JP5219280B2 - Photosensitive composition, coating agent, coating film, and method for producing photosensitive composition - Google Patents

Description

  The present invention relates to a photosensitive composition, a coating agent and coating film thereof, and a method for producing the photosensitive composition.

  In recent years, due to problems such as global warming, environmentally conscious products and methods for producing the same have been retroactively introduced worldwide. In general, a photocurable resin has attracted attention because it emits less volatile organic compounds (hereinafter referred to as VOC) and requires less energy for curing.

  Applications of photo-curing resins include paints and coatings for cars, trains, buildings, etc., coating and adhesion of optical discs such as DVDs and Blu-ray discs, inks for inkjet printers, gravure printing, flexographic printing, and liquid crystal and PDP displays. Wide variety of materials such as color filter forming materials, sealing materials for liquid crystals and organic EL.

As the photocuring reaction mode, a cationic polymerization reaction and a radical polymerization reaction are well known.
As the radical polymerization reaction, it is common to cure acrylate or methacrylate-based materials. However, radical polymerization systems are susceptible to polymerization inhibition by oxygen, and have a problem that they are inferior in practicality because they often do not exhibit desired performance when they are reacted in air.

Therefore, in order to solve the above-described problems, a cationic polymerization material that is difficult to inhibit polymerization by oxygen is desired.
Examples of the cationic polymerization material include the following.
Patent Document 1 describes an ultraviolet curable epoxy resin composition containing an epoxy resin, a cationic polymerization initiator, and a silane coupling agent.
Patent Document 2 describes a photocurable resin composition containing an epoxy resin, a cationic photopolymerization initiator, a silane coupling agent, and silica powder.
Patent Document 3 describes a photocurable epoxy resin composition containing an epoxy resin, a photocationic polymerization initiator, a silane coupling agent, and a photosensitizer.

Japanese Patent Laid-Open No. 2-113022 JP-A-6-57103 JP 2002-105177 A

  However, development of a composition capable of exhibiting even higher performance is demanded particularly as a photosensitive composition, and the above-described conventionally disclosed resin compositions still have a point to be improved in terms of performance. There are many.

  Then, this invention is made | formed in view of the said situation, and it aims at providing the photosensitive composition excellent in photocurability and adhesiveness, the coating agent containing the same, and the coating film using the same. To do.

  As a result of intensive studies to solve the above problems, the present inventor has obtained a resin composition obtained by cohydrolytic condensation of an epoxy resin and a specific alkoxysilane compound, and a photoacid generator, It has been found that a photosensitive composition excellent in photocurability and adhesiveness, a coating agent containing the same, and a coating film using the same can be provided by containing the present invention.

（式（１）中、ｎ＝０〜３であり、Ｒ^１は水素原子又は有機基を示す。また、複数のＲ^２は、同一又は異なっていてもよく、水素原子又は炭素数１〜８のアルキル基を示す。）
前記アルコキシシラン化合物は、
（Ｂ）ｎ＝１〜２であり、Ｒ^１として、少なくとも１つの環状エーテル基を有する、少なくとも１種のアルコキシシラン化合物と、
（Ｃ）ｎ＝１〜２であり、Ｒ^１として、少なくとも１つのアリール基を有する、少なくとも１種のアルコキシシラン化合物と、
を含み、かつ、下記式（２）で表される（Ｂ）及び（Ｃ）の混合指標αが、０．００１〜１９である樹脂組成物と、光酸発生剤と、を含有する感光性組成物；
混合指標α＝（αｃ）／（αｂ） （２）
（式（２）中、αｂ：前記（Ｂ）成分の含有量（ｍｏｌ％）、αｃ：前記（Ｃ）成分の含有量（ｍｏｌ％））。
［２］
前記アルコキシシラン化合物として、
（Ｄ）前記一般式（１）において、ｎ＝０である、少なくとも１種のアルコキシシラン化合物を、さらに含む［１］に記載の感光性組成物。
［３］
下記式（３）で表される前記アルコキシシラン化合物の混合指標βが、０．０１〜１．４である、［１］又は［２］に記載の感光性組成物；
混合指標β＝｛（β^ｎ２）／（β^ｎ０＋β^ｎ１）｝ （３）
（式（３）中、
β^ｎ２：前記一般式（１）において、ｎ＝２であるアルコキシシラン化合物の含有量（ｍｏｌ％）、
β^ｎ０：前記一般式（１）において、ｎ＝０であるアルコキシシラン化合物の含有量（ｍｏｌ％）、
β^ｎ１：前記一般式（１）において、ｎ＝１であるアルコキシシラン化合物の含有量（ｍｏｌ％）、
ここで、０≦｛（β^ｎ０）／（β^ｎ０＋β^ｎ１＋β^ｎ２）｝≦０．１である）。
［４］
下記式（４）で表される、前記（Ａ）エポキシ樹脂と前記アルコキシシラン化合物との混合指標γが、０．０２〜１５である、請求項１〜３のいずれか一項に記載の感光性組成物；
混合指標γ＝（γａ）／（γｓ） （４）
（式（４）中、
γａ：エポキシ樹脂の質量（ｇ）、
γｓ：一般式（１）において、ｎ＝０〜２であるアルコキシシラン化合物の質量（ｇ））
［５］
オキセタン化合物をさらに含有する、［１］〜［４］のいずれか一項に記載の感光性組成物。
［６］
［１］〜［５］のいずれか一項に記載の感光性組成物を含むコーティング剤。
［７］
［１］〜［５］のいずれか一項に記載の感光性組成物、又は［６］に記載のコーティング剤を、光により硬化させて得られる塗膜。
［８］
（Ａ）エポキシ樹脂と、下記一般式（１）で表されるアルコキシシラン化合物と、を共加水分解縮合させて得られうる樹脂組成物に、光酸発生剤を添加することを少なくとも行う、樹脂組成物の製造方法；

（式（１）中、ｎ＝０〜３であり、Ｒ^１は、水素原子又は有機基を示す。また、複数のＲ^２は、同一又は異なっていてもよく、水素原子又は炭素数１〜８のアルキル基を示す。）
前記アルコキシシラン化合物は、
（Ｂ）ｎ＝１〜２であり、Ｒ^１として、少なくとも１つの環状エーテル基を有する、少なくとも１種のアルコキシシラン化合物と、
（Ｃ）ｎ＝１〜２であり、Ｒ^１として、少なくとも１つのアリール基を有する、少なくとも１種のアルコキシシラン化合物と、
を含み、かつ、下記式（２）で表される（Ｂ）及び（Ｃ）の混合指標αが、０．００１〜１９であり、
混合指標α＝（αｃ）／（αｂ）（２）
（式（２）中、αｂ：前記（Ｂ）成分の含有量（ｍｏｌ％）、αｃ：前記（Ｃ）成分の含有量（ｍｏｌ％））。 That is, the present invention is as follows.
[1]
(A) an epoxy resin;
An alkoxysilane compound represented by the following general formula (1):
A resin composition obtained by cohydrolyzing and condensing

(In the formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. The plurality of R ² may be the same or different, and may be a hydrogen atom or a carbon number of 1 to 8. Represents an alkyl group of
The alkoxysilane compound is
(B) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one cyclic ether group;
(C) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one aryl group;
And (B) and (C) represented by the following formula (2), the mixing index α is 0.001 to 19 and a photoacid generator containing a photoacid generator Composition;
Mixing index α = (αc) / (αb) (2)
(In formula (2), αb: content (mol%) of the component (B), αc: content (mol%) of the component (C)).
[2]
As the alkoxysilane compound,
(D) The photosensitive composition according to [1], further including at least one alkoxysilane compound in which n = 0 in the general formula (1).
[3]
The photosensitive composition according to [1] or [2], wherein a mixing index β of the alkoxysilane compound represented by the following formula (3) is 0.01 to 1.4;
Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
(In formula (3),
β ⁿ² : content (mol%) of the alkoxysilane compound in which n = 2 in the general formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n = 0 in the general formula (1),
β ⁿ¹ : content (mol%) of the alkoxysilane compound in which n = 1 in the general formula (1),
Here, 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1).
[4]
The photosensitivity as described in any one of Claims 1-3 whose mixing parameter | index (gamma) of the said (A) epoxy resin and the said alkoxysilane compound represented by following formula (4) is 0.02-15. Sex composition;
Mixing index γ = (γa) / (γs) (4)
(In formula (4),
γa: mass of epoxy resin (g),
γs: mass (g) of alkoxysilane compound in which n = 0 to 2 in the general formula (1)
[5]
The photosensitive composition as described in any one of [1]-[4] which further contains an oxetane compound.
[6]
[1] A coating agent comprising the photosensitive composition according to any one of [5].
[7]
A coating film obtained by curing the photosensitive composition according to any one of [1] to [5] or the coating agent according to [6] with light.
[8]
(A) A resin that at least adds a photoacid generator to a resin composition obtained by cohydrolyzing and condensing an epoxy resin and an alkoxysilane compound represented by the following general formula (1) A method for producing the composition;

(In formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. The plurality of R ² may be the same or different, and may be a hydrogen atom or a carbon number of 1 to 3. 8 represents an alkyl group.)
The alkoxysilane compound is
(B) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one cyclic ether group;
(C) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one aryl group;
And the mixture index α of (B) and (C) represented by the following formula (2) is 0.001 to 19,
Mixing index α = (αc) / (αb) (2)
(In formula (2), αb: content (mol%) of the component (B), αc: content (mol%) of the component (C)).

