JP2008038114A - Photosensitive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition, in which good adhesiveness which conventional cationic curing resins have is further improved, exhibiting excellent adhesion also to flexible materials such as resins and films. <P>SOLUTION: The photosensitive composition comprises (a) an epoxy compound, (b) one or more kinds of compounds selected from a group consisting of a vinyl ether compound having a hydroxy group and oxetanes, (c) an energy ray-sensitive cation polymerization initiator and (d) phosphates. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention can form a cured coating film at extremely high speed by irradiation of energy rays, and the coating film formed thereby can be applied to various materials such as resin, metal, glass, and soft materials such as films. The present invention relates to a photosensitive composition and a cured composition having good adhesion.

In recent years, UV curable resins have attracted attention because they do not discharge organic solvents and are fast-cured. Their uses include coating and adhesion of optical discs such as DVDs and Blu-ray discs, inkjet printers, gravure printing, and flexographic printing. Ink, liquid crystal and PDP display color filter forming materials, liquid crystal and organic EL sealing materials. Among them, a method using a (meth) acrylate-based material that is cured by a radical polymerization reaction is known. However, the radical curing system has a disadvantage that the curing shrinkage is large, and this shrinkage causes a disadvantage that the adhesion to the substrate is lowered. As a method for solving this problem, it is possible to use a cationic curing material instead of a radical curing system. Cationic curable materials using materials such as epoxy, vinyl ether, oxetane, etc. (a) are less susceptible to curing inhibition by oxygen, and therefore have excellent surface and thin film curability, (b) small cure shrinkage, (c) radical curing Compared to the system, it has excellent features such as better adhesion to substrates such as glass.
Examples of the cationic curable material include the following.

International Publication No. 2005/019299 Pamphlet JP 2000-26830 A JP 2001-125474 A

In Patent Document 1, although it has excellent fast curability and good adhesion to a substrate such as glass, it is not described in PC and other resin substrates. In Patent Document 2, a composition containing an epoxy compound, a compound having rubber elasticity, and a plasticizer is described, but the viscosity remains high and a problem remains.
Patent Document 3 proposes a composition in which a cationic curable compound and a radical curable compound are used in combination. However, since the composition contains a radical system, there is a problem in adhesiveness. Thus, a cationically polymerizable curable material that simultaneously satisfies higher adhesiveness, viscosity, and curability is desired.

  The present invention further improves the good adhesiveness of conventional cationic curable resins, and provides a composition having good adhesiveness to soft materials such as resins and films, and at the same time satisfying fast curability. For the purpose.

As a result of intensive studies to solve the above problems, the present inventors have found a cationically polymerizable photosensitive composition having excellent adhesion to various base materials, particularly soft materials such as resins and films, and the present invention. It came to make.
That is, the present invention is as follows.
1. containing at least one selected from the group consisting of (a) an epoxy compound, (b) a vinyl ether compound having a hydroxyl group, and oxetanes, (c) an energy ray-sensitive cationic polymerization initiator, and (d) phosphate esters And a photosensitive composition.
2. (d) Phosphate esters are triethyl phosphate, tributyl phosphate, tri-phosphate phosphate
2. One or more selected from the group consisting of 2-ethylhexyl, The photosensitive composition as described in any one of.
3. The content of (d) phosphoric acid esters is 500 ppm to 50000 ppm in terms of phosphorus. Or 2. The photosensitive composition as described in any one of.

4. (e) The above-mentioned 1. which further contains one or more selected from the group consisting of polyhydric phenol compounds and derivatives of the polyhydric phenol compounds. ~ 3. The photosensitive composition of any one of these.
5. (e) One or more selected from the group consisting of a polyphenol compound and a derivative of the polyphenol compound is composed of 3-5 phenolic aromatic rings, and at any ortho position of all the hydroxyl groups thereof. And a compound having two or more phenolic aromatic rings in which neither an alkyl group having 4 or more carbon atoms or a cycloalkyl group is substituted, and at least one ortho position of the hydroxyl group is unsubstituted. 4. above. The photosensitive composition as described in any one of.
6. The above-mentioned 1. containing a (f) reactive organosilicon compound represented by the following general formula (1) and / or a hydrolyzate thereof. ~ 5. The photosensitive composition of any one of these.
(R ₁ ) _n SiX _4-n (1)
(In the formula, R ₁ represents an alkyl group having 1 to 20 carbon atoms, X represents a hydrolyzable group, and n represents an integer of 0 to 3).

