JP2011037973A - Photosensitive composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition which has excellent photocurability (surface hardening, internal hardening) which is not inhibited by oxygen and humidity in atmosphere. <P>SOLUTION: The photosensitive composition includes 40 mass% or more and 84.9 mass% or less of an epoxy compound (a) having 2 or more epoxy groups in the molecule, 15 mass% or more and 50 mass% or less of a silane compound (b) having one or more epoxy groups and a group having hydrolyzability in the molecule, and 0.1 mass% or more and 10 mass% or less of an energy ray sensitive cationic polymerization initiator (c). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photosensitive composition and a cured product thereof, and a photosensitive adhesive, a photosensitive coating material, and a photosensitive inkjet ink.

  Curing systems using energy rays such as ultraviolet rays have become an effective method for improving productivity and solving recent environmental problems. The mainstream of the current photocuring system is a radical curable material using a (meth) acrylate material. On the other hand, cationically 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, and (b) have a small cure shrinkage and a wide base. It has good adhesiveness to the material, and (c) the active species has a long life and the curing gradually proceeds even after light irradiation (dark reaction). Excellent features compared to curable materials. Therefore, in recent years, application of cationic curable materials to paints, adhesives, display sealants, printing inks, three-dimensional modeling, silicone release paper, photoresists, sealants for electronic components, etc. has been studied. (For example, refer nonpatent literature 1).

  An epoxy compound is mentioned as a compound mainly used as a photocationic curable material. Among these, highly reactive alicyclic epoxy compounds are frequently used (see, for example, Patent Document 1). Since the alicyclic epoxy compound does not cause curing inhibition by oxygen even in the air, the alicyclic epoxy compound has excellent surface curability as compared with the radical curable material. However, since the reaction rate decreases as the polymerization proceeds, there is a problem that the internal curability is insufficient and sufficient cured properties cannot be obtained. Moreover, since there are few kinds of compounds which can be used, it is difficult to control the physical properties of the obtained cured product.

On the other hand, glycidyl-type epoxy compounds are more abundant than the alicyclic epoxy compounds, but have insufficient reactivity when photocationically cured. Therefore, it is necessary to use a special initiator such as SbF ₆ or AsF _{6 that} has a safety problem, or to use thermosetting together.

  In contrast, the vinyl ether compound is known to have high cationic polymerizability, but the cured film obtained by homopolymerization has a larger curing shrinkage than the epoxy and oxetane, and the adhesiveness to the substrate is reduced. There's a problem. Thus, many attempts have been made to increase the polymerizability of the epoxy compound and maintain the adhesiveness by using a vinyl ether compound in combination with the alicyclic epoxy compound (see, for example, Patent Documents 2 and 3).

US Pat. No. 3,794,576 JP-A-6-298911 JP-A-9-328634

Masahiro Kadooka, et al. “Industrial development of cationic curing technology” MATERIAL STAGE, Technical Information Association, May 10, 2002, Volume 2, No. 2, p. 39-p. 92

  However, in the composition in which the vinyl ether compound is simply used in combination with the epoxy compound as described above, the hydrophilicity is increased by the mixing of the vinyl ether compound, so that the composition is easily inhibited by curing when the humidity in the curing atmosphere is high.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a photosensitive composition having excellent photocurability (surface curability and internal curability) that is not inhibited by oxygen and humidity in the atmosphere. And

  As a result of intensive studies to solve the above problems, the present inventor has solved the above problems with a photosensitive composition containing a specific epoxy compound, a specific silane compound, and a photocationic polymerization initiator in a specific ratio. The present inventors have found out that it is possible to achieve the present invention.

That is, the present invention is as follows.
[1]
An epoxy compound (a) having two or more epoxy groups in the molecule of 40% by mass or more and 84.9% by mass or less;
In the molecule, silane compound (b) having one or more epoxy groups and a hydrolyzable group (15% by mass to 50% by mass),
Energy ray sensitive cationic polymerization initiator (c) 0.1 mass% or more and 10 mass% or less,
A photosensitive composition comprising:
[2]
The above-mentioned [1], further comprising 1% by mass or more and 44% by mass or less of a hydroxyl group-containing compound (d) having one or more hydroxyl groups and one or more vinyl ether groups or oxetanyl groups in the molecule. Photosensitive composition.
[3]
Contains 3-5 phenolic aromatic rings,
All of the ortho positions of the phenolic aromatic ring hydroxyl group are not substituted with any of a methylol group, an alkyl group having 4 or more carbon atoms, or a cycloalkyl group, and
The polynuclear phenol compound (e) having 0.1 to 40% by mass of the polynuclear phenol compound (e) having two or more phenolic aromatic rings in which at least one ortho position of the phenolic hydroxyl group of the phenolic aromatic ring is unsubstituted [ The photosensitive composition of [1] or [2].
[4]
The photosensitive composition according to any one of [1] to [3], wherein the epoxy group of the epoxy compound (a) is an alicyclic epoxy group.
[5]
The polynuclear phenol compound (e) includes a polynuclear phenol compound (f) represented by the following formula (1) and a polynuclear phenol compound (g) represented by the following formula (2), and
The content (f / (f + g)) of the component (f) with respect to the total of the component (f) and the component (g) is 40% by mass or more, [1] to [4] Photosensitive composition.
Wherein R ¹ , R ² and R ³ are alkyl groups having 1 to 5 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, halogen atoms, hydroxyl groups, aryl groups or aralkyls. R ¹ , R ² and R ³ may be different from each other or the same, m ¹ represents an integer of 0 to 3, and n ¹ represents an integer of ¹ to 3).
(In the formula, R ¹ , R ² and R ³ are the same as defined in formula (1), m ² represents an integer of 0 to 3, and n ² represents 0 or an integer of 4 or more.)
[6]
The component (e) includes a polynuclear phenol compound (h) represented by the following formula (3) and a polynuclear phenol compound (i) represented by the following formula (4), and
The photosensitive composition according to any one of the above [1] to [4], wherein the content (h / (h + i)) of the component (h) with respect to the sum of the component (h) and the component (i) is 40% by mass or more. Sex composition.
(Wherein, ^{n 3} is an integer of 1-3.)
(In the formula, n ⁴ represents 0 or an integer of 4 or more.)
[7]
Hardened | cured material obtained by irradiating at least actinic light to the photosensitive composition in any one of said [1]-[6].
[8]
A photosensitive adhesive comprising the photosensitive composition according to any one of the above [1] to [6].
[9]
A photosensitive coating material comprising the photosensitive composition according to any one of the above [1] to [6].
[10]
A photosensitive inkjet ink comprising the photosensitive composition according to any one of the above [1] to [6] and a colorant.
[11]
A cured product obtained by irradiating the photosensitive adhesive of [8], the photosensitive coating material of [9], or the photosensitive inkjet of [10] with at least actinic rays.

