JP2011001422A - Photosensitive resin composition, photosensitive inkjet ink using the same, photosensitive adhesive, photosensitive coating agent, and semiconductor sealing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having an excellent curing property that curing is not suppressed by humidity of which the cured product has a film physical property being excellent in toughness and flexibility.SOLUTION: The photosensitive resin composition includes a compound (a) represented by formula (1) (wherein Rrepresents 1-5C alkyl, 5-10C cycloalkyl, 1-5C alkoxy, halogen, hydroxyl, aryl or aralkyl; mrepresents an integer of 2-5; and nrepresents an integer of 0-20).

Description

  The present invention relates to a photosensitive resin composition, a photosensitive inkjet ink using the same, a photosensitive adhesive, a photosensitive coating agent, and a semiconductor sealing material.

  A photocuring system using energy rays such as ultraviolet rays is an effective method for improving productivity and solving environmental problems in recent years. The mainstream of the current photocuring system is a radical curing material using a (meth) acrylate-based material. However, the radical curable material is susceptible to curing inhibition by oxygen and has a problem that adhesion to a substrate is low due to large curing shrinkage.

  In recent years, therefore, attention has been focused on cationically curable materials in order to solve these problems. Cationic curable materials are (a) less susceptible to curing inhibition by oxygen and therefore excellent in microdroplet and thin film curability, (b) have small cure shrinkage, and have good adhesion to a wide range of substrates. c) Since the active species has a long lifetime and curing proceeds gradually even after light irradiation (dark reaction), it has excellent features compared to radical curing materials, such as being able to keep the amount of residual monomers low. Therefore, the application of cationically curable materials to paints, adhesives, display sealants, printing inks, three-dimensional modeling, silicone release paper, photoresists, sealants for electronic components, etc. is being studied (non-patent) Reference 1).

  Epoxy compounds are mainly used in the photocationic curable material. Among them, alicyclic epoxy compounds that are relatively rich in reactivity are frequently used (see Patent Document 1). In addition, various attempts have been made on photocationic curable materials using epoxy compounds. For example, many attempts have been made to increase the reactivity of an epoxy compound by using a vinyl ether compound in combination with an alicyclic epoxy compound (see Patent Documents 2 to 4). Attempts have been made to use an oxetane compound in combination with an epoxy compound for the purpose of reducing the influence of humidity (see Patent Document 5). Furthermore, an attempt has been made to use all of an epoxy compound, a vinyl ether compound, and an oxetane compound (see Patent Document 6).

US Pat. No. 3,794,576 JP-A-6-298911 JP-A-9-328634 Japanese Patent No. 4235698 Japanese Patent No. 4158460 Japanese translation of PCT publication No. 2008-52162

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, general cationic curable materials are likely to be hindered by moisture in the air. Therefore, it is easily affected by the humidity of the atmosphere at the time of curing, and it is difficult to obtain stable curability. When using an epoxy compound as a photocationic curing material, since it does not cause inhibition of curing by oxygen even in the air, it has excellent surface curability compared to radical curing materials, but the internal reactivity is insufficient, There is a problem that sufficient mechanical properties cannot be obtained.

  The technique disclosed in Patent Document 1 does not cause inhibition of curing by oxygen even in the air, and thus has excellent surface curability as compared with radical curing materials, but the internal reactivity is insufficient and sufficient There is a problem that it is not possible to obtain proper mechanical characteristics.

  In the techniques disclosed in Patent Documents 2 to 4, since the reaction is easily inhibited by moisture due to the incorporation of vinyl ether, the hardness of the cured product is lowered under high humidity, and sufficient surface curability cannot be obtained. There is a problem.

  In the technique disclosed in Patent Document 5, since the oxetane compound is not copolymerized with the epoxy compound, the effect of improving the reactivity of the epoxy compound cannot be obtained. As a result, there is a problem that a cured product having sufficient mechanical properties cannot be obtained, and the use is limited because a large amount of unreacted components remain.

  In the technique disclosed in Patent Document 6, since the vinyl ether compound is not copolymerized with the oxetane compound, a homopolymer of an oxetane compound having low flexibility is by-produced. As a result, there exists a problem that the softness | flexibility of hardened | cured material falls and it becomes easy to enter a crack.

  The present invention has been made in view of the above circumstances, and has excellent curability that does not inhibit curing due to humidity, and the cured product has film properties excellent in toughness and flexibility. The purpose is to provide goods.

  As a result of intensive studies to solve the above problems, the present inventor has found that a photosensitive resin composition containing a compound having an oxetanyl group and a vinyl ether group in one molecule achieves the object thereof, thereby forming the present invention. It came to.

（式中、Ｒ^１は炭素数１〜５のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数１〜５のアルコキシ基、ハロゲン原子、水酸基、アリール基又はアラルキル基を表し、ｍ^１は２〜５の整数を表し、ｎ^１は０〜２０の整数を表す。）
［２］
分子中にエポキシ基を１個以上有するエポキシ化合物（ｂ）と、
エネルギー線感受性カチオン重合開始剤（ｃ）と、をさらに含む［１］の感光性樹脂組成物。
［３］
３〜５個のフェノール性芳香環を含み、
前記フェノール性芳香環のフェノール性水酸基のオルト位の全てが、メチロール基、炭素数４以上のアルキル基、又はシクロアルキル基のいずれにも置換されておらず、かつ、
前記フェノール性水酸基の少なくとも１個のオルト位が無置換であるフェノール性芳香環を、２個以上有する、多核フェノール化合物（ｄ）を、さらに含む［１］又は［２］の感光性樹脂組成物。
［４］
前記（ａ）成分５〜７０質量％と、
前記（ｂ）成分２５〜９０質量％と、
前記（ｃ）成分０．１〜１０質量％と、
を含む、［２］又は［３］の感光性樹脂組成物。
［５］
前記（ｄ）成分０．１〜４０質量％を、さらに含む、［３］又は［４］の感光性樹脂組成物。
［６］
前記（ｄ）成分が、下記式（２）で表される多核フェノール化合物（ｅ）と、下記式（３）で表される多核フェノール化合物（ｆ）と、をさらに含み、かつ、
前記（ｅ）成分及び前記（ｆ）成分の合計に対する前記（ｅ）成分の割合（ｅ／（ｅ＋ｆ））が４０質量％以上である、［３］〜［５］のいずれか一つの感光性樹脂組成物。

（式中、Ｒ^２、Ｒ^３及びＲ^４は、炭素数１〜５のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数１〜５のアルコキシ基、ハロゲン原子、水酸基、アリール基又はアラルキル基を表し、Ｒ^２、Ｒ^３及びＲ^４は、互いに異なっていても同一でもよく、ｍ^２は０〜３の整数を表し、ｎ^２は１〜３の整数を表す。）

