JP2011001420A - Photosensitive resin composition, photosensitive inkjet ink, 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 photocurable property (surface curing property and inside curing property) that curing is not suppressed by humidity and a high storage stability of which the cured product has a mechanical characteristic being excellent in toughness and flexibility and has an excellent film physical property in which a high adhesion property and suppression of curling of a base material are further made compatible.SOLUTION: The photosensitive resin composition includes 5-80 mass% of compound (a) represented by formula (1) (wherein Rrepresents 1-5C alkyl, 5-10C cycloalkyl, 1-5C alkoxy, halogen, hydroxyl, aryl or aralkyl; m1 represents an integer of 2-5; and nrepresents an integer of 0-20), 1-40 mass% of a branched compound (b) having two or more of hydroxyl groups in one molecule and having a weight-average molecular weight of 1,000 or more and 5-90 mass% of a reactive organic silicone compound (c).

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 radically 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-based release paper, photoresists, sealants for electronic components, and the like (for example, Non-patent document 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 (for example, 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, for example, Patent Documents 2 and 3). Attempts have also been made to use polyfunctional vinyl ether compounds (see, for example, Patent Documents 4 and 5). Furthermore, an attempt has been made to improve the reactivity and control the mechanical properties of the cured product by using a specific phenol resin as a material in which an epoxy compound and a vinyl ether compound are used in combination (see, for example, Patent Document 6).

  On the other hand, 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, for example, Patent Document 7). Furthermore, an attempt has been made to use all of an epoxy compound, a vinyl ether compound, an oxetane compound, and a hydroxyl group-containing compound (for example, see Patent Document 8).

US Pat. No. 3,794,576 JP-A-6-298911 JP-A-9-328634 Japanese Patent No. 2667934 Japanese Patent Laid-Open No. 4-120182 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, a general cationic curable material has a slower reaction rate than a radical curable material. Therefore, a device for increasing the reaction rate has been devised, but there is a problem that stability during storage is lowered. A material having a low stability during storage and a large increase in viscosity makes it difficult to obtain a stable ejection performance, particularly when used as an inkjet ink. And general cationic curable material tends to cause reaction inhibition 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.

  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.

  The techniques disclosed in Patent Documents 2 and 3 have a problem that the hardness of the cured product is extremely lowered due to copolymerization with a highly flexible vinyl ether compound, and sufficient mechanical properties cannot be obtained. The techniques disclosed in Patent Documents 4 and 5 have been made for the purpose of improving this problem, but the effect is insufficient.

  The technique disclosed in Patent Document 6 is susceptible to reaction inhibition by moisture, and there is a problem that the hardness of the cured product is lowered under high humidity, and sufficient mechanical properties cannot be obtained.

  In the technique disclosed in Patent Document 7, since the oxetane compound is not copolymerized with the epoxy compound, the effect of improving the reactivity of the epoxy compound cannot be obtained. Moreover, the oxetane compound is not sufficiently reactive, and a large amount of unreacted components remain. As a result, there is a problem that a cured product having sufficient mechanical properties cannot be obtained, and the application is limited.

  In the technique disclosed in Patent Document 8, since a vinyl ether compound is not copolymerized with an oxetane compound, a homopolymer of an oxetane compound having low flexibility is by-produced. As a result, the flexibility of the cured product is reduced and cracks are likely to occur. Further, when a large amount of oxetane compound is used, there is a problem that the use is limited because the adhesion to a resin substrate such as acrylic or a glass substrate is lowered.

  The present invention has been made in view of the above circumstances, has excellent photocurability (surface curability, internal curability) and high storage stability without curing inhibition due to humidity, and the cured product has toughness. It is an object of the present invention to provide a photosensitive resin composition having excellent flexibility and mechanical properties, and having excellent film properties that achieve both high adhesion and suppression of substrate curl.

  As a result of intensive studies to solve the above problems, the present inventor has obtained a compound having an oxetanyl group and a vinyl ether group in one molecule, a compound having two or more hydroxyl groups in one molecule, a reactive organosilicon compound, The present inventors have found that a photosensitive resin composition containing, achieves the object, and has made the present invention.

（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］
前記樹枝状化合物（ｂ）は、ポリエステルポリオールデンドリマーである、［１］の感光性樹脂組成物。
［３］
前記樹枝状化合物（ｂ）が下記式（２）で表される化合物である、［１］又は［２］の感光性樹脂組成物。

（式中、Ｘ^１及びＸ^２は、それぞれ独立に、水素原子、下記式（３）又は下記式（４）で表される置換基を表し、ｎ^２は１〜１０の整数を表す。）

（式中、Ｒ^２は、炭素数１〜３０のアルキル基、シクロアルキル基、アリール基、又はアラルキル基を表す。）
［４］
前記反応性有機ケイ素化合物（ｃ）が、下記式（５）で表されるアルコキシシラン、又は下記式（６）で表されるシランカップリング剤である、［１］〜［３］のいずれか一つの感光性樹脂組成物。

（式中、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立に、炭素数１〜２０のアルキル基、シクロアルキル基、アリール基、又はアラルキル基を表し、ｎ^３は２以下の整数を表す。）

（式中、Ｒ^７はエチレン基又はプロピレン基を表し、Ｙは有機官能基を表し、Ｚは加水分解性基を表し、ｎ^４は０〜１の整数を表す。）
［５］
カチオン重合性化合物３０〜８０質量％を、さらに含む、［１］〜［４］のいずれか一つの感光性樹脂組成物。
［６］
前記カチオン重合性化合物は、分子中にエポキシ基を１つ以上有するエポキシ化合物（ｄ）である、［５］の感光性樹脂組成物。
［７］
エネルギー線感受性カチオン重合開始剤（ｅ）及び／又はエネルギー線感受性ラジカル重合開始剤（ｆ）を、合計して０．１〜１０質量％をさらに含む、［１］〜［６］のいずれか一つの感光性樹脂組成物。
［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]
5-80 mass% of compounds (a) represented by the following formula (1),
1 to 40% by mass of a dendritic compound (b) having two or more hydroxyl groups in one molecule and having a weight average molecular weight of 1,000 or more;
A photosensitive resin composition comprising 5 to 90% by mass of a reactive organosilicon compound (c).

(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]
The photosensitive resin composition according to [1], wherein the dendritic compound (b) is a polyester polyol dendrimer.
[3]
The photosensitive resin composition of [1] or [2], wherein the dendritic compound (b) is a compound represented by the following formula (2).

(Wherein, X ¹ and X ² each independently represent a hydrogen atom, a substituent represented by the following formula (3) or the following formula (4), and n ² represents an integer of 1 to 10).

(In the formula, R ² represents an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.)
[4]
Any one of [1] to [3], wherein the reactive organosilicon compound (c) is an alkoxysilane represented by the following formula (5) or a silane coupling agent represented by the following formula (6): One photosensitive resin composition.