  The photosensitive composition of the present invention has excellent photocurability (surface curability and internal curability) that is not hindered by atmospheric oxygen and humidity.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

  The photosensitive composition of the present embodiment comprises an epoxy compound (a) having 2 or more epoxy groups in the molecule (40) to 84.9% by mass, one or more epoxy groups in the molecule, and hydrolysis. A silane compound (b) having a functional group and 15 mass% to 50 mass% and an energy ray sensitive cationic polymerization initiator (c) 0.1 mass% to 10 mass%.

  In the present embodiment, an epoxy compound (a) having two or more epoxy groups in the molecule is used in order to realize excellent photocurability. Such a compound is not particularly limited as long as it satisfies the above requirements, and examples thereof include a glycidyl ether type epoxy compound and an alicyclic epoxy compound.

  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 novolak type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, and bisphenol A alkylene oxide adducts. Diglycidyl ether, diglycidyl ether of bisphenol F alkylene oxide adduct, diglycidyl ether of hydrogenated bisphenol A alkylene oxide adduct, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, Butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexane dimethanol 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, methylenebis (2,7-dihydroxynaphthalene) tetraglycidyl ether, 1,6-dihydroxynaphthalenediglycidyl ether, and the like. Among these, since it is excellent in photocurability, a bisphenol A type epoxy compound is preferable.

  Specific examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy). Cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy -6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ) Ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), propylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4 -Cyclohexanedimethanol di (3,4-epoxycyclohexanecarboxylate) and the like. Among these, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is preferable because of excellent photocurability.

  As a bifunctional alicyclic epoxy compound, “Celoxide 2021P”, “Celoxide 2000”, “Celoxide 3000” (trade name, manufactured by Daicel Chemical Industries), “UVR-6110”, “UVR-6105” are commercially available. "UVR-6128", "ERLX-4360" (trade name, manufactured by Dow Chemical Japan Co., Ltd.) and the like.

  Among these, an alicyclic epoxy compound is preferable because of excellent photocurability. The epoxy compound (a) may be used alone or in combination of two or more.

  The silane compound (b) is a silane compound having at least one epoxy group in the molecule and having a hydrolyzable group. The hydrolyzable group may be a group that generates a hydroxyl group by hydrolysis, and examples thereof include a halogen atom, an alkoxy group, an acyloxy group, an amino group, an enoxy group, an oxime group, and a hydride group. Among these, an alkoxy group is preferable because it is excellent in the pot life of the photosensitive composition.

Examples of the silane compound (b) include a hydrolyzable group-containing silane represented by the following formula (5), a hydrolyzable group-containing silane represented by the following formula (6), and the like.

^{_{(R 4 -R 5 a) b}} R 6 c SiX 4-b-c (5)

In the formula, R ⁴ represents a 3,4-epoxycyclohexyl group, a glycidyl group, or a glycidoxy group. R ⁵ represents an alkanediyl group, alkenediyl group, alkynediyl group, or arenediyl group having 1 to 10 carbon atoms. X represents a hydrolyzable group. R ⁶ represents an alkyl group, alkenyl group or alkynyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. a represents an integer of 0 or 1. b represents an integer of 1 to 3. c represents an integer of 0-2. However, (b + c) <4.

^{_{(R 4 -R 5 a) X}} 2 Si-R 7 -SiX 2 (R 5 a -R 4) (6)

In formula, R < ⁴ >, R < ⁵ >, X, and a are the same definitions as Formula (5), and R < ⁷ > represents a C1-C6 alkylene group or a phenylene group.

R ⁴ is preferably a 3,4-epoxycyclohexyl group. R ⁵ is preferably an ethylene group. R ⁶ is preferably a methyl group. R ⁷ is preferably a phenylene group.

  Specific examples of the silane compound (b) include 3-glycidoxyethyltrimethoxysilane, 3-glycidoxyethylmethyldimethoxysilane, 3-glycidoxyethyltriethoxysilane, and 3-glycidoxyethylmethyldiethoxy. Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyl Diethoxysilane, 2- ( , 4-epoxycyclohexyl) propyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) propylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) propyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ) Propylmethyldiethoxysilane and the like. Among these, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is preferable because of excellent photocurability.

  The silane compound (b) may be used alone or in combination of two or more. The hydrolysis condensate of the silane compound described above can be used in the same manner.

In the photocuring reaction, the silane compound (b) undergoes cationic polymerization by first hydrolyzing the hydrolyzing group to generate a silanol group and then condensing the silanol groups. Furthermore, the epoxy group of the silane compound (b) is cationically polymerized with other cationically polymerizable compounds including the epoxy compound (a). The present inventor has found that the addition of these silane compounds can particularly reduce the inhibition of curing under high humidity of 60% or higher relative humidity. Although the mechanism is not certain, it is presumed as follows from the reaction formula of the silane compound (b). The reaction in which hydrolyzable groups condense to form a siloxane bond is a reaction that consumes water as a whole. For this reason, this reaction is accelerated by humidity and forms a high molecular weight siloxane bond chain. The siloxane bond chain is bonded to the epoxy compound (a) having a reduced molecular weight due to curing inhibition via the side chain epoxy group. Crosslinking between coalesces. This increases the molecular weight of the entire system, and exhibits excellent photocurability even under high humidity. For example, when the hydrolyzable group X is an alkoxy group (—OR ′), the overall reaction formula of the hydrolysis reaction, condensation reaction, and hydrolysis group condensation reaction is as follows.
Hydrolysis reaction: 2Si—OR ′ + 2H ₂ O → 2Si—OH + 2R′—OH
Condensation reaction: 2Si—OH → Si—O—Si + H ₂ O
Overall reaction formula: 2Si—OR ′ + H ₂ O → Si—O—Si + 2R′—OH

  The energy ray-sensitive cationic polymerization initiator (c) refers to a compound capable of generating a substance that initiates cationic polymerization upon irradiation with energy rays. Preferable examples include onium salts that generate a Lewis acid upon irradiation.

