JP2019156803A - New compound, photoinitiator containing that compound, and photosensitive resin composition containing that photoinitiator - Google Patents

Abstract

To provide a new compound that functions as an amine or base catalyst with high basic strength by irradiation with an active energy ray, and also has a high quantum yield of cleavage.SOLUTION: The invention provides a compound represented by the formula (1) in the figure. (In the formula, Rto Rare each independently H, a hydroxy group, an alkoxy group, or the like; and X is, e.g., an amino group having, e.g., a substituent.)SELECTED DRAWING: None

Description

  The present invention relates to a novel compound, a photopolymerization initiator containing the compound and generating a base and a radical upon irradiation with active energy rays, and a photosensitive resin composition containing the photopolymerization initiator.

  Conventionally known are photoacid generators that generate strong acids upon irradiation with active energy rays such as light, infrared rays, electron beams or X-rays, and chemically amplified resists in which the photoacid generators are blended into resin components. It is used for various purposes.

  In such a chemically amplified resist, a strong acid generated by irradiation with active energy rays acts on the resin component as a catalyst, and pattern formation is performed by changing the solubility of the resin in the developer. Various resist materials have been developed for the purpose of increasing sensitivity and resolution, but the combinations of photoacid generators and resins are limited, and the development of new chemically amplified resists is required. It has been.

  Photocuring technology for monomers and prepolymers by irradiation with active energy rays is roughly divided into three types: radical, cationic and anionic. Of these, light is the most widely developed object. This is a technique for polymerizing a vinyl monomer by irradiating a radical initiator with light. In addition, research has been conducted on a technique for generating an acid by the action of light and performing cationic polymerization using the acid as a catalyst.

  However, in the case of a radical polymerization system, since the polymerization reaction is inhibited by oxygen in the air, special measures for blocking oxygen are necessary. In the case of a cationic polymerization system, although it is advantageous in that it is not inhibited by oxygen, it has been pointed out that it may corrode due to strong acid generated from a photoacid generator remaining after curing or may be modified by a resin. For this reason, development of the photosensitive resin composition which does not contain corrosive substances, such as a strong acid, and does not receive the inhibition by the oxygen in the air but progresses rapidly with high efficiency is strongly desired.

  As one means for overcoming the above problems, a photosensitive resin composition using a method using a polymerization reaction or chemical reaction by a base catalyst, for example, a method of chemically modifying a resin using a base generated by the action of light as a catalyst. Application to photoresists and photo-curing materials is being studied. More specifically, an epoxy group-containing resin (compound) is cured by causing a crosslinking reaction by the action of a base, and an amine that acts as an initiator or a catalyst by the action of light or heat is used as an epoxy resin. There has been proposed a method of generating in a layer and then curing by heat treatment.

  For example, Patent Documents 1 to 4 describe photobase generators that generate strong organic bases. However, since the photobase generators of Patent Documents 1 to 4 are ionic in molecules, they have low solubility in organic solvents that are widely used in industry, and also have low storage stability when mixed with resins. Was demanded.

  Patent Document 5 describes a photosensitive resin composition using an α-aminoketone compound as a latent base catalyst. However, the α-aminoketone compound described in the same document is not practical because the amount of the base generated by irradiation with active energy rays is small and the base-catalyzed reaction cannot sufficiently proceed, and is excellent in solubility and storage stability. There has been a demand for a photobase generator that can generate a strong base with high efficiency by light irradiation.

JP 2005-264156 A Japanese Patent Laid-Open No. 2007-10185 Japanese Patent No. 5725515 Japanese Patent No. 5556193 Japanese Patent No. 3250072

  The present invention has been made in view of the above problems, and is a novel compound that functions as an amine or base catalyst having a high base strength by irradiation with active energy rays and has a high quantum yield of cleavage, and an excellent compound containing the compound. It is an object to provide a photopolymerization initiator having high sensitivity and a photosensitive resin composition containing the photopolymerization initiator.

As a result of diligent studies to solve the above problems, the present inventors have solved the above problems with a photobase generator derivatized with indandione known as a compound having high excited state stability. As a result, the present invention has been completed.
In other words, this study
(1) The following formula (1)

(In Formula (1), R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group or an organic group other than the above substituents. R _{2 to} R ₅ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, Mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, cyano group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group or the above-mentioned Represents an organic group other than a substituent, and two or more selected from R _{2 to} R ₅ may be bonded to each other to form a ring structure, and X represents the following formulas (1-1) to (1- 3)

(In Formula (1-1), (1-2) or (1-3), R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group or a heterocyclic group, or R ₇ and R ₈ are R ₉ and R ₁₁ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₁₀ represents an alkylene group or an arylene group, and A represents an oxygen atom or a sulfur atom. Or NR _12. R ₁₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁₃ and R ₁₄ each independently represents an amino group or a substituted amino group. Represents a group. )
A compound represented by
(2) The compound according to item (1), wherein R ₁ is a phenyl group,
(3) The compound according to (1) or (2) above, wherein R _{2 to} R ₅ are each independently a hydrogen atom, an alkylthioether group or an arylthioether group,
(4) The compound according to item (3), wherein R _{2 to} R ₅ are hydrogen atoms,
(5) A photopolymerization initiator containing the compound according to any one of (1) to (4) above,
(6) A photosensitive resin composition comprising a photopolymerization initiator according to (5) above, and a polymer precursor that can be polymerized by light irradiation or by light irradiation and heating in the presence of the photopolymerization initiator,
(7) A compound in which the polymer precursor has a substituent selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group, an acryloyl group, a methacryloyl group, a maleimide group and a thiirane group; a polysiloxane precursor; a polyimide precursor and The photosensitive resin composition according to the above item (6), which contains one or more selected from the group consisting of polybenzoxazole precursors,
(8) The photosensitive resin composition according to the above item (7), wherein the polymer precursor includes a compound having an epoxy group, and (9) the photosensitive material according to any one of the above items (6) to (8). Cured product of the adhesive resin composition,
About.

  The compound represented by the formula (1) of the present invention is an amine having a high base strength or an amine that functions as a base catalyst upon irradiation with active energy rays, and has a high quantum yield of cleavage. It can be used as a photopolymerization initiator having excellent sensitivity compared to a base generator. Furthermore, since the photosensitive resin composition of the present invention containing the compound does not generate an acid that corrodes a metal when irradiated with active energy rays, it can be suitably used for a material made of a metal.

FIG. 4 is a graph showing changes in LC peak with respect to exposure dose in the photolysis evaluation of the compound synthesized in Example 1. These are the graphs which showed LC peak area change with respect to the exposure amount in the photolysis evaluation of the compound synthesize | combined in Example 1. FIG.

  The present invention is described in detail below. The active energy ray in the present invention includes not only visible light but also a particle beam such as an electron beam and radiation or ionizing radiation that collectively refers to an electromagnetic wave and a particle beam, unless the wavelength is specified. . In this specification, irradiation with active energy rays is also referred to as exposure. Note that active energy rays with wavelengths of 365 nm, 405 nm, and 436 nm may be referred to as i-line, h-line, and g-line, respectively.

  The compound of the present invention has a structure represented by the following formula (1).

In formula (1), R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group, or an organic group other than the above substituents.
The alkoxy group represented by R _{1 in the} formula (1) is preferably an alkoxy group having 1 to 18 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, n -Butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, iso-pentoxy group, neo-pentoxy group, n-hexyloxy group, n-dodecyloxy group and the like.

Specific examples of the organic group represented by R _{1 in the} formula (1) include alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, alkynyl groups having 2 to 18 carbon atoms, and 6 to 12 carbon atoms. Examples thereof include an aryl group, an acyl group having 1 to 18 carbon atoms, an aroyl group having 7 to 18 carbon atoms, a nitro group, a cyano group, an alkylthio group having 1 to 18 carbon atoms, and a halogen atom.

Examples of the organic group having 1 to 18 carbon atoms as specific examples of the organic group represented by R _{1 in the} formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an iso-butyl group. , Sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group And a linear alkyl group such as a linear or branched alkyl group and a cyclic alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, preferably an alkyl group having 2 to 6 carbon atoms, It is more preferably a linear or branched alkyl group having 2 to 6 carbon atoms.

Examples of the alkenyl group having 2 to 18 carbon atoms as specific examples of the organic group represented by R _{1 in the} formula (1) include a vinyl group, a propenyl group, a 1-butenyl group, an iso-butenyl group, a 1-pentenyl group, 2- Pentenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2,2-dicyanovinyl group, 2-cyano-2-methylcarboxylvinyl group and 2 -Cyano-2-methylsulfone vinyl group and the like.

Examples of the alkynyl group having 2 to 18 carbon atoms as specific examples of the organic group represented by R _{1 in the} formula (1) include an ethynyl group, a 1-propynyl group, and a 1-butynyl group.
Specific examples of the organic group having 6 to 12 carbon atoms as the organic group represented by R _{1 in the} formula (1) include a phenyl group, a naphthyl group, and a tolyl group, and these are aryl groups having 6 to 10 carbon atoms. It is preferable.
Examples of the acyl group having 1 to 18 carbon atoms as specific examples of the organic group represented by R _{1 in the} formula (1) include formyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n -Butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonyl group, neo-pentylcarbonyl group, 2-methylbutylcarbonyl group, nitrobenzylcarbonyl group and the like.

Specific examples of the aroyl group having 7 to 18 carbon atoms as the organic group represented by R _{1 in the} formula (1) include a benzoyl group, a toluoyl group, a naphthoyl group, and a phthaloyl group.
As specific examples of the organic group represented by R _{1 in the} formula (1), the alkylthio group having 1 to 18 carbon atoms is methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group. Group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, 2-methylbutylthio group, 1-methylbutylthio group, neo-pentylthio group, 1,2-dimethylpropylthio group, and Examples include 1,1-dimethylpropylthio group.

Examples of the halogen atom as a specific example of the organic group represented by R _{1 in} Formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
R ₁ in the formula (1) is preferably an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, further preferably a phenyl group, a naphthyl group, or a tolyl group, Particularly preferred is a phenyl group.

In formula (1), R _{2 to} R ₅ are each independently a hydrogen atom, halogen atom, hydroxyl group, alkoxy group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, cyano group, sulfino group. , A sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group, or an organic group other than the aforementioned substituents. Two or more selected from R _{2 to} R ₅ may be bonded to each other to form a ring structure, and the ring structure may include a hetero atom bond.

