JP2008007694A - Photosensitive composition for adhesive agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition for adhesive agents, with which cured materials excellent in curability, adhesion with plastic, glass, metal, and the like, transparency, and flexibility can be produced. <P>SOLUTION: The photosensitive composition for adhesive agents comprises a urethan(meth)acrylate (A) formed of a compound (a1) having hydroxy and (meth)acryloyl groups, polyol (a2), and polyisocyanate (b), a monofunctional (meth)acryloyl group-containing compound (B), an epoxy compound (C), a photoinitiator (D), and a cationic photopolymerization initiator (E). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photosensitive composition for an ultraviolet curable adhesive. More specifically, the present invention relates to a photosensitive composition for an ultraviolet curable adhesive having excellent curability, adhesiveness and flexibility.

  Conventionally, a composition for a photosensitive adhesive has a high curing rate and can improve productivity, and is suitable for bonding a thermoplastic resin that does not require heat to be cured and easily deforms, etc. Therefore, they are widely used as adhesives and sealing agents for optical members, electrical / electronic members, etc. (see, for example, Patent Document 1). As the composition, a radical curable composition using a (meth) acrylate resin is mainly used, but the composition is (1) susceptible to curing inhibition by oxygen, and (2) cure shrinkage. In order to eliminate such disadvantages as large, (3) poor adhesion to metal, and (4) poor heat resistance, a composition for cationically curable adhesives such as epoxy, vinyl ether, oxetane, etc. has been developed in recent years. In particular, a photosensitive epoxy resin composition having a relatively fast reactivity (for example, see Patent Document 2) has been used.

JP 2004-161935 A JP 2002-235066 A

However, these photosensitive epoxy resin compositions have a slower reaction rate than (meth) acrylate resin compositions, do not exhibit sufficient performance immediately after UV irradiation, and need to be heated or cured. Since the object is hard and brittle, there are problems such as deterioration of adhesiveness, cracks, cracks and cracks.
The object of the present invention is to make up for the drawbacks of the above (meth) acrylate resin and epoxy resin composition, have good curability, and have excellent adhesiveness, transparency and flexibility with plastic, glass, metal, etc. It is providing the photosensitive composition which gives an agent.

  As a result of intensive studies to solve the above problems, the present inventor has reached the present invention. That is, the present invention relates to a urethane (meth) acrylate (A) formed from a compound (a1) having a hydroxyl group and a (meth) acryloyl group, a polyol (a2) and a polyisocyanate (b), a monofunctional (meth) acryloyl group. A photosensitive composition for an adhesive comprising the containing compound (B), the epoxy compound (C), the photopolymerization initiator (D), and the photocationic polymerization initiator (E); an optical composition comprising the composition An adhesive or sealing agent for a member; and a laminate obtained by curing a laminate comprising three layers of a substrate, a coating layer of the composition on the substrate, and a transparent substrate on the coating layer.

The photosensitive composition of the present invention has the following effects.
(1) Excellent curability during ultraviolet irradiation.
(2) A cured product obtained by curing the composition is excellent in transparency, flexibility and adhesiveness.

The urethane (meth) acrylate (A) in the present invention is formed from a compound (a1) having a hydroxyl group and a (meth) acryloyl group, a polyol (a2) and a polyisocyanate (b).
In (a1), the number of carbon atoms (hereinafter abbreviated as C) is 4 or more and the number average molecular weight [hereinafter abbreviated as Mn, and measurement is performed by gel permeation chromatography (GPC) method. ] 5,000 or less, such as the following, and mixtures of two or more thereof.
(A11) Hydroxyl group-containing (meth) acrylic acid compound and its alkylene oxide (hereinafter abbreviated as AO) (C2-4) adduct (Meth) acrylic acid-2-hydroxyethyl, -2-hydroxypropyl, -2-hydroxybutyl And these AO adducts (molecular weight 160 or more and Mn 5,000 or less) and the like;
(A12) ε-caprolactone adduct of (a11) (molecular weight 230 or more and Mn 5,000 or less)
(Meth) acrylic acid-2-hydroxyethyl-ε-caprolactone 2 mol adduct, etc .;
(A13) Reaction product of (meth) acrylic acid and diol (Mn 300 to 5,000) Mono (meth) acrylate of diol (Mn 300 to 5,000, such as polycarbonate diol, polyethylene glycol, polyester diol);

(A14) Reaction product of (meth) acrylic acid and epoxide C8-30, such as 3-phenoxy-2-hydroxypropyl (meth) acrylate, 3-biphenoxy-2-hydroxypropyl (meth) acrylate, etc .;
(A15) Reaction product of (meth) acrylic acid and a tri- or higher functional polyol (molecular weight of 92 or more and Mn 5,000 or less) Glycerin (hereinafter abbreviated as GR) mono- and di (meth) acrylate, trimethylolpropane (hereinafter referred to as Abbreviated as TMP) mono- and di (meth) acrylate, pentaerythritol (hereinafter abbreviated as PE) mono-, di- and tri (meth) acrylate, diTMP mono-, di- and tri (meth) acrylate, diPE mono -, Di-, tri-, tetra- and penta (meth) acrylates, and these AO adducts (addition mole number 1 to 100), etc .;
(A16) Reaction product of (meth) acrylic acid and polyalkadiene (alkadiene is C4-5) polyol or hydrogenated product thereof (excluding (a13) and (a15)). ]
Examples of the polyalkadiene polyol include butadiene polyol (Mn 300 to 5,000) and isoprene polyol (Mn 300 to 5,000). Examples of the hydrogenated polyalkadiene polyol include hydrogenated butadiene polyol (Mn 300 to 5,000). ), Hydrogenated isoprene polyol (Mn 300 to 5,000) and the like, and the hydrogenation rate is preferably 50 to 98 mol%, more preferably 80 to 95 mol%.
Of these, (a11), (a14) and (a15) are preferred from the viewpoint of reactivity with polyisocyanate (b) described later, and (a11) and (a15) are more preferred.