（式中、Ｒ^２、Ｒ^３及びＲ^４は、式（２）の定義と同じであり、ｍ^３は０〜３の整数を表し、ｎ^３は０又は４以上の整数を表す。）
［７］
前記（ｄ）成分が、下記式（４）で表される多核フェノール化合物（ｇ）と、
下記式（５）で表される多核フェノール化合物（ｈ）と、をさらに含み、かつ、
前記（ｇ）成分及び前記（ｈ）成分の合計に対する前記（ｇ）成分の割合（ｇ／（ｇ＋ｈ））が４０質量％以上である、［３］〜［５］のいずれか一つの感光性樹脂組成物。

（式中、ｎ^４は１〜３の整数を表す。）

（式中、ｎ^５は０又は４以上の整数を示す）
［８］
［１］〜［７］のいずれか一つの感光性樹脂組成物と、着色剤と、を含む、感光性インクジェットインク。
［９］
［１］〜［７］のいずれか一つの記載の感光性樹脂組成物を含む、感光性接着剤。
［１０］
［１］〜［７］のいずれか一つの感光性樹脂組成物を含む、感光性コーティング剤。
［１１］
［１］〜［７］のいずれか一つの感光性樹脂組成物を含む、半導体封止材。 That is, the present invention is as follows.
[1]
The photosensitive resin composition containing the compound (a) represented by following formula (1).

(Wherein R ¹ represents an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, an aryl group, or an aralkyl group, m ¹ Represents an integer of 2 to 5, and n ¹ represents an integer of 0 to 20.)
[2]
An epoxy compound (b) having at least one epoxy group in the molecule;
The photosensitive resin composition according to [1], further comprising an energy ray-sensitive cationic polymerization initiator (c).
[3]
Contains 3-5 phenolic aromatic rings,
All of the ortho positions of the phenolic hydroxyl group of the phenolic aromatic ring are not substituted with any of a methylol group, an alkyl group having 4 or more carbon atoms, or a cycloalkyl group, and
The photosensitive resin composition according to [1] or [2], further comprising a polynuclear phenol compound (d) having two or more phenolic aromatic rings in which at least one ortho position of the phenolic hydroxyl group is unsubstituted. .
[4]
5 to 70% by mass of the component (a),
25 to 90% by mass of the component (b),
0.1 to 10% by mass of the component (c),
The photosensitive resin composition according to [2] or [3].
[5]
The photosensitive resin composition according to [3] or [4], further comprising 0.1 to 40% by mass of the component (d).
[6]
The component (d) further includes a polynuclear phenol compound (e) represented by the following formula (2) and a polynuclear phenol compound (f) represented by the following formula (3), and
The photosensitive property according to any one of [3] to [5], wherein a ratio (e / (e + f)) of the component (e) to the total of the component (e) and the component (f) is 40% by mass or more. Resin composition.

(Wherein R ² , R ³ and R ⁴ are 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 ² , R ³ and R ⁴ may be different or the same, m ² represents an integer of 0 to 3 and n ² represents an integer of 1 to 3)

(In the formula, R ² , R ³ and R ⁴ are the same as defined in formula (2), m ³ represents an integer of 0 to ³ , and n ³ represents 0 or an integer of 4 or more.)
[7]
The (d) component is a polynuclear phenol compound (g) represented by the following formula (4):
A polynuclear phenol compound (h) represented by the following formula (5), and
The photosensitive property according to any one of [3] to [5], wherein a ratio (g / (g + h)) of the component (g) with respect to a total of the component (g) and the component (h) is 40% by mass or more. Resin composition.

(Wherein n ⁴ represents an integer of 1 to 3)

(In the formula, n ⁵ represents 0 or an integer of 4 or more)
[8]
A photosensitive inkjet ink comprising the photosensitive resin composition according to any one of [1] to [7] and a colorant.
[9]
[1] A photosensitive adhesive comprising the photosensitive resin composition according to any one of [7].
[10]
The photosensitive coating agent containing the photosensitive resin composition any one of [1]-[7].
[11]
A semiconductor encapsulant comprising the photosensitive resin composition according to any one of [1] to [7].

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the photosensitive resin composition which has the outstanding sclerosis | hardenability which does not have the hardening inhibition by humidity, and the cured | curing material has the film physical property which was excellent in toughness and a softness | flexibility.

It is sectional drawing of the one aspect | mode of the OLED display element using the semiconductor sealing material of this embodiment.

  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. And this invention can be deform | transformed suitably and implemented within the range of the summary.

  The photosensitive resin composition of the present embodiment includes a compound (a) having one or more oxetanyl groups and vinyl ether groups in one molecule represented by the following formula (1).

(Wherein R ¹ represents an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, an aryl group, or an aralkyl group, m ¹ Represents an integer of 2 to 5, and n ¹ represents an integer of 0 to 20.)

  By including the compound (a) in the photosensitive resin composition of the present embodiment, it becomes possible to copolymerize the epoxy compound and the vinyl ether compound and the oxetane compound, and to suppress the by-product of the homopolymer of the oxetane compound. Can do. As a result, it is possible to obtain a cured product having excellent photocurability (surface curability and internal curability) that is not inhibited by humidity, and having film properties excellent in toughness and flexibility. Since the toughness and flexibility of the cured product are excellent, the flexibility of the cured product can be improved.

The compound (a) will be described.
Of the compounds represented by formula (1), those in which n ¹ is ¹ to 20 include, for example, a compound represented by formula (6) and a compound represented by formula (7) as a basic compound. It can obtain by making it react in presence of. In addition, in the formula (1), a compound in which n ¹ is 0 can be obtained by reacting acetylene with a compound represented by the formula (7). The reaction at this time is carried out under pressure or normal pressure. Can be done.

(In the formula, m ⁶ represents an integer of 2 to 5, n ⁶ represents an integer of 1 to 20, and X represents a halogen atom, a tosyl group, a benzenesulfonyl group, or a methanesulfonyl group.)

(In the formula, R ⁷ represents a methyl group or an ethyl group.)

  Specific examples of the compound represented by the formula (6) include 2-chloroethyl vinyl ether, 4-chlorobutyl vinyl ether, 2-bromoethyl vinyl ether, 4-bromobutyl vinyl ether, 2-vinyloxyethyl tosylate, 4-vinyl Roxybutyl tosylate, and mixtures thereof.

  Specific examples of the compound represented by the formula (7) include 3-methyl-3-hydroxymethyl oxetane and 3-ethyl-3-hydroxymethyl oxetane. These compounds can be synthesized from trimethylolethane, trimethylolpropane and the like by the method of Pattison [J. Am. Chem. Soc., 79 (1957) 3455-3456].

  The usage-amount of the compound represented by Formula (7) in the said method is 0.1 mol or more normally with respect to 1 mol of compounds represented by Formula (6), Preferably it is 0.2-2.0 mol. .

  The reaction temperature of the compound represented by the formula (6) and the compound represented by the formula (7) is usually 20 to 120 ° C., preferably 60 to 90 ° C., and the reaction time is usually 30 minutes to 24 hours. Preferably it is 1 to 10 hours.