Examples of onium salts include diazonium salts of Lewis acids, iodonium salts of Lewis acids, sulfonium salts of Lewis acids, and the like. In these, the cation part is aromatic diazonium, aromatic iodonium, and aromatic sulfonium, respectively, and the anion part is BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , [BX ₄ ] ⁻ (where X is at least two or more. Represents a phenyl group substituted with a fluorine or trifluoromethyl group.) And the like.

  Specifically, triarylsulfonium salt of phosphorous hexafluoride, phenyldiazonium salt of boron tetrafluoride, diphenyliodonium salt of phosphorous hexafluoride, diphenyliodonium salt of antimony hexafluoride, tri-arsenic hexafluoride 4-methylphenylsulfonium salt, tri-4-methylphenylsulfonium salt of antimony tetrafluoride, diphenyliodonium salt of tetrakis (pentafluorophenyl) boron, acetylacetone aluminum salt and orthonitrobenzylsilyl ether mixture, phenylthiopyridium salt And phosphorus hexafluoride allene-iron complex. Among these, a triarylsulfonium salt of phosphorus hexafluoride is preferable because of its good pot life and low toxicity.

  As commercial products of onium salts, “CD-1012” (trade name, manufactured by SARTOMER), “PCI-019”, “PCI-021” (trade name, manufactured by Nippon Kayaku Co., Ltd.), “Optomer SP-150”, “Optomer SP-170” (trade name, manufactured by Asahi Denka), “UVI-6990” (trade name, manufactured by Dow Chemical), “CPI-100P”, “CPI-100A” (trade name, manufactured by San Apro) ), “TEPBI-S” (trade name, manufactured by Nippon Shokubai Co., Ltd.), “RHODORSIL PHOTOINITIATOR 2074” (trade name, manufactured by Rhodia), and the like can be used. The energy ray-sensitive cationic polymerization initiator (c) may be used alone or in combination of two or more.

  When the photosensitive composition of this embodiment contains a hydroxyl group-containing compound (d) having one or more hydroxyl groups and one or more of a vinyl ether group or an oxetanyl group, the photocuring rate at a relative humidity of 30% or less is obtained. Since it improves, it is preferable. The hydroxyl group-containing compound (d) has both a hydroxyl group and a cationic polymerizable group (vinyl ether group or oxetanyl group) in one molecule.

  Although the reason why the photocuring rate is increased at a relative humidity of 30% or less by including the hydroxyl group-containing compound (d) is not clear, the hydroxyl group of the hydroxyl group-containing compound (d) is probably added to the silane compound (b) by hydrolysis. In addition to directly condensing with the decomposing group, it is considered that the hydrophilicity of the photosensitive composition is increased and moisture is absorbed to promote condensation of the hydrolyzing group of the silane compound (b). In addition, the vinyl ether group or oxetanyl group is polymerized with a cationically polymerizable group such as an epoxy compound (a), and the hydroxyl group is high by reacting with a hydrolyzable group or a cationically polymerizable group of the silane compound (b). It is thought that the photocuring speed is achieved.

  Examples of the vinyl ether compound having a hydroxyl group used as the hydroxyl group-containing compound (d) include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, cyclohexane dimethanol monovinyl ether, cyclohexanediol monovinyl ether, 9-hydroxynonyl vinyl ether, propylene glycol monovinyl ether, Neopentyl glycol monovinyl ether, glycerol divinyl ether, glycerol monovinyl ether, trimethylolpropane divinyl ether, trimethylolpropane monovinyl ether, pentaerythritol monovinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, diethylene glycol monovinyl ether, Ethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, tricyclodecane diol monovinyl ether, tricyclodecanedimethanol monovinyl ether and the like. Among these, hydroxybutyl vinyl ether is preferable from the viewpoint of increasing the photocuring rate at a relative humidity of 30% or less.

  Examples of the oxetane compound having a hydroxyl group used as the hydroxyl group-containing compound (d) include compounds represented by the following formula (7).

In the formula, R ⁸ represents an alkyl group, an alkenyl group or an alkynyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. R ⁹ represents an alkanediyl group, alkenediyl group, alkynediyl group, or arenediyl group having 1 to 10 carbon atoms. R ⁸ is preferably a lower alkyl group having 1 to 4 carbon atoms, and particularly preferably an ethyl group. R ⁹ is preferably a methylene group.

  These hydroxyl group-containing compounds (d) may be used alone or in combination of two or more.

  The photosensitive composition of this embodiment contains 3 to 5 phenolic aromatic rings, and all of the ortho positions of the hydroxyl groups of this phenolic aromatic ring are methylol groups, alkyl groups having 4 or more carbon atoms, and cycloalkyl groups. A polynuclear phenol compound (e) having at least two phenolic aromatic rings that are not substituted on any of the above and at least one ortho position of the hydroxyl group of the phenolic aromatic ring is unsubstituted, Furthermore, it is preferable to include. The polynuclear phenol compound (e) contains a plurality of phenolic aromatic rings. Here, the phenolic aromatic ring is an aromatic ring having a phenolic hydroxyl group. In the present embodiment, the phenolic hydroxyl group plays an important role in the photocrosslinking reaction. By using a polynuclear phenol compound having such a phenolic hydroxyl group, more excellent photocurability is obtained in the photosensitive composition. Can be granted.

  The polynuclear phenol compound (e) does not have a methylol group at any ortho position of all of its hydroxyl groups. That is, what is generally called a resol resin and has a methylol group in the molecule is not included in the polynuclear phenol compound (e). 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 there is a problem that the film hardness obtained after curing decreases with time.

  The polynuclear phenol compound (e) does not have an alkyl group or cycloalkyl group having 4 or more carbon atoms in the ortho position. That is, a phenol compound generally called a radical inhibitor or an antioxidant such as a hindered phenol having a particularly bulky t-butyl group is not included in the polynuclear phenol compound (e). This is because in the polynuclear phenol compound (e), the phenolic hydroxyl group is directly involved in the photocuring reaction, and therefore, it is not preferable that the bulky substituent that becomes an inhibitor of the reaction is substituted at the ortho position of the phenolic hydroxyl group.

  The polynuclear phenol compound (e) comprises 3 to 5 phenolic aromatic rings, and at least two phenolic aromatic rings in which at least one ortho position of the hydroxyl group is unsubstituted in the molecule. Have. In one or two phenolic aromatic rings, a crosslinked 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.