The polyol (a2) in the present invention includes C2 or more and Mn400 or less, such as the following, and a mixture of two or more thereof excluding the above (a1).
(A21) Dihydric alcohol (C2-20 or more), for example, C2-12 aliphatic dihydric alcohol [(di) alkylene glycol (ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-, 2) , 3-, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 3-methylpentanediol (hereinafter EG, DEG, PG, DPG, BD, HD, NPG and MPD, respectively) Abbreviation), dodecanediol, etc.], dihydric alcohols having a C6-10 alicyclic skeleton [1,3- and 1,4-cyclohexanediol, cyclohexanedimethanol (hereinafter abbreviated as CHDM), etc.], C8 ~ 20 araliphatic dihydric alcohol [xylylene glycol, bis Hydroxyethyl) benzene];
(A22) Trihydric to octahydric or higher polyhydric alcohols such as (cyclo) alkanepolyol and intramolecular or intermolecular dehydrates [GR, TMP, PE, sorbitol (hereinafter abbreviated as SO) and diPE , 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diGR and other polyGR, etc.], saccharides and derivatives thereof [sucrose, glucose, fructose, mannose, lactose, glucoside (methylglucoside) And so on];

(A23) Polyether polyol, for example, polyethylene glycol (hereinafter abbreviated as PEG) (Mn 200 to 20,000), polypropylene glycol (hereinafter abbreviated as PPG) (Mn 200 to 20,000), polytetramethylene glycol (hereinafter abbreviated as PTMG) ) (Mn 400-10,000);
(A24) Polyester polyol (Mn 400 to 20,000), for example, ester of adipic acid and BD and HD, ester of maleic anhydride and NPG, succinic acid and bisphenol A ethylene oxide (hereinafter abbreviated as EO) 4 mol addition An ester with a product; polycaprolactone polyol (Mn 400 to 10,000), for example, an ε-caprolactone adduct of HD, an ε-caprolactone adduct of TMP;
(A25) Polycarbonate polyol (Mn 500 to 10,000), for example, BD or HD polycarbonate diol, adipic acid-modified HD polycarbonate diol;
(A26) polybutadiene polyol (Mn 500 to 10,000), polyisoprene polyol (Mn 500 to 10,000) and hydrogenated products thereof;
(A27) Epoxy resin (Mn 300 to 5,000), for example, a reaction product of 1,6 hexanediol diglycidyl ether and 2 mol of acetic acid, a 5 mol ring-opening polymer of bisphenol A diglycidyl ether;
(A28) AO 1 to 50 mol adduct of (a21) to (a27) excluding (a23) above, for example, AO 1 to 50 mol adduct of bisphenol A.

  Of these, (a23), (a24), (a25) and (a28) are preferable from the viewpoint of adhesion and toughness of the cured product, and (a24) and (a28) are more preferable.

  The weight ratio of (a1) to (a2) is preferably 1/99 to 90/10, more preferably 3/97 to 40/60, from the viewpoints of curability and flexibility of the cured product described later.

The polyisocyanate (hereinafter sometimes abbreviated as PI) (b) in the present invention includes, for example, the following and a mixture of two or more thereof.
(B1) C (excluding C in the NCO group, the same shall apply hereinafter) 6 to 20 aromatic polyisocyanate diisocyanate (hereinafter abbreviated as DI), for example, 1,3- and / or 1,4-phenylene DI, 2 , 4- and / or 2,6-tolylene DI (TDI), 4,4′- and / or 2,4′-diphenylmethane DI (MDI), m- and p-isocyanatophenylsulfonyl isocyanate, 4,4 ′ -Diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene DI, and m -And p-isocyanatophenylsulfonyl isocyanate; and trifunctional or higher functional PI (such as triisocyanate) such as crude TDI, crude MDI (polyisocyanate). Polyphenylene polyisocyanates) and 4,4 ', 4 "- triphenylmethane triisocyanate

(B2) C2-18 aliphatic polyisocyanate DI, such as ethylene DI, tetramethylene DI, hexamethylene DI (HDI), heptamethylene DI, octamethylene DI, nonamethylene DI, decamethylene DI, dodecamethylene DI, 2,2, 4- and / or 2,4,4-trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethylcaproate, 2,6-diisocyanatoethylcaproate, bis (2-isocyanatoethyl) fumarate Bis (2-isocyanatoethyl) carbonate and trimethylhexamethylene diisocyanate (TMDI); and trifunctional or higher functional PI (such as triisocyanate), such as 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4- Isocyanate Methyloctane, 1,3,6-hexamethylene triisocyanate and lysine ester triisocyanate (phosgenates of the reaction product of lysine and alkanolamine, such as 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2 -And / or 3-isocyanatopropyl-2,6-diisocyanatohexanoate)

(B3) C4-45 cycloaliphatic polyisocyanates DI, such as isophorone DI (IPDI), 2,4- and / or 2,6-methylcyclohexane DI (hydrogenated TDI), dicyclohexylmethane-4,4′-DI (Hydrogenated MDI), cyclohexylene DI, methylcyclohexylene DI, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate and 2,5- and / or 2,6-norbornane DI , Dimer acid DI (DDI); and tri- or higher functional PI (such as triisocyanate), for example, bicycloheptane triisocyanate (b4) C8-15 aromatic aliphatic polyisocyanate m- and / or p-xylylene DI (XDI), Diethylbenzene DI and α, α, α ′, α′-tetramethylxylylene D I (TMXDI)
(B5) Nurateated product of (b1) to (b4) (b6) Modified product of (b1) to (b4) other than (b5) Carbodiimide, urethane, urea, uretoimine, allophanate, biuret, oxazolidone and / or Modified products having a uretdione group.
Among these PIs, the aliphatic ones among (b2), (b3), and (b5) are preferable from the viewpoint of transparency of the cured product described later.

  In the production of the urethane (meth) acrylate (A), the equivalent ratio of the NCO group and the hydroxyl group is not particularly limited, but is preferably 1: 1.1 to 1.1: 1 from the viewpoint of the storage stability of (A). More preferably, it is 1: 1.05 to 1.05: 1.

The conditions for the urethanization reaction in the production of (A) are not particularly limited. For example,
[1] A part of (a1) and / or (a2) and all (b) are mixed, and usually 40 to 120 ° C., preferably 60 to 100 ° C. from the viewpoint of reactivity and stability of the mixture. After reacting for 2-20 hours to produce an NCO-terminated prepolymer, the remaining (a1) and / or (a2) is added to produce (A) under similar conditions, or all (a1) and A method in which (a2) and a part of (b) are reacted under the same conditions as above to produce an OH-terminated prepolymer, then the remaining (b) is added, and (A) is produced under the same conditions [ Prepolymer method];
[2] A method (one-shot (collective reaction) method) in which (a1), (a2), and (b) are mixed and reacted under the same conditions as described above to produce (A).
Of these, from the viewpoint of molecular weight control, the prepolymer method is preferred, and the method via an NCO-terminated prepolymer is more preferred.

  Further, if necessary, the reaction may be carried out by diluting with a solvent (ethyl acetate, methyl ethyl ketone, toluene, etc.). The amount of the solvent used is usually 5,000% or less based on the total weight of (a1), (a2) and (b), and the preferable upper limit is 1,000% from the viewpoint of the reaction rate, from the viewpoint of handling of the mixture A preferred lower limit is 10%.

  The urethanization reaction can be carried out at normal pressure, reduced pressure or increased pressure. The progress of the urethanization reaction can be judged, for example, by measuring the NCO% and hydroxyl value of the reaction system.

  In the production of (A), it is preferable to use the urethanization catalyst (U) from the viewpoint of reaction time. (U) includes an organic bismuth compound (U1), an organic tin compound (U2), an organic titanium compound (U3), a tertiary amine, and a quaternary ammonium salt (U4).

