TWI591081B - Photocurable composition - Google Patents

Description

Photocurable composition

The present invention relates to a photocurable composition and a cured product of the photocurable composition, and more specifically to a photocurable composition capable of obtaining a cured product excellent in adhesion to a substrate, and a light using the same A hardenable adhesive.

The photocurable composition is a composition which is cured by irradiation with an active energy ray such as ultraviolet rays, and has excellent advantages such as excellent quick-curing property. Therefore, it is used in various fields such as an adhesive, a paint, and various resists. A photocurable composition is known to contain an acrylate compound. For example, Patent Document 1 discloses a mixture of urethane acrylate, polyester acrylate or urethane acrylate and polyester acrylate. A solid photocurable film adhesive comprising a photocurable material, a solid polyvinyl acetal, and a photoinitiator.

On the other hand, a melamine resin or a urea resin obtained by passing a compound having a reactive methylol group as a thermosetting resin is known as a heat curing agent or a thermal crosslinking agent.

For example, Patent Document 2 discloses the use of methoxyl A photocurable acrylic coloring composition containing melamine as an adhesion improving agent, Patent Document 3 discloses a photocurable coating sheet which can be used as a melamine crosslinking agent, and Patent Document 4 discloses that melamine can be used. The resin is a light and thermosetting composition of a curing agent, and Patent Document 5 discloses a curable composition containing a melamine compound as a crosslinking agent or an adhesion improving agent, but none of these uses a melamine compound as an adhesive. The active ingredient.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 05-214302

[Patent Document 2] Japanese Patent Laid-Open No. Hei 5-188591

[Patent Document 3] Japanese Special Fair 7-015011

[Patent Document 4] Japanese Patent Laid-Open No. Hei 10-147745

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2005-089651

However, the photocurable resin has the above-described advantages, but there is still room for improvement in adhesion to a substrate such as a film made of various resins.

Therefore, an object of the present invention is to provide a photocurable composition capable of obtaining a cured product excellent in adhesion to a substrate, and a photocurable adhesive using the same.

In order to solve the above problems, the inventors of the present invention have found that a compound having an active methylol group as a thermosetting component and an optical compound as a main component can be blended in a photocurable composition. The above problems have been completed and the present invention has been completed.

That is, the photocurable composition of the present invention is characterized by comprising (A) a compound having a plurality of active alkanol groups, (B) an alcohol compound, and (C) a polyfunctional acrylic oligomer and (D) Photoinitiator.

In the photocurable composition of the present invention, the (B) alcohol compound is preferably an acrylate compound having a hydroxyl group, a methacrylate compound having a hydroxyl group, an acrylamide compound having a hydroxyl group or a methacrylic acid having a hydroxyl group. Amine compound.

In the photocurable composition of the present invention, the (B) alcohol compound is preferably a polyol compound.

In the photocurable composition of the present invention, the above (A) compound having a plurality of active alkanol groups is preferably selected from the group consisting of polyalkanolized melamine, polyalkanolized acetylene urea, polyalkanol hydroxyethylene urea, and polyalkanolization. One or more compounds of the group consisting of urea, polyalkanol benzoguanamine, polyalkanolamide, and polyalkanol acrylamide.

In the photocurable composition of the present invention, the compound (A) having a plurality of active alkanol groups is preferably a compound having one or more kinds of skeletons selected from the group 1 below.

In the photocurable composition of the present invention, the compound (A) having a plurality of active alkanol groups is preferably a polyalkanolized melamine represented by the following general formula (I).

(In the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxyl group, the alkyl group The methylene group in the middle can also be interrupted by an oxygen atom).

In the photocurable composition of the present invention, the compound (A) having a plurality of active alkanol groups is preferably a polyalkanolated urea represented by the following general formula (III).

(wherein R ⁵¹ and R ⁵⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxyl group, and the methylene group in the alkyl group may be interrupted by an oxygen atom. R ⁵² and R ⁵³ each independently represents a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, n = 1 or 2, and when n = 2, R ⁵² and R ^{53 are} bonded to each other to form a dimer).

In the photocurable composition of the present invention, the (C) polyfunctional acrylic oligomer is preferably a urethane acrylate oligomer or a urethane methacrylate oligomer.

In the photocurable composition of the present invention, the photoinitiator (D) is preferably a photoacid generator.

The photocurable composition of the present invention preferably further contains (E) a polyfunctional acrylate compound or a polyfunctional methacrylate compound.

The photocurable composition of the present invention preferably further contains (F) a monofunctional acrylic monomer.

The photocurable adhesive of the present invention is characterized by being obtained from the photocurable composition of any of the above.

According to the present invention, it is possible to provide a photocurable composition capable of obtaining a cured product excellent in adhesion to a substrate, and a photocurable adhesive using the same.

Hereinafter, the photocurable composition of the present invention and a cured product thereof will be described in detail.

The component (A) in the present invention is a compound having a plurality of reactive alkanol groups. The reactive alkanol group has a methylene group adjacent to an oxygen atom, and the reactivity by the acid catalyst is high. The number of carbon atoms of the reactive alkanol group is preferably from 1 to 5. The component (A) of the present invention is not used as a thermosetting agent or a thermal crosslinking agent, but is a photocurable resin which exhibits a polymerization reaction by the action of a photoinitiator due to light irradiation.

In the present invention, the compound having a plurality of active alkanol groups as (A) is not particularly limited as long as it has a plurality of active alkanol groups in the molecule. An amine-based resin such as melamine resin, guanamine resin, sulfonium diamine resin, urea resin, aniline resin or the like; melamine monomer, urea, hydroxyethylene urea (glyoxal urea), acetylene urea, benzoguanamine can be used. An alkanolation of an amine group of spiramide, hydrazine, dicyandiamide, acrylamide, amide, or the like. The alkanolation can be carried out by a known method.

The compound (A) having a plurality of active alkanol groups used in the present invention is preferably a compound having a skeleton selected from the following Group 1 from the viewpoint of easiness of synthesis.

The aforementioned (A) compound having a plurality of active alkanol groups used in the present invention, specifically, polyalkanolized melamine, polyalkanolized acetylene urea, polyalkanol hydroxyethylene urea, polyalkanolated urea, poly An alkanolated benzoguanamine, a polyalkanolamide, a polyalkanol acrylamide, or the like, which may also be a component containing a portion of the self-condensed oligomer. Further, the compound (A) having a plurality of active alkanol groups may be used singly or in combination of plural kinds.

As the compound (A) having a plurality of active alkanol groups used in the present invention, the polyalkanolated melamine represented by the following general formula (I) is preferred because it is easy to synthesize and has high adhesion.

