JP6605821B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition capable of pattern formation, and a cured product of the photosensitive resin composition.

  In general, a photosensitive resin composition is a photosensitive resin obtained by adding a photoinitiator, and can be polymerized, cured, or developed by energy ray (light) irradiation. It is used for various photoresists, photo-curing adhesives and the like.

Photoinitiators are classified into photoradical generators, photoacid generators, and photobase generators, depending on the active species generated by energy beam (light) irradiation. The photoradical generator has advantages such as a high curing rate and no active species remaining after curing. On the other hand, since the inhibition of curing by oxygen occurs, it is necessary to provide a layer that blocks oxygen in curing the thin film. There are disadvantages.
Photoacid generators have the advantage that they are not inhibited by oxygen, but have the disadvantages that the active species of acid remains to corrode the metal substrate and denature the cured resin.
Photobase generators are attracting attention because they are less likely to cause problems such as curing inhibition by oxygen and corrosion due to residual active species. For example, various photobase generators are disclosed in Patent Documents 1 to 3 and the like.

Special table 2001-513765 gazette International Publication WO 2010/064631 International Publication WO2010 / 064632

However, photobase generators generally have a problem of low sensitivity (low curability) compared to photoacid generators.
Accordingly, an object of the present invention is to provide a photosensitive resin composition that can be cured with high sensitivity (low exposure amount) and in which an unexposed portion can be alkali developed (pattern formation), and a cured product of the photosensitive resin composition. It is in.

  The present inventors have intensively studied to solve the above problems, and found that the above problems can be solved by using a photobase generator having a specific structure, and have completed the present invention.

（式中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、無置換若しくは置換基を有している炭素原子数１〜２０の脂肪族炭化水素基又は無置換若しくは置換基を有しているフェニル基又はナフチル基であるか、Ｒ^１及びＲ^２が、互いに連結して形成する窒素原子及び炭素原子からなる環であり、
Ｒ^１２は、無置換若しくは置換基を有している炭素原子数１〜２０の脂肪族炭化水素基又はＡｒ^２を表し、
Ａｒ^２は、無置換又は置換基を有している芳香環を表し、
ｎは、０又は１を表し、
Ｒ^３は、無置換若しくは置換基を有している炭素原子数１〜２０の脂肪族炭化水素基、
無置換若しくは置換基を有している炭素原子数６〜２０の芳香族炭化水素基又は無置換若しくは置換基を有している炭素原子数２〜２０の複素環基を表し、
Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立に、水素原子、シアノ基、ニトロ基、−ＯＲ^１１、−ＣＯＯＲ^１１、−ＣＯ−Ｒ^１１、−ＳＲ^１１、ハロゲン原子、無置換若しくは置換基を有している炭素原子数１〜２０の脂肪族炭化水素基、無置換若しくは置換基を有している炭素原子数６〜２０の芳香族炭化水素基又は無置換若しくは置換基を有している炭素原子数２〜２０の複素環基を表し、Ｒ^１１は、無置換若しくは置換基を有している炭素原子数１〜２０の脂肪族炭化水素基、無置換若しくは置換基を有している炭素原子数６〜２０の芳香族炭化水素基又は無置換若しくは置換基を有している炭素原子数２〜２０の複素環基を表す。） That is, the present invention relates to a photosensitive resin composition containing (A) a photobase generator represented by the following general formula (2), (B) a curable resin, and (C) an alkali developable resin.

(In the formula, each of R ¹ and R ² independently has a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted group. A phenyl group or a naphthyl group, or R ¹ and R ² are a ring composed of a nitrogen atom and a carbon atom formed by being linked to each other;
R ¹² represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or Ar ² ;
Ar ² represents an unsubstituted or substituted aromatic ring,
n represents 0 or 1,
R ³ is an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms,
An unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms or an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms,
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a cyano group, a nitro group, —OR ¹¹ , —COOR ¹¹ , —CO—R ¹¹ , — SR ¹¹ , halogen atom, unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms Represents a group or a heterocyclic group having 2 to 20 carbon atoms which is unsubstituted or substituted, and R ¹¹ is an aliphatic hydrocarbon having 1 to 20 carbon atoms which is unsubstituted or substituted. Represents a group, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms. )

  Moreover, this invention relates to the hardened | cured material formed by irradiating the said photosensitive resin composition with an energy ray.

  The photosensitive resin composition of the present invention can be cured with an energy beam having a lower exposure amount than that of a conventional anion curable photosensitive resin composition, and a non-irradiated portion of the energy beam can be developed with an alkaline aqueous solution.