Examples of (U1) include the following and a mixture of two or more thereof.
(U11) Organic bismuth carboxylate represented by the general formula Bi (COOR) ₃ , where R is a monovalent aliphatic group [C1-20, such as alkyl (methyl, ethyl, n- and i-propyl, n-, i-, sec- and t-butyl, octyl, 2-ethylhexyl, decyl and dodecyl) and alkenyl (1-, 2- and i-propenyl, 1-, 2- and 3-butenyl) groups], aromatic (fatty ) Group (C6-20, such as phenyl, toluyl, xylenyl, benzyl, phenethyl and hexylphenyl) groups and alicyclic (C3-10, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl) groups.
Among these R, a C2-12 aliphatic group and a C5-10 alicyclic group are preferable from the viewpoint of hydrolysis resistance.
(U12) Organic bismuth alkoxide The organic bismuth alkoxide is represented by the general formula Bi (OR) ₃ , R is the same as described above, and R is preferably the same as described above from the viewpoint of hydrolysis resistance.
(U13) Compound having dicarbonyl group and Bi chelate compound The compound having a dicarbonyl group includes C4-15, for example, acetylacetone, acetylacetic acid, acetoacetoxyethyl (meth) acrylate, and the chelate compound includes these Bi chelate compounds are included.

Examples of (U2) include trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin maleate, and stannous octoate.
Examples of (U3) include tetraalkyl (C2-12) titanate and alkylene dicarboxylic acid (C3-12) titanium.
As the tertiary amine in (U4), for example, triethylenediamine, tetraalkyl (C1-3) alkylene (C2-6) diamine (for example, tetramethylethylenediamine, tetramethylhexylenediamine), diazabicycloalkene {1, 8-diazabicyclo [5,4,0] undecene-7 [DBU [manufactured by San Apro Co., Ltd., registered trademark]] and the like}.
Examples of the quaternary ammonium salt in (U4) include tetraalkyl (C1-4) ammonium bromide and tetraalkyl (C1-4) ammonium perchlorate.

  Of these, (U1) and (U2) are preferable from the viewpoint of reactivity and non-coloring property, and (U1) is more preferable from the viewpoint of safety and molecular weight control of (A). Of (U1), (U11) and (U13) are more preferable from the viewpoint of reactivity and stability as a catalyst, and (U11) is particularly preferable from the viewpoint of non-coloration.

  The amount of (U) used is preferably 0.001 to 1%, more preferably 0.05 to 0.2% from the viewpoints of reactivity and transparency based on the weight of (A).

When the organic bismuth carboxylate (U11) is used as the urethanization catalyst (U), an organic acid may be further contained from the viewpoint of the stability of (U11). Examples of organic acids include aliphatic carboxylic acids (C2 to C20, such as acetic acid, propionic acid, isopropionic acid, butyric acid, isovaric acid, octanoic acid, 2-ethylhexanoic acid and dodecanoic acid), and alicyclic carboxylic acids (C4 -10, such as cyclobutanoic acid, cyclopentanoic acid and cyclohexane acid), aromatic carboxylic acids (C7-15, such as benzoic acid, terephthalic acid, phthalic acid and trimellitic acid), α-unsaturated carboxylic acids [C3-10, Eg (meth) acrylic acid, cinnamic acid and maleic acid] and 2-hydroxyethyl (meth) acrylate and polybasic acids (C2-15 such as oxalic acid, succinic acid, adipic acid, phthalic acid, trimellitic acid and their And acid ester) and a mixture of two or more thereof.
Of these, aliphatic and alicyclic carboxylic acids are preferred from the viewpoint of hydrolysis resistance of (U11).

The weight ratio of (U11) to the organic acid is preferably 0.001 / 1 to 9/1, more preferably 0.01 / 1 to 4/1, from the viewpoint of the stability of (U11).
As a method of using the organic acid, it is preferable to add a liquid which is previously mixed with (U11) and made liquid from the viewpoint of the solubility of the catalyst and the urethanization reaction.

Examples of the monofunctional (meth) acryloyl group-containing compound (B) in the present invention include C4 or more and Mn2,000 or less, for example, the following, and a mixture of two or more thereof.
(B1) (Meth) acrylate of aliphatic monohydric alcohol (C1-30) Lauryl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl acrylate, etc. (B2) of alicyclic monohydric alcohol (C6 to C20) ((Meth) acrylate cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadiylmethyl (meth) acrylate, etc. (B3) (meth) acrylate of araliphatic monohydric alcohol (C7 to C15) benzyl (meth) Acrylates, phenylethyl (meth) acrylates, etc. (B4) Heterocycle-containing compounds (C5 to C15) (meth) acryloyl group-containing compounds Tetrafurfuryl (meth) acrylate, (meth) acryloylmorpholine, etc. (B5) Aliphatic, fatty Ring-containing, araliphatic Each monohydric alcohol (C1-30) AO 1-30 mol adduct ((meth) acrylate (lauryl alcohol) EO2 mol adduct (meth) acrylate, lauryl alcohol PO3 mol adduct (meth) acrylate, cyclohexyl alcohol (Meth) acrylate of EO3 mole adduct of (4), (meth) acrylate of PO4 mole adduct of benzyl alcohol, etc. (B6) [alkyl (C1-20)] of AO1-30 mole adduct of phenol (C6-30) ( (Meth) acrylate (meth) acrylate of PO3 mol adduct of phenol, (meth) acrylate of EO1 mol adduct of nonylphenol, etc. (B7) hydroxyl group-containing (meth) acrylate Among the above (a1), monofunctional [[a11 ) To (a14) and (a16)] and the like.
Of these, (B3), (B4), (B5) and (B7) are preferable from the viewpoint of flexibility and adhesiveness of the cured product, and (B3), (B5) and (B7) are more preferable. is there.

  Examples of the epoxy compound (C) in the present invention include an alicyclic epoxy compound (C1), a glycidyl type epoxy compound (C2), and a mixture of two or more thereof. Among these, (C1) is preferable from the viewpoint of reaction rate.

Examples of (C1) include C4 or more and Mn 3,000 or less, such as the following, and a mixture of two or more thereof.
(C11) monofunctional alicyclic epoxy compound cyclohexane oxide, cyclopentane oxide, α-pinene oxide 3,4-epoxyvinylcyclohexane and the like;
(C12) Bifunctional alicyclic epoxy compound 2- (3,4-epoxy) cyclohexyl-5,5-spiro- (3,4-epoxy) cyclohexane-m-dioxane, 3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, vinylcyclohexane dioxide, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, exo-exobis (2,3-epoxycyclopentyl) ether, endo-exobis (2,3-epoxycyclopentyl) ether, 2,2-bis (4- ( 2,3-epoxypropoxy ) Cyclohexyl) propane, 2,6-bis (2,3-epoxypropoxycyclohexyl-p-dioxane), 2,6-bis (2,3-epoxypropoxy) norbornene, limonene dioxide, 2,2-bis (3 , 4-epoxycyclohexyl) propane, dicyclopentadiene dioxide, 1,2-epoxy-6- (2,3-epoxypropoxy) hexahydro-4,7-methanoindane, p- (2,3-epoxy) cyclopentylphenyl- 2,3-epoxypropyl ether, 1- (2,3-epoxypropoxy) phenyl-5,6-epoxyhexahydro-4,7-methanoindane, o- (2,3-epoxy) cyclopentylphenyl-2,3- Epoxypropyl ether), 1,2-bis [5- (1,2-epoxy) -4,7 Hexahydromethanoindanoxyl] ethane, cyclopentenylphenyl glycidyl ether, methylene bis (3,4-epoxycyclohexane) ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate) etc;
(C13) polyfunctional (trivalent to 20-valent or higher) alicyclic epoxy compound ε-caprolactone (1-10 mol) adduct of 3,4-epoxycyclohexanemethanol and polyvalent (3-20 valent) alcohol ( Esterified products of GR, TMP, PE, DPE, hexapentaerythritol), and the like.
Of these, (C12) and (C13) are preferable from the viewpoint of reactivity, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is more preferable.

