KR102669269B1 - Compound, latent base generator, photosensitive resin composition containing the compound, and cured product - Google Patents

Abstract

The object of the present invention is to develop a novel compound that exhibits sufficient absorption of long-wavelength ultraviolet rays (particularly, 365 nm) and has satisfactory sensitivity (base generation ability), a latent base generator containing the compound, and a polymerization initiator using the compound. The object is to provide a photosensitive resin composition containing and a cured product thereof.
The present invention provides a compound represented by the following general formula (I). Furthermore, the present invention provides a latent base generator containing the above compound, a polymerization initiator containing the above compound, a photosensitive resin composition containing the above polymerization initiator (A) and a photosensitive resin (B), and a cured product thereof and its preparation. Provides a method.
(Refer to the specification for definitions of symbols in the formula.)

Description

Compound, latent base generator, photosensitive resin composition containing the compound, and cured product

The present invention relates to a novel compound useful as a polymerization initiator used in a photosensitive resin composition, a latent base generator containing the compound, a photosensitive resin composition formed by adding the compound to a photosensitive resin, and a cured product of the photosensitive resin composition. will be.

In general, photosensitive resin compositions are made by adding a photopolymerization initiator to photosensitive resin, and can be polymerized, cured, or developed by irradiation with energy rays (light), so they are used in photocurable inks, photosensitive printing plates, various photoresists, photocurable adhesives, etc. there is.

Photopolymerization initiators are divided into photoradical generators, photoacid generators, and photobase generators, depending on the active species generated by energy ray (light) irradiation. Photo radical generators have the advantage of having a fast curing speed and no active species remaining after curing. However, since curing is inhibited by oxygen, they have the disadvantage of having to provide a layer to block oxygen in the curing of thin films. While photoacid generators have the advantage of not being inhibited by oxygen, they have the disadvantage of corroding metal substrates or denaturing resin after curing due to residual acid of active species. Photobase generators are attracting attention because they are difficult to cause problems such as curing inhibition by oxygen and corrosion by remaining active species, but they generally have the problem of low sensitivity (low curing property) compared to photoacid generators. Photobase generators are disclosed, for example, in Patent Documents 1 to 4, etc.

US Patent Publication US6551761 (2003.04.22) US Patent Publication US8957212 (2015.02.17) International Publication WO2010/064632 (2010.06.10) US Patent Publication US9594302 (2017.03.14)

Therefore, the object of the present invention is to provide a novel compound that exhibits sufficient absorption of long-wavelength ultraviolet rays (particularly, 365 nm) and has satisfactory sensitivity (base generation ability), a potential base generator containing the compound, and the compound. The object is to provide a photosensitive resin composition containing a polymerization initiator and a cured product thereof.

The present inventor conducted intensive studies and found that compounds having a specific structure have high sensitivity (base generation ability) as a polymerization initiator.

The present invention achieves the above object by providing the following [1] to [9].

[1] A compound represented by the following general formula (I).

(In the formula, R ¹ represents a hydrogen atom, a cyano group, an unsubstituted or substituted aliphatic hydrocarbon group of 1 to 20 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon group of 6 to 20 carbon atoms,

R ² , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently hydrogen atom, cyano group, nitro group, -OR ⁸ , -COOR ⁸ , -CO-R ⁸ , -SR ⁸ , halogen atom, radish An aliphatic hydrocarbon group with 1 to 20 carbon atoms that is substituted or has a substituent, an aromatic hydrocarbon group with 6 to 20 carbon atoms that is unsubstituted or has a substituent, or a group with 2 to 20 carbon atoms that is unsubstituted or has a substituent. Indicates a group containing summons,

R ³ contains an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group or heterocycle with 6 to 20 carbon atoms, and also contains an unsubstituted or substituted group. Represents a group having 2 to 20 carbon atoms,

R ⁸ contains a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group with 6 to 20 carbon atoms or a heterocycle, and is also unsubstituted. Or it represents a group with 2 to 20 carbon atoms that has a substituent,

X ¹ is -NR ¹¹ R ¹² , a group represented by (a) or (b) below,

R ¹¹ and R ¹² are each independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or

R ¹¹ and R ¹² are connected to each other, and are unsubstituted or have a substituent and are a ring with 1 to 20 carbon atoms consisting of a hydrogen atom, a nitrogen atom and a carbon atom, or a ring that is unsubstituted or has a substituent and is also a hydrogen atom, an oxygen atom and a nitrogen atom. It forms a ring with 1 to 20 carbon atoms, consisting of an atom and a carbon atom,

n represents 0 or 1.)

(In the formula, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom or the number of unsubstituted or substituent carbon atoms It is an aliphatic hydrocarbon group of 1 to 20 carbon atoms or an aromatic hydrocarbon group of 6 to 20 carbon atoms that is unsubstituted or has a substituent, or

At least one set of R ¹³ and R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ¹⁹ and R ²⁰ and R ²¹ and R ²² is connected to each other, is unsubstituted or has a substituent, and also contains a hydrogen atom or a nitrogen atom. and a ring having 1 to 20 carbon atoms consisting of a carbon atom, or a ring having 1 to 20 carbon atoms that is unsubstituted or has a substituent and is made of a hydrogen atom, an oxygen atom, a nitrogen atom and a carbon atom,

* represents the number of combinations.)

[2] In [1], at least one of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in the general formula (I) is a nitro group, benzoyl group or o-methylbenzoyl group as a substituent. The underlying compound that has

[3] In [1] or [2], at least one of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in the general formula (I) is a group represented by the following general formula (II) compound.

(In the formula, R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are each independently hydrogen atom, cyano group, nitro group, -OR ³⁰ , -COOR ³⁰ , -CO-R ³⁰ , -SR ³⁰ , halogen Contains an atom, an aliphatic hydrocarbon group with 1 to 20 carbon atoms that is unsubstituted or has a substituent, an aromatic hydrocarbon group or heterocycle with 6 to 20 carbon atoms that is unsubstituted or has a substituent, and is also unsubstituted or has a substituent. Represents a group having 2 to 20 carbon atoms or a group represented by the following general formula (III),

R ³⁰ contains an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group or heterocycle with 6 to 20 carbon atoms, and also contains an unsubstituted or substituted group. Represents a group having 2 to 20 carbon atoms,

At least one of R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ represents a nitro group, -CO-R ³⁰ or a group represented by the following general formula (III),

* indicates the number of bonds.)

(In the formula, R ³¹ represents an aliphatic hydrocarbon group with 1 to 20 carbon atoms that is unsubstituted or has a substituent, or an aromatic hydrocarbon group with 6 to 20 carbon atoms that is unsubstituted or has a substituent,

X ² is -NR ³² R ³³ , a group represented by (a') or (b') below,

R ³² and R ³³ are each independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or

R ³² and R ³³ are connected to each other, and are unsubstituted or have a substituent and are a ring with 1 to 20 carbon atoms consisting of a hydrogen atom, a nitrogen atom and a carbon atom, or a ring that is unsubstituted or has a substituent and is also a hydrogen atom, an oxygen atom and a nitrogen atom. It forms a ring with 1 to 20 carbon atoms, consisting of an atom and a carbon atom,

m represents 0 or 1, and * represents the number of bonds.)

(In the formula, R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ are each independently a hydrogen atom or the number of unsubstituted or substituent carbon atoms It is an aliphatic hydrocarbon group of 1 to 20 carbon atoms or an aromatic hydrocarbon group of 6 to 20 carbon atoms that is unsubstituted or has a substituent, or

At least one set of R ³⁴ and R ³⁵ , R ³⁶ and R ³⁷ , R ³⁸ and R ³⁹ , R ⁴⁰ and R ⁴¹ , and R ⁴² and R ⁴³ is connected to each other, is unsubstituted or has a substituent, and also contains a hydrogen atom or a nitrogen atom. and a ring having 1 to 20 carbon atoms consisting of a carbon atom, or a ring having 1 to 20 carbon atoms that is unsubstituted or has a substituent and is made of a hydrogen atom, an oxygen atom, a nitrogen atom and a carbon atom,

* indicates the number of bonds.)