  By this invention, the photosensitive composition excellent in photocurability and adhesiveness, the coating agent containing the same, and the coating film using the same are obtained.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to this embodiment, It can implement in various deformation | transformation within the range of the summary.

(Resin composition)
The photosensitive composition of the present embodiment is
(A) an epoxy resin;
An alkoxysilane compound represented by the following general formula (1):
Is a resin composition obtained by cohydrolysis condensation,

(In formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. Also, the plurality of R ² are the same or different and are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Is shown.)
The alkoxysilane compound is
(B) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one cyclic ether group;
(C) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one aryl group;
And (B) and (C) represented by the following formula (2) are obtained by mixing a photoacid generator with a resin composition having a mixing index α of 0.001 to 19 .
Mixing index α = (αc) / (αb) (2)
(In formula (2), αb: content (mol%) of the component (B), αc: content (mol%) of the component (C)).

  This inventor is a photosensitive composition excellent in photocurability and adhesiveness, comprising a resin composition obtained by cohydrolytic condensation of an epoxy resin and a specific alkoxysilane compound, and a photoacid generator. And a coating agent containing the same, and a coating film using the same.

((A) Epoxy resin)
The (A) epoxy resin in the present embodiment refers to a compound having an oxirane ring, usually two or more oxirane rings in the molecule, excluding an alkoxysilane compound and a condensate thereof described later, and satisfying the above requirements. If it is, it will not specifically limit. These may be used alone or in combination.

  The epoxy equivalent (WPE) of the epoxy resin is preferably 100 to 600 g / eq, more preferably 100 to 500 g / eq, and still more preferably 100 to 300 g / eq.

  Depending on the composition balance with the alkoxysilane compound represented by the general formula (1), when the epoxy equivalent (WPE) is less than 100 g / eq, the storage stability of the photosensitive composition may be lowered, and 600 g / When eq is exceeded, there exists a possibility that the adhesiveness of a coating film may deteriorate. Although the use of the photosensitive composition of this embodiment is not specifically limited, When using as a coating agent, it is preferable that the epoxy equivalent of an epoxy resin is 100-300 g / eq.

  The epoxy resin is preferably a liquid having a viscosity at 25 ° C. of 1000 Pa · s or less, more preferably 500 Pa · s or less, and still more preferably 100 Pa · s or less. When the viscosity at 25 ° C. exceeds 1000 Pa · s, the fluidity as a liquid is lost, and the compatibility with the alkoxysilane compound described later tends to deteriorate. In addition, when the viscosity at 25 ° C. is more than 500 Pa · s and 1000 Pa · s or less (500 Pa · s <viscosity ≦ 1000 Pa · s), it can be used by adjusting the temperature at the time of production, selecting a solvent, etc. Since manufacturing conditions tend to be somewhat limited, it is preferably 500 Pa · s or less.

A resin composition obtained by using an epoxy resin having a viscosity of more than 1000 Pa · s as a raw material has a high possibility of increasing the viscosity, and as a result, the viscosity of the photosensitive composition containing the resin also increases and the coating property deteriorates. There is a case.
The photosensitive composition of the present embodiment can be blended with the below-described diluent and the like to reduce the viscosity. However, in recent years, low VOC photosensitive compositions and coating agents have been retroactively used. The viscosity of the epoxy resin is important in that it is required to be equal to or lower than a predetermined viscosity even without blending etc.
In the present embodiment, it is possible to select a solid epoxy resin as the epoxy resin, but the reaction temperature condition is limited or the flow of the obtained photosensitive composition is performed when performing the cohydrolysis condensation described later. May impair sex.

  The type of the epoxy resin is not particularly limited, and a polyfunctional epoxy resin that is a glycidyl etherified product of an alicyclic epoxy resin, an aliphatic epoxy resin, a polyphenol compound, or a polyfunctional epoxy resin that is a glycidyl etherified product of various novolak resins. Examples include epoxy resins, aromatic hydrides of aromatic epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, and the like.

  Among them, alicyclic epoxy resins and glycidyl etherified products of polyphenol compounds are easily available and can provide good physical properties as a cured product of the intended photosensitive composition of the present embodiment. A polyfunctional epoxy resin and an aliphatic epoxy resin are preferable, and a polyfunctional epoxy resin which is a glycidyl etherified product of an alicyclic epoxy resin and a polyphenol compound is more preferable. These epoxy resins may be used alone or in combination.

(Alicyclic epoxy resin)
The alicyclic epoxy resin is not particularly limited as long as it is an epoxy resin having an alicyclic epoxy group, and examples thereof include an epoxy resin having a cyclohexene oxide group, a tricyclodecene oxide group, a cyclopentene oxide group, and the like. Can be mentioned.

  Specific examples of the alicyclic epoxy resin include 4-vinyl epoxycyclohexane, dioctyl epoxyhexahydrophthalate, and di-2-ethylhexyl epoxyhexahydrophthalate as monofunctional alicyclic epoxy compounds. Examples of the bifunctional alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4 -Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, bis (3,4-epoxy-6-methyl) (Cyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethyl Glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexane carboxylate), 1,2,8,9- diepoxylimonene, and the like. Examples of the polyfunctional alicyclic epoxy compound include 1,2-epoxy-4- (2-oxiranyl) cyclohexene adduct of 2,2-bis (hydroxymethyl) -1-butanol. Examples of the polyfunctional alicyclic epoxy compound include Epolide GT401, EHPE3150 (Daicel Chemical Industries, Ltd.) and the like. Typical examples of the alicyclic epoxy resin are shown below.

(Aliphatic epoxy resin)
The aliphatic epoxy resin is not particularly limited, and specifically, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, pentaerythritol, xylylene glycol derivatives, etc. Examples thereof include glycidyl ethers of polyhydric alcohols. Typical examples of the aliphatic epoxy resin are shown below.

(Polyfunctional epoxy resin)
The polyfunctional epoxy resin which is a glycidyl etherified product of a polyphenol compound is not particularly limited, and specifically, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethylbisphenol A, dimethyl Bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenylphenol, 1- (4-hydroxyphenyl)- 2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene -Bis (3-methyl-6-tert-butyl) Ruphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, 2,6-di (t-butyl) hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, 1,1-di (4-hydroxyphenyl) fluorene, etc. Examples thereof include phenols having a fluorene skeleton, polyfunctional epoxy resins which are glycidyl etherified products of polyphenol compounds of phenolized polybutadiene. Among the above, many types having excellent transparency and fluidity are commercially available and are available at low cost, and tend to have excellent crack resistance when cured, so phenols having a bisphenol A skeleton A polyfunctional epoxy resin that is a glycidyl etherified product is preferred.

  A typical example of a polyfunctional epoxy resin which is a glycidyl etherified product of phenols having a bisphenol skeleton is shown below.

When a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound is used as the epoxy resin, these repeating units (n in the chemical formula showing the above representative examples) are not particularly limited, Preferably it is less than 20, More preferably, it is 0.001-5, More preferably, it is 0.01-2.
When the repeating unit is less than 0.001, the reactivity with the alkoxysilane compound may be deteriorated, and when it exceeds 20, the fluidity may be lowered, which may cause a practical problem. From the viewpoint of the balance between the above-described reactivity and fluidity, the repeating unit is particularly preferably from 0.01 to 2.

(Polyfunctional epoxy resin that is glycidyl etherified product of novolak resin)
The polyfunctional epoxy resin that is a glycidyl etherified product of novolak resin is not particularly limited, and examples thereof include phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, and naphthol. Glycidyl etherification products of various novolac resins such as novolak resins made from various phenols such as phenols, xylylene skeleton-containing phenol novolak resins, dicyclopentadiene skeleton-containing phenol novolak resins, biphenyl skeleton-containing phenol novolak resins, and fluorene skeleton-containing phenol novolak resins. Etc. A typical example of a polyfunctional epoxy resin which is a glycidyl etherified product of a novolak resin is shown below.

