KR20160034844A - Heat-curable adhesive composition - Google Patents

Abstract

The present invention provides a thermosetting adhesive composition excellent in transparency and adhesiveness, and more specifically, it relates to a thermosetting adhesive composition which is excellent in transparency and adhesiveness and which is obtained from two or more ethylenically unsaturated monomers containing, as an essential component of a thermosetting adhesive composition, an ethylenically unsaturated monomer having a hydroxyl group as an essential component (A) obtained with a weight average molecular weight of 10,000 to 500,000 and a block isocyanate, preferably a block isocyanate (B) having a deviation starting temperature of 80 to 200 占 폚. As the thermosetting adhesive composition, a urethanization promoting catalyst or a block-off catalyst may be used.

Description

HEAT-CURABLE ADHESIVE COMPOSITION [0002]

The present invention relates to a thermosetting adhesive composition comprising a copolymer obtained from two or more ethylenically unsaturated monomers having an ethylenically unsaturated monomer having a hydroxyl group as an essential component and a block isocyanate, a pressure-sensitive adhesive and a film obtained from the thermosetting pressure- . The pressure-sensitive adhesive and film of the present invention are particularly useful for optical members such as plastic film, paper, glass, metal foil, liquid crystal panel, PDP, and touch panel.

BACKGROUND ART [0002] Thermosetting compositions are used in the fields of inks, paints, various coatings, adhesives, vehicles, building materials, sealing agents and the like.

For example, Patent Document 1 discloses a thermosetting coating composition containing a hydroxyl group-containing acrylic resin. Patent Document 2 discloses a thermosetting coating composition containing a hydroxyl group-containing acrylic resin having a weight average molecular weight of 100,000 to 1,000,000 and a thermosetting Patent Document 3 discloses a thermosetting coating composition comprising a hydroxyl group-containing acrylic resin and a block isocyanate as essential components, and Patent Document 4 discloses a thermosetting coating composition comprising a resin composition capable of reacting with an isocyanate group Discloses a thermosetting coating composition comprising a compound having two or more functional groups in one molecule and a block isocyanate. Patent Document 5 discloses a thermosetting coating composition comprising a block isocyanate compound and an active hydrogen capable of reacting with an isocyanate group Discloses an electrophotographic photoconductor having an intermediate layer obtained by coating and thermosetting a coating liquid for forming an intermediate layer containing a binder resin having an organic group. Patent Document 6 discloses an electrophotographic photoconductor comprising an acrylic resin containing a hydroxyl group and having a number average molecular weight of 3000 to 50,000, A clear coated stainless steel sheet containing an isocyanate resin is disclosed.

Japanese Laid-Open Patent Publication No. 05-202335 Japanese Patent Publication No. 07-015015 Japanese Laid-Open Patent Publication No. 08-012927 Japanese Laid-Open Patent Publication No. 09-169950 JP-A-2010-140001 U.S. Patent Application Publication No. 2013/0011615

An object of the present invention is to provide a thermosetting adhesive composition excellent in transparency and adhesiveness.

Disclosure of the Invention The present invention has been made based on the above finding, and it is an object of the present invention to provide a copolymer (A) having a weight average molecular weight of 10,000 to 500,000 obtained from two or more ethylenically unsaturated monomers having an ethylenically unsaturated monomer having a hydroxyl group as essential constituents, (B) as an essential component. The above-mentioned object is achieved by providing a thermosetting adhesive composition.

The present invention also provides a film having a pressure-sensitive adhesive layer obtained from the thermosetting pressure-sensitive adhesive composition.

The thermosetting adhesive composition of the present invention is particularly useful as a pressure-sensitive adhesive since it is excellent in transparency and adhesiveness.

The thermosetting adhesive composition of the present invention comprises a copolymer (A) having a weight average molecular weight of 10,000 to 500,000 and a block isocyanate (B) obtained from two or more ethylenically unsaturated monomers having an ethylenically unsaturated monomer containing a hydroxyl group as essential constituents, As an essential component. Hereinafter, each component will be described in order.