Examples of the halogen represented by R _{2 to} R ₅ in formula (1) include the same halogen atoms as specific examples of the organic group represented by R _{1 in} formula (1).
Examples of the alkoxy group represented by R _{2 to} R ₅ in formula (1) include the same alkoxy groups as those represented by R _{1 in} formula (1).

Specific examples of the organic group represented by R _{2 to} R _{5 in} the formula (1) include an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, an alkoxy group. Examples thereof include a carbonyl group, a carbamoyl group, a thiocarbamoyl group, a carboxyl group, a carboxylate group, an acyl group, an acyloxy group, and a hydroxyimino group.
The alkyl group, aryl group and acyl group as specific examples of the organic group represented by R _{2 to} R ₅ in formula (1) include an alkyl group and aryl as specific examples of the organic group represented by R _{1 in} formula (1). The same as the group and the acyl group.

These organic groups may contain a bond such as a heteroatom other than hydrocarbon in the organic group, and the organic group may have a substituent other than hydrocarbon group. It may be linear or branched. The organic group in R ₂ , R ₃ and R ₅ is usually a monovalent organic group, but may be a divalent or higher valent organic group in the case of forming a cyclic structure to be described later.

The bond other than the hydrocarbon that may be contained in the organic group represented by R _{2 to} R ₅ is not particularly limited as long as the effect of the present invention is not impaired. For example, an ether bond, a thioether bond, a carbonyl bond, a thiol Examples include carbonyl bond, ester bond, amide bond, urethane bond, carbonate bond, sulfonyl bond, sulfinyl bond, azo bond and the like. From the viewpoint of heat resistance, the bonds other than hydrocarbons in the organic group include ether bonds, thioether bonds, carbonyl bonds, thiocarbonyl bonds, ester bonds, amide bonds, urethane bonds, imino bonds (-N = C (-R )-, -C (= NR)-: where R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, and a sulfinyl bond, and a thioether bond is more preferable. The organic group having a thioether bond is preferably an alkyl group having a thioether bond or an aryl group having a thioether bond, and the position of the thioether bond (sulfur atom) in these substituents is within the organic group (for example, an ethyl group). Even if it is a methylthiomethyl group (—CH ₂ SCH ₃ group) having a thioether bond therein, outside the organic group (for example, an ethyl thioether group having a thioether bond outside the ethyl group (—SC ₂ H ₅ group)) It does not matter.

The substituent other than the hydrocarbon group that the organic group represented by R _{2 to} R ₅ may have is not particularly limited as long as the effects of the present invention are not impaired. For example, a halogen atom, a hydroxyl group, a mercapto group, a sulfide Group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxy group Rato group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxyimino group, saturated or unsaturated alkyl ether group, saturated or unsaturated alkyl thioether group, Aryl ether groups and aryls Thioether group, an amino group _{(-NH 2, -NHR, -NRR '} : wherein, R and R' each independently represents an hydrocarbon group) include an ammonio group. The hydrogen contained in the substituent may be substituted with a hydrocarbon group. Moreover, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic. Among them, examples of the substituent other than the hydrocarbon group in the organic group of R ₂ , R ₃ , and R ₅ include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, and a thiocyanato group. , Isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group A group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, a hydroxyimino group, a saturated or unsaturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, and an aryl thioether group are preferred.

A cyclic structure formed by combining two or more selected from R _{2 to} R ₅ with each other includes a saturated or unsaturated alicyclic hydrocarbon, heterocyclic ring, and condensed ring, and the alicyclic hydrocarbon, heterocyclic ring. The structure may be a combination of two or more selected from the group consisting of a ring and a condensed ring. For example, R ₂ and R ₃ are bonded and / or R ₃ and R ₄ are bonded, and the atoms of the benzene ring to which R ₂ , R ₃ , and R ₅ are bonded share a naphthalene, anthracene, A condensed ring such as phenanthrene or indene may be formed.

Preferable specific examples of the organic group represented by R _{2 to} R ₅ include an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group and a propyl group; a cycloalkyl group having 4 to 23 carbon atoms such as a cyclopentyl group and a cyclohexyl group. A cycloalkenyl group having 4 to 23 carbon atoms such as cyclopentenyl group and cyclohexenyl group; an aryloxyalkyl group having 7 to 26 carbon atoms such as phenoxymethyl group, 2-phenoxyethyl group and 4-phenoxybutyl group (-ROAr); Group); Aralkyl group having 7 to 20 carbon atoms such as benzyl group and 3-phenylpropyl group; Alkyl group having 2 to 21 carbon atoms having cyano group such as cyanomethyl group and β-cyanoethyl group; Hydroxyl group such as hydroxymethyl group And an alkoxy group having 1 to 20 carbon atoms such as an alkyl group having 1 to 20 carbon atoms, a methoxy group, and an ethoxy group An amide group having 2 to 21 carbon atoms such as an acetamide group or a benzenesulfonamide group (C ₆ H ₅ SO ₂ NH—), an alkylthioether group having 1 to 20 carbon atoms such as a methylthio group or an ethylthio group (—SR group) ), An acyl group having 1 to 20 carbon atoms such as acetyl group and benzoyl group, an ester group having 2 to 21 carbon atoms such as methoxycarbonyl group and acetoxy group (-COOR group and -OCOR group), phenyl group, naphthyl group, C6-C20 aryl group, electron-donating group and / or electron-withdrawing group substituted by C6-C20 aryl group such as biphenyl group and tolyl group, electron-donating group and / or electron-withdrawing group A benzyl group and a cyano group substituted with an alkylthioether group or an arylthioether group, preferably an alkyl group having 1 to 20 carbon atoms. More preferably thioether group, more preferably an alkyl thioether group having 1 to 8 carbon atoms, particularly preferably an alkyl thioether group having 1 to 4 carbon atoms. The alkyl moiety may be linear, branched or cyclic.

Further, in the case of a compound in which at least one of R _{2 to} R ₅ is a hydroxyl group, the solubility in a basic aqueous solution and the like is improved as compared with a compound not containing a hydroxyl group in R ₂ , R ₃ , R ₅ and R ₆ , The absorption wavelength of the compound represented by the formula (1) can be increased.
The R ₂ to R ₅ in the formula (1) each independently represent a hydrogen atom, an alkyl thioether group or preferably a thioether group, and more preferably all are hydrogen atoms. When R _{2 to} R ₅ have an alkyl thioether group or an aryl thioether group, R ₃ or R ₄ is preferably an alkyl thioether group or an aryl thioether group.

  In formula (1), X represents a substituent represented by any of the following formulas (1-1) to (1-3).

In formula (1-1), R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group or a heterocyclic group, or R ₇ and R ₈ are bonded to form a heterocyclic ring.
Specific examples of the alkyl group represented by R ₇ and R _{8 in} the formula (1-1) include an alkyl group having 1 to 18 carbon atoms as a specific example of the organic group represented by R _{1 in} the formula (1), and will be described later. the same thing can be mentioned an alkyl group as a substituent having a heterocyclic group represented by R ₇ and R ₈ of formula (1-1).
The heterocyclic group represented by R ₇ and R _{8 in} the formula (1-1) is not particularly limited as long as it is a residue obtained by removing one hydrogen atom from the heterocyclic ring of the heterocyclic compound, and examples thereof include a furanyl group and a thienyl group. , Thienothienyl group, pyrrolyl group, imidazolyl group, N-methylimidazolyl group, thiazolyl group, oxazolyl group, pyridyl group, pyrazyl group, pyrimidyl group, quinolyl group, indolyl group, benzopyrazyl group, benzopyrimidyl group, benzothienyl group, naphthothienyl group, Benzofuranyl group, benzothiazolyl group, pyridinothiazolyl group, benzimidazolyl group, pyridinoimidazolyl group, N-methylbenzoimidazolyl group, pyridino-N-methylimidazolyl group, benzoxazolyl group, pyridinooxazolyl group, benzothia Diazolyl group, pyridinothiadiazolyl group, Zone oxadiazolyl group, pyridinoporphyrazine oxadiazolyl group, a carbazolyl group, and a phenoxazinyl group and phenothiazinyl group, a pyridyl group, an imidazolyl group, a N- methylimidazolyl group preferably, a pyridyl group is more preferable.

The heterocyclic group represented by R ₇ and R _{8 in} Formula (1-1) may have a substituent.
Although the substituent which the heterocyclic group which R < ₇ > and R < ₈ > of Formula (1-1) represent has does not have a restriction | limiting, For example, an alkyl group, an alkoxy group, an aromatic group, a heterocyclic group, a halogen atom, a hydroxyl group, a mercapto group , A nitro group, an alkyl-substituted amino group, an aryl-substituted amino group, an unsubstituted amino group (NH ₂ group), a cyano group, an isocyano group, and the like, and an alkyl group, an aromatic group, a heterocyclic group, and a halogen atom are more preferable. An aromatic group and a heterocyclic group are more preferable.

Specific examples of the alkyl group as a substituent that the heterocyclic group represented by R ₇ and R _{8 in} Formula (1-1) has include a methyl group, an ethyl group, a propyl group, an iso-propyl group, an n-butyl group, iso-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, t-pentyl group, sec-pentyl group, n-hexyl group, iso-hexyl group, n-heptyl group, sec-heptyl group, n-octyl group, n-nonyl group, sec-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, It is preferably an alkyl group having 1 to 20 carbon atoms such as n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-eicosyl group, and an alkyl group having 1 to 12 carbon atoms. More preferably in, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

The alkoxy group as the substituent that the heterocyclic group represented by R ₇ and R _{8 in} Formula (1-1) has is a substituent in which an oxygen atom and an alkyl group are bonded, and specific examples of the alkyl group that the alkoxy group has As, for example, the same thing as the alkyl group described in the term of the alkyl group as a substituent which the heterocyclic group which R < ₇ > and R < ₈ > of Formula (1-1) represent has, and a preferable thing are also mentioned. It is done.