(In the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxyl group, the alkyl group The methylene group in the middle can also be interrupted by an oxygen atom).

In the above general formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and an isopropyl group. Base, butyl, s-butyl, t-butyl, isobutyl, pentyl, isopentyl, t-pentyl, 2-methoxyethyl, 3-methoxypropyl, 4-methyl Oxybutyl, methoxyethoxyethyl, 3-methoxybutyl and the like.

Further, as the compound (A) having a plurality of active alkanol groups used in the present invention, the polyalkanolated urea represented by the following general formula (III) is preferable because it is easy to synthesize and has high adhesion. .

(wherein R ⁵¹ and R ⁵⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxyl group, and the methylene group in the alkyl group may be interrupted by an oxygen atom. R ⁵² and R ⁵³ each independently represents a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, n = 1 or 2, and when n = 2, R ⁵² and R ^{53 are} bonded to each other to form a dimer).

Further, as the compound (A) having a plurality of active alkanol groups used in the present invention, the polyalkanolated urea represented by the following general formula (IV) or (V) is easy to synthesize, and high adhesion can be obtained. Therefore, it is better.

(wherein R ⁵⁵ and R ⁶⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxyl group, and the methylene group in the alkyl group may be interrupted by an oxygen atom. R ⁵⁶ , R ⁵⁷ , R ⁵⁸ and R ⁵⁹ each independently represent a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms).

(wherein R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxyl group, and the methylene group in the alkyl group may also be oxygenated Atomic interrupt).

Examples of the alkyl group having 1 to 5 carbon atoms which can be taken from the above R ⁵¹ , R ⁵⁴ , R ⁵⁵ , R ⁶⁰ and R ⁶¹ to R ⁶⁴ are the same as those described above.

Examples of the alkoxy group having 1 to 5 carbon atoms which can be taken from the above R ⁵² , R ⁵³ and R ⁵⁶ to R ⁵⁹ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and the like. .

The above (A) has a compound having a plurality of active alkanol groups, and the active alkanol groups may be condensed with each other to form an oligomer.

(A) A compound having a plurality of reactive alkanol groups, which may be used alone or as a mixed monomer and oligomer, and may be used in the form of a resin.

A commercially available product may be used as the compound having a plurality of active alkanol groups, and examples thereof include Cymel 303, 235, 254, 325, 1128, 1156, 1170 (manufactured by MT Aqua Polymer Co., Ltd.), and Mycoat 102, 105, 506 ( MT Aqua Polymer Co., Ltd.), U-VAN 20N, 20SB, 20SE60, 122, 125, 128, 220, 225, 2020 (manufactured by Mitsui Chemicals, Inc.), Nikalac MW-30M, MW-30HM, MW-390, MW-100LM, MX-750LM, MX-45, MX a melamine resin such as -410 (manufactured by Sanwa Chemical Co., Ltd.); a guanamine resin such as Nikalac BL-60 or BX-4000; a urea resin such as Nikalac MX-270, MX-280 or MX-290.

The (B) alcohol compound is added to improve adhesion, and a known one can be used without particular limitation. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, isoamyl alcohol, tert-pentanol, n-hexanol, Tert-hexanol, n-heptanol, isoheptanol, tert-heptanol, n-octanol, 2-ethylhexanol, tert-octanol, n-nonanol, isodecyl alcohol, tert-nonanol, N-nonanol, isodecyl alcohol, lauryl alcohol, myristyl alcohol, palmitol, stearyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol a monohydric alcohol such as monobutyl ether and the alkylene oxide adducts thereof; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, isoprene glycol, 3-methyl-1,3-butanediol, 1,2-hexanediol 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,2-octanediol, octanediol (2-ethyl-1,3-hexanediol), 2- Butyl-2-ethyl-1,3-propanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-tetradecanediol, 1,2-hexadecane Alcohol, 1,2-octadecanediol, 1,12-octadecanediol, diethylene glycol, triethylene glycol, polyethylene glycol, An aliphatic diol such as propylene glycol; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, alcohol containing a spiro skeleton Tricyclic ring An alicyclic alcohol such as an alkyl dimethylol group or a pentacyclopentadecane dimethylol group; and an alkylene oxide adduct thereof; a diol of a sorbitol, a methyl diethanolamine or the like; and the like Alkylene oxide adduct; glycerin, polyglycerol, 1,2,3-butanetriol, 1,2,4-butanetriol, 2-methyl-1,2,3-propanetriol, 1,2 , 3-pentanetriol, 1,2,4-pentanetriol, 1,3,5-pentanetriol, 2,3,4-pentanetriol, 2-methyl-2,3,4-butane Alcohol, trimethylolethane, di-trimethylolpropane, 2,3,4-hexanetriol, 2-ethyl-1,2,3-butanetriol, trimethylolethane, three Hydroxymethylpropane, 4-propyl-3,4,5-heptanetriol, pentamethylglycerol (2,4-dimethyl-2,3,4-pentanetriol), triethanolamine, triisopropyl a trihydric alcohol such as an alkanolamine or the like, and an alkylene oxide adduct thereof; a polyhydric alcohol such as pentaerythritol, dipentaerythritol, tetramethylolpropane or sorbitol; and the alkylene oxide adducts; Citrate 2-hydroxyethyl ester, oxetane, 3-ethyl-3-hydroxymethyl oxetane, 2-hydroxyethyl (3-ethyl-3-oxetane) Alkylmethyl)ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl)ether, etc. having a hydroxyl group Oxetane compounds; acrylate compounds having hydroxyl groups; hydroxyl groups having a methyl acrylate compound; acrylamide compound having hydroxyl groups; hydroxyl group of a compound having a methyl acrylamide and the like.

(B) The ratio of use of the alcohol compound to the compound having a plurality of alkanol groups in the above (A) is preferably 20 parts by mass based on 100 parts by mass of the compound having a plurality of alkanol groups (A). 800 parts by mass, more preferably 50 to 300 parts by mass.

The (C) polyfunctional acrylic oligomer used in the present invention may, for example, be a urethane acrylate oligomer, an acrylate acrylate oligomer, a polyether acrylate oligomer, or a polyester acrylate. Oligomer, amine group Formate methacrylate oligomer, methacrylate epoxy ester oligomer, polyether methacrylate oligomer, polyester methacrylate oligomer, etc., especially urethane Acrylate oligomers or urethane methacrylate oligomers are preferred.