  The reaction between the compound represented by formula (6) and the compound represented by formula (7) can be carried out in an inert solvent in the presence of a basic compound. Examples of the inert solvent include aprotic polar solvents such as N, N-dimethylacetamide, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone, N, N-dimethylimidazolidone, and nonpolar materials such as toluene, hexane, and heptane. Organic solvents, tetrahydrofuran, diglyme, dioxane, trioxane, and mixed solvents thereof.

  The usage-amount of an inert solvent is 0-500 mL normally with respect to 0.1 mol of compounds represented by Formula (6), Preferably it is 50-300 mL. In addition, the reaction can be allowed to proceed while removing low-boiling substances out of the reaction system.

  Specific examples of the basic compound include alkali metal compounds such as sodium hydride, potassium hydride and sodium hydroxide, alkali metals such as sodium metal and potassium metal, and alkali metal alcoholates such as sodium methylate. The usage-amount is 1.0 mol or more normally with respect to 1.0 molar equivalent of the compound represented by Formula (6), Preferably it is 1.2-10 mol.

  After completion of the above reaction, the reaction mixture is cooled to room temperature and extracted with water, diethyl ether, hexane, or the like. Next, a desiccant such as anhydrous sodium sulfate or synthetic zeolite is added to the organic layer and dried. At this time, a decolorizing agent such as activated carbon may be added. Thereafter, the reaction mixture is filtered, and the desired product (compound (a) represented by formula (1)) can be obtained by distillation under reduced pressure or the like.

As an alternative method, for example, the compound represented by the formula (1) where n ¹ is an integer of ¹ to 20 includes a compound represented by the formula (8) and a compound represented by the formula (9). It can be obtained by reacting in the presence of a compound.

（式中、ｍ^８は２〜５の整数を表し、ｎ^８は１〜２０の整数を表す。）

(In the formula, m ⁸ represents an integer of 2 to 5, and n ⁸ represents an integer of 1 to 20.)

(Wherein R ⁸ represents a methyl group or an ethyl group, and X represents a halogen atom, a tosyl group, a benzenesulfonyl group, or a methanesulfonyl group.)

  Specific examples of the compound represented by the formula (8) include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, and mixtures thereof.

  Specific examples of the compound represented by the formula (9) include 3-methyl-3-chloromethyloxetane, 3-ethyl-3-chloromethyloxetane, 3-ethyl-3-bromomethyloxetane, and a mixture thereof. Can be mentioned.

  The usage-amount of the compound represented by Formula (9) is 0.1 mol or more normally with respect to 1 mol of compounds represented by Formula (8), Preferably, it is 0.2-2.0 mol.

  The reaction temperature of the compound represented by the formula (8) and the compound represented by the formula (9) is usually 0 to 100 ° C, preferably 40 to 70 ° C. The reaction time is usually 30 minutes to 24 hours, preferably 1 to 10 hours.

  The reaction between the compound represented by formula (8) and the compound represented by formula (9) is carried out according to the reaction between the compound represented by formula (6) and the compound represented by formula (7). be able to. The reaction may be carried out in the above-mentioned inert solvent in the presence of the above-mentioned basic compound. The usage-amount of a basic compound is 1.0 mol or more normally with respect to 1.0 molar equivalent of the compound represented by Formula (9), Preferably it is 1.2-10 mol.

  It is preferable that the photosensitive resin composition of this embodiment further contains an epoxy compound (b). Since the compound (a) which the photosensitive resin composition of this embodiment contains can superpose | polymerize with an epoxy compound (b), the reactivity as an epoxy compound can be improved more. Furthermore, no impurities remain as unreacted components of the compound (a) and the epoxy compound (b). Thereby, the hardened | cured material which has the outstanding toughness and a softness | flexibility can be obtained.

  Examples of the epoxy compound (b) having one or more epoxy groups in the molecule include glycidyl ether type epoxy compounds and alicyclic epoxy compounds.

  Specific examples of glycidyl ether type epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, and bisphenol A alkylene oxide adducts. Diglycidyl ether of dialkylidyl ether, alkylene oxide adduct of bisphenol F, diglycidyl ether of alkylene oxide adduct of hydrogenated bisphenol A, 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.

  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, vinylcyclohexenedioxide, 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- And cyclohexanedimethanol di (3,4-epoxycyclohexanecarboxylate).

  Examples of the bifunctional alicyclic epoxy compound include “Celoxide 2021P”, “Celoxide 2000”, “Celoxide 3000” (trade name, manufactured by Daicel Chemical Industries), “UVR-6110”, “UVR-6105”, “UVR-”. 6128 "," ERLX-4360 "(trade name, manufactured by Dow Chemical Japan Co., Ltd.) and the like can be used.

  As the trifunctional or higher polyfunctional alicyclic epoxy compound, “Epolide GT300”, “Epolide GT400” (trade name, manufactured by Daicel Chemical Industries, Ltd.) and the like can be used.

  Of these, alicyclic epoxy compounds are preferred because of their excellent cationic polymerization reactivity. These compounds having an epoxy group can be used singly or in combination of two or more.

  The photosensitive resin 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. A polynuclear phenol compound (d) having at least two phenolic aromatic rings which are not substituted on any of the groups and at least one ortho position of the hydroxyl group of the phenolic aromatic ring is unsubstituted. It is preferable to further include.

  Since the compound (a) contained in the photosensitive resin composition of the present embodiment can be polymerized with the polynuclear phenol compound (d), not only can the reactivity of the polynuclear phenol compound (d) be improved, but also the toughness A cured product having excellent flexibility can be obtained. As a result, problems such as those normally occurring when using a resol-type phenolic resin or the like, the hardness of the cured product gradually lowering with time, do not occur.

  All of the ortho positions of all the phenolic hydroxyl groups of the polynuclear phenol compound (d) do not have a methylol group. That is, the polynuclear phenol compound (d) does not include a compound having a methylol group in the molecule, generally called a resol resin. This is because the methylol group has reactivity with the epoxy group, but the bond formed by the reaction is unstable under acidic conditions, and the film hardness obtained after curing decreases with time.

  Furthermore, all of the ortho positions of all the phenolic hydroxyl groups of the polynuclear phenol compound (d) do not have an alkyl group or a cycloalkyl group having 4 or more carbon atoms. That is, phenol compounds generally called radical inhibitors and antioxidants such as hindered phenols having a particularly bulky t-butyl group are not included. This is because in the polynuclear phenol compound (d), 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.

  Furthermore, the polynuclear phenol compound (d) has 3 to 5 phenolic aromatic rings, and at least one ortho position of the phenolic hydroxyl group is unsubstituted in the molecule, Have at least two or more. In one or two phenolic aromatic rings, a crosslinked structure cannot be formed efficiently in the photocuring reaction, and in the case of six or more, a phenolic hydroxyl group not involved in the crosslinking reaction is generated and curable. It is because it adversely affects the mechanical properties of the cured product.