[4] A latent base generator containing the compound according to any one of [1] to [3].

[5] A polymerization initiator containing the compound according to any one of [1] to [3].

[6] A photosensitive resin composition containing the polymerization initiator (A) and the photosensitive resin (B) according to [5].

[7] The photosensitive resin composition according to [6], wherein the photosensitive resin (B) is an epoxy resin or a phenol resin.

[8] A cured product obtained from the photosensitive resin composition according to [6] or [7].

[9] A method for producing a cured product comprising a step of irradiating an energy line to the photosensitive resin composition according to [6] or [7].

Hereinafter, preferred embodiments of the present invention will be described in detail.

The novel compound of the present invention is a carbamoyloxime compound represented by the above general formula (I). The carbamoyl oxime compound has geometric isomers due to the double bond of the oxime, but the general formula (I) does not distinguish them.

That is, in this specification, the compound represented by the general formula (I), and the compounds and exemplary compounds that are preferred forms of the compound described later represent a mixture of geometric isomers or one of them, and are not limited to isomers of the indicated structures.

On the other hand, when the methylene group in the group represented by R ¹ to R ⁸ and R ¹¹ to R ²² in the general formula (I) is substituted by a group containing a carbon atom, the number of carbon atoms included is the specified number of carbon atoms. do.

Unsubstituted aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹ to R ⁸ and R ¹¹ to R ²² in the general formula (I) include, for example, methyl, ethyl, propyl, isopropyl, butyl, and iso. Butyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, Dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, etc. are mentioned. In addition, R ¹ to R ⁸ , R ¹¹ to R ²² have methylene groups in these aliphatic hydrocarbon groups -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-, - Contributions substituted with SO ₂ -, -NR-, -NR-CO-, -CO-NR-, -NR-COO-, -OCO-NR- or -SiRR'- are also possible. However, these substituted divalent groups are not adjacent to each other.

R and R' are unsubstituted aliphatic hydrocarbon groups, and examples of the unsubstituted aliphatic hydrocarbon groups include unsubstituted aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹ to R ⁸ and R ¹¹ to R ²² above. You can use the same flag as the one mentioned above.

Unsubstituted aromatic hydrocarbon groups having 6 to 20 carbon atoms represented by R ¹ to R ⁸ and R ¹¹ to R ²² in the general formula (I) include phenyl, naphthyl, phenanthryl, pyrenyl, biphenyl, and aliphatic. Examples include phenyl, naphthyl, phenanthryl, pyrenyl, and biphenyl substituted by a hydrocarbon group. In addition, R ¹ to R ⁸ and R ¹¹ to R ²² are the alkylene portion of these aromatic hydrocarbon groups or the methylene group of the bonding portion between the aromatic ring and the aliphatic hydrocarbon group is -O-, -COO-, -OCO-, -CO-, - Substituted by CS-, -S-, -SO-, -SO ₂ -, -NR-, -NR-CO-, -CO-NR-, -NR-COO-, -OCO-NR- or -SiRR'- It can also be a contribution. However, these substituted divalent groups are not adjacent to each other.

Examples of the aliphatic hydrocarbon group include the same groups as those exemplified as the unsubstituted aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹ to R ⁸ and R ¹¹ to R ²² .

R and R' are unsubstituted aliphatic hydrocarbon groups, and examples of the unsubstituted aliphatic hydrocarbon groups include unsubstituted aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹ to R ⁸ and R ¹¹ to R ²² above. You can use the same flag as the one mentioned above.

An aliphatic hydrocarbon group having 1 to 20 carbon atoms and having substituents represented by R ¹ to R ⁸ , R ¹¹ to R ²² and 6 to 6 carbon atoms having substituents represented by R ¹ to R ⁸ and R ¹¹ to R ²² Examples of the aromatic hydrocarbon group of 20 include those in which the hydrogen atom of the unsubstituted product described above is substituted with a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH or -SO ₂ H. You can.

R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ¹⁹ and R ²⁰ and R ^{21 and R 22 ,} and R ³² and R ³³ , R ³⁴ and R ³⁵ , R ³⁶ and R ³⁷ , R ³⁸ and R ³⁹ , R ⁴⁰ and R ^{41, and at least one set of R 42 and} R ⁴³ are linked together to form a ring consisting of a hydrogen atom, a nitrogen atom and a carbon atom with 1 to 20 carbon atoms. Examples include groups containing a bonded nitrogen atom, such as pyrrole group, pyrrolidine group, imidazole group, imidazolidine group, imidazoline group, pyrazole group, pyrazolidine group, piperidine group, piperazine group, etc. , and the hydrogen atom of these rings may be substituted by a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH, -SO ₂ H, or an aliphatic hydrocarbon group.

Examples of the aliphatic hydrocarbon group include the same groups as those exemplified as the unsubstituted aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹ to R ⁸ and R ¹¹ to R ²² .

R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ¹⁹ and R ²⁰ and R ^{21 and R 22 ,} and R ³² and R ³³ , R ³⁴ and R ³⁵ , R At least one set of ³⁶ and R ³⁷ , R ³⁸ and R ³⁹ , R ⁴⁰ and R ⁴¹ , and R ⁴² and R ⁴³ is connected to each other to form a hydrogen atom, oxygen atom, nitrogen atom and carbon having 1 to 20 carbon atoms Rings made of atoms include groups containing a bonded nitrogen atom, such as morpholine group, oxazole group, oxazoline group, and oxadiazole group, and the hydrogen atoms of these rings are fluorine atom, chlorine atom, and bromine atom. , iodine atom, cyano group, nitro group, hydroxyl group, thiol group, -COOH, -SO ₂ H or an aliphatic hydrocarbon group.

Examples of the aliphatic hydrocarbon group include the same groups as those exemplified as the unsubstituted aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹ to R ⁸ and R ¹¹ to R ²² .

In the general formula (I), groups containing unsubstituted heterocycles having 2 to 20 carbon atoms represented by R ² to R ⁸ include tetrahydrofuran group, dioxoranyl group, tetrahydropyranyl group, and morpholylfuran group. , thiophene group, methylthiophene group, hexylthiophene group, benzothiophene group, pyrrole group, pyrrolidine group, imidazole group, imidazolidine group, imidazoline group, pyrazole group, pyrazolidine group, piperi Dean group and piperazine group, and tetrahydrofuran group, dioxoranyl group, tetrahydropyranyl group, morpholylfuran group, thiophene group, methylthiophene group, hexylthiophene group, benzothiophene group, substituted with aliphatic hydrocarbon group, Examples include pyrrole group, pyrrolidine group, imidazole group, imidazolidine group, pyrazole group, pyrazolidine group, piperidine group, and piperazine group. In addition, R ² to R ⁸ represent the alkylene portion of the group containing these heterocycles and the methylene group of the bonding portion between the heterocycle and the alkyl group being -O-, -COO-, -OCO-, -CO-, -CS-, - Contributions substituted with S-, -SO-, -SO ₂ -, -NR-, -NR-CO-, -CO-NR-, -NR-COO-, -OCO-NR- or -SiRR'- can also be made. However, these substituted divalent groups are not adjacent to each other.

Meanwhile, in this specification, “2 to 20” in “a group containing a heterocycle having 2 to 20 carbon atoms” specifies the number of carbon atoms in the “group containing a heterocycle” rather than a “heterocycle”. .

Examples of the aliphatic hydrocarbon group include those exemplified as the unsubstituted aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹ to R ⁸ and R ¹¹ to R ²² .

R and R' are unsubstituted aliphatic hydrocarbon groups, and examples of the unsubstituted aliphatic hydrocarbon groups include unsubstituted aliphatic hydrocarbon groups having 1 to 20 carbon atoms represented by R ¹ to R ⁸ and R ¹¹ to R ²² above. You can use the same flag as the one mentioned above.

As a group containing a heterocycle having 2 to 20 carbon atoms and having a substituent represented by R ² to R ⁸ , the hydrogen atom of the group containing the unsubstituted heterocycle described above is a fluorine atom, a chlorine atom, a bromine atom, Examples include those substituted with an iodine atom, cyano group, nitro group, hydroxyl group, thiol group, -COOH or -SO ₂ H. On the other hand, when the group to be substituted contains a carbon atom or has a substituent, the number of these carbon atoms is the specified number of carbon atoms.