Examples of the urethane acrylate oligomer include polycarbonate urethane acrylate, polyester urethane acrylate, and polyether urethane acrylate. An ester urethane acrylate or the like can be obtained by a reaction of an isocyanate compound obtained by reacting a polyol with a diisocyanate and an acrylate monomer having a hydroxyl group. The polyhydric alcohol may, for example, be a polycarbonate diol, a polyester polyol, a polyether polyol or a polycaprolactone polyol.

The above epoxy acrylate oligomer can be obtained, for example, by an esterification reaction of an oxirane ring of a low molecular weight bisphenol type epoxy resin or a novolak epoxy resin with acrylic acid.

The polyether acrylate oligomer can be obtained by a dehydration condensation reaction of a polyhydric alcohol to obtain a polyether oligomer having a hydroxyl group at both terminals, followed by esterification of a hydroxyl group at both terminals thereof with acrylic acid.

The above polyester acrylate oligomer, for example, can be obtained by condensation of a polycarboxylic acid with a polyhydric alcohol to obtain a polyester oligomer having a hydroxyl group at both terminals, and then esterifying the hydroxyl groups at both ends thereof with acrylic acid, thereby obtaining .

In the (C) polyfunctional acrylic oligomer used in the present invention, polyfunctional means difunctional or higher, but usually 20 or less.

The molecular weight of the (C) polyfunctional acrylic oligomer used in the present invention is preferably from 500 to 5,000.

The photoinitiator (D) used in the present invention may be used alone or in combination of two or more.

The photoinitiator acts to generate an acid to react (A) a compound having a plurality of reactive alkanol groups with (B) an alcohol compound, or (C) a polyfunctional acrylic oligomer or a polyfunctional (F) described later. The effect of curing of an acrylate compound or a polyfunctional methacrylate compound.

Any of the above-mentioned photoacid generators can be used without any particular limitation as long as it produces Lewis acid by light irradiation. For example, a sulfonic acid derivative, a carboxylic acid derivative, a phosphonium salt or a derivative thereof, a phosphate ester, a decyl sulfonate, a hydroxy quinone imide, a metal salt or the like can be used, and among them, a cerium salt is particularly high in acid generating ability. Therefore, it is better. The representative of the onium salt may be a salt of a cation and an anion represented by the following general formula [A] ^r+ [B] _s ^t- (only the number of the r system 1 to 4, the number of the t system 1 to 4, the s system) The coefficient that keeps the charge neutral.)

Here, the cation [A] ^{r+ is} preferably 鎓, and its structure can be expressed, for example, by the following general formula [(R ⁷ ) _f Q] ^r+ .

Here, R ⁷ is an organic group having 1 to 60 carbon atoms and may contain an atom other than any carbon atom. f is an integer from 1 to 5. The f R ⁷ may be independently the same or different. Further, it is preferred that at least one of them is an organic group having an aromatic ring as described above. The Q group is selected from atoms or groups of atoms grouped by S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N=N. Further, when the valence of Q in the cation [A] ^r+ is q, the relationship of r = fq must be established (only N = N is regarded as the valence of 0).

Further, the anion [B] ^{t- is} preferably a halide complex, and its structure can be represented, for example, by the general formula [LX _g ] ^t- .

a metal or a semi-metal of the central atom of the L-based halide complex, and is B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, and the like. X-based halogen atom. g is an integer from 3 to 7. Further, when the valence of L in the anion [B] ^t- is p, the relationship of t = gp must be established.

Specific examples of the anion [LX _g ] ^t- of the above general formula include quinone (pentafluorophenyl) borate, tetrakis(3,5-difluoro-4-methoxyphenyl)borate, and tetrafluoroboric acid. Root (BF ₄ ) ^- , hexafluorophosphate (PF ₆ ) ^- , hexafluoroantimonic acid (SbF ₆ ) ^- , hexafluoroarsenic acid (AsF ₆ ) ^- , hexachloroantimonic acid (SbCl ₆ ) ^- and the like.

Further, the anion [B] ^{t- is} preferably a structure represented by the following general formula and [LX _g-1 (OH)] ^t- . L, X, and g are the same as described above. Further, examples of other anions which can be used include perchloric acid ions (ClO ₄ ) ^- , trifluoromethyl sulfite ions (CF ₃ SO ₃ ) ^- , fluorosulfonic acid ions (FSO ₃ ) ^- , toluenesulfonic acid anions, Trinitrobenzenesulfonic acid anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraarylborate, ruthenium (pentafluorophenyl)borate, and the like.

In the present invention, among the above-mentioned cerium salts, the aromatic sulfonium salts of the following (1) to (3) are particularly effective. One of these may be used alone or in combination of two or more.

(1) an aryldiazonium salt such as phenyldiazonium hexafluorophosphoric acid, 4-methoxyphenyldiazonium hexafluoroantimonic acid or 4-methylphenyldiazonium hexafluorophosphate

(2) Diphenylphosphonium hexafluoroantimonic acid, bis(4-methylphenyl)phosphonium hexafluorophosphate, bis(4-tert-butylphenyl)phosphonium hexafluorophosphate, tolyl Diaryl sulfonium salt such as cumene quinone (pentafluorophenyl)boronic acid

(3) a phosphonium salt of a phosphonium cation, a hexafluoroantimonium ion, a quinone (pentafluorophenyl) borate ion or the like represented by the following group 2 or group 3;

Further, as the photoacid generator, other preferred ones may also be (η ⁵ -2,4-cyclopentadien-1-yl)[(1,2,3,4,5,6-η)- An iron-aromatic complex such as (1-methylethyl)benzene]-iron-hexafluorophosphoric acid, or aluminum ginseng (ethyl acetonate), ginseng (ethyl pyruvate acetate), ginseng (salt) A mixture of an aluminum complex such as aldehyde) aluminum and a sterol such as triphenyl decyl alcohol.

Among the above photoacid generators, an aromatic sulfonium salt, an aromatic sulfonium salt, and an iron-aromatic hydrocarbon complex are preferably used from the viewpoint of practical surface and light sensitivity, and it is more preferable from the viewpoint of sensitivity. It is an aromatic onium salt represented by the following general formula (II).

^{(Wherein, R 21, R 22, R} 23, R 24, R 25, R 26, R 27, R 28, R 29, R 30, R 39, R 40, R 41, R 42 ^, and R ⁴³ lines were Independently represents a hydrogen atom; a halogen atom; a linear or branched alkyl group having 1 to 10 carbon atoms which may be interrupted by a halogen atom or an epoxy group and interrupted by an oxygen atom or a sulfur atom; an alkyl group having 1 to 10 carbon atoms; An oxy group; or an ester group having 2 to 10 carbon atoms; R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ each independently represent a hydrogen atom; a halogen atom; a linear or branched alkyl group having 1 to 10 carbon atoms which is substituted by a halogen atom or an epoxy group and which can be interrupted by an oxygen atom or a sulfur atom.