  Examples of such polynuclear phenol compounds include various polynuclear phenol compounds represented by the following formulas (10) to (14) and (18), and various polynuclear compounds represented by the following formulas (2) and (4). Examples thereof include a phenol compound and a polynuclear phenol compound having 3 to 5 phenolic aromatic rings, which is a Friedel-Crafts reaction adduct of a 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.

(Wherein R ⁹ , R ¹⁰ and R ¹¹ 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 ⁹ in each benzene ring, R ¹⁰ and R ¹¹ may be the same or different from each other, p ⁹ , p ¹⁰ and p ¹¹ represent an integer of 0 to 4, and may be the same or different from each other, and q ⁹ , q ¹⁰ and q ¹¹ are , 1-3, which may be the same or different from each other, and p + q ≦ 5 in the corresponding p and q, wherein any one of R ⁹ , R ¹⁰ and R ¹¹ has 4 or In the case of 5, R ⁹ , R ¹⁰ or R ¹¹ is not located in the ortho position with respect to the hydroxyl group on the benzene ring.)

(In the formula, the definitions of R ⁹ , R ¹⁰ , R ¹¹ , p ⁹ , p ¹⁰ , p ¹¹ , q ⁹ , q ¹⁰ and q ¹¹ are the same as those in formula (10).)

(In the formula, the definitions of R ⁹ , R ¹⁰ , R ¹¹ , p ⁹ , p ¹⁰ , p ¹¹ , q ⁹ , q ¹⁰ and q ¹¹ are the same as those in formula (10).)

(In the formula, R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ represent an alkyl group or an alkoxy group having 1 to 3 carbon atoms, and may be the same or different from each other. R ¹² and R ¹³ may be the same or different from each other, p ¹² and p ¹³ represent an integer of 0 to 4, may be the same or different from each other, and q ¹² and q ¹³ are an integer of 1 to 3. And may be the same as or different from each other, where p + q ≦ 5 in the corresponding p and q.)

(In the formula, B represents a group represented by the following formula (15), (16), or (17), and R ¹⁶ , R ¹⁷ , R ^18, and R ¹⁹ are defined as R ⁹ in formula (10), (It is the same as R ¹⁰ and R ¹¹ , and the definitions of p ¹⁶ , p ¹⁷ , p ¹⁸ and p ¹⁹ are the same as p ⁹ , p ¹⁰ and p ^{11 in} formula (10).)

(In the formula, the definitions of R ²⁰ , R ²¹ , and R ²² are the same as R ⁹ , R ¹⁰ , and R ¹¹ in formula (10), and the definitions of p ²⁰ and p ²¹ are p ^{9 in} formula (10)). , P ¹⁰ , and p ¹¹ , and the definitions of q ²⁰ and q ²¹ are the same as q ⁹ , q ¹⁰ , and q ^{11 in} formula (10), and x represents an integer of 1 to 3. )

(Wherein R ² , R ³ and R ⁴ are 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 ² , R ³ and R ⁴ may be different or the same, m ² represents an integer of 0 to 3 and n ² represents an integer of 1 to 3)

(Wherein n ⁴ represents an integer of 1 to 3)

  Among these, the polynuclear phenol compound (e) represented by the above formula (2) and the polynuclear phenol compound (g) corresponding to the addition compound represented by the above formula (4) are preferable. The polynuclear phenol compound (e) is preferable because it can compatibilize the compound (a) and the epoxy compound (b) and is excellent in reactivity. The polynuclear phenol compound (g) is preferable because a cured product having low water absorption and excellent water resistance can be obtained.

In the polynuclear phenol compound (e), m ² is preferably an integer of 1 to 3, more preferably 1. When m ² is an integer of 1 to 3, the substituent R ² is preferably bonded to the para position with respect to the hydroxyl group of the benzene ring. R ² is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group, or an aralkyl group.

  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.

  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 aryl group include a phenyl group, a naphthyl group, and a biphenyl group. Examples of the aralkyl group include a benzyl group, an α-methylbenzyl group, an α, α′-dimethylbenzyl group, and the like.

  The cycloalkyl group having 5 to 10 carbon atoms is preferably a cyclohexyl group.

The polynuclear phenol compounds (e) and (f) can be prepared 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 ^{2 in the} formula (2)). , N ³ ) in the formula (3) can be obtained as a condensate represented by an integer of 0 or more. Here, R is a substituent represented by any of R ² , R ³ and R ⁴ 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 hours. The method of making it react for 10 hours is mentioned. At this time, although depending on the reaction conditions, the polynuclear phenol compound (f) represented by the following formula (3) produced as a by-product by controlling the mixing ratio of R-substituted phenol or phenol and aldehydes The production amount of can be controlled.

(In the formula, R ² , R ³ and R ⁴ are the same as defined in formula (2), m ³ represents an integer of 0 to ³ , and n ³ 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 too little, the content of polynuclear phenol compounds (f) consisting of 6 or more phenolic aromatic rings will increase. To do. When the content of the polynuclear phenol compound (e) component in the obtained condensate is too small, the unreacted raw material and the polynuclear phenol compound (f) can be removed by a method such as distillation or reprecipitation.

  In the present embodiment, the ratio (e / (e + f)) of the polynuclear phenol compound (e) to the total of the polynuclear phenol compounds (e) and (f) is preferably 40% by mass or more, and 50% by mass. More preferably, it is more preferably 60% by mass or more.

The reason why the content (e / (e + f)) of the polynuclear phenol compound (e) is preferably 40% by mass or more will be described based on the structure of the polynuclear phenol compound (f).
In formula (3), when n ³ is 0, a decrease in the reactivity of the photosensitive resin composition can be suppressed, so the content (e / (e + f)) of the polynuclear phenol compound (e) is 40% by mass or more. It is preferable. When n ³ is 4 or more in formula (3), it is possible to reduce the remaining 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 (e / (e + f)) of a polynuclear phenol compound (e) is 40 mass% or more.

  Among the commercially available products, preferred examples of the polynuclear phenol compound (e) include a novel molecular weight distribution intensive novolak resin “PAPS” (trade name, manufactured by Asahi Organic Materials Industries Co., Ltd.).

  Specific examples of the R-substituted phenol used for the synthesis of the polynuclear phenol compound (e) include phenol, p-cresol, m-cresol, p-ethylphenol, m-ethylphenol, p-propylphenol, m-propylphenol, p-isopropylphenol, m-isopropylphenol, pt-butylphenol, mt-butylphenol, p-sec-butylphenol, m-sec-butylphenol, pt-amylphenol, mt-amylphenol, p- Phenylphenol, m-phenylphenol, p-cumylphenol, p- (α-methylbenzyl) phenol, m- (α-methylbenzyl) phenol, p-cyclohexylphenol, p-methoxyphenol, m-methoxyphenol, p -Chloro Phenol, m-chlorophenol, catechol, resorcinol, hydroquinone and the like can be mentioned.

The polynuclear phenol compounds (g) and (h) can be obtained by conducting 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 mixing ratio of dicyclopentadiene and phenol to be used, the amount of various polynuclear phenol compounds (h) represented by the following formula (5) generated as a by-product can be controlled. it can.