≪ Component (A) >

The polymer (A) having a weight average molecular weight of 10,000 to 500,000 obtained from two or more monomers having the hydroxyl group-containing ethylenically unsaturated monomer as an essential component can be obtained by copolymerizing a plurality of hydroxyl group-containing ethylenically unsaturated monomers, An ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having no hydroxy group.

As the hydroxyl group-containing ethylenically unsaturated monomer, a hydroxyl group-containing acrylic ester obtained by an esterification reaction of an aliphatic polyhydric alcohol and acrylic acid can be used. For example, 4-hydroxybutyl acrylate, 2- Hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2- Hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, and the like.

Examples of the ethylenically unsaturated monomer having no hydroxy group include vinyl acetate, glycidyl acrylate, morpholine acrylate, glycidyl acrylate, methyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, Acrylic acid esters such as acrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, lauryl acrylate, methoxyethyl acrylate, dimethylaminomethyl acrylate, But are not limited to, poly (ethoxy) ethyl acrylate, butoxyethoxyethyl acrylate, hexyl acrylate, phenoxyethyl acrylate, tetrahydrofuryl acrylate, vinyl acrylate, allyl acrylate, benzyl acrylate, methyl acrylate, butyl acrylate, Ethylene glycol diacrylate, di Diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylol ethane triacrylate , Trimethylol ethane triacrylate, trimethylol propane triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, tricyclodecane dimethylol diacrylate, tri Acrylonitrile, [acryloylethyl] isocyanurate, polyester acrylate oligomer, dimethylacrylamide, glycidyl methacrylate, morpholine methacrylate, glycidyl methacrylate, methyl methacrylate, butyl methacrylate , Isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate , N-octyl methacrylate, isooctyl methacrylate, isononyl methacrylate, stearyl methacrylate, lauryl methacrylate, methoxyethyl methacrylate, dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate , Aminopropyl methacrylate, dimethylaminopropyl methacrylate, ethoxyethyl methacrylate, poly (ethoxy) methacrylate, butoxyethoxyethyl methacrylate, ethylhexyl methacrylate, phenoxy methacrylate Ethyl acrylate, ethyl methacrylate, tetrahydrofuryl methacrylate, vinyl methacrylate, allyl methacrylate, benzyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol di Methacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylol ethane trimethacrylate, tri But are not limited to, trimethylolpropane trimethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, tricyclodecane dimethylol dimethacrylate, tri [methacryl Acrylate monomers such as esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols such as ethyl acrylate, isopropyl acrylate, butyl acrylate, isopropyl acrylate, butyl acrylate,

Unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene;

Vinylbenzene sulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, and vinylbenzenesulfonic acid. Unsaturated aromatic compounds such as vinylbenzyl methyl ether and vinyl benzyl glycidyl ether;

Vinyl alcohols such as allyl alcohol and crotyl alcohol;

Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether.

Among the ethylenically unsaturated monomers having no hydroxy group, acrylic monomers are preferable in terms of adhesiveness, and among them, acrylic monomers are more preferable.

In the copolymer (A) obtained from two or more ethylenically unsaturated monomers having the hydroxyl group-containing ethylenically unsaturated monomer as essential components and having a weight average molecular weight of 10,000 to 500,000, the content of the hydroxyl group-containing ethylenically unsaturated monomer The ratio is 20 to 100%, preferably 50 to 99%. If it is too small, adhesion tends to become insufficient, and if it is too large, there is a fear of gelation.

The copolymer (A) obtained from two or more ethylenically unsaturated monomers having the hydroxyl group-containing ethylenically unsaturated monomer as an essential component has a weight average molecular weight of 10,000 to 500,000, preferably 20,000 to 200,000, The hydroxyl value is preferably 20 to 600, more preferably 50 to 500. If the weight average molecular weight is less than 10,000, the viscosity is lowered. If the weight average molecular weight is larger than 500,000, the adhesion may be deteriorated. If the hydroxyl value is less than 20, sufficient adhesion may not be obtained. If the hydroxyl value is more than 600, compatibility may be poor and the composition may become cloudy.