Hereinafter, preferred embodiments of the present invention will be described in detail.
<(A) Photobase generator>
Examples of the unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ and R ² in the general formula (1) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s -Butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl , Cyclopentyl, cyclohexyl, cyclohexylmethyl and the like, and these aliphatic hydrocarbon groups include -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-,- SO ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—COO—, —OCO—NR— or It may be interrupted by -SiRR'-. However, these discontinuing divalent groups are not adjacent to each other.
R and R ′ are unsubstituted aliphatic hydrocarbon groups, and the unsubstituted aliphatic hydrocarbon group is an unsubstituted aliphatic hydrocarbon having 1 to 20 carbon atoms represented by R ¹ above. Examples thereof include the same groups as those exemplified as the group.
In addition, the ring formed by connecting R ¹ and R ² to form a nitrogen atom and a carbon atom includes a pyrrole group, a pyrrolidine group, an imidazole group, an imidazolidine group, a pyrazole as a group including a bonded nitrogen atom. Group, pyrazolidine group, piperidine group, piperazine group and the like. These rings may be condensed with a benzene ring or may have a substituent. Examples of the substituent include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group and t-butyl group, methylol group, ethylol group and propylol group. And a hydroxyalkyl group such as a butyrol group.

Examples of the substituent that the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ and R ² may have include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, and a thiol group. , —COOH or —SO ₂ H, and when the group to be substituted contains carbon atoms, the number including these carbon atoms is the predetermined number of carbon atoms.

As the substituent that the phenyl group or naphthyl group represented by R ¹ and R ² may have, in addition to those mentioned as the substituent for the aliphatic hydrocarbon group having 1 to 20 carbon atoms, There are 20 aliphatic hydrocarbon groups.

Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ¹² include the same groups as those described above for R ¹ .

The unsubstituted aromatic ring represented by Ar ¹ and Ar ² includes a benzene ring, naphthalene ring, fluorene ring, pyridine ring, furan ring, thiophene ring, oxazole ring, isoxazole ring, thiadiazole ring, carbazole ring, benzofuran ring, benzo An aromatic ring selected from the group consisting of a thiophene ring, a benzoxazole ring, a benzothiadiazole ring, a benzocarbazole ring, and a naphthofuran ring, and among these, at least one of Ar ¹ and Ar ² is a carbazole ring, a benzoxazole ring, or a benzothiadiazole It is preferably a ring or a benzocarbazole ring.

As the substituent that the aromatic ring represented by Ar ¹ and Ar ² may have, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, —COOH, SO ₂ H, a carbon atom Examples thereof include a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, and examples of the hydrocarbon group having 1 to 20 carbon atoms include the aliphatic hydrocarbon group used in the description of R ¹ or Phenyl, naphthyl or fluorenyl can be mentioned, and when it is phenyl, naphthyl or fluorenyl, it can be further substituted with the aliphatic hydrocarbon group used in the description of R ¹ . In the case of phenyl, naphthyl or fluorenyl, the linking moiety with the aromatic ring is —O—, —COO—, —OCO—, —CO—, —CS—, —S—, —SO—, —SO ₂ —. , —NR—, —NR—CO—, —CO—NR—, —NR—COO—, —OCO—NR— or —SiRR′— may be interrupted once.
R and R ′ are unsubstituted aliphatic hydrocarbon groups, and the unsubstituted aliphatic hydrocarbon group is an unsubstituted aliphatic hydrocarbon having 1 to 20 carbon atoms represented by R ¹ above. Examples thereof include the same groups as those exemplified as the group.

The photobase generator represented by the general formula (1) used in the present invention has geometric isomers due to oxime double bonds, but these are not distinguished.
That is, in the present specification, the compound represented by the above general formula (1), and the compounds and exemplary compounds which are preferred forms of the compound described below represent a mixture of both or one of them, It is not limited to the structure shown.

（式中、Ｒ¹、Ｒ²、Ｒ¹²、Ａｒ¹及びｎは、上記一般式（１）と同様の基を表し、
Ｒ³は、無置換若しくは置換基を有している炭素原子数１〜２０の脂肪族炭化水素基、無置換若しくは置換基を有している炭素原子数６〜２０の芳香族炭化水素基又は無置換若しくは置換基を有している炭素原子数２〜２０の複素環基を表し、
Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹及びＲ¹⁰は、それぞれ独立に、水素原子、シアノ基、ニトロ基、−ＯＲ¹¹、−ＣＯＯＲ¹¹、−ＣＯ−Ｒ¹¹、−ＳＲ¹¹、ハロゲン原子、無置換若しくは置換基を有している炭素原子数１〜２０の脂肪族炭化水素基、無置換若しくは置換基を有している炭素原子数６〜２０の芳香族炭化水素基又は無置換若しくは置換基を有している炭素原子数２〜２０の複素環基を表し、Ｒ¹¹は、無置換若しくは置換基を有している炭素原子数１〜２０の脂肪族炭化水素基、無置換若しくは置換基を有している炭素原子数６〜２０の芳香族炭化水素基又は無置換若しくは置換基を有している炭素原子数２〜２０の複素環基を表す。） Among the photobase generators represented by the general formula (1), those represented by the following general formula (2) can be preferably used.