  Examples of such polynuclear phenol compounds include various polynuclear phenol compounds represented by the following formulas (8) to (12), and various polynuclear phenol compounds represented by the following formulas (1) and (3). And polynuclear phenol compounds having 3 to 5 phenolic aromatic rings, which are Friedel-Crafts reaction adducts of low molecular weight chain polybutadiene and phenol. Here, the low molecular weight means a weight average molecular weight of 1000 or less. The weight average molecular weight can be measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase and polystyrene as a standard substance.

In the formula, R ¹⁰ , R ¹¹ and R ¹² represent an alkyl group or an alkoxy group having 1 to 5 carbon atoms, and may be the same or different from each other, and p R ¹⁰ , R ¹¹ and R in each benzene ring R ¹² may be the same as or different from each other. p ¹⁰ , p ¹¹ and p ¹² represent an integer of 0 to 4 and may be the same or different from each other, and q ¹⁰ , q ¹¹ and q ¹² represent an integer of 1 to 3 and may be the same or different from each other. In the corresponding p and q, p + q ≦ 5. However, when any carbon number of R ¹⁰ , R ¹¹ and R ¹² is 4 or 5, the R ¹⁰ , R ¹¹ and R ¹² are not located in the ortho position with respect to the hydroxyl group on the benzene ring.

In the formula, R ¹³ , R ¹⁴ and R ¹⁵ have the same definitions as R ¹⁰ , R ¹¹ and R ¹² in formula (8), and p ¹³ , p ¹⁴ and p ¹⁵ are p ¹⁰ , p ^{11 in} formula (8). And p ^12, and q ¹³ , q ^14, and q ¹⁵ are the same definitions as q ¹⁰ , q ^11, and q ^{12 in} Formula (8).

In the formula, R ¹³ , R ¹⁴ and R ¹⁵ have the same definitions as R ¹⁰ , R ¹¹ and R ¹² in formula (8), and p ¹³ , p ¹⁴ and p ¹⁵ are p ¹⁰ , p ^{11 in} formula (8). And p ^12, and q ¹³ , q ^14, and q ¹⁵ are the same definitions as q ¹⁰ , q ^11, and q ^{12 in} Formula (8).

In the formula, R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ represent an alkyl group or an alkoxy group having 1 to 3 carbon atoms, and may be the same or different from each other, and p R ^{16 s} in each benzene ring, R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same as or different from each other. p ¹⁶ and ^{p 17} each represents an integer of 0 to 4, may be the same or ^{different, q 16} and ^{q 17} represents an integer of 1 to 3, it may be the same or different from each other. However, in the corresponding p and q, p + q ≦ 5.

In the formula, R ²⁰ represents a group represented by the following formula (13), (14) or (15), and R ²¹ , R ²² , R ²³ and R ²⁴ represent R ¹⁰ , R ¹¹ and R in formula (8). have the same definition as ^{R 12, p 21, p 22} , p 23 and ^{p 24} are the same as defined ^{p 10, p 11} and ^{p 12} of the formula (8).

In the formula, R ¹ , R ² and R ³ are each 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. R ¹ , R ² and R ³ may all be different from or identical to each other, m ¹ represents an integer of 0 to 3, and n ¹ represents an integer of ¹ to 3.

Wherein, ^{n 3} is an integer of 1-3.

  Among these, the polynuclear phenol compound (f) represented by the formula (1) and the polynuclear phenol compound (h) corresponding to the addition compound represented by the formula (3) are preferable.

  The polynuclear phenol compound (f) is preferable because it has excellent compatibility and reactivity with the epoxy compound (a), the silane compound (b), and the hydroxyl group-containing compound (d). The polynuclear phenol compound (h) is preferable because a cured product having low hygroscopicity and excellent water resistance can be obtained.

In the polynuclear phenol compound (f), m ¹ is preferably an integer of ¹ to 3, and more preferably 1. Further, when m ¹ is an integer of ¹ to 3, R ¹ , R ² and R ³ are preferably bonded to the para position with respect to the hydroxyl group of the benzene ring. Here, R ¹ , R ² and R ³ are 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. 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. As the cycloalkyl group having 5 to 10 carbon atoms, a cyclohexyl group having 6 carbon atoms is preferable. Examples of the alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, t-butoxy group, sec-butoxy group and the like. Examples of the cycloalkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and a biphenyl group. Examples of the aralkyl group include benzyl group, α-methylbenzyl group, α, α ′ dimethylbenzyl group and the like.

The polynuclear phenol compounds (f) and (g) can be obtained by, for example, reacting a phenol having a substituent represented by R (R-substituted phenol) or a phenol with an aldehyde to give n (n ^{1 in the} formula (1)). , N ² ) in formula (2) can be obtained as a condensate represented by an integer of 0 or more. Here, R is a substituent represented by any of R ^{1 to} R ³ described above. The R-substituted phenol is not limited to one substitution, and may have two or more substituents.

  The condensation reaction can be performed by a known method. For example, in the presence of an acid catalyst such as hydrochloric acid, oxalic acid, or p-toluenesulfonic acid, aldehydes such as formaldehyde, paraformaldehyde, formalin, and the above R-substituted phenol or phenol are used at 0 to 150 ° C. for several hours to several tens of hours. The method of making it react is mentioned. Depending on the reaction conditions at this time, various polynuclear phenol compounds represented by the following formula (2) (g) produced as a by-product by controlling the mixing ratio of R-substituted phenol or phenol and aldehydes (g ) Can be controlled.

^Wherein, R 1, ^{R 2} and ^{R 3} are as defined in the formula (1), ^{m 2} represents an integer of 0 to 3, ^{n 2} represents 0 or an integer of 4 or more.

  For example, if there are too many R-substituted phenols than aldehydes, the content of phenol dinuclear compounds will increase, and conversely if there are too few R-substituted phenols than aldehydes, a polynuclear phenol compound having 6 or more phenolic aromatic rings. The content of (f) increases. When the content of the polynuclear phenol compound (f) in the obtained condensate is too small, the unreacted raw material and the polynuclear phenol compound (g) can be removed by a method such as distillation or reprecipitation.

  In the present embodiment, the content (f / (f + g)) of the polynuclear phenol compound (f) with respect to the sum of the polynuclear phenol compounds (f) and (g) is preferably 40% by mass or more, and 50% by mass or more. It is more preferable that it is 60 mass% or more.