≪ Component (B) >

The block isocyanate (B) is obtained by masking an isocyanate group of an isocyanate compound with a blocking agent. When the block isocyanate compound is stabilized at around room temperature and is heat treated, the blocking agent is separated and the active isocyanate group is regenerated. The block isocyanate is obtained by reacting an isocyanate compound with a blocking agent .

Examples of the isocyanate compound include aliphatic monoisocyanates such as methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate and octadecyl isocyanate;

Benzene isocyanate, benzene isocyanate,? -Phenetyl isocyanate,? -Naphthyl isocyanate, biphenyl isocyanate, benzyl phenyl isocyanate, phenoxy phenyl isocyanate, phenethyl isocyanate, 4-chlorophenyl isocyanate, 2,4-dichlorophenyl isocyanate, Methyl isocyanate, isopropyl phenyl isocyanate and diisopropyl phenyl isocyanate, P-toluyl isocyanate, isopropyl benzyl isocyanate, m-isopropenyl-isocyanate, isopropyl benzyl isocyanate, aromatic monoisocyanates such as?,? - dimethylbenzyl isocyanate;

2-acryloyloxyethyl isocyanate, 2-methacryloyloxypropyl isocyanate, allyl isocyanate, 1-butene-3-isocyanate, 2-acryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, Unsaturated monoisocyanates such as methyl propene-3-isocyanate;

2,4- and / or 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, p-phenylenediisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, -Dimethyldiphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, dianisidine diisocyanate, tetramethylxylylene diisocyanate, o-triazine diisocyanate, diphenyl ether diisocyanate, 2 , Bis (diisocyanate tolyl) phenylmethane, 3,3'-dimethoxybenzidine-4,4'-diisocyanate, 4,4'-diisocyanatobiphenyl (isocyanatomethyl) decahydronaphthalene, , 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 1,1'-methylenebis (3-methyl-4-isocyanatobenzene), 1,3- 1-methylethyl) benzene, 1,3-bis (2-isocyanato-2-propyl) Group diisocyanate;

Alicyclic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, trans-1,4-cyclohexyldiisocyanate and norbornenedisocyanate;

Diisocyanate, diethylene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4 and / or (2,4,4) -trimethylhexamethylene diisocyanate, lydidine diisocyanate, cyclohexane diisocyanate, (Isocyanatomethyl) cyclohexane, 3- (2'-isocyanatocyclohexyl) propyl isocyanate, isopropylidenebis (cyclohexylisocyanate), 2,2'-bis (isocyanatomethyl) Propane, 2,6-bis (isocyanatomethyl) tetrahydrodicyclopentadiene, bis (isocyanatomethyl) dicyclopentadiene, bis (isocyanatomethyl) adamantane, 2,5-diisocyanate methyl Aliphatic diisocyanates such as norbornene;

Bis (isocyanatomethyl) tetrahydrothiophene, bis (isocyanatomethyl) thiophene, and other heterocyclic diisocyanates;

Also, diisocyanates such as carbodiimide-modified, isocyanurate-modified, and biuret-modified products of these diisocyanate compounds are exemplified by isocyanurate trimer of diisocyanate, buret trimer, trimethylolpropane Duct cargo etc .;

Triphenylmethane diisocyanate, triphenylmethane triisocyanate, 1-methylbenzene-2,4,6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, N, N ', N' "-tri (1-isocyanathexyl) , Lysine triisocyanate, tris (phenylisocyanate) thiophosphate, 4,4 ', 4 "-triisocyanate-2,5-dimethoxyphenylamine, 1,3,5-triisocyanatocyclohexane, 1,3,5 - tris (isocyanatomethyl) cyclohexane, and the like,

Further, there are trifunctional or higher isocyanate compounds such as carbodiimide-modified, isocyanurate-modified or biuret-modified products of these isocyanate compounds.