(Nuclear hydride of aromatic epoxy resin)
The nuclear hydride of the aromatic epoxy resin is not particularly limited. For example, glycidyl etherified products of phenol compounds (bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, etc.) or various phenols (phenols) , Cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.) and hydrides of glycidyl ethers of novolac resins Can be mentioned.

(Heterocyclic epoxy resin)
The heterocyclic epoxy resin is not particularly limited, and examples thereof include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.

(Glycidyl ester epoxy resin)
The glycidyl ester-based epoxy resin is not particularly limited, and examples thereof include epoxy resins composed of carboxylic acids such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester.

(Glycidylamine epoxy resin)
The glycidylamine epoxy resin is not particularly limited. For example, an epoxy resin obtained by glycidylating amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivative, and diaminomethylbenzene derivative. Etc.

(Epoxy resin obtained by glycidylation of halogenated phenols)
Epoxy resins obtained by glycidylation of halogenated phenols are not particularly limited. For example, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated Examples thereof include epoxy resins obtained by glycidyl etherification of halogenated phenols such as bisphenol S and chlorinated bisphenol A.

The epoxy resin mentioned above can use a polyol together.
The polyol is not particularly limited as long as it is a compound having two or more hydroxyl groups in the molecule. For example, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,2-hexanediol, 1,6- Examples include hexanediol.

(Alkoxysilane compound)
The alkoxysilane compound in this embodiment shows the silicon compound which has 1-4 alkoxyl groups, and is represented by following General formula (1).

(In formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. Also, the plurality of R ² are the same or different and are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Is shown.)

R ¹ in the general formula (1) represents a hydrogen atom or an organic group, and is not particularly limited. In addition to an organic group having a cyclic ether group and an organic group having an aryl group, which will be described later, for example, an alkyl group , A vinyl group, a methacryl group, a mercapto group, an organic group having an isocyanate group, and the like. Among them, an alkyl group is preferable.

  Here, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a butyl group (n-butyl, i-butyl, t-butyl, sec-butyl), and a pentyl group (n -Pentyl, i-pentyl, neopentyl, etc.), hexyl group (n-hexyl, i-hexyl, etc.), heptyl (n-heptyl, i-heptyl, etc.), octyl group (n-octyl, i-octyl, t-octyl) Etc.), nonyl (n-nonyl, i-nonyl etc.), decyl group (n-decyl, i-decyl etc.), dodecyl group (n-dodecyl, i-dodecyl etc.), and these are linear or Any of a branched alkyl group may be used.

  Among these, an alkyl group having 10 or less carbon atoms is preferable, and a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, and n-hexyl group are more preferable. In addition, hydrogen atoms or a part or all of the main chain skeleton of these alkyl groups are ether groups, ester groups, carbonyl groups, siloxane groups, halogen atoms such as fluorine, methacryl groups, acrylic groups, mercapto groups, amino groups, It may be substituted with at least one group selected from the group consisting of hydroxyl groups.

Moreover, several R < ² > in the above-mentioned general formula (1) is the same or different, respectively, and shows a hydrogen atom or a C1-C8 alkyl group. R ² is not particularly limited as long as it satisfies the above requirements, but is preferably a methyl group or an ethyl group.

(OR ² ) in the above general formula (1) is replaced with another hydrolyzable group (a chloro group, an acetoxy group, an isopropenoxy group, an amino group, etc.) instead of a hydroxyl group or an alkoxyl group having 1 to 8 carbon atoms. May be used as (OR ² ). Examples of such silane compounds include methyltrichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane and the like.

((B) component)
The component (B) of the alkoxysilane compound represented by the general formula (1) is at least one kind in the general formula (1), where n = 1 to 2 and R ¹ has at least one cyclic ether group. This is an alkoxysilane compound.

  The cyclic ether group refers to an organic group having an ether in which carbon of a cyclic hydrocarbon is substituted with oxygen, and usually means a cyclic ether group having a 3- to 6-membered ring structure. Among them, a 3-membered or 4-membered cyclic ether group having a large ring strain energy and high reactivity is preferable, and a 3-membered ether group is particularly preferable.

  Specific examples of the cyclic ether group include, for example, a glycidoxyalkyl group having oxyglycidyl groups having 4 or less carbon atoms such as β-glycidoxyethyl, γ-glycidoxypropyl, γ-glycidoxybutyl, and the like, glycidyl Group, β- (3,4-epoxycyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, β- (3,4 epoxyepoxycyclohexyl) ) Alkyl substituted with a cycloalkyl group having 5 to 8 carbon atoms having an oxirane group such as propyl group, β- (3,4-epoxycyclohexyl) butyl group, β- (3,4-epoxycyclohexyl) pentyl group Groups and the like.

  Among the above, glycidoxy in which an oxyglycidyl group is bonded to a C1-C3 alkyl group such as β-glycidoxyethyl group, γ-glycidoxypropyl group, β- (3,4-epoxycyclohexyl) ethyl group, etc. An alkyl group having 3 or less carbon atoms substituted with a C5-C8 cycloalkyl group having an alkyl group or an oxirane group is preferred.

  Specific examples of the component (B) include, for example, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (methyl) dibutoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2,3 -Epoxypropyl (phenyl) dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 2- (3,4-epoxy Hexyl) ethyl triethoxysilane, 2,3-epoxypropyl trimethoxysilane, 2,3-epoxy propyl triethoxy silane, and the like. These may be used alone or in combination.

((C) component)
The component (C) of the alkoxysilane compound represented by the general formula (1) is such that the component (C) is n = 1 to 2 in the general formula (1), and R ¹ is at least one aryl group. At least one alkoxysilane compound.

  An aryl group refers to a functional group or substituent derived from an aromatic hydrocarbon (simple aromatic ring or polycyclic aromatic hydrocarbon). The aryl group is not particularly limited as long as it matches this, but in consideration of steric hindrance in the higher order structure, a phenyl group, a benzyl group, and the like are preferable.

  Specific examples of the component (C) include, for example, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, phenyltriethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, dimethoxydiphenylsilane, diphenyldiethoxysilane, phenyl Examples include trimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane. These may be used alone or in combination.

“(B) at least one alkoxysilane compound having general formula (1) where n = 1 to 2 and R ¹ having at least one cyclic ether group”, and “(C) general formula In (1), n = 1 to 2 and R ¹ has at least one aryl group, and the mixing ratio of “at least one alkoxysilane compound” is a mixing index calculated by the following formula (2): It is represented by α.
Mixing index α = (αc) / (αb) (2)
(In formula (2), αb: content of component (B) (mol%), αc: content of component (C) (mol%)).

  In the present embodiment, it is important that the mixing index α is in the range of 0.001 to 19. When the mixing index α is less than 0.001, the fluidity and storage stability of the resin composition are lowered, and when it exceeds 19, the fluidity of the resin composition and the crack resistance of the cured product are deteriorated. In particular, when considering use in a sealing material application, since high crack resistance is required, the mixing index α is preferably 0.2 to 5, and more preferably 0.3 to 2.

((D) component)
In addition to the components (A) to (C) described above, the resin composition in the present embodiment includes, as the component (D), n = 0 indicating the number of R ¹ in the general formula (1), that is, (OR ^The alkoxysilane compound having 4 of ² ) may be further cohydrolyzed and condensed.

  Examples of the component (D) include tetramethoxysilane and tetraethoxysilane. These may be used alone or in combination.

(Other alkoxysilane compounds)
Moreover, the resin composition in this embodiment may further cohydrolyze and condense the alkoxysilane compound represented by the general formula (1) other than the components (B) to (D) described above. Examples of such compounds include dimethyldimethoxysilane, dimethylethoxysilane, hydroxymethyltrimethylsilane, methoxytrimethylsilane, methyltrimethoxysilane, mercaptomethyltrimethoxysilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, bis (2-chloro Ethoxy) methylsilane, ethoxytrimethylsilane, diethoxymethylsilane, ethyltriethoxysilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, ethoxydimethylvinylsilane, 3-chloropropyldimethoxymethylsilane, chloromethyldiethoxymethylsilane , Methyltris (ethylmethylketoxime) silane, trimethylpropoxysilane, trimethoxyisopropoxysilane, diethoxydi Tilsilane, 3- [dimethoxy (methyl) silyl] propane-1-thiol, trimethoxy (propyl) silane, (3-mercaptopropyl) trimethoxysilane, 3-aminopropyltrimethoxysilane, diethoxymethylvinylsilane, butoxytrimethylsilane, Butyltrimethoxysilane, methyltriethoxysilane, methoxyltriethoxysilane, triethoxyvinylsilane, diethoxydiethylsilane, dimethoxyldipropoxysilane, ethyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane Allyltriethoxysilane, 3-bromopropyltriethoxysilane, 3-allylaminopropyltrimethoxysilane, hexyloxytrimethylsilane, propyltriethoxysilane, Xyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3-ureidopropyltriethoxysilane, Methoxytripropylsilane, dibutoxydimethylsilane, methyltripropoxysilane, methyltriisopropoxysilane, octyloxytrimethylsilane, pentyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, hexyltriethoxysilane, Examples include 3-methacryloxypropyltriethoxysilane, octyltriethoxysilane, dodecyloxytrimethylsilane, and diethoxydodecylmethylsilane.