The aromatic group as a substituent of the heterocyclic group represented by R ₇ and R _{8 in} the formula (1-1) is particularly limited as long as it is a residue obtained by removing one hydrogen atom from the aromatic ring of the aromatic compound. For example, a phenyl group, a biphenyl group, a terphenyl group, a quarterphenyl group, a tolyl group, an indenyl group, a naphthyl group, an anthryl group, a fluorenyl group, a pyrenyl group, a phenanthenyl group, a mestil group, and the like can be mentioned. Group, terphenyl group, quarterphenyl group, naphthyl group or anthryl group are preferable, and phenyl group, biphenyl group, terphenyl group or naphthyl group are more preferable.
Specific examples of the heterocyclic group as a substituent of the heterocyclic group represented by R ₇ and R _{8 in} Formula (1-1) include those of the heterocyclic group represented by R ₇ and R ₈ in Formula (1-1). The same thing as the heterocyclic group described in the term is mentioned, A preferable thing is also the same.

Specific examples of the halogen atom as the substituent having a heterocyclic group represented by R ₁ and R ₂ of formula (1-1), a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a fluorine atom or chlorine An atom is preferable and a fluorine atom is more preferable.
The alkyl-substituted amino group as the substituent of the heterocyclic group represented by R ₇ and R _{8 in} the formula (1-1) is not limited to either a monoalkyl-substituted amino group or a dialkyl-substituted amino group. As an alkyl group in an amino group, the same thing as the alkyl group described in the term of the alkyl group as a substituent which the heterocyclic group which R < ₇ > and R < ₈ > of Formula (1-1) have has, for example is mentioned, and preferable The same can be mentioned.

The aryl-substituted amino group as a substituent of the heterocyclic group represented by R ₇ and R _{8 in} the formula (1-1) is not limited to either a monoaryl-substituted amino group or a diaryl-substituted amino group, and these aryl-substituted amino groups As the aryl group in the amino group, for example, the aromatic group and the heterocyclic ring described in the paragraph of the aromatic group and the heterocyclic group as the substituent of the heterocyclic group represented by R ₇ and R _{8 in} the formula (1-1) The same thing as a group is mentioned, A preferable thing is also the same.

The heterocyclic ring formed by combining R ₇ and R _{8 in} the formula (1-1) is not particularly limited as long as it is a ring structure composed of two or more elements. For example, a thiophene ring, a furan ring, a pyrrole ring , A pyridine ring, a piperidine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyrazine ring and a thiazine ring, and a piperidine ring or an imidazole ring is preferable, and an imidazole ring is more preferable.
The heterocyclic ring formed by combining R ₇ and R _{8 in} Formula (1-1) may have a substituent.
Although there is no limitation on the substituent having a heterocyclic _ring and _{R 7} and _{R 8} are formed by bonding of the formula (1-1), such as substituted with a heterocyclic group _{which R 7} and _{R 8} of formula (1-1) represents The same thing as a group is mentioned.

R ₇ and R ₈ in Formula (1-1) are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, or R ₇ and R ₈ may be bonded to form a heterocyclic ring. Preferably, it is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or more preferably R ₇ and R ₈ are bonded to form a heterocyclic ring, and a hydrogen atom or a cyclic alkyl group having 4 to 6 carbon atoms. or it is, or more preferably R ₇ and R ₈ form a heterocyclic ring bonded, is particularly preferable to form a heterocyclic ring bonded R ₇ and R _8, heterocyclic imidazole ring or Most preferred is a piperidine ring.

In formula (1-2), R ₉ and R ₁₁ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
The alkyl group having 1 to 4 carbon atoms represented by R ₉ and R _{11 in} formula (1-2) is an alkyl group having 1 to 18 carbon atoms as a specific example of the organic group represented by R _{1 in} formula (1). Among the alkyl groups described in the item, those having 1 to 4 carbon atoms can be given.
R ₉ and R ₁₁ in Formula (1) are preferably each independently a hydrogen atom or a methyl group.

In formula (1-2), R ₁₀ represents an alkylene group or an arylene group.
The alkylene group represented by R _{10 in the} formula (1) is a divalent linking group obtained by removing two hydrogen atoms from a saturated hydrocarbon, and the saturated hydrocarbon can be linear, branched or cyclic. Although not limited, it is preferably a divalent linking group obtained by removing two hydrogen atoms from a saturated hydrocarbon having 1 to 6 carbon atoms, and is a linear or branched saturated hydrocarbon having 1 to 4 carbon atoms. A divalent linking group in which two hydrogen atoms are removed from the group is more preferable, and a methylene group, an ethylene group, or an n-propylene group is still more preferable.

The arylene group represented by R _{10 in the} formula (1) is a divalent linking group obtained by removing two hydrogen atoms from an aromatic hydrocarbon compound. Specific examples of the aromatic hydrocarbon compound that can be an arylene group include benzene, naphthalene, anthracene, phenanthrene, pyrene, and fluorene.

In formula (1-2), A represents an oxygen atom, a sulfur atom or NR ₁₂ , and R ₁₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
The alkyl group having 1 to 4 carbon atoms represented by R _{12 in the} formula (1-2) is described in the section of the alkyl group having 1 to 18 carbon atoms as a specific example of the organic group represented by R _{1 in} the formula (1). Among these alkyl groups, those having 1 to 4 carbon atoms can be mentioned.
As A in Formula (1-2), an oxygen atom or a sulfur atom is preferable, and an oxygen atom is more preferable.

In formula (1-3), R ₁₃ and R ₁₄ each independently represent an amino group or a substituted amino group.
Specific examples of the substituted amino group represented by R ₉₁₃ and R _{14 in} formula (1-3) include an alkyl-substituted amino group as a substituent of the heterocyclic group represented by R ₇ and R ₈ in formula (1-1). And the same aryl-substituted amino group.

R ₁₃ and R _{14 in} formula (1-3) are preferably each independently an alkyl-substituted amino group and an aryl-substituted amino group, and more preferably an alkyl-substituted amino group.

  When the compound represented by the formula (1) of the present invention is irradiated with active energy rays, a radical and a basic compound are generated with a cleavage reaction and a decarboxylation reaction as shown by the following formula, Radical polymerization of the polymer precursor having a radical polymerizable group can be initiated by the generated radical. Further, the basic compound generated simultaneously with the radical can not only undergo a crosslinking reaction with the polymer precursor described later, but also can lower the curing start temperature of the polymer precursor by the catalytic action of the generated base.

Next, a method for synthesizing the compound represented by the formula (1) of the present invention will be described.
In the case of a compound in which X in formula (1) is a substituent represented by formula (1-1) and R ₇ is a hydrogen atom, Photopolym. Sci. By applying the method described in Technol 27, 2, 2014, for example, a benzoin derivative represented by the following formula (21) is reacted with paraformaldehyde in the presence of a metal hydroxide at room temperature for 30 minutes. The intermediate compound represented by the formula (22-2) is represented by the formula (1) by reacting the intermediate compound with an isocyanate in the presence of a catalyst of an organic compound such as tin or lead. Can be obtained. The purification method is the same as described above. Incidentally, formula (21), (22-2) and _{R 1} through _{R 5} and _{R 8} of isocyanates in has the same meaning as _{R 1} to _{R 5} and _{R 8} in the formula (1).

  As a synthesis method without using isocyanates, an intermediate compound represented by the formula (22-3) is synthesized by reacting an intermediate compound represented by the formula (22-2) with carbodiimidazole. A compound represented by the formula (1) can be obtained by reacting with an amine compound.

  Specific examples of the compound represented by the formula (1) are shown in the following formulas (a) to (h), but the present invention is not limited to these.

  When the compound represented by the formula (1) of the present invention is used as a photopolymerization initiator, exposure is performed in order to generate radicals and basic compounds that can sufficiently contribute to the polycondensation reaction of the polymer precursor. It is necessary to have absorption for at least part of the wavelength. Since the wavelength of a high-pressure mercury lamp, which is a general exposure light source, is 365 nm, 405 nm, and 436 nm, it is preferable to have absorption for at least one of the active energy rays having these wavelengths. In such a case, it is preferable because the number of applicable polymer precursors is further increased.

  When the compound represented by the formula (1) is used as a photopolymerization initiator, the molar extinction coefficient is 100 or more for an active energy ray having a wavelength of 365 nm, or 1 for an active energy ray having a wavelength of 405 nm. It is preferable from the viewpoint that the number of applicable polymer precursors is further increased.

Note that the compound represented by the formula (1) of the present invention has absorption in the wavelength region is represented by the formula (1) in a solvent (for example, acetonitrile) having no absorption in the wavelength region. The concentration of the base generator is 1 × 10 ⁻⁴ mol / L or less (usually about 1 × 10 ^{−4 to} 1 × 10 ⁻⁵ mol / L. The base generator may be appropriately adjusted so as to obtain an appropriate absorption intensity. )) And the absorbance can be confirmed by measuring the absorbance with an ultraviolet-visible spectrophotometer (for example, UV-2550, manufactured by Shimadzu Corporation).

The photopolymerization initiator (photobase generator) containing the compound represented by the formula (1) of the present invention has excellent sensitivity as compared with conventionally known photobase generators, and thus can be applied in various ways. . The structure and physical properties change depending on the base such as an acid-base indicator, not limited to the combination with a polymer precursor described later, which can undergo a polycondensation reaction by heating with a basic substance or in the presence of a basic substance. Various photosensitive compositions are obtained in combination with the compound.
Such a photosensitive composition may be used as a paint, a printing ink, a sealant, or an adhesive, or a display device, a semiconductor device, an electronic component, a micro electro mechanical system (MEMS), an optical member, or an architecture. It can be used as a material forming material.
For example, an image forming layer containing at least a photopolymerization initiator (photobase generator) containing a compound represented by the formula (1) of the present invention and an acid-base indicator is coated on or impregnated on the substrate. In such an image forming medium, when the image forming layer is exposed, the photobase generator generates a base that reacts with an acid-base indicator to form an image. It can also be applied to display devices.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention includes a photopolymerization initiator containing a compound represented by the formula (1) and a polymer that can be polymerized by light irradiation or light irradiation and heating in the presence of the photopolymerization initiator. Contains a precursor. The change in solubility accompanying the polymerization reaction of the polymer precursor causes a difference in solubility between the exposed portion and the unexposed portion, that is, the solubility contrast increases, so that the photosensitive resin of the present invention A cured product pattern can be formed using the composition.

