JP6011956B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition that can be cured at room temperature by light irradiation.

  A photosensitive resin composition containing an acid generator that generates an acid upon irradiation with light is applied as a photoresist material, a photocuring material, or the like. The acid generated from the acid generator acts as a catalyst or a polymerization initiator. When a photosensitive resin composition containing an acid generator or the like is used as a photoresist material to form a pattern, for example, acid generation The agent is irradiated with light to generate a strong acid serving as a catalyst, and the resin component is chemically modified. Then, a pattern is formed by the change in solubility of the chemically modified resin component.

  Such a photoresist material is required to have a high resolution and sensitivity and to be able to form a pattern with high etching resistance. In particular, as a deep ultraviolet resist material, a pattern resistant to oxygen plasma etching is formed. There is a need for materials that can be used. Various photoresist materials comprising a photosensitive resin composition containing an acid generator have been provided for the purpose of high sensitivity, high resolution, etc., but a combination of a photoacid generator and a resin material is provided. Since the types are limited to some extent, a new photosensitive system that does not use an acid generator has been demanded.

  In addition, various studies have been made to improve the photocuring speed of monomers, oligomers, or polymers, and radical photopolymerization systems that polymerize many vinyl monomers using radical species generated by the action of light as initiators. These materials have been widely targeted for development. In addition, active studies have been made on cationic polymerization materials that generate an acid by the action of light and use this acid as a catalyst. However, in the case of radical photopolymerization-type materials, since the polymerization reaction is inhibited and the curing reaction is suppressed by oxygen in the air, a special device for blocking oxygen has been required. In addition, in the case of a cationic polymerization material, there is no oxygen inhibition like a radical photopolymerization material, but the strong acid generated from the photoacid generator remains after curing, which causes the presence of the strong acid. The corrosivity and the possibility of denaturation of the resin have been problems.

  Against this background, in order to obtain a resist material that can form a pattern with high resolution and sensitivity and high etching resistance, a curing technology that rapidly solidifies a liquid substance using active energy rays is further improved in performance. Therefore, a photosensitive resin composition using a new photosensitive system that is not affected by oxygen in the air and does not contain corrosive substances such as strong acids that are generated and that has a highly efficient reaction is strong. It was desired.

  As one of the means for overcoming the above problems, a method using a polymerization reaction or chemical reaction by a base catalyst, for example, a method of generating a base by the action of light and chemically denaturing a resin using this as a catalyst, A means for applying a photosensitive resin composition using a base generated by the above as a catalyst to a photoresist material, a photocuring material or the like has been studied. A compound having an epoxy group or an oxetane group is cured by causing a crosslinking reaction by the action of a base, and an amine as an initiator or a catalyst is caused in the epoxy resin layer by the action of light or heat. There is provided a method of generating and then curing by heat treatment (see, for example, Patent Document 1 and Patent Document 2). However, these methods have been lacking in practicality due to problems such as the limitation of the intensity of the base that can be generated and the fact that the reaction for generating the base by the action of light is not performed rapidly.

  On the other hand, since the thiol group represented by -SH has high reactivity with various functional groups, it is a functional group that can be used as a curing functional group of the curable resin composition. A thiol compound having a thiol group can serve as a curing accelerator for an epoxy resin, particularly when used in combination with an epoxy resin or an oxetane resin, and can provide a curable resin composition excellent in curing ability. In the photosensitive resin composition containing these and a base generator, the basic compound generated from the photobase generator by light irradiation may further accelerate the curing reaction between the epoxy resin or oxetane resin and the thiol compound. Since this is possible, studies are underway (see, for example, Patent Document 3).

JP 2005-264156 A Japanese Patent Laid-Open No. 2007-10185 JP 2007-77382 A

  However, the conventional photosensitive resin composition combining an epoxy resin, a thiol compound and a base generator does not generate a base efficiently by light irradiation, and it is difficult to cure reliably at room temperature. Many of these require heating after light irradiation, and improvements have been demanded.

  In addition, conventional photosensitive resin compositions that combine an oxetane resin, a thiol compound, and a base generator do not generate a base efficiently by light irradiation, and are often difficult to cure reliably. It was done.

  The present invention has been made in view of the above-described problems, and a photosensitizer capable of performing a curing reaction between an epoxy resin and a thiol compound by containing a base generator that generates a base by irradiation with light. An object of the present invention is to provide a photosensitive resin composition that can be easily and efficiently cured at room temperature. In addition, a photosensitive resin composition capable of performing a curing reaction between an oxetane-based resin and a thiol compound by containing a base generator that generates a base upon irradiation with light can be efficiently and simply cured. It is in providing a conductive resin composition.

In order to solve the above problems, a photosensitive resin composition according to the first invention of the present invention is represented by an epoxy resin having a plurality of epoxy groups, a thiol compound having a plurality of thiol groups, and the following formula (X). And a base generator composed of a carboxylate , which is liquid at room temperature .

（式（Ｘ）中、Ａ⁻は下記式（IV）、（Ｖ）、（VI）及び（VII）のいずれかで表されるカルボン酸であり、Ｂ^＋は下記式（Ｉ）、式（Ｉ−ｃ）、式（Ｉ−ｄ）、式（Ｉ−ｅ）、式（Ｉ−ｆ）、式（Ｉ−ｇ）、式（Ｉ−ｈ）で表されるグアニジン類、式（II）、式（II−ｃ）、式（II−ｄ）で表されるホスファゼン誘導体、式（III）で表されるアミジン類、のいずれかからなる塩基類、を示す。）

（式（Ｖ）及び式（VI）中、Ｒ_１、Ｒ_２、Ｒ_３はＣＨ_２ＣＯＯ⁻、ＣＨ（ＣＨ_３）ＣＯＯ⁻またはＨを示し、かかるＣＨ_２ＣＯＯ⁻またはＣＨ（ＣＨ_３）ＣＯＯ⁻はＲ_１、Ｒ_２、Ｒ_３のいずれか１つの基に付され、残りの２つの基にはＨが付される。）

（式（VII）中、Ｒ_１、Ｒ_２、Ｒ_３はＣＨ_２ＣＯＯ⁻またはＨを示し、かかるＣＨ_２ＣＯＯ⁻はＲ_１、Ｒ_２、Ｒ_３のいずれか１つの基に付され、残りの２つの基にはＨが付される。）

(In the formula (X), A ⁻ is a carboxylic acid represented by any one of the following formulas (IV), (V), (VI) and (VII), and B ⁺ represents the following formula (I), formula ( Ic), formula (Id), formula (Ie), formula (If), formula (Ig), guanidines represented by formula (Ih), formula (II) And a phosphazene derivative represented by the formula (II-c) and the formula (II-d) and an amidine represented by the formula (III).