Examples of (C2) include C7 or more and Mn 5,000 or less, such as the following, and mixtures of two or more thereof.
(C21) Monofunctional glycidyl ether type epoxy compound Alkyl (C4-18) glycidyl ether, phenyl glycidyl ether, alkyl (C1-12) phenyl glycidyl ether, glycidyl ether of phenol AO adduct (addition mole number 1-20 mol) (C22) Polyfunctional glycidyl ether type epoxy compound Bisphenol A type and -F type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, hydrogenated bisphenol A type epoxy compound, AO adduct of bisphenol A or -F Diglycidyl ether, hydrogenated bisphenol A AO adduct diglycidyl ether, EG, PG, NPG, BD, HD, CHDM, PEG and PPG diglycidyl ether, TMP And / or triglycidyl ether, PE tri and / or tetraglycidyl ether, SO hepta and / or hexaglycidyl ether, resorcin diglycidyl ether, dicyclopentadiene / phenol-added glycidyl ether, methylene bis (2,7-dihydroxynaphthalene) tetra Glycidyl ether, 1,6-dihydroxynaphthalene diglycidyl ether, polybutadiene diglycidyl ether and the like.
Of these, bisphenol A-type and -F-type epoxy compounds and phenol novolac-type epoxy compounds are more preferable from the viewpoint of reactivity (C22).

  Examples of the photopolymerization initiator (D) in the present invention include hydroxybenzoyl compounds (2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzoin alkyl ether, etc.), benzoylformate Examples include compounds (such as methylbenzoylformate), thioxanthone compounds (such as isopropylthioxanthone), benzophenones (such as benzophenone), phosphate compounds (such as 1,3,5-trimethylbenzoyldiphenylphosphine oxide), and benzyldimethyl ketal. Of these, from the viewpoint of non-coloring of the cured product, hydroxybenzoyl compounds (particularly 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexyl phenyl ketone) and phosphate compound ( In particular, 1,3,5-trimethylbenzoyldiphenylphosphine oxide).

Examples of the photocationic polymerization initiator (E) of the present invention include allylsulfonium salts [triphenylsulfonium phosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, p- (phenylthio). Phenyldiphenylsulfonium hexafluoroantimonate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] phenylsulfide-bis-hexafluoroantimonate, etc.], allyl iodonium salts [diphenyliodonium hexafluorophosphate, diphenyliodonium Hexafluoroantimonate, etc.], sulfonate [o-nitrobenzyl tosylate, p-nitro dimethoxyanthracene sulfonate] Njiruesuteru, tosylate acetophenone, etc.], include ferrocene [(2,4-cyclopentadiene-1-yl) [(1-methylethyl) benzene] -Fe (II) hexafluorophosphate, etc.].
Of these, allylsulfonium salts and sulfonic acid esters are preferable from the viewpoint of reactivity.

  The proportion of each component based on the total weight of (A) to (E) constituting the composition of the present invention is preferably urethane (meth) acrylate (A) from the viewpoints of flexibility, toughness, handleability, and adhesiveness. Is 10 to 79.8%, more preferably 20 to 50%; the monofunctional (meth) acryloyl group-containing compound (B) is preferably 10 to 79.8% from the viewpoint of flexibility, reactivity and dimensional stability. More preferably 15 to 40%; the epoxy compound (C) is preferably 5 to 69.8%, more preferably 10 to 50% from the viewpoint of adhesion, dimensional stability and reactivity; photopolymerization initiator (D) Is preferably from 0.1 to 3.0%, more preferably from 0.3 to 2.0% from the viewpoint of reactivity and light resistance; the photocationic polymerization initiator (E) is preferably from the viewpoint of reactivity and toughness 0.1-5.0 , More preferably 0.5 to 3.0%.

The composition of the present invention preferably further contains a compound (F) having at least one epoxy group and at least one (meth) acryloyl group. By containing (F), the transparency of the cured product can be improved.
Examples of (F) include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexanemethyl (meth) acrylate, and (C12), (C13) and (C22) and (meta ) Acrylic acid partial reactants and mixtures thereof.
Of these, 3,4-epoxycyclohexanemethyl (meth) acrylate and (C12), (C13) and a partial reaction product of (meth) acrylic acid are preferable from the viewpoint of reactivity.
The amount of (F) used is usually 40% or less based on the total weight of (A) to (E), preferably 1 to 30%, more preferably 5 to 20% from the viewpoint of transparency and flexibility. is there.

  The composition of the present invention may further contain other polyfunctional (meth) acrylate (G). (G) includes C8 or more and Mn 500,000 or less, and these may be used alone or in combination of two or more.

(G1) Di (meth) acrylate (G11) polyoxyalkylene (alkylene is C2-4) (molecular weight 106 or more and Mn 3,000 or less) di (meth) acrylate PEG (Mn400), PPG (Mn200) and PTMG (Mn650) ) Di (meth) acrylates, etc. (G12) Di (meth) acrylates of AO 2-30 mol adducts of bisphenol compounds, Di (meth) of EO 2 mol and PO4 mol adducts of bisphenol A, -F and -S Diacrylate (G13) Di (meth) acrylate of C2-30 aliphatic dihydric alcohol EG, PG, NPG and HD di (meth) acrylate etc. (G14) Divalent having C6-30 alicyclic skeleton Di (meth) acrylate of alcohol dimethylol tricyclodecane, cyclohexa Dimethanol and di (meth) acrylate of hydrogenated bisphenol A, etc.