New compounds represented by the ^above general formula (I ^{) include} compounds ^{in which} , a compound in which R ¹¹ and R ¹² are aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and a compound in which R ¹¹ and R ¹² are connected to each other to form a ring having 1 to 20 carbon atoms consisting of a hydrogen atom, a nitrogen atom and a carbon atom. , or a compound in which R ¹¹ and R ¹² are linked to each other to form a ring having 1 to 20 carbon atoms consisting of a hydrogen atom, an oxygen atom, a nitrogen atom, and a carbon atom is preferable.

In addition, because of excellent UV sensitivity, long absorption wavelength, and excellent solubility in resins, at least one of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ is a nitro group, cyano group, or hydroxyl group. , a carboxyl group or a thiol group, or a group compound having these groups as a substituent is preferable, a nitro group or a group compound having a nitro group as a substituent is more preferable, and in particular, a group compound in which R ³ has a nitro group as a substituent is more preferable. desirable. The group having a nitro group as a substituent is preferably a nitrophenyl group.

Moreover, when used as a polymerization initiator, because of its excellent sensitivity, at least one of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is a benzoyl group, o-methylbenzoyl group or trifluoromethyl group, Compounds that are groups having these groups as substituents are also preferable, and in particular, compounds that are groups in which R ³ has a benzoyl group as a substituent are preferable. The group having a benzoyl group as a substituent is preferably a benzoylphenyl group.

Compounds in which at least one of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in the general formula (I) has a nitro group, benzoyl group or o-methylbenzoyl group as a substituent have an absorption wavelength range. It is preferable because it has a long wavelength (365 nm) and has excellent sensitivity when used as a polymerization initiator.

In the present invention, the following compounds are preferred because they have excellent UV sensitivity and curability when used in a photosensitive resin composition, and also have excellent sensitivity when used as a polymerization initiator.

In the general formula (I), R ¹ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, R ² , R ⁴ , R ⁵ , R ⁶ and R ⁷ are hydrogen atoms, and X ¹ is -NR ¹¹ R ¹² and R ¹¹ and R ¹² are an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or R ¹¹ and R ¹² are connected to each other and form a ring having 1 to 20 carbon atoms consisting of a hydrogen atom, a nitrogen atom and a carbon atom. , or a group compound that forms a ring with 1 to 20 carbon atoms consisting of a hydrogen atom, an oxygen atom, a nitrogen atom, and a carbon atom, and R ³ has a nitro group or benzoyl group as a substituent.

The compound in which at least one of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in the general formula (I) is a group represented by the general formula (II) has a long absorption wavelength range (365 nm) When used as a polymerization initiator, it is preferable because it has excellent sensitivity.

In general formula (II), the unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ²⁵ to R ⁴³ and the aromatic hydrocarbon group having 6 to 20 carbon atoms include R ¹ to R ⁸ , R The same groups as those exemplified include unsubstituted or substituted aliphatic hydrocarbon groups having 1 to 20 carbon atoms and unsubstituted or substituted aromatic hydrocarbon groups having 6 to 20 carbon atoms, respectively, represented by ¹¹ to R ²² .

In general formula (II), the group containing an unsubstituted or substituted heterocycle having 2 to 20 carbon atoms represented by R ²⁵ to R ³⁰ includes the group containing 2 to 20 carbon atoms represented by R ² to R ⁸ above. The same group as the group containing a substituted or substituted heterocycle can be mentioned.

One of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in the general formula (I) is a group represented by the general formula (II), and the other is a hydrogen atom, unsubstituted or has a substituent. Compounds that are an aliphatic hydrocarbon group with 1 to 6 carbon atoms or an aromatic hydrocarbon group with 6 to 12 carbon atoms that are unsubstituted or have a substituted group are preferred because they have excellent sensitivity and are easy to produce.

Compounds in which R ¹ in the general formula (I) is an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 12 carbon atoms or an unsubstituted or substituted aromatic hydrocarbon group with 6 to 12 carbon atoms are easy to produce. It is desirable in that respect.

A compound in which n in the general formula (I) is 0 is preferred because it has excellent sensitivity when used as a polymerization initiator.

The compound in which n in the general formula (I) is 1 is preferable because a cured product with excellent transparency can be obtained when used as a polymerization initiator.

Among the new compounds represented by the general formula (I), specific examples of compounds where n is 0 include the following compounds No. 1 to No. 74. However, the present invention is not limited in any way by the following compounds.

Among the new compounds represented by the general formula (I), specific examples of compounds where n is 1 include the following compounds No. 75 to No. 152. However, the present invention is not limited in any way by the following compounds.

The carbamoyloxime compound of the present invention represented by the general formula (I) is not particularly limited, but when n=0, it can be produced by the following method according to the following Scheme 1.

That is, indole compound 2 is obtained by reacting a known and commercially available indole compound 1 with an aryl halide or alkyl halide compound. A ketone compound is obtained by reacting this indole compound 2 with acid chloride, and an oxime compound is obtained by reacting the ketone compound with hydroxylamine hydrochloride. Next, the carbamoyloxime compound of the present invention represented by the general formula (I) is obtained by reacting the oxime compound with 4-nitrophenyl chloroformate and a primary or secondary amine in the presence of triethylamine.

^Meanwhile , Scheme 1 below shows the case where X ¹ is -NR ¹¹ R ¹² , but by changing the amine to be used, a compound where

Oxime compounds and carbamoyloxime compounds can also be produced by the method described in Japanese Patent Publication No. 4223071.

Scheme 1

(In the formula, R ¹ to R ¹² are the same as the general formula (I) above.)

In addition, the compound with n = 1 in the general formula (I) is not particularly limited, but can be produced by the following method according to Scheme 2 below.

That is, ketone compound 2 is obtained by reacting the indole compound 2 with acid chloride, and oxime compound 2 is obtained by reacting the ketone compound with isobutyl nitrite. Next, the carbamoyloxime compound 2 of the present invention represented by the general formula (I) is obtained by reacting the oxime compound 2 with 4-nitrophenyl chloroformate and a primary or secondary amine in the presence of triethylamine.

^Meanwhile , Scheme 2 below shows the case where X ¹ is -NR ¹¹ R ¹² , but by changing the amine to be used, a compound where

Oxime compounds and carbamoyloxime compounds can also be produced by the method described in Japanese Patent Publication No. 4223071.

Scheme 2

(In the formula, R ¹ to R ¹² are the same as the general formula (I) above.)

The novel compound of the present invention has excellent curing properties of photosensitive resins and high sensitivity to energy rays, so it can be suitably used as a polymerization initiator, which is a photobase generator described below, and can also be used in chemically amplified resists, etc.

Next, the polymerization initiator of the present invention, the latent base generator, and the photosensitive resin composition of the present invention are explained. Meanwhile, for points not specifically explained, the description in the new compound of the present invention is appropriately applied.

<Latent base generator>

The latent base generator of the present invention contains at least one compound represented by the above general formula (I). The content of the compound represented by the general formula (I) in the polymerization initiator is preferably 1 to 100% by mass, more preferably 50 to 100% by mass.

A latent base generator is one that generates a base by light or heat, and can be used as a polymerization initiator, base catalyst, or pH adjuster. In the present invention, a latent photobase generator that generates a base by irradiating light is more preferable because it has excellent operability.

<Polymerization initiator (A)>

In the polymerization initiator of the present invention and the photosensitive resin composition of the present invention, the polymerization initiator (A) contains at least one compound represented by the above general formula (I). The content of the compound represented by the general formula (I) in the polymerization initiator is preferably 1 to 100% by mass, more preferably 50 to 100% by mass.

In the photosensitive resin composition of the present invention, the content of the polymerization initiator (A) is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the photosensitive resin (B). It is preferable that the content of the polymerization initiator (A) is 1 part by mass or more because it is easy to prevent curing failure due to lack of sensitivity, and it is preferable that the content of the polymerization initiator (A) is 20 parts by mass or less because volatile substances can be suppressed when irradiated with light or heated. do.