(Wherein R ¹ , R ² , R ¹² , Ar ¹ and n represent the same groups as in the general formula (1),
R ³ represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or Represents an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms,
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a cyano group, a nitro group, —OR ¹¹ , —COOR ¹¹ , —CO—R ¹¹ , — SR ¹¹ , halogen atom, unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms Represents a group or an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms, and R ¹¹ is an unsubstituted or substituted aliphatic hydrocarbon having 1 to 20 carbon atoms Represents a group, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms. )

In the general formula (2), an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ³ is the same as that exemplified in the description of R ¹ above. (However, there is no group which interrupts the bond part with the nitrogen atom couple | bonded with R < ³ >), and an unsubstituted C6-C20 aromatic hydrocarbon group is phenyl, naphthyl, phenanthryl. , Pyrenyl and biphenyl, and phenyl, naphthyl, phenanthryl, pyrenyl and biphenyl substituted with an aliphatic hydrocarbon group (similar to those exemplified in the description of R ¹ above), and these aromatic hydrocarbons. The bond between the alkylene moiety and aromatic hydrocarbon group in the group and the aliphatic hydrocarbon group of this substituent is -O-, -COO-, -OCO-, -CO-, -CS-, -S- , -SO-, -S _{2 -, - NR -, -} NR-CO -, - CO-NR -, - NR-COO -, - OCO-NR- or may be interrupted by -SiRR'- (although these interrupts divalent Group shall not be next to each other.)
Examples of the unsubstituted heterocyclic group having 2 to 20 carbon atoms represented by R ³ include tetrahydrofuran, dioxolanyl, tetrahydropyranyl, morpholylfuran, thiophene, methylthiophene, hexylthiophene, benzo A thiophene group, a pyrrole group, a pyrrolidine group, an imidazole group, an imidazolidine group, a pyrazole group, a pyrazolidine group, a piperidine group and a piperazine group, and an aliphatic hydrocarbon group (the same groups as those exemplified in the description of R ¹ above) Substituted tetrahydrofuran group, dioxolanyl group, tetrahydropyranyl group, morpholylfuran group, thiophene group, methylthiophene group, hexylthiophene group, benzothiophene group, pyrrole group, pyrrolidine group, imidazole group, imidazolidine group, pyrazole group, Pyrazolidine group, Examples include a peridine group and a piperazine group, and an alkylene part in these heterocyclic groups and a bond part between the heterocyclic ring and an aliphatic hydrocarbon group replacing it are -O-, -COO-, -OCO-, -CO -, - CS -, - S -, - SO -, - SO 2 -, - NR -, - NR-CO -, - CO-NR -, - NR-COO -, - OCO-NR- or - It may be interrupted by SiRR'- (provided that these interrupted divalent groups are not adjacent to each other).
R and R ′ are unsubstituted aliphatic hydrocarbon groups, and the unsubstituted aliphatic hydrocarbon group is an unsubstituted aliphatic hydrocarbon having 1 to 20 carbon atoms represented by R ¹ above. Examples thereof include the same groups as those exemplified as the group.

As the group that substitutes for the aliphatic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group represented by R ³ , a hydrogen atom is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, Examples thereof include those substituted with a hydroxyl group, a thiol group, —COOH, or —SO ₂ H. In addition, when the group to be interrupted contains a carbon atom, and when it has a substituent containing a carbon atom, the number including the number of carbon atoms becomes the predetermined number of carbon atoms.

Examples of the aliphatic hydrocarbon group, aromatic hydrocarbon group, and heterocyclic group represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ^10, and R ¹¹ are exemplified in the above R ³ . The same groups as those described above can be used, but the bonding portion between these groups and the carbazole ring is also represented by —O—, —COO—, —OCO—, —CO—, —CS—, —S—, — _{SO -, - SO 2 -,} - NR -, - NR-CO -, - CO-NR -, - NR-COO -, - can be interrupted once OCO-NR- or -SiRR'-. R and R ′ are unsubstituted aliphatic hydrocarbon groups, and the unsubstituted aliphatic hydrocarbon group is an unsubstituted aliphatic hydrocarbon having 1 to 20 carbon atoms represented by R ¹ above. Examples thereof include the same groups as those exemplified as the group.
Further, as the substituent that these groups may have, the same substituents used in the description of R ³ can be used.
In addition, the group represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ in the general formula (2) is interrupted or substituted by a group containing a carbon atom. The number including those carbon atoms is the predetermined number of carbon atoms.

As the photobase generator represented by the general formula (1), a compound in which R ¹ or R ² is a phenyl group from the viewpoint of excellent UV sensitivity and curability when used in a curable composition; R ¹ And a compound in which neither of R ² is a hydrogen atom; a compound in which R ¹ and R ² are linked to each other to form a ring; a compound in which n is 0 is preferred, and R ¹ and R ² are linked to each other to form an imidazole A compound in which a ring is formed; a compound in which R ¹ and R ² are connected to each other to form a piperidine ring is more preferable.