In the compound represented by the above formula (II), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² and R ^{33 .} Examples of the halogen atom represented by R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ include fluorine, chlorine, bromine and iodine.

R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ^a linear chain of 1 to 10 carbon atoms represented by R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ which may be substituted by a halogen atom or an epoxy group and interrupted by an oxygen atom or a sulfur atom. Or a branched alkyl group, which may, for example, be methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, pentyl, isopentyl, t-pentyl, Hexyl, cyclohexyl, heptyl, octyl, decyl, ethyloctyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl , methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoromethyl, trifluoromethyl Base, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl Base, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, decafluorohexyl, pentafluoroheptyl, heptafluorooctyl, methoxymethyl, 1,2- Oxyethyl, methoxyethyl, methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, t-butylthiomethyl, 4-pentene Oxymethyl, trichloroethoxymethyl, bis(2-chloroethoxy)methyl, methoxycyclohexyl, 1-(2-chloroethoxy)ethyl, 1-methyl-1 -methoxyethyl, ethyldithioethyl, trimethyldecylethyl, t-butyldimethylnonyloxymethyl, 2-(trimethyldecyl)ethoxymethyl, T-Butoxycarbonylmethyl, ethyloxycarbonylmethyl, ethylcarbonylmethyl, t-butoxycarbonylmethyl, acryloxyethyl, methacryloxyethyl, 2- Methyl-2-adamantyloxycarbonylmethyl, ethyl ethylethyl, 2-methoxy-1-propenyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-hydroxyl Propyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, 1,2-dihydroxyethyl and the like.

The number of carbon atoms represented by R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ Examples of the alkoxy group of 1 to 10 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an s-butoxy group, a t-butoxy group, an isobutoxy group, and a pentyloxy group. , isopentyloxy, t-pentyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethoxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, 2-methoxyethoxy, 3- Methoxypropoxy, 4-methoxybutoxy, 2-butoxyethoxy, methoxyethoxyethoxy, methoxyethoxyethoxyethoxy, 3- Methoxybutoxy, 2-methylthioethoxy, trifluoromethoxy, and the like.

The number of carbon atoms represented by R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ Examples of the ester group of 2 to 10 include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a phenoxycarbonyl group, an ethyloxy group, a propenyloxy group, a butoxy group, and a chloroethylene group. A group, a dichloroacetoxy group, a trichloroacetoxy group, a trifluoroacetoxy group, a t-butylcarbonyloxy group, a methoxyethoxycarbonyl group, a benzhydryloxy group or the like.

As the photoradical initiator, a conventionally known compound can be used, and examples thereof include benzophenone, phenyl biphenyl ketone, 1-hydroxy-1-benzyl decyl cyclohexane, benzoin, and benzyl group. Methyl ketal, 1-benzyl-1-dimethylamino-1-(4'-morpholinylbenzyl)propane, 2-morpholinyl-2-(4'-methylindenyl)benzyl Mercaptopropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl hydrazine, 4-benzyl fluorenyl-4'- Diphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzyl hydrazinopropane, 2-hydroxy-2-(4'-isopropyl)benzylidene propane, 4-butylbenzyl hydrazine Trichloromethane, 4-phenoxybenzylhydrazine methylene chloride, methyl benzalkonate, 1,7-bis(9'-acridinyl)heptane, 9-n-butyl-3,6 - bis(2'-morpholinylisobutyl) carbazole, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloro) Methyl)-s-triazine, 2-naphthyl-4,6-bis(trichloromethyl)-s-triazine, 2,2-bis(2-chlorophenyl)-4,5,4' , 5'-tetraphenyl-1-2'-biimidazole, 4,4-azobisisobutyronitrile, triphenylphosphine, camphorquinone, benzammonium peroxide 1,1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylindolyl)], ethyl ketone, 1-[9-ethyl-6-(2 -Methylbenzylindenyl)-9H-indazol-3-yl]-, 1-(0-ethenylhydrazine) and the like. Commercially available products include N-1414, N-1717, N-1919, PZ-408, NCI-831, NCI-930 (made by ADEKA), IRGACURE 369, IRGACURE 907, IRGACURE OXE 01, and IRGACURE OXE 02 (BASF (share) company system) and so on.

The ratio of use of the (D) photoinitiator to the compound (A) having a plurality of active alkanol groups is not particularly limited, and may be used in a usual ratio in a range not inhibiting the object of the present invention. For example, the (C) photoinitiator is preferably 0.05 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the compound having a plurality of active alkanol groups. When the amount is too small, the curing tends to be insufficient, and if it is too large, the strength of the cured product may be adversely affected.

In the photocurable composition of the present invention, (E) a polyfunctional acrylate compound or a polyfunctional methacrylate compound may be further added as needed.

Examples of the polyfunctional acrylate compound include acrylate acrylate, urethane acrylate, polyester acrylate, polyether acrylate, alcohol acrylate, and the like; and a polyfunctional methacrylate compound, which can be cited as a Epoxy acrylate, urethane methacrylate, polyester methacrylate, polyether methacrylate, methacrylate of alcohol, and the like.

The acryl epoxy ester is, for example, a conventionally known aromatic epoxy resin, alicyclic epoxy resin, or aliphatic epoxy resin. Acrylate obtained by the reaction of acrylic acid. Among these acrylate acrylates, particularly preferred are acrylates of aromatic epoxy resins, which are obtained by reacting polyglycidyl ether having at least one aromatic nucleus or an alkylene oxide adduct thereof with acrylic acid. Acrylate obtained. For example, an acrylate obtained by reacting glycidyl ether obtained by reacting bisphenol A or an alkylene oxide adduct thereof with epichlorohydrin, and acrylic acid; and an epoxy phenol novolak resin and acrylic acid Acrylate or the like obtained by the reaction. The methacrylic acid epoxy ester is, for example, an acrylate obtained by reacting a conventionally known aromatic epoxy resin, alicyclic epoxy resin, or aliphatic epoxy resin with methacrylic acid. Among these methacrylate epoxy esters, a particularly preferred one is a methacrylate of an aromatic epoxy resin, which is a polyglycidyl ether having at least one aromatic nucleus polyphenol or an alkylene oxide adduct thereof. A methacrylate obtained by reacting methacrylic acid. For example, a glycidyl ether obtained by reacting bisphenol A or an alkylene oxide adduct thereof with epichlorohydrin, and a methacrylic acid ester obtained from methacrylic acid; and an epoxy phenol varnish A methacrylate obtained by reacting a resin with methacrylic acid or the like.

