrs. pressure-sensitive adhesive composition.
The pressure-sensitive adhesive composition of claim 1, wherein the pressure-sensitive adhesive composition comprises at least one of an isocyanate crosslinking agent (D) and an imidazole compound (E) represented by Formula 1 below:
[Formula 1]

In said Formula (1), R <^1> , R <^2> and R <^3> are respectively independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1-C10 linear or branched alkyl group.
The said isocyanate crosslinking agent (D) is an adhesive composition of Claim 3 which is contained in 0.05-5 mass parts with respect to 100 mass parts of said (meth) acryl copolymers (A).
The pressure-sensitive adhesive composition according to claim 3, wherein the imidazole compound (E) is contained at 0.05 to 5 parts by mass with respect to 100 parts by mass of the (meth) acryl copolymer (A).
The pressure-sensitive adhesive composition of claim 3, wherein the pressure-sensitive adhesive composition further comprises a silane coupling agent.
The optical member provided with the adhesive layer formed from the adhesive composition in any one of Claims 1-6.
The weight average molecular weight of the (meth) acryl copolymer (A) in the said adhesive composition is 1 million-1.8 million g / mol, The adhesive force of the said adhesive layer by JIS Z0237 is 0.5-9 N / 25mm. Optical member.
The optical member according to claim 7, wherein the pressure-sensitive adhesive composition is adhered, and the gel fraction of the pressure-sensitive adhesive layer is 50 to 95% under 23 ° C. and 50% RH.
The surface protection film provided with the adhesive layer formed from the adhesive composition in any one of Claims 1-5.
The weight average molecular weight of the (meth) acryl copolymer (A) in the said adhesive composition is 150,000-90,000 g / mol, The adhesive force of the said adhesive layer by JIS Z0237 is 0.05-0.3 N / 25mm. Surface protection film.
The surface protective film according to claim 10, wherein the pressure-sensitive adhesive composition is attached, and then the gel fraction of the pressure-sensitive adhesive layer is 70-100% under 23 ° C and 50% RH.
The adhesive sheet provided with the adhesive layer formed from the adhesive composition in any one of Claims 1-5.
The weight average molecular weight of the (meth) acryl copolymer (A) in the pressure-sensitive adhesive composition is 150,000-950,000 g / mol, and the adhesive force of the pressure-sensitive adhesive layer according to JIS Z0237 is 0.05-20 N / 25mm. Adhesive sheet.
The pressure-sensitive adhesive sheet according to claim 13, wherein the pressure-sensitive adhesive composition is attached, and the gel fraction of the pressure-sensitive adhesive layer is 70-100% at 23 ° C. and 50% RH.