As the photobase generator represented by the general formula (1), Ar ² is a phenyl group, a naphthyl group, or a nitro group because it has excellent UV sensitivity, has a long absorption wavelength, and is excellent in solubility in a resin. , A phenyl group or a naphthyl group substituted with —COOH or an aliphatic hydrocarbon group having 1 to 20 carbon atoms (including those interrupted by —O—, —COO—, —OCO—, —CO—) More preferred is a compound that is
Moreover, as a photobase generator represented by the general formula (2), in addition to the configuration preferred in the general formula (1), R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ And a compound in which at least one of R ¹⁰ is a cyano group, a hydroxyl group, a carboxyl group or a thiol group; R ³ is an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms (—O— , -COO-, -OCO-, and -CO-), a phenyl group or a naphthyl group is more preferred, and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^A compound in which at least one of ⁹ and R ¹⁰ is a nitro group, particularly a compound in which R ⁹ is a nitro group; a compound in which R ³ is an unsubstituted aliphatic hydrocarbon group having 1 to 10 carbon atoms is particularly preferred.

  Specific examples of the novel compound represented by the general formula (1) include the following compound Nos. 1-No. 43. However, the present invention is not limited by the following compounds.

  The photobase generator represented by the general formula (1) is not particularly limited and can be produced by a known method.

  In the photosensitive resin composition of the present invention, the content of the (A) photobase generator is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the (B) curable resin. Part. (A) If the content of the photobase generator is less than 1 part by mass, poor curing due to insufficient sensitivity may occur, and if it exceeds 20 parts by mass, there are many volatile substances during light irradiation or heating. There is a possibility.

<(B) curable resin>
The (B) curable resin used in the present invention indicates a resin having an anion-polymerizable functional group or a resin whose curing temperature is lowered using a base as a catalyst, and is polymerized by irradiation with energy rays such as ultraviolet rays. It is a photosensitive resin to be cured or a cured resin having a lower curing temperature. The anionic polymerizable functional group means a functional group that can be polymerized by a base generated from a photobase generator by an active energy ray such as ultraviolet rays, for example, an epoxy group, an episulfide group, a cyclic monomer (σ-valerolactone, ε-caprolactam), and the like, and resins having a base as a catalyst and a low curing temperature include urethane bond formation reaction between isocyanate and alcohol, addition reaction between epoxy and hydroxyl group, addition reaction between epoxy and carboxylic acid group, epoxy And an acid anhydride copolycondensation reaction, epoxy and thiolic acid group addition reaction, (meth) acrylic group Michael addition reaction, polyamic acid dehydration condensation reaction, and the like. Examples of (B) curable resins include epoxy resins, oxetane resins, polyamide resins, polyurethane resins, nylon resins, and polyester resins. These resins may be used alone or in combination of two or more. Among these, an epoxy resin is preferable because the reaction proceeds quickly and the adhesiveness is good.

Examples of the epoxy resin include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol) , Ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), 4,4′-dihydroxybenzophenone, isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4 -Bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobi Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as sphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol; ethylene glycol, propylene glycol, Polyglycidyl ethers of polyhydric alcohols such as butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, Succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebashi Acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, aliphatic such as endomethylenetetrahydrophthalic acid, aromatic or Glycidyl esters of alicyclic polybasic acids and homopolymers or copolymers of glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, di Epoxy compounds having a glycidylamino group such as glycidyl orthotoluidine; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6 Methylcyclo Epoxidized products of cyclic olefin compounds such as xylmethyl-6-methylcyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene, epoxidized acrylonitrile-butadiene copolymer, epoxidized styrene- Examples include epoxidized conjugated diene polymers such as butadiene copolymer and heterocyclic compounds such as triglycidyl isocyanurate. In addition, these epoxy resins may be those internally crosslinked by a prepolymer of a terminal isocyanate or those having a high molecular weight with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.). .
Among the epoxy resins, those having a glycidyl group are preferable from the viewpoint of excellent curability, and those having a bi- or higher functional glycidyl group are more preferable.

  The oxetane resin is a compound having a 4-membered ring ether (oxetanyl group) in the molecule. Specific examples include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (cyclohexyloxymethyl) oxetane, phenol novolak oxetane, 1,3- Bis [(3-ethyloxetane-3-yl) methoxy] benzene, oxetanylsilsesquioxane, oxetanyl silicate, and the like.

  As the polyamide resin, the acid dianhydride is ethylenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride. 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,2,3,3-biphenyltetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride Diamines include (o-, m- or p-) phenylenediamine, (3,3'- or 4,4 '-) diaminodiphenyl ether, diaminobenzophenone, (3,3'- or 4,4'- ) Resins made from diaminodiphenylmethane or the like.

As the polyurethane resin, as diisocyanates, polyfunctional isocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and polyols (polyfunctional alcohols) such as polyether polyol, polyester polyol, and polycarbonate polyol are used as raw materials. Resin to be used.
Examples of the nylon resin include resins made from cyclic monomers such as ε-caprolactam and lauryl lactam.
Examples of the polyester resin include resins made from cyclic monomers such as δ-valerolactone and β-propiolactone.