(In the formula, n ⁵ represents 0 or an integer of 4 or more.)

  In the present embodiment, the content ratio (g / (g + h)) of the polynuclear phenol compound (g) to the total of the polynuclear phenol compounds (g) and (h) 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 (g / (g + h)) of the polynuclear phenol compound (g) is preferably 40% by mass or more will be described based on the structure of the polynuclear phenol compound (g).
In the formula (5), when n ⁵ is 0, a decrease in the reactivity of the photosensitive resin composition can be suppressed, so the content (g / (g + h)) of the polynuclear phenol compound (g) is 40% by mass or more. It is preferable.
When n ⁵ is 4 or more in the formula (5), the remaining of unreacted phenolic hydroxyl groups 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 (g / (g + h)) of a polynuclear phenol compound (g) is 40 mass% or more.

  Among the commercially available products, preferred examples of the polynuclear phenol compound (g) include Nisseki special phenol resin “DPP-6125” (trade name, manufactured by Nippon Petrochemical Co., Ltd.).

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

It is preferable that the photosensitive resin composition of this embodiment contains the said compound (a), an epoxy resin (b), and an energy ray sensitive cationic polymerization initiator (c).
The energy ray-sensitive cationic polymerization initiator (c) in the present embodiment refers to a compound capable of generating a substance that initiates cationic polymerization by energy ray irradiation. Preferable examples include onium salts that generate a Lewis acid by irradiation.

Examples of such onium salts include Lewis acid diazonium salts, Lewis acid iodonium salts, Lewis acid sulfonium salts, etc., and these cation moieties are aromatic diazonium, aromatic iodonium and aromatic sulfonium, respectively. The anion moiety is composed of BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , [BX ₄ ] ⁻ (wherein X represents a phenyl group substituted with at least two fluorine or trifluoromethyl groups) and the like. Onium salts prepared.

  Specifically, boron difluoride phenyldiazonium salt, phosphorus hexafluoride diphenyliodonium salt, antimony hexafluoride diphenyliodonium salt, arsenic hexafluoride tri-4-methylphenylsulfonium salt, antimony tetrafluoride Tri-4-methylphenylsulfonium salt, tetrakis (pentafluorophenyl) boron diphenyliodonium salt, acetylacetone aluminum salt and orthonitrobenzylsilyl ether mixture, phenylthiopyridium salt, phosphorus hexafluoride allene-iron complex, etc. It is done.

  As commercially available products, “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 Co., Ltd.), "UVI-6990" (trade name, manufactured by Dow Chemical Company), "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. As the energy ray-sensitive cationic polymerization initiator (c), those mentioned above may be used alone or in combination of two or more.

  In this embodiment, it is also possible to use a vinyl ether compound in combination. Of these, a hydroxyl group-containing vinyl ether compound is preferred.

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

  Examples of the hydroxyl group-containing vinyl ether compound include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexanediol monovinyl ether, 9-hydroxynonyl vinyl ether, propylene glycol monovinyl ether, neopentyl glycol monovinyl ether, glycerol divinyl ether, glycerol. Monovinyl ether, Trimethylolpropane divinyl ether, Trimethylolpropane monovinyl ether, Pentaerythritol monovinyl ether, Pentaerythritol divinyl ether, Pentaerythritol trivinyl ether, Diethylene glycol monovinyl ether, Triethylene glycol monovinyl ether, Tet Ethylene glycol monomethyl ether, tricyclodecane diol monovinyl ether, tricyclodecanedimethanol monovinyl ether and the like.

  Furthermore, in this embodiment, an oxetane compound can be used in combination. Examples of such oxetane compounds 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 It is done. Moreover, in this embodiment, the oxetane compound which has a hydroxyl group can also be used, and the compound represented by following formula (19) is mentioned.

(In the formula, R ²⁰ represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group or other alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, or furyl. R ²¹ represents an alkylene group having 1 to 6 carbon atoms such as methylene, ethylene, propylene, butylene, or oxyethylene, oxypropylene in which an ether is bonded to an alkylene group having 1 to 6 carbon atoms, Represents an oxyalkylene group such as oxybutylene.)

Of these, R ²⁰ is preferably a lower alkyl group, particularly preferably an ethyl group. R ²¹ is preferably a methylene group.

  In the photosensitive resin composition of the present embodiment, another polymerization initiator that generates a substance that initiates cationic polymerization by heating can be used in combination with the polymerization initiator (c). Specific examples of 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, other compounds exhibiting cationic polymerizability can be added to such an extent that the curability and film physical properties at the time of curing are not adversely affected. As these compounds, for example, low molecular weight epoxy compounds other than those described above can be used as a diluent. Further, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiro orthoester compound, or the like can be used.

  The photosensitive resin composition of the present embodiment further includes (meth) acrylate monomers and oligomers, vinyl (meth) acrylate, and the like for the purpose of accelerating curability with respect to energy rays (improvement of sensitivity) as necessary. You may add a radically polymerizable compound, a photo radical initiator, etc. Among these, in particular, a vinyl acrylate compound having both a vinyl group and an acrylate group in one molecule has a low viscosity and a cationic polymerizability, so that the viscosity can be lowered while maintaining high sensitivity. It is an effective diluent for use in 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, slip agents, etc. Can also be added. Of these, when reducing moisture permeability, it is effective to add a fine inorganic filler and a silane coupling agent.

  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. These 1 type can be used individually or in combination of 2 or more types.

  The silane coupling agent is an alkoxysilane compound having a reactive group such as an epoxy group, a carboxyl group, or a methacryloyl group. Specifically, γ-glycidoxypropyltrimethoxysilane, trimethoxysilylbenzoic acid, γ- Examples include methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. These are used alone or in combination of two or more. be able to.

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

  In the photosensitive resin composition of the present embodiment, the content of the compound (a) having one or more oxetanyl groups and vinyl ether groups in one molecule is preferably 5 to 70% by mass, more preferably 10 to 10% by mass. 40% by mass. By setting the content to 5% by mass or more, the effect of improving the conversion rate of the epoxy group by the vinyl ether compound is excellent, so that the residual unreacted epoxy group can be reduced. Moreover, since the hardness of hardened | cured material can be made high by setting it as 70 mass% or less content, sufficient mechanical characteristics of hardened | cured material can be acquired.

  Content of the compound (b) which has at least 1 or more epoxy group in 1 molecule in the photosensitive resin composition becomes like this. Preferably it is 25-90 mass%, More preferably, it is 50-70 mass%. By setting the content to 25% by mass or more, the hardness of the cured product can be increased, so that sufficient mechanical properties of the cured product can be obtained. Moreover, since content of a vinyl ether compound increases and it is excellent in the conversion rate improvement effect of an epoxy group by setting it as content of 90 mass% or less, the residue of an unreacted epoxy group can be reduced.