These may be used alone or in combination of two or more.

Of these isocyanate compounds, isocyanates other than aromatic isocyanates are preferable from the viewpoint of transparency, and alicyclic diisocyanates and aliphatic diisocyanates are more preferable.

Examples of the blocking agent include carboxylic acid esters such as dimethyl malonate, diethyl malonate, dibenzyl malonate, and diethyl malonate;

Active methylene compounds such as malonic acid, acetylacetone, and acetoacetic acid esters (such as methyl acetoacetate and ethyl acetoacetate);

(MEK oxime), methyl isobutyl ketoxime (MIBK oxime), dimethyl ketoxime, diethyl < RTI ID = 0.0 > Oxime compounds such as ketoxime;

Monohydric alcohols such as methanol, ethanol, propanol, butanol, 2-ethylhexanol, heptanol, hexanol, octanol, isononyl alcohol, stearyl alcohol and benzyl alcohol;

Glycol derivatives such as methyl glycol, ethyl glycol, ethyl diglycol, ethyl triglycol, butyl glycol, butyl diglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and propylene glycol monomethyl ether;

Phenols such as phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, octylphenol, nonylphenol, nitrophenol and chlorophenol, or isomers thereof;

Ester containing hydroxyl groups such as methyl lactate and amyl lactate; Amine compounds such as dibutylamine, diisopropylamine, di-tert-butylamine, di-2-ethylhexylamine, dicyclohexylamine, benzylamine, diphenylamine, aniline and carbazole;

Imine compounds such as ethyleneimine and polyethyleneimine;

Alcohol amines such as monomethylethanolamine, diethylethanolamine and triethylethanolamine;

lactams such as? -pyrrolidone,? -butyrolactam,? -propiolactam,? -butyrolactam,? -valerolactam and? -caprolactam;

Mercaptans such as butyl mercaptan, hexyl mercaptan, and dodecyl mercaptan;

Imidazoles such as imidazole and 2-ethylimidazole;

Acid amides such as acetanilide, acrylamide, acetic acid amide and dimeric acid amide;

Acid imides such as succinic acid imide, maleic acid imide and phthalic acid imide;

Urea compounds such as thiourea, ethyleneurea and the like;

Benzotriazoles; And pyrazoles such as 3,5-dimethylpyrazole. These may be used singly or in combination of two or more kinds.

The blocking reaction for obtaining the block isocyanate (B) is carried out by a known reaction method. The addition amount of the blocking agent is usually 1 to 2 equivalents, preferably 1.05 to 1.5 equivalents, relative to the free isocyanate groups. The reaction temperature for the blocking reaction is usually 50 to 150 ° C, preferably 60 to 120 ° C. The reaction time is preferably about 1 to 7 hours. In addition, catalysts and solvents (aromatic hydrocarbon-based, ester-based, ether-based, ketone-based, and mixed solvents of two or more thereof) may be added.

The block isocyanate (B) may be a commercially available product such as a car lens MOI-BM, MOI-BP (manufactured by Showa Denko K.K.), dyrenate MF-K60B, SBN-70D, MF- BI-7950, BI-7960, BI-7961, BI-7963, BI-7982, and BI- BI-7991, and BI-7992 (manufactured by Baxenden).

It is more preferable that the dissociation starting temperature of the block isocyanate (B) is 80 to 200 ° C and 90 to 110 ° C. If it is higher than 200 ° C, there is a fear of damaging the substrate. If it is lower than 80 ° C, side reaction may occur and liquid stability may deteriorate.

The content of the block isocyanate (B) is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the copolymer (A) obtained from two or more ethylenically unsaturated monomers having the hydroxyl group-containing ethylenically unsaturated monomer as an essential component Do.