  By using the cationically polymerizable photosensitive composition of the present invention and its cured product, adhesion to a soft material such as a resin or a film is improved, and at the same time, good viscosity stability and fast curability are realized. Furthermore, since the photosensitive composition of the present invention and its cured product are excellent in processability and have little shrinkage upon curing, inks, adhesives, paints, film coatings, pattern forming materials, especially ink for inkjet printers, gravure printing Useful for applications such as adhesives, coating materials, color filter forming materials for liquid crystal and PDP displays, photoresists, sealing materials, sealing materials, insulating materials, etc. .

The present invention will be specifically described below.
The epoxy compound of component (a) in the present invention refers to a cationically polymerizable compound having an epoxy group. The cationic polymerizable compound refers to a compound that undergoes polymerization by a Lewis acid such as proton. Examples of the epoxy compound include a glycidyl ether type epoxy compound and an alicyclic epoxy compound, and among them, a compound having at least two epoxy groups in one molecule is preferable.

Specific examples of glycidyl ether type epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, and alkylphenol novolak type epoxy compounds such as p-tert-butylphenol novolac type epoxy compounds. , Hydrogenated bisphenol A type epoxy compound, diglycidyl ether of bisphenol A alkylene oxide adduct, diglycidyl ether of bisphenol F alkylene oxide adduct, diglycidyl ether of hydrogenated bisphenol A alkylene oxide adduct, tetrabromobisphenol Type A epoxy compound, ethylene glycol diglycidyl ether, propylene glycol diglycid Ether, neopentyl glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane di and / or triglycidyl ether Pentaerythritol tri and / or tetraglycidyl ether, sorbitol hepta and / or hexaglycidyl ether, resorcin diglycidyl ether, dicyclopentadiene / phenol addition type glycidyl ether, methylene bis (2,7-dihydroxynaphthalene) tetraglycidyl ether, 1, 6-dihydroxynaphthalenediglycidyl ether, 1,5-di It can be given mud carboxymethyl-naphthalene diglycidyl ether.

  Specific examples of the alicyclic epoxy compound include, as monofunctional alicyclic epoxy compounds, 4-vinyl epoxycyclohexane (for example, Celoxide 2000: manufactured by Daicel Chemical Industries, Ltd.), epoxyhexahydrophthalate dioctyl, epoxyhexahydrophthalic acid Examples thereof include di-2-ethylhexyl and ETHB (manufactured by Daicel Chemical Industries). As the bifunctional alicyclic epoxy compound, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (for example, Celoxide 2021: manufactured by Daicel Chemical Industries, Cyracure UVR-6105: manufactured by Dow Chemical Japan Co., Ltd.) 3,4-epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate (for example, Celoxide 2080 manufactured by Daicel Chemical Industries, Ltd.), 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4- Epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate (eg UVR-6128: manufactured by Dow Chemical Japan), vinylcyclohexene dioxide, bis (3,4-epoxy-6-methyl) Cyclohexyl Methyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,3 4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), 1,2,8,9-diepoxy limonene (for example, Celoxide 3000: manufactured by Daicel Chemical Industries, Ltd.). As the polyfunctional alicyclic epoxy compound, 1,2-epoxy-4- (2-oxiranyl) cyclohexene adduct of 2,2-bis (hydroxymethyl) -1-butanol (for example, EHPE3150: manufactured by Daicel Chemical Industries, Ltd.) ) And the like. Examples of the polyfunctional alicyclic epoxy compound include Epolide GT300, GT400, EHPE3150 (manufactured by Daicel Chemical Industries).

As specific examples of the other epoxy compounds, epoxidized polybutadiene (for example, Epolide PB3600: manufactured by Daicel Chemical Industries, Ltd.), Epofriend AT501, CT310 (produced by Daicel Chemical Industries, Ltd.), and the like can be used.
As the epoxy group compound, a compound having at least two epoxy groups in one molecule is preferable, and an alicyclic epoxy compound is preferable because of excellent cationic polymerization reactivity. Epoxy compounds may be used alone or in combination of two or more.

The actual blending ratio of the (a) epoxy compound in the photosensitive composition used in the present invention is preferably 30 to 98% by weight, although it depends on the molecular weight of each compound. When in this range, it has good curability. A more preferred range is 30 to 89% by weight. Furthermore, an even more preferable range is 55 to 89% by weight.
Moreover, the photocured material which has the further outstanding sclerosis | hardenability and water resistance can be obtained by adding the vinyl ether compound and / or oxetane which have a component (b) hydroxyl group in the photosensitive composition of this invention.