The reason why the content (f / (f + g)) of the polynuclear phenol compound (f) is preferably 40% by mass or more will be described based on the structure of the polynuclear phenol compound (f). In formula (2), when n ² is 0, a decrease in the reactivity of the photosensitive composition can be suppressed, so the content (f / (f + g)) of the polynuclear phenol compound (f) is 40% by mass or more. Is preferred. In the formula (2), when n ² is 4 or more, it is possible to reduce the residual unreacted phenolic hydroxyl group after the photocuring reaction, improve the water resistance of the cured product, and suppress yellowing due to light irradiation. Since it can do, it is preferable that the content rate (f / (f + g)) of a polynuclear phenol compound (f) is 40 mass% or more.

  Among the commercially available products of the polynuclear phenol (f), for example, a novel molecular weight distribution intensive novolak resin “PAPS” (trade name, manufactured by Asahi Organic Materials Co., Ltd.) can be mentioned.

  Specific examples of the R-substituted phenol used for the synthesis of the polynuclear phenol compound (f) 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, m-methoxyphenol, p -Chloro Phenol, m-chlorophenol, catechol, resorcinol, hydroquinone and the like can be mentioned.

On the other hand, the polynuclear phenol compounds (h) and (i) can be obtained by performing a Friedel-Crafts reaction of dicyclopentadiene and phenol in the presence of an acid catalyst such as BF ₃ . In this case, by determining the amount ratio of dicyclopentadiene and phenol to be used, the production amount of various polynuclear phenol compounds (i) represented by the following formula (4) produced as a by-product can be controlled. it can.

In the formula, n ⁴ represents 0 or an integer of 4 or more.

  In the present embodiment, the content (h / (h + i)) of the polynuclear phenol compound (h) with respect to the sum of the polynuclear phenol compounds (h) and (i) is preferably 40% by mass or more, and 50% by mass or more. It is more preferable that it is 60 mass% or more.

The reason why the content (h / (h + i)) of the polynuclear phenol compound (h) is preferably 40% by mass or more will be described based on the structure of the polynuclear phenol compound (h). When n ⁴ is 0 in the formula (4), the decrease in the reactivity of the photosensitive composition can be suppressed, so that the content (h / (h + i)) of the polynuclear phenol compound (h) is 40% by mass or more. Is preferred. When n ⁴ is 4 or more in the formula (4), the remaining unreacted phenolic hydroxyl group after the photocuring reaction is reduced, the water resistance of the cured product can be improved, and yellowing due to light irradiation is suppressed. Since it can do, it is preferable that the content rate (h / (h + i)) of a polynuclear phenol compound (h) is 40 mass% or more.

  Preferable examples of the commercially available polynuclear phenol compound (h) include “DPP-6125” in the Nisseki special phenol resin “DPP” series (manufactured by Nippon Petrochemical Co., Ltd.).

  As the polynuclear phenol compound (e), one of the various polynuclear phenol compounds described above may be used alone or in combination of two or more.

  In addition to the energy ray-sensitive cationic polymerization initiator (c), the photosensitive composition of the present embodiment can be used in combination with another polymerization initiator that generates a substance that initiates cationic polymerization by heating. Examples of such other polymerization initiators include 4,4′-bis (diethylamino) benzophenone, 2,4-diethylthioxanthone, isopropylthioxanthone, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and the like. Is mentioned.

  In addition to the hydroxyl group-containing compound (d), polyfunctional vinyl ether or oxetane that does not contain a hydroxyl group can be used in combination with the photosensitive composition of the present embodiment.

  Examples of the vinyl ether include ethylene glycol divinyl ether, butanediol divinyl ether, cyclohexane dimethanol divinyl ether, cyclohexane diol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, glycerol trivinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether. Examples include vinyl ether.

  Examples of oxetane include 1,4-bis ([(3-ethyloxetane-3-yl) methoxy] methyl) benzene, bis [1-ethyl (3-oxetanyl)] methyl ether, 1,3-bis [( 3-ethyloxetane-3-yl) methoxy] benzene, 4,4′-bis [(3-ethyloxetane-3-yl) methoxy] biphenyl, phenol novolac oxetane, oxetanylsilsesquioxane and the like.

  You may add another cationically polymerizable compound in the grade which does not have a bad influence on the sclerosis | hardenability of the photosensitive composition of this embodiment, or the film | membrane physical property at the time of hardening. As other cationically polymerizable compounds, for example, low molecular weight epoxy compounds other than those described above can be used as diluents, and examples thereof include cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiro orthoester compounds, and the like. . Furthermore, commonly used diols such as polyethylene glycol such as ethylene glycol, propylene glycol, diethylene glycol and triethylene glycol and polypropylene glycol, and polyhydric alcohols such as glycerin, trimethylolpropane and pentaerythritol can also be used.

  In the photosensitive composition of the present embodiment, for the purpose of promoting curability to energy rays (improving sensitivity), radically polymerizable compounds such as (meth) acrylate monomers, oligomers and vinyl (meth) acrylate, A photo radical initiator or the like may be added as necessary. Among these, a vinyl (meth) acrylate compound having a vinyl group and an acrylate group in one molecule has a low viscosity and is cationically polymerizable, so that the viscosity can be reduced while maintaining high sensitivity. Therefore, it is a particularly effective diluent when used for inkjet applications. In addition, antifoaming agents, leveling agents, polymerization inhibitors, waxes, antioxidants, non-reactive polymers, fine particle inorganic fillers, silane coupling agents, light stabilizers, UV absorbers, antistatic agents, slips An agent or the like can also be added.

  For the purpose of particularly reducing the moisture permeability of the photosensitive composition, it is preferable to add a fine particle inorganic filler. The fine particle inorganic filler is an inorganic filler having an average primary particle diameter of 0.005 to 10 μm, and specifically includes silica, alumina, talc, calcium carbonate, mica and the like.

  The fine particle inorganic filler can be used both of the untreated surface and the treated surface. Examples of the surface-treated fine particle inorganic filler include methoxylated, trimethylsilylated, octylsilylated, or surface treated with silicone oil. You may use these 1 type individually or in combination of 2 or more types.

  Next, the composition ratio of each component in the photosensitive composition used in the present embodiment will be described. The “parts” shown below are all “parts by mass” unless otherwise specified.

  The content of the epoxy compound (a) in the photosensitive composition is 40% by mass or more and 84.9% by mass or less, and preferably 50% by mass or more and 80% by mass or less. By setting it as the above content, a high photocuring speed can be achieved.

  Content of the silane compound (b) in a photosensitive composition is 15 to 50 mass%, and it is preferable that it is 15 to 40 mass%. By setting it as the above content, a high photocuring speed at a relative humidity of 60% or more can be achieved.