(Wherein R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and n ³ is an integer of 2 or less. Represents.)

(In the formula, R ⁷ represents an ethylene group or a propylene group, Y represents an organic functional group, Z represents a hydrolyzable group, and n ⁴ represents an integer of 0 to 1).
[5]
The photosensitive resin composition according to any one of [1] to [4], further comprising 30 to 80% by mass of a cationic polymerizable compound.
[6]
[5] The photosensitive resin composition according to [5], wherein the cationically polymerizable compound is an epoxy compound (d) having one or more epoxy groups in a molecule.
[7]
Any one of [1] to [6], further comprising 0.1 to 10% by mass in total of the energy beam sensitive cationic polymerization initiator (e) and / or the energy beam sensitive radical polymerization initiator (f). Photosensitive resin composition.
[8]
A photosensitive inkjet ink comprising the photosensitive resin composition according to any one of [1] to [7] and a colorant.
[9]
A photosensitive adhesive comprising the photosensitive resin composition according to any one of [1] to [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].

  The present invention has excellent photocurability (surface curability, internal curability) that does not hinder curing due to humidity and high storage stability, and the cured product has mechanical properties with excellent toughness and flexibility. Furthermore, it is possible to provide a photosensitive resin composition having excellent film properties that achieves both higher adhesion and suppression of substrate curl.

It is the schematic diagram which showed an example of reaction which a dendritic compound (b) produces | generates. It is the figure which showed an example using the chain extension agent and the chain terminator in reaction which a dendritic compound (b) produces | generates. 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 is represented by the following formula (1): 5 to 80% by mass of a compound (a) having one or more oxetanyl groups and vinyl ether groups in one molecule, and in one molecule 1 to 40% by mass of a dendritic compound (b) having two or more hydroxyl groups and having a weight average molecular weight of 1000 or more, and 5 to 90% by mass of a reactive organosilicon compound (c).

(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.
Among the compounds represented by the formula (1), the compound in which n ^{1 in} the formula (1) is an integer of ¹ to 20 is represented by, for example, the compound represented by the formula (7) and the formula (8). The compound is obtained by reacting in the presence of a basic compound. A compound in which n ¹ in formula (1) is 0 can be obtained, for example, by reacting acetylene with a compound of formula (8). The reaction at this time can be performed under pressure or normal pressure.

(In the formula, m ⁷ represents an integer of 2 to 5, n ⁷ 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 ⁸ represents a methyl group or an ethyl group.)

  Specific examples of the compound represented by the formula (7) 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 (8) 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 (8) in the said method is 0.1 mol or more normally with respect to 1 mol of compounds represented by Formula (7), Preferably it is 0.2-2.0 mol. .

  The reaction temperature of the compound represented by the formula (7) and the compound represented by the formula (8) 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 (7) and the compound represented by formula (8) 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 the like, or a mixed solvent thereof.

  The usage-amount of an inert solvent is 0-500 mL normally with respect to 0.1 mol of compounds represented by Formula (7), 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 (7), 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, a compound represented by the formula (1) where n ¹ is an integer of ¹ to 20 includes a compound represented by the formula (9) and a compound represented by the formula (10). It can be obtained by reacting in the presence of a compound.

（式中、ｍ^９は２〜５の整数を表し、ｎ^９は１〜２０の整数を表す。）

(In the formula, m ⁹ represents an integer of 2 to 5, and n ⁹ represents an integer of 1 to 20.)

(In the formula, R ¹⁰ 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 (9) 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 (10) include 3-methyl-3-chloromethyloxetane, 3-ethyl-3-chloromethyloxetane, 3-ethyl-3-bromomethyloxetane, and mixtures thereof. Can be mentioned.

  The usage-amount of the compound represented by Formula (10) is 0.1 mol or more normally with respect to 1 mol of compounds represented by Formula (9), Preferably it is 0.2-2.0 mol.

  The reaction temperature of the compound represented by Formula (9) and the compound represented by Formula (10) 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 (9) and the compound represented by formula (10) is carried out according to the reaction between the compound represented by formula (7) and the compound represented by formula (8). 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 (10), Preferably it is 1.2-10 mol.

  The photosensitive resin composition of the present embodiment contains a dendritic compound (b) having two or more hydroxyl groups in one molecule and having a weight average molecular weight of 1000 or more. Hereinafter, the resinous compound (b) will be described.

  Here, the “dendritic compound” refers to a compound having a shape in which molecular chains are branched many times. With such a structure, it is possible to obtain a composition having good performance characteristics and having a viscosity low enough to be used without a solvent or by adding a very small amount of a solvent. Examples of such resinous compounds include dendrimers.

  As the structure of the dendritic compound (b), an initiator having one or more reactive groups (A) is located in the center of the dendritic compound (b), and two or more reactive groups (A) and reactive groups ( The reactive group (B) of the chain extender having B) is bonded to the reactive group (A) of the initiator, and the reactive group (A) of the chain extender is reacted with another reactive group (B ) And a dendritic structure. The dendritic structure of the dendritic compound (b) having such a structure has a possibility of elongation. A chain is formed by the reaction of the reactive group (A) of the chain extender and the reactive group (B) of another chain extender one after another, and the above dendritic structure can be further branched.

  Examples of such a dendritic compound (b) include dendrimers having the structure of FIG. FIG. 1 is a schematic diagram showing an example of a reaction in which a dendritic compound (b) is generated. FIG. 1 shows the reaction of an initiator molecule (I) having four reactive groups (A) with a chain extender (II) having two reactive groups (A) and one reactive group (B). The reaction to obtain a step dendrimer is shown. First, the reactive group (A) of the initiator molecule (I) reacts with the reactive group (B) of the chain extender (II). Thereby, a first-stage dendrimer (sometimes referred to as “first generation”) is formed. Subsequently, the reactive group (A) at the terminal of the first stage dendrimer reacts with the reactive group (B) of another chain extender (III). Thereby, a second stage dendrimer (sometimes referred to as “second generation”) is formed. By repeating this chain reaction, it is possible to obtain a dendrimer that is more branched (branched).

  Here, the reactive group (A) is not limited as long as it generates a bond by reacting with the reactive group (B). Examples of the reactive group (A) include a hydroxyl group. The reactive group (B) is not particularly limited as long as it forms a bond by reacting with the reactive group (A). For example, when the reactive group (A) is a hydroxyl group, examples of the reactive group (B) include those that can react with the reactive group (A) to form an ester bond. Specifically, when the reactive group (A) is a hydroxyl group, examples of the reactive group (B) include a carboxyl group. In this case, the hydroxyl group and the carboxyl group can react to form an ester bond.