Examples of the vinyl ether compound having a hydroxyl group include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexanediol monovinyl ether, 9-hydroxynonyl vinyl ether, propylene glycol monovinyl ether, neopentyl glycol monovinyl ether, glycerol divinyl ether, glycerol mono Vinyl ether, trimethylolpropane divinyl ether, trimethylolpropane monovinyl ether, pentaerythritol monovinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene Glycol monovinyl ether, tricyclodecane diol monovinyl ether and tricyclodecanedimethanol monovinyl ether and the like.

Oxetanes refer to 4-membered ethers and are not particularly limited as long as they are compounds having at least one oxetane ring in the molecule. For example, when improving photocurability, especially when improving curability in a long wavelength region lamp such as a xenon lamp, it is preferable to use an epoxy compound and an oxetane compound in combination.
Specific examples of the compound having one oxetane ring include 3-ethyl-3-hydroxymethyloxetane (for example, Aron oxetane OXT-101: manufactured by Toagosei Co., Ltd.), 3- (meth) allyloxymethyl-3-ethyloxetane 3-ethyl-3- (cyclohexyloxy) methyloxetane, 3-ethyl-3- (2-ethylcyclohexyloxymethyl) oxetane (for example, Alonoxetane OXT-212: manufactured by Toagosei Co., Ltd.), (3-ethyl-3 -Oxetanylmethoxy) methylbenzene, 3-ethyl-3- (phenoxymethyl) oxetane (for example, Aron Oxetane OXT-211 manufactured by Toagosei Co., Ltd.), 4-fluoro- [1- (3-ethyl-3-oxetanylmethoxy) Methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetani Methoxy) methyl] benzene, [1- (3-ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3 -Oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclo Pentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrophenyl Furyl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl ( 3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl ( 3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanyl) Me Til) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, and the like.

Specific examples of the compound having two or more oxetane rings include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis ( Oxymethylene)) bis- (3-ethyloxetane), bis [1-ethyl (3-oxetanyl)] methyl ether, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (for example, aron oxetane OXT-121: manufactured by Toagosei Co., Ltd.), 3-ethyl-3-{[(3-ethyloxetanyl) methoxy] methyl} oxetane (for example, Aron Oxetane OXT-221: manufactured by Toagosei Co., Ltd.) 1,3-bis [ (3-ethyloxetane-3-yl) methoxy] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1, 3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, tri Ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, tri Methylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, penta Erythritol Tris (3 Ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3) -Oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl) -3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis 3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F bis (3-ethyl-3-oxetanylmethyl) ether, Examples include oxetanyl silsesquioxane, oxetanyl silicate, phenol novolac oxetane and the like.
Among the oxetane compounds, OXT-101, OXT-221 and OXT-121 are preferable from the viewpoints of curability and cured film performance, OXT-101 is more preferable from the viewpoint of curability, and OXT-121 is more preferable from the viewpoint of moisture permeability resistance. preferable. These vinyl ether compounds and / or oxetanes having a hydroxyl group may be used singly or in combination of two or more.

Moreover, as a component (b), the vinyl ether compound which has a hydroxyl group is preferable at the point of rapid curability.
The actual blending ratio of the vinyl ether compound having a hydroxyl group (b) and / or oxetanes in the photosensitive composition is preferably 1 to 69% by weight, although it depends on the molecular weight of each compound. When in this range, it has good curability and cured film properties. A more preferred range is 10 to 69% by weight. Furthermore, an even more preferable range is 10 to 44% by mass.
Moreover, the compounding ratio with the (a) epoxy compound is preferably such that the epoxy compound contains more than the component (b).

The energy ray-sensitive cationic polymerization initiator of component (c) used in the present invention is a compound capable of releasing a substance that initiates cationic polymerization by irradiation with energy rays, and particularly preferred is an acid generated by irradiation. It is an onium salt that is generated. Examples of such compounds include diazonium salts, iodonium salts, sulfonium salts, and the like. In these, the cation portion is aromatic diazonium, aromatic iodonium, and aromatic sulfonium, respectively, and the anion portion is BF ₄ ⁻ , PF ₆ ^−. , SbF ₆ ⁻ , [BX ₄ ] ⁻ (wherein X is a phenyl group substituted with at least two fluorine or trifluoromethyl groups) and the like.