  The content of the polynuclear phenol compound (d) in the photosensitive resin composition is preferably 0.1 to 40% by mass, more preferably 0.5 to 20% by mass. By setting the content to 0.1% by mass or more, the reactivity can be increased, so that residual unreacted epoxy groups can be reduced. Moreover, since it can suppress that a crosslinked structure becomes excessive by setting it as content of 40 mass% or less, the softness | flexibility of hardened | cured material can be made favorable.

  The content of the energy ray sensitive cationic polymerization initiator (c) in the photosensitive resin composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 8% by mass. By setting the content to 0.1% by mass or more, a sufficient amount of the active cationic substance generated by energy beam irradiation is obtained, and sufficient curability can be obtained. Further, by setting the content to 10% by mass or less, it is economically preferable because an expensive initiator need not be used excessively, the light transmittance does not decrease, and the film bottom is sufficiently cured. Is preferable.

  The content of the fine particle inorganic filler is preferably 0 to 70% by mass, more preferably 0.1 to 60% by mass in the photosensitive resin composition. Moreover, in the photosensitive resin composition, the content of the silane coupling agent is preferably 0 to 70% by mass, and more preferably 0.1 to 60% by mass.

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

  As the colorant used in the present embodiment, various organic pigments and inorganic pigments can be used. 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; iron oxide, permanent brown, and para Brown pigments such as brown; Red pigments 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, Man Purple, first bilet, methyl violet lake, indanthrene brilliant violet, dioxazine violet, etc .; ultramarine, bitumen, cobalt blue, alkali blue lake, metal-free phthalocyanine blue, copper phthalocyanine blue, indanthrene blue and Blue pigments such as indigo; green pigments such as chromium green, chromium oxide, emerald green, naphthol green, green gold, acid green lake, malachite green lake, phthalocyanine green, and polychlorobrom copper phthalocyanine; other fluorescent pigments, metal powder Examples thereof include pigments and extender pigments. Content of these pigments in the photosensitive resin composition of this embodiment becomes like this. Preferably it is 1-50 mass%, More preferably, it is 5-25 mass%.

  If necessary, a pigment dispersant may be used for the pigment, for example, higher fatty acid salts, alkyl sulfates, alkyl ester sulfates, alkyl sulfonates, sulfosuccinates, naphthalene sulfonates, alkyl phosphates. , Activators such as polyoxyalkylene alkyl ether phosphates, polyoxyalkylene alkyl phenyl ethers, glycerin esters, sorbitan esters, polyoxyethylene fatty acid amides; styrene, styrene derivatives, vinyl naphthalene derivatives, acrylic acid, acrylic acid derivatives, maleic Examples thereof include block copolymers or random copolymers composed of two or more monomers selected from acids, maleic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid and fumaric acid derivatives, and salts thereof.

  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.

  Furthermore, it can be set as the photosensitive coating agent containing the photosensitive resin composition of this embodiment. Since the photosensitive resin 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 and substrates that are required to be cured at high speed without heating. Used for. An example of this is an anti-reflection coating forming material used for flat panel displays (FPD), etc., and after coating and curing on a substrate, a film having a refractive index of 1.4 or less is formed. In order to achieve this, the photosensitive resin composition of the present embodiment is obtained by containing porous fine particles having voids.

  Examples of such porous fine particles include silica particles having an average particle diameter of 5 nm to 1 μm. From the viewpoint of transparency of the photosensitive resin composition, silica particles having an average particle diameter of 5 to 100 nm are preferable. 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 porous fine particles in the range of 10 to 70 parts by mass with respect to 100 parts by mass of the photosensitive resin composition, and using a homogenizer or the like. It is preferable to disperse uniformly in the inside.

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

  Moreover, the photosensitive resin composition of this embodiment can be hardened in a short time by apply | coating to a base material etc. to make a thin film, and performing an energy ray irradiation and a heating to this thin film. For curing of the photosensitive resin composition, energy beam irradiation and heating may be used in combination, or only one of them may be used. The photosensitive resin composition of the present embodiment can be sufficiently put into practical use without containing a solvent or the like, but may be diluted with a solvent or the like for viscosity adjustment, or a sol containing porous fine particles or the like. It is good also as a form. When diluted with a solvent, etc., and when used in the form of a sol containing porous fine particles, etc., in order to volatilize the solvent component in advance, before light irradiation, it is about several minutes at 50 to 150 ° C. Heating may be performed. Moreover, hardening can be further accelerated | stimulated by heating similarly after exposure. Furthermore, since the photosensitive resin composition of the present embodiment is cured by light irradiation, it can be used as a photosensitive adhesive. The photosensitive adhesive containing the photosensitive resin composition of the present embodiment can be used in the above-described form and the like, and can exhibit excellent adhesiveness without being inhibited by curing due to humidity.

  Furthermore, it can be set as the semiconductor sealing material containing the photosensitive resin composition of this embodiment. The semiconductor sealing material in the present embodiment can be used as a sealing material for OLED display elements and the like. FIG. 1 is a cross-sectional view of one aspect of an OLED display element using the semiconductor encapsulant of this embodiment. In the OLED display element A, a hole injection electrode 2, a hole transport layer 3, a light emitting layer 4, and an electron injection electrode 5 are sequentially formed on a substrate 1 and then sealed with the semiconductor sealing material 6 of this embodiment. Then, the substrate 7 can be formed by a method of pasting together. Such full sealing with a solid film is a particularly effective method when a flexible material is used as the base materials 1 and 7.

  As a method of forming a multilayer structure in which the hole injection electrode 2, the hole transport layer 3, the light emitting layer 4, and the electron injection electrode 5 are sequentially laminated on the substrate 1, a resistance heating vapor deposition method that is a known method, An ion beam sputtering method, an ink jet method that can be formed at normal pressure, a printing method, or the like can be used. Next, the method for applying the semiconductor encapsulant of the present embodiment on the multilayer structure is not particularly limited as long as the semiconductor encapsulant can be uniformly applied, but for example, printing such as screen printing or flexographic printing. Examples thereof include a method according to the method and a method of applying using a dispenser.

  After bonding the base material 7 to the semiconductor sealing material 6 of the present embodiment, the semiconductor sealing material 6 can be cured by irradiating energy rays such as light from the base material 7 side or the base material 1 side. . Any energy ray may be used as long as it cures the semiconductor sealing material 6, and examples thereof include light and radiation. The light source that can be used here is not particularly limited as long as it can cure the semiconductor sealing material 6 within a predetermined working time. For example, a light source that can irradiate light having a wavelength of ultraviolet light or visible light is used. Can do. Specific examples include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a metal halide lamp, and an electrodeless discharge lamp. Thus, the semiconductor sealing material of this embodiment can be used for sealing various semiconductor elements including OLED display elements. In particular, since the semiconductor encapsulant of the present embodiment can produce a cured product at room temperature when it is used as a cured product, it prevents thermal deterioration and thermal deformation of the substrate and elements found in conventional thermosetting resins. Can do. Further, since it has high adhesion to a substrate or an element, it can be preferably used for sealing a semiconductor element of a precision device such as an FPD, and particularly preferably used for sealing an OLED display element.