  Although the compound used as an initiator is not specifically limited, For example, diol, triol, tetraol etc. are mentioned. The initiator may be low molecular or high molecular.

  As the diol, an aliphatic diol, an alicyclic diol, or an aromatic diol can be used, and different types may be used in combination.

  The aliphatic diol may be linear or branched.

  Examples of the linear aliphatic diol include 1,3-propanediol, 1,2-ethanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and polytetrahydrofuran. Etc. The carbon number of the linear aliphatic diol is not particularly limited, but is preferably 2 to 18 carbon atoms.

  Examples of the branched aliphatic diol include dimethylolpropane, neopentyl glycol, 2-propyl-2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 2,2,4-trimethylpentane-1,3-diol, trimethylhexane-1,6-diol 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol and the like. In the case of a branched aliphatic diol, the number of carbon atoms is not particularly limited, and a polymer such as polypropylene glycol may be used.

  Examples of the alicyclic diol include cycloform dimethanol and pentaerythritol cyclic formal such as 1,3-dioxane-5,5-dimethanol.

  Examples of the aromatic diol include 1,4-xylylene glycol and 1-phenyl-1,2-ethanediol. In addition, a reaction product of a polyfunctional phenol compound and an alkylene oxide or a derivative thereof can be used. Preferred phenolic compounds include bisphenol A, hydroquinone and resorcinol. Also preferred are ester-type diols such as neopentyl-hydroxypivalate (hydroxypivalate ester of neopentyl glycol).

  Corresponding 1,2-epoxides and α-olefin oxides can be used as substances instead of 1,2-diols. Examples of such compounds include ethylene oxide, propylene oxide, 1,2-butylene oxide, and styrene oxide.

  The triol may be either an alicyclic triol or an aromatic triol. Specific examples of the triol include trimethylolpropane, trimethylolethane, trimethylolbutane, 3,5,5-trimethyl-2,2-dihydroxymethylhexane-1-ol, and the like. Also included are triols having both primary and secondary hydroxyl groups, such as glycerol and 1,2,6-hexanetriol.

  Furthermore, in addition to alicyclic triols and aromatic triols, adducts (products resulting from addition reactions) corresponding to alkylene oxide and its derivatives can also be used.

  The tetraol may be an alicyclic tetraol or an aromatic tetraol. For example, pentaerythritol, ditrimethylolpropane, diglycerol, ditrimethylolethane and the like can be mentioned. In addition to alicyclic tetraol and aromatic tetraol, adducts corresponding to alkylene oxide and derivatives thereof can also be used.

  The chain extender is not limited as long as it reacts with the reactive group (A) of the initiator and the chain reaction proceeds. Examples of the chain extender when the reactive group (A) is a hydroxyl group include, for example, a monovalent carboxylic acid having two or more hydroxyl groups; two or more hydroxyl groups in which one or more hydroxyl groups are substituted with hydroxyalkyl And monovalent carboxylic acids having

  Specific examples of chain extenders include α, α-bis (hydroxymethyl) -propionic acid (dimethylolpropionic acid), α, α-bis (hydroxymethyl) -butyric acid, α, α, α-tris (hydroxymethyl). ) -Acetic acid, α, α-bis (hydroxymethyl) -valeric acid, α, α-bis (hydroxy) -propionic acid, α-phenylcarboxylic acid having at least two phenolic hydroxyl groups (for example, 3, 5-dihydroxybenzoic acid) and the like. Further, those in which one or two or more hydroxyl groups of the chain extender described above are substituted with hydroxyalkyl can also be used.

  Furthermore, a chain terminator can be reacted with the chain extender bound to the end of the dendritic compound (b). The chain terminator can react with the reactive group (A) such as a chain extender to form a bond, but may be a compound that does not further chain. For example, when the reactive group (A) is a hydroxyl group, a carboxyl group-containing compound capable of reacting with the hydroxyl group to form an ester is exemplified, and the type is not limited. Examples of the chain terminator include monovalent saturated carboxylic acids or saturated fatty acids, or anhydrides thereof; unsaturated fatty acids; monovalent unsaturated carboxylic acids.

  Thus, the hydroxyl group at the end of the polymer chain of the dendritic compound (b) can react with the chain terminator. The selection of the chain terminator is important in adjusting the properties of the dendritic compound (b). Therefore, the kind of chain terminator can be selected based on the use of the photosensitive resin composition of this embodiment.

The monovalent saturated carboxylic acid or saturated fatty acid may be linear or branched. Moreover, an anhydride may be sufficient. Such monovalent saturated carboxylic acid or saturated fatty acid is represented by the following formula, for example.
C _y H _{2y + 1} —COOH (wherein y represents an integer of 1 to 32)

  Examples of the monovalent saturated carboxylic acid or saturated fatty acid include acetic acid, propionic acid, butyric acid, valeric acid, isobutyric acid, trimethylacetic acid, caproic acid, caprylic acid, heptanoic acid, capric acid, pelargonic acid, lauric acid, myristic acid, Examples include palmitic acid, stearic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, isostearic acid, isononanoic acid, and 2-ethylhexanoic acid.

  Examples of the unsaturated fatty acid include oleic acid, ricinoleic acid, linoleic acid, linolenic acid, erucic acid, soybean fatty acid, flaxseed fatty acid, dehydrated castor fatty acid, tall oil fatty acid, tung oil fatty acid, sunflower fatty acid, safflower fatty acid and the like. .

  Examples of the monovalent unsaturated carboxylic acid include acrylic acid and methacrylic acid.

  Examples of the formation process of the dendritic compound (b) include a method in which an initiator is reacted with a chain extender at a temperature of 0 to 300 ° C., for example, 50 to 280 ° C., preferably 100 to 250 ° C. Thereafter, the obtained reaction product can be reacted with a chain terminator.

  The molar ratio of the initiator hydroxyl group to the chain extender (initiator hydroxyl group: chain extender) is 1: 1 to 2000 from the viewpoint of advancing the reaction for extending the chain while suppressing the formation of by-products. The range of 1 is preferable, and the range of 1: 1 to 1100: 1 is more preferable.

  During the reaction, water is by-produced, but it is preferable to remove this water continuously. Examples of the method for continuously removing water include injection of an inert gas into a reaction vessel, vacuum distillation, azeotropic distillation, and the like.

Although the said reaction can be performed without using a catalyst, you may use a normal esterification catalyst. Specifically, Bronsted acids such as naphthalenesulfonic acid, para-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, sulfuric acid, phosphoric acid; Lewis acids such as BF ₃ , AlCl ₃ , SnCl ₄ ; Examples thereof include titanates such as tetrabutyl titanate; zinc powder or organic zinc compound; tin powder or organic tin compound. This first step is preferably performed in the presence of an acid catalyst. In that case, if necessary, the obtained product may be neutralized before reacting with the chain terminator.