The mixing ratio of “alkoxysilane compound where n = 2”, “alkoxysilane compound where n = 1” and “alkoxysilane compound where n = 0” of the alkoxysilane compound in this embodiment is expressed by the following formula (3 ) Is expressed by a mixture index β calculated in (1).
Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
In the above formula (3),
β ⁿ² : content (mol%) of the alkoxysilane compound in which n = 2 in the general formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n = 0 in the general formula (1),
β ⁿ¹ : content (mol%) of an alkoxysilane compound in which n = 1 in the general formula (1),
And 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1.

  In the resin composition of the present embodiment, the mixing index β is preferably 0.01 to 1.4, more preferably 0.03 to 1.2, and still more preferably 0.05 to 1.0. Depending on the composition, if the mixing index β is less than 0.01, the fluidity of the resin composition may deteriorate, and if it exceeds 1.4, the crack resistance may deteriorate.

The mixing ratio of the (A) epoxy resin and the alkoxysilane compound “alkoxysilane compound where n = 0 to 2” in the present embodiment is represented by a mixing index γ calculated by the following formula (4).
Mixing index γ = (γa) / (γs) (4)
In the above formula (4),
γa: mass of epoxy resin (g),
γs: Mass (g) of alkoxysilane compound in which n = 0 to 2 in the general formula (1)

  The mixing index γ is preferably 0.02 to 15, more preferably 0.04 to 7, and still more preferably 0.08 to 5. Depending on the composition, if the mixing index γ is less than 0.02, when the resin composition is a cured product, there may be a problem in crack resistance as the cured product. There is a possibility that the light resistance of will deteriorate.

(Cohydrolysis condensation process)
In the present embodiment, first, the resin composition can be obtained by cohydrolyzing and condensing the above-described (A) epoxy resin and the above-described alkoxysilane compound represented by the formula (1).
The “cohydrolytic condensation” in the present embodiment means a hydrolysis condensation reaction performed in the presence of an epoxy resin, and is clearly distinguished from a reaction in the absence of an epoxy resin.

The “cohydrolytic condensation” in the present embodiment is composed of at least two steps of a reflux step without dehydration and a subsequent dehydration condensation step.
The above-mentioned “refluxing process without dehydration” means that the reaction is carried out while returning the water and solvent blended for cohydrolysis and the water and solvent derived from the alkoxysilane compound generated during the reaction to the reaction solution. It is a process. Although the method is not particularly limited, the reaction is usually carried out while attaching a cooling pipe to the upper part of the reaction vessel and refluxing the generated water or solvent.
The above-mentioned “dehydration condensation step” is a step in which the condensation reaction is performed while removing the blended water and solvent and the water and solvent generated in the above “refluxing step without dehydration”. The method is not particularly limited, but usually the reaction is carried out by distillation under reduced pressure using a rotary evaporator or the like.

The heating temperature during the cohydrolysis condensation reaction is preferably 130 ° C. or lower, more preferably 0 to 120 ° C., and still more preferably 0 to 100 ° C.
If it exceeds 130 ° C., the resin composition may be altered depending on the composition. The reaction time for cohydrolytic condensation is preferably 0.5 to 24 hours, more preferably 1 to 12 hours. If it is less than 0.5 hour, the remaining amount of unreacted substances may increase depending on the composition.

The resin composition of this embodiment may be performed by adding a hydrolysis-condensation catalyst during the co-hydrolysis condensation of the above-described (A) epoxy resin and alkoxysilane compound.
The hydrolysis condensation catalyst is not particularly limited as long as it promotes a conventionally known hydrolysis condensation reaction. For example, a metal (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, Strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth, etc., organic metals (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium) Strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth and other organic oxides, organic acid salts, organic halides, alkoxides, etc.), inorganic bases Magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.), organic base (Ammonia, tetramethylammonium hydroxide, etc.).

Of the organic metals described above, organotin is preferred.
Organotin refers to those in which at least one organic group is bonded to a tin atom, and examples of the structure include monoorganotin, diorganotin, triorganotin, tetraorganotin, etc. Among them, Diorganotin is preferred.

  Examples of the organic tin include tin tetrachloride, monobutyltin trichloride, monobutyltin oxide, monooctyltin trichloride, tetra n-octyltin, tetra n-butyltin, dibutyltin oxide, dibutyltin diacetate, dibutyltin dioctate, dibutyl Tin diversate, dibutyltin dilaurate, dibutyltin oxylaurate, dibutyltin stearate, dibutyltin dioleate, dibutyltin / silicon ethyl reactant, dibutyltin salt and silicate compound, dioctyltin salt and silicate compound, dibutyltin bis ( Acetylacetonate), dibutyltin bis (ethyl malate), dibutyltin bis (butylmalate), dibutyltin bis (2-ethylhexylmalate), dibutyltin bis (benzylmalate), dibutyltin bis Allyl malate), dibutyltin bis (oleylmalate), dibutyltin malate, dibutyltin bis (O-phenylphenoxide), dibutyltin bis (2-ethylhexylmercaptoacetate), dibutyltin bis (2-ethylhexylmercaptopropionate) Dibutyltin bis (isononyl 3-mercaptopropionate), dibutyltin bis (isooctylthioglycolate), dibutyltin bis (3-mercaptopropionate), dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, Dioctyltin dioctate, dioctyltin didodecyl mercapto, dioctyltin versatate, dioctyltin distearate, dioctyltin bis (ethyl malate), dioctyltin bis (octylmalate), dioctyl Rutin malate, dioctyltin bis (isooctylthioglycolate), dioctyltin bis (2-ethylhexyl mercaptoacetate), dibutyltin dimethoxide, dibutyltin diethoxide, dibutyltin dibutoxide, dioctyltin dimethoxide, dioctyltin diethoxide, dioctyltin dibutoxide, Examples include tin octylate and tin stearate. Among these, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, and dioctyltin diacetate are preferable.

  These hydrolytic condensation catalysts may be used alone or in combination. For example, organic acid tin and alkaline organic tin can be used in combination, or after reacting with an organic acid salt such as tin, treatment with an inorganic base is also possible. In this case, the inorganic base is preferably a hydroxide of a polyvalent cation such as magnesium hydroxide, calcium hydroxide, strontium hydroxide or barium hydroxide.

  Since the curing of the photosensitive composition in the present embodiment is mainly based on a cationic polymerization reaction using a photoacid generator, coexistence of an alkaline substance may not be preferable. When an alkaline substance is used as the hydrolysis-condensation catalyst, it is preferable to take measures such as suppression of the addition amount or treatment with an ion exchange resin.

The addition amount of the hydrolysis-condensation catalyst is not particularly limited, but the preferable addition amount can be obtained from the mixing index δ which is a ratio to (OR ² ) in the above general formula (1). Here, the mixing index δ is expressed by the following formula (5).
Mixing index δ = (δe) / (δs) (5)
In formula (5),
δe: addition amount of hydrolytic condensation catalyst (mol number),
δs: Indicates the amount (mol number) of (OR ² ) in the general formula (1).

  The mixing index δ is preferably 0.0005 to 5, more preferably 0.001 to 1, and still more preferably 0.005 to 0.5. Depending on the composition of the photosensitive composition, if the mixing index δ is less than 0.0005, the effect of promoting hydrolysis condensation may be difficult to obtain. If it exceeds 5, the ring opening of the cyclic ether group is promoted. Or it may lead to deterioration of storage stability.

In the step of obtaining the resin composition of the present embodiment by cohydrolysis condensation, the amount of water added is not particularly limited, but the preferred amount added is the ratio to (OR ² ) in the above general formula (1). Can be obtained from the mixing index ε. Here, the mixture index ε is expressed by the following (6).
Mixing index ε = (εw) / (εs) (6)
In formula (6),
εw: amount of water added (in mol),
εs: Indicates the amount (mol number) of (OR ² ) in the general formula (1).