<Polymer precursor>
The polymer precursor contained in the photosensitive resin composition of the present invention refers to a compound that can be cured to a high molecular weight by a polymerization reaction caused by a radical or basic substance or by heating in the presence of a basic substance. means. Examples of the polymerization reaction include a polycondensation reaction between polymer precursors induced by radicals, a basic compound (amines) generated from the compound represented by the formula (1) by irradiation with active energy rays, and a high amount. Examples include both polycondensation reactions with molecular precursors, but the basic compound generated from the compound represented by formula (1) acts as a catalyst and serves to lower the reaction start temperature during heat curing. Is also included in the embodiment of the photosensitive resin composition of the present invention. The molecular weight of the polymer precursor is not particularly limited, but is preferably about 500 to 10,000 in terms of weight (or number) average molecular weight.

  The polymer precursor contained in the photosensitive resin composition of the present invention includes a compound that can be polymerized by a polymerization reaction induced by radicals generated from the compound represented by the formula (1), represented by the formula (1). A compound capable of undergoing a polycondensation reaction by a basic substance generated from the compound to be produced or by heating in the presence of the basic substance, and a reaction of the polycondensation reaction by the action of the basic compound as a catalyst. Any compound that can lower the reaction start temperature can be used without particular limitation. Although the specific example of a polymer precursor is given to the following, the polymer precursor which the photosensitive resin composition of this invention can contain is not limited to these.

<Polymer precursor that becomes polymer by radical polymerization reaction>
Examples of the polymer precursor that can be polymerized by a polymerization reaction induced by radicals generated from the compound represented by the formula (1) include radically polymerizable substituents including compounds having radically polymerizable substituents. As a compound to have, the compound which has a double bond in a molecule | numerator is preferable, and the compound which has an allyl group, an acryloyl group, a methacryloyl group, or a maleimide group is preferable.

  Specific examples of the compound having an acryloyl group or a methacryloyl group (excluding a compound having an epoxy group) include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, and 1,9-nonanediol diacrylate. And diacrylates of diols such as 1,10-decanediol diacrylate; ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene Glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol and ethylene Diacrylate of diol obtained by adding at least one of xylene and propylene oxide and diacrylate of glycol such as caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate; diacrylate of EO addition product of bisphenol A, bisphenol A And diacrylates having a cyclic structure such as diacrylate, tricyclodecane dimethanol diacrylate, hydrogenated dicyclopentadienyl diacrylate, and cyclohexyl diacrylate.

  Specific examples of commercially available compounds having an acryloyl group or a methacryloyl group include light acrylate 1,6HX-A, 1,9ND-A, 3EG-A, and 4EG-A (all trade names, manufactured by Kyoeisha Chemical Co., Ltd.); HDDA, 1,9-NDA, DPGDA and TPGDA (all trade names, manufactured by Daicel Ornex Co., Ltd.), Biscote # 195, # 230, # 230D, # 260, # 310HP, # 335HP and # 700HV (all trade names, Osaka Organic Chemical Industry Co., Ltd.), Aronix M-208, M-211B, M-220, M-225, M-240, M-270 (all trade names, manufactured by Toagosei Co., Ltd.) and the like.

  Among these, from the viewpoint of viscosity and compatibility with the compound represented by the formula (1), diacrylates of diols having an alkyl chain having 4 to 12 carbon atoms, particularly 1,4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1,9-nonanediol diacrylate and 1,10-decanediol diacrylate are preferred.

<Polymer precursor that becomes polymer by intermolecular reaction>
The polymer precursor that can be polymerized by a basic substance generated from the compound represented by the formula (1) or by an intermolecular reaction by heating in the presence of the basic substance, reacts with the basic substance. And a compound having a substituent capable of increasing the molecular weight by a reaction (crosslinking reaction) that forms a bond between molecules by heating in the presence of the basic substance. Substituents that can react with basic substances and substituents that can react to form a bond between molecules by heating in the presence of basic substances include epoxy groups, oxetane groups, thiirane groups, isocyanate groups, hydroxyl groups. And silanol groups. The polymer precursor also includes a compound that undergoes hydrolysis / polycondensation between molecules, and examples of the substituent that can undergo hydrolysis / polycondensation reaction between molecules include -SiX of a polysiloxane precursor (where, X is a hydrolyzable group selected from the group consisting of an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group, an amide group, and a halogen.

Examples of the compound having a substituent capable of reacting with a basic substance include compounds having at least one of the above-mentioned substituents. For example, a compound having one or more epoxy groups in the molecule, one or more compounds in the molecule Examples thereof include compounds having an oxetane group and compounds having one or more thiirane groups in the molecule.
Although the compound which has an epoxy group is demonstrated concretely below, it can be used similarly about the compound which has an oxetane group and a thiirane group.

<Compound having an epoxy group>
The compound having an epoxy group is not particularly limited as long as it has one or more epoxy groups in the molecule, and conventionally known compounds can be used.
The photopolymerization initiator containing the compound represented by the formula (1) of the present invention also generally has a function as a curing catalyst for a compound having one or more epoxy groups in the molecule.
When a compound having one or more epoxy groups in the molecule is used, a compound having two or more functional groups having reactivity with the epoxy group may be used in combination. Examples of the functional group having reactivity with the epoxy group include a carboxyl group, a phenolic hydroxyl group, a mercapto group, a primary or secondary aromatic amino group, and the like. Examples of the compound having two or more functional groups having reactivity with an epoxy group in the molecule include compounds in which the functional group is introduced into a polymer side chain having a weight average molecular weight of 3,000 to 100,000. The embodiment used in combination is one of the preferred embodiments. When the weight average molecular weight of the polymer is less than 3,000, the strength of the film is lowered and the surface of the cured film is tacked (sticky), which may cause impurities and the like to easily adhere to the surface. If it is large, the melt viscosity or viscosity when dissolved in a solvent may increase.

  Examples of the compound having one or more epoxy groups in the molecule include bisphenol A type epoxy resin derived from bisphenol A and epichlorohydrin, bisphenol F type epoxy resin derived from bisphenol F and epichlorohydrin, and bisphenol S type epoxy resin. , Phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type Epoxy resin, fluorene type epoxy resin, trifunctional type epoxy resin and polyfunctional type epoxy resin such as tetrafunctional type epoxy resin, glycidyl ester type epoxy And glycidylamine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, aliphatic chain epoxy resins, etc., and these epoxy resins may be halogenated or hydrogenated. Good. Examples of commercially available epoxy resins include JER Coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 manufactured by Japan Epoxy Resin Co., Ltd., Epicron 830 manufactured by DIC Corporation, EXA835LV, HP4032D, HP820, EP4100 series, EP4000 series, EPU series manufactured by ADEKA Co., Ltd., Celoxide series (2021, 2021P, 2083, 2085, 3000 etc.) manufactured by Daicel Chemical Industries, Ltd., Epolide series, EHPE series, Toto Kasei's YD series, YDF series, YDCN series, YDB series, Nagase ChemteX's Denacol series, Kyoeisha Chemical's Epolite series, etc. It is not limited to these. Two or more of these epoxy resins may be used in combination. Among these, grades with different molecular weights are widely available, and bisphenol-type epoxy resins are preferable because adhesiveness and reactivity can be arbitrarily set.

<Compound having oxetane group>
Examples of the compound having an oxetane group include 4,4 ′-(3-ethyloxetane-3-ylmethyloxymethyl) biphenyl (OXBP), 3-ethyl-3-hydroxymethyloxetane (EHO), 1,4-bis [{ (3-Ethyl-3-oxetanyl) methoxy} methyl] benzene (XDO), di [1-ethyl (3-oxetanyl)] methyl ether (DOX), di [1-ethyl (3-oxetanyl)] methyl ether (DOE) ), 1,6-bis [(3-ethyl-3-oxetanyl) methoxy] hexane (HDB), 9,9-bis [2-methyl-4- {2- (3-oxetanyl)} butoxyphenyl] fluorene, Bifunctional oxetane compounds such as 9,9-bis [4- [2- {2- (3-oxetanyl)} butoxy] ethoxyphenyl] fluorene, Include polyfunctional oxetane compounds such Kisetan novolak resin

<Compound having thiirane group>
The compound having a thiirane group has at least one thiirane ring in the molecule. Specific examples thereof include bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropylthiol). ) Ethane, bis (2,3-epithiopropylthio) propane, bis (2,3-epithiopropylthio) butane, bis (5,6-epithio-3-thiohexane) sulfide, bis (2,3-epi Thiopropyl) disulfide, bis (3,4-epithiobutyl) disulfide, bis (4,5-epithiopentyl) disulfide, bis (5,6-epithiohexyl) disulfide, but bis (2,3-epi Thiopropyl) sulfide and bis (2,3-epithiopropyl) disulfide are particularly preferred.

  On the other hand, examples of the compound that crosslinks between molecules include a combination of a compound having two or more isocyanate groups in the molecule and a compound having two or more hydroxyl groups in the molecule. By the reaction with the hydroxyl group, a urethane bond is formed between the molecules, and the polymer can be formed.

<Compound having an isocyanate group>
The compound having an isocyanate group is not particularly limited as long as it has two or more isocyanate groups in the molecule, and known compounds can be used. As such a compound, in addition to low molecular weight compounds represented by p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, oligomers, A compound having an isocyanate group in the side chain or terminal of a polymer having a weight average molecular weight of 3,000 or more may be used.

<Compound having a hydroxyl group>
The compound having an isocyanate group is usually used in combination with a compound having a hydroxyl group in the molecule. The compound having such a hydroxyl group is not particularly limited as long as it has two or more hydroxyl groups in the molecule, and known compounds can be used. As such compounds, in addition to low molecular weight compounds such as ethylene glycol, propylene glycol, glycerin, diglycerin and pentaerythritol, compounds having a hydroxyl group in the side chain or terminal of a polymer having a weight average molecular weight of 3,000 or more May be used.