  As the dendritic compound (b), a polyester polyol dendrimer compound is preferable, and among them, a compound represented by the following formula (2) is more preferable. In particular, a polyester polyol dendrimer compound obtained by using pentaerythritol as an initiator, dimethylolpropionic acid as a chain extender, and lauric acid as a chain terminator is preferable (FIG. 2 described later). It is preferable to use a dendrimer having such a structure because a photosensitive resin composition having good compatibility with other components and excellent cured product properties can be obtained.

(Wherein, X ¹ and X ² each independently represent a hydrogen atom, a substituent represented by the following formula (3) or the following formula (4), and n ² is an integer of 1 to 10).

（式中、Ｒ^２は、炭素数１〜３０のアルキル基、シクロアルキル基、アリール基、又はアラルキル基を表す。）

(In the formula, R ² represents an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.)

  It is preferable that the dendritic compound (b) has the above-described structure because a hydroxyl group present at the terminal and an active species cause a chain transfer reaction and a free acid generated as a result of the reaction can improve the monomer conversion rate.

  FIG. 2 is a diagram showing an example in which a chain extender and a chain terminator are used in the reaction in which the dendritic compound (b) is generated. First, pentaerythritol, which is an initiator molecule, is reacted with dimethylolpropionic acid, which is a chain extender, to produce a 1.5-stage dendrimer. In this step, methanesulfonic acid is used as a catalyst. Subsequently, as a final reaction step, a chain terminator composed of lauric acid can be reacted with the dendrimer.

  The dendritic compound (b) has a weight average molecular weight of 1000 or more. By setting the molecular weight to 1000 or more, both reduction of the surface tackiness of the cured product and improvement of the hardness can be achieved. When the weight average molecular weight is large, various physical properties tend to be improved, and when the weight average molecular weight is small, compatibility with other components tends to be good and viscosity tends to decrease. From this point of view, the weight average molecular weight of the dendritic compound (b) can be controlled according to the desired application and properties. It can be measured by gel permeation chromatography (GPC) using tetrahydrofuran as a mobile phase and polystyrene as a standard substance.

  As the polyester polyol dendrimer compound used as the branched compound (b), a commercially available product can be used. For example, a polyester polyol dendrimer compound (see FIG. 2) obtained using pentaerythritol as an initiator, dimethylolpropionic acid as a chain extender, and lauric acid as a chain terminator is, for example, “BOLTORN H20”, Available as “BOLTORN H30”, “BOLTORNH40”, “BOLTORN H2003”, “BOLTORN H2004”, “BOLTORN P1000” (all trade names, manufactured by Pellstorpure Bay). Moreover, the dendrimer described in Japanese Patent No. 2574201 can also be suitably used.

  The type of the reactive organosilicon compound (c) used in the present embodiment is not particularly limited, but an alkoxysilane represented by the formula (5) or a silane coupling agent represented by the following formula (6) is preferable. Used. Here, the “reactive organosilicon compound” refers to a compound that causes a hydrolysis reaction and / or a polymerization reaction by an acid or a radical generated by irradiation with energy such as light.

(Wherein R ^{3 to} R ⁶ each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group, and n ³ represents an integer of 2 or less.)

N ^{3 in the} above formula (5) is 2 or less. n ³ adhesion to transparency and substrate of the cured film obtained by irradiation exceeds 2 deteriorates. Specifically, in the compound represented by Formula (5), the compound having n ³ of 1 is preferably contained in an amount of 50 mol% or more, more preferably 80 mol% or more, and more preferably 90 mol% or more. More preferably.

  Such an alkoxysilane compound is not particularly limited as long as it satisfies the above requirements, and specifically, for example, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, methyldimethoxy Silane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, tetrapropoxysilane, tetrabutoxy Silane etc. are mentioned.

(In the formula, R ⁷ represents an ethylene group or a propylene group, Y represents an organic functional group, Z represents a hydrolyzable group, and n ⁴ represents an integer of 0 to 1).

  Y may be an organic functional group, and the type thereof is not limited, and examples thereof include an amino group, a vinyl group, a methacryl group, an isocyanate group, a mercapto group, a ureido group, an epoxy group, and a halogen atom.

  Z should just be a hydrolysable group, The kind is not limited, For example, a methoxy group, an ethoxy group, 2-methoxyethoxy group etc. are mentioned.

  Examples of the silane coupling agent represented by the formula (6) include vinyl silane, acrylic silane, epoxy silane, and amino silane.

  Examples of the vinyl silane include vinyl trichlorosilane, vinyl tris (β-methoxyethoxy) silane, vinyl triethoxysilane, and vinyl trimethoxysilane.

  Examples of the acrylic silane include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and the like.

  Examples of the epoxy silane include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane.

  As aminosilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl- γ-aminopropyltrimethoxysilane and the like can be mentioned.

  Examples of other silane coupling agents include γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane.

  It is preferable that the photosensitive resin composition of this embodiment further contains a cationically polymerizable compound. As a result, the hydroxyl group and the active species cause a chain transfer reaction, and the free acid generated as a result of the reaction can improve the monomer conversion rate and promote the hydrolysis reaction of the reactive organosilicon compound. Examples of the cationic polymerizable compound include an epoxy compound, a vinyl ether compound, and an oxetane compound.

  As the cationic polymerizable compound, an epoxy compound (d) having one or more epoxy groups in the molecule is preferable. By including the epoxy compound (d), the hardness of the cured product and the adhesion to each substrate can be improved. Examples of the epoxy compound (d) 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 2021”, “Celoxide 2080”, “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.

  It is preferable that the photosensitive resin composition of this embodiment further contains an energy beam sensitive cationic polymerization initiator (e) and / or an energy beam sensitive radical polymerization initiator (f).

  The energy ray-sensitive cationic polymerization initiator (e) refers to a compound capable of generating a substance that initiates cationic polymerization by irradiation with energy rays. 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 commercial 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)," UVI-6990 "(trade name, manufactured by Dow Chemical)," CPI-100P "," CPI-100A "(trade name, manufactured by San Apro)," TEPBI-S "(trade name, manufactured by Nippon Shokubai Co., Ltd.)," RHODORSIL PHOTOINITIATOR 2074 "(trade name, manufactured by Rhodia) and the like can be used. As the energy ray-sensitive cationic polymerization initiator (e), those described above may be used alone or in combination of two or more.