(In the formula (V) and the formula (VI), R ₁ , R ₂ and R ₃ represent CH ₂ COO ⁻ , CH (CH ₃ ) COO ⁻ or H, and such CH ₂ COO ⁻ or CH (CH ₃ ) COO ^- it is subjected to either one group of _{R 1, R 2, R 3} , the remaining two groups H are attached).

(In the formula _{(VII), R 1, R} 2, R 3 is _CH 2 COO ^- indicates or H, according _CH 2 COO ^- is subjected to either one group of _{R 1, R 2, R 3} , remaining H is attached to these two groups.)

（式（Ｉ）中、Ｒ_１〜Ｒ_５はそれぞれ、独立して水素原子、アルキル基またはアリール基（アルキル基は環状構造でもよい。）を示す。）

(In formula (I), R _{1 to} R ₅ each independently represent a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

（式（II）中、Ｒ_１〜Ｒ_７はそれぞれ、独立して水素原子、アルキル基またはアリール基（アルキル基は環状構造でもよい。）を示す。）

(In formula (II), R _{1 to} R ₇ each independently represent a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

（式（III）中、ｎは１〜３の整数を示す。）

(In formula (III), n represents an integer of 1 to 3.)

The photosensitive resin composition according to the second aspect of the present invention, the thiol compound having oxetane down resins, more thiol groups with a plurality of oxetanyl groups, bases consisting of carboxylic acid salt represented by the following formula (X) A generator is contained.

（式（Ｘ）中、Ａ⁻は下記式（IV）、（Ｖ）、（VI）及び（VII）のいずれかで表されるカルボン酸であり、Ｂ^＋は下記式（Ｉ）、式（Ｉ−ｃ）、式（Ｉ−ｄ）、式（Ｉ−ｅ）、式（Ｉ−ｆ）、式（Ｉ−ｇ）、式（Ｉ−ｈ）で表されるグアニジン類、式（II）、式（II−ｃ）、式（II−ｄ）で表されるホスファゼン誘導体、式（III）で表されるアミジン類、のいずれかからなる塩基類、を示す。）

（式（Ｖ）及び式（VI）中、Ｒ_１、Ｒ_２、Ｒ_３はＣＨ_２ＣＯＯ⁻、ＣＨ（ＣＨ_３）ＣＯＯ⁻またはＨを示し、かかるＣＨ_２ＣＯＯ⁻またはＣＨ（ＣＨ_３）ＣＯＯ⁻はＲ_１、Ｒ_２、Ｒ_３のいずれか１つの基に付され、残りの２つの基にはＨが付される。）

（式（VII）中、Ｒ_１、Ｒ_２、Ｒ_３はＣＨ_２ＣＯＯ⁻またはＨを示し、かかるＣＨ_２ＣＯＯ⁻はＲ_１、Ｒ_２、Ｒ_３のいずれか１つの基に付され、残りの２つの基にはＨが付される。）

(In the formula (X), A ^- it is of the formula (IV), a (V), the carboxylic acid represented by any one of (VI) and (VII), ^{B +} is below formula (I), the formula ( Ic), formula (Id), formula (Ie), formula (If), formula (Ig), guanidines represented by formula (Ih), formula (II) And a phosphazene derivative represented by the formula (II-c) and the formula (II-d) and an amidine represented by the formula (III).

(In the formula (V) and the formula (VI), R ₁ , R ₂ and R ₃ represent CH ₂ COO ⁻ , CH (CH ₃ ) COO ⁻ or H, and such CH ₂ COO ⁻ or CH (CH ₃ ) COO ^- it is subjected to either one group of _{R 1, R 2, R 3} , the remaining two groups H are attached).

(In the formula _{(VII), R 1, R} 2, R 3 is _CH 2 COO ^- indicates or H, according _CH 2 COO ^- is subjected to either one group of _{R 1, R 2, R 3} , remaining H is attached to these two groups.)

（式（Ｉ）中、Ｒ_１〜Ｒ_５はそれぞれ、独立して水素原子、アルキル基またはアリール基（アルキル基は環状構造でもよい。）を示す。）

(In formula (I), R _{1 to} R ₅ each independently represent a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

（式（II）中、Ｒ_１〜Ｒ_７はそれぞれ、独立して水素原子、アルキル基またはアリール基（アルキル基は環状構造でもよい。）を示す。）

(In formula (II), R _{1 to} R ₇ each independently represent a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

（式（III）中、ｎは１〜３の整数を示す。）

(In formula (III), n represents an integer of 1 to 3.)

In the photosensitive resin composition according to the present invention, in the configuration described above, the bases are represented by the formula (I) , formula (Ic), formula (Id), formula (Ie), formula (I). -f), the formula (I-g), guanidines of the formula (I-h), or the formula (II), formula (II-c), the phosphazene derivative of the formula (II-d) It is characterized by being.

The photosensitive resin composition according to the first aspect of the present invention comprises, in addition to a thiol compound serving as a curing accelerator, an epoxy resin, a carboxylic acid that is decarboxylated by light irradiation, a guanidine having a high base strength, and a phosphazene derivative. Alternatively, since a carboxylate combined with amidines is contained as a base generator, a carboxylic acid that is decarboxylated by light irradiation generates a free base with high efficiency, and a base with high base strength such as guanidines By extracting H ⁺ from thiol (RSH), RS ⁻ can be efficiently generated. Then, since the reaction with the epoxy resin proceeds in a chain manner due to the generated RS ⁻ , the photosensitive resin composition is liquid at room temperature where the curing at the room temperature level is performed efficiently and reliably. The photosensitive resin composition of the present invention exhibiting such effects can be suitably used for, for example, a highly sensitive photocuring material, resist material, and the like.

The second photosensitive resin composition according to the invention of the present invention is to provide oxetane down resins, in addition to the thiol compound to be curing accelerator, carboxylic acid and base strength to decarboxylation by light irradiation is high guanidines, Since it contains a carboxylate combined with phosphazene derivatives or amidines as a base generator, a carboxylic acid that is decarboxylated by light irradiation generates a free base with high efficiency and a high base strength such as guanidines. The base can withdraw H ⁺ from thiol (RSH) and efficiently generate RS ⁻ . Then, the generated RS ^- by reaction with oxetane emission resins to proceed like a chain reaction, a photosensitive resin composition which curing is carried out efficiently and reliably. The photosensitive resin composition of the present invention exhibiting such effects can be suitably used for, for example, a highly sensitive photocuring material, resist material, and the like.