  The mixing index ε is preferably 0.1 to 5, more preferably 0.2 to 3, and still more preferably 0.3 to 1.5. Depending on the composition of the resin composition, if the mixing index ε is less than 0.1, the hydrolysis reaction may not proceed, and if it exceeds 5, the storage stability of the composition may decrease.

  The addition of water in the co-hydrolysis condensation described above is mainly performed by hydrolysis of the alkoxysilane compound, and therefore needs to be performed in the “refluxing process without dehydration”. The timing of the addition is not particularly limited, and may be added first or gradually during the reaction using a feed pump or the like.

  The cohydrolysis condensation reaction of the present embodiment can be performed without a solvent or in a solvent. The solvent is not particularly limited as long as it is an organic solvent that can dissolve an epoxy resin and an alkoxysilane compound and is inactive to these, and for example, an aprotic polar solvent such as tetrahydrofuran or dioxane is preferably used. Can be used. Moreover, since it is easy to obtain, alcohol solvents such as methanol, ethanol, butanol, isopropanol, and n-butanol can be used. However, these promote the ring opening of the epoxy group. May not be suitable for use.

  The amount of the solvent added is preferably 0.01 to 20 times, more preferably 0.02 to 15 times, and more preferably 0.02 to 15 times the total mass of the epoxy resin and alkoxysilane compound subjected to the cohydrolysis condensation reaction. The amount is preferably 0.03 to 10 times. Since the molecular weight of the resin composition can be controlled by the addition amount of the solvent, a resin composition having an appropriate molecular weight and, therefore, an appropriate viscosity can be obtained by setting the range of the addition amount described above.

(Photoacid generator)
The photoacid generator of the present embodiment is not particularly limited as long as it is a compound that releases an acid when irradiated with light and initiates polymerization. Among them, an onium salt is preferable. Specific examples include, for example, diazonium salts, iodonium salts, sulfonium salts, and the like. In these, the cation portion is aromatic diazonium, aromatic iodonium, 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. Typical examples of the photoacid generator are shown below.

  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, arsenic hexafluoride tri-4-methylphenylsulfonium salt, antimony tetrafluoride tri-4-methylphenylsulfonium salt, tetrakis (pentafluorophenyl) borate triarylsulfonium salt, tetrakis (pentafluoro) Phenyl) borate diaryl iodonium salt, acetylacetone aluminum salt and orthonitrobenzylsilyl ether mixture, phenylthiopyridinium salt, phosphorus hexafluoride allene-iron complex and the like. As commercially available products, CD-1012 (manufactured by SARTOMER), PCI-019, PCI-021 (manufactured by Nippon Kayaku Co., Ltd.), Optmer SP-150, Optmer SP-170 (manufactured by ADEKA Corporation), UVI- 6990, UVI-6974 (manufactured by Dow Chemical Co., Ltd.), CPI-100P, CPI-100A, CPI-100L (manufactured by Sun Apro), TEPBI-S (manufactured by Nippon Shokubai Co., Ltd.), Rhodorsil 2074 (manufactured by Rhodia) It is done. These can be used alone or in combination of two or more. Of these, sulfonium salts and iodonium salts are preferable from the viewpoint that the cured product is less colored, and sulfonium salts are particularly preferable in view of curability.

  Furthermore, other additions that exhibit cationic polymerizability can be added to the photosensitive composition to an extent that does not adversely affect the curing. 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.

  Since the curing of the photosensitive composition in the present embodiment is mainly based on a cationic polymerization reaction using a photoacid generator, coexistence of an alkaline substance may not be preferable. From this viewpoint, it is preferable that the photosensitive composition of the present embodiment does not contain an alkaline substance.

  The photosensitive composition of this embodiment contains the above resin composition and the above photoacid generator, a composition that undergoes a polymerization reaction upon irradiation with light, and can be cured with a high molecular weight. Refers to things.

(Oxetane compound)
You may mix | blend an oxetane compound or a vinyl ether compound with the photosensitive composition of this embodiment. Among these, it is preferable to blend an oxetane compound.
The oxetane compound is not particularly limited as long as it is a compound containing an oxetane ring. For example, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, bis (3- Ethyl-3-oxetanylmethyl) ether, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2,3-epoxypropoxymethyl) oxetane and the like. Typical examples of oxetane compounds are shown below. By blending the oxetane compound described above, the polymerization rate can be increased or the viscosity of the composition can be decreased.

  Although the compounding quantity of the said oxetane compound is not specifically limited, Preferably, it mix | blends by the mass ratio of resin composition: oxetane compound = 20: 80-95: 5 (total is 100). More preferably, it is 40: 60-80: 20. When the blending ratio of the resin composition is less than 5, the curing reaction may not proceed normally, and when it exceeds 95, the adhesiveness of the cured product may be inferior.

  Further, in order to improve the compatibility between the resin composition and the oxetane compound, for example, an appropriate combination of an oxetane compound having an aromatic ring is suitable for a resin composition using an epoxy resin having a bisphenol skeleton as a raw material. It is also necessary to select an appropriate combination.

  Further, in addition to the above, a vinyl ether compound can be blended. The vinyl ether compound is not particularly limited as long as it has a hydroxyl group. Specific examples thereof include, for example, 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 Le, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tricyclodecane diol monovinyl ether, tricyclodecanedimethanol monovinyl ether and the like.

  In general, although an epoxy compound has a fast onset of polymerization, it is said that the subsequent polymerization reaction is not fast. However, the present inventors surprisingly mixes an oxetane compound with the resin composition having an epoxy group. Thus, it was found that the polymerization rate can be accelerated and a photosensitive composition excellent in photocurability and adhesiveness can be obtained. Furthermore, in this embodiment, depending on the selection of the oxetane compound, it is possible to reduce the viscosity of the resin composition.

  The viscosity of the photosensitive composition of the present embodiment needs to be 1000 Pa · s or less in terms of fluidity. If it is in the said range, the viscosity will not be specifically limited, However, Preferably it is 0.05-50 Pa.s, Most preferably, it is 0.2-30 Pa.s. If it exceeds 1000 Pa · s, the fluidity is impaired and it is not suitable for practical use.

(Coating agent)
The coating agent of this embodiment contains the said photosensitive composition. The coating agent of the present embodiment is not particularly limited as long as it is a material for forming and coating a coating film on the surface of a substance, and its main use purpose is as follows.
(1) Protection of coatings and substrates, imparting durability, maintaining aesthetics (protection from ultraviolet rays, infrared rays, oxidation, corrosion, scratches, dust, dirt, temperature, humidity, etc.)
(2) Glossiness imparting to coatings and substrates (3) Water repellent processing to coatings and substrates (4) Non-slip processing of flooring materials, etc. (5) Sealing and insulation of electronic components It is also possible to blend pigments and pigments and use them as paints and inks.

(Coating)
The coating film of this embodiment is obtained by curing the above-described photosensitive composition or coating agent with light.
As a method for producing the coating film of the present embodiment, the photosensitive composition or coating agent is cured by irradiating at least predetermined light (ultraviolet rays, near ultraviolet rays, visible light, near infrared rays, infrared rays, etc.). (Photocuring) is not particularly limited.

The light is preferably ultraviolet light or visible light, and more preferably ultraviolet light.
Examples of the light source include low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, UV lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, argon ion laser, helium cadmium laser, Examples of the light source include a helium neon laser, a krypton ion laser, various semiconductor lasers, a YAG laser, an excimer laser, a light emitting diode, a CRT light source, and a plasma light source.

  Also, brush coating, roller coating, spray coating, bar coater, roll coater, baking coating, dip coating, electrodeposition coating, electrostatic coating, powder coating, vapor deposition, plating, and other coating technologies, inkjet, laser printing, rotary press You may combine with printing techniques, such as printing, gravure printing, and screen printing, and the thermosetting technique by a thermal energy.

(Photosensitive composition, coating agent and coating film)
In the photosensitive composition, the coating agent and the coating film thereof according to the present embodiment, various organic resins, inorganic fillers, colorants, leveling agents, lubricants, and the like, as long as the effects of the present embodiment are not impaired. Surfactants, silicone compounds, diluents (reactive diluents, non-reactive diluents, etc.), antioxidants, light stabilizers and the like can be appropriately added. In addition, other additives for resin in general (plasticizers, flame retardants, stabilizers, antistatic agents, impact resistance enhancers, foaming agents, antibacterial / antifungal agents, conductive fillers, antifogging agents, crosslinking agents, etc.) The material provided as may be blended.