(G2) Poly (trivalent to hexavalent or higher) (meth) acrylate (G21) C3-40 polyvalent (trivalent to hexavalent or higher) alcohol poly (meth) acrylate TMP tri (meth) acrylate , GR tri (meth) acrylate, TMP PO3 molar adduct tri (meth) acrylate, TMP EO3 molar adduct tri (meth) acrylate, PE tri (meth) acrylate, PE tetra (meth) acrylate, Tetra (meth) acrylate of PE EO4 mole adduct, hexa (meth) acrylate of diPE, etc. (G3) Polyester (meth) acrylate Multivalent (2-4) carboxylic acid, Multivalent (2-8 or more) A plurality of ester bonds and a plurality of ester bonds obtained by esterification of an alcohol and a (meth) acryloyl group-containing compound Polyester (meth) acrylate having a meth) acryloyl group and having a molecular weight of 150 or more and Mn 4,000 or less As the polyvalent (2-4) carboxylic acid, for example, an aliphatic polyvalent carboxylic acid [C3-20, such as malonic acid, maleic acid, etc. (Anhydride), adipic acid, sebacic acid, succinic acid, a reaction product of acid anhydride (a reaction product of diPE and maleic anhydride, etc.), an alicyclic polyvalent carboxylic acid [C5-30, such as cyclohexanedicarboxylic acid, Tetrahydro (anhydride) phthalic acid and methyltetrahydro (anhydride) phthalic acid] and aromatic polycarboxylic acids [C8-30, such as isophthalic acid, terephthalic acid, phthalic acid (anhydride) and trimellitic acid (anhydride)] Can be mentioned.
Examples of the polyvalent (2 to 8 or more) alcohols include the polyols exemplified as the above (a2).
Examples of the (meth) acryloyl group-containing compound include C2-30, such as (meth) acrylic acid and hydroxymethyl (meth) acrylate.
(G4) Polyalkadiene having a (meth) acryloyl group at the side chain and / or terminal thereof Polybutadiene di (meth) acrylate (Mn500 to 500,000), etc. (G5) Epoxy (meth) acrylate The epoxy compound (C) and ( A reaction product of (meth) acrylate other than the compound (F) having at least one epoxy group and at least one (meth) acryloyl group. 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Meth) acrylic acid 2 mol adduct, (meth) acrylic acid 2 mol adduct of bisphenol A type epoxy compound, etc. (G6) Siloxane polymer having (meth) acryloyl group at side chain and / or terminal of dimethylpolysiloxane (Mn 300-20,000)
Dimethylpolysiloxane di (meth) acrylate and the like.
Among these, (G1), (G2) and (G3) are preferable from the viewpoint of toughness of the cured product.

  The use amount of (G) is usually 100% or less based on the total weight of (A) to (E), preferably 5 to 50%, particularly preferably 10 to 30% from the viewpoint of the elasticity and toughness of the cured product. It is.

  If necessary, the composition of the present invention may further contain a photosensitizer (H). Examples of (H) include benzophenone, 4,4′-bis (diethylamino) benzophenone, 2,4′-diethylthioxanthone, isopropylthioxanthone, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and the like. It is done.

The composition of the present invention may further contain various additives (J) as necessary as long as the effects of the present invention are not impaired. (J) includes inorganic fine particles (J1), pigment (J2), dispersant (J3), antifoaming agent (J4), leveling agent (J5), silane coupling agent (J6), thixotropic agent (increase) One or more additives selected from the group consisting of (viscous agent) (J7), slip agent (J8), antioxidant (J9) and ultraviolet absorber (J10) are included.
The total use amount of (J) is usually 60% or less, preferably 0.005 to 50%, based on the total weight of the composition of the present invention.

  Examples of the inorganic fine particles (J1) include alumina [aluminum oxide, aluminum hydroxide, alumina white (alumina hydrate), silica alumina (a fused material of alumina and silica, alumina surface coated with silica, etc.)], zirconia , Metal carbide (tungsten carbide, titanium carbide, silicon carbide, boron carbide, etc.), diamond, carbon black (channel black, furnace black, thermal black, acetylene black, etc.), silica (fine powder silicic acid, hydrous silicic acid, diatom, Colloidal silica, etc.), silicates (fine powdered magnesium silicate, talc, soapstone, stearite, calcium silicate, magnesium aluminosilicate, sodium aluminosilicate, etc.), carbonates (sedimentation (active, dry, heavy or light) ) Calcium carbonate Magnesium carbonate, etc.], clay (kaolinic clay, sericite clay, vilophyllite clay, montmorillonite clay, bentonite, acidic clay, etc.), sulfate [aluminum sulfate (sulfate band, satin white, etc.), barium sulfate ( Barite powder, precipitated barium sulfate, lithopone, etc.), magnesium sulfate, calcium sulfate (stone koji) (anhydrous koji, hemihydrate koji, etc.)], lead white, mica powder, zinc white, titanium oxide, activated calcium fluoride , Cement, lime, calcium sulfite, molybdenum disulfide, and microballoons.

Of these, preferred are alumina, silica, silicate, carbonate, sulfate and titanium oxide, more preferably silica, calcium carbonate, from the viewpoint of scratch resistance and composition of the cured product, and non-coloration of the cured product. Barium sulfate and titanium oxide.
(J1) may be used in combination of two or more, or two or more may be combined (for example, titanium oxide is fused to silica). The shape of (J1) is not particularly limited, and may be any of, for example, an indefinite shape, a spherical shape, a hollow shape, a porous shape, a petal shape, an agglomerated shape, and a granular shape (an elliptic sphere shape, a star shape, a square shape, etc.).
The amount of (J1) used is usually 50% or less based on the total weight of the composition of the present invention, preferably 30% or less, more preferably 3 to 25% from the viewpoint of the flexibility of the cured product.

Examples of the pigment (J2) include the following.
(1) Azo pigments Insoluble monoazo pigments (toluidine red, permanent carmine FB, fast yellow G, etc.), insoluble disazo pigments (disazo yellow AAA, disazo orange PMP, etc.), azo lakes (soluble azo pigments) (lake red C, brilliant carmine) 6B etc.), condensed azo pigments, chelate azo pigments, etc .;
(2) Polycyclic pigments: phthalocyanine blue, indanthrone blue, quinacridone red, dioxazine violet, etc .;
(3) Dyeing lakes Basic dyes (Victoria Pure Blue BO lake, etc.), acidic dyes (alkali blue toner, etc.), etc .;
(4) Others Azine pigments (aniline black, etc.), daylight fluorescent pigments, nitroso pigments, nitro pigments, natural pigments, etc .;
The amount of (J2) used is usually 50% or less based on the total weight of the composition, preferably 40% or less, and more preferably 30% or less from the viewpoint of the flexibility of the cured product.

  Examples of the dispersant (J3) include organic dispersants [polymer dispersants (Mn 2,000 to 500,000) and low molecular dispersants (molecular weight of 100 or more and less than Mn 2,000)] and inorganic dispersants.

  Examples of the polymer dispersant include formalin condensates of naphthalene sulfonate [alkali metals (Na and K etc., the same applies hereinafter) salts, ammonium salts, etc.], polystyrene sulfonate (salts are the same as above, and the same applies below). ), Polyacrylate, poly (2-4) carboxylic acid (maleic acid / glycerin / monoallyl ether copolymer, etc.) salt, carboxymethyl cellulose (Mn 1,000-10,000) and polyvinyl alcohol (Mn 1,000- 100,000).