FIG. 4 is a diagram showing a change in UV spectrum of the base generator obtained in Production Example 1. It is the figure which showed the relationship between the exposure amount and the pencil hardness in Test Example 1. It is the figure which showed the relationship between the exposure amount in the test example 2, and pencil hardness. FIG. 6 is a diagram showing a change in UV spectrum (wavelength: 254 nm) of the base generator obtained in Production Example 5. FIG. 6 is a diagram showing a change in UV spectrum (wavelength: 365 nm) of the base generator obtained in Production Example 5. It is the figure which showed the relationship (Example 2) of the exposure amount and pencil hardness in Test example 3. FIG. It is the figure which showed the relationship (Example 3) between the exposure amount and the pencil hardness in Test Example 3. It is the figure which showed the relationship (Example 4) of the exposure amount and pencil hardness in Test example 3. FIG. It is the figure which showed the relationship (Example 5) of the exposure amount and pencil hardness in Test example 3. FIG.

First photosensitive resin composition according to the invention of the present invention, (a) Epoxy resins, (ii) a thiol compound, a base generator, consisting of a carboxylic acid salt represented by (c) formula (X) It is included as a basic configuration. The photosensitive resin composition according to the second aspect of the present invention, (d) oxetane down resins, (ii) a thiol compound, base generator comprising a carboxylic acid salt represented by (c) formula (X) , As a basic configuration. As for the contents of the present application, “epoxy resin” indicates “epoxy resin”, and “oxetane resin” indicates “oxetane resin”.

(A) Epoxy resin:
As the epoxy resin constituting the photosensitive resin composition of the present invention, an epoxy resin having at least one epoxy group can be used. In addition, if an epoxy resin having at least two epoxy groups is used, the epoxy resin is made more efficient by ring-opening polymerization of the epoxy group by allowing (ro) thiol compound and (c) base generator to act on the resin. It can be cured as a polymer well.

  Usable epoxy resins include diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, diethylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl. Ether, sorbitol polyglycidyl ether, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, alkylphenol glycidyl ether, polyethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol Diglycidyl ether, glycerin Liglycidyl ether, diglycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, cresyl glycidyl ether, aliphatic diglycidyl ether, polyfunctional glycidyl ether, tertiary fatty acid monoglycidyl ether, spiroglycol diglycidyl ether, glycidylpropoxytrimethoxy Silane etc. are mentioned. These epoxy resins may be halogenated or hydrogenated, and these epoxy resins include derivatives. And these epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.

As the (i) epoxy resin constituting the photosensitive resin composition according to the present invention, the epoxy equivalent is preferably 43 to 10,000. When the epoxy equivalent is within this range, it is possible to suppress or prevent a decrease in crosslinking density and a decrease in reaction rate.

(D) Oxetane resin:
As the oxetane-based resin, a monomeric oxetane-based resin, a dimer oxetane-based resin, or the like can be used. Usable oxetane resins include, for example, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 1,4-benzenedicarboxylate bis [(3-ethyl-3-oxetanyl) Methyl] ester, xylylene oxetane such as 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3-((((3-ethyloxetane-3-yl) methoxy) methyl ) Oxetane (or 3-(((3-ethyloxetane-3-yl) methoxy) methyl) -3-ethyloxetane), 3-ethylhexyloxetane, 3-ethyl-3-hydroxyoxetane, 3-ethyl- 3-hydroxymethyl oxetane, oxetated phenol novolak, etc. are mentioned. These oxetane resins may be used alone or in combination of two or more.

(B) Thiol compounds:
The (ro) thiol compound constituting the photosensitive resin composition of the present invention acts as a curing functional group for epoxy or oxetane when used in combination with (i) an epoxy resin or (d) an oxetane resin. As the thiol compound, a polythiol compound having two or more thiol groups is preferably used. For example, ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), dipentaerythritol hexakis. (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3 -Mercaptoisobutyrate), dipentaerythritol hexakis (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), tris [(3-mercaptopropionyloxy) Ethyl] isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), diethylene glycol bis (3-mercaptopropionate) Pionate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H , 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate) and the like, and polythiol compounds having 2 to 5 thiol groups. Among these, in consideration of reactivity and ease of handling, pentaerythritol tetrakis (3-mercaptobutyrate), tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate) ) Is preferably used. These thiol compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  (B) The amount of the thiol compound used is (i) epoxy resin or (d) oxetane resin, thiol equivalent (SH equivalent) / epoxy equivalent (or oxetane equivalent) = 0.3 / 1.7 to The ratio is preferably 1.7 / 0.3, and more preferably 0.8 / 1.2 to 1.2 / 0.8. If this ratio is in the range of 0.3 / 1.7 to 1.7 / 0.3, a large amount of unreacted thiol group or epoxy group (or oxetane group) remains in the cured product. It can prevent, and can suppress the fall tendency of the mechanical property of hardened | cured material.

(C) Base generator represented by the formula (X):
The (c) base generator applied to the photosensitive resin composition according to the present invention is a carboxylic acid that is decarboxylated by light irradiation, a guanidine represented by the following formula (I), and a formula (II). A phosphazene derivative and a amidine represented by the formula (III), and a compound comprising a carboxylate salt.

（式（Ｘ）中、Ａｒ基は芳香環であり、当該芳香環は置換基としてベンゾイル基、ニトロ基、アルコキシ基、アルキル基を含んでもよく、当該芳香環の置換基は環構造をとることができる。また、Ｒ’、Ｒ’’は、それぞれ水素原子、アルコキシ基、アルキル基、水酸基、またはアリール基、Ｂは下記式（Ｉ）で表されるグアニジン類、式（II）で表されるホスファゼン誘導体、式（III）で表されるアミジン類、のいずれかからなる塩基類、を示す。）

(In the formula (X), the Ar group is an aromatic ring, and the aromatic ring may include a benzoyl group, a nitro group, an alkoxy group, or an alkyl group as a substituent, and the substituent of the aromatic ring has a ring structure. R ′ and R ″ are each a hydrogen atom, an alkoxy group, an alkyl group, a hydroxyl group, or an aryl group, and B is a guanidine represented by the following formula (I) and a formula (II). A phosphazene derivative, or an amidine represented by the formula (III).

（式（Ｉ）中、Ｒ_１〜Ｒ_５はそれぞれ、独立して水素原子、アルキル基またはアリール基（アルキル基は環状構造でもよい。）を示す。）

(In formula (I), R _{1 to} R ₅ each independently represent a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

（式（II）中、Ｒ_１〜Ｒ_７はそれぞれ、独立して水素原子、アルキル基またはアリール基（アルキル基は環状構造でもよい。）を示す。）

(In formula (II), R _{1 to} R ₇ each independently represent a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

（式（III）中、ｎは１〜３の整数を示す。）

(In formula (III), n represents an integer of 1 to 3.)