  Here, the organic resin is not particularly limited, and examples thereof include an epoxy resin, an acrylic resin, a polyester resin, and a polyimide resin. Among these, those having a highly reactive organic group such as an epoxy resin are preferable.

  Examples of inorganic fillers include silicas (melted crushed silica, crystal crushed silica, spherical silica, fumed silica, colloidal silica, precipitated silica, etc.) silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, sulfuric acid Barium, calcium sulfate, mica, talc, clay, aluminum oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber And molybdenum disulfide, and the like, preferably silicas, calcium carbonate, aluminum oxide, aluminum hydroxide, calcium silicate, and the like. Further, considering the physical properties of the cured product, silicas are more preferable. These inorganic fillers may be used alone or in combination.

  The colorant is not particularly limited as long as it is a substance used for the purpose of coloring. For example, phthalocyanine, azo, disazo, quinacridone, anthraquinone, flavantron, perinone, perylene, dioxazine, condensed azo, azomethine-based various organic materials Inorganic pigments such as system dyes, titanium oxide, lead sulfate, chrome yellow, zinc yellow, chrome vermilion, valve shell, cobalt violet, bitumen, ultramarine, carbon black, chrome green, chrome oxide, cobalt green and the like. These colorants may be used alone or in combination.

  The leveling agent is not particularly limited. For example, oligomers having a molecular weight of 4000 to 12000 made of acrylates such as ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, hydrogenated castor oil And titanium-based coupling agents. These leveling agents may be used alone or in combination.

  The lubricant is not particularly limited, and hydrocarbon lubricants such as paraffin wax, microwax and polyethylene wax, higher fatty acid lubricants such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid, stearylamide Higher fatty acid amide lubricants such as palmitylamide, oleylamide, methylenebisstearamide, ethylenebisstearamide, hydrogenated castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono-, di-, tri -, Or tetra-) higher fatty acid ester lubricants such as stearate, alcohol lubricants such as cetyl alcohol, stearyl alcohol, polyethylene glycol, polyglycerol, lauric acid, myristic acid, palmitic acid, stearic acid, Examples include metal soaps that are metal salts such as magnesium, calcium, cadmium, barium, zinc, and lead such as rachidic acid, behenic acid, ricinoleic acid, and naphthenic acid, and natural waxes such as carnauba wax, candelilla wax, beeswax, and montan wax. . These lubricants may be used alone or in combination.

  The surfactant refers to an amphiphilic substance having a hydrophobic group having no affinity for the solvent in the molecule and an amphiphilic group (usually a hydrophilic group) having an affinity for the solvent. Moreover, the kind is not specifically limited, For example, a silicon-type surfactant, a fluorine-type surfactant, etc. are mentioned. Surfactants may be used alone or in combination.

  Examples of the silicone compound include, but are not limited to, silicone resin, silicone condensate, silicone partial condensate, silicone oil, silane coupling agent, silicone oil, polysiloxane, and the like. Or what modified | denatured by introduce | transducing an organic group into a side chain is also contained. The modification method is not particularly limited. For example, amino modification, epoxy modification, alicyclic epoxy modification, carbinol modification, methacryl modification, polyether modification, mercapto modification, carboxyl modification, phenol modification, silanol modification, polyether modification. , Polyether / methoxy modification, diol modification and the like.

  The reactive diluent is not particularly limited. For example, alkyl glycidyl ether (alkyl monoglycidyl ether, alkylcoglycidyl ether, etc.), phenyl glycidyl ether, monoglycidyl ether of alkylphenol, trimethylolpropane triglycidyl ether, orthocresyl Glycidyl ether, metaparacresyl glycidyl ether, glycidyl methacrylate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, hexahydrophthalic acid diglycidyl ester, alkanoic acid glycidyl ester, Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol Glycidyl ether, polypropylene glycol diglycidyl ether, fatty acid-modified epoxy, polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyglycol diglycidyl ether, 1,2: 8,9 diepoxylimonene, and the like.

  The non-reactive diluent is not particularly limited, and examples thereof include high-boiling solvents such as benzyl alcohol, butyl diglycol, and propylene glycol monomethyl ether.

  Other diluents are not particularly limited. For example, any organic solvent, glycerin, polyol, water, propylene glycol diglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol poly A glycidyl ether etc. are mentioned.

  The antioxidant is not particularly limited, and examples thereof include organic phosphorus antioxidants such as triphenyl phosphate and phenylisodecyl phosphite, and organic sulfur antioxidants such as distearyl-3,3′-thiodipropinate. And phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol.

  The light stabilizer is not particularly limited, and examples thereof include benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based, nickel-based, and triazine-based ultraviolet absorbers, hindered amine-based light stabilizers, and the like.

You may add the following substance further to the photosensitive composition of this embodiment, a coating agent, and its coating film.
For example, solvents, oils and fats, processed oils, natural resins, synthetic resins, pigments, dyes, pigments, release agents, preservatives, adhesives, deodorants, flocculants, cleaning agents, deodorants, pH adjusters, photosensitive materials, Ink, electrode, plating solution, catalyst, resin modifier, plasticizer, softener, agrochemical, insecticide, fungicide, pharmaceutical raw material, emulsifier / surfactant, rust inhibitor, metal compound, filler, cosmetic / pharmaceutical raw material , Dehydrating agent, drying agent, antifreeze, adsorbent, colorant, rubber, foaming agent, colorant, abrasive, mold release agent, flocculant, antifoaming agent, curing agent, reducing agent, flux agent, film treatment agent, Casting raw materials, minerals, acids / alkalis, shot agents, antioxidants, surface coating agents, additives, oxidants, explosives, fuels, bleaches, light emitting elements, fragrances, concrete, fibers (carbon fibers, aramid fibers, glass) Fiber), glass, metal, excipient, disintegrant, Mixture, fluidizing agents, gelling agents, stabilizers, preservatives, buffering agents, suspending agents, thickeners, and the like.

(Use of photosensitive composition, coating agent, and coating film of this embodiment)
Applications of the photosensitive composition, the coating agent, and the coating film of the present embodiment are not particularly limited. For example, the coating agent (painting, resin, plastic, metal, steel pipe, automobile, building, optical fiber application, etc.) ), Optical disk (DVD, CD, Blu-ray disc, etc.) coating and adhesion, ink (inkjet printer, gravure printing, flexographic printing, printed wiring board resist, UV printing application, etc.) printing plate making material (PS flat plate, photosensitive resin relief plate) , Photosensitive materials for screen plates, etc.), photoresist (resist for semiconductor, resist for printed wiring board, resist for photofabrication, etc.), printed wiring board, pattern formation of various electronic parts including IC, LSI, liquid crystal Color filter forming material for PDP display, liquid crystal and organic EL Sealing materials, semiconductor / LED peripheral materials (sealing materials, lens materials, substrate materials, die bonding materials, chip coating materials, laminated plates, optical fibers, optical waveguides, optical filters, adhesives for electronic components, coating materials, sealing materials , Insulation materials, photoresists, encap materials, potting materials, light transmission layers and interlayer insulation layers of optical disks, printed wiring boards, laminates, light guide plates, antireflection films, etc.), paints (corrosion resistant paints, maintenance, ship paints, etc.) Corrosion-resistant lining, primer for automobiles and home appliances, beverage / beer can, exterior lacquer, extrusion tube coating, general anticorrosion coating, maintenance process, lacquer for woodworking products, electrodeposition primer for automobiles, other industrial electrodeposition coatings, beverages・ Beer can inner surface lacquer, coil coating, drum / can inner surface coating, wood coating, acid-resistant lining, wire enamel, Rim paint, automotive primer, beautiful and anticorrosive coating of various metal products, pipe inner and outer surface coating, electrical component insulation coating, etc.), composite materials (chemical plant pipes and tanks, aircraft materials, automotive parts, various sports equipment, Carbon fiber composite materials, aramid fiber composite materials, etc.), civil engineering and building materials (floor materials, pavement materials, membranes, anti-slip and thin layer pavements, concrete jointing / uplifting, anchor embedded bonding, precast concrete bonding, tile bonding, concrete Repair of cracks in structures, grouting and leveling of pedestals, anticorrosion and waterproofing of water and sewage facilities, anticorrosive laminated lining of tanks, anticorrosion of iron structures, mastic coating of exterior walls of buildings, etc., adhesives (metal and glass)・ Adhesives of the same or different materials such as ceramics, cement concrete, wood, plastic, etc., automobiles, railway vehicles -Adhesives for assembly of aircraft, etc., adhesives for manufacturing prefabricated composite panels, etc .: Includes one-pack type, two-pack type and sheet type. ), Aircraft / automobile / plastic molding jigs (resin molds such as press molds, stretched dies, matched dies, vacuum molding / blow molding molds, master models, casting patterns, laminated jigs, various inspection jigs, etc.), It can be used as a modifier / stabilizer (fiber resin processing, stabilizer for polyvinyl chloride, additive to synthetic rubber, etc.) and the like. Among these, it is suitable for coating agents, paints, adhesives, and optical modeling resin applications.