<(C) Alkali developable resin>
The alkali-developable resin is a resin that contains one or more functional groups among phenolic hydroxyl groups, thiol groups, and carboxyl groups and that can be developed with an alkaline solution, preferably a compound having two or more phenolic hydroxyl groups, carboxyl Examples thereof include a group-containing resin, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more thiol groups.

Examples of the compound having two or more phenolic hydroxyl groups include phenol novolac resin, alkylphenol volac resin, bisphenol A type novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, polyvinylphenols, bisphenol F Bisphenol S type phenolic resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, and condensate of dihydroxynaphthalene and aldehydes.
In addition, as a phenol resin, a compound having a biphenyl skeleton or a phenylene skeleton, or both, and as a phenolic hydroxyl group-containing compound, phenol, orthocresol, paracresol, metacresol, 2,3-xylenol, 2,4- Xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol You may use the phenol resin which synthesize | combined using these and which have various frame | skeletons. These may be used alone or in combination of two or more.

  As the carboxyl group-containing resin, a known resin containing a carboxyl group can be used. Due to the presence of the carboxyl group, the resin composition can be made alkali developable. In addition to the carboxyl group, a compound having an ethylenically unsaturated bond in the molecule may be used. In the present invention, as the carboxyl group-containing resin, for example, an ethylenically unsaturated group such as the following (I) It is preferable to use only a carboxyl group-containing resin having no double bond.

  Specific examples of the carboxyl group-containing resin that can be used in the present invention include the compounds listed below (any of oligomers and polymers).

  (I) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene. The lower alkyl refers to an alkyl group having 1 to 5 carbon atoms.

  (II) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (III) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (IV) Bifunctional epoxy resin such as diisocyanate and bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its partial acid anhydride modified product, carboxyl group-containing dialcohol compound and diol compound.

  (V) During the synthesis of the above resin (II) or (IV), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing urethane resin.

  (VI) During the synthesis of the resin of (II) or (IV), one isocyanate group and one or more (meth) acryloyl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. The carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.

  (VII) (B) A polyfunctional epoxy resin exemplified as a curable resin is reacted with an unsaturated monocarboxylic acid such as (meth) acrylic acid, and phthalic anhydride, tetrahydrophthalic anhydride, hexahydro are added to the hydroxyl group present in the side chain. A carboxyl group-containing resin to which a dibasic acid anhydride such as phthalic anhydride is added.

  (VIII) (B) a difunctional acid such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc., on the hydroxyl group present in the side chain by reacting the polyfunctional epoxy resin exemplified as the curable resin with a saturated monocarboxylic acid A carboxyl group-containing resin to which an anhydride is added.

  (IX) A carboxyl obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the resulting hydroxyl group Group-containing resin.

  (X) (B) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin exemplified as the curable resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.

  (XI) A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide. .

  (XII) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide is allowed to react with a saturated monocarboxylic acid. A carboxyl group-containing resin obtained by reacting a basic acid anhydride.

  (XIII) A reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride with a product.

  (XIV) A reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, with a saturated monocarboxylic acid. A carboxyl group-containing resin obtained by reacting with a polybasic acid anhydride.

  (XV) A carboxyl group obtained by reacting a polybasic acid anhydride with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. Containing resin.

  (XVI) Obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, and a unsaturated carboxylic acid containing monocarboxylic acid. A carboxyl group-containing resin obtained by reacting a reaction product with a polybasic acid anhydride.

  (XVII) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and a saturated monocarboxylic acid React with acid and react with polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid etc. to the alcoholic hydroxyl group of the resulting reaction product Carboxyl group-containing resin obtained by allowing

  (XVIII) reacting an epoxy compound having a plurality of epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol; Carboxyl groups obtained by reacting polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid with the alcoholic hydroxyl group of the obtained reaction product Containing resin.

  (XIX) an epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth) Reaction with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and the resulting alcoholic hydroxyl group of the reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as an acid.

  (XX) One epoxy group and one or more (meth) acryloyl groups in a molecule such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, etc. in any one of the resins (I) to (XIX) above A carboxyl group-containing resin formed by adding a group-containing compound.

  Examples of the compound having a thiol group include trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, ethylene glycol bisthioglycolate, 1,4-butanediol bisthioglycolate, trimethylolpropane tris. Thioglycolate, pentaerythritol tetrakisthioglycolate, di (2-mercaptoethyl) ether, 1,4-butanedithiol, 1,3,5-trimercaptomethylbenzene, 1,3,5-trimercaptomethyl-2 , 4,6-trimethylbenzene, terminal thiol group-containing polyether, terminal thiol group-containing polythioether, thiol compound obtained by reaction of epoxy compound and hydrogen sulfide, reaction of polythiol compound and epoxy compound Thiol compounds, and the like with terminal thiol groups to be.

  In the photosensitive resin composition of the present invention, the blending amount of the (C) alkali-developable resin is preferably 50 to 1000 parts by mass and less than 50 parts by mass with respect to 100 parts by mass of the (B) curable resin. In some cases, it may become insoluble in an alkaline solution, and when it is more than 1000 parts by mass, curing failure may occur during irradiation with energy rays.