  The base generator represented by the formula (X) includes, as the bases B, guanidines represented by the formula (I), phosphazene derivatives represented by the formula (II), and amidines represented by the formula (III). It is a carboxylate salt that is composed and decarboxylated by irradiation with light, and as a result, bases such as free guanidines, phosphazene derivatives, and amidines are generated. The scheme is as shown in the following scheme 1 (guanidines), scheme 2 (phosphazene derivatives) and scheme 3 (amidines).

(Scheme 1)

(Scheme 2)

(Scheme 3)

  In the base generator represented by the formula (X), Ar constituting the carboxylic acid to be decarboxylated by light irradiation is an aromatic ring, preferably an aryl group or a naphthyl group. Moreover, these aromatic rings can contain a benzoyl group, a nitro group, an alkoxy group, and an alkyl group as a substituent. It is preferable that carbon number of an alkoxy group and an alkyl group shall be 1-4. In addition, the substituent of this aromatic ring can take a ring structure.

  Further, R ′ and R ″ constituting the carboxylic acid are each a substituent such as a hydrogen atom, an alkoxy group, an alkyl group, a hydroxyl group, or an aryl group. It is preferable that carbon number of an alkoxy group and an alkyl group shall be 1-4.

  In the base generator applied to the photosensitive resin composition of the present invention, examples of the target carboxylic acid include ketoprofen (2- (1-carboxyethyl) benzophenone represented by the following formula (IV), for example. Can be used. Among the carboxylic acids that cause photodecarboxylation, ketoprofen has the highest quantum yield (photodecarboxylation efficiency) (about φ = 0.75), and by using ketoprofen as the carboxylic acid, an extremely efficient base generator Function as.

  As the carboxylic acid, xanthone acetic acid represented by the following formula (V), thioxanthone acetic acid represented by the following formula (VI), and nitrophenyl acetic acid represented by the formula (VII) are used. Also good. These carboxylic acids also have a high quantum yield (photodecarboxylation efficiency) of about φ = 0.64 (xanthone acetic acids and thioxanthone acetic acids are about the same) and φ = 0.6 (nitrophenyl acetic acid). A photochemically free base can be generated with high efficiency.

In formula (V) and formula (VI), R ₁ , R ₂ and R ₃ represent CH ₂ COOH, CH (CH ₃ ) COOH or H, and such CH ₂ COOH or CH (CH ₃ ) COOH represents R ₁ , R ₂ , or R ₃ is attached to any one group, and the remaining two groups are attached to H. In the formula (VII), R ₁ , R ₂ and R ₃ represent CH ₂ COOH or H, and the CH ₂ COOH is attached to any one group of R ₁ , R ₂ and R ₃ , and the rest H is attached to the two groups.

Examples of the bases B constituting the base generator represented by the formula (X) include guanidines represented by the following formula (I) and phosphazene derivatives represented by the following formula (II). Incidentally, _R 1 to R ₅ in formula (I), each of _R 1 to R ₇ in Formula (II), independently represent a hydrogen atom or an alkyl group or an aryl group (the alkyl group may be cyclic structure.) The alkyl group preferably has 1 to 4 carbon atoms.

（式（Ｉ）中、Ｒ_１〜Ｒ_５はそれぞれ、独立して水素原子、アルキル基またはアリール基（アルキル基は環状構造でもよい。）を示す。）

(In formula (I), R _{1 to} R ₅ each independently represent a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

（式（II）中、Ｒ_１〜Ｒ_７はそれぞれ、独立して水素原子、アルキル基またはアリール基
（アルキル基は環状構造でもよい。）を示す。）

(In formula (II), R _{1 to} R ₇ each independently represent a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

  Examples of the guanidine represented by the formula (I) that can be used as the base include, for example, guanidine represented by the following formula (Ia) having a guanidine structure and 1, 1 represented by the following formula (Ib). 1,3,3-tetramethylguanidine (TMG), 1,5,7-triaza-bicyclo [4.4.0] dec-5-ene (1,5,7-) represented by the following formula (Ic) triaza-bicyclo [4.4.0] dec-5-ene: TBD), MTBD shown in formula (Id), ETBD shown in formula (Ie), ITBD shown in formula (If), formula Examples thereof include compounds represented by (Ig) or formula (Ih) (formulas (Ia) to (Ih) represent proton adducts).

  Moreover, as a phosphazene derivative represented by the formula (II) that can be used as a base, the following formula (II-a), formula (II-b), formula (II-c), (II-d) Or the compound shown to a formula (II-e) etc. is mentioned (it represents a proton adduct about Formula (II-a)-a formula (II-e)).

  Furthermore, examples of the bases B constituting the base generator represented by the formula (X) include amidines represented by the following formula (III).

（式（III）中、ｎは１〜３の整数を示す。）

(In formula (III), n represents an integer of 1 to 3.)

  Examples of amidines represented by formula (III) that can be used as bases include diazabicyclononene (DBN) represented by the following formula (III-a) having an amidine structure, and the following formula (III- and diazabicycloundecene (DBU) shown in b).

  In order to produce the base generator represented by the formula (X), the desired carboxylic acid and the guanidines, phosphazene derivatives and amidines to be generated, which are bases, can be easily produced. it can.

  Such a base generator is a compound (carboxylate) represented by the formula (X) described above, and a predetermined guanidine, phosphazene derivative, or amidine is used as a binding target of the carboxylic acid constituting the compound. Therefore, if the acid dissociation constant (pKa) is a base generator of formula (I) and formula (II), it generally exceeds 13.5, and if it is a base generator of formula (III), about 12 to 13 (Both in an aqueous solvent) (conventionally about 10 even with a tertiary amine), which is very basic and acts as an excellent photobase generator with high reaction efficiency during polymerization.

When such a base generator is applied to a combination of an epoxy resin (or oxetane resin) and a thiol compound, the base first extracts H ⁺ from thiol (RSH) to generate RS ⁻ (Scheme 4).

(Scheme 4)

The generated RS ⁻ initiates a chain polymerization reaction of the epoxy resin (Scheme 5). In Scheme 4 and Scheme 5, the base is described as TBD.

(Scheme 5)

In order to cure an epoxy resin by an anion curing reaction using a combination of an epoxy resin and a thiol, as shown in Scheme 4 described above, first, H ⁺ is extracted from thiol (RSH) by a base (in the scheme, TBD) RS ^- it is necessary to generate a but, since H ⁺ withdrawal efficiency also depends on the base strength, higher base strength is higher elimination reaction is liable to occur, cures with high efficiency by using guanidines, phosphazene derivative or amidines Will go on.