  The content of the energy ray sensitive cationic polymerization initiator (c) in the photosensitive composition is 0.1% by mass or more and 10% by mass or less, preferably 0.2% by mass or more and 5% by mass or less. If it exceeds 10% by mass, an expensive initiator is excessively used, which is not preferable economically, and it is not preferable because the light transmittance is lowered and the film bottom is not sufficiently cured. When the amount is less than 0.1% by mass, the amount of the active cationic substance generated by energy beam irradiation is insufficient, and sufficient curability cannot be obtained.

  The content of the hydroxyl group-containing compound (d) in the photosensitive composition is preferably 1% by mass or more and 44% by mass or less, and more preferably 10% by mass or more and 40% by mass or less. By setting it as the above numerical range, a high photocuring speed can be achieved even when the relative humidity of the photosensitive composition of the present embodiment is 30% or less.

  The content of the polynuclear phenol compound (e) in the photosensitive composition is preferably 0.1% by mass or more and 40% by mass or less, and more preferably 0.5 or more and 20% by mass or less. By setting it as the above numerical range, the photocuring speed of the photosensitive composition of the present embodiment can be improved.

  The content of the fine particle inorganic filler used as necessary is preferably 0.1% by mass or more and 44% by mass or less, more preferably 0.1% by mass or more and 40% by mass or less in the photosensitive composition. is there.

  The photosensitive composition of the present embodiment is applied to a substrate or the like to form a thin film, and the thin film can be cured in a short time by irradiation with energy rays or heating. Although hardening of the photosensitive composition can be performed by energy beam irradiation, you may use energy beam irradiation and a heating together. The photosensitive composition of the present embodiment is sufficiently practical without containing a solvent or the like, but may be diluted with a solvent or the like for viscosity adjustment, or in the form of a sol containing porous fine particles or the like It is good. When diluted with a solvent, etc., or when used in the form of a sol containing porous fine particles, etc., light irradiation is performed at 50 to 150 ° C. for several minutes in order to volatilize the solvent component in advance. You may go before. Moreover, hardening can be further accelerated | stimulated by heating similarly after exposure. Furthermore, since the photosensitive composition of the present embodiment is cured by light irradiation, it can be used as a photosensitive adhesive. The photosensitive adhesive containing the photosensitive composition of the present embodiment can be used in the above-described form or the like, and can exhibit excellent adhesiveness without being inhibited by curing due to humidity.

  The photosensitive composition of this embodiment is useful as a photosensitive adhesive because it has excellent curability and excellent adhesion to various substrates. In particular, since the polymerization conversion rate by energy beam irradiation is high, the productivity is excellent, and further, the moisture resistance is also excellent. For this reason, it is suitable as a sealant for flat panel displays (FPD) such as liquid crystal displays, organic EL (OLED) displays, and electronic papers that require not only good adhesiveness but also high reliability. Among these, since the OLED display sealant is required to have high moisture permeability, the sealant of this embodiment can be suitably used. Since the photosensitive composition of the present embodiment can cure a thin film at high speed in the air, it can be suitably used as a coating material for resin films, substrates and the like that are required to be cured at high speed without heating. Is done.

  Furthermore, it can be set as the photosensitive coating material containing the photosensitive composition of this embodiment. Since the photosensitive composition of the present embodiment can cure a thin film at high speed in the air, it is also suitable as a coating material for resin films, substrates and the like that are required to be cured at high speed without heating. used. As such an example, a coating material for forming an antireflection film used for FPD or the like can be mentioned. Porous fine particles having voids in the photosensitive composition of the present embodiment in order to form a film having a refractive index of 1.4 or less after the photosensitive composition is applied and cured on a substrate It is obtained by containing.

  Examples of such porous fine particles include silica particles having an average particle diameter of 5 nm to 1 μm, and silica particles having an average particle diameter of 5 to 100 nm are preferable from the viewpoint of resin transparency. Specific examples of commercially available products include “Aerosil” (trade name, manufactured by Nippon Aerosil Co., Ltd.), a fumed silica having a hydrophilic or hydrophobic surface, and a pearl necklace-shaped silica sol in which silica particles are connected in a straight chain. There is a certain “Snowtex PS” (trade name, manufactured by Nissan Chemical Co., Ltd.). These porous fine particles are preferably used by adding a total of 10 to 70 parts by mass of the porous fine particles with respect to 100 parts by mass of the photosensitive composition, and using a homogenizer or the like in the photosensitive composition. It is preferable to disperse uniformly.

  The photosensitive coating material thus obtained is placed on the surface of a transparent substrate (for example, a resin substrate such as polymethyl methacrylate, polycarbonate, polystyrene, or triacetyl cellulose, or an inorganic material substrate such as glass). It can be formed in a thickness range of 10 nm to 1 μm as an antireflection film or a scratch prevention film. Since it is necessary to form a relatively thin film with high precision, the microgravure method, roll coat method, flow coat method, spin coat method, die coat method, cast transfer method, spray coat method, etc. Used.

  Furthermore, it can be set as the photosensitive inkjet ink by adding a coloring agent to the photosensitive composition of this embodiment. The photosensitive composition of the present embodiment also has a feature that it is relatively easy to reduce the viscosity. In combination with excellent photocurability, the photosensitive composition is mixed with an appropriate colorant to form a photosensitive inkjet ink. Can also be suitably used.

  Examples of the colorant used in the present embodiment include organic pigments and / or inorganic pigments. Specifically, white pigments such as titanium oxide, zinc white, lead white, litbon, and antimony oxide, black pigments such as aniline black, iron black, and carbon black, yellow lead, yellow iron oxide, Hansa Yellow (100, 50, 30 etc.), yellow pigments such as titanium yellow, benzine yellow and permanent yellow, orange pigments such as chrome vermilon, permanent orange, balkan first orange and indanthrene brilliant orange, brown such as iron oxide, permanent brown and para brown Pigment, Red, such as Bengala, Cadmium Red, Antimony Zhu, Permanent Red, Rhodamine Lake, Alizarin Lake, Thioindigo Red, PV Carmine, Monolite Face Tread, and Quinacridone Red Pigment, Cobalt Purple, Manganese Purple, Purple pigments such as first bilet, methyl violet lake, indanthrene brilliant violet, dioxazine violet, ultramarine, bitumen, cobalt blue, alkali blue lake, metal-free phthalocyanine blue, copper phthalocyanine blue, indanthrene blue and indigo Blue pigments such as chrome green, chromium oxide, emerald green, naphthol green, green gold, acid green lake, malachite green lake, phthalocyanine green, and polychlorobrom copper phthalocyanine, other various fluorescent pigments, metal powder pigments, Examples include extender pigments. The total content of the pigment in the photosensitive composition of the present embodiment is preferably 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 25% by mass or less.