The urethane acrylate is preferably an acrylate obtained by reacting a hydroxy group-containing acrylate with an isocyanate and one or more kinds of a hydroxyl group-containing polyester or a hydroxyl group-containing polyether, or An acrylate or the like obtained by reacting a hydroxy group-containing acrylate with an isocyanate. Preferably, the urethane methacrylate is obtained by reacting a hydroxy group-containing methacrylate with an isocyanate with one or more kinds of hydroxyl group-containing polyesters or hydroxyl group-containing polyethers. Methacrylate or reaction of a hydroxyl group-containing methacrylate with an isocyanate Methyl acrylate and the like.

The hydroxyl group-containing polyester used herein is preferably a polyester having a hydroxyl group obtained by reacting one or more aliphatic polyols with one or more kinds of polybasic acids. Examples of the aliphatic polyhydric alcohol include 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, and polyethylene glycol. Glycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, and the like. Examples of the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride, and trimellitic acid.

The polyether containing a hydroxyl group is preferably a polyether having a hydroxyl group obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol, and examples of the aliphatic polyhydric alcohol include the above. The compounds are the same. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

The hydroxy group-containing acrylate is preferably a hydroxyl group-containing acrylate obtained by esterification of an aliphatic polyol with acrylic acid, and examples of the aliphatic polyol include the same as the above compound. Among the hydroxy group-containing acrylic acid, a hydroxy group-containing acrylate obtained by esterification reaction of an aliphatic diol with acrylic acid is particularly preferable, and examples thereof include 2-hydroxyethyl acrylate. The hydroxy group-containing methacrylate is preferably a hydroxyl group-containing methacrylate obtained by esterification of an aliphatic polyol with methacrylic acid, and examples of the aliphatic polyol include the same as the above compound. . Among the hydroxy group-containing methacrylic acids, a hydroxy group-containing methacrylate obtained by esterification of an aliphatic diol with methacrylic acid is particularly preferable, and examples thereof include 2-hydroxyethyl methacrylate.

The isocyanate is preferably a compound having one or more isocyanate groups in the molecule, and particularly preferably a methyl phenyl diisocyanate or a divalent isocyanate compound such as hexamethylene diisocyanate or isophorone diisocyanate.

The polyester acrylate is preferably a polyester acrylate obtained by reacting a hydroxyl group-containing polyester with acrylic acid, and the polyester methacrylate is preferably a hydroxyl group-containing polyester and a methyl group. A polyester methacrylate obtained by reacting acrylic acid. The hydroxyl group-containing polyester used herein is preferably one or two or more kinds of aliphatic polyols; and esterification with one or more kinds of monobasic acids, polybasic acids, and phenols. The hydroxyl group-containing polyester obtained by the reaction may be the same as the above compound as the aliphatic polyol. Examples of the monobasic acid include formic acid, acetic acid, butylcarboxylic acid, and benzoic acid. Examples of the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride, and trimellitic acid. Examples of the phenols include phenol, p-nonylphenol, and bisphenol A.

The polyether acrylate is preferably a polyether acrylate obtained by reacting a hydroxyl group-containing polyether with acrylic acid, and the polyether methacrylate is preferably a hydroxyl group-containing polyether and a methyl group. Polyether methacrylate obtained by the reaction of acrylic acid. The hydroxyl group-containing polyether used herein is preferably a hydroxyl group-containing polyether obtained by adding one or two or more kinds of alkylene oxides to an aliphatic polyol, and is an aliphatic polyol. The same as the above compounds can be mentioned. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

The acrylate of the aforementioned alcohol, preferably, is made in the molecule The acrylate having an aromatic or aliphatic alcohol having at least one hydroxyl group and an alkylene oxide adduct thereof and reacting with acrylic acid may, for example, be 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate or acrylic acid. 2-hydroxypropyl ester, isoamyl acrylate, lauryl acrylate, stearyl acrylate, isooctyl acrylate, tetrahydrofuran methyl acrylate, isodecyl acrylate, benzyl acrylate, 1,3-butanediol diacrylate , 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene Alcohol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ε-caprolactone modified dipentaerythritol hexaacrylate, and the like. Further, among these acrylates, polyacrylates of polyhydric alcohols are particularly preferred. The methacrylate of the above alcohol is preferably an methacrylic acid obtained by reacting an aromatic or aliphatic alcohol having at least one hydroxyl group in the molecule and an alkylene oxide adduct thereof with methacrylic acid. Examples of the ester include 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, isoamyl methacrylate, lauryl methacrylate, and methacrylic acid. Aliphatic ester, isooctyl methacrylate, tetrahydrofuran methyl methacrylate, isodecyl methacrylate, benzyl methacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol Dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, poly Ethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, ε-caprolactone modification Dipentaerythritol hexamethacrylate or the like. Further, among these methacrylates, polymethacrylates of polyhydric alcohols are particularly preferred.

Commercial products of the above (E) polyfunctional acrylate compound and polyfunctional methacrylate compound include SA1002 (manufactured by Mitsubishi Chemical Corporation), Viscoat 195, Viscoat 230, Viscoat 260, Viscoat 215, Viscoat 310, and Viscoat 214HP. Viscoat 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 400, Viscoat 700, Viscoat 540, Viscoat 3000, Viscoat 3700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Kayarad R-526, HDDA, NPGDA, TPGDA, MANDA, R- 551, R-712, R-604, R-684, PET-30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C, DPHA-2I, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, EB-645, EB-648, EB-3700 (made by Daicel.UCB), T-1420, T-2020 , T-2040, TPA-320, TPA-330, RP-1040, RP-2040, R-011, R-300, R-205 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-220, M -233, M-240, M-215, M-305, M-309, M-310, M-315, M-325, M-400, M-408, M-450, M-6200, M-6400 (made by East Asia Synthetic Co., Ltd.), Light Acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP-A Company system), New Frontier ASF-400 (manufactured by Nippon Steel Chemical Co., Ltd.), Lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (made by Showa Denko), NK ESTER A-BPE-4 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

The content of the (E) polyfunctional acrylate compound or the polyfunctional methacrylate compound is not particularly limited, and may be used in a substantially usual ratio within a range not inhibiting the object of the present invention, for example, relative to (A) 100 parts by mass of the compound having a plurality of active alkanol groups is preferably (E) a polyfunctional acrylate compound or a polyfunctional methacrylate compound in an amount of from 0.5 to 100 parts by mass, more preferably from 1 to 30 parts by mass. When the amount is too small, the adhesion tends to be insufficient, and if it is too large, the strength of the cured product may be adversely affected.