<Photosensitive resin (B)>

The photosensitive resin (B) used in the present invention refers to a resin that uses an anionically polymerizable functional group or base as a catalyst and has a low curing temperature, and is a photosensitive resin that polymerizes and cures by irradiating energy rays such as ultraviolet rays or has a low curing temperature. It is a hardening resin that is converted to heat. The anionic polymerizable functional group refers to a functional group that can be polymerized by a base generated from a photobase generator by active energy rays such as ultraviolet rays, and includes, for example, an epoxy group, an episulfide group, and a cyclic monomer (δ-vale). Rolactone, ε-caprolactam), a catalyst for urethane bond formation by isocyanate and alcohol, a Michell addition catalyst of a (meth)acrylic group, and a catalyst for the crosslinking reaction of a silicone resin. Examples of the photosensitive resin (B) include epoxy resin, phenol resin, polyamide resin, polyurethane resin, nylon resin, polyester resin, and silicone resin. These resins may be used individually, or two or more types may be used together. Among them, the combination of epoxy resin and phenol resin is suitable because the reaction proceeds quickly and has good adhesiveness.

Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol; Dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis(orthocresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), 4,4'-dihydroxybenzophenone, isopropylidenebis (orthocresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hyde Roxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak , polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as octylphenol novolak, resorcinol novolak, and terpene phenol; Polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A-ethylene oxide adducts. ; Maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimeric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, glycidyl esters of aliphatic, aromatic, or cycloaliphatic polybasic acids such as pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and endomethylenetetrahydrophthalic acid, and homopolymers or copolymers of glycidyl methacrylate; Epoxy compounds having a glycidylamino group such as N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, and diglycidyl orthotoluidine; Vinylcyclohexenediepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6- Epoxidized products of cyclic olefin compounds such as methylcyclohexanecarboxylate and bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; Epoxidized conjugated diene polymers such as epoxidized polybutadiene, epoxidized acrylonitrile-butadiene copolymer, and epoxidized styrene-butadiene copolymer, and heterocyclic compounds such as triglycidyl isocyanurate. In addition, these epoxy resins may be internally crosslinked with a terminal isocyanate prepolymer or may have a high molecular weight with a polyhydric active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphoric acid ester, etc.).

Among the above-mentioned epoxy resins, those having a glycidyl group are preferable because of their excellent curability, and those having a bifunctional or higher glycidyl group are more preferable.

As the phenol resin, a phenol resin having two or more hydroxy groups per molecule is preferable, and generally known ones can be used. Phenol resins include, for example, bisphenol A type phenol resin, bisphenol E type phenolic resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolak resin, bisphenol A novolak type phenolic resin, and glycidyl ester type. Phenol resin, aralkyl novolak type phenol resin, biphenyl aralkyl type phenol resin, cresol novolak type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene Skeletal-modified novolak-type phenol resin, phenol-aralkyl-type phenol resin, naphthol aralkyl-type phenol resin, dicyclopentadiene-type phenol resin, biphenyl-type phenol resin, alicyclic phenol resin, polyol-type phenol resin, phosphorus-containing phenol resin. , phenolic resins containing polymerizable unsaturated hydrocarbon groups, and silicone resins containing hydroxyl groups, but are not particularly limited. These phenol resins can be used individually or in combination of two or more types.

Examples of the polyamide resin include acid dianhydride, ethylene tetracarboxylic dianhydride, 1,2,3,4-benzene tetracarboxylic dianhydride, and 1,2,3,4-cyclohexane tetracarboxylic acid dianhydride. Anhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2,3,3-biphenyltetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic acid Dianhydrides and diamines include (o-, m- or p-)phenylenediamine, (3,3'- or 4,4'-)diaminodiphenyl ether, diaminobenzophenone, (3,3'- Alternatively, resins made from 4,4'-)diaminodiphenylmethane or the like can be mentioned.

The polyurethane resin includes diisocyanates such as polyfunctional isocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate, and polyols such as polyether polyol, polyester polyol, and polycarbonate polyol. Resins made from (polyfunctional alcohol) as a raw material, etc. can be mentioned.

In addition, examples of the nylon resin include resins made from cyclic monomers such as ε-caprolactam and lauryllactam.

In addition, examples of the polyester resin include resins made from cyclic monomers such as δ-valerolactone and β-propiolactone.

In addition, examples of the silicone resin include methyl silicone resin, methyl/phenyl silicone resin, and organic resin-modified silicone resin.

<Additives>

In the photosensitive resin composition of the present invention, additives such as inorganic compounds, colorants, latent epoxy curing agents, chain transfer agents, sensitizers, and solvents can be used as optional components.

Examples of the inorganic compounds include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; Layered clay minerals, Milori blue, calcium carbonate, magnesium carbonate, cobalt-based, manganese-based, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, and selenides. , aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper, etc. These inorganic compounds are used as fillers, antireflection agents, conductive materials, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellent agents, etc., for example.

The coloring material may include pigments, dyes, natural pigments, etc. These colorants can be used individually or in combination of two or more types.

Examples of the pigment include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; isoindoline compounds; quinacridone compounds; antanthrone compounds; Perinone compounds; perylene compounds; diketopyrrolopyrrole compounds; thioindigo compounds; dioxazine compounds; triphenylmethane compound; Quinophthalone compounds; naphthalenetetracarboxylic acid; Azo dye, metal complex compound of cyanine dye; lake pigment; Carbon black obtained by a furnace method, a channel method, or a thermal method, or carbon black such as acetylene black, Ketjen black, or lamp black; The carbon black is adjusted or coated with an epoxy resin, the carbon black is previously dispersed in a resin solution and 20 to 200 mg/g of the resin is adsorbed, the carbon black is subjected to an acidic or alkaline surface treatment, Carbon black with an average particle diameter of 8 nm or more and a DBP oil absorption of 90 ml/100 g or less, carbon black with a total oxygen amount calculated from CO and CO ₂ in volatile components at 950°C of 9 mg or more per 100 m2 of surface area; Graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon airgel, fullerene; Aniline Black, Pigment Black 7, Titanium Black; Chromium oxide rust, Milori blue, cobalt rust, cobalt blue, manganese, ferrocyanide, ultramarine phosphate, royal blue, ultramarine, cerulean blue, viridian, emerald green, lead sulfate, lead yellow, zinc sulfur, Bengala ( Organic or inorganic pigments such as red iron (III) oxide, cadmium red, synthetic iron black, and umber can be used. These pigments can be used individually or in combination.

As the pigment, a commercially available pigment can be used, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90. , 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 2 20 , 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114 , 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc. are mentioned.

The dyes include azo dyes, anthraquinone dyes, indigoid dyes, trialrylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, and inda dyes. Dyes such as min dye, oxazine dye, phthalocyanine dye, and cyanine dye can be mentioned, and these may be used in combination.

Examples of the latent epoxy curing agent include dicyandiamide, modified polyamine, hydrazide, 4,4'-diaminodiphenylsulfone, boronamine trifluoride complex salt, imidazole, guanamine, and imidazole. , ureas, and melamine.

As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-mercaptopropionic acid. -[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethane Sulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl(4-methylthio)phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1- Mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3 -Mercapto compounds such as pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropanetris (3-mercaptopropionate), and pentaerythritol tetrakis (3-mercaptopropionate), Disulfide compounds obtained by oxidizing the above mercapto compounds, alkyl iodides such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid, trimethylolpropane tris (3-mercap toisobutyrate), butanediolbis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthiol Oglycolate, Trimethylolpropane Tristioglycolate, Butanediol Bisthiopropionate, Trimethylolpropane Tristiopropionate, Trimethylolpropane Tristioglycolate, Pentaerythritol Tetrachistiopropionate, Pentaerythritol Tetra Kistioglycolate, trishydroxyethyltristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, the following compound No.C1, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate and aliphatic polyfunctional thiol compounds, such as Karenz MT BD1, PE1, and NR1 manufactured by Showa Denko.

