JP6315204B2 - Negative photosensitive resin composition - Google Patents

Description

  The present invention relates to a negative photosensitive resin composition and a cured film obtained therefrom. More specifically, the present invention relates to a photosensitive resin composition suitable for use in display materials, a cured film thereof, and various materials using the cured film.

  The epoxy cation polymerization UV curable resin containing an epoxy compound and a photoacid generator has high transparency, and the photosensitive resin composition containing the resin can increase the sensitivity of exposure. It is known that thick film photolithography is possible, that is, the photosensitive resin composition layer obtained by applying the photosensitive resin composition can be thickened (for example, Patent Document 1). However, since the coating film is tacky after coating and before exposure, handling properties are poor. In addition, development with an organic solvent is essential because development with an aqueous alkali solution is not possible. Alkali development is considered possible by introducing a carboxyl group into the polymer. However, in the copolymerization of a monomer having an epoxy group and a monomer having a carboxyl group, the reaction between the epoxy group and the carboxyl group is likely to occur during the polymerization. It is difficult to control the synthesis of the polymer. Even if the reaction can be controlled to synthesize a polymer, the storage stability is low.

  As a material capable of alkali development, a radical polymerization negative material containing a polymer having an acryloyl group, a polyfunctional acrylic monomer, and a photo radical initiator is known (for example, Patent Document 2). In this type of invention, when the unreacted acryloyl group is reacted at the time of post-baking until sufficient reliability is obtained with the exposure amount at the time of pattern formation, a high temperature of 200 ° C. or higher is required, and the substrate can be used only in a limited amount was there.

  On the other hand, the positive type material has a high resolution, but usually, the coating film obtained from the positive type material is exposed and developed in many cases, so that the solvent resistance is insufficient, and it is difficult to increase the film thickness and transparency. Low (for example, Patent Document 3).

  From these points, transparency is high, alkali development is possible, and handling property is high even when the coating film is thickened, shrinkage at the time of post-baking is small, and the cured film can be thickened, and low-temperature post-baking can be performed. Materials that are possible are desired. In addition, when a thermal radical generator is added to the conventional system, it is expected that the storage stability is lowered or that development failure occurs during pattern formation.

International Publication WO2008 / 007764 Pamphlet JP 2004-302389 A JP-A-8-339082

  The present invention has been made in view of the above circumstances, and it is possible to increase the thickness of a coating film even with a low-viscosity solution. The resulting coating film has no tack before exposure and has high resolution by alkali development. Patterns can be formed, patterning sensitivity is excellent, transparency is high, shrinkage is small after post-baking, and the cured film can be thickened, and even after low-temperature post-baking, the cured film has high solvent resistance and is excellent. Another object of the present invention is to provide a negative photosensitive resin composition having high reliability, a cured film thereof, an interlayer insulating film for display comprising the cured film, and an optical filter.

As a result of intensive studies to solve the above problems, the present inventors have found the present invention.
That is, as a first aspect, a photosensitive resin composition containing the following component (A), component (B), component (C), component (D), and solvent (E).
(A) component: a copolymer obtained by copolymerizing at least (i) N-alkoxymethyl (meth) acrylamide and (ii) a monomer mixture containing a monomer having an alkali-soluble group,
(B) component: a compound having two or more polymerizable groups,
Component (C): photopolymerization initiator,
(D) component: a polymer containing a hydroxy group,
(E) solvent,
As a second aspect, as the component (F), a thermal acid generator is further contained in the photosensitive resin composition in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). Photosensitive resin composition of
As a third aspect, (ii) the photosensitive resin composition according to the first aspect, wherein the monomer having an alkali-soluble group (ii) is maleimide,
As a fourth aspect, the photosensitive resin composition according to the first aspect or the third aspect, wherein the component (A) is a copolymer of a monomer mixture containing a monomer further having a hydroxy group,
As 5th viewpoint, the photosensitive resin composition as described in the 1st viewpoint thru | or 4th viewpoint which further contains a crosslinking agent as (G) component,
As a sixth aspect, a cured film obtained using the photosensitive resin composition according to any one of the first aspect to the fifth aspect,
As a seventh aspect, an interlayer insulating film for a liquid crystal display comprising the cured film according to the sixth aspect,
As an eighth aspect, an optical filter comprising the cured film according to the sixth aspect,
It is about.

According to the present invention, by curing N-alkoxymethyl (meth) acrylamide in an alkali-soluble resin, there is no influence on pattern formation, and a cured film having sufficient solvent resistance and reliability even after low-temperature post-baking is obtained. can get. Therefore, the photosensitive resin composition of this invention can be used for formation of the cured film with respect to the material which cannot endure the high temperature of 200 degreeC or more. In addition, the photosensitive resin composition of the present invention has no tack before exposure, can be developed with an alkali, can form a coating film with high transparency, resolution and patterning sensitivity even with a thick film. Since the shrinkage after baking is small, a thick cured film can be formed, and is therefore optimal for forming a structure as an optical member.
Moreover, according to this invention, the interlayer insulation film for displays and optical filter which consist of the said cured film can be provided.