In the photocurable composition of the present invention, a (F) monofunctional acrylic monomer may be further added. Examples of the functional acrylic monomer include a monofunctional acrylate compound, a monofunctional methacrylate compound, a monofunctional acrylamide compound, a monofunctional methacrylamide compound, and the like, and examples thereof include 2-hydroxyethyl acrylate. , 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, tert-butyl acrylate, N-octyl acrylate, isooctyl acrylate, isodecyl acrylate, isodecyl acrylate, acrylic acid Monofunctional acrylate compound of stearyl ester, lauryl acrylate, behenyl acrylate, methoxyethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, etc.; 2-hydroxyethyl methacrylate , 2-hydroxypropyl methacrylate, allyl methacrylate, butyl methacrylate, third butyl methacrylate, cyclohexyl methacrylate, stearyl methacrylate, methacrylic acid laurel Monofunctional methacrylate compound such as ester; acrylamide, propylene decylmorpholine, dimethyl acrylamide, dimethylaminopropyl acrylamide, isopropyl acrylamide, N-methoxy Methyl propyl Monofunctional acrylamide compound such as eneamine; methyl propyl Ionylamine, N-(3-dimethylaminopropyl)methacrylamide, N-alkoxymethylmethacrylamide, and the like.

Further, a photo sensitizer may be further added to the photocurable composition of the present invention, and examples thereof include an unsaturated ketone represented by a chalcone derivative or dibenzylideneacetone, and diphenylethylenedione or 1,2-dione derivative, benzoin derivative, anthracene derivative, naphthoquinone derivative, anthracene derivative, xanthene derivative, thioxanthene derivative, xanthone represented by camphor a polymethine group such as a derivative, a thioxanthone derivative, a coumarin derivative, a coumarin derivative, an anthocyanin derivative, a merocyanin derivative, or an oxyphthalocyanine (Oxonol) derivative ( Polymethine) a pigment, an acridine derivative, a pyridazine derivative, a thiazine derivative, an oxazine derivative, a porphyrin derivative, an anthracene derivative, an anthracene derivative, a squarylium derivative, a purpurin Derivatives, tetraphenylpurine derivatives, triarylmethane derivatives, tetrabenzofluorene derivatives, tetrapyrazinoporphyrazine derivatives, anthocyanin derivatives, tetraazapine derivatives , tetraquinoxaline and laverazine derivatives, naphthalocyanine derivatives, ellagyanin derivatives , pyranthene derivative, thiopyranidine derivative, tetraphylline derivative, olefin derivative, spiropyran derivative, spirooxazine derivative, thiospirol derivative, metal aromatic hydrocarbon Condensed polycyclic aromatic derivatives of complex compounds, organic hydrazine complexes, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, anthracene derivatives, fused tetraphenyl derivatives, anthracene derivatives, condensed pentabenzene derivatives, and the like And acridine derivatives, benzothiazole derivatives and the like. More specifically, it can be cited by Ohara Shinto et al., "Pigment Handbook" (1986, Kodansha), Okawa Keisuke, etc., "Chemistry of Functional Pigments" (1981, CMC), Chissen Chung San-lang, et al., "Special Functional Materials" (1986, CMC), but not limited to the pigments and sensitizers. Others include ultraviolet to near-infrared regions. Light shows the absorbed pigment or sensitizer. These may be used alone or in combination of plural kinds.

In the photocurable composition of the present invention, a thermal polymerization initiator may be used as needed.

A thermal polymerization initiator which is a compound which generates a cationic species or a Lewis acid by heating. For example, a salt of a phosphonium salt, a thiophene sulfonium salt, a tetrahydrothiophene sulfonium salt, a benzylammonium salt, a pyridinium salt, a phosphonium salt or the like; a diethylenetriamine, a triamethylenetriamine, a tetraamethyleneamine, etc. Polyalkyl polyamines; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophorone diamine An aromatic polyamine such as m-xylenediamine, diaminodiphenylmethane or diaminodiphenylphosphonium; and the above polyamines, phenyl glycidyl ether, butyl glycidyl ether, Polyepoxy radical addition of various epoxy resins such as bisphenol A-diglycidyl ether, diglycidyl ether such as bisphenol F-diglycidyl ether or glycidyl ester of carboxylic acid by a general method a modified product; an amide-modified product obtained by reacting the organic polyamine with a carboxylic acid such as phthalic acid, isophthalic acid or a dimer acid by a general method; and the aldehyde of the polyamine and formaldehyde a mani made of phenols such as phenol, cresol, xylenol, tert-butylphenol, resorcin or the like having at least one hydroformylation site in the core, which is produced by a general method. Mannich modified material; polycarboxylic acid (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, azelaic acid) Acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipate, 3-methyladipate, 3-methylglutaric acid, 2-methyloctanedioic acid, 3,8 - an aliphatic dicarboxylic acid such as dimethyl sebacic acid, 3,7-dimethylsebacic acid, hydrogenated dimer acid or dimer acid; phthalic acid, terephthalic acid, isophthalic acid, An aromatic dicarboxylic acid such as naphthalene dicarboxylic acid; an alicyclic dicarboxylic acid such as cyclohexane dicarboxylic acid; a tricarboxylic acid such as a trimer of trimellitic acid, symmetrical trimellitic acid or castor oil; An acid anhydride such as a tetracarboxylic acid such as pyromellitic acid; dicyandiamide, an imidazole, a carboxylic acid ester, a sulfonate or an amine quinone.

A commercially available product may be used as the above-mentioned thermal polymerization initiator, and examples thereof include Adekaopton CP77, Adekaopton CP66 (made by Adeka Co., Ltd.), CI-2639, CI-2624 (made by Nippon Soda Co., Ltd.), San-Aid SI-60L, San. -Aid SI-80L, San-Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.), etc.

The amount of the thermal polymerization initiator to be used is not particularly limited, and is preferably in the range of 0.001 to 10 parts by mass based on 100 parts by mass of the total solid content of the photocurable composition. When the thermal polymerization initiator is used, it is preferred to heat the photocurable composition of the present invention at 130 to 180 ° C for 20 minutes to 1 hour.

In the photocurable composition of the present invention, a decane coupling agent can be used as needed.