  And by applying these salts to epoxy resins and thiol compounds as base generators in combination with carboxylic acids that are decarboxylated by light irradiation, bases with high efficiency and high base strength are generated by light irradiation, and thiol compounds Since the epoxy resin is polymerized in a chain manner, the photosensitive resin composition can be efficiently cured at room temperature by light irradiation.

A scheme in the case of an oxetane-based resin is shown below. As in the case of the epoxy resin described above, the generated RS ⁻ initiates a chain polymerization reaction of the oxetane resin. Here, the base is described as B.

(Scheme corresponding to oxetane resin)

In addition, as the range of the wavelength and exposure amount of irradiation light in the photosensitive resin composition according to the present invention, the type and amount of the base generator, and the epoxy resin, oxetane resin, and thiol constituting the photosensitive resin composition What is necessary is just to determine suitably according to the kind etc. of a compound etc., For example, what is necessary is just to select and apply from the range of 190-400 nm as a wavelength, and 100-10000 mJ / cm < ² > as an exposure amount, The sensitizer mentioned later is used. Therefore, it is possible to use a higher wavelength region. For example, when ketoprofen, xanthone acetic acid, and nitrophenyl acetic acid are used as the carboxylic acid, the ketoprofen and nitrophenyl acetic acid may be around 254 nm, and the xanthone acetic acid and thioxanthone acetic acid may be around 254 nm or around 365 nm. Good. Although irradiation time of irradiation light may be possible even for several seconds, it may be about 10 seconds or more, and preferably 1.5 to 20 minutes.

  The content of the base generator in the photosensitive resin composition of the present invention is preferably 0.1 to 60 parts by mass with respect to 100 parts by mass of the epoxy resin or oxetane resin. When the content of the base generator is less than 0.1 parts by mass, the epoxy resin or the oxetane resin may not be allowed to react rapidly, whereas when the content of the base generator exceeds 60 parts by mass. The presence of the base generator may adversely affect the solubility of the epoxy resin or oxetane resin in the solvent, and the presence of an excessive amount of the base generator leads to high costs. The content of the base generator is preferably 1 to 60 parts by mass, more preferably 2 to 30 parts by mass, and more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin or oxetane resin. It is more preferable to set it as 2-15 mass parts.

  In order to form a pattern using such a photosensitive resin composition, for example, the resin composition is dissolved in an organic solvent to prepare a coating solution, and the prepared coating solution is applied to an appropriate solid surface such as a substrate. And then dried to form a coating film. And after performing pattern exposure with respect to the formed coating film and generating a base, it heat-processes on predetermined conditions, The polymerization reaction of the base reactive compound contained in the photosensitive resin composition is carried out. To encourage.

  If necessary, the photosensitive resin composition of the present invention preferably contains a base proliferating agent that generates a base proliferatively by the action of a base. By including a base proliferating agent in the photosensitive resin composition of the present invention, the sensitivity of the resin composition can be further improved. In particular, when the light does not reach the deep part of the resin film (when the photosensitive layer is thick or contains a large amount of dye or pigment, etc.), the action of the photochemically generated base in the surface layer and the base by the base proliferating agent When the growth reaction is started, bases are generated thermochemically and in a chain manner, so that a base-catalyzed reaction in the deep part of the membrane can be expected. The base proliferating agent that can be used is not particularly limited, and examples thereof include JP-A No. 2000-330270 and JP-A No. 2002-128750. Arimitsu, M.M. Miyamoto and K.M. Ichimura, Angew. Chem. Int. Ed. , 39, 3425 (2000), and the like. The addition amount of the base proliferating agent may be appropriately determined depending on the base generator or base-reactive compound used, but is preferably in the range of 1 to 40% by mass with respect to the entire photosensitive resin composition. It is particularly preferable that the content be in the range of ˜20% by mass.

In the photosensitive resin composition of the present invention, a sensitizer can be added in order to expand the photosensitive wavelength region and increase the sensitivity. The sensitizer that can be used is not particularly limited. For example, benzophenone, p, p′-tetramethyldiaminobenzophenone, p, p′-tetraethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene. , Pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro -4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2- ert-butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis (5 , 7-dimethoxycarbonylcoumarin) or coronene. These sensitizers may be used alone or in combination of two or more.

  In the photosensitive resin composition of the present invention, the addition amount of the sensitizer may be appropriately determined depending on the base generator used, the epoxy resin or oxetane resin, the thiol compound, the required sensitivity, and the like. It is preferable that it is the range of 1-30 mass% with respect to the whole photosensitive resin composition. If the sensitizer is less than 1% by mass, the sensitivity may not be sufficiently increased. On the other hand, if the sensitizer exceeds 30% by mass, the sensitivity may be excessive. The addition amount of the sensitizer is particularly preferably in the range of 5 to 20% by mass with respect to the entire photosensitive resin composition.

  When the photosensitive resin composition of the present invention is applied to a predetermined substrate, a solvent may be appropriately contained as necessary. By including a solvent in the photosensitive resin composition, the coating ability can be increased, and workability is improved. The solvent is not particularly limited. For example, aromatic hydrocarbon compounds such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, and diethylbenzene; cyclohexane, cyclohexene, dipentene, n-pentane, isopentane, n-hexane, Saturated or unsaturated hydrocarbon compounds such as isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, tetrahydronaphthalene, squalane; diethyl ether, di-n-propyl ether, Di-isopropyl ether, dibutyl ether, ethyl propyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibuty Ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol methyl ethyl Ether, tetrahydrofuran, 1,4-dioxane, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, ethylcyclohexane, methylcyclohexane, p-menthane, o- Ethers such as dipropyl ether and dibutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone and cycloheptanone; Examples thereof include esters such as ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, methyl cellosolve, ethyl acetate cellosolve, butyl cellosolve, ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate, and butyl stearate. One of these solvents may be used alone, or two or more of these solvents may be used in combination.

  In the photosensitive resin composition of the present invention, the content of the solvent is, for example, uniformly applied when a photosensitive resin composition is applied on a predetermined substrate to form a layer of the photosensitive resin composition. The selection may be made as appropriate.

  In addition, you may make it add an additive suitably to the photosensitive resin composition of this invention in the range which does not inhibit the objective and effect of this invention. Examples of additives that can be used include fillers, pigments, dyes, leveling agents, antifoaming agents, antistatic agents, ultraviolet absorbers, pH adjusters, dispersants, dispersion aids, surface modifiers, Examples thereof include a plasticizer, a plastic accelerator, an anti-sagging agent, and a curing accelerator. One of these may be used alone, or two or more may be used in combination.