More specific examples include boron difluoride aryldiazonium salts, phosphorus hexafluoride triarylsulfonium salts, phosphorus hexafluoride diaryliodonium salts, antimony hexafluoride triarylphosphonium salts, antimony hexafluoride. Diaryl iodonium salt, tri-4-methylphenylsulfonium salt of arsenic hexafluoride, tri-4-methylphenylsulfonium salt of antimony tetrafluoride, triarylsulfonium salt of tetrakis (pentafluorophenyl) borate, tetrakis (pentafluoro) Phenyl) borate diaryl iodonium salt, acetylacetone aluminum salt and orthonitrobenzylsilyl ether mixture, phenylthiopyridinium salt, phosphorus hexafluoride allene-iron complex and the like. Specific examples of the onium salt include CD-1012 (manufactured by SARTOMER), PCI-019, PCI-021 (manufactured by Nippon Kayaku Co., Ltd.), Optmer SP-150, Optmer SP-170 (manufactured by Asahi Denka Co., Ltd.), UVI- 6990 (manufactured by Dow Chemical Company), CPI-100P, CPI-100A (manufactured by San Apro), TEPBI-S (manufactured by Nippon Shokubai Co., Ltd.), Rhodorsil 2074 (manufactured by Rhodia) and the like. These can be used alone or in combination of two or more. Among these, a sulfonium salt or an iodonium salt initiator with less coloration of the cured film is preferable, and a sulfonium salt is more preferable from the viewpoint of curability.

A photosensitizer such as benzophenone, benzoin isopropyl ether, thioxanthone, anthracene, and derivatives of these compounds can be used in combination with the component (c). Specific examples include 4,4′-bis (diethylamino) benzophenone, 2,4′-diethylthioxanthone, isopropylthioxanthone, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and the like can be mentioned.
The content of component (c) is preferably 0.1 to 20% by weight, more preferably 0.2 to 15% by weight. From the viewpoint of productivity, it is desirable not to use an initiator excessively. If an initiator is used excessively, the light transmittance may be lowered, the film bottom may be insufficiently cured, and the corrosivity may be increased. Moreover, when there are too few, the quantity of the active cationic substance generated by energy ray irradiation may be insufficient, and sufficient curability and hardened | cured material may no longer be obtained.

By adding the component (d) phosphate ester to the photosensitive composition in the present invention, good adhesiveness is realized. Examples of phosphate esters include triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, and the like.
Among these, from the viewpoint of adhesiveness, triethyl phosphate, tributyl phosphate, and tri-2-ethylhexyl phosphate are more preferable. Moreover, it is preferable that the addition amount of a component (d) is 50-100,000 ppm with respect to the total amount of another component. When in this range, it has good adhesion and curability. More preferably, it is 100-50000 ppm. Furthermore, when it contains 500 ppm or more as a phosphorus component, it has much more preferable adhesiveness. Further more preferable addition amount is a case of containing 600 ppm or more as a phosphorus component.

The component (e) polyhydric phenol compound used in the present invention is a compound comprising a plurality of phenolic aromatic rings. Here, the phenolic aromatic ring is an aromatic ring having a phenolic hydroxyl group.
A derivative of a polyhydric phenol compound is a compound in which a hydrogen atom of a phenolic hydroxyl group is substituted with a polymerizable functional group. The polymerizable functional group mentioned here reacts during cationic polymerization.

The polyhydric phenol compound and derivative (e) thereof preferably have no methylol group at any ortho position of all the hydroxyl groups thereof. That is, it is preferable not to have a methylol group in a molecule generally called a resol resin. Although the methylol group has reactivity with the epoxy group, the bond formed as a result of the reaction is unstable under acidic conditions, and the film hardness obtained after curing is not preferred because it has a problem of decreasing with time. Furthermore, the polyhydric phenol compound (e) preferably has no alkyl group or cycloalkyl group having 4 or more carbon atoms in the ortho position, and is generally a radical such as a hindered phenol such as a bulky t-butyl group. Those other than phenolic compounds called inhibitors and antioxidants are preferred. This is because the phenolic hydroxyl group of the polyhydric phenol compound (e) is directly involved in the photocuring reaction, so that a bulky substituent that becomes an inhibitor of the reaction is substituted at the ortho position of the phenolic hydroxyl group is not preferable. Because.