<(D) Additive>
In the photosensitive resin composition of the present invention, additives such as an inorganic compound, a coloring material, a latent epoxy curing agent, a chain transfer agent, a sensitizer, and a solvent can be used as optional components.

  Examples of the inorganic compound include nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, alumina, and other metal oxides; layered clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, Gold, silver, copper, etc. are mentioned. These inorganic compounds are used as, for example, a filler, an antireflection agent, a conductive material, a stabilizer, a flame retardant, a mechanical strength improver, a special wavelength absorber, and an ink generating agent.

  Examples of the color material include pigments, dyes, and natural pigments. These color materials can be used alone or in admixture of two or more.

Examples of the pigment include a nitroso compound; a nitro compound; an azo compound; a diazo compound; a xanthene compound; a quinoline compound; an anthraquinone compound; a coumarin compound; a phthalocyanine compound; an isoindolinone compound; an isoindolinone compound; Compound; perylene compound; diketopyrrolopyrrole compound; thioindigo compound; dioxazine compound; triphenylmethane compound; quinophthalone compound; naphthalenetetracarboxylic acid; azo dye, metal complex compound of cyanine dye; lake pigment; furnace method, channel method or thermal Carbon black obtained by the method, or carbon black such as acetylene black, ketjen black or lamp black; Prepared by coating or coating with epoxy resin, carbon black previously dispersed with resin in a solvent and adsorbed 20 to 200 mg / g of resin, carbon black treated with acidic or alkaline surface, average Carbon black having a particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, a carbon black having a total oxygen amount calculated from CO and CO ₂ in a volatile content at 950 ° C. of 9 mg or more per 100 m ^{2 of} surface area; Graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese series, Ferrus Organics such as fluoride, phosphate blue, bitumen, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, synthetic iron black, amber, etc. Alternatively, an inorganic pigment can be used. These pigments can be used alone or in combination.

  Commercially available pigments can also be used as the pigment, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

  As the above dyes, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes And dyes such as cyanine dyes, and a plurality of these may be used in combination.

  Examples of the latent epoxy curing agent include dicyandiamide, modified polyamine, hydrazides, 4,4′-diaminodiphenylsulfone, boron trifluoride amine complex, imidazoles, guanamines, imidazoles, ureas, and melamine. Can be mentioned.

  As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-Mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercapto Phenol, 2- Lucaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3 -Mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Iodinated alkyl compound, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4 Dimethyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, the following compound No. C1, aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, Showen Denko Karenz MT BD1, PE1, NR1, and the like.

As the solvent, usually, the above-mentioned components ((A) photobase generator, (B) curable resin, (C) alkali developable resin, etc.) can be dissolved or dispersed, such as methyl ethyl ketone, methyl amyl. Ketones such as ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol Ether solvents such as dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol; ethylene glycol monomethyl ether, ethylene Cellosolve solvents such as recall monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol Ether ester solvents such as 1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate; BTX solvents such as benzene, toluene, xylene; hexane, heptane, octane , Aliphatic hydrocarbon solvents such as cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits, swazol # 310 (Cosmo Paraffin solvents such as Yamaseki Oil Co., Ltd., Solvesso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; Dimethyl sulfoxide; water or the like can be used, and these solvents can be used alone or as a mixed solvent of two or more.
Among these, ketones or ether ester solvents, in particular, propylene glycol-1-monomethyl ether-2-acetate or cyclohexanone are preferably used from the viewpoint of alkali developability, patternability, film-forming property, and solubility.
In the photosensitive resin composition of the present invention, the content of the solvent is not particularly limited, each component is uniformly dispersed or dissolved, and the photosensitive resin composition of the present invention is in a liquid or pasty form suitable for each application. In general, it is preferable that the solvent is contained in a range in which the solid content (all components other than the solvent) in the photosensitive resin composition of the present invention is 10 to 90% by mass.

  In the photosensitive resin composition of the present invention, a surfactant, a silane coupling agent, a melamine compound and the like can be further used in combination.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates; higher amines Cationic surfactants such as halogenates and quaternary ammonium salts; Nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides; amphoteric surfactants; silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

  As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. A silane coupling agent is preferably used.

Examples of the melamine compound include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Examples include compounds in which (at least two) are alkyl etherified.
Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed.
Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used.
Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable from the viewpoints of solubility in a solvent and difficulty in crystal precipitation from the photosensitive resin composition.

  In the photosensitive resin composition of the present invention, (A) a photobase generator, (B) a curable resin, and (C) an optional component other than an alkali-developable resin (excluding inorganic compounds, color materials, and solvents) The amount used is appropriately selected according to the purpose of use and is not particularly limited, but is preferably 50 parts by weight or less in total with respect to 100 parts by weight of (B) curable resin.