The photosensitive resin composition according to the first invention of the present invention described above has a high base strength and a carboxylic acid that is decarboxylated by light irradiation in addition to a thiol compound that serves as a curing accelerator, relative to an epoxy resin. Since it contains a carboxylate that combines guanidines, phosphazene derivatives or amidines as a base generator, a carboxylic acid that is decarboxylated by light irradiation generates a free base with high efficiency and a base such as guanidines. A strong base can extract H ⁺ from thiol (RSH) and generate RS ⁻ efficiently. Then, the generated RS ^- because the reaction between the epoxy-based resin proceeds in a chain makes a photosensitive resin composition cured at room temperature level is carried out efficiently and reliably.

The photosensitive resin composition according to the second invention of the present invention is a oxetane resin, in addition to a thiol compound serving as a curing accelerator, a carboxylic acid that is decarboxylated by light irradiation, and a guanidine having a high base strength. Since it contains a carboxylate combined with phosphazene derivatives or amidines as a base generator, a carboxylic acid that is decarboxylated by light irradiation generates a free base with high efficiency and a high base strength such as guanidines. The base can withdraw H ⁺ from thiol (RSH) and efficiently generate RS ⁻ . And, since the reaction with the oxetane resin proceeds in a chain manner due to the generated RS ^{−, the} photosensitive resin composition can be cured efficiently and reliably.

  And the photosensitive resin composition of this invention which show | plays this effect can be used suitably for a highly sensitive photocuring material, a resist material, etc., for example.

  The molded body applied as a photo-curing material can be used as a member in a field where characteristics such as heat resistance, dimensional stability, and insulation are effective, for example, paint or printing ink, color filter, film for flexible display, semiconductor, etc. Widely used as equipment, electronic parts, interlayer insulation films, wiring coating films, optical circuits, optical circuit parts, antireflection films, holograms, optical members or building materials, printed materials, color filters, films for flexible displays, A semiconductor device, an electronic component, an interlayer insulating film, a wiring coating film, an optical circuit, an optical circuit component, an antireflection film, a hologram, an optical member, a building member, or the like is provided. In addition, the formed pattern has heat resistance and insulation, for example, color filters, flexible display films, electronic components, semiconductor devices, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, reflective It can be advantageously used as a protective film, other optical member or electronic member.

  The aspect described above shows one aspect of the present invention, and the present invention is not limited to the above-described embodiment, and has the configuration of the present invention and can achieve the objects and effects. It goes without saying that modifications and improvements within the scope are included in the content of the present invention. Further, the specific structure, shape, and the like in carrying out the present invention are not problematic as other structures, shapes, and the like as long as the objects and effects of the present invention can be achieved. The present invention is not limited to the above-described embodiments, and modifications and improvements within the scope that can achieve the object of the present invention are included in the present invention.

  For example, in the above-described embodiment, a compound in which one guanidine, phosphazene derivative or amidine is added to the carboxylic acid represented by the formula (X) as a base generator constituting the photosensitive resin composition of the present invention. However, the present invention is not limited to this, and examples of the base generator include those obtained by adding two carboxylic acids to amidines and the like. As an example, a compound obtained by adding two carboxylic acids of the formula (X) to 1,5,7-triaza-bicyclo [4.4.0] dec-5-ene (TBD) is shown as the following formula (X ′). It was.

In addition, the specific structure, shape, and the like in the implementation of the present invention may be other structures as long as the object of the present invention can be achieved.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, this invention is not limited to this Example at all.

[Example 1]
Production of photosensitive resin composition (1):
The photosensitive resin composition which concerns on this invention was manufactured using the method of following (1) and (2).

(1) Production of base generator (Production Example 1):
To a solution of 0.50 g (2.0 × 10 ⁻³ mol) of 2-xanthone acetic acid represented by the following formula (Va) in tetrahydrofuran (THF), 0.27 g of TBD represented by the formula (Ic) (2. 0 × 10 ⁻³ mol) was added dropwise, and the white solid obtained by mixing at room temperature for 1 hour was subjected to suction filtration, washed with tetrahydrofuran (THF), and dried under reduced pressure to reduce the white solid of the base generator to 0. Obtained .33 g (43% yield). The decomposition point was 232.9 ° C. (DSC).

¹ H-NMR (300 MHz, CD ₃ OD): d (ppm) 1.93-1.98 (4H, m, CH), 3.32-3.33 (8H, m, CH), 3.64 ( _{2H, s, CH 2),} 7.41-8.25 (7H, m, Ar-H)

Confirmation of photolysis behavior:
About the base generator obtained in (1), methanol was used as a solvent, and the photodegradation behavior was confirmed using the following measurement method. As a result, the base generator obtained in (1) showed an increase in absorption intensity near 237 nm with the exposure dose of light irradiation, and the photodegradation behavior could be confirmed.

(Measuring method)
The wavelength is 2 in the methanol solution (3 × 10 ⁻⁵ mol / L) of the base generator obtained in (1).
Irradiate with light of 54 nm or 365 nm, and UV-visible spectrophotometer (MultiSpec-1
500 / manufactured by Shimadzu Corporation), and the change with time of the UV spectrum was confirmed.

Confirmation of base generation ability by light irradiation:
A methanol solution prepared by adjusting the base generator obtained in (1) to 9.0 × 10 ⁻³ mol / L is put in a quartz cell, and a predetermined amount of light having a wavelength of 365 nm is irradiated and photodecomposed, The UV spectrum was measured when 1 mL of a phenol red solution previously adjusted to 5.0 × 10 ⁻⁵ mol / L was added. The results are shown in FIG.

FIG. 1 is a diagram showing changes in UV spectrum. As shown in FIG. 1, when the base generator obtained in (1) is exposed, the absorption near 562 nm increases, so that a free base is generated by irradiating the base generator with light. It was confirmed that

(2) Production of photosensitive resin composition:
Epoxy (manufactured by EX-614B / Nagase _ChemteX) resin is a sorbitol polyglycidyl ether (M W = 406) 0.50g ( 1.2 × 10 -3 mol), pentaerythritol tetrakis a thiol compound ( 3-mercaptobutyrate) (Kalenz MT (registered trademark) PE-1 / manufactured by Showa Denko KK) 0.67 g (1.2 × 10 ⁻³ mol) base generation obtained in (1) The photosensitive resin composition of the present invention was obtained by adding 0.05 g of an agent (10 parts by mass with respect to 100 parts by mass of the epoxy resin) (10 mol% with respect to the monomer unit of the epoxy resin and the thiol compound). .

[Comparative Example 1]
A photosensitive resin composition was produced in the same manner as in Example 1 except that a base generator using an equimolar amount of cyclohexylamine was used instead of TBD in Example 1 (1).

[Reference Example 1]
A photosensitive resin composition was produced in the same manner as in Example 1 except that no base generator was contained.