  The energy ray sensitive radical polymerization initiator (f) refers to a compound capable of generating a substance that initiates radical polymerization by irradiation with energy rays. Specifically, the triazine derivatives described in JP-B-59-1281, JP-B-61-9621, JP-A-60-60104, etc., JP-A-59-1504 and JP-A-61. No. 3,243,807, Japanese Patent Publication No. 43-23684, Japanese Patent Publication No. 44-6413, Japanese Patent Publication No. 44-6413, Japanese Patent Publication No. 47-1604, etc. , 567,453, U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,853. Organic azide compounds described in Japanese Patent Publication No. 36-22062, Japanese Patent Publication No. 37-13109, Japanese Patent Publication No. 38-18015, Japanese Patent Publication No. 45-9610, etc. Quinonediazides, various oniums described in JP-B-55-39162, JP-A-59-14023, and the like and “Macromolecules, Vol. 10, page 1307 (1977)” Compounds, azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent 109,851, European Patent 126,712, “Journal of Imaging”・ Science (J. Imag. Sci.), Vol. 30, p. 174 (1986) ”, etc., described in JP-A-6-213861 and JP-A-6-255347 ( Oxo) sulfonium organoboron complexes, titanocenes described in JP-A-61-151197, Transition metal complexes containing transition metals such as ruthenium described in Coordination Chemistry Review, Vol. 84, 85, 277 (1988) and JP-A-2-182701. Examples include 2,4,5-triarylimidazole dimer, carbon tetrabromide, and organic halogen compounds described in JP-A-59-107344 as described in Kaihei 3-209477. These can 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. Among these, a hydroxyl group-containing vinyl ether compound is more preferable.

  Examples of the vinyl ether compound include 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. Examples include vinyl ether.

  Hydroxyl group-containing vinyl ether compounds 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, tetraethylene Glycol monovinyl ether, tricyclodecane diol monovinyl ether, tricyclodecanedimethanol monovinyl ether and the like.

  In this embodiment, an oxetane compound can be used in combination. As such oxetane compounds, 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 novolak oxetane, oxetanylsilsesquioxane and the like. Moreover, in this embodiment, the oxetane compound which has a hydroxyl group can also be used, and the compound represented by following formula (11) is mentioned.

(In the formula, R ¹¹ 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 ¹² represents an alkylene group having 1 to 6 carbon atoms, or an oxyalkylene group in which an ether is bonded to an alkylene group having 1 to 6 carbon atoms.)

In the formula (11), R ¹¹ is preferably a lower alkyl group, and more preferably an ethyl group. R ¹² 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 initiators (e) and (f). 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. Moreover, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiro orthoester compound, or the like can also 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, light stabilizers, ultraviolet absorbers, antistatic agents, slip agents, etc. may be added. it can. 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.

  Next, the composition ratio of each component in the photosensitive resin composition used in the present embodiment will be described. “Parts” shown below are all 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 5 to 80% by mass, preferably 10 to 40% by mass. It is. When the amount is less than 5% by mass, the effect of improving the conversion rate of the epoxy group by the vinyl ether compound is insufficient, so that an unreacted epoxy group remains. Moreover, since the hardness of hardened | cured material will fall when more than 80 mass%, sufficient mechanical characteristics of hardened | cured material cannot be acquired.

  The content of the dendritic compound (b) in the photosensitive resin composition is 1.0 to 40% by mass, preferably 2.0 to 20% by mass. When the amount is less than 1.0% by mass, the effect of improving the reaction rate is insufficient, and even higher adhesion and the effect of suppressing the curling of the substrate cannot be obtained. Moreover, when more than 40 mass%, the viscosity of the photosensitive resin composition becomes too high, and handling becomes difficult.

  The content of the reactive organosilicon compound (c) in the photosensitive resin composition is 5 to 90% by mass, preferably 10 to 60% by mass. When it is less than 5% by mass, the hardness of the cured product is lowered, and even higher adhesion and the effect of suppressing substrate curl cannot be obtained. Moreover, when more than 90 mass%, the softness | flexibility of hardened | cured material will fall and it will become easy to enter a crack.

  The content of the cationic polymerizable compound in the photosensitive resin composition is preferably 30 to 80% by mass, and more preferably 50 to 70% by mass. By setting it as 30 mass% or more, the hardness of hardened | cured material becomes favorable and can make the mechanical property of hardened | cured material sufficient. Moreover, since content of a dendritic compound (b) can be made into an appropriate quantity by setting it as 80 mass% or less, the conversion rate improvement effect of an epoxy group is excellent, and the residue of an unreacted epoxy group can be reduced. And it is preferable for the content of the cationically polymerizable compound to be the above, since both a high reaction rate and good cured properties can be achieved.

  The total content of the energy beam sensitive cationic polymerization initiator (e) and the energy beam sensitive radical polymerization initiator (f) in the photosensitive resin composition is preferably 0.1 to 10% by mass. It is more preferable that it is 2-8 mass%. By setting the content to 0.1% by mass or more, a sufficient amount of the active substance generated by energy beam irradiation is obtained, and sufficient curability can be obtained. Moreover, it is economically preferable by setting it as 10 mass% or less, and since the light transmittance does not fall and the hardening of a film bottom part can fully be performed, it is preferable.

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

  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%, 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. As an example, a coating material for forming an antireflection film used for a flat panel display (FPD) or the like is used. After coating and curing on a base material, a film having a refractive index of 1.4 or less is applied. In order to form it, the photosensitive resin composition of this 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, and silica particles having an average particle diameter of 5 to 100 nm are preferable from the viewpoint of resin transparency. Specific examples of commercially available products include “Aerosil” (trade name, manufactured by Nippon Aerosil Co., Ltd.), a fumed silica having a hydrophilic or hydrophobic surface, and a pearl necklace-shaped silica sol in which silica particles are connected in a straight chain. There is a certain “Snowtex PS” (trade name, manufactured by Nissan Chemical Co., Ltd.). These porous fine particles are preferably used by adding a total of 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. 3 is a cross-sectional view of one aspect of an OLED display element using the semiconductor sealing material of the present embodiment. The OLED display element A is formed by sequentially forming the hole injection electrode 2, the hole transport layer 3, the light emitting layer 4 and the electron injection electrode 5 on the substrate 1, and then sealing 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 a hole injection electrode 2, a hole transport layer 3, a light emitting layer 4, and an electron injection electrode 5 are sequentially laminated on the base material 1, a resistance heating vapor deposition method, A beam sputtering method, an inkjet 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 degradation and 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 a dendritic compound (b) having two or more hydroxyl groups and having a weight average molecular weight of 1,000 or more, a polyester polyol dendrimer compound “BOLTORN H2003” (trade name, manufactured by Pelstorpure Baie; number of hydroxyl groups in one molecule) 12, weight average molecular weight 2500) 5% by mass, and as reactive organosilicon compound (c), tetraethoxysilane “TSL8124” (trade name, manufactured by Momentive Performance Materials Japan) 15% by mass, As an epoxy compound (d) having at least one epoxy group, 3,4-epoxy As a cyclocyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 60 mass% and an energy ray-sensitive cationic polymerization initiator (e), the content of sulfonium salt is A photosensitive resin composition was obtained by sufficiently mixing 50% by mass of “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) 5% by mass.