  You may use a pigment dispersant for the said pigment as needed. Examples of pigment dispersants include higher fatty acid salts, alkyl sulfates, alkyl ester sulfates, alkyl sulfonates, sulfosuccinates, naphthalene sulfonates, alkyl phosphates, polyoxyalkylene alkyl ether phosphates, Activators such as oxyalkylene alkyl phenyl ether, glycerin ester, sorbitan ester, polyoxyethylene fatty acid amide, or styrene, styrene derivative, vinyl naphthalene derivative, acrylic acid, acrylic acid derivative, maleic acid, maleic acid derivative, itaconic acid, itacone Examples thereof include block copolymers, random copolymers and salts thereof composed of two or more monomers selected from acid derivatives, fumaric acid and fumaric acid derivatives.

  As a method for dispersing the pigment, for example, various dispersing machines such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, and a paint shaker can be used. Further, a centrifuge or a filter may be used for the purpose of removing coarse particles of the pigment dispersion.

  The average particle size of the pigment particles in the pigment ink is selected in consideration of the stability in the ink, image density, glossiness, light resistance, etc., but the particle size is also selected appropriately from the viewpoint of improving gloss and improving texture. It is preferable to do.

  As described above, the photosensitive composition of the present embodiment makes use of its characteristics, and includes the above-mentioned applications, paints, adhesives, inks, film coating materials, more specifically, UV ink for inkjet; liquid crystal Sealing material for display panels such as EL and organic EL; Adhesive for optical components such as adhesive for bonding optical discs; CD, DVD, and Blu-ray (registered trademark) Disc, which is a next generation optical disc It can be suitably used as a surface protective layer forming material; a coating material for forming an antireflection film; a hard coating material and the like.

  The present invention will be described based on examples. Unless otherwise specified, “parts” in Examples and Comparative Examples means “parts by mass” and “%” means “% by mass”.

<Measurement of tack-free exposure>
On the glass substrate, the photosensitive composition was apply | coated to the film thickness of 12 micrometers using the wire bar. Then, an ultraviolet ray irradiation device “MSA-0151-B3” (manufactured by Sen Engineering Co., Ltd.) using a high pressure mercury lamp “H015-L312” (manufactured by Sen Engineering Co., Ltd.) as a light source is used to irradiate a predetermined amount of ultraviolet rays. The photosensitive composition was cured. Thereafter, the cured body was observed with a finger, and the minimum exposure amount required for the surface to harden and become non-sticky was determined as the UV integrated light meter “UIT-” using a light receiver “UVD-S365” (USHIO INC.). 250 "(USHIO INC.). The temperature and humidity during curing were measured with a digital thermometer and humidity meter “WF-301” (manufactured by Custom).

[Example 1]
As an epoxy compound (a) having two or more alicyclic epoxy groups in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, Daicel Chemical Industries, Ltd.) (Product) 57.9 parts, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane “LS-” as the silane compound (b) having one or more epoxy groups in the molecule and a hydrolyzable group. 3990 "(trade name, manufactured by Shin-Etsu Silicone Co., Ltd.)," CPI-100P "(trade name, manufactured by San Apro Co., Ltd.) 3 having a sulfonium salt content of 50 mass% as an energy ray-sensitive cationic polymerization initiator (c) 3 A photosensitive composition was obtained by sufficiently mixing 8 parts. When the tack-free exposure amount of this photosensitive composition at a temperature of 20 ° C. and a relative humidity of 20% was measured, it was 150 mJ · cm ⁻² .

[Example 2]
The photosensitive composition obtained in Example 1 was tested in the same manner as in Example 1 except that the tack-free exposure was measured at a relative humidity of 70% during curing. As a result, the tack-free exposure amount was 100 mJ · cm ⁻² .

[Example 3]
In Example 1, the test was conducted in the same manner as in Example 1 except that 19 parts of hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) was further used as the hydroxyl group-containing compound (d) to prepare a photosensitive composition. It was. As a result, the tack-free exposure amount was 100 mJ · cm ⁻² .

[Example 4]
The photosensitive composition obtained in Example 3 was tested in the same manner as in Example 1 except that the tack-free exposure was measured at a relative humidity of 70% during curing. As a result, the tack-free exposure amount was 100 mJ · cm ⁻² .

[Example 5]
In Example 3, as the polynuclear phenol compound (e), a p-tert-butyl-phenol novolac resin “PAPS-PTBPN” having a phenol 3-5 nucleus content of 50 mass% (trade name, Asahi Organic Materials Co., Ltd.) The test was conducted in the same manner as in Example 3 except that 3.3 parts of the product was further used to prepare the photosensitive composition. As a result, the tack-free exposure amount was 30 mJ · cm ⁻² .

[Example 6]
The photosensitive composition obtained in Example 5 was tested in the same manner as in Example 3 except that the tack-free exposure was measured at a relative humidity of 70% during curing. As a result, the tack-free exposure amount was 30 mJ · cm ⁻² .

[Example 7]
About the photosensitive composition obtained in Example 5, 3-glycidoxypropyltrimethoxysilane “LS-” as a silane compound (b) having at least one epoxy group in the molecule and a hydrolyzable group. 2940 "(trade name, manufactured by Shin-Etsu Silicone) was used in the same manner as in Example 5 except that 16 parts were used. As a result, the tack-free exposure amount was 200 mJ · cm ⁻² .

[Example 8]
About the photosensitive composition obtained in Example 7, it measured similarly to Example 7 except having measured the tack-free exposure amount by the relative humidity 70% at the time of hardening. As a result, the tack-free exposure amount was 200 mJ · cm ⁻² .

[Example 9]
In Example 3, a photosensitive composition was prepared using 9 parts of “DPP-6125” (trade name, manufactured by Shin Nippon Petrochemical Co., Ltd.), which is a dicyclopentadiene phenol resin, as the polynuclear phenol compound (e). The test was performed in the same manner as in Example 3 except for the above. As a result, the tack-free exposure amount was 30 mJ · cm ⁻² .
[Example 10]
The photosensitive composition obtained in Example 9 was measured in the same manner as in Example 9 except that the tack-free exposure amount was measured at a relative humidity of 70% during curing. As a result, the tack-free exposure amount was 30 mJ · cm ⁻² .