  The method of using the photosensitive resin composition of the present invention includes (1) a step of forming a coating film of the photosensitive resin composition of the present invention on a substrate, and (2) a mask having a predetermined pattern shape on the coating film. Pattern formation by: irradiating energy rays (light) through (3) baking process after exposure; (4) developing film after exposure; and (5) heating the film after development. Cured product can be obtained.

(1) As a step of forming a coating film of the photosensitive resin composition of the present invention on a substrate, a known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing, dipping, etc. It can be applied on a supporting substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.
Moreover, when the photosensitive resin composition contains a solvent, it is preferable to remove a solvent using a hotplate, oven, etc. after coating.

  In the step (2) of irradiating the coating film with energy rays (light) through a mask having a predetermined pattern shape, the light source of the energy rays used is an ultrahigh pressure mercury lamp, a high pressure mercury lamp, medium pressure mercury. Wavelength of 2000 angstrom to 7000 angstrom obtained from lamp, low pressure mercury lamp, mercury vapor arc lamp, xenon arc lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, excimer lamp, germicidal lamp, light emitting diode, CRT light source, etc. High energy rays such as electromagnetic energy, electron beam, X-ray, radiation, etc. can be used, but preferably an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp that emits light having a wavelength of 300 to 450 nm A xenon arc lamp or the like is used.

  Further, by using laser light as an exposure light source, a laser direct drawing method for directly forming an image from digital information such as a computer can be used without using a mask. The laser direct writing method is useful because it can improve not only productivity but also resolution and positional accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used. A laser, a nitrogen laser, an argon ion laser, a helium cadmium laser, a helium neon laser, a krypton ion laser, various semiconductor lasers, a YAG laser, or the like that emits light in the visible to infrared region can also be used. When these laser beams are used, a sensitizing dye that absorbs the visible to infrared region is preferably added.

  In the baking step after (3) exposure, heating at about 40 to 150 ° C. is preferable from the viewpoint of the curing rate after irradiation with the energy beam.

In the step (4) of developing the film after exposure, the alkaline developer is a mixture of an aqueous solution of an alkaline compound and, if necessary, a water-soluble organic solvent, a surfactant or the like. Examples of the alkaline compound in the alkaline developer include inorganic alkali compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine, and triethanolamine. , Pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, etc. Examples include cyclic tertiary amines, amines such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and ammonium compounds.
In the patterning of the photosensitive resin composition of the present invention, not only an alkali developer but also an organic solvent can be used, and examples of the organic solvent used include cyclopentanone.

  The step (5) of heating the coating after development is not an essential step, but is preferable because the hardness of the cured film is further improved. Post bake is preferably performed at 160 ° C. to 250 ° C. for 5 minutes to 3 hours using a heating device such as a hot plate or oven.

  The photosensitive resin composition of the present invention comprises: a photoresist for electronics; an electroplating resist; an etching resist; a dry film; a solder resist; a color filter for various display applications; a plasma display panel; Resist for forming such structures in the manufacturing process of display devices and LCDs; Composition for encapsulating electrical and electronic components; Solder resist; Magnetic recording material; Micro mechanical parts; Waveguide; Optical switch; Mask; Etching mask; Color test system; Glass fiber cable coating; Stencil for screen printing; Material for producing three-dimensional objects by stereolithography; Microelectronic circuit; Photoresist material for printed wiring board; UV and visible laser direct Photoresist materials for image systems; Pudding Can be used in various applications of the photoresist material or the protective film or the like used for the dielectric layer formed sequentially in the laminated circuit board, there is no particular limitation on the application.

  The photosensitive resin composition of the present invention to which a color material is added is suitably used as a resist constituting each pixel such as RGB in a color filter and a black matrix resist forming a partition of each pixel. Furthermore, in the case of a black matrix resist to which an ink repellent agent is added, it is preferably used for a partition for an ink jet color filter having a profile angle of 50 ° or more. As the ink repellent agent, a fluorosurfactant and a composition containing a fluorosurfactant are preferably used.

  When the photosensitive resin composition of the present invention is used for the above-mentioned partition for an ink jet type color filter, the partition formed from the photosensitive resin composition of the present invention partitions the transferred body, on the partitioned transferred body An optical element is manufactured by a method of forming an image region by applying droplets to the recesses by an ink jet method. At this time, it is preferable that the droplets contain a colorant and the image area is colored. In this case, the optical element produced by the manufacturing method described above is formed from a plurality of colored areas on the substrate. And at least a partition that separates each colored region of the pixel group.

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

  The insulating film is used for the insulating resin layer in a laminate in which an insulating resin layer is provided on a peelable support substrate, and the laminate can be developed with an alkaline aqueous solution. The film thickness is preferably 10 to 100 μm.