<Urethanization promoting catalyst or block-off catalyst>

In the thermosetting adhesive composition of the present invention, it is possible to use a urethanization promoting catalyst or a block-off catalyst in order to make the curing sufficiently and to shorten the curing time. Examples of the urethanization promoting catalyst or the block-off catalyst include dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin maleate, dibutyltin distearate, dioctyl Tetravalent organotin compounds such as tin dilaurate, dioctyltin divisate, dibutyltin oxide, dibutyltin bis (triethoxysilicate), and the reaction product of dibutyltin oxide and phthalic acid ester, dibutyltin bis (Acetylacetonate), divalent organic tin compounds such as tin octylate and tin naphthenate such as EXCESTARC-501 manufactured by Asahi Glass Co., Ltd. of tin chelate compound, zirconium tetrakis (acetylacetonate), titanium tetrakis Nate), aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), acetylacetone cobalt, acetylacetone Chelate compounds of various metals such as tin, iron, acetyl acetone copper, acetylacetone magnesium, acetylacetone bismuth, acetylacetone nickel, acetylacetone zinc and acetylacetone manganese, titanate esters such as tetra-n-butyl titanate and tetrapropyl titanate Zinc diacylate, zinc diacetate, zinc diacetate, zinc dioleate, zinc diyrylate, zinc bisacetoacetate, zinc dibenzoate, bis (zinc monoacetate) oxide, bis Iron, cobalt, copper, zirconium, lead, zinc, and the like, such as lead octylate or zirconium octylate, zinc diacetylbenzoylmethane, zinc lauroylbenzoylmethane, Bismuth and the like, and metal organic acid salts with various organic acids such as octylic acid, stearic acid, naphthenic acid, A compound;

Diethylamine, triethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1,4-diazabicyclo [2.2 , 2] octane (DABCO), N-methylmorpholine, N-ethylmorpholine, N-alkylpiperazine, dimethylaniline, p- dimethylaminotoluidine, 1,8-diazabicyclo [5.4.0] undecene- 7, 1,5-diazabicyclo [4.3.0] nonene-5;

Salts of amines and carboxylic acids; 2-hydroxyethyl tri-n-butylammonium, 2,2-dimethylpropionate, 2-hydroxyethyl tri-n-butylammonium, 2,2-dimethyl butanoate, 2-hydroxypropyl tri Butyl ammonium, 2,2-dimethylpropionate, 2-hydroxypropyl tri-n-butylammonium 2,2-dimethyl butanoate, 2-hydroxypropyl tri-n-butylammonium 2,2- Ethyl 2-methylpropionate, 2-hydroxypropyl tri-n-butylammonium 2-ethyl 2-methylbutanoate, 2-hydroxypropyl tri-n-butylammonium 2-ethyl 2-methylpropionate, -Hydroxypropyl tri-n-butylammonium 2-ethyl 2-methyl pentanoate, 2-hydroxypropyl tri-n-octylammonium 2,2-dimethylpropionate, 2-hydroxypropyl tri n - octylammonium 2,2-dimethyl butanoate, 2-hydroxypropyl triamylammonium 2,2-dimethyl butanoate, 2-hydroxypropyl triamyl Monyum penta-2,2-dimethyl quaternary ammonium salts, such as no-benzoate; Organic phosphoric acids such as monomethylphosphoric acid, di-n-butylphosphoric acid and triphenylphosphoric acid;

Photo cationic catalysts such as sulfonium salts, thiophenium salts, thioranium salts, benzylammonium, pyridinium salts and hydrazinium salts;

An organic carboxylic acid, an aromatic carboxylic acid, a sulfonic acid, a nonylphenol, and the like can be used as long as it is at least one member selected from the group consisting of a phenol, a melamine, a dicyandiamide, a guanamine or a derivative thereof, And saturated organic acid salts of organic acids.

These may be used alone or in combination of two or more.

The urethanization promoting catalyst or the block-off catalyst is used in an amount of 0.001 to 20 parts by mass based on 100 parts by mass of the copolymer (A) obtained from two or more ethylenically unsaturated monomers having the hydroxyl group-containing ethylenically unsaturated monomer as an essential component desirable.