[Test Example 1]
Curing confirmation at room temperature (1) (Comparison with amine):
The photosensitive resin composition obtained in Example 1, Comparative Example 1 and Reference Example 1 was dissolved in methanol to obtain a sample solution. This sample solution was bar-coated on a glass substrate to form a film, heated at 60 ° C. for 30 seconds and prebaked to prepare a coating film having a thickness of 14.0 μm. The coating film was irradiated with monochromatic light of 365 nm at room temperature (25 ° C.) without heating, with exposure doses of 0 (blank), 1000 and 10000 mJ / cm ² for 100 seconds, and after 30 minutes had elapsed. The hardness of the film was measured for pencil hardness in accordance with JIS K5600-5-4, and compared and evaluated. The results are shown in FIG.

FIG. 2 is a diagram showing the relationship between the exposure amount and pencil hardness in Test Example 1. As shown in FIG. 2, it was confirmed that Example 1 was cured at room temperature by light irradiation. On the other hand, Comparative Example 1 containing cyclohexylamine as a base generator did not cure at room temperature even when the exposure amount was 10,000 mJ / cm ^2, as in Reference Example 1 containing no base generator.

[Test Example 2]
Confirmation of curing at room temperature (2) (time dependence):
About the photosensitive resin composition obtained in Example 1, the coating film with a thickness of 14.0 micrometers was prepared on the glass substrate by the method similar to the method shown in Test Example 1. The coating film was irradiated with a monochromatic light of 365 nm at room temperature (25 ° C.) without heating, with exposure doses of 0, 1000 and 10000 mJ / cm ² for 100 seconds. The hardness of the coating film after the lapse of minutes was measured by pencil hardness according to JIS K5600-5-4, and compared and evaluated. The results are shown in FIG.

  FIG. 3 is a diagram showing the relationship between the exposure amount and the pencil hardness in Test Example 2. As shown in FIG. 3, the photosensitive resin composition of Example 1 begins to cure immediately after light irradiation at room temperature, and then progresses as time passes and increases the exposure amount. It was confirmed that curing was promoted.

[Production Example 2]
Production of base generator (2):
Diazabicyclononene (DBN) represented by the formula (III-a) was added to a tetrahydrofuran (THF) solution of 0.25 g (0.93 × 10 ⁻³ mol) of methylxanthone acetic acid represented by the following formula (Vb). After 0.11 g (0.93 × 10 ⁻³ mol) was added dropwise and mixed at room temperature for 1 hour, the solvent was distilled off under reduced pressure. Thereafter, impurities were extracted and removed using ether as a poor solvent and tetrahydrofuran (THF) as a good solvent to obtain 0.24 g (yield 65%) of a yellow viscous liquid as a base generator.

[Production Example 3]
Production of base generator (3):
To a solution of 0.25 g (0.93 × 10 ⁻³ mol) of methylxanthone acetic acid shown in the above formula (Vb) in tetrahydrofuran (THF), diazabicycloundecene shown in the formula (III-b) ( DBU) 0.14 g (0.93 × 10 ⁻³ mol) was added dropwise and mixed for 1 hour at room temperature, and then the solvent was distilled off under reduced pressure. Thereafter, impurities were extracted and removed using ether as a poor solvent and tetrahydrofuran (THF) as a good solvent to obtain 0.26 g (yield 66%) of a yellow viscous liquid as a base generator.

[Production Example 4]
Production of base generator (4):
To a tetrahydrofuran (THF) solution of 0.30 g (1.1 × 10 ⁻³ mol) of methylxanthone acetic acid shown in the above formula (Vb) was added 1,5,7-shown in the formula (Ic). After 0.16 g (1.1 × 10 ⁻³ mol) of triaza-bicyclo [4.4.0] dec-5-ene (TBD) was added dropwise and mixed at room temperature for 1 hour, the solvent was distilled off under reduced pressure. The obtained solid was washed with tetrahydrofuran (THF) and dried under reduced pressure to obtain 0.26 g (yield 58%) of a white solid as a base generator.

[Production Example 5]
Production of base generator (5):
To an ethanol solution of 0.10 g (0.37 × 10 ⁻³ mol) of methylxanthone acetic acid shown in the above formula (Vb), imino-tris (dimethylamino) phosphorane 0 shown in the formula (II-e) .16 g (0.37 × 10 ⁻³ mol) was added dropwise, and the yellow viscous liquid obtained by mixing at room temperature for 1 hour was washed with ether, so that 0.10 g of the yellow viscous liquid of the base generator was obtained ( Yield 60%).

Confirmation of photolysis behavior:
For the base generator obtained in Production Example 5, the photodegradation behavior was confirmed using the following measurement method using methanol as a solvent. As a result, it was observed that the base generator obtained in Production Example 5 increased in absorption intensity around 240 nm with the exposure dose of light irradiation, and the photodegradation behavior could be confirmed.

(Measuring method)
The methanol solution (1.0 × 10 ⁻⁵ mol / L) of the base generator obtained in Production Example 5 was irradiated with light having a wavelength of 254 nm or 365 nm, and an ultraviolet-visible spectrophotometer (MultiSpec-1500 / Co., Ltd.) The time course of the UV spectrum was confirmed using Shimadzu Corporation.

Confirmation of base generation ability by light irradiation:
A methanol solution prepared with 2 ml (8.9 × 10 ⁻³ mol / L) of the base generator obtained in Production Example 5 was placed in a quartz cell and irradiated with a predetermined amount of light having a wavelength of 254 nm and 365 nm, and photolysis was performed. Then, the UV spectrum was measured when 2 mL of a phenol red solution that had been adjusted to 5.0 × 10 ⁻⁵ mol / L in advance was added to this solution. The results are shown in FIG. 4 (254 nm) and FIG. 5 (365 nm).

  4 and 5 are diagrams showing changes in the UV spectrum. As shown in FIG. 4 and FIG. 5, the base generator obtained in Production Example 5 is reduced in absorption near 424 nm and increased in absorption near 562 nm as it is exposed. It was confirmed that free base was generated by light irradiation.

[Example 2]
Production of photosensitive resin composition (2):
Oxetane resin 3 - (((3-ethyloxetan-3-yl) methoxy) methyl) -3- ethyloxetane (OXT-221, manufactured by Toagosei _(Inc.)) (M W = 214) 0.20 g ( 9.33 × 10 ⁻⁴ mol), pentaerythritol tetrakis (3-mercaptobutyrate) which is a thiol compound (Karenz MT (registered trademark) PE-1 / manufactured by Showa Denko KK) 0.19 g (3.50 × ^10-4 mol), the base generator obtained in Production Example 2 is contained in an amount of 0.039 g (20 parts by mass with respect to 100 parts by mass of the oxetane resin), whereby the photosensitive resin composition of the present invention is contained. Obtained.