The solvent is usually a solvent capable of dissolving or dispersing each of the components (polymerization initiator (A) and photosensitive resin (B), etc.), such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, Ketones such as methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; Ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; Ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and Texanol; Cellosolv-based solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol-based solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; Ether esters such as ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethoxyethyl propionate. System solvent; BTX-based solvents such as benzene, toluene, and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; Terpene hydrocarbon oils such as turpentine, D-limonene, and pinene; Paraffin-based solvents such as mineral spirits, Swasol #310 (Cosmo Matsuyama Sekiyu Co., Ltd.), and Solvetso #100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichlorethylene, methylene chloride, and 1,2-dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Carbitol-based solvent; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide; N-methylpyrrolidone; dimethyl sulfoxide; Water and the like can be used, and these solvents can be used alone or as a mixed solvent of two or more kinds.

Among these, ketones or ether ester solvents, especially propylene glycol-1-monomethyl ether-2-acetate or cyclohexanone, are preferably used in terms of alkali developability, patterning properties, film forming properties, and solubility. do.

In the photosensitive resin composition of the present invention, the content of the solvent is not particularly limited, and any amount is sufficient as long as each component is uniformly dispersed or dissolved and the photosensitive resin composition of the present invention exhibits a liquid or paste form suitable for each application. , it is preferable to contain the solvent in a range where the amount of solid content (all components other than the solvent) in the photosensitive resin composition of the present invention is 10 to 90 mass%.

Additionally, the photosensitive resin composition of the present invention can improve the properties of the cured product by using an organic polymer. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, and (meth)acrylic acid-methyl methacrylate. Crylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylic Amide, saturated polyester, phenol resin, phenoxy resin, etc. can be mentioned.

When using the organic polymer, the amount used is preferably 10 to 500 parts by mass per 100 parts by mass of the photosensitive resin (B).

Additionally, surfactants, silane coupling agents, melamine compounds, etc. can be used in combination with the photosensitive resin composition of the present invention.

The surfactant includes fluorine-based surfactants such as perfluoroalkyl phosphate ester and perfluoroalkyl carboxylate; Anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates; Cationic surfactants such as higher amine halide salts and quaternary ammonium salts; Nonionic surfactants such as polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, and fatty acid monoglyceride; amphoteric surfactant; Surfactants such as silicone-based surfactants can be used, and these may be used in combination.

As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among them, those having an isocyanate group, methacryloyl group, or epoxy group, such as KBE-9007, KBM-502, and KBE-403. A silane coupling agent is suitably used.

The melamine compounds include active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. and compounds in which all or part (at least two) are alkyl etherified.

Here, the alkyl group constituting the alkyl ether may include a methyl group, an ethyl group, or a butyl group, and may be the same or different from each other. Additionally, the methylol group that is not alkyl etherified may be self-condensed within one molecule or may be condensed between two molecules, resulting in the formation of an oligomer component.

Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, etc. can be used.

Among these, alkyl etherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferable due to their solubility in solvents and difficulty in crystallizing from the photosensitive resin composition.

In the photosensitive resin composition of the present invention, the amount of any component other than (A) the polymerization initiator and the photosensitive resin (B) (however, inorganic compounds, colorants, and solvents are excluded) is appropriately selected and specifically limited depending on the purpose of use. However, the total amount is preferably 50 parts by mass or less per 100 parts by mass of the photosensitive resin (B).

The photosensitive resin composition of the present invention can be cured by irradiating energy rays. The cured product is formed into an appropriate shape depending on the intended use. For example, in the case of forming a film-like cured product, the photosensitive resin composition of the present invention can be used by known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, etc., using soda glass, quartz, etc. It can be applied to supports such as glass, semiconductor substrates, metal, paper, and plastic. Additionally, once it is applied on a support such as a film, it can be transferred onto another support, and there are no restrictions on the application method.

Light sources of energy rays used when curing the photosensitive resin composition of the present invention include ultra-high pressure mercury lamps, high-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, carbon arc lamps, metal halide lamps, Electromagnetic wave energy with a wavelength of 2000 angstroms to 7000 angstroms obtained from fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light-emitting diodes, CRT light sources, etc., or high-energy rays such as electron beams, X-rays, and radiation can be used, preferably Ultra-high pressure mercury lamps, mercury vapor arc lamps, carbon arc lamps, and xenon arc lamps that emit light with a wavelength of 300 to 450 nm are used.

Moreover, the laser direct drawing method, which creates an image directly from digital information such as on a computer without using a mask by using a laser light as the exposure light source, can improve not only productivity but also resolution and positioning accuracy. It is useful, and light with a wavelength of 340 to 430 nm is suitably used as the laser light, including excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, and YAG laser. Light that emits light in the visible to infrared range can also be used. When using these laser lights, a sensitizing dye that absorbs the above range from visible to infrared is preferably added.

In addition, curing the photosensitive resin composition of the present invention usually requires heating after irradiation of the above energy rays, and heating at about 40 to 150°C is preferable from the viewpoint of curing rate.

The photosensitive resin composition of the present invention can be used as a photocurable paint or varnish; light curable adhesive; Coating agent for metal; printed board; Color filters in color liquid crystal display devices such as color TVs, PC monitors, portable information terminals, and digital cameras; Color filter of CCD image sensor; Electrode materials for plasma display panels; powder coating; printing ink; printing plate; glue; Dental compositions; gel coat; Photoresist for electronics; electroplating resist; etching resist; dry film; solder resist; resists for manufacturing color filters for various display applications or for forming their structures in the manufacturing process of plasma display panels, electroluminescent displays, and LCDs; Compositions for encapsulating electrical and electronic components; solder resist; magnetic recording materials; Minor mechanical parts; waveguide; optical switch; Mask for plating; etching mask; color test system; Fiberglass cable coating; Stencils for screen printing; Materials for manufacturing three-dimensional objects by stereolithography; Materials for holographic recording; image recording material; microelectronic circuit; decolorizing materials; Decolorizing materials for image recording materials; Decolorizing materials for image recording materials using microcapsules; Photoresist materials for printed wiring boards; Photoresist materials for UV and visible laser direct imaging systems; It can be used for various purposes, such as a photoresist material or protective film used in forming a dielectric layer in sequential stacking of printed circuit boards, and there is no particular limitation on its use.

The photosensitive resin composition of the present invention can also be used for the purpose of forming spacers for liquid crystal display panels and protrusions for vertically aligned liquid crystal display elements. In particular, it is useful as a photosensitive resin composition for simultaneously forming protrusions and spacers for vertically aligned liquid crystal display devices.

The spacer for the liquid crystal display panel includes (1) forming a coating film of the photosensitive resin composition of the present invention on a substrate, (2) irradiating energy lines (light) to the coating film through a mask having a predetermined pattern shape. , (3) a baking step after exposure, (4) a step of developing the film after exposure, and (5) a step of heating the film after development.

The photosensitive resin composition of the present invention to which a colorant is added is suitably used as a resist constituting each pixel such as RGB in a color filter or a resist for a black matrix forming a partition of each pixel. Moreover, in the case of a resist for a black matrix to which an ink repellent agent is added, it is preferably used for a partition wall for an inkjet color filter with a profile angle of 50° or more. As the ink repellent agent, a fluorine-based surfactant and a composition containing a fluorine-based surfactant are suitably used.

When used in the partition for the inkjet color filter, the partition formed from the photosensitive resin composition of the present invention partitions the image of the transferred object, and droplets are deposited on the concave part of the divided object by the inkjet method. The optical element is manufactured by a method of forming an image area by providing ). At this time, it is preferable that the droplet contains a colorant and the image area is colored. In this case, the optical element manufactured by the above manufacturing method includes a pixel group consisting of a plurality of colored areas on a substrate and the pixel group. It has at least a partition wall that isolates each colored area.

The photosensitive resin composition of the present invention can also be used as a composition for a protective film or insulating film. In this case, it may contain an ultraviolet absorber, alkylation-modified melamine and/or acrylic-modified melamine, a mono- or bifunctional (meth)acrylate monomer containing an alcoholic hydroxyl group in the molecule, and/or silica sol.