<Silane coupling agent>

In the thermosetting adhesive composition of the present invention, a silane coupling agent may be used if necessary.

Examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyl Alkenyl functional alkoxysilanes such as vinyl trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane, alkoxy functional alkoxysilanes such as trimethoxysilane, 3-methacryloxypropyl tri Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, Epoxyfunctional alkoxysilanes such as glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl ) -γ-Aminov Aminopropyltrimethoxysilane such as ethyltrimethoxysilane,? -Aminopropyltrimethoxysilane,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane, and N-phenyl-? -Aminopropyltrimethoxysilane, mercapto functionalities such as? -Mercaptopropyltrimethoxysilane Titanium alkoxides such as alkoxysilane, titanium tetraisopropoxide and titanium tetra-n-butoxide, titanium chelates such as titanium dioctyloxybis (octylene glycolate) and titanium diisopropoxybis (ethylacetoacetate) Zirconium chelates such as zirconium tetraacetylacetonate and zirconium tributoxymonoacetylacetonate; zirconium acylates such as zirconium tributoxymonostearate; and isocyanate silanes such as methyltriisocyanate silane.

The silane coupling agent is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the copolymer (A) obtained from two or more ethylenically unsaturated monomers having the hydroxyl group-containing ethylenically unsaturated monomer as an essential component.

<Solvent>

In the thermosetting adhesive composition of the present invention, usually, a solvent obtained by dissolving or dispersing the above components (A) and (B) and other optional components, for example, methyl ethyl ketone, methyl amyl ketone, diethyl Ketones such as ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone;

Ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and dipropylene glycol dimethyl ether;

Esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol;

Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;

Alcohol-based solvents such as methanol, ethanol, iso-or n-propanol, iso- or n-butanol, and amyl alcohol;

Propylene glycol monomethyl ether-2-acetate (PGM), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, etc. Ether-based solvent;

BTX type solvents such as benzene, toluene and xylene;

Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane;

Terpene type hydrocarbon oils such as turpentine oil, D-limonene, and pinene;

Paraffin solvents such as mineral spirits, Swazol # 310 (Cosmo Matsuyama Sekiyu) and Solvesso # 100 (Exxon Kagaku);

Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichlorethylene, methylene chloride, and 1,2-dichloroethane;

Halogenated aromatic hydrocarbon solvents such as chlorobenzene;

A solvent such as acetone, acetonitrile, carbon dioxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, water These solvents may be used singly or as a mixed solvent of two or more kinds.

The thermosetting adhesive composition of the present invention is applied onto a supporting substrate by a known means such as a roll coater, a curtain coater, various printing, immersion and the like. In addition, it may be once transferred onto a supporting substrate such as a film, and then transferred onto another supporting substrate.

The support substrate is not particularly limited, but preferable examples thereof include inorganic materials such as silicon wafer, calcite, quartz, paper, wood, and metal; Cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, and nitrocellulose; Polyamide; Polyimide; Polyurethane; Epoxy resin; Polycarbonate; Polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethanol-4,4'-dicarboxylate, polybutyl Polyesters such as polyethylene, polypropylene, polymethylpentene, polytetrafluoroethylene, and cycloolefin polymers; polyesters such as polyethylene terephthalate; Vinyl compounds such as polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; Acrylic resins such as polymethyl methacrylate and polyacrylic acid ester; Polycarbonate; Polysulfone; Polyethersulfone; Polyether ketones; Polyetherimide; Polyoxyethylene, novolene resin, and the like.

The support substrate may be subjected to a surface treatment by a conventionally known method such as a corona discharge treatment, a flame treatment, a plasma treatment, a glow discharge treatment, a roughening treatment or a chemical treatment, or a surface treatment by an ITO film, an anchor coat agent, Coating may be performed.