[Example 2]
As a compound (a) having one or more oxetanyl groups and vinyl ether groups in one molecule, 10% by mass of 3-ethyl-3-[(vinyloxy) methyl] oxetane (manufactured by Maruzen Petrochemical Co., Ltd.), As a dendritic compound (b) having 2 or more hydroxyl groups and having a weight average molecular weight of 1000 or more, 5% by mass of a polyester polyol dendrimer compound “BOLTORN H2003” (trade name, manufactured by Pelstorpure Baie), reactive organic As silicon compound (c), tetraethoxysilane “TSL8124” (trade name, manufactured by Momentive Performance Materials Japan) 10 mass%, and epoxy compound (d) having one or more epoxy groups in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexa Carboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 60% by mass, monohydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) 10% by mass, and energy ray sensitive cationic polymerization initiator (e) A photosensitive resin composition was obtained by sufficiently mixing 5% by mass of “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) having a sulfonium salt content of 50% by mass.

[Example 3]
As a compound (a) having one or more oxetanyl groups and vinyl ether groups in one molecule, 10% by mass of 3-ethyl-3-[(vinyloxy) methyl] oxetane (manufactured by Maruzen Petrochemical Co., Ltd.), As a dendritic compound (b) having 2 or more hydroxyl groups and having a weight average molecular weight of 1000 or more, 5% by mass of a polyester polyol dendrimer compound “BOLTORN H2003” (trade name, manufactured by Pelstorpure Baie) and reactivity As an organosilicon compound (c), 10% by mass of tetraethoxysilane “TSL8124” (trade name, manufactured by Momentive Performance Materials Japan) and an epoxy compound (d) having one or more epoxy groups in the molecule 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl Carboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 60 mass% and 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane “OXT-221” (Trade name, manufactured by Toa Gosei Co., Ltd.) 10% by mass and “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) having a sulfonium salt content of 50% by mass as an energy ray-sensitive cationic polymerization initiator (e) ) 5% by mass was sufficiently mixed to obtain a photosensitive resin composition.

[Example 4]
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 a dendritic compound (b) having 2 or more hydroxyl groups and having a weight average molecular weight of 1000 or more, 5% by mass of a polyester polyol dendrimer compound “BOLTORN H2003” (trade name, manufactured by Pelstorpure Baie) and reactivity As the organosilicon compound (c), 15% by mass of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane “A-186” (trade name, manufactured by Momentive Performance Materials Japan), As an epoxy compound (d) having one or more epoxy groups, 3,4-epoxycyclohexane 60% by mass of rumethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) and an energy ray-sensitive cationic polymerization initiator (e) having a sulfonium salt content of 50% by mass % “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) 5 mass% was sufficiently mixed to obtain a photosensitive resin composition.

[Example 5]
As a compound (a) having one or more oxetanyl groups and vinyl ether groups in one molecule, 3-ethyl-3-[(vinyloxy) methyl] oxetane (manufactured by Maruzen Petrochemical Co., Ltd.) 10% by mass in one molecule As a dendritic compound (b) having two or more hydroxyl groups and having a weight average molecular weight of 1000 or more, 5% by mass of a polyester polyol dendrimer compound “BOLTORN H2003” (trade name, manufactured by Pelstorpure Baie), reactive organosilicon As compound (c), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane “A-186” (trade name, manufactured by Momentive Performance Materials Japan) 10% by mass, an epoxy group in the molecule As the epoxy compound (d) having one or more, 3,4-epoxycyclohexylme Lu-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 60% by mass, monohydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) 10% by mass, energy ray sensitive cationic polymerization As an initiator (e), a photosensitive resin composition was obtained by sufficiently mixing 5% by mass of “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) having a sulfonium salt content of 50% by mass.

[Example 6]
As a compound (a) having one or more oxetanyl groups and vinyl ether groups in one molecule, 10% by mass of 3-ethyl-3-[(vinyloxy) methyl] oxetane (manufactured by Maruzen Petrochemical Co., Ltd.), As a dendritic compound (b) having 2 or more hydroxyl groups and having a weight average molecular weight of 1000 or more, a reaction with 5% by mass of a polyester polyol dendrimer compound “BOLTORN H2003” (trade name, manufactured by Pelstorpure Baie) As a functional organosilicon compound (c), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane “A-186” (trade name, manufactured by Momentive Performance Materials Japan) 10% by mass, As an epoxy compound (d) having at least one epoxy group, 3,4-epoxycyclohexane 60% by mass of silmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) and 3-ethyl-3 {[((3-ethyloxetane-3-yl) methoxy] methyl } Oxetane “OXT-221” (trade name, manufactured by Toa Gosei Co., Ltd.) 10% by mass, and energy ray sensitive cationic polymerization initiator (e) having a sulfonium salt content of 50% by mass “CPI-100P” ( A photosensitive resin composition was obtained by sufficiently mixing 5% by mass (trade name, manufactured by San Apro Co., Ltd.).

[Example 7]
As a compound (a) having one or more oxetanyl groups and vinyl ether groups in one molecule, 70% by mass of 3-ethyl-3-[(vinyloxy) methyl] oxetane (manufactured by Maruzen Petrochemical Co., Ltd.), As a dendritic compound (b) having 2 or more hydroxyl groups and having a weight average molecular weight of 1000 or more, a reaction with 2% by mass of a polyester polyol dendrimer compound “BOLTORN H2003” (trade name, manufactured by Pellstorpure Baie) As a functional organosilicon compound (c), 8% by mass of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane “A-186” (trade name, manufactured by Momentive Performance Materials Japan), in the molecule As an epoxy compound (d) having at least one epoxy group, 3,4-epoxycyclohexyl 15% by mass of rumethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) and an energy ray-sensitive cationic polymerization initiator (e) having a sulfonium salt content of 50% by mass % “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) 5 mass% was sufficiently mixed to obtain a photosensitive resin composition.

[Example 8]
As a compound (a) having one or more oxetanyl groups and vinyl ether groups in one molecule, 10% by mass of 3-ethyl-3-[(vinyloxy) methyl] oxetane (manufactured by Maruzen Petrochemical Co., Ltd.), As a dendritic compound (b) having 2 or more hydroxyl groups and having a weight average molecular weight of 1000 or more, a reaction with 35% by mass of a polyester polyol dendrimer compound “BOLTORN H2003” (trade name, manufactured by Pellstorpure Baie) As a functional organosilicon compound (c), 5% by mass of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane “A-186” (trade name, manufactured by Momentive Performance Materials Japan), in the molecule As an epoxy compound (d) having at least one epoxy group, 3,4-epoxycyclohexane Silmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 45% by mass and an energy ray-sensitive cationic polymerization initiator (e) having a sulfonium salt content of 50% by mass % “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) 5 mass% was sufficiently mixed to obtain a photosensitive resin composition.