  Although the Example which demonstrated this embodiment concretely is illustrated below, this embodiment is not limited to a following example, unless the summary is exceeded.

  The physical properties in Examples and Comparative Examples were evaluated as follows.

<Epoxy equivalent (WPE)>
It was measured according to “JIS K 7236: 2001 (How to determine epoxy equivalent of epoxy resin)”.
<Viscosity>
Measurement was performed under the following conditions.
Rotating E-type viscometer: “TV-22” manufactured by Toki Sangyo Co., Ltd.
Rotor: 3 ° × R14 (Other rotors may be selected as necessary.)
Measurement temperature: 25 ° C
Sample volume: 0.4mL

<Calculation of mixing index α>
The mixing index α was calculated from the following formula (2).
Mixing index α = (αc) / (αb) (2)
here,
αb: (B) In the general formula (1), n = 1 to 2, and R ¹ is an alkoxysilane compound content (mol%) having at least one cyclic ether group,
αc: (C) Content (mol%) of an alkoxysilane compound having n = 1 to 2 and having at least one aryl group as R ¹ in the general formula (1).

<Calculation of mixing index β>
The mixing index β was calculated from the following formula (3).
Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
here,
β ⁿ² : content (mol%) of the alkoxysilane compound in which n = 2 in the general formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n = 0 in the general formula (1),
β ⁿ¹ : content (mol%) of an alkoxysilane compound in which n = 1 in the general formula (1),
At this time, 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1.

<Calculation of mixing index γ>
The mixing index γ was calculated from the following equation (4).
Mixing index γ = (γa) / (γs) (4)
here,
γa: mass of epoxy resin (g),
γs: Mass (g) of the alkoxysilane compound in which n = 0 to 2 in the general formula (1).

<Calculation of mixing index δ>
The mixing index δ was calculated from the following equation (5).
Mixing index δ = (δe) / (δs) (5)
here,
δe: addition amount of hydrolytic condensation catalyst (mol number),
δs: The amount (mol number) of (OR ² ) in the general formula (1).

<Calculation of mixing index ε>
The mixing index ε was calculated from the following equation (6).
Mixing index ε = (εw) / (εs) (6)
here,
εw: amount of water added (in mol),
.epsilon.s: The amount of the general formula ^{(1) (OR 2) (} mol number).

<Calculation of mixing index ζ>
The mixing index ζ was calculated from the following equation (7).
Mixing index ζ = (ζf) / (ζk) (7)
here,
ζf: addition amount (number of moles) of curing agent,
ζk: The amount (mol number) of cyclic ether groups contained in the epoxy resin and the alkoxysilane compound.

<Calculation of mixing index η>
The mixing index η was calculated from the following formula (8).
Mixing index η = (ηg) / (ηk) (8)
here,
ηg: mass (g) of curing accelerator,
ηk: mass (g) of epoxy resin and alkoxysilane compound.

<Measurement of viscosity of photosensitive composition>
The container containing the composition immediately after production was sealed and the temperature was adjusted at 25 ° C. for 1 hour, and then the viscosity at 25 ° C. was measured.
When the viscosity was 1000 Pa · s or less, it was judged that there was fluidity.

<Preparation method a of coating film>
According to the following procedure, a coating film was produced in air under conditions of an air temperature of 23 ° C. and a humidity of 55% RH.
(1) The following substrates were prepared, and each surface was wiped dry with ethanol (Wako Pure Chemical Industries, Ltd., 99.5%).
Substrate: Polyethylene terephthalate resin (hereinafter referred to as PET)
Polycarbonate resin (hereinafter referred to as PC)
Polymethyl methacrylate resin (hereinafter referred to as PMMA)
(2) The photosensitive composition of an Example or the composition of a comparative example was apply | coated on the said board | substrate using the bar-coater (# 3).
(3) The substrate was set in a UV curing device (manufactured by Fusion UV Systems Japan Co., Ltd.), and the following conditions were repeated three times for curing.
Light source and light quantity: High pressure mercury lamp (120 W / cm ² )
Belt conveyor speed: 10 m / min (4) Further, the substrate was heat-treated at 100 ° C. for 1 hour to be post-cured.

<Preparation method b of coating film>
According to the following procedure, a coating film was produced in air under conditions of an air temperature of 23 ° C. and a humidity of 55% RH.
(1) The following substrates were prepared, and each surface was wiped dry with ethanol (Wako Pure Chemical Industries, Ltd., 99.5%).
Substrate: PET
(2) The photosensitive composition of an Example or the composition of a comparative example was apply | coated on the said board | substrate using the bar-coater (# 3).
(3) The substrate was set in a UV curing device (manufactured by Fusion UV Systems Japan Co., Ltd.), and the following conditions were repeated 5 times and cured.
Light source and light quantity: High pressure mercury lamp (120 W / cm ² )
Belt conveyor speed: 5m / min

<Photocurability of coating film>
The above-mentioned coating film was measured according to “JIS K5600-5-4: 1999 General Test Method for Paints—Part 5: Mechanical Properties of the Coating Film—Section 4: Scratch Strength (Pencil Method)” and 3B to 6H When it was, it was judged that photocurability was favorable.

<Adhesiveness of coating film>
The above-mentioned coating film was measured in accordance with “JIS K5600-5-6: 1999 General Test Method for Paints—Part 5: Mechanical Properties of Coating Film—Section 6: Adhesion (Crosscut Method)”.
The result is a three-step evaluation of ○: hardly peeled, Δ: partially peeled, ×: almost peeled, and the adhesion is good when the result is better than the standard. It was judged.

<Comprehensive judgment>
When the above-mentioned photosensitive composition had fluidity and the photocurability and adhesiveness of the coating film were good, it was judged as acceptable as a comprehensive judgment.

The raw materials used in Examples and Comparative Examples are shown in the following (1) to (9).
(1) Epoxy resin (1-1) Epoxy resin A: Poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as Bis-A epoxy resin)
・ Product name: “AER”, manufactured by Asahi Kasei Epoxy Corporation
Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
Epoxy equivalent (WPE): 187 g / eq
Viscosity (25 ° C.): 14.3 Pa · s
(1-2) Epoxy resin B: 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate (hereinafter referred to as alicyclic epoxy resin)
・ Product name: “Celoxide 2021P” manufactured by Daicel Chemical Industries, Ltd.
Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
Epoxy equivalent (WPE): 131 g / eq
Viscosity (25 ° C.): 227 mPa · s
(2) Alkoxysilane compound H: 3-glycidoxypropyltrimethoxysilane (hereinafter referred to as GPTMS)
・ Product name: “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.
(3) Alkoxysilane compound I: phenyltrimethoxysilane (hereinafter referred to as PTMS)
・ Product name: “KBM-103” manufactured by Shin-Etsu Chemical Co., Ltd.
(4) Alkoxysilane compound J: Dimethyldimethoxysilane (hereinafter referred to as DMDMS)
・ Product name: “KBM-22” manufactured by Shin-Etsu Chemical Co., Ltd.
(5) Alkoxysilane compound K: tetraethoxysilane (hereinafter referred to as TEOS)
・ Product name: “KBE-04”, manufactured by Shin-Etsu Chemical Co., Ltd.
(6) Solvent (6-1) Tetrahydrofuran: Wako Pure Chemical Industries, Ltd., stabilizer-free type (hereinafter referred to as THF)
(7) Hydrolysis condensation catalyst: Dibutyltin dilaurate (Wako Pure Chemical Industries, Ltd., hereinafter referred to as DBTDL)
(8) Photoacid generator (8-1) Hexafluorophosphate mixture of triallylsulfonium-Trade name: "UVI-6990" (hereinafter referred to as UVI-6900) manufactured by Union Carbide.
(8-2) Hexafluoroantimonate of aromatic sulfonium-Trade name: "San-Aid SI-80L" (hereinafter referred to as SI-80L) manufactured by Sanshin Chemical Industry Co., Ltd.
(9) Oxetane compound (9-1) 3-ethyl-3- (phenoxymethyl) oxetane-Product name: “OXT-211” (hereinafter referred to as POX) manufactured by Toagosei Co., Ltd.