Further, as long as the effect of the present invention is not impaired (preferably 80% or less by mass of the thermosetting pressure-sensitive adhesive composition of the present invention (excluding the above solvent)) and, if necessary, other acrylic resins, epoxy resins, A colorant such as a resin composition, an inorganic filler, an organic filler, a pigment and a dye, a photopolymerization initiator, a photosensitizer, a defoaming agent, a thickener, a surfactant, a leveling agent, a flame retardant, a plasticizer, Various kinds of resin additives such as an inhibitor, a flow regulator, an adhesion promoter, and a tackifier may be added.

The thermosetting adhesive composition of the present invention can be applied to a variety of applications such as resist materials for printed wiring boards, resist inks, pigment resist inks for car filters, semiconductor encapsulants, inks, plastic coatings, paper printing, film coatings, A polarizing plate, a photo-polarizing prism, various optical filters, and the like in a variety of coating fields, FRP, lining, and in the fields of electronics such as insulating varnish, insulating sheet, laminated plate, plasma display panel, An optical anisotropic material, an adhesive, an insulating material, a structural material, an optical waveguide clad, and the like.

When the thermosetting adhesive composition of the present invention is used as one component of a liquid resist, it is cured by heat under the conditions of 100 to 200 DEG C and 1 to 90 minutes. The curing is preferably carried out in an inert gas atmosphere, but the curing can be carried out even in an air atmosphere.

The film using the thermosetting pressure-sensitive adhesive composition of the present invention as a pressure-sensitive adhesive layer is not particularly limited in terms of its shape, but usually the undercoat layer, the antireflection layer, the hard coat layer, the lubricant layer, , A liquid crystal layer, and the like. Examples of the method of providing a pressure-sensitive adhesive layer on a film include (1) a method of coating a transparent support, (2) a method of providing a pressure-sensitive adhesive layer between any two adjacent ones selected from a transparent support and any layer, A method of providing an adhesive layer may be mentioned. The thickness of the pressure-sensitive adhesive layer is preferably 2 to 400 mu m.

Example

Hereinafter, the present invention will be described in more detail with reference to Production Examples and Examples, but the present invention is not limited to these Examples.

Hereinafter, the thermosetting adhesive composition of the present invention and the cured product obtained by curing the thermosetting adhesive composition will be specifically described with reference to Examples, Evaluation Examples and Comparative Examples. In the Examples and Comparative Examples, parts mean parts by mass.

Production Examples 1 to 25 and Comparative Production Examples 1 to 4 Production of acrylic polymers (A-1) to (A-25) and comparative acrylic polymers (A-1) to (A-4)

A reaction vessel equipped with a condenser, a nitrogen inlet tube, a thermometer and a stirrer was charged with a monomer, azoisobutyronitrile as an initiator and ethyl acetate as a solvent in accordance with the formulations of Table 1 to Table 4 to prepare a solution did. (A-1) to (A-25) and Comparative Acrylic Polymers (A'-1) to (A'-1) were prepared by stirring the solution while injecting nitrogen gas at 60 캜 for 8 hours. 4), respectively. On the other hand, the units in [Table 1] to [Table 4] represent the mass part.

* 1: 4-Hydroxybutyl acrylate

* 2: Butyl acrylate

* 3: 2-Ethylhexyl acrylate

* 4: Dimethylacrylamide

* 5: Styrene

* 6: Methyl acrylate

* 7: 2-Hydroxyethyl methacrylate

* 8: Cyclohexyl acrylate

* 9: Lauryl acrylate

[Examples 1 to 36 and Comparative Examples 1 to 4] Production of a cured product of a thermosetting adhesive composition

The components shown in [Table 5] to [Table 8] below were sufficiently mixed to obtain thermosetting adhesive compositions of each of Examples and Comparative Examples. A thermosetting adhesive composition of each of the Examples and Comparative Examples was applied to a sticky adhesive PET film A4300 available from Toyobo Co., Ltd. using a bar coater # 90 and dried at 120 ° C for 10 minutes. And a test piece was obtained by bonding to a glass plate. On the other hand, the unit represents a mass part.