As the decane coupling agent, for example, dimethyl dimethoxy decane, dimethyl diethoxy decane, methyl ethyl dimethoxy decane, methyl ethyl diethoxy decane, methyl trimethoxy decane can be used. An alkyl functional alkoxy oxime such as methyl triethoxy decane, ethyl trimethoxy decane or ethyl trimethoxy decane Alkenyl functional alkoxydecane, 3-methylpropenyloxypropane, etc. of alkane, vinyltrichlorodecane, vinyltrimethoxydecane, vinyltriethoxydecane, allyltrimethoxydecane, etc. Triethoxy decane, 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyl Methyldimethoxydecane, 2-methylpropenyloxypropyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldiethoxy Epoxy-functional alkoxydecane, N-β(aminoethyl)-γ-aminopropyltrimethyl, such as decane or β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane Amino-functional alkoxydecane, γ-mercaptopropyltrimethoxy, etc., such as oxydecane, γ-aminopropyltriethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane An alkoxytitanium such as a decyl functional alkoxydecane, a tetraisopropoxide titanium oxide or a tetra-n-butoxide titanium oxide such as decane, a titanium dioctyloxy bis(octyl glycolate), or a titanium diisopropoxy bis ( Ethyl acetate a zirconium chelate compound such as a titanium chelate compound, a zirconium tetrakisylpyruvate, a zirconium tributyloxypyridylpyruvate or a zirconium chelate such as zirconium tributoxymonostearate or the like; Isocyanate decane or the like such as methyl triisocyanate decane.

In the photocurable composition of the present invention, a polymer having no hydroxyl group may be further added to alleviate the stress. The molecular weight of the polymer is preferably from 5,000 to 50,000.

In the photocurable composition of the present invention, a solvent which can dissolve or disperse the components (A) to (D) can be usually used as needed. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cyanidin, ethyl cyanidin, chloroform, dichloromethane, hexane, heptane, octane, cyclohexane may be added. Alkane, benzene, toluene, xylene, methanol, ethanol, isopropanol.

The photocurable composition of the present invention is applied to a support substrate by a known method such as a roll coater, a curtain coater, or various printing or dipping. Further, once applied to a support substrate such as a film, it may be transferred onto another support substrate, and the application method is not limited.

The support substrate is not particularly limited, and preferred examples thereof include a glass plate, a polyethylene terephthalate plate, a polycarbonate plate, a polyimide plate, a polyamide plate, and a polymethyl methacrylate. Plate, polystyrene board, polyvinyl chloride board, polyolefin board, cycloolefin polymer board, polytetrafluoroethylene board, triethylene glycol cellulose board, norbornene board, polyvinyl alcohol board, cellulose acetate board Polyarlate plates, polyfluorene plates, polyether enamel plates, ruthenium wafers, reflectors, calcite plates, quartz plates, glass plates, paper, wood, metal plates, etc.

The substrate may be subjected to surface treatment by a conventionally known method such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, or pharmaceutical treatment, or an anchor coating agent or a primer. Coating.

Further, as long as the effects of the present invention are not impaired, coloring agents, defoaming agents, tackifiers, and surfactants of other monomers, other photoinitiators, inorganic fillers, organic fillers, pigments, dyes, and the like may be added as needed. Various kinds of resin additives such as a leveling agent, a flame retardant, a plasticizer, a stabilizer, a polymerization inhibitor, a UV absorber, an antioxidant, an antistatic agent, a flow regulator, and a subsequent accelerator.

The photocurable composition of the present invention is cured by irradiation with an active energy ray. Examples of the active energy ray include ultraviolet rays, electron beams, X-rays, radiation, high-frequency waves, etc., and ultraviolet rays are economical and most good. Examples of the ultraviolet light source include ultraviolet lasers, mercury lamps, xenon lasers, and metal halide lamps.

Specific applications of the photocurable composition of the present invention include, in addition to the adhesive, paints, coating agents, lining agents, inks, resists, liquid resists, printing plates, insulating varnishes, and insulation. Fresnel, laminate, printed circuit board, semiconductor encapsulant, molding material, putty, glass fiber impregnating agent, wood filler, 稜鏡 lens sheet used for backlight of liquid crystal display device, Fresnel lens used for screen of projection television, etc. a lens portion of a lens sheet such as a sheet or a lenticular lens sheet, or an optical lens such as a backlight such as a lens, an optical element, an optical connector, an optical waveguide, an optical molding mold, or the like, for example, as a coating The substrate to which the agent can be applied may, for example, be metal, wood, rubber, plastic, glass, ceramics, or the like.

When the photocurable composition of the present invention is used for an adhesive application, the photocurable composition may be applied to a support substrate, and if necessary, a laminate in which another layer such as a protective layer is laminated may be irradiated with ultraviolet rays or the like. the active energy ray, light at the same time or before or after irradiation of the irradiation light, in order to promote the hardening to advance the laminate 40 ~ 120 ℃, 0.01 ~ 20kg / cm ² is about 5 to 10 minutes of heat and pressure by irradiation with an active energy ray .

[Examples]

The invention is further illustrated by the following examples and the like, but the invention is not limited by the examples.

Hereinafter, specific examples, evaluation examples, and comparative examples are used. The photocurable composition of the present invention and the cured product obtained by curing the photocurable composition will be described. In the examples and comparative examples, the parts mean parts by mass.

[Examples 1 to 54 and Comparative Examples 1 to 6]

The components were sufficiently mixed at the blending ratios shown in the following Tables 1 to 10 to obtain photocurable compositions of the respective Examples and Comparative Examples. For various substrates: TAC (triethyl fluorenyl cellulose), COP (cycloolefin polymer), PMMA (polymethyl methacrylate), PET (polyethylene terephthalate), rod applicator The photocurable composition was applied to a thickness of 5 to 10 μm, bonded to a PET substrate, and irradiated with ultraviolet light at an energy of 1000 mJ/cm ² over a PET substrate using a cold mirror type mercury lamp. After the irradiation, the mixture was allowed to stand at 30 ° C × 50% Rh for 24 hours to obtain a test piece.

As the compound (A) having a plurality of active alkanol groups, the following compounds (A-1) to (A-2) are used.

Compound A-1: MW-30M (Methylated melamine resin manufactured by Sanhe Chemical Co., Ltd.)

Compound A-2: MW-270 (Methylated urea resin manufactured by Sanhe Chemical Co., Ltd.)

As the (B) alcohol compound, the following compounds (B-1) to (B-4) were used.

Compound B-1: Actflow UME-2005 (manufactured by Kyoeisha Chemical Co., Ltd.)