(Synthesis Example 1)
Resin composition A: Resin composition A was produced and evaluated by the following procedure.
(1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer.
(2) According to the composition ratio in Table 1, in an atmosphere of 25 ° C., the alicyclic epoxy resin, the alkoxysilane compound and THF are placed in a flask containing a stirrer, mixed and stirred, and further hydrolyzed with water. A condensation catalyst was added and mixed and stirred.
(3) Subsequently, a cooling tube was set on the flask, and it was immediately immersed in an oil bath at 80 ° C. to start stirring, and reacted for 8 hours while refluxing.
(4) After completion of the reaction, after cooling to 25 ° C., the cooling tube was removed from the flask, and the solution was collected.
(5) The above solution was distilled off at 400 Pa and 50 ° C. for 1 hour using an evaporator, and then dehydrated and condensed while being distilled off at 80 ° C. for 5 hours.
(6) After completion of the reaction, the mixture was cooled to 25 ° C. to obtain a resin composition A.
(7) Table 3 shows the mixing indices α1 to ε1 in this resin composition.
(8) Further, according to the above method, the epoxy equivalent (WPE) of the resin composition A obtained in the above (6) was measured.
The said resin composition was epoxy equivalent (WPE) = 193g / eq, and showed the appropriate value. The viscosity was 12.7 Pa · s <1000 Pa · s, indicating good fluidity.

(Synthesis Example 2)
Resin composition B: According to the composition ratio in Table 1, resin composition B was synthesized and evaluated in the same manner as in Synthesis Example 1. Table 3 shows the mixing indices α2 to ε2.
The epoxy equivalent (WPE) of the resin composition B was 152 g / eq, which was an appropriate value. Further, the viscosity was 0.93 Pa · s <1000 Pa · s, indicating good fluidity.

Example 1
Photosensitive composition 1 and its coating film were produced and evaluated by the following procedures.
(1) The photosensitive composition 1 was obtained by using the resin composition A of Synthesis Example 1 above, mixing and stirring in accordance with the formulation in Table 2, and degassing under vacuum. The viscosity of the photosensitive composition 1 was 12.6 Pa · s <1000 Pa · s, and the liquid was excellent in fluidity.
(2) According to the above-mentioned “coating film preparation method a”, the photosensitive composition 1 was applied to the three types of substrates (PET, PC, PMMA), and a coating film was prepared using a UV curing device. .
(3) The above-mentioned coating film was measured in accordance with “JIS K5600-5-4: 1999 Paint General Test Method—Part 5: Mechanical Properties of Coating Film—Section 4: Scratch Strength (Pencil Method)”. The results are shown in Table 3.
(4) The above-mentioned coating film was measured according to “JIS K5600-5-6: 1999 General Test Method for Coating Materials—Part 5: Mechanical Properties of Coating Film—Section 6: Adhesiveness (Cross Cut Method)” The results are shown in Table 3.
As shown above, the photosensitive composition 1 is excellent in fluidity, the photocurability of the coating film is good, and the adhesiveness is better than that of the comparative example 1, which is the reference. It was judged.

(Example 2)
Photosensitive composition 2 was produced in the same manner as in Example 1 according to the formulation in Table 2. However, the belt conveyor speed of the UV curing device was set to 10 m / min. The evaluation results are shown in Table 3.
The viscosity of the photosensitive composition 2 was 3.2 Pa · s <1000 Pa · s, and the liquid was excellent in fluidity.
As shown above, the photosensitive composition 2 is excellent in fluidity, the photocurability of the coating film is good, and the adhesiveness is better than that of Comparative Example 1 as a reference. It was judged.

(Example 3)
Photosensitive composition 3 was produced according to the formulation shown in Table 2 and evaluated in the same manner as in Example 1.
The viscosity of the photosensitive composition 3 was 1.0 Pa · s <1000 Pa · s, and the liquid was excellent in fluidity.
Next, the photosensitive composition 3 was used and PET was used as a substrate to produce a coating film according to the above-described “coating film preparation method b”. The results are shown in Table 3.
As shown above, the photosensitive composition 3 is excellent in fluidity, has good photocurability of the coating film, and has better adhesiveness than the comparative example 3, which is a reference, and therefore passes as a comprehensive judgment. It was judged.

(Comparative Example 1)
Photosensitive composition 4 was produced in the same manner as in Example 1 according to the formulation in Table 2. The evaluation results are shown in Table 3.
The viscosity of the photosensitive composition 4 was 13.8 Pa · s <1000 Pa · s, and the liquid was excellent in fluidity.
However, as shown in Table 3, although the photosensitive composition 4 was excellent in fluidity, it was judged to be unacceptable as a comprehensive judgment because the adhesiveness of the coating film was poor.

(Comparative Example 2)
Photosensitive composition 5 was produced in the same manner as in Example 1 according to the formulation in Table 2. GPTMS was used as the silane coupling agent. The evaluation results are shown in Table 3.
The viscosity of the photosensitive composition 5 was 12.1 Pa · s <1000 Pa · s, and the liquid was excellent in fluidity.
However, as shown in Table 3, although the photosensitive composition 5 was excellent in fluidity, the effect of improving the adhesiveness of the coating film was not observed, and it was judged as rejected as a comprehensive judgment.

(Comparative Example 3)
Photosensitive composition 6 was produced in the same manner as in Example 3 according to the formulation in Table 2. The evaluation results are shown in Table 3.
The viscosity of the photosensitive composition 6 was 0.3 Pa · s <1000 Pa · s, and the liquid was excellent in fluidity.
However, as shown in Table 3, although the photosensitive composition 6 was excellent in fluidity, it was judged to be unacceptable as a comprehensive judgment because the adhesiveness of the coating film was poor.

  As is apparent from the above results, the photosensitive composition containing a resin composition obtained by cohydrolytic condensation of an epoxy resin and a specific alkoxysilane compound and a photoacid generator is fluid. The coating agent and coating film using the same were excellent in photocurability and adhesiveness.

  The photosensitive composition, coating agent, and coating film of the present embodiment have industrial applicability as, for example, paints, adhesives, electronic materials, and the like.

Claims (8)

(A) an epoxy resin;
An alkoxysilane compound represented by the following general formula (1):
A resin composition obtained by cohydrolyzing and condensing

(In the formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. The plurality of R ² may be the same or different, and may be a hydrogen atom or a carbon number of 1 to 8. Represents an alkyl group of
The alkoxysilane compound is
(B) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one cyclic ether group;
(C) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one aryl group;
And (B) and (C) represented by the following formula (2), the mixing index α is 0.001 to 19 and a photoacid generator containing a photoacid generator Composition;
Mixing index α = (αc) / (αb) (2)
(In formula (2), αb: content (mol%) of the component (B), αc: content (mol%) of the component (C)). As the alkoxysilane compound,
(D) The photosensitive composition of Claim 1 which further contains the at least 1 sort (s) of alkoxysilane compound which is n = 0 in the said General formula (1). The photosensitive composition of Claim 1 or 2 whose mixing parameter | index (beta) of the said alkoxysilane compound represented by following formula (3) is 0.01-1.4;
Mixed index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
(In formula (3),
β ⁿ² : content (mol%) of alkoxysilane compound in which n = 2 in the general formula (1),
β ⁿ⁰ : content (mol%) of an alkoxysilane compound in which n = 0 in the general formula (1),
β ⁿ¹ : content (mol%) of an alkoxysilane compound in which n = 1 in the general formula (1),
Here, 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1). The photosensitivity as described in any one of Claims 1-3 whose mixing parameter | index (gamma) of the said (A) epoxy resin and the said alkoxysilane compound represented by following formula (4) is 0.02-15. Sex composition;
Mixing index γ = (γa) / (γs) (4)
(In formula (4),
γa: mass of epoxy resin (g),
γs: mass (g) of alkoxysilane compound in which n = 0 to 2 in the general formula (1)   The photosensitive composition as described in any one of Claims 1-4 which further contains an oxetane compound.   The coating agent containing the photosensitive composition as described in any one of Claims 1-5.   The coating film obtained by hardening the photosensitive composition as described in any one of Claims 1-5, or the coating agent of Claim 6 with light. And (A) an epoxy resin, the alkoxysilane compound, the co-hydrolysis are that the resin composition obtained by condensation of the following general formula (1), at least performs adding a photoacid generator, a photosensitive A method for producing the composition;

(In the formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. The plurality of R ² may be the same or different, and may be the same or different. 8 represents an alkyl group.)
The alkoxysilane compound is
(B) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one cyclic ether group;
(C) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one aryl group;
And the mixture index α of (B) and (C) represented by the following formula (2) is 0.001 to 19,
Mixing index α = (αc) / (αb) (2)
(In formula (2), αb: content (mol%) of the component (B), αc: content (mol%) of the component (C)).