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

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

[Examples 1 to 7, 10] Preparation of photosensitive resin composition After blending at the composition ratio shown in Table 1 below, the mixture was kneaded in a three-roll mill to prepare the photosensitive resin composition of the present invention. The obtained photosensitive resin composition was apply | coated to the glass substrate (it adjusted so that the film thickness after a prebaking might be 6 micrometers), and was dried for 2 minutes with a 90 degreeC hotplate. After irradiation with 50 mJ / cm ^{2 with a} high-pressure mercury lamp (manufactured by HOYA CANDEO OPTRONICS CORPORATION, irradiation illuminance 20 mW / cm ² ), the mixture was heated at 100 ° C. for 50 minutes. It developed using the developing solution of the following Table 1.
From the film thickness change before and after the development in the irradiated part, the curability of the photosensitive resin composition was evaluated, and the developability of the non-irradiated part was evaluated. The results are shown in Table 1 below.

<Curing property>
This represents the film thickness after development when the film thickness before development is 100. The closer to 100, the higher the curability and the better the development resistance. As the developer used for the evaluation, an alkaline aqueous solution (hereinafter referred to as TMAH developer) prepared so that TMAH containing 5% by mass of ethanolamine was 3% by mass was used.
<Developability>
In the case where development was possible with cyclopentanone (organic solvent), ○, in the case where development was possible with a TMAH developer, ◎, and in case where development was not possible even with cyclopentanone, ×.

＜（Ａ）光塩基発生剤＞
Ｎｏ．３６：上記化合物Ｎｏ．３６
Ｎｏ．４１：上記化合物Ｎｏ．４１
Ｎｏ．４２：上記化合物Ｎｏ．４２
＜（Ｂ）硬化性樹脂＞
ＥＰＰＮ−２０１：フェノールノボラック型エポキシ樹脂、エポキシ当量１９３ｇ／ｅｑ．、日本化薬社製
Ｇ−０１１００：エポキシ基含有アクリル系ポリマー、エポキシ当量１７０ｇ／ｅｑ．、Ｍｗ＝１２，０００、日油社製
＜（Ｃ）アルカリ現像性樹脂＞
ＴＲＲ−５０１０Ｇ：クレゾールノボラック型フェノール樹脂、水酸基当量１２０ｇ／ｅｑ．、Ｍｗ＝８，０００、旭有機材工業社製
ＭＥＨ−７５００：トリスフェノールメタンノボラック型フェノール樹脂、水酸基当量９５−９９ｇ／ｅｑ．、明和化成社製
ＧＤＰ−６０９５ＬＲ：ジシクロペンタジエン変性型フェノール樹脂、水酸基当量１６８−１７１ｇ／ｅｑ．、Ｍｗ＝４４３、群栄化学工業社製

<(A) Photobase generator>
No. 36: Compound No. 36
No. 41: Compound No. 41
No. 42: Compound No. 42
<(B) curable resin>
EPPN-201: phenol novolac type epoxy resin, epoxy equivalent 193 g / eq. Manufactured by Nippon Kayaku Co., Ltd. G-01100: Epoxy group-containing acrylic polymer, epoxy equivalent 170 g / eq. , Mw = 12,000, manufactured by NOF Corporation <(C) Alkali developable resin>
TRR-5010G: Cresol novolac type phenol resin, hydroxyl group equivalent of 120 g / eq. , Mw = 8,000, manufactured by Asahi Organic Materials Co., Ltd. MEH-7500: Trisphenol methane novolak type phenol resin, hydroxyl group equivalent 95-99 g / eq. Manufactured by Meiwa Kasei Co., Ltd. GDP-6095LR: dicyclopentadiene-modified phenol resin, hydroxyl equivalents 168-171 g / eq. , Mw = 443, manufactured by Gunei Chemical Industry Co., Ltd.

Claims (3)

(A) A photosensitive resin composition containing a photobase generator represented by the following general formula (2) , (B) a curable resin, and (C) an alkali developable resin.

(In the formula, each of R ¹ and R ² independently has a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted group. A phenyl group or a naphthyl group, or R ¹ and R ² are a ring composed of a nitrogen atom and a carbon atom formed by being linked to each other;
R ¹² represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or Ar ² ;
Ar ² represents an unsubstituted or substituted aromatic ring,
n is to table a 0 or 1,
R ³ is an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms,
An unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms or an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms,
R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a cyano group, a nitro group, —OR ¹¹ , —COOR ¹¹ , —CO—R ¹¹ , — SR ¹¹ , halogen atom, unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms Represents a group or a heterocyclic group having 2 to 20 carbon atoms which is unsubstituted or substituted, and R ¹¹ is an aliphatic hydrocarbon having 1 to 20 carbon atoms which is unsubstituted or substituted. Represents a group, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms. ) The aromatic ring represented by Ar ² in the general formula (2) is a benzene ring, naphthalene ring, fluorene ring, pyridine ring, furan ring, thiophene ring, oxazole ring, isoxazole ring, thiadiazole ring, carbazole ring, benzofuran ring, The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is an aromatic ring selected from a benzothiophene ring, a benzoxazole ring, a benzothiadiazole ring, a benzocarbazole ring, and a naphthofuran ring. Hardened | cured material formed by irradiating the photosensitive resin composition of Claim 1 or 2 with an energy ray.