Furthermore, the polyhydric phenol compound (e) is composed of 3 to 5 phenolic aromatic rings, and at least a phenolic aromatic ring in which at least one ortho position of the hydroxyl group is unsubstituted in the molecule. It is preferable to have two or more. In one or two phenolic aromatic rings, a crosslinking structure cannot be efficiently formed in the photocuring reaction, and in the case of six or more, a phenolic hydroxyl group that does not participate in the crosslinking reaction is generated and the curability and It adversely affects the physical properties of the cured film.
Preferred polyhydric phenol compounds include, for example, compounds represented by the following general formula (2).

（式中Ｒは、炭素数１〜５のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数１〜５のアルコキシ基、ハロゲン原子、水酸基、アリール基またはアラルキル基を示し、式中の複数のＲはすべて互いに異なっていても同一でもよく、ｍは０〜３の整数、ｎは１〜３の整数である）、

(In the formula, R represents an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, an aryl group, or an aralkyl group. A plurality of R may be the same or different from each other, m is an integer of 0 to 3, and n is an integer of 1 to 3);

The polynuclear phenol compound represented by the general formula (2) is excellent in compatibility and reactivity with the epoxy compound of component (a) and vinyl ether or oxetane containing a hydroxyl group.
In the polyhydric phenol compound represented by the general formula (2), m is preferably 1 to 3, and more preferably 1. When m is 1 to 3, the substituent R is preferably bonded to the para position with respect to the hydroxyl group of the benzene ring. R is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group or an aralkyl group. For example, examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a sec-butyl group, and a t-amyl group. Preferred examples of the cycloalkyl group having 5 to 10 carbon atoms include a cyclohexyl group having 6 carbon atoms. Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, Examples include butoxy group, t-butoxy group, sec-butoxy group and the like. Examples of the aryl group include a phenyl group, a naphthyl group, and a biphenyl group. Examples of the aralkyl group include a benzyl group, an α-methylbenzyl group, an α, α ′ dimethylbenzyl group, and the like.
As a commercially available product, for example, a novel molecular weight distribution-intensive novolak resin: PAPS (product name: manufactured by Asahi Organic Materials Co., Ltd.) is preferably used as the polyhydric phenol (e) of the present invention.

Specific examples of the R-substituted phenol used for the synthesis of the polyhydric phenol compound (e) include phenol, p-cresol, m-cresol, p-ethylphenol, m-ethylphenol, p-propylphenol, m- Propylphenol, p-isopropylphenol, m-isopropylphenol, pt-butylphenol, mt-butylphenol, p-sec-butylphenol, m-sec-butylphenol, pt-amylphenol, mt-amylphenol P-phenylphenol, m-phenylphenol, p-cumylphenol, p- (α-methylbenzyl) phenol, m- (α-methylbenzyl) phenol, p-cyclohexylphenol, p-methoxyphenol,
Examples include m-methoxyphenol, p-chlorophenol, m-chlorophenol, catechol, resorcinol, hydroquinone and the like.
As addition amount of the polyhydric phenol compound of a component (e), 0.1 to 40 weight% is preferable, More preferably, it is 0.5 to 20 weight%. When it is within this range, it is possible to achieve both favorable curability and water resistance.

The present invention further makes it possible to add the component (f) reactive organosilicon compound represented by the general formula (1) for the purpose of achieving both low viscosity and curability. (F) The reactive organosilicon compound is not particularly limited as long as it is a compound satisfying the requirement of the general formula (1). Specifically, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, dimethoxydiisopropoxysilane, diethoxydiisopropoxysilane, diethoxydibutoxy Tetraalkoxysilanes such as silane, trialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltriethoxysilane, ethyltributoxysilane, cyclohexyltriethoxysilane, and phenyltriisopropoxysilane Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane, phenylethyldiethoxysilane, etc. Kokishishiran acids may be used in combination of two or more even alone. Further, (f) a reactive organosilicon compound according to an existing method (for example, JP-A-60-18657, JP-A 2000-1648, Sakuo Sakuo, "Science of Sol-Gel Method" p.9). A hydrolyzate of a reactive organosilicon compound obtained by carrying out a condensation reaction using one or more of them may be used.
When the reactive organosilicon compound of component (f) is added, the amount added is (a) epoxy compound + (b) hydroxyl group-containing vinyl ether and / or oxetane by weight ratio, and component (a) + component It is preferable that (b) / component (f) is in the range of 10/100 to 500/100. When it is within this range, it is possible to achieve both excellent curability and excellent workability.