  Hereinafter, examples of embodiments of the present invention will be specifically described. In addition, this invention is not limited to a following example.

1. Production of photosensitive resin composition Production of the photosensitive resin composition was performed by the following method.

[Example 1]
As a compound (a) having one or more oxetanyl groups and vinyl ether groups in one molecule, 15% by mass of 3-ethyl-3-[(vinyloxy) methyl] oxetane (manufactured by Maruzen Petrochemical Co., Ltd.), As an epoxy compound (b) having one or more epoxy groups, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 60% by mass, 15% by mass of monohydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) and “CPI-100P” having a sulfonium salt content of 50% by mass as an energy ray-sensitive cationic polymerization initiator (c) 5% by mass) and phenol as polynuclear phenol compound (d) 5 mass% of p-tert-butyl-phenol novolak resin “PAPS-PTBPN” (trade name, manufactured by Asahi Organic Materials Co., Ltd .; weight average molecular weight 890) having a content of ˜5 nuclei of 50 mass% is sufficiently mixed As a result, a photosensitive resin composition was obtained.

[Example 2]
As a compound (a) having one or more oxetanyl groups and vinyl ether groups in one molecule, 15% by mass of 3-ethyl-3-[(vinyloxy) methyl] oxetane (manufactured by Maruzen Petrochemical Co., Ltd.), As an epoxy compound (b) having one or more epoxy groups, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 60% by mass, 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane “OXT-221” (trade name, manufactured by Toagosei Co., Ltd.) 15% by mass, an energy ray-sensitive cationic polymerization initiator ( c) “CPI-100P” having a sulfonium salt content of 50 mass% (trade name, SunApp P-tert-butyl-phenol novolak resin “PAPS-PTBPN” (trade name, Asahi Yu) with 5% by mass of polynuclear phenol compound (d) and 50% by mass of phenol 3-5 nuclei as polynuclear phenol compound (d) A photosensitive resin composition was obtained by sufficiently mixing 5% by mass) (manufactured by Kogyo Kogyo Co., Ltd.).

[Example 3]
As a compound (a) having one or more oxetanyl groups and vinyl ether groups in one molecule, 30% by mass of 3-ethyl-3-[(vinyloxy) methyl] oxetane (manufactured by Maruzen Petrochemical Co., Ltd.), As an epoxy compound (b) having one or more epoxy groups, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 60% by mass, As energy ray-sensitive cationic polymerization initiator (c), 5% by mass of “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) having a sulfonium salt content of 50% by mass, and phenol 3 as a polynuclear phenol compound (d) P-tert-butyl-phenol novolak having a content of ˜5 nuclei of 50% by mass Fat "PAPS-PTBPN" (trade name, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) 5 wt%, to obtain a photosensitive resin composition by mixing sufficiently.

[Example 4]
As a compound (a) having at least one oxetanyl group and one vinyl ether group in one molecule, 30% by mass of 3-ethyl-3-[(vinyloxy) methyl] oxetane (manufactured by Maruzen Petrochemical Co., Ltd.) As an epoxy compound (b) having one or more epoxy groups, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 65% by mass, As an energy ray-sensitive cationic polymerization initiator (c), a photosensitive resin is sufficiently mixed with 5% by mass of “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) having a sulfonium salt content of 50% by mass. A composition was obtained.

[Example 5]
As a compound (a) having at least one oxetanyl group and one vinyl ether group in one molecule, 5% by mass of 3-ethyl-3-[(vinyloxy) methyl] oxetane (manufactured by Maruzen Petrochemical Co., Ltd.), As an epoxy compound (b) having one or more epoxy groups, 90% by mass of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) As an energy ray-sensitive cationic polymerization initiator (c), a photosensitive resin is sufficiently mixed with 5% by mass of “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) having a sulfonium salt content of 50% by mass. A composition was obtained.

[Example 6]
As a compound (a) having one or more oxetanyl groups and vinyl ether groups in one molecule, 65% by mass of 3-ethyl-3-[(vinyloxy) methyl] oxetane (manufactured by Maruzen Petrochemical Co., Ltd.), As an epoxy compound (b) having one or more epoxy groups, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 30% by mass, As an energy ray-sensitive cationic polymerization initiator (c), a photosensitive resin is sufficiently mixed with 5% by mass of “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) having a sulfonium salt content of 50% by mass. A composition was obtained.

[Comparative Example 1]
As an epoxy compound (b) having one or more epoxy groups in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 65 mass And 15% by mass of monohydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) and 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane “OXT-221” (trade name) , Manufactured by Toa Gosei Co., Ltd.) 15% by mass, and as an energy ray-sensitive cationic polymerization initiator (c), 5% by mass of “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) having a sulfonium salt content of 50% by mass % Was sufficiently mixed to obtain a photosensitive resin composition.

[Comparative Example 2]
As an epoxy compound (b) having one or more epoxy groups in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 60 mass And 15% by mass of monohydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) and 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane “OXT-221” (trade name) , Manufactured by Toa Gosei Co., Ltd.) 15% by mass, and as an energy ray-sensitive cationic polymerization initiator (c), 5% by mass of “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) having a sulfonium salt content of 50% by mass And a polynuclear phenol compound (d) having a content of phenol 3-5 nuclei of 50 mass% tert- butyl - phenol novolak resin "PAPS-PTBPN" (trade name, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) 5 wt%, to obtain a photosensitive resin composition by mixing sufficiently.

[Comparative Example 3]
As an epoxy compound (b) having one or more epoxy groups in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 65 mass , 30% by mass of monohydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) and “CPI-100P” (trade name) having a sulfonium salt content of 50% by mass as an energy ray-sensitive cationic polymerization initiator (c) (San Apro Co., Ltd.) 5% by mass was sufficiently mixed to obtain a photosensitive resin composition.

[Comparative Example 4]
As an epoxy compound (b) having one or more epoxy groups in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 60 mass , 30% by mass of monohydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) and “CPI-100P” (trade name) having a sulfonium salt content of 50% by mass as an energy ray-sensitive cationic polymerization initiator (c) : Manufactured by San Apro Co., Ltd.) 5% by mass, and p-tert-butyl-phenol novolac resin “PAPS-PTBPN” (trade name, 50% by mass of phenol 3-5 nuclei as polynuclear phenol compound (d)) Asahi Organic Materials Co., Ltd.) 5% by mass, and fully mixed with photosensitive resin It was obtained Narubutsu.

[Comparative Example 5]
As an epoxy compound (b) having one or more epoxy groups in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 60 mass %, 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane “OXT-221” (trade name, manufactured by Toagosei Co., Ltd.), and energy ray-sensitive cationic polymerization As the initiator (c), 5% by mass of “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) having a sulfonium salt content of 50% by mass, and 3-5 nuclei of phenol as the polynuclear phenol compound (d) P-tert-butyl-phenol novolac resin “PAPS-PTBPN” with a content of 50% by mass (product) To obtain a photosensitive resin composition by mixing sufficiently with Asahi Organic Chemicals Industry Co., Ltd.) 5 wt%, the.