[Comparative Example 1]
The test was conducted in the same manner as in Example 1 except that the photosensitive composition was prepared without using the silane compound (b). As a result, the tack-free exposure amount was 150 mJ · cm ⁻² .

[Comparative Example 2]
In Comparative Example 1, the test was performed in the same manner as Comparative Example 1 except that the tack-free exposure amount was measured at a relative humidity of 70% during curing. As a result, even when ultraviolet rays were irradiated at 200 mJ · cm ^{−2, the} surface was not sticky, and the tack-free exposure amount could not be measured.

[Comparative Example 3]
The test was conducted in the same manner as in Example 3 except that the photosensitive composition was prepared without using the silane compound (b). As a result, the tack-free exposure amount was 100 mJ · cm ⁻² .

[Comparative Example 4]
In Comparative Example 3, the test was performed in the same manner as Comparative Example 3 except that the tack-free exposure amount was measured at a relative humidity of 70% during curing. As a result, even when ultraviolet rays were irradiated at 200 mJ · cm ^{−2, the} surface was not sticky, and the tack-free exposure amount could not be measured.

[Comparative Example 5]
The test was conducted in the same manner as in Example 1 except that the photosensitive composition was prepared without using the silane compound (b) containing a hydrolyzable group. As a result, the tack-free exposure amount was 30 mJ · cm ⁻² .

[Comparative Example 6]
In Comparative Example 5, the test was performed in the same manner as Comparative Example 5 except that the tack-free exposure amount was measured at a relative humidity of 70% during curing. As a result, even when ultraviolet rays were irradiated at 200 mJ · cm ^{−2, the} surface was not sticky, and the tack-free exposure amount could not be measured.

[Comparative Example 7]
The test was conducted in the same manner as in Example 7 except that the photosensitive composition was prepared without using the silane compound (b) containing a hydrolyzable group. As a result, the tack-free exposure amount was 200 mJ · cm ⁻² .

[Comparative Example 8]
In Comparative Example 7, the test was performed in the same manner as in Comparative Example 5 except that the tack-free exposure amount was measured at a relative humidity of 70% during curing. As a result, even when ultraviolet rays were irradiated at 200 mJ · cm ^{−2, the} surface was not sticky, and the tack-free exposure amount could not be measured.

[Comparative Example 9]
The test was conducted in the same manner as in Example 9 except that the photosensitive composition was prepared without using the silane compound (b) containing a hydrolyzable group. As a result, the tack-free exposure amount was 30 mJ · cm ⁻² .

[Comparative Example 10]
In Comparative Example 9, the test was performed in the same manner as in Comparative Example 9, except that the tack-free exposure amount was measured at a relative humidity of 70% during curing. As a result, even when ultraviolet rays were irradiated at 200 mJ · cm ^{−2, the} surface was not sticky, and the tack-free exposure amount could not be measured.

  Since the photosensitive composition of the present invention is excellent in curability, adhesion of cured products to various substrates, curing water resistance, and flexibility, photosensitive coating materials, inkjet inks, adhesives, especially organic EL It can utilize suitably in field | areas, such as a sealing agent for flat panel displays (FPD).

Claims (11)

An epoxy compound (a) having two or more epoxy groups in the molecule of 40% by mass or more and 84.9% by mass or less;
In the molecule, silane compound (b) having one or more epoxy groups and a hydrolyzable group (15% by mass to 50% by mass),
Energy ray sensitive cationic polymerization initiator (c) 0.1 mass% or more and 10 mass% or less,
A photosensitive composition comprising:   The hydroxyl group containing compound (d) which has 1 or more of hydroxyl groups and 1 or more of either a vinyl ether group or an oxetanyl group in a molecule | numerator is further included 1 mass% or more and 44 mass% or less. Photosensitive composition. Contains 3-5 phenolic aromatic rings,
All of the ortho positions of the phenolic aromatic ring hydroxyl group are not substituted with any of a methylol group, an alkyl group having 4 or more carbon atoms, or a cycloalkyl group, and
The polynuclear phenol compound (e), further comprising 0.1 to 40% by mass of a polynuclear phenol compound (e) having two or more phenolic aromatic rings in which at least one ortho position of the phenolic hydroxyl group of the phenolic aromatic ring is unsubstituted. 3. The photosensitive composition according to 1 or 2.   The photosensitive composition as described in any one of Claims 1-3 whose epoxy group of the said epoxy compound (a) is an alicyclic epoxy group. The polynuclear phenol compound (e) includes a polynuclear phenol compound (f) represented by the following formula (1) and a polynuclear phenol compound (g) represented by the following formula (2), and
The content rate (f / (f + g)) of the said (f) component with respect to the sum total of the said (f) component and the said (g) component is 40 mass% or more, As described in any one of Claims 1-4. Photosensitive composition.
Wherein R ¹ , R ² and R ³ are alkyl groups having 1 to 5 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, halogen atoms, hydroxyl groups, aryl groups or aralkyls. R ¹ , R ² and R ³ may be different from each other or the same, m ¹ represents an integer of 0 to 3, and n ¹ represents an integer of ¹ to 3).
(In the formula, R ¹ , R ² and R ³ are the same as defined in formula (1), m ² represents an integer of 0 to 3, and n ² represents 0 or an integer of 4 or more.) The component (e) includes a polynuclear phenol compound (h) represented by the following formula (3) and a polynuclear phenol compound (i) represented by the following formula (4), and
The photosensitivity as described in any one of Claims 1-4 whose content rate (h / (h + i)) of the said (h) component with respect to the sum total of the said (h) component and the said (i) component is 40 mass% or more. Sex composition.
(Wherein, ^{n 3} is an integer of 1-3.)
(In the formula, n ⁴ represents 0 or an integer of 4 or more.)   Hardened | cured material obtained by irradiating at least actinic light to the photosensitive composition as described in any one of Claims 1-6.   The photosensitive adhesive agent containing the photosensitive composition as described in any one of Claims 1-6.   The photosensitive coating material containing the photosensitive composition as described in any one of Claims 1-6.   The photosensitive inkjet ink containing the photosensitive composition and colorant as described in any one of Claims 1-6.   A cured product obtained by irradiating the photosensitive adhesive according to claim 8, the photosensitive coating material according to claim 9, or the photosensitive inkjet according to claim 10 with at least actinic rays.