[Example 9]
As a compound (a) having one or more oxetanyl groups and vinyl ether groups in one molecule, 10% by mass of 3-ethyl-3-[(vinyloxy) methyl] oxetane (manufactured by Maruzen Petrochemical Co., Ltd.), As a dendritic compound (b) having 2 or more hydroxyl groups and having a weight average molecular weight of 1000 or more, a reaction with 5% by mass of a polyester polyol dendrimer compound “BOLTORN H2003” (trade name, manufactured by Pelstorpure Baie) As a functional organosilicon compound (c), 70% by mass of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane “A-186” (trade name, manufactured by Momentive Performance Materials Japan), in the molecule As an epoxy compound (d) having at least one epoxy group, 3,4-epoxycyclohexane Silmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 10 mass%, and energy ray sensitive cationic polymerization initiator (e) has a sulfonium salt content of 50 mass. % “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) 5 mass% was sufficiently mixed to obtain a photosensitive resin composition.

[Example 10]
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 a dendritic compound (b) having two or more hydroxyl groups and having a weight average molecular weight of 1,000 or more, a polyester polyol dendrimer compound “BOLTORN H2004” (trade name, manufactured by Pellstorpure Baie; number of hydroxyl groups in one molecule) 6, 5% by mass of the weight average molecular weight 3200) and 15% by mass of tetraethoxysilane “TSL8124” (trade name, manufactured by Momentive Performance Materials Japan) as the reactive organosilicon compound (c), As an epoxy compound (d) having at least one epoxy group, 3,4-epoxy compound Chlohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 60% by mass and an energy ray-sensitive cationic polymerization initiator (e) having a sulfonium salt content A photosensitive resin composition was obtained by sufficiently mixing 50% by mass of “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) 5% by mass.

[Comparative 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.), P-tert-butyl-phenol novolak resin “PAPS-PTBPN” (trade name) having a content of phenol 3-5 nuclei of 50% by mass as a compound having two or more hydroxyl groups and having a weight average molecular weight of 890 Asahi Organic Materials Co., Ltd.) 5% by mass, and as reactive organic silicon compound (c), tetraethoxysilane “TSL8124” (trade name, manufactured by Momentive Performance Materials Japan) 15% by mass, As an epoxy compound (d) having one or more epoxy groups therein, 3,4-epoxycyclohexylmethyl-3,4-epoxy 60% by mass of cyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) and “CPI-100P having a sulfonium salt content of 50% by mass as an energy ray-sensitive cationic polymerization initiator (e)” (Trade name, manufactured by San Apro Co., Ltd.) 5% by mass was sufficiently mixed to obtain a photosensitive resin composition.

[Comparative 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 a compound having two or more hydroxyl groups, 5% by mass of propylene glycol and as a reactive organosilicon compound (c), tetraethoxysilane “TSL8124” (trade name, manufactured by Momentive Performance Materials Japan) 15 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, Daicel Chemical Industries, Ltd.) as an epoxy compound (d) having 1% by mass and one or more epoxy groups in the molecule 60% by mass, energy ray sensitive cationic polymerization Dosage (e), the content of the sulfonium salt was obtained in 50 wt% "CPI-100P" (trade name, San-Apro Ltd.) 5 wt%, the photosensitive resin composition by mixing sufficiently.

[Comparative Example 3]
As a compound (b) having two or more hydroxyl groups in one molecule and having a weight average molecular weight of 1,000 or more, 5% by mass of “BOLTORN H2003” (trade name, manufactured by Pelstorpure Baie), a reactive organosilicon compound As (c), tetraethoxysilane “TSL8124” (trade name, manufactured by Momentive Performance Materials Japan) 15% by mass and an epoxy compound (d) having one or more epoxy groups in the molecule, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 60% by mass, monohydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) 15% by mass, As an energy ray sensitive cationic polymerization initiator (e) Then, a photosensitive resin composition was obtained by sufficiently mixing 5% by mass of “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) having a sulfonium salt content of 50% by mass.

[Comparative Example 4]
As a compound (b) having two or more hydroxyl groups in one molecule and having a weight average molecular weight of 1,000 or more, “BOLTORN H2003” (trade name, manufactured by Pelstorpure Baie) 5% by mass, a reactive organosilicon compound ( c), tetraethoxysilane “TSL8124” (trade name, manufactured by Momentive Performance Materials Japan) 15% by mass, and epoxy compound (d) having one or more epoxy groups in the molecule, -Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 60% by mass 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 5% by mass of “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) having a sulfonium salt content of 50% by mass are sufficiently mixed as the energy ray-sensitive cationic polymerization initiator (e). Thus, a photosensitive resin composition was obtained.

[Comparative Example 5]
As a compound (b) having two or more hydroxyl groups in one molecule and having a weight average molecular weight of 1,000 or more, “BOLTORN H2003” (trade name, manufactured by Pelstorpure Baie) 5% by mass, an epoxy group in the molecule As epoxy compound (d) having one or more, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 60% by mass, monohydroxy 15% by mass of butyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.) and 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane “OXT-221” (trade name, Toa Gosei Co., Ltd.) 15% by mass) and a sulfonium salt as an energy ray-sensitive cationic polymerization initiator (e) "CPI-100P" in the content of 50 mass% to obtain a photosensitive resin composition by a (trade name, San-Apro Ltd.) 5 mass%, the sufficiently mixed.

[Comparative Example 6]
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 a compound (b) having two or more hydroxyl groups and having a weight average molecular weight of 1,000 or more, 5% by mass of “BOLTORN H2003” (trade name, manufactured by Pelstrom Puer & Co.) and one epoxy group in the molecule As an epoxy compound (d) having the above, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 75% by mass, energy ray-sensitive cationic polymerization As the initiator (e), “CPI-100P having a sulfonium salt content of 50 mass% To obtain a photosensitive resin composition by a (trade name, San-Apro Ltd.) 5 mass%, the sufficiently mixed.

[Comparative Example 7]
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 a compound (b) having two or more hydroxyl groups and having a weight average molecular weight of 1,000 or more, 5% by mass of “BOLTORN H2003” (trade name, manufactured by Pelstrom Puer & Co.) and one epoxy group in the molecule As the epoxy compound (d) having the above, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate “Celoxide 2021P” (trade name, manufactured by Daicel Chemical Industries, Ltd.) 60% by mass, monohydroxybutyl vinyl ether ( Maruzen Petrochemical Co., Ltd.) 15% by mass and energy ray sensitive cationic polymerization A photosensitive resin composition was obtained by sufficiently mixing 5% by mass of “CPI-100P” (trade name, manufactured by San Apro Co., Ltd.) having a sulfonium salt content of 50% by mass as an initiator (e). .