<Polysiloxane precursor>
Examples of the compound that undergoes hydrolysis and polycondensation between molecules include, for example, a polysiloxane precursor. As the polysiloxane precursor, Y _n SiX _(4-n) (where Y represents an alkyl group, fluoroalkyl group, vinyl group, phenyl group, or hydrogen which may have a substituent, and X represents And a hydrolyzable group selected from the group consisting of an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group, an amide group, and a halogen atom, and n represents an integer of 0 to 3. And the hydrolyzed polycondensates of the organosilicon compounds. Among them, those in which n is 0 to 2 in the above formula Y _n SiX _(4-n) are preferable. Further, from the viewpoint that the silica-dispersed oligomer solution is easily prepared and easily available, the hydrolyzable group is preferably an alkoxy group. There is no restriction | limiting in particular as said organosilicon compound, A well-known thing can be used. For example, trimethoxysilane, triethoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrit-butoxysilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltriethoxysilane , N-propyltriethoxysilane, n-hexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane , Diphenyldimethoxysilane, vinyltrimethoxysilane, trifluoropropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, β- (3 4-epoxycyclohexyl) ethyltrimethoxysilane, fluoroalkylsilanes known as fluorine-based silane coupling agents, and their hydrolysis condensates or cohydrolysis condensates; and mixtures thereof.

<Polymer precursor that becomes polymer by intramolecular ring closure>
Examples of the polymer precursor that can be increased in molecular weight by intramolecular ring-closing reaction include a polyimide precursor and a polybenzoxazole precursor. These precursors may be a mixture of two or more kinds of polymer precursors.
Hereinafter, although the polyimide precursor and polybenzoxazole precursor which are the preferable polymer precursors of this invention are demonstrated, this invention is not limited to these.

<Polyimide precursor>
As the polyimide precursor, a polyamic acid having a repeating unit represented by the following chemical formula (8) is preferably used. In formula (8), R ₁₁ is a tetravalent organic group. R ₁₂ is a divalent organic group. R ₁₃ and R ₁₄ are a hydrogen atom or an organic group. n is a natural number of 1 or more. Examples of the case where R ₁₃ and R ₁₄ are organic groups are represented by an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and C _n H _2n OC _m H _{2m + 1} containing an ether bond therein. The structure etc. can be mentioned.

  Polyamic acid is preferable because it can be obtained by simply mixing acid dianhydride and diamine in a solution, so that it can be synthesized by a one-step reaction, and can be synthesized easily and at low cost.

  When the polymer precursor is a polyamic acid having a repeating unit represented by the above formula (8), the temperature required for imidization is usually lower than 300 ° C., preferably 250 ° C. or less due to the catalytic effect of the basic substance. Is possible. General polyamic acid had to be used at a temperature required for imidization of 300 ° C. or higher, so its use was limited. However, it became possible to lower the temperature required for imidization, and thus a wider range. Applicable to usage.

  As a method for producing a polyimide precursor, a conventionally known method can be applied. For example, a method of synthesizing a polyamic acid which is a precursor from an acid dianhydride and a diamine, an ester acid or an amic acid monomer obtained by reacting a monohydric alcohol, amino compound or epoxy compound with the acid dianhydride A method of reacting a diamino compound or a derivative thereof with the carboxylic acid of, but not limited to,

<Polybenzoxazole precursor>
As the polybenzoxazole precursor, polyamide alcohol having a repeating unit represented by the following chemical formula (9) is preferably used.

In the formula (9), R ₁₅ is a divalent organic group, and R ₁₆ is a tetravalent organic group. The polyamide alcohol having a repeating unit represented by the formula (9) may be composed of a single repeating unit or may be composed of two or more kinds of repeating units.

  Examples of the dicarboxylic acid and its derivatives applicable to the reaction for obtaining the polybenzoxazole precursor include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-benzophenone dicarboxylic acid, and 3,4′-benzophenone dicarboxylic acid. Acid, 3,3′-benzophenone dicarboxylic acid, 4,4′-biphenyl dicarboxylic acid, 3,4′-biphenyl dicarboxylic acid, 3,3′-biphenyl dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 3,4 '-Diphenyl ether dicarboxylic acid, 3,3'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 3,4'-diphenyl sulfone dicarboxylic acid, 3,3'-diphenyl sulfone dicarboxylic acid, 4,4'- Hexafluoroisopropylidene dibenzoic acid, 4 4′-dicarboxydiphenylamide, 1,4-phenylenediethanoic acid, 1,1-bis (4-carboxyphenyl) -1-phenyl-2,2,2-trifluoroethane, bis (4-carboxyphenyl) Tetraphenyldisiloxane, bis (4-carboxyphenyl) tetramethyldisiloxane, bis (4-carboxyphenyl) sulfone, bis (4-carboxyphenyl) methane, 5-t-butylisophthalic acid, 5-bromoisophthalic acid, 5 -Fluoroisophthalic acid, 5-chloroisophthalic acid, 2,2-bis- (p-carboxyphenyl) propane, 4,4 '-(p-phenylenedioxy) dibenzoic acid, 2,6-naphthalenedicarboxylic acid, or These acid halides and active esters with hydroxybenzotriazole, etc. It can be exemplified, but the invention is not limited thereto. These may be used alone or in combination of two or more.

  Specific examples of hydroxydiamine applicable to the reaction for obtaining the polybenzoxazole precursor include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone, bis- ( 3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2 , 2-bis- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3- Droxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4′-diamino-3,3′-dihydroxybenzophenone, 3,3′-diamino-4,4 ′ -Dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3 -Diamino-2,4-dihydroxybenzene, 3-diamino-4,6-dihydroxybenzene and the like are exemplified, but not limited thereto. These may be used alone or in combination of two or more.

  Polymer precursors such as polyimide precursors and polybenzoxazole precursors have a film thickness of 1 μm in order to increase the sensitivity of the photosensitive resin composition and obtain a pattern shape that accurately reproduces the mask pattern. Furthermore, it is preferable that the transmittance is at least 5% or more with respect to the exposure wavelength, and it is more preferable that the transmittance is 15% or more. The high transmittance of polymer precursors such as polyimide precursors and polybenzoxazole precursors with respect to the exposure wavelength means that there is less loss of active energy rays, and a highly sensitive photosensitive resin composition. You can get things.

  Further, when exposure is performed using a high-pressure mercury lamp, which is a general exposure light source, the transmittance with respect to an active energy ray having a wavelength of at least 436 nm, 405 nm, and 365 nm has a thickness of 1 μm. When formed on a film, it is preferably 5% or more, more preferably 15%, and particularly preferably 50% or more.

  The weight average molecular weight of a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor is preferably in the range of 3,000 to 1,000,000, depending on its use, and is preferably 5,000 to 500. Is more preferably in the range of 10,000 to 500,000. When the weight average molecular weight is less than 3,000, it is difficult to obtain sufficient strength when a coating film or film is used. In addition, the strength of the film is reduced when heat treatment or the like is performed to obtain a polymer such as polyimide. On the other hand, when the weight average molecular weight exceeds 1,000,000, the viscosity increases, the solubility tends to decrease, and it is difficult to obtain a coating film or film having a smooth surface and a uniform film thickness.

  The molecular weight used here refers to a value in terms of polystyrene by gel permeation chromatography (GPC), and may be the molecular weight of a polymer precursor itself such as a polyimide precursor, or chemical imidization with acetic anhydride or the like. The thing after processing may be used.

  The solvent used for the synthesis of the polyimide precursor or polybenzoxazole precursor is preferably a polar solvent, and representative examples include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide. , N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethylsulfoxide, hexamethylphosphoamide, pyridine, dimethylsulfone, tetramethylenesulfone, dimethyltetra Examples include methylene sulfone, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, and these solvents are used alone or in combination of two or more. In addition to these, non-polar solvents such as benzene, benzonitrile, 1,4-dioxane, tetrahydrofuran, butyrolactone, xylene, toluene, cyclohexanone, and the like can be used as a solvent. It is used as a reaction regulator, a volatilization regulator of a solvent from the product, a film smoothing agent, and the like.

  Since the solubility of polyamic acid and polybenzoxazole precursor is reduced by increasing the molecular weight by the action of a basic substance, the basicity generated from the photopolymerization initiator containing the compound represented by the formula (1) By combining with a decrease in solubility due to the substance, there is an advantage that the contrast of the solubility of the exposed portion and the unexposed portion of the photosensitive resin composition of the present invention can be further increased.

The content of the polymer precursor in the photosensitive resin composition of the present invention is 30% by mass with respect to the entire solid content of the photosensitive resin composition from the viewpoint of film physical properties of the pattern obtained, particularly film strength and heat resistance. Preferably, it is more than 50% by mass.
Moreover, content of the photoinitiator containing the compound represented by Formula (1) in the photosensitive resin composition of this invention is 0 normally with respect to solid content of the polymer precursor contained in the photosensitive resin composition. .1 to 95% by mass, preferably 0.5 to 60% by mass. If the content of the photopolymerization initiator is less than 0.1% by mass, the solubility contrast between the exposed part and the unexposed part may not be sufficiently increased. If the content exceeds 95% by mass, the photosensitive resin composition is cured. There is a risk that various properties of the object may be difficult to express. A compound represented by formula (1) when a basic compound generated by light irradiation from a photopolymerization initiator containing a compound represented by formula (1) is used as a curing agent, such as when combined with an epoxy compound. The content of the photopolymerization initiator to be contained is usually 0.1 to 95% by mass, preferably 0.5 to 60% by mass, based on the solid content of the polymer precursor contained in the photosensitive resin composition.
In addition, content of the photoinitiator containing the compound represented by Formula (1) in case the basic compound generate | occur | produced from the compound represented by Formula (1) acts as a catalyst is the photosensitive resin composition. The amount is usually 0.1 to 30% by mass, preferably 0.5 to 20% by mass, based on the solid content of the polymer precursor contained.

<Other ingredients>
The photosensitive resin composition of the present invention may be a simple mixture of a photopolymerization initiator containing a compound represented by the formula (1) and a polymer precursor, but further, a solvent, light or thermosetting. Other components such as a non-polymerizable binder resin other than the functional component and the polymer precursor may be blended.

  Various general-purpose solvents can be used as a solvent for dissolving, dispersing or diluting the photosensitive resin composition. When polyamic acid is used as the polymer precursor, a solution obtained by the synthesis reaction of polyamic acid is used as it is, and a photopolymerization initiator containing the compound represented by formula (1) is used as needed. Other components may be mixed.