The following are mentioned as a low molecular weight dispersing agent.
(1) Polyoxyalkylene type AO (C2-4) of aliphatic alcohol (C4-30), [alkyl (C1-30)] phenol, aliphatic amine (C4-30) and aliphatic amide (C4-30) 1-30 mol adducts As aliphatic alcohols, n-, i-, sec- and t-butanol, octanol, dodecanol etc .; (alkyl) phenols as phenol, methylphenol and nonylphenol etc .; as aliphatic amines , Laurylamine, methylstearylamine and the like; and aliphatic amides include stearic acid amide and the like.
(2) Polyhydric alcohol type Monomers of C4-30 fatty acids (lauric acid, stearic acid, etc .; the same shall apply hereinafter) and polyhydric (divalent to hexavalent or higher) alcohols (eg, GR, PE, SO and sorbitan). Ester Compound (3) Carboxylate Type Alkali Metal Salt of C4-30 Fatty Acid (4) Sulfate Ester Type C4-30 Fatty Alcohol (same as above, the same shall apply hereinafter) and Aliphatic Alcohol AO (C2- 4) Sulfate alkali metal salts of 1-30 mol adducts, etc.

(5) Sulfonate salt type [Alkyl (C1-30)] phenol (same as above, sulfonate alkali metal salt of the same) (6) Phosphate ester type C4-30 aliphatic alcohol and aliphatic alcohol AO (C2-4) 1-30 mol adduct mono- or diphosphate salts [alkali metal salts, quaternary ammonium salts, etc.]
(7) C1-30 aliphatic amines [primary (laurylamine, etc.), secondary (dibutylamine, etc.) and tertiary amine (dimethylstearylamine, etc.) hydrochloride, triethanolamine And C4-30 fatty acid monoester inorganic acid (hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, etc.) (8) quaternary ammonium salt type C4-30 quaternary ammonium (butyltrimethylammonium, diethyllauryl) And inorganic acid salts of methylammonium and dimethyldistearylammonium.

Examples of inorganic dispersants include alkali metal salts of polyphosphoric acid and phosphoric acid-based dispersants (phosphoric acid, monoalkyl phosphoric acid ester, dialkyl phosphoric acid ester and the like).
The amount of (J3) used is usually 10% or less, preferably 0.05 to 5%, based on the total weight of the composition of the present invention.

Defoaming agents (J4) include lower alcohols (C1-6) (methanol, butanol, etc.), higher alcohols (C8-18) (octyl alcohol, hexadecyl alcohol, etc.), higher fatty acids (C10-20) (oleic acid) , Stearic acid, etc.), higher fatty acid esters (C11-30) (glycerin monolaurate, etc.), phosphate esters (tributyl phosphate, etc.), metal soaps (calcium stearate, aluminum stearate, etc.), polyethers [PEG (Mn200- 10,000), PPG (Mn 200 to 10,000), etc.], silicone (dimethylsilicone oil, alkyl-modified silicone oil, fluorosilicone oil, etc.) and mineral oil (silica powder dispersed in mineral oil), etc. Can be mentioned.
The amount of (J4) used is usually 3% or less, preferably 0.01-2%, based on the total weight of the composition of the present invention.

As the leveling agent (J5), PEG type nonionic surfactant (nonylphenol EO 1 to 40 mol adduct, stearic acid EO 1 to 40 mol adduct, etc.), polyhydric alcohol type nonionic surfactant (sorbitan palmitic acid monoester) Sorbitan stearic acid monoester, sorbitan stearic acid triester, etc.), fluorine-containing surfactant (perfluoroalkyl EO 1-50 mol adduct, perfluoroalkyl carboxylate, perfluoroalkyl betaine, etc.), modified silicone oil [e.g. Polyether-modified silicone oil and (meth) acrylate-modified silicone oil].
The amount of (J5) used is usually 3% or less, preferably 0.1 to 2%, based on the total weight of the composition of the present invention.

Examples of the silane coupling agent (J6) include amino group-containing silane coupling agents (γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-phenylaminopropyl trimethoxysilane, etc.), ureido group-containing silane. Coupling agents (ureidopropyltriethoxysilane, etc.), vinyl group-containing silane coupling agents [vinylethoxysilane, vinylmethoxysilane, vinyltris (β-methoxyethoxy) silane, etc.], methacrylate groups-containing silane coupling agents (γ-methacrylic) Loxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, etc.), epoxy group-containing silane coupling agents (γ-glycidoxypropyltrimethoxysilane, etc.), isocyanate group-containing silane coupling agents (γ- Isocyanate-propyltriethoxysilane, etc.), polymer-type silane coupling agents (polyethoxydimethylsiloxane, polyethoxydimethylsiloxane, etc.), cationic silane coupling agents [N- (N-benzyl-β-aminoethyl) -γ-amino Propyltrimethoxysilane hydrochloride, etc.].
The amount of (J6) used is usually 10% or less, preferably 0.5 to 7%, based on the total weight of the composition of the present invention.

Examples of the thixotropic agent (J7) include inorganic thixotropic agents (bentonite, organically treated bentonite, colloidal calcium carbonate, etc.) and organic thixotropic agents (hydrogenated castor oil wax, calcium stearate, aluminum oleate, polymerized linseed oil) Etc.).
The amount of (J7) used is usually 20% or less, preferably 0.5 to 10%, based on the total weight of the composition of the present invention.

Examples of slip agents (J8) include higher fatty acid esters (such as butyl stearate), higher fatty acid amides (such as ethylene bis stearic acid amide and oleic acid amide), metal soaps (such as calcium stearate and aluminum oleate), and wax [paraffin wax. And polyolefin wax (polyethylene wax, polypropylene wax, carboxyl group-containing polyethylene wax, etc.)] and silicone (for example, dimethyl silicone oil, alkyl-modified silicone oil and fluorosilicone oil).
The amount of (J8) used is usually 5% or less, preferably 0.01-2%, based on the total weight of the composition of the present invention.

Antioxidants (J9) include hindered phenol compounds [triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis. [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,5-di- t-butyl-4-hydroxybenzylphosphonate diethyl ester] and amine compounds (n-butylamine, triethylamine, diethylaminomethyl methacrylate, etc.).
The amount of (J9) used is usually 3% or less, preferably 0.005 to 2%, based on the total weight of the composition of the present invention.

Examples of the ultraviolet absorber (J10) include benzotriazole compounds [2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2 -(3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, etc.], triazine compounds [ 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol], benzophenone (such as 2-hydroxy-4-n-octyloxybenzophenone), An oxalic acid anilide compound (2-ethoxy-2'-ethyl oxalic acid bisanilide etc.) is mentioned.
The amount of (J10) used is usually 3% or less, preferably 0.005 to 2%, based on the total weight of the composition of the present invention.

  When the additive is the same between (J1) to (J10), the amount of each additive exerting the corresponding additive effect is not used regardless of the effect as the other additive, Considering that the effects as other additives can be obtained at the same time, the amount used is adjusted according to the purpose of use.