As the block isocyanate (B), the following compounds (B-1) to (B-5) and the comparative compound (B'-1) were used. On the other hand, HDI represents "hexamethylene diisocyanate", IPDI represents "isophorone diisocyanate", DMP represents "dimethyl pyrazole", DEM represents "diethyl malonate" and MEKO represents " "

Compound B-1: BI-7960

(Block isocyanate, product of Baxenden / isocyanate compound: HDI Buret, blocking agent: DMP,

Compound B-2: BI-7950

(Block isocyanate, product of Baxenden / isocyanate compound: IPDI, blocking agent: DMPI, separation starting temperature: 100 占 폚)

Compound B-3: BI-7951

(Block isocyanate manufactured by Baxenden: isocyanate compound: IPDI trimmer, blocking agent: DMP,

Compound B-4: BI-7961

(Block isocyanate, product of Baxenden: isocyanate compound: HDI Buret, blocking agent: DMP, separation starting temperature: 100 占 폚)

Compound B-5: BI-7963

(Block isocyanate; product of Baxenden: isocyanate compound: HDI Buret, blocking agent: DEM, dissociation initiation temperature: 60 DEG C)

Compound B-6: BI-7982

(Block isocyanate, product of Baxenden: isocyanate compound: HDI trimmer, blocking agent: DMP,

Compound B-7: BI-7991

(Block isocyanate; product of Baxenden: isocyanate compound: HDI Buret, blocking agent: DMP / DEM,

Compound B-8: BI-7992

(Block isocyanate; product of Baxenden: isocyanate compound: HDI trimmer, blocking agent: DMP / DEM,

Compound B-9: Dyuranate MF-K60B (manufactured by Asahi Kasei Chemical Co., Ltd.)

Compound B-10: Dyuranate SBN-70D (manufactured by Asahi Kasei Chemical Co., Ltd.)

Compound B-11: Dyuranate MF-B90B (manufactured by Asahi Kasei Chemical Co., Ltd.)

Compound B-12: Dyuranate TPA-B80B (manufactured by Asahi Kasei Chemical Co., Ltd.)

As the urethane curing accelerating catalyst, the following compounds (C-1) to (C-4) were used.

Compound C-1: Adecastab OT-1 (manufactured by ADEKA)

Compound C-2: Adecastab 465E (product of ADEKA)

Compound C-3: Adecastab 465L (manufactured by ADEKA)

Compound C-4: Adekastab OT-9 (manufactured by ADEKA)

[Evaluation Examples 1 to 36 and Comparative Evaluation Examples 1 to 4]

The test pieces obtained in Examples 1 to 36 and Comparative Examples 1 to 4 were evaluated for tackiness and optical properties according to the following methods. The results are shown in Tables 5 to 10 above.

(Tackiness)

The tackiness of the test piece obtained according to JIS K6854-3 was evaluated. On the other hand, a glass plate was used as a substrate for evaluating the tackiness.

(Optical characteristics)

Using a haze meter NDH5000 manufactured by Nippon Denshoku Co., Ltd., the difference between the maximum total light transmittance and the minimum total light transmittance was measured and the optical characteristics were evaluated.

As can be seen from [Table 5] to [Table 10], the thermosetting adhesive composition of the present invention is excellent in transparency and adhesiveness, and is suitably used for a pressure-sensitive adhesive.

Claims (4)

(A) having a weight average molecular weight of 10,000 to 500,000 and a block isocyanate (B) obtained from two or more ethylenically unsaturated monomers having an ethylenically unsaturated monomer having a hydroxyl group as essential constituents Sensitive adhesive composition. The thermosetting adhesive composition according to claim 1, wherein the block initiating temperature of the block isocyanate (B) is 80 to 200 占 폚. A thermosetting pressure-sensitive adhesive obtained from the thermosetting pressure-sensitive adhesive composition according to claim 1 or 2. A film having the pressure-sensitive adhesive layer obtained from the thermosetting pressure-sensitive adhesive according to claim 3.