Compound B-2: Actflow UMB-2005 (Kyoeisha Chemical Co., Ltd. system)

Compound B-3: 2-hydroxy-3-phenoxypropyl acrylate

Compound B-4: glycerol dimethacrylate

Compound B-5: 2-hydroxyethyl acrylate

Compound B-6: 2-hydroxyethyl methacrylate

Compound B-7: 4-hydroxybutyl acrylate

Compound B-8: Blemmer AE-200 (manufactured by Nippon Oil Co., Ltd.)

Compound B-9: Placcel FA1DDM (manufactured by Daicel Co., Ltd.)

Compound B-10: Hydroxyethyl acrylamide

Compound B-11: N-methylol acrylamide

Compound B-12: Placcel 303 (manufactured by Daicel Co., Ltd.)

Compound B-13: 2-hydroxyethyl acrylate + 4-hydroxybutyl acrylate reaction (MW 10000)

Compound B-14: butyral resin KS-1 (made by Sekisui Chemical Co., Ltd.)

As the (C) polyfunctional acrylic oligomer, the following compounds (C-1) to (C-3) were used.

Compound C-1: U-200PA (Amino acrylate acrylate manufactured by Shin-Nakamura Chemical Co., Ltd.)

Compound C-2: UA-4200 (Amino acrylate acrylate manufactured by Shin-Nakamura Chemical Co., Ltd.)

Compound C-3: 1,6 hexanediol-based polycarbonate diol + isophorone diisocyanate + HEA reactant (MW 10000)

Compound C-4: a reactant of polyhydric alcohol + isophorone diisocyanate + 2-hydroxyethyl acrylate obtained from polyethylene glycol and adipic acid (MW10000)

Compound C-5: A-600 (polyethylene glycol diacrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.)

As the (D) photoinitiator, the following compounds (D-1) to (D-3) were used.

Compound D-1: Irg-184 (manufactured by BASF Corporation)

Compound D-2: Irg-819 (manufactured by BASF Corporation)

Compound D-3: SP-150 (made by ADEKA)

As the (E) polyfunctional acrylate compound or polyfunctional methacrylate compound, the following compounds (E-1) to (E-3) are used.

Compound E-1: DPHA (dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate)

Compound E-2: Trimethylolpropane triacrylate

Compound E-3: A-9300S (ethoxylated trimeric isocyanate triacrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.)

As the (F) monofunctional acrylic monomer, the following compounds (F-1) to (F-7) were used.

Compound F-1: cyclohexyl methacrylate

Compound F-2: Phenoxyethyl acrylate

Compound F-3: Propenylmorphomorpholine

Compound F-4: Dimethyl acrylamide

Compound F-5: dimethylaminopropyl acrylamide

Compound F-6: Isopropyl acrylamide

Compound F-7: N-methoxymethylpropenamide

As another component, the following compound (G-1) was used.

Compound G-1: 9,10-bis(n-butoxy)anthracene

[Evaluation Examples 1 to 54 and Comparative Evaluation Examples 1 to 6]

The test pieces obtained in the above Examples 1 to 54 and Comparative Examples 1 to 6 were subjected to the following evaluations. The results are shown in Tables 1 to 10 above.

(90° peel strength)

The test piece was cut into a width of 15 mm, and the base material was stretched and peeled in the direction of 90°, and the strength was measured.

(warm water test)

The test piece was cut into a width of 15 mm and a length of 4 mm, and immersed in warm water of 60 ° C for 5 hours. The surface of the test piece was visually confirmed to have no change ○

There is peeling at the end face △

Stripping ×

To evaluate.

As is apparent from the above Tables 1 to 10, the photocurable composition of the present invention containing the components (A) to (D) is excellent in adhesion. On the other hand, the photocurable composition of the comparative example containing the (A) component or (B) component and the polyfunctional acrylate compound as a main component is inferior in adhesiveness. In the production process of the test pieces of the above-mentioned examples and the comparative examples, the heat treatment was not carried out, and it was found that the component (A) of the present invention does not function as a light hardening agent but acts as a light curing component. Further, in comparison with the examples 7 and 8 and the examples other than the examples, it was confirmed that the component (E) and the component (F) were contained, and the adhesion was further improved.

Claims (12)

A photocurable composition comprising (A) a compound having a plurality of active alkanol groups, (B) an alcohol compound, (C) a polyfunctional acrylic oligomer, and (D) a photoinitiator, and The proportion of the above (B) alcohol compound is from 20 to 800 parts by mass based on 100 parts by mass of the compound having a plurality of active alkanol groups in the above (A). The photocurable composition of claim 1, wherein the (B) alcohol compound is an acrylate compound having a hydroxyl group, a methacrylate compound having a hydroxyl group, an acrylamide compound having a hydroxyl group or a methyl propylene having a hydroxyl group. Amidoxime compound. The photocurable composition of claim 1, wherein the (B) alcohol compound is a polyol compound. The photocurable composition of claim 1, wherein the (A) compound having a plurality of reactive alkanol groups is selected from the group consisting of polyalkanol melamine, polyalkanol acetylene urea, polyalkanol hydroxyethylene urea, polyalkanolization One or more compounds in the group consisting of urea, polyalkanol benzoguanamine, polyalkanolated spiroamine, and polyalkanol acrylamide. The photocurable composition of claim 1, wherein the compound (A) having a plurality of active alkanol groups is a compound having a skeleton selected from the group consisting of one or more of the following groups The photocurable composition of claim 5, wherein the (A) compound having a plurality of reactive alkanol groups is a polyalkanolized melamine represented by the following general formula (I) (In the formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxyl group, the alkyl group The methylene group in the middle can also be interrupted by an oxygen atom). The photocurable composition of claim 5, wherein the compound (A) having a plurality of reactive alkanol groups is a polyalkanolated urea represented by the following general formula (III) (wherein R ⁵¹ and R ⁵⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxyl group, and the methylene group in the alkyl group may be interrupted by an oxygen atom; R ⁵² and R ⁵³ each independently represents a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, n = 1 or 2, and when n = 2, R ⁵² and R ^{53 are} bonded to each other to form a dimer). The photocurable composition of claim 1, wherein the (C) polyfunctional acrylic oligomer has a molecular weight of 500 or more. The photocurable composition of claim 1, wherein the (D) photoinitiator is a photoacid generator. The photocurable composition of claim 1, which further comprises (E) a polyfunctional acrylate compound or a polyfunctional methacrylate compound. The photocurable composition of claim 1, which further comprises (F) a monofunctional acrylic monomer. A photocurable adhesive obtained by the photocurable composition according to any one of claims 1 to 11.