  The composition of the present invention may be diluted with a solvent as necessary in order to adjust the viscosity to be suitable for coating during coating. The amount of the solvent used is usually 2,000% or less, preferably 10 to 500%, based on the weight of the composition before adding the solvent. Moreover, the viscosity of a coating liquid is the temperature (usually 5-60 degreeC) at the time of use, and is 5-500,000 mPa * s normally, Preferably it is 50-10,000 mPa * s from a viewpoint of stable coating.

The solvent is not particularly limited as long as it dissolves the resin component in the composition of the present invention. Specifically, the aromatic hydrocarbon (C7 to 10, for example, toluene, xylene and ethylbenzene). Ester or ether ester (C4-10, eg ethyl acetate, butyl acetate and methoxybutyl acetate), ether (C4-10, eg diethyl ether, tetrahydrofuran, EG monoethyl ether, EG monobutyl ether, PG monomethyl ether and DEG monoethyl ether), ketones (C3-10, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone), alcohols (C1-10, such as methanol, ethanol, n- and i-propanol). n-, i-, sec- and t-butanol, 2-ethylhexyl alcohol and benzyl alcohol), amides (C3-6, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.), sulfoxides (C2-4, such as dimethyl) Sulfoxide), water, and a mixed solvent of two or more thereof.
Of these, esters, ketones and alcohols having a boiling point of 70 to 100 ° C. are preferred, and ethyl acetate, methyl ethyl ketone, i-propanol and mixtures thereof are more preferred.

The glass transition temperature (Tg) of the cured product obtained by irradiating the composition of the present invention with ultraviolet rays is preferably 0 to 70 ° C., more preferably 20 to 50 ° C. from the viewpoint of toughness and flexibility.
Here, Tg is obtained by measuring the cured product of the present invention in a strip shape of 5 mm × 50 mm × 1 mm and using a viscoelastic spectrum measuring apparatus [Reogel E-4000, manufactured by UBM Co., Ltd.] at a frequency of 10 Hz.

The laminate of the present invention is obtained by curing a laminate composed of a base material, a coating layer of the above composition on the base material, and a transparent base material on the coating layer.
Specifically, the laminate is prepared by diluting the above composition with a solvent if necessary, coating the substrate (I), if necessary, and then drying the transparent substrate (II) thereon. It is manufactured by bonding and then curing by ultraviolet irradiation.

Although it does not specifically limit as transparent base material (II), Usually, resin of Mn 100,000-10,000,000, for example, polyethylene terephthalate, polymethyl methacrylate, polycarbonate, triacetyl cellulose, and polymethyl methacrylate-styrene copolymer resin And inorganic base materials (glass, quartz, etc.).
These may be either plate-shaped or film-shaped, but a film shape of 0.1 to 5 mm is preferable from the viewpoint of productivity.

  Examples of the material of the base material layer (I) include the same materials and metals (copper, aluminum, iron, etc.) as the above (II). (I) preferably has a plate shape of 3 to 50 mm from the viewpoint of rigidity.

In coating the composition of the present invention, a commonly used apparatus such as a coating machine [bar coater, gravure coater, roll coater (size press roll coater, gate roll coater, etc.), air knife coater, spin coater, blade coater, etc. ] Can be used.
The coating film thickness (film thickness after drying) is usually 0.5 to 300 μm, and the preferable upper limit is 250 μm from the viewpoint of drying properties and curability, and the preferable lower limit is 1 μm from the viewpoint of curability and adhesiveness.

  When the composition of the present invention is used after being diluted with a solvent, it is preferably dried after coating. Examples of the drying method include hot air drying (such as a dryer). The drying temperature is usually 10 to 200 ° C., the upper limit is preferably 150 ° C. from the viewpoint of preventing deformation of the substrate (I) and the surface smoothness, and the lower limit is preferably 30 ° C. from the viewpoint of the drying speed.

When the composition of the present invention is applied and then cured by ultraviolet irradiation, a known ultraviolet irradiation device [for example, trade name “Eye Grandage”, manufactured by Eyegraphic Co., Ltd.] can be used. The dose of the ultraviolet radiation is typically 10~10,000mJ / cm ^2, a preferred upper limit of a flexible point of view of the cured product, 5,000 mJ / cm ^2, preferably lower from the viewpoint of curability of the composition, 100 mJ / cm ² .

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by this.

Production Example 1
In a reaction vessel equipped with a stirrer, a condenser and a thermometer, PTMG [trade name “PTMG-2000”, manufactured by Mitsubishi Chemical Corporation, Mn2,000] 100 parts, IPDI 16.7 parts and bismuth tri (2- Ethyl hexanoate) (2-ethylhexanoic acid 50% solution) 0.05 part was charged and reacted at 100 ° C. for 4 hours, then 5.8 parts of 2-hydroxyethyl acrylate was added and reacted at 100 ° C. for 6 hours. Thus, urethane acrylate (A-1) was obtained. The Mn of (A-1) was 4,890.

Production Example 2
A reaction vessel similar to Production Example 1 was charged with 100 parts of PEG [trade name “New Pole PEG-600”, manufactured by Sanyo Chemical Industries, Ltd., Mn600] and 54.6 parts of hydrogenated MDI, and reacted at 110 ° C. for 4 hours. After that, 9.7 parts of 2-hydroxyethyl acrylate and 0.03 part of bismuth tri (2-ethylhexanoate) (2-ethylhexanoic acid 50% solution) were added as a catalyst and reacted at 80 ° C. for 4 hours. Urethane acrylate (A-2) was obtained. Mn of (A-2) was 3,950.

Production Example 3
In a reaction vessel similar to Production Example 1, PTMG [trade name “PTMG-1000”, manufactured by Mitsubishi Chemical Corporation, Mn 1,000] 100 parts, 9.8 parts BD, 78.6 parts hydrogenated MDI, and 2-hydroxyethyl After charging 23.2 parts of acrylate and uniformly mixing, 0.05 part of bismuth tri (2-ethylhexanoate) (2-ethylhexanoic acid 50% solution) was added as a catalyst and reacted at 80 ° C. for 6 hours to obtain urethane acrylate. (A-3) was obtained. The Mn of (A-3) was 2,120.

Examples 1-6
It compounded according to the weight ratio shown in Table 1, and obtained the photosensitive composition (Examples 1-6) of this invention. The viscosity at 25 ° C. of each composition was measured with a BL type viscometer [manufactured by Tokyo Keiki Co., Ltd.].
Next, hardened | cured material was created according to the following evaluation method, and the transmittance | permeability, adhesive strength, and tensile elongation rate were evaluated. The results are shown in Table 3.
Comparative Examples 1-4
Comparative photosensitive compositions (Comparative Examples 1 to 4) obtained by blending according to the weight ratio shown in Table 1 were evaluated in the same manner as in Examples 1 to 6. The results are shown in Table 3.