  To the photosensitive composition of the present invention, other additives exhibiting cationic polymerizability can be added to such an extent that the curability and film physical properties at the time of curing are not adversely affected. Examples of these compounds include polyfunctional vinyl ethers that do not contain a hydroxyl group. Specifically, for example, ethylene glycol divinyl ether, butanediol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, glycerol trivinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether A vinyl ether etc. can be mentioned.

In addition, examples include cyclic ether compounds other than epoxy compounds, oxetane compounds, vinyl ether compounds, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiro orthoester compounds, cyclic carbonate compounds, and the like.
Also, conventionally used polyhydric alcohols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane and pentaerythritol can be used as long as the curability is not impaired.

  The photosensitive composition of the present invention further includes (meth) acrylate monomers and oligomers, and photo radical initiators, antifoaming agents, leveling agents, polymerization inhibitors, waxes, antioxidants, A reactive polymer, fine particle inorganic filler, silane coupling agent, light stabilizer, ultraviolet absorber, antistatic agent, slip agent, corrosion inhibitor and the like can also be added. Examples of the corrosion inhibitor include ion exchangers, polyvalent carboxylic acids, hydroxycarboxylic acids, organic tin compounds, and sulfide compounds.

The light source that can be used to cure the photosensitive composition of the present invention is not particularly limited as long as it can be cured within a predetermined working time, and is usually irradiated with light having a wavelength of ultraviolet or visible light. Examples thereof include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, xenon lamps, metal halide lamps, and electrodeless discharge lamps.
In addition, in order to accelerate | stimulate hardening, you may heat the hardened | cured material obtained by the said method with a thermostat, an infrared heater, etc.

The present invention will be described based on examples.
<Characteristic evaluation of cured film>
(1) Tack-free exposure (TFED): The film after exposure was palpated and the minimum exposure required for the surface to harden and become non-sticky was determined.
○: TFED 120 mJ / cm ² or less ×: TFED exceeding 120 mJ / cm ² ○ was passed, and × was rejected.
(2) Conversion: The conversion was determined by calculating the reaction rate from the rate of decrease in absorption of the epoxy group before and after UV irradiation by FT-IR.
◎: 90% or more ○: 70% or more and less than 90% ×: less than 70% ◎, ○ was passed and × was rejected.
(3) Adhesiveness: A cross-cut tape peeling test was performed on the cured film (thickness: about 10 μm) formed on the PC substrate, and the residual rate was measured.
◎: Remaining cell 100/100 ○: Remaining cell 80/100 or more and less than 100/100 ×: Remaining cell 80/100 or less ◎, ○ was passed and × was rejected.

[Example 1]
As a component corresponding to the epoxy compound of component (a), 60 parts by weight of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, as component (b), 18 parts by weight of hydroxybutyl vinyl ether, component (c) 4) parts by weight of sulfonium PF ₆ salt type CPI-100P (product name: manufactured by San Apro) as an energy ray-sensitive cationic polymerization initiator, and the content of phenol (3) -5 nuclei as a component (e) polyhydric phenol compound. 50 parts by weight of p-tert-Bu-phenol novolak resin (PAPS series: Asahi Organic Materials Co., Ltd.) 3 parts by weight, component (f) 15 parts by weight of tetraethoxysilane as a reactive organosilicon compound, and component (d) 0.30 parts by weight of phosphoric acid with respect to components (a), (b), (c), (e), (f) A transparent photosensitive composition was obtained by sufficiently mixing the material to which triethyl was added.

The viscosity of the photosensitive composition thus obtained was measured using a viscometer (TVE-20LT) when stored at 23 ° C. for 40 days. The viscosity change before and after storage was 1 mPa · s. The storage stability was good.
In addition, in order to evaluate the characteristics of the photosensitive composition, first, coating was performed to a film thickness of 12 μm using a bar coater, and then TFED and conversion were measured with a 400 W high pressure mercury lamp exposure machine (manufactured by Sen Special Light Source). did. Next, the equivalent of TFED was irradiated, and the adhesiveness of the obtained cured film was evaluated. The results are shown in Table 1.