The insulating film is used for the insulating resin layer in a laminate in which the insulating resin layer is provided on a peelable support substrate, the laminate is capable of development with an aqueous alkaline solution, and the insulating resin layer has a film thickness of 10 to 100 μm. It is desirable.

The photosensitive resin composition of the present invention can be used as a photosensitive paste composition by containing an inorganic compound. The photosensitive paste composition can be used to form fired patterns such as partition patterns, dielectric patterns, electrode patterns, and black matrix patterns of a plasma display panel.

Example

Hereinafter, the present invention will be described in more detail through examples and comparative examples, but the present invention is not limited to these examples.

[Preparation Example 1] Synthesis of oxime 1

<Step 1>

In a 200 ml four-necked flask, add 1.0 eq. of indole, 1.2 eq. of 4-fluoronitrobenzene, and 3.0 eq. of potassium carbonate. and N,N-dimethylformamide (500% by weight of the theoretical amount) were added, and heated and stirred at 130°C for 3 hours under a nitrogen flow of 20 mL/min. After cooling to room temperature, 50 g of ion-exchanged water was added and stirred for 1 hour. After filtering and extracting the precipitate, it was dried under reduced pressure at 50°C to constant weight, and N-nitrophenylindole was obtained in a yield of 85%.

<Step 2>

In a 200 ml four-necked flask, 1.0 eq. of N-nitrophenylindole obtained in step 1 and 2.5 eq. of aluminum chloride were added. and dichloroethane (500% by weight of the theoretical amount) were added, and stirring was performed at 5°C on an ice bath. 1.3eq. of myristoyl chloride was added dropwise thereto. After raising the temperature to room temperature, the mixture was stirred for 3 hours, 50 g of ion-exchanged water was added, and the organic layer was separated. After drying the organic layer with anhydrous sodium sulfate, the solvent was distilled off, ethanol was added, and crystallization was performed. The crystals obtained by filtration were dried under reduced pressure at 50°C to constant weight, and Ketone Compound 1 was obtained in a yield of 65%.

<Step 3>

In a 100 mL four-necked flask, 1.0 eq. of the ketone compound obtained in step 2 and 2.0 eq. of hydroxylamine hydrochloride were added. and pyridine (200% by weight of the theoretical amount) were added, and heated and stirred at 95°C for 2.5 hours under a nitrogen flow of 20 mL/min. After cooling to room temperature, 50 g of ion-exchanged water was added to separate the organic layer. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the mixture was dried under reduced pressure at 50°C to constant weight to obtain oxime body 1 in a yield of 88%.

[Preparation Example 2] Synthesis of oxime 2

In Preparation Example 1, the same operation was performed except that the 4-fluoronitrobenzene in <Step 1> was replaced with 4-fluorobenzophenone and the myristoyl chloride in <Step 2> was replaced with n-octanoyl chloride, and the oxime Sieve 2 was obtained with an overall yield of 11%.

[Example 1] Synthesis of Compound No. 1

Nitrogen was flowed into a 100 mL four-necked flask, 1.0 eq. of oxime body 1, dichloromethane (500% by weight of theoretical quantity), and 2.0 eq. of triethylamine were added, and the mixture was stirred at 5°C on an ice bath. 1.1 eq. of 4-nitrophenyl chloroformate dissolved in dichloromethane was added dropwise thereto. After the dropwise addition was completed, the mixture was stirred at room temperature for 30 minutes. After cooling to 5°C on an ice bath again, 1.1 eq. of piperidine was added dropwise. The mixture was stirred at room temperature for 3 hours, and the solvent was distilled off under reduced pressure. Ethyl acetate and 5% by mass NaOH aqueous solution were added thereto, and the organic layer was separated. The organic layer was washed three times with ion-exchanged water and then concentrated. Methanol was added to the residue for crystallization, and compound No. 1 was obtained as a yellow powdery compound in a yield of 70%. TG-DTA (melting point/°C) and ¹ H-NMR of the obtained solid were analyzed. The results are shown in [Table 1] and [Table 2].

[Example 2] Synthesis of Compound No.2

The same operation as in Example 1 was performed except that oxime body 1 described in Example 1 was replaced with oxime body 2, and compound No. 2 was obtained in a yield of 54%. TG-DTA (melting point/°C) and ¹ H-NMR of the obtained solid were analyzed. The results are shown in [Table 1] and [Table 2].

[Production Example 3] Synthesis of oxime 3

In Preparation Example 1, the same operation was performed except that the 4-fluoronitrobenzene in <Step 1> was replaced with 4-fluorobenzophenone and the myristoyl chloride in <Step 2> was replaced with n-octanoyl chloride, producing a ketone. Compound 2 was obtained.

<Step 3>

1.0 eq. of the above-mentioned ketone compound 2, DMF (300% by weight of theoretical quantity), and 1.2 eq. of hydrochloric acid were added to a 100 ml four-necked flask in this order, and stirred at 5°C on an ice bath. 1.2eq. of isobutyl nitrite was added dropwise thereto. After raising the temperature to room temperature, it was stirred for 6 hours. Afterwards, 50 g of ion-exchanged water and ethyl acetate were added to separate the organic layer. The organic layer was washed with water three times and concentrated under reduced pressure with an evaporator to obtain oxime body 3. The obtained oxime body 3 was used in the next reaction without purification.

[Example 3] Synthesis of Compound No.75

Nitrogen was flowed into a 100 mL four-necked flask, 1.0 eq. of oxime 3, dichloromethane (500% by weight of theoretical quantity), and 2.0 eq. of triethylamine were added, and the mixture was stirred at 5°C on an ice bath. 1.1 eq. of 4-nitrophenyl chloroformate dissolved in dichloromethane was added dropwise thereto. After the dropwise addition was completed, the mixture was stirred at room temperature for 30 minutes. After cooling to 5°C on an ice bath again, 1.1 eq. of piperidine was added dropwise. The mixture was stirred at room temperature for 5 hours, and the solvent was distilled off under reduced pressure. Ethyl acetate and 5% by mass NaOH aqueous solution were added thereto, and the organic layer was separated. The organic layer was washed with ion-exchanged water three times and then concentrated. Methanol was added to the residue for crystallization, and compound No. 75 was obtained as a yellow powdery compound in a yield of 30%. TG-DTA (melting point/°C) and ¹ H-NMR of the obtained solid were analyzed. The results are shown in [Table 1] and [Table 2].

[Example 4] Synthesis of Compound No.76

The same operation as in Example 3 was performed except that the piperidine described in Example 3 was replaced with morpholine, and compound No. 76 was obtained in a yield of 51%. TG-DTA (melting point/°C) and ¹ H-NMR of the obtained solid were analyzed. The results are shown in [Table 1] and [Table 2].

[Example 5] Synthesis of Compound No.77

The same operation as in Example 3 was performed except that 1.1 eq. of piperidine described in Example 3 was replaced with 0.50 eq. of piperazine, and compound No. 77 was obtained in a yield of 43%. TG-DTA (melting point/°C) and ¹ H-NMR of the obtained solid were analyzed. The results are shown in [Table 1] and [Table 2].

[Example 6] Synthesis of Compound No. 152

The same operation as in Example 3 was performed except that the piperidine described in Example 3 was replaced with dibutylamine, and compound No. 152 was obtained in a yield of 38%. TG-DTA (melting point/°C) and ¹ H-NMR of the obtained solid were analyzed. The results are shown in [Table 1] and [Table 2].

[Comparative Example 1] The following comparative compound No. 1 was used.

[Evaluation Examples 1 to 5 and Comparative Evaluation Example 1] Evaluation of optical resolution

Compounds No. 1, No. 75, No. 76, No. 77, No. 152 and the following comparative compound No. 1 were adjusted to 1.0 × 10 ^-4 mol of acetonitrile solution and placed in a quartz cell with a lid. This sample was irradiated with ultraviolet light using an ultra-high pressure mercury lamp as a light source under the conditions of 100 mJ/cm2, 500 mJ/cm2, and 1000 mJ/cm2 (integrated light amount at 365 nm), and decomposition was examined. For evaluation of decomposability, HPLC was used, and the peak at the time of unirradiation was set as 0, and the amount of decomposition was expressed as a percentage. The results are shown in [Table 3].