Evaluation method (1) Transmittance (evaluation of transparency)
(I) Cured product preparation method Spacer frame (width) set on the periphery of glass plate [trade name “MICRO SLIDE GLASS water plate”, Matsunami Glass Co., Ltd., vertical 76 mm × width 26 mm × thickness 1.3 mm] The sample was filled in a frame of 5 mm and thickness of 100 μm, and a glass plate was further stacked thereon, and air was pushed out by sandwiching it with a nip roller.After that, an ultraviolet irradiation device [trade name “Eye Grandage”, eye graphic ( Irradiation lamp was a metal halide lamp, the same applies hereinafter], and was irradiated with 1,000 mJ / cm ² of ultraviolet light to obtain a cured product.
(Ii) Transmittance measuring method The transmittance was measured using a total light transmittance measuring device [trade name “haze-gard dual”, manufactured by BYK Gardner Co., Ltd.] in accordance with JIS K-7361-1.

(2) Adhesive strength (evaluation of adhesiveness)
(I) Cured material preparation method In accordance with JIS K-6854-1, in the frame of a spacer frame (width 5 mm, thickness 100 μm) set on the periphery of the substrate [vertical 70 mm × width 50 mm × thickness 10 mm] Further, a PET film [trade name “A4100”, manufactured by Toyobo Co., Ltd., length 150 mm × width 50 mm × thickness 200 μm] was stacked thereon, and air was pushed out by being sandwiched by nip rollers. Then, using an ultraviolet irradiation device, 1,000 mJ / cm ² of ultraviolet rays were irradiated and cured to obtain a 90 ° C. peeling test piece.
Base material (1) PMMA: [trade name “Acrylite L”, manufactured by Mitsubishi Rayon Co., Ltd.]
(2) Glass plate: [trade name “GLASS PLATE”, manufactured by ASONE Corporation]
(Ii) Adhesive strength measurement method According to JIS K-6854-1, autograph [AG100kNG or AG100NIS, manufactured by Shimadzu Corporation, the same shall apply hereinafter. The T peel (90 ° C. peel) test was performed at a room temperature of 23 ° C. and a tensile speed of 50 mm / min to measure the adhesive strength.
(3) Curability The cured product surface of the test piece after the adhesive strength test was placed on paper [trade name “Kyogami KB-K39N”, manufactured by KOKUYO Co., Ltd., A4 plate], and allowed to stand for 1 hour. The test piece was removed and the presence or absence of stains remaining on the paper was observed with the naked eye and evaluated according to the following criteria.

○: No stain ×: There is a stain

(4) Tensile elongation (evaluation of flexibility)
(I) Cured product preparation method Glass plate [trade name “GLASS PLATE”, manufactured by ASONE Co., Ltd., coated on the surface with a fluorine release agent [trade name “Daifree GA-6010”, manufactured by Daikin Industries, Ltd.] After filling the sample into a frame of a spacer frame (width 10 mm, thickness 1 mm) set in the periphery of the vertical 200 mm × width 200 mm × thickness 5 mm], and sandwiching it with a glass plate coated with a release agent in the same manner The air was pushed out by being sandwiched between nip rollers. Thereafter, ultraviolet rays of 1,000 mJ / cm ² were irradiated using an ultraviolet irradiation device. Thereafter, the glass plate was removed, and a test piece type 5 of JIS K-7127 was punched out from the cured product to obtain a test piece for a tensile test.
(Ii) Tensile Elongation Rate Test Method The obtained test piece was subjected to a tensile test at a room temperature of 23 ° C. and a tensile speed of 10 mm / min using an autograph in accordance with JIS K-7127 to measure the tensile elongation rate.

IBXA: Isobornyl acrylate [Brand name "Light acrylate IBXA", Kyoei
Manufactured by Chemical Co., Ltd.]
M101: Phenoxy DEG acrylate [trade name “Aronix M-101”, Tojo
Synthetic Co., Ltd.]
ACMO: acryloylmorpholine [trade name “ACMO”, manufactured by Kojin Co., Ltd.]
EP828: Bisphenol A diglycidyl ether [trade name “Epicoat 828”, di
Made by Japan Epoxy Resin Co., Ltd.]
C3000: Limonene dioxide [Brand name "Celoxide 3000", Daicel Chemical Industries
Manufactured by]
C2021: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane
Carboxylate [trade name “Celoxide 2021”, Daicel Chemical Industries (
Made by Co., Ltd.]
A200: 3,4-epoxycyclohexanemethyl acrylate [trade name “cycloma
-A200 ", manufactured by Daicel Chemical Industries, Ltd.]
GMA: Glycidyl methacrylate [trade name “Blemmer G”, manufactured by NOF Corporation]
BA641: EO-modified bisphenol A diacrylate [trade name “Neomer BA-641
"Sanyo Chemical Industries, Ltd.]
VR77: Bisphenol A diglycidyl ether diacrylate [trade name "Lipoxy
VR-77 ", Showa Polymer Co., Ltd.]
TPO: 1,3,5-trimethylbenzoyldiphenylphosphine oxide [trade name
"Lucirin TPO", manufactured by BASF Corporation]
I184: 1-hydroxycyclohexyl phenyl ketone [trade name “Irgacure 18
4 ", manufactured by Ciba Specialty Chemicals Co., Ltd.]
SP170: 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] fe
Nyl sulfide-bis-hexafluoroantimonate [trade name "ADEKA
Putmer SP-170 ", manufactured by Asahi Denka Kogyo Co., Ltd.]

  From the results in Table 1, it can be seen that the composition of the present invention is clearly superior in adhesion and flexibility as compared with the comparative composition. In particular, compared with Comparative Examples 2-4, it is excellent in adhesiveness, sclerosis | hardenability, and a softness | flexibility.

  The cured product obtained by curing the photosensitive composition for adhesives of the present invention is excellent in transparency, flexibility, and adhesiveness to various base materials (plastic, glass, metal, etc.), so an optical film (antireflection) Film, hard coating film, light diffusing sheet, etc.), adhesive for optical disks, sealant for display panels (liquid crystal, organic EL, etc.), adhesive for optical members, or sealant It is.

Claims (6)

Urethane (meth) acrylate (A) formed from a compound (a1) having a hydroxyl group and a (meth) acryloyl group, a polyol (a2) and a polyisocyanate (b), a monofunctional (meth) acryloyl group-containing compound (B) A photosensitive composition for adhesives, comprising: an epoxy compound (C), a photopolymerization initiator (D), and a photocationic polymerization initiator (E). The proportions based on the total weight of (A) to (E) are 10 to 79.8% for (A), 10 to 79.8% for (B), 5 to 69.8% for (C), (D The composition according to claim 1, wherein 0.1) to 0.1% and (E) is 0.1 to 5.0%. The composition according to claim 1 or 2, further comprising a compound (F) having at least one (meth) acryloyl group and at least one epoxy group. The adhesive agent or sealing agent of an optical member which consists of a composition in any one of Claims 1-3. The laminated body formed by hardening the laminated body which consists of a base material and the coating layer of the composition in any one of Claims 1-4 on a base material, and the transparent base material on a coating layer. The composition according to any one of claims 1 to 4 is coated on a substrate, and another transparent substrate is bonded onto the coated surface, followed by curing by irradiation with ultraviolet rays. Method.