[Example 2]
The same procedure as in Example 1 except that triethyl phosphate was used as component (d) and 1.00 parts by weight with respect to components (a), (b), (c), (e), and (f). A photosensitive composition was obtained and evaluated. The results are shown in Table 1.
[Example 3]
As in Example 1, except that triphenyl phosphate is used as component (d) and 0.55 parts by weight are used for components (a), (b), (c), (e), and (f). Thus, a photosensitive composition was obtained and evaluated. The results are shown in Table 1.

[Example 4]
As in Example 1, except that tributyl phosphate is used as component (d) and 0.60 parts by weight are used for components (a), (b), (c), (e), and (f). A photosensitive composition was obtained and evaluated. The results are shown in Table 1.
[Example 5]
As a component corresponding to the epoxy compound of component (a), 35 parts by weight of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and Alonoxetane OXT-121 (manufactured by Toagosei Co., Ltd.) as component (b) 63 parts by weight, 2 parts by weight of iodonium salt type Rhodorsil 2047 (manufactured by Rhodia) as an energy ray-sensitive cationic polymerization initiator of component (c), and as component (d), components (a), (b), (c) On the other hand, a transparent photosensitive composition was obtained by sufficiently mixing a product added with 0.80 part by weight of triphenyl phosphate. Characteristic evaluation was performed in the same manner as in Example 1.

[Comparative Example 1]
Photosensitivity comprising only an epoxy resin comprising 96 parts by weight of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate as component (a) and 4 parts by weight of CPI-100P as component (c). A composition was obtained. The performance evaluation results of this composition are shown in Table 1.
[Comparative Example 2]
48 parts by weight of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate as component (a), 48 parts by weight of Alonoxetane OXT-121 as component (b), and CPI-100P as component (c) The transparent photosensitive composition was obtained by mix | blending in the ratio of 4 weight part, and mixing sufficiently. Characteristic evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

  From the above results, the cationically polymerizable photosensitive composition according to the present invention is superior to the conventional cationic photosensitive composition comprising the epoxy resin alone system shown in the comparative example and the combined system of the epoxy resin and the oxetane compound. It can be seen that the resin exhibits sufficient resin adhesiveness while having photocurability. From this, the cationically polymerizable photosensitive composition according to the present invention and the composition for ink jet printers using the cured product thereof, flexographic printing, gravure printing composition, optical disk for forming the light transmission layer, and the present invention. Flat panel displays such as LCDs, organic ELDs, and potential papers that use a cationically polymerizable photosensitive composition as a sealing material or a color filter can be expected to be highly reliable due to the excellent adhesiveness of the photosensitive composition. It is possible to improve productivity from rapid curing.

  Since the photosensitive composition of the present invention and the cured product thereof have much better adhesion than the conventional photosensitive composition composed of a cationic polymerizable composition, printing on a soft material such as a film or resin It can be suitably used for adhesive application.

Claims (6)

  (A) containing at least one selected from the group consisting of an epoxy compound, (b) a vinyl ether compound having a hydroxyl group, and oxetanes, (c) an energy ray-sensitive cationic polymerization initiator, and (d) phosphate esters. A photosensitive composition characterized by the above.   The photosensitive composition according to claim 1, wherein (d) the phosphate ester is at least one selected from the group consisting of triethyl phosphate, tributyl phosphate, and tri-2-ethylhexyl phosphate.   (D) Content of phosphoric acid ester is 500 ppm-50000 ppm in conversion of phosphorus, The photosensitive composition of Claim 1 or 2.   (E) The photosensitive composition of any one of Claims 1-3 which further contains 1 or more types chosen from the group which consists of a polyhydric phenol compound and the derivative | guide_body of this polyhydric phenol compound.   (E) One or more selected from the group consisting of a polyphenol compound and a derivative of the polyphenol compound is composed of 3-5 phenolic aromatic rings, and at any ortho position of all the hydroxyl groups thereof, A compound having two or more phenolic aromatic rings in which neither an alkyl group having 4 or more carbon atoms or a cycloalkyl group is substituted, and at least one ortho position of the hydroxyl group is unsubstituted. 4. The photosensitive composition according to 4. The photosensitive composition of any one of Claims 1-5 containing the (f) reactive organosilicon compound and / or its hydrolyzate represented by following General formula (1).
(R ₁ ) _n SiX _4-n (1)
(In the formula, R ₁ represents an alkyl group having 1 to 20 carbon atoms, X represents a hydrolyzable group, and n represents an integer of 0 to 3).