HPLC: Hitachi High-Technology product, UV detector Chrom master5430

Development solvent: acetonitrile/water/ammonium acetate

=90/10/0.2 (volume ratio)

Flow rate: 1㎖/min

Column: Inertsil ODS-2

Column temperature: 40℃

Detection: 254nm

From the results in [Table 3], the new compound of the present invention has high decomposition ability to UV light, and therefore has a large amount of base generated by decomposition, and exhibits highly sensitive curability in the photosensitive resin composition.

[Examples 7 to 12 and Comparative Example 1] Preparation of photosensitive composition

The formulations shown in [Table 4] were performed, and photosensitive compositions No. 1 to No. 6 and comparative photosensitive composition No. 1 were obtained. Meanwhile, the numerical values of the formulations in the table represent parts by mass.

In addition, the symbol of each component in the table represents the following component.

A-1 Compound No.1

A-2 Compound No.2

A-3 Compound No.75

A-4 Compound No.76

A-5 Compound No.77

A-6 Compound No.152

A'-1 Comparative compound No.1

B-1 EPPN-201

(Phenol novolak type epoxy resin, epoxy equivalent weight 193g/eq., Nippon Kayaku company product)

B-2TRR-5010G

(Cresol novolac type phenolic resin, hydroxyl equivalent weight 120g/eq., Mw=8,000, Asahi Yukizai Kogyo product)

C-1 FZ-2122

(Polyether-modified polysiloxane, Toray Dow Corning product)

D-1 Cyclopentanone (solvent)

[Evaluation Examples 6 to 17, and Comparative Evaluation Examples 2 and 3] Evaluation of the photosensitive composition and cured product

For photosensitive compositions No. 1 to No. 6, comparative photosensitive composition No. 1, and their cured products, line width sensitivity and residual film rate of the cured products were evaluated in the following order. The results are listed in [Table 5].

[Method of producing and evaluating evaluation samples]

Photosensitive compositions No. 1 to No. 6 and comparative photosensitive composition No. 1 (approximately 2.0 cc) were coated on a glass substrate with a spin coater (500 rpm × 2 seconds → 1800 rpm × 15 seconds → slope × 5 seconds), respectively, and hot coated. Prebaking was performed on the plate (90°C x 120 seconds).

After that, the UV light was exposed in sections using a Topcon exposure machine (60, 120 mJ/cm2, gap: 20㎛, illuminance: 20.0mW/cm2).

After exposure, post-baking was performed on a hot plate (120°C x 5 minutes), developed with PGMEA (temperature: 23°C, 200 rpm x 10 seconds), and washed with IPA (isopropyl alcohol) (200 rpm x 10 seconds → dried: 500 rpm × 5 seconds).

For the obtained sample, the line width and residual film ratio of the pattern with a mask opening of 20 μm at each exposure dose were measured.

From the results in [Table 5] above, the photosensitive composition of the present invention showed a large line width (high sensitivity) and a high residual film rate (high curability) compared to the comparative photosensitive composition. Therefore, the compound of the present invention is superior as a polymerization initiator. It's obvious.

[Examples 13 to 15, and Comparative Examples 2 and 3] Preparation of photosensitive composition

The formulations shown in [Table 6] were performed, and photosensitive compositions No. 7 to No. 9 and comparative photosensitive compositions No. 2 and No. 3 were obtained. Meanwhile, the numerical values of the formulations in the table indicate mass (g).

In addition, the symbol of each component in the table represents the following component.

A'-2 Comparative compound No.2

B-3 KR-300

(Methyl/phenyl silicone resin, 50% xylene solution, Shin-Etsu Chemical Co., Ltd. product)

B-4 tetraethoxysilane

[Evaluation Examples 18 to 20, and Comparative Evaluation Examples 4 and 5] Evaluation of the photosensitive composition and cured product

Photosensitive compositions No. 7 to No. 9, comparative photosensitive compositions No. 2 and No. 3, and their cured products were evaluated for tackiness and transparency in the following procedures. The results are listed in [Table 7].

[Method of producing and evaluating evaluation samples]

Photosensitive compositions No.7 to No.9 and comparative photosensitive compositions No.2 and No.3 (approximately 4.0 cc) were applied to a glass substrate using a spin coater (500 rpm × 2 seconds → 1800 rpm × 15 seconds → slope × 5 seconds), respectively. It was coated and prebaked on a hot plate (90°C x 120 seconds).

Afterwards, it was exposed to ultraviolet light using a Topcon exposure machine (1000mJ/cm2, gap: 20㎛, illuminance: 20.0mW/cm2).

After exposure, post-baking was performed on a hot plate (120°C x 5 minutes).

For the obtained sample, the surface was rubbed with a cotton swab to check whether stickiness remained. Those with no stickiness remaining were rated as ○, and those with remaining stickiness were rated as ×. Compounds with an evaluation of ○ are preferable as polymerization initiators because they have high curability.

Additionally, for the obtained sample, the ultraviolet and visible absorption spectra were measured using a spectrophotometer, and the transmittance at 400 nm was compared. Compounds with a transmittance of 80% or more are preferable as polymerization initiators because they have high transparency, while compounds with a transmittance of less than 80% have low transparency and are therefore undesirable as polymerization initiators for applications requiring transparency.

Spectrophotometer: Hitachi Hi-Tech Spectrophotometer U-3900

From the results in [Table 7] above, it is clear that the compound of the present invention is a polymerization initiator with excellent curability and transparency in compositions using silicone resin.

[Examples 16 and 17, and Comparative Example 4] Preparation of photosensitive composition

The formulations shown in [Table 8] were performed to obtain photosensitive compositions No. 10 and No. 11, and comparative photosensitive composition No. 4. Meanwhile, the numerical values of the formulations in the table indicate mass (g).

In addition, the symbol of each component in the table represents the following component.

A'-3 Comparative compound No.3

B-5 PEMP

(Tetrafunctional thiol monomer, SC product from Yuki Chemical Co., Ltd.)

[Evaluation Examples 21 and 22, and Comparative Evaluation Example 6] Evaluation of the photosensitive composition and cured product

Sensitivity was evaluated for photosensitive compositions No. 10 and No. 11, comparative photosensitive composition No. 4, and their cured products in the following procedure. The results are listed in [Table 9].

[Method of producing and evaluating evaluation samples]

Photosensitive compositions No. 10 and No. 11, and comparative photosensitive composition No. 4 (coated amount of about 4.0 cc) were each coated on a glass substrate with a spin coater (500 rpm × 2 seconds → 1800 rpm × 15 seconds → slope × 5 seconds), Prebaking was performed on a hot plate (90°C x 120 seconds).

After that, the step tablet was placed on the coating film and exposed to ultraviolet light (365 nm, 385 nm, 395 nm) using an LED exposure machine (3000 mJ/cm 2, illuminance: 20.0 mW/cm 2).

After exposure, post-baking was performed on a hot plate (100°C x 20 minutes), developed with PGMEA (30 seconds), and washed with IPA (isopropyl alcohol) (10 seconds).

For the obtained sample, the number of stages in which the film remained after development was recorded. A photosensitive resin composition having 5 or more stages is preferable because it has excellent sensitivity, and a photosensitive resin composition having 10 or more stages is particularly preferable.

From the results in [Table 9] above, it is clear that the compound of the present invention is a polymerization initiator with excellent curing properties in compositions using thiol as an epoxy resin and curing agent.

[Examples 18 and 19, and Comparative Example 5] Preparation of photosensitive composition

By carrying out the formulations shown in [Table 10], photosensitive compositions No. 12 and No. 13 and comparative photosensitive composition No. 5 were obtained. Meanwhile, the numerical values of the formulations in the table indicate mass (g).

In addition, the symbol of each component in the table represents the following component.

B-6 polyamic acid

(Obtained by reacting 3,3',4,4'-biphenyltetracarboxylic dianhydride and bis(4-aminophenyl)ether in N,N-dimethylacetamide. Weight average molecular weight is about 10000.)