[Example 3]
Manufacture of photosensitive resin products (3)
Oxetane resin 3 - (((3-ethyloxetan-3-yl) methoxy) methyl) -3- ethyloxetane (OXT-221, manufactured by Toagosei _(Inc.)) (M W = 214) 0.20 g ( 9.33 × 10 ⁻⁴ mol), pentaerythritol tetrakis (3-mercaptobutyrate) which is a thiol compound (Karenz MT (registered trademark) PE-1 / manufactured by Showa Denko KK) 0.19 g (3.50 × ^10-4 mol), the base generator obtained in Production Example 3 is contained in an amount of 0.037 g (18.5 parts by mass with respect to 100 parts by mass of the oxetane-based resin). I got a thing.

[Example 4]
Manufacture of photosensitive resin products (4)
Oxetane resin 3 - (((3-ethyloxetan-3-yl) methoxy) methyl) -3- ethyloxetane (OXT-221, manufactured by Toagosei _(Inc.)) (M W = 214) 0.20 g ( 9.33 × 10 ⁻⁴ mol), pentaerythritol tetrakis (3-mercaptobutyrate) which is a thiol compound (Karenz MT (registered trademark) PE-1 / manufactured by Showa Denko KK) 0.19 g (3.50 × ^10-4 mol), by containing 0.038 g of the base generator obtained in Production Example 4 (19 parts by mass with respect to 100 parts by mass of the oxetane resin), the photosensitive resin composition of the present invention is contained. Obtained.

[Example 5]
Manufacture of photosensitive resin products (5)
Oxetane resin 3 - (((3-ethyloxetan-3-yl) methoxy) methyl) -3- ethyloxetane (OXT-221, manufactured by Toagosei _(Inc.)) (M W = 214) 0.20 g ( 9.33 × 10 ⁻⁴ mol), pentaerythritol tetrakis (3-mercaptobutyrate) which is a thiol compound (Karenz MT (registered trademark) PE-1 / manufactured by Showa Denko KK) 0.19 g (3.50 × ^10-4 mol), the base generator obtained in Production Example 5 is contained in an amount of 0.042 g (21 parts by mass with respect to 100 parts by mass of the oxetane resin), whereby the photosensitive resin composition of the present invention is contained. Obtained.

[Test Example 3]
Curing confirmation test:
The photosensitive resin composition obtained in Examples 2 to 5 was dissolved in 0.1 g of methanol to obtain a sample solution. This sample solution was bar-coated on a glass substrate to form a film, heated at 60 ° C. for 60 seconds and prebaked to prepare a coating film having a thickness of 50 μm. The coating film was irradiated with monochromatic light of 365 nm at room temperature (25 ° C.) with an exposure amount of 0 (blank), 100, 1000, 5000 and 10000 mJ / cm ² , and not heated, and 60 ° C. The hardness of the coating film heated at 80 ° C. and 100 ° C. for 5 minutes was measured in accordance with JIS K5600-5-4, and compared and evaluated. The results are shown in FIG. 6 (Example 2), FIG. 7 (Example 3), FIG. 8 (Example 4), and FIG. 9 (Example 5), respectively.

  6 to 9 are diagrams showing the relationship between the exposure amount and the pencil hardness in Test Example 3. FIG. As shown in FIGS. 6 to 9, it was confirmed that Examples 2 to 5 were cured by light irradiation.

  The present invention can be advantageously used as a photosensitive resin material that provides a photo-curing material, a resist material (pattern forming material), and the like.

Claims (3)

It contains an epoxy resin having a plurality of epoxy groups, a thiol compound having a plurality of thiol groups, and a base generator composed of a carboxylate represented by the following formula (X), and is liquid at room temperature Photosensitive resin composition.

(In the formula (X), A ^- it is of the formula (IV), a (V), the carboxylic acid represented by any one of (VI) and (VII), ^{B +} is below formula (I), the formula ( Ic), formula (Id), formula (Ie), formula (If), formula (Ig), guanidines represented by formula (Ih), formula (II) And a phosphazene derivative represented by the formula (II-c) and the formula (II-d) and an amidine represented by the formula (III).

(In the formula (V) and the formula (VI), R ₁ , R ₂ and R ₃ represent CH ₂ COO ⁻ , CH (CH ₃ ) COO ⁻ or H, and such CH ₂ COO ⁻ or CH (CH ₃ ) COO ^- it is subjected to either one group of _{R 1, R 2, R 3} , the remaining two groups H are attached).

(In the formula _{(VII), R 1, R} 2, R 3 is _CH 2 COO ^- indicates or H, according _CH 2 COO ^- is subjected to either one group of _{R 1, R 2, R 3} , remaining H is attached to these two groups.)

(In formula (I), R _{1 to} R ₅ each independently represent a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

(In formula (II), R _{1 to} R ₇ each independently represent a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

(In formula (III), n represents an integer of 1 to 3.) A photosensitive resin composition comprising an oxetane resin having a plurality of oxetanyl groups, a thiol compound having a plurality of thiol groups, and a base generator composed of a carboxylate represented by the following formula (X).

(In the formula (X), A ^- it is of the formula (IV), a (V), the carboxylic acid represented by any one of (VI) and (VII), ^{B +} is below formula (I), the formula ( Ic), formula (Id), formula (Ie), formula (If), formula (Ig), guanidines represented by formula (Ih), formula (II) And a phosphazene derivative represented by the formula (II-c) and the formula (II-d) and an amidine represented by the formula (III).

(In the formula (V) and the formula (VI), R ₁ , R ₂ and R ₃ represent CH ₂ COO ⁻ , CH (CH ₃ ) COO ⁻ or H, and such CH ₂ COO ⁻ or CH (CH ₃ ) COO ^- it is subjected to either one group of _{R 1, R 2, R 3} , the remaining two groups H are attached).

(In the formula _{(VII), R 1, R} 2, R 3 is _CH 2 COO ^- indicates or H, according _CH 2 COO ^- is subjected to either one group of _{R 1, R 2, R 3} , remaining H is attached to these two groups.)

(In formula (I), R _{1 to} R ₅ each independently represent a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

(In formula (II), R _{1 to} R ₇ each independently represent a hydrogen atom, an alkyl group or an aryl group (the alkyl group may be a cyclic structure).)

(In formula (III), n represents an integer of 1 to 3.) The bases are represented by the formula (I) , formula (Ic), formula (Id), formula (Ie), formula (If), formula (Ig), formula (Ih) guanidines represented by), or the formula (II), formula (II-c), according to claim 1 or claim 2, characterized in that a phosphazene derivative represented by formula (II-d) Photosensitive resin composition.

Images