  Usable general-purpose solvents include, for example, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and the like; ethylene glycol monomethyl ether, ethylene glycol mono Glycol monoethers (so-called cellosolves) such as ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc. Ketones; ethyl acetate, butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetate esters of the glycol monoethers (for example, methyl cellosolve acetate, ethyl cellosolve acetate), Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, esters such as dimethyl oxalate, methyl lactate, ethyl lactate; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin; methylene chloride 1,1-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, 1-chlorobutane, 1-chloropentane, chlorobenzene, bromobenzene, o- Halogenated hydrocarbons such as dichlorobenzene and m-dichlorobenzene; N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide Amides such as N-methyl-2-pyrrolidone, pyrrolidones such as N-acetyl-2-pyrrolidone; lactones such as γ-butyrolactone and α-acetyl-γ-butyrolactone; sulfoxides such as dimethyl sulfoxide, dimethyl sulfone , Sulfones such as tetramethylene sulfone and dimethyltetramethylene sulfone, phosphoric acid amides such as hexamethylphosphoamide, and other organic polar solvents, and further aromatics such as benzene, toluene, xylene and pyridine. Group hydrocarbons and Other organic nonpolar solvents are also included. These solvents are used alone or in combination.

  Among them, polar solvents such as propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, toluene, etc. Aromatic hydrocarbons and mixed solvents composed of these solvents are preferred.

  The photosensitive resin composition of the present invention can contain a photocurable component. As the photocurable component, a compound having one or more ethylenically unsaturated bonds can be used. For example, an amide monomer, a (meth) acrylate monomer, a urethane (meth) acrylate oligomer, a polyester (meth) Aromatic vinyl compounds such as acrylate oligomers, epoxy (meth) acrylates, hydroxyl group-containing (meth) acrylates, and styrene can be exemplified. In addition, when the polyimide precursor has a carboxylic acid component such as polyamic acid in the structure, the use of an ethylenically unsaturated bond-containing compound having a tertiary amino group results in an ionic bond with the carboxylic acid of the polyimide precursor. When the photosensitive resin composition is formed, the dissolution rate contrast between the exposed area and the unexposed area is increased.

You may use together the photoinitiator (photobase generator) other than the photoinitiator containing the compound represented by Formula (1) with the photosensitive resin composition of this invention.
The photopolymerization initiator that can be used in combination is not particularly limited, and for example, a photoradical polymerization initiator can be used. As this radical photopolymerization initiator, any compound can be used as long as it generates radicals by light, laser, electron beam or the like and can initiate radical polymerization reaction.

  Examples of the photopolymerization initiator that can be used in combination include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; 2-hydroxy-2-methyl-1-phenyl-propane-1- Alkylphenones such as ON; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl-1- [4 Amino such as-(methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, N, N-dimethylaminoacetophenone Acetophenones; 2-methyl Anthraquinones such as anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc. Thioxanthones; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 2,4,5-triarylimidazole dimer; Riboflavin tetrabutyrate; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole Thiol compounds such as 2,4,6-tris-s-triazine, 2,2,2-tribromoethanol, tribromomethylphenylsulfone and other organic halogen compounds; Benzophenones such as 4,4'-bisdiethylaminobenzophenone or xanthones; acylphosphines such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Fin oxides: bis (cyclopentadienyl) diphenyltitanium, bis (cyclopentadienyl) dichlorotitanium, bis (cyclopentadienyl) -bis (2,3,4,5,6 pentafluorophenyl) titanium, bis (Cyclopentadienyl) -bis (2,6-difluoro-3- (pyrrol-1-yl) phenyl) titanocenes such as titanium and the like.

  These known and commonly used photopolymerization initiators can be used alone or as a mixture of two or more thereof. Further, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4- Photoinitiator aids such as tertiary amines such as dimethylaminobenzoate, triethylamine, triethanolamine can be added.

  Examples of commercially available photopolymerization initiators include Irgacure 261, 184, 369, 651, 500, 819, 907, 784, 2959, Darocur 1116, 1173, CGI 1700, CGI 1750, CGI 1850, CG-24-61, Lucillin TPO, CGI-784 (trade name, manufactured by BASF Japan), DAICATII (trade name, manufactured by Daicel Chemical Industries), UVAC1591 (trade name, manufactured by Daicel UCB), Rhodosil Photo Initiator 2074 (Rhodia) Company name), Ubekrill P36 (product name made by UCB), Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B, ONE (product names made by Fratelli Lamberti), etc. Et That.

  When using the photoinitiator which can be used together, the mixture ratio of the photoinitiator which can be used together has the preferable range of 0.5-10 mass parts in 100 mass parts of photosensitive resin compositions of this invention.

  A photobase generator other than the formula (1) can be used instead of the photopolymerization initiator or in combination with the photopolymerization initiator. The photobase generator is a catalyst for the addition reaction between a (meth) acrylate compound having an epoxy group and a thermosetting component when the molecular structure is changed by light irradiation such as ultraviolet light or visible light, or the molecule is cleaved. Is a compound that produces one or more basic substances that can function as Examples of the basic substance to be generated include secondary amines and tertiary amines.

  Examples of photobase generators that can be used in combination include α-aminoacetophenone compounds, oxime ester compounds, acyloxyimino groups, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzyl carbamate groups, alcohols, and the like. Examples thereof include compounds having a substituent such as an oxybenzyl carbamate group. Of these, oxime ester compounds and α-aminoacetophenone compounds are preferred. As the α-aminoacetophenone compound, those having two or more nitrogen atoms are particularly preferable. Other photobase generators include WPBG-018 (trade name: 9-anthrylmethylN, N′-diethylcarbamate, manufactured by Wako Pure Chemical Industries), WPBG-027 (trade name: (E) -1- [3- (2-hydroxyphenyl). ) -2-propenoyl] piperidine), WPBG-082 (trade name: guanidinium2- (3-benzoylphenyl) propionate), WPBG-140 (trade name: 1- (anthraquinon-2-yl) ethylimidocarboxylate) it can. The α-aminoacetophenone compound has a benzoin ether bond in the molecule, and when irradiated with light, cleavage occurs in the molecule to produce a basic substance (amine) that exhibits a curing catalytic action. Specific examples of the α-aminoacetophenone compound include (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, manufactured by BASF Japan Ltd.) and 4- (methylthiobenzoyl) -1-methyl. -1-morpholinoethane (Irgacure 907, trade name, manufactured by BASF Japan Ltd.), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl]- A commercially available compound such as 1-butanone (Irgacure 379, trade name, manufactured by BASF Japan Ltd.) or a solution thereof can be used.

  As the oxime ester compound that can be used in combination, any compound that generates a basic substance by light irradiation can be used. Examples of the oxime ester compound include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, NCI-831 manufactured by Adeka, and the like as commercial products. Moreover, the compound which has two oxime ester groups in the molecule | numerator described in the patent 4344400 gazette can also be used suitably.

  In addition, JP-A-2004-359639, JP-A-2005-097141, JP-A-2005-220097, JP-A-2006-160634, JP-A-2008-094770, JP-A-2008-509967, Specific examples include carbazole oxime ester compounds described in JP2009-040762A and JP2011-80036A.

A base proliferating agent that generates a base by a decomposition or rearrangement reaction by the action of a small amount of base generated from the base generator may be used in combination. Examples of the base proliferating agent include a compound having 9-fluorenylmethyl carbamate bond, 1,1-dimethyl-2-cyanomethyl carbamate bond ((CN) CH ₂ C (CH ₃ ) ₂ OC (O) NR ₂ ), A compound having a paranitrobenzyl carbamate bond, a compound having a 2,4-dichlorobenzyl carbamate bond, and other urethane compounds described in paragraphs 0010 to 0032 of JP 2000-330270 A And urethane compounds described in paragraphs 0033 to 0060 of JP-A-2008-250111.

  In some cases, the addition of a sensitizer may be effective when it is desired to make the base generator sufficiently use the energy of the active energy ray having a wavelength that transmits the polymer to improve the sensitivity. In particular, when the absorption of the polyimide precursor is also at a wavelength of 360 nm or more, the effect of adding a sensitizer is great. Specific examples of compounds called sensitizers include thioxanthone and derivatives thereof such as diethylthioxanthone, coumarins and derivatives thereof, ketocoumarin and derivatives thereof, ketobiscoumarin and derivatives thereof, cyclopentanone and derivatives thereof , Cyclohexanone and derivatives thereof, thiopyrylium salts and derivatives thereof, thixanthene series, xanthene series and derivatives thereof. Specific examples of coumarin, ketocoumarin and derivatives thereof include 3,3′-carbonylbiscoumarin, 3,3′-carbonylbis (5,7-dimethoxycoumarin), 3,3′-carbonylbis (7-acetoxycoumarin). ) And the like. Specific examples of thioxanthone and derivatives thereof include diethyl thioxanthone and isopropyl thioxanthone. Furthermore, benzophenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1,2-benzanthraquinone, 1,2-naphthoquinone, etc. Is mentioned. Since these exhibit a particularly excellent effect in combination with a base generator, a sensitizer exhibiting an optimal sensitizing action is appropriately selected depending on the structure of the base generator.

  In order to impart processing characteristics and various functionalities to the photosensitive resin composition of the present invention, various organic or inorganic low-molecular or high-molecular compounds may be blended. For example, dyes, surfactants, leveling agents, plasticizers, fine particles and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate, and these may have a porous or hollow structure. The function or form includes pigments, fillers, fibers, and the like.

  Moreover, the blending ratio of optional components other than the solvent is preferably in the range of 0.1 to 95% by mass with respect to the entire solid content of the photosensitive resin composition. When the content is less than 0.1% by mass, the effect of adding the additive is difficult to be exhibited. When the content exceeds 95% by mass, the properties of the finally obtained resin cured product are hardly reflected in the final product.

  The photosensitive resin composition of the present invention can be used in various coating processes and molding processes to produce films and molded articles having a three-dimensional shape.

  When a polyimide precursor or a polybenzoxazole precursor is used as a polymer precursor as an embodiment of the photosensitive resin composition of the present invention, the resulting polyimide and polybenzoxazole have heat resistance, dimensional stability, and insulating properties. From the viewpoint of securing the above properties, the 5% weight loss temperature measured in nitrogen of the polyimide and polybenzoxazole is preferably 250 ° C. or higher, more preferably 300 ° C. or higher. In particular, when used in applications such as electronic parts that pass through the solder reflow process, if the 5% weight loss temperature is 300 ° C. or less, defects such as bubbles occur due to the decomposition gas generated in the solder reflow process. There is a fear.