The photosensitive resin composition of the present invention is a photosensitive resin composition containing the following component (A), component (B), component (C), component (D) and solvent (E).
Component (A): a copolymer obtained by copolymerizing a plurality of monomers containing at least (i) N-alkoxymethyl (meth) acrylamide and (ii) a monomer having an alkali-soluble group,
(B) component: a compound having two or more polymerizable groups,
Component (C): photopolymerization initiator,
(D) component: a polymer having a hydroxy group,
(E) Solvent.

<(A) component>
The component (A) is a copolymer obtained by copolymerizing a plurality of monomers containing at least (i) N-alkoxymethyl (meth) acrylamide and (ii) a monomer having an alkali-soluble group.

In the present invention, the copolymer refers to a polymer obtained by copolymerization using a monomer having an unsaturated double bond, such as acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, and styrene.
The copolymer of component (A) may be any copolymer having such a structure, and is not particularly limited with respect to the main chain skeleton and side chain type of the polymer constituting the copolymer.

  However, if the number average molecular weight of the copolymer of component (A) is excessively greater than 100,000, the developability of the unexposed area is lowered, while the number average molecular weight is less than 2,000 and excessively low. If it is, the components may be eluted during development because the exposed area is not sufficiently cured. Accordingly, the copolymer of component (A) has a number average molecular weight in the range of 2,000 to 100,000.

（Ａ）成分に用いるＮ−アルコキシメチル（メタ）アクリルアミドは式（１）の構造で表される。式中Ｒ^１は水素原子、ハロゲン原子または炭素原子数１乃至６のアルキル基を表す。式中Ｒ^２は水素原子、または炭素原子数１乃至１０のアルキル基を表す。
これらのモノマーの具体例としては、Ｎ−（メトキシメチル）アクリルアミド、Ｎ−（メトキシメチル）メタクリルアミド、Ｎ−（ｎ−ブトキシメチル）アクリルアミド、Ｎ−（ｎ−ブトキシメチル）メタクリルアミド、Ｎ−（イソブトキシメチル）アクリルアミド、Ｎ−（イソブトキシメチル）メタクリルアミド等が挙げられる。(I) N-alkoxymethyl (meth) acrylamide:

N-alkoxymethyl (meth) acrylamide used for the component (A) is represented by the structure of the formula (1). In the formula, R ¹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms. In the formula, R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
Specific examples of these monomers include N- (methoxymethyl) acrylamide, N- (methoxymethyl) methacrylamide, N- (n-butoxymethyl) acrylamide, N- (n-butoxymethyl) methacrylamide, N- ( Isobutoxymethyl) acrylamide, N- (isobutoxymethyl) methacrylamide and the like.

(Ii) Monomers containing alkali-soluble groups:
Examples of the monomer having an alkali-soluble group include monomers having a carboxyl group, a phenolic hydroxy group, an acid anhydride group, and a maleimide group.
Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl). ) Maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, 4-vinylbenzoic acid and the like.
Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide and the like.
Examples of the monomer having an acid anhydride group include maleic anhydride and itaconic anhydride.
Examples of the monomer having a maleimide group include maleimide.

Moreover, in this invention, when obtaining the copolymer which has a specific functional group (N-alkoxymethyl group and alkali-soluble group), the monomer which can be copolymerized with the monomer which has a specific functional group can be used together. .
Specific examples of such monomers include acrylic ester compounds, methacrylic ester compounds, N-substituted maleimide compounds, acrylonitrile compounds, acrylamide compounds, methacrylamide compounds, styrene compounds and vinyl compounds.
Hereinafter, although the specific example of the said monomer is given, it is not limited to these.

  Examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert- Butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2 -Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, diethylene glycol monoacrylate, caprolactone 2- (acryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, 5 -Acryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone, acryloylethyl isocyanate, 8-ethyl-8-tricyclodecyl acrylate, glycidyl acrylate, and the like.

  Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert- Butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ -Butyrolactone methacrylate, 2-propyl-2 Adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2- (methacryloyloxy) ) Ethyl ester, poly (ethylene glycol) ethyl ether methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone, methacryloyl ethyl isocyanate, and 8-ethyl-8-tricyclodecyl methacrylate glycidyl methacrylate , Etc.

  Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

  Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.

  Examples of the N-substituted maleimide compound include N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

  Examples of the acrylonitrile compound include acrylonitrile.

  In addition, the copolymer which made the (A) component copolymerize the monomer which has a hydroxyl group among the said copolymerizable monomers is preferable at the point which thermosetting property improves and the reliability of a cured film improves. Examples of the monomer having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3 -Dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone and the like.

  The method for obtaining a copolymer having a specific functional group used in the present invention is not particularly limited. For example, a monomer having a specific functional group, another monomer having a non-reactive functional group capable of copolymerization, and initiation of polymerization if desired. It can be obtained by carrying out a polymerization reaction at a temperature of 50 to 110 ° C. in a solvent in which an agent or the like coexists. In that case, the solvent used will