D-2 NMP (solvent)

[Evaluation Examples 23 to 26, and Comparative Evaluation Examples 7 and 8] Evaluation of the photosensitive composition and cured product

For photosensitive compositions No. 12 and No. 13, comparative photosensitive composition No. 5, and their cured products, line width sensitivity and residual film rate of the cured products were evaluated in the following order. The results are listed in [Table 11].

[Method of producing and evaluating evaluation samples]

Photosensitive compositions No. 12 and No. 13, and comparative photosensitive composition No. 5 (coated amount of about 4.0 cc) were each coated on a glass substrate with a spin coater (500 rpm × 2 seconds → 1800 rpm × 15 seconds → slope × 5 seconds), Prebaking was performed on a hot plate (100°C x 10 minutes).

After that, the UV light was exposed separately using a Topcon exposure machine (1000, 3000mJ/cm2, gap: 20㎛, illuminance: 20.0mW/cm2).

After exposure, post-baking was performed on a hot plate (100°C for 30 minutes), developed with IPA (temperature: 23°C, 200 rpm x 10 seconds → drying: 500 rpm x 5 seconds), and then heated at 300°C for an additional hour. did.

For the obtained sample, the line width and residual film ratio of the pattern with a mask opening of 20 μm at each exposure dose were measured.

From the results in [Table 12] above, it is clear that the compound of the present invention is a polymerization initiator with excellent curability in a resin composition using polyamic acid.

Additionally, the compounds of the present invention can also be used as thermal base generators.

[Reference Example 1]

A coating film was produced in the same manner as above using the photosensitive composition No. 11. The coating film was heated at 150°C for 60 minutes using an oven. When the obtained film was developed with IPA, it was confirmed that the film remaining rate was 40.5% and that it had been cured.

[Reference Example 2]

Heating and development were performed in the same manner as in Reference Example 1, except that a composition without the addition of A-1 (Compound No. 1) was used, and no film remained.

From these results, it is clear that the compound of the present invention can also be used as a thermal base generator.

When used as a polymerization initiator, the novel compound of the present invention can generate a base more efficiently than a conventional photobase generator, and thus can cure the photosensitive resin even at a low exposure amount.

Claims (9)

A compound represented by the following general formula (I).

(In the formula, R ¹ represents a cyano group, an unsubstituted or substituted aliphatic hydrocarbon group of 1 to 20 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon group of 6 to 20 carbon atoms,
R ² , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently hydrogen atom, cyano group, nitro group, -OR ⁸ , -COOR ⁸ , -CO-R ⁸ , -SR ⁸ , halogen atom, radish An aliphatic hydrocarbon group with 1 to 20 carbon atoms that is substituted or has a substituent, an aromatic hydrocarbon group with 6 to 20 carbon atoms that is unsubstituted or has a substituent, or a carbon atom that contains a heterocycle and is also unsubstituted or has a substituent. It represents the numbers 2 to 20,
R ³ contains an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group or heterocycle with 6 to 20 carbon atoms, and also contains an unsubstituted or substituted group. Represents a group having 2 to 20 carbon atoms,
R ⁸ contains a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group with 6 to 20 carbon atoms or a heterocycle, and is also unsubstituted. Or it represents a group with 2 to 20 carbon atoms that has a substituent,
X ¹ is -NR ¹¹ R ¹² , a group represented by (a) or (b) below,
R ¹¹ and R ¹² are each independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or
R ¹¹ and R ¹² are connected to each other, and are unsubstituted or have a substituent and are a ring with 1 to 20 carbon atoms consisting of a hydrogen atom, a nitrogen atom and a carbon atom, or a ring that is unsubstituted or has a substituent and is also a hydrogen atom, an oxygen atom and a nitrogen atom. It forms a ring with 1 to 20 carbon atoms, consisting of an atom and a carbon atom,
n represents 0 or 1.)

(In the formula, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom or the number of unsubstituted or substituent carbon atoms It is an aliphatic hydrocarbon group of 1 to 20 carbon atoms or an aromatic hydrocarbon group of 6 to 20 carbon atoms that is unsubstituted or has a substituent, or
At least one set of R ¹³ and R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ¹⁹ and R ²⁰ and R ²¹ and R ²² is connected to each other, is unsubstituted or has a substituent, and also contains a hydrogen atom or a nitrogen atom. and a ring having 1 to 20 carbon atoms consisting of a carbon atom, or a ring having 1 to 20 carbon atoms that is unsubstituted or has a substituent and is made of a hydrogen atom, an oxygen atom, a nitrogen atom and a carbon atom,
* indicates the number of bonds.) According to paragraph 1,
A compound in which at least one of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in the general formula (I) has a nitro group, benzoyl group or o-methylbenzoyl group as a substituent. According to paragraph 1,
A compound in which at least one of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in the general formula (I) is a group represented by the following general formula (II).

(In the formula, R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are each independently hydrogen atom, cyano group, nitro group, -OR ³⁰ , -COOR ³⁰ , -CO-R ³⁰ , -SR ³⁰ , halogen Contains an atom, an aliphatic hydrocarbon group with 1 to 20 carbon atoms that is unsubstituted or has a substituent, an aromatic hydrocarbon group or heterocycle with 6 to 20 carbon atoms that is unsubstituted or has a substituent, and is also unsubstituted or has a substituent. Represents a group having 2 to 20 carbon atoms or a group represented by the following general formula (III),
R ³⁰ contains an unsubstituted or substituted aliphatic hydrocarbon group with 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group or heterocycle with 6 to 20 carbon atoms, and also contains an unsubstituted or substituted group. Represents a group containing 2 to 20 carbon atoms,
At least one of R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ represents a nitro group, -CO-R ³⁰ or a group represented by the following general formula (III),
* indicates the number of bonds.)

(In the formula, R ³¹ represents an aliphatic hydrocarbon group with 1 to 20 carbon atoms that is unsubstituted or has a substituent, or an aromatic hydrocarbon group with 6 to 20 carbon atoms that is unsubstituted or has a substituent,
X ² is -NR ³² R ³³ , a group represented by (a') or (b') below,
R ³² and R ³³ are each independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or
R ³² and R ³³ are connected to each other, and are unsubstituted or have a substituent and are a ring with 1 to 20 carbon atoms consisting of a hydrogen atom, a nitrogen atom and a carbon atom, or a ring that is unsubstituted or has a substituent and is also a hydrogen atom, an oxygen atom and a nitrogen atom. It forms a ring with 1 to 20 carbon atoms, consisting of an atom and a carbon atom,
m represents 0 or 1, and * represents the number of bonds.)

(In the formula, R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ are each independently a hydrogen atom or the number of unsubstituted or substituent carbon atoms It is an aliphatic hydrocarbon group of 1 to 20 carbon atoms or an aromatic hydrocarbon group of 6 to 20 carbon atoms that is unsubstituted or has a substituent, or
At least one set of R ³⁴ and R ³⁵ , R ³⁶ and R ³⁷ , R ³⁸ and R ³⁹ , R ⁴⁰ and R ⁴¹ , and R ⁴² and R ⁴³ is connected to each other, is unsubstituted or has a substituent, and also contains a hydrogen atom or a nitrogen atom. and a ring having 1 to 20 carbon atoms consisting of a carbon atom, or a ring having 1 to 20 carbon atoms that is unsubstituted or has a substituent and is made of a hydrogen atom, an oxygen atom, a nitrogen atom and a carbon atom,
* indicates the number of bonds.) A latent base generator comprising the compound according to any one of claims 1 to 3. A polymerization initiator comprising the compound according to any one of claims 1 to 3. A photosensitive resin composition containing the polymerization initiator (A) and the photosensitive resin (B) according to claim 5. According to clause 6,
A photosensitive resin composition wherein the photosensitive resin (B) is an epoxy resin or a phenol resin. A cured product of the photosensitive resin composition according to claim 6. A method for producing a cured product comprising a step of irradiating an energy ray to the photosensitive resin composition according to claim 6.