  The glass transition temperature of the polyimide and polybenzoxazole obtained from the photosensitive resin composition of the present invention is preferably as high as possible from the viewpoint of heat resistance, but in applications where a thermoforming process is considered like an optical waveguide, It preferably exhibits a glass transition temperature of about 120 to 450 ° C., more preferably about 200 to 380 ° C.

  Here, the glass transition temperature in the present invention is tan δ (tan δ = loss elastic modulus (tan δ) by dynamic viscoelasticity measurement when polyimide and polybenzoxazole obtained from the photosensitive resin composition can be formed into a film shape. It is obtained from the peak temperature of E ″) / storage elastic modulus (E ′)). The dynamic viscoelasticity measurement can be performed, for example, with a viscoelasticity measuring device Solid Analyzer RSAII (manufactured by Rheometric Scientific) at a frequency of 3 Hz and a heating rate of 5 ° C./min. When the polyimide and polybenzoxazole obtained from the photosensitive resin composition cannot be formed into a film shape, the determination is made based on the temperature at the inflection point of the baseline of differential thermal analysis (DTA).

  From the viewpoint of dimensional stability of the polyimide and polybenzoxazole film obtained from the photosensitive resin composition of the present invention, the linear thermal expansion coefficient is preferably 60 ppm or less, and more preferably 40 ppm or less. In the case of forming a film on a silicon wafer in a manufacturing process of a semiconductor element or the like, 20 ppm or less is more preferable from the viewpoint of adhesion and warpage of the substrate.

The linear thermal expansion coefficient in this invention can be calculated | required with the thermomechanical analyzer (TMA) of the film of the polyimide and polybenzoxazole obtained from the photosensitive resin composition obtained by this invention. Using a thermomechanical analyzer (for example, Thermo Plus TMA8310 (manufactured by Rigaku Corporation), the heating rate is 10 ° C./min, and the tensile load is 1 g / 25,000 μm so that the weight per cross-sectional area of the evaluation sample is the same. ² is obtained.

  As described above, according to the present invention, a photosensitive resin composition can be obtained by a simple method of simply mixing a photopolymerization initiator containing a compound represented by formula (1) with a polymer precursor. Because it is possible, it is excellent in cost performance. The aromatic component-containing carboxylic acid constituting the photopolymerization initiator containing the compound represented by the formula (1) and the basic substance can be obtained at low cost, and the price as the photosensitive resin composition can be suppressed. . The photosensitive resin composition of the present invention can be applied to promote the reaction of a wide variety of polymer precursors to the final product by the photopolymerization initiator containing the compound represented by the formula (1). The polymer structure obtained can be selected from a wide range. Also, due to the catalytic effect of basic substances such as amines generated by irradiation of active energy rays, the processing temperature required for reactions such as cyclization such as imidation from a polyimide precursor or polybenzoxazole precursor to the final product, for example Therefore, it is possible to reduce the load on the process and damage to the product due to heat. Furthermore, the base generator of the present invention that generates a base by irradiation with active energy rays and heating can utilize the heating step when the step of obtaining the final product from the polymer precursor includes the heating step. The amount of energy beam irradiation can be reduced, and the process can be used effectively.

  The photosensitive resin composition of the present invention, the photosensitive resin composition of the present invention is a printing ink, paint, sealing agent, adhesive, electronic material, optical circuit component, molding material, resist material, building material, stereolithography, It can be used for all known fields and products in which resin materials such as optical members are used. It can be suitably used both for applications that are used by exposing the entire surface, such as paints, sealants, and adhesives, and for applications that form patterns such as permanent films and release films.

  The photosensitive resin composition of the present invention can be used in a wide range of fields, products, such as paints, printing inks, sealants, adhesives, or displays, in which properties such as heat resistance, dimensional stability, and insulation are effective. It is suitably used as a material for forming a device, a semiconductor device, an electronic component, a micro electro mechanical system (MEMS), an optically shaped object, an optical member, or a building material. For example, specifically, as a forming material for an electronic component, a sealing material and a layer forming material can be used for a printed wiring board, an interlayer insulating film, a wiring covering film, and the like. Moreover, as a forming material of a display device, a layer forming material or an image forming material can be used for a color filter, a film for flexible display, a resist material, an alignment film, and the like. Further, as a material for forming a semiconductor device, a resist material, a layer forming material such as a buffer coat film, or the like can be used. Further, as a material for forming an optical component, it can be used as an optical material or a layer forming material for a hologram, an optical waveguide, an optical circuit, an optical circuit component, an antireflection film, or the like. Moreover, as a building material, it can use for a coating material, a coating agent, etc. It can also be used as a material for an optically shaped object. A printed matter, a paint, a sealant, an adhesive, a display device, a semiconductor device, an electronic component, a microelectromechanical system, an optically shaped article, an optical member, or a building material is provided.

  Since it has the above features, the photosensitive resin composition of the present invention can also be used as a pattern forming material. In particular, when a photosensitive resin composition containing a polyimide precursor or a polybenzoxazole precursor is used as a pattern forming material (resist), the pattern formed thereby is a permanent film made of polyimide or polybenzoxazole. Functions as a component that imparts heat resistance and insulation, such as color filters, flexible display films, electronic components, semiconductor devices, interlayer insulation films, wiring coating films, optical circuits, optical circuit components, antireflection films, etc. It is suitable for forming an optical member or an electronic member.

<Pattern formation method>
The pattern forming method of the present invention comprises forming a coating film or a molded body comprising the photosensitive resin composition of the present invention, irradiating the coating film or molded body with an active energy ray in a predetermined pattern, and after irradiation or It develops, after heating simultaneously with irradiation, changing the solubility of the said irradiation site | part, and developing.

  The photosensitive resin composition of the present invention is coated on some support to form a coating film, or a molded body is formed by a suitable molding method, and the coating film or molded body is formed into a predetermined pattern. By irradiating with active energy rays and heating after irradiation or simultaneously with irradiation, the photopolymerization initiator containing the compound represented by formula (1) is cleaved only in the exposed area to generate radicals and basic substances. . The basic substance acts as a catalyst for promoting the high molecular weight reaction of the polymer precursor in the exposed area.

  When using a polymer precursor whose thermosetting temperature is lowered by the catalytic action of a base, such as a polyimide precursor or a polybenzoxazole precursor, first, these polymer precursors and the formula (1) are used. The part which wants to leave the pattern on the coating film of the photosensitive resin composition which combined the photoinitiator containing the compound to form or the molded object which consists of this photosensitive resin composition is exposed. The heat curing temperature of the exposed portion is selectively lowered by a basic substance generated by exposure or by heating simultaneously with exposure. After the exposure or simultaneously with the exposure, the exposed portion is cured, but the unexposed portion is heat-treated at a temperature at which it is not cured, and only the exposed portion is cured. The heat treatment for generating the basic substance and the heat treatment for curing only the exposed portion (post-exposure baking) may be the same step or different steps. Next, the unexposed portion is dissolved with a predetermined developer (such as an organic solvent or a basic aqueous solution) to form a pattern made of a thermoset. The pattern is further heated as necessary to complete thermosetting. Through the above steps, a desired negative two-dimensional resin pattern (general plane pattern) or a three-dimensional resin pattern (three-dimensionally shaped shape) is obtained.

  In addition, when using a polymer precursor that initiates the reaction by the catalytic action of a base, such as a compound having an epoxy group or a cyanate group and a polymer, first, these polymer precursor and formula ( The part which wants to leave the coating film of the photosensitive resin composition which combined the photoinitiator containing the compound represented by 1) or the pattern on the molded object which consists of this photosensitive resin composition is exposed. Polymerization reaction of a compound having an acryloyl group, an epoxy group or a cyanate group in an exposed portion occurs due to a radical and a basic substance generated by exposure or heating simultaneously with the exposure, and only the exposed portion is cured. The heat treatment for generating the basic substance and the heat treatment for curing only the exposed portion (post-exposure baking) may be the same step or different steps. Next, the unexposed portion is dissolved with a predetermined developer (such as an organic solvent or a basic aqueous solution) to form a pattern made of a thermoset. The pattern is further heated as necessary to complete thermosetting. Through the above steps, a desired negative two-dimensional resin pattern (general plane pattern) or a three-dimensional resin pattern (three-dimensionally shaped shape) is obtained.

  The photosensitive resin composition of the present invention includes propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and γ-butyrolactone. After being dissolved in a polar solvent such as toluene, aromatic hydrocarbons such as toluene, and a mixed solvent containing a plurality of these solvents, dipping, spraying, flexographic printing, gravure printing, screen printing, spin coating By applying the coating method to the surface of a substrate such as a silicon wafer, metal substrate, ceramic substrate, resin film, etc., and heating to remove most of the solvent, a non-sticky coating film is formed on the surface of the substrate. Can be given. Although there is no restriction | limiting in particular in the thickness of a coating film, it is preferable that it is 0.5-50 micrometers, and it is more desirable that it is 1.0-20 micrometers from a sensitivity and a development speed surface. The drying conditions of the applied coating film are, for example, 80 to 100 ° C. and 1 to 20 minutes.

  This coating film is exposed to an active energy ray through a mask having a predetermined pattern to be exposed in a pattern, and after heating, an unexposed portion of the film is developed and removed with an appropriate developer, and thereby desired. A patterned film can be obtained.

  The exposure method and the exposure apparatus used in the exposure process are not particularly limited, and may be contact exposure or indirect exposure. A contact / proximity exposure machine using a g-line stepper, i-line stepper, ultrahigh pressure mercury lamp, or mirror projection exposure machine. Alternatively, a projector or a radiation source that can irradiate ultraviolet rays, visible rays, X-rays, electron beams, or the like can be used.