2. Evaluation method Evaluation of the photocurability of the photosensitive resin composition and the mechanical properties of the cured product were performed by the following methods.
<Monomer conversion>
On the biaxially stretched polypropylene (OPP) film which surface-treated, the photosensitive resin composition of each Example and each comparative example was apply | coated uniformly by thickness 12 micrometers using the bar coater. Then, the said film was exposed so that it might become the integrated light quantity of 40 mJ / cm < ² > using the ultraviolet irradiation device (made by Sen Engineering Co., Ltd.) provided with the high pressure mercury lamp. The reaction conditions for light irradiation were as follows: temperature: 23 ° C., humidity: 60% RH.
As for the conversion rate in the photosensitive resin composition, each absorption before and after ultraviolet irradiation of an epoxy group, a vinyl group, and an oxetanyl group was measured by FT-IR (“Nicolet 6700”, manufactured by Thermo Fisher Scientific Co., Ltd.). The average reaction rate was calculated from the reduction rate of these functional groups and used as the addition rate. A monomer addition rate of 60% or more was judged to be at least a practically acceptable level.
◎: Monomer conversion 90% or more ○: Monomer conversion 75% or more, less than 90% Δ: Monomer conversion 60% or more, less than 75% ×: Monomer conversion 60% or less

<Surface tackiness>
On the glass substrate, the photosensitive resin composition of each Example and each comparative example was uniformly apply | coated by 12 micrometers in thickness using the bar coater. Then, the said glass substrate was exposed so that it might become the integrated light quantity of 40 mJ / cm < ² > using the ultraviolet irradiation device (made by Sen Engineering Co., Ltd.) provided with the high pressure mercury lamp. The environment during curing was temperature: 23 ° C. and humidity: 60% RH.
○: Evaluation was made by touching the coating film with a finger 30 seconds after completion of exposure. There is no stickiness and fingers do not stick.
X: Evaluation was performed by touching the coating film with a finger 30 seconds after completion of exposure. There is stickiness and fingers stick.

<Flexibility>
On the biaxially stretched polypropylene (OPP) film which surface-treated, the photosensitive resin composition of each Example and each comparative example was apply | coated uniformly by thickness 12 micrometers using the bar coater. Then, the said film was exposed using the ultraviolet irradiation device (made by Sen Engineering Co., Ltd.) provided with the high pressure mercury lamp so that it might become the integrated light quantity of 40 mJ / cm < ² >, and hardened | cured material was obtained. Flexibility was judged visually by performing a 180-degree bending test of the cured product using a cylindrical mandrel tester “BD2000” (manufactured by Co-Tech Co., Ltd.) having a diameter of 10 mmφ.
○: No change ×: Cracks or other cracks occurred

3. Evaluation Results Table 1 shows the list of compound names used in each Example and each Comparative Example, and Table 2 and Table 3 show the evaluation results of each Example and each Comparative Example.

  As shown in Tables 2 and 3, it was confirmed that the photosensitive resin compositions of Examples 1 to 6 were excellent in any of the monomer addition rate, the surface tack test, and the flexibility test. On the other hand, it was confirmed that the photosensitive resin compositions of Comparative Examples 1 to 5 were defective in at least one of the monomer addition rate, the surface tack test, and the flexibility test. As mentioned above, it was shown that the photosensitive resin composition of this embodiment is excellent in curability (surface tackiness and monomer conversion rate) and flexibility in the air upon irradiation with energy rays.

  Since the photosensitive resin composition of the present invention can be made into a cured product having excellent curability (surface tack and monomer conversion) and flexibility in the atmosphere by irradiation with energy rays, the paint, adhesive, ink, Film coating, more specifically, UV ink for inkjet, sealing material for display panels such as liquid crystal and organic EL, adhesive for bonding optical disks, CD, DVD, and Blu-ray Disc (Blu- ray (registered trademark) Disc) 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.

A OLED display elements 1 and 7 Base material 2 Hole injection electrode 3 Hole transport layer 4 Light emitting layer 5 Electron injection electrode 6 Semiconductor sealing material

Claims (11)

The photosensitive resin composition containing the compound (a) represented by following formula (1).

(Wherein R ¹ represents an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, an aryl group, or an aralkyl group, m ¹ Represents an integer of 2 to 5, and n ¹ represents an integer of 0 to 20.) An epoxy compound (b) having at least one epoxy group in the molecule;
The photosensitive resin composition according to claim 1, further comprising an energy ray sensitive cationic polymerization initiator (c). Contains 3-5 phenolic aromatic rings,
All of the ortho positions of the phenolic hydroxyl group of the phenolic aromatic ring are not substituted with any of a methylol group, an alkyl group having 4 or more carbon atoms, or a cycloalkyl group, and
The photosensitive resin composition according to claim 1 or 2, further comprising a polynuclear phenol compound (d) having two or more phenolic aromatic rings in which at least one ortho position of the phenolic hydroxyl group is unsubstituted. . 5 to 70% by mass of the component (a),
25 to 90% by mass of the component (b),
0.1 to 10% by mass of the component (c),
The photosensitive resin composition of Claim 2 or 3 containing this.   The photosensitive resin composition of Claim 3 or 4 which further contains the said (d) component 0.1-40 mass%. The component (d) further includes a polynuclear phenol compound (e) represented by the following formula (2) and a polynuclear phenol compound (f) represented by the following formula (3), and
The photosensitivity as described in any one of Claims 3-5 whose ratio (e / (e + f)) of the said (e) component with respect to the sum total of the said (e) component and the said (f) component is 40 mass% or more. Resin composition.

(Wherein R ² , R ³ and R ⁴ are 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 ² , R ³ and R ⁴ may be different or the same, m ² represents an integer of 0 to 3 and n ² represents an integer of 1 to 3)

(In the formula, R ² , R ³ and R ⁴ are the same as defined in formula (2), m ³ represents an integer of 0 to ³ , and n ³ represents 0 or an integer of 4 or more.) The (d) component is a polynuclear phenol compound (g) represented by the following formula (4):
A polynuclear phenol compound (h) represented by the following formula (5), and
The photosensitivity as described in any one of Claims 3-5 whose ratio (g / (g + h)) of the said (g) component with respect to the sum total of the said (g) component and the said (h) component is 40 mass% or more. Resin composition.

(Wherein n ⁴ represents an integer of 1 to 3)

(In the formula, n ⁵ represents 0 or an integer of 4 or more)   The photosensitive inkjet ink containing the photosensitive resin composition as described in any one of Claims 1-7, and a coloring agent.   The photosensitive adhesive agent containing the photosensitive resin composition as described in any one of Claims 1-7.   The photosensitive coating agent containing the photosensitive resin composition as described in any one of Claims 1-7.   The semiconductor sealing material containing the photosensitive resin composition as described in any one of Claims 1-7.

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