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.
◎: 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>
Using a bar coater, the photosensitive resin compositions of each Example and each Comparative Example were uniformly applied on a glass substrate with a thickness of 12 μm. 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 made 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

<Curing speed>
An ultraviolet irradiation device (Hamamatsu Photonics Co., Ltd.) equipped with a high-pressure mercury lamp by applying the photosensitive resin composition of each example and each comparative example at a thickness of 100 μm on a glass substrate of a dynamic viscoelastic device (manufactured by Anton Paar) Was used, and the curing behavior was measured while exposing the glass substrate so that the amount of light was 10 mW / cm ² . In this measurement, from the initial liquid state (G ′ (storage elastic modulus) <G ″ (loss elastic modulus); tan δ> 1), the gelation point (G ′ = G ″; tan δ = 1) is reached. The state of changing to a solid state (G ′> G ″; tan δ <1) can be analyzed in detail. The curing speed was measured by the time from the start of exposure until the gel point was reached. The environment during curing was temperature: 23 ° C. and humidity: 60% RH.
A: Time at which the gel point was reached is less than 150 seconds from the start of exposure. ○: Time at which the gel point was reached was from 150 seconds to less than 200 seconds from the start of exposure. X: Time after reaching the gel point was 200 seconds or more from the start of exposure.

<Storage stability>
About each state immediately after preparation of the photosensitive resin composition of each Example and each comparative example, and after leaving still in 60 degreeC oven for 10 days, a rotary E-type viscosity meter (the Toki Sangyo Co., Ltd. make, "TV Viscosity at 25 ° C. was measured using “-22 type”). And the viscosity increase amount of the photosensitive resin composition from immediately after preparation to after leaving still for 10 days was calculated | required, and the following references | standards evaluated.
○: Increase in viscosity is less than 1.0 mPa · s ×: Increase in viscosity is 1.0 mPa · s or more

<Hardness>
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. Then, it left still for a whole day and night under the atmosphere of room temperature 23 degreeC and humidity 50 mass%, and performed the pencil hardness measurement by the method based on JIS5600-5-4.
◎: 2H or more ○: H or more and less than 2H ×: Less than H

<Adhesion>
The photosensitive resin composition of each Example and each Comparative Example was uniformly applied with a thickness of 12 μm on a glass substrate and an acrylic plate using a bar coater. Then, the said glass substrate and the acrylic board were exposed so that it might become the integrated light quantity 160mJ / 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. Then, the crosscut method test was done by the method based on JIS5600-5-6.
○: No peeling ×: Some or all peeling occurred

<Substrate curl test>
The photosensitive resin composition of each Example and each Comparative Example was uniformly applied to a thickness of 12 μm on a biaxially stretched polypropylene (OPP) film having a thickness of 19 μm subjected to surface treatment using a 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 160 mJ / cm < ² > of integrated light quantity. The environment during curing was temperature: 23 ° C. and humidity: 60% RH. Thereafter, the sample was left standing for a whole day and night in an atmosphere of a room temperature of 23 ° C. and a humidity of 50% by mass, and was measured visually.
○: No curling of base material ×: Curling of base material occurs

3. Evaluation Results Tables 1 and 2 show the evaluation results of Examples and Comparative Examples. In addition, Table 3 shows components in the photosensitive resin composition represented by abbreviations in Tables 1 and 2.

As shown in Table 1 and Table 2, the photosensitive resin compositions of Examples 1 to 6 are monomer conversion, surface tackiness, flexibility, curing speed, storage stability, hardness, adhesion, and substrate. All of the curl tests were confirmed to be excellent. On the other hand, the photosensitive resin compositions of Comparative Examples 1 to 7 are defective in at least one of monomer conversion, surface tack, flexibility, curing speed, storage stability, hardness, adhesion, and substrate curl test. It was confirmed that.
From the above, the photosensitive resin composition of the present embodiment has excellent photocurability (surface curability, internal curability) and high storage stability, and the cured product has excellent mechanical properties. It was shown that the film had excellent film properties that achieved both high adhesion and suppression of substrate curl.

  The photosensitive resin composition of the present invention has excellent photocurability (surface curability and internal curability) without curing inhibition due to humidity and high storage stability, and the cured product has excellent toughness and flexibility. In addition, it has excellent mechanical properties and has excellent film properties that achieve both high adhesion and suppression of substrate curling, so that it can be applied to paints, adhesives, inks, film coatings, more specifically UV inks for inkjet, Surface protective layer forming material for display panel sealing materials such as liquid crystal and organic EL, optical disc bonding adhesive, CD, DVD, and Blu-ray Disc (Blu-ray (registered trademark) Disc) which is the next generation optical disc, It can be suitably used as a coating material for forming an antireflection film, a hard coating material, or the like.

DESCRIPTION OF SYMBOLS 1,7 Base material 2 Hole injection electrode 3 Hole transport layer 4 Light emitting layer 5 Electron injection electrode 6 Semiconductor sealing material

Claims (11)

5-80 mass% of compounds (a) represented by the following formula (1),
1 to 40% by mass of a dendritic compound (b) having two or more hydroxyl groups in one molecule and having a weight average molecular weight of 1,000 or more;
A photosensitive resin composition comprising 5 to 90% by mass of a reactive organosilicon compound (c).

(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.)   The photosensitive resin composition according to claim 1, wherein the dendritic compound (b) is a polyester polyol dendrimer. The photosensitive resin composition according to claim 1, wherein the dendritic compound (b) is a compound represented by the following formula (2).

(Wherein, X ¹ and X ² each independently represent a hydrogen atom, a substituent represented by the following formula (3) or the following formula (4), and n ² represents an integer of 1 to 10).

(In the formula, R ² represents an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group.) The reactive organic silicon compound (c) is an alkoxysilane represented by the following formula (5) or a silane coupling agent represented by the following formula (6). The photosensitive resin composition as described in 2.

(Wherein R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and n ³ is an integer of 2 or less. Represents.)

(In the formula, R ⁷ represents an ethylene group or a propylene group, Y represents an organic functional group, Z represents a hydrolyzable group, and n ⁴ represents an integer of 0 to 1).   The photosensitive resin composition as described in any one of Claims 1-4 which further contains 30-80 mass% of cationically polymerizable compounds.   The photosensitive resin composition according to claim 5, wherein the cationically polymerizable compound is an epoxy compound (d) having one or more epoxy groups in a molecule.   The energy ray-sensitive cationic polymerization initiator (e) and / or the energy ray-sensitive radical polymerization initiator (f) are further included in a total amount of 0.1 to 10% by mass. The photosensitive resin composition as described.   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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