The heating temperature for heating before exposure or after exposure or simultaneously with exposure to deprotect the protecting group to generate a base is appropriately selected depending on the polymer precursor to be combined and the purpose, and is not particularly limited. Heating by the temperature (for example, room temperature) of the environment where the photosensitive resin composition is placed may be used, and in that case, a base is gradually generated. In addition, since the base is also generated by heat generated as a by-product during irradiation with active energy rays, heating may be performed substantially simultaneously with the heat generated as a by-product during irradiation with active energy rays. The heating temperature for generating the base is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, and more preferably 100 ° C. or higher from the viewpoint of increasing the reaction rate and efficiently generating amine. It is further more preferable, and it is especially preferable that it is 120 degreeC or more. However, depending on the polymer precursors used in combination, for example, the unexposed part may be cured by heating at 60 ° C. or higher, so that the suitable heating temperature is not limited to the above. For example, in the case of an epoxy resin, a preferable heat treatment temperature range is appropriately selected depending on the type of the epoxy resin, but is usually about 100 ° C. to 150 ° C.
In addition, you may heat and perform only deprotection of a protecting group before exposure. The heating for deprotection of the protective group before irradiation with the active energy ray may be a coating film drying step or another heating step. In this case, as the heating temperature, a temperature capable of deprotection may be selected as appropriate, but it is preferably 50 to 180 ° C., and the time is preferably 10 seconds to 60 minutes.

  The coating film of the photosensitive resin composition of the present invention is a post-exposure bake (Post Exposure) between the exposure process and the development process in order to physically accelerate the crosslinking reaction or to perform a reaction to cure only the exposed area. Bake: PEB) is preferably performed. The PEB undergoes a curing reaction such as an imidization ratio between an exposed portion where the basic compound is present and an unexposed portion where the basic compound is not present due to the action of the basic compound generated by irradiation with active energy rays and heating. It is preferable to carry out the reaction at different temperatures. For example, in the case of imidization, the preferable heat treatment temperature range is usually about 60 to 200 ° C., more preferably 120 to 200 ° C. When the heat treatment temperature is lower than 60 ° C., the imidization efficiency is poor, and it becomes difficult to cause a difference in the imidization ratio between the exposed portion and the unexposed portion under realistic process conditions. On the other hand, when the heat treatment temperature exceeds 200 ° C., imidization may proceed even in an unexposed portion where no amine is present, and a difference in solubility between the exposed portion and the unexposed portion hardly occurs. This heat treatment may be performed by any known method, and examples thereof include, but are not limited to, a circulation oven in an air or nitrogen atmosphere, heating with a hot plate, and the like. From the photopolymerization initiator containing the compound represented by the formula (1) of the present invention, radicals and basic compounds are generated by irradiation with active energy rays and heating, and heat treatment for generating the basic compounds; The PEB treatment may be the same process or a separate process.

(Developer)
The developer used in the development process is not particularly limited as long as it is a solution or solvent that can selectively dissolve the unexposed area, and is adjusted to a polymer precursor used from a basic aqueous solution or an organic solvent. It is possible to select appropriately.

The basic aqueous solution as the developer is not particularly limited, but for example, other than tetramethylammonium hydroxide (TMAH) aqueous solution having a concentration of 0.01 to 10% by mass, preferably 0.05 to 5% by mass. , Diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl Examples include aqueous solutions containing methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, tetramethylammonium and the like as solutes.
These solutes may be used singly or in combination of two or more, and as long as the water content in the developer is 50% or more, preferably 70% or more, an organic solvent or the like. May be included.

Further, the organic solvent as the developer is not particularly limited, but polar such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolacron, dimethylacrylamide, etc. Solvents, alcohols such as methanol, ethanol and isopropanol, esters such as ethyl acetate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone, other tetrahydrofuran, chloroform, acetonitrile, etc. These may be used alone or in combination of two or more.
After development, washing is performed with water or a poor solvent. In this case, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water.
After washing, the pattern is stabilized by drying at 80 to 100 ° C. In order to make this relief pattern heat resistant, a patterned high heat resistant resin layer is formed by heating at a temperature of 180 to 500 ° C., preferably 200 to 350 ° C. for several tens of minutes to several hours. Ru

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, these Examples are only the illustrations for demonstrating this invention suitably, and do not limit this invention at all. In addition, the part in a synthesis example and an Example is a mass part.

Example 1 Synthesis of Compound Represented by Formula (1) of the Present Invention (Step 1) Synthesis of Intermediate Compound Represented by Formula (31) 2-Phenyl-1,3-indandione In 8.0 parts, 0.54 parts of potassium carbonate, 91.9 parts of water and 10.3 parts of ethanol were added and stirred, and 38% formaldehyde was added dropwise to this solution. After stirring at room temperature for 3 hours, the resulting solid was collected by suction filtration. The recovered crystals were washed with a large amount of water to obtain 7.6 parts of an intermediate compound represented by the following formula (31).

(Step 2) Synthesis of Compound of the Present Invention Represented by Formula (32) 5.0 parts of the intermediate compound represented by formula (31) obtained in Step 1, 30 parts of toluene and 0.08 tin octylate Part was placed in a flask and stirred at 60 ° C. until uniform. To this solution, 4.5 parts of phenyl isocyanate was added and stirred at 60 degrees for 3 hours. Water was added to the obtained reaction liquid and washed three times, and then the obtained solution was added dropwise to an excess amount of n-hexane to precipitate a solid. The obtained solid was collected by suction filtration to obtain 3.9 parts of the compound of the present invention (photopolymerization initiator (A-1)) represented by the following formula (32).

Example 2 Synthesis of Compound Represented by Formula (1) of the Present Invention (Step 3) Synthesis of Compound of Present Invention Represented by Formula (33) 8.2 parts of 1,1′-carbonyldiimidazole in a flask And 27 parts of toluene was added and stirred until uniform. Next, 7.1 parts of the intermediate compound represented by the formula (31) obtained in the step 1 was added, and stirring was continued for 3 hours at room temperature. 6.3 parts of the compound of the present invention represented by (33) (photopolymerization initiator (A-2)) was obtained.

Example 3 Synthesis of Compound Represented by Formula (1) of the Present Invention (Step 4) Synthesis of Compound of Present Invention Represented by Formula (34) Represented by Formula (33) obtained in Step 3 in a flask Then, 5.5 parts of the compound of the present invention and 30 parts of THF were added and stirred at 60 ° C. until uniform. To this solution, 2.2 parts of 1,1,3,3-tetramethylguanidine was added dropwise and stirred at 60 ° C. for 3 hours. After adding water to the obtained solution and washing it three times, the concentrated solution is purified by column chromatography to obtain the compound of the present invention represented by the following formula (34) (photopolymerization initiator (A-3)). Of 2.8 parts.

(Photodegradability evaluation of photobase generator (A-1))
The photobase generator 1 1.073 × 10 ⁻⁵ mol obtained in Example 1 was dispensed into a measuring flask and diluted to 10 ml with acetonitrile to prepare an evaluation solution. This solution was placed in a quartz cell, exposed to a predetermined amount of light from the side with a high-pressure mercury lamp, 0.5 ml was taken, and the photolysis behavior was followed by high performance liquid chromatography. The results are shown in FIG. Moreover, the photolysis rate was computed by plotting the peak area change of the photobase generator (A-1) with respect to the exposure amount. The results are shown in FIG.

Examples 4 to 6 Preparation of photosensitive resin composition Each component was mixed according to the blending amount (parts by mass) shown in Table 1 to obtain a photosensitive resin composition.

(Preparation of film made of photosensitive resin composition and heat treatment)
A film having a film thickness of about 5 μm was formed on a Si substrate by spin-coating the photosensitive resin compositions obtained in Examples 4 to 6, and then heat-treated at 100 ° C. for 1 minute using an oven. (Bake before exposure) was performed, and the solvent was distilled off.

(Exposure treatment and heat treatment)
The film on the Si substrate obtained above was subjected to 3 passes under the condition that the exposure amount of 1 pass was 100 mJ / cm ² (height from the belt conveyor to the high pressure mercury lamp) using a belt conveyor type high pressure mercury lamp exposure machine. Exposure was performed. Thereafter, heat treatment (baking after exposure) at 100 ° C. for 30 minutes was performed using an oven to obtain a cured product (cured film having a thickness of about 5 μm) of each photosensitive resin composition.

The following evaluation was performed about the hardened | cured material of each photosensitive resin composition obtained above, and the result was shown in Table 1.
(1) Pencil hardness:
It measured with the weight of 750g by the method according to JISK-5600.

The compound represented by the formula (1) of the present invention is an amine having a high base strength or an amine that functions as a base catalyst upon irradiation with active energy rays, and has a high quantum yield of cleavage. It can be used as a photopolymerization initiator having excellent sensitivity compared to a base generator. Furthermore, since the photosensitive resin composition of the present invention containing the compound does not generate an acid that corrodes a metal when irradiated with active energy rays, it can be suitably used for a material made of a metal.

Claims (9)

Following formula (1)

(In Formula (1), R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group or an organic group other than the above substituents. R _{2 to} R ₅ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, Mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, cyano group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group or the above-mentioned Represents an organic group other than a substituent, and two or more selected from R _{2 to} R ₅ may be bonded to each other to form a ring structure, and X represents the following formulas (1-1) to (1- 3)

(Formula (1-1), (in 1-2) or (1-3), each of _{R 7} and _{R 8} independently represent a hydrogen atom, or an alkyl group or a heterocyclic group, or _{R 7} and _{R 8} R ₉ and R ₁₁ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₁₀ represents an alkylene group or an arylene group, and A represents an oxygen atom or a sulfur atom. Or NR _12. R ₁₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₁₃ and R ₁₄ each independently represents an amino group or a substituted amino group. Represents a group. )
A compound represented by The compound according to claim 1, wherein R ₁ is a phenyl group. The compound according to claim 1 or 2, wherein R _{2 to} R ₅ are each independently a hydrogen atom, an alkylthioether group or an arylthioether group. The compound according to claim 3, wherein R _{2 to} R ₅ are hydrogen atoms. The photoinitiator containing the compound as described in any one of Claims 1 thru | or 4. A photosensitive resin composition comprising the photopolymerization initiator according to claim 5 and a polymer precursor that can be polymerized by light irradiation or by light irradiation and heating in the presence of the photopolymerization initiator. A compound in which the polymer precursor has a substituent selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group, an acryloyl group, a methacryloyl group, a maleimide group and a thiirane group; a polysiloxane precursor; a polyimide precursor and a polybenzoxazole The photosensitive resin composition of Claim 6 containing 1 or more types selected from the group which consists of a precursor. The photosensitive resin composition of Claim 7 in which a polymer precursor contains the compound which has an epoxy group. A cured product of the photosensitive resin composition according to any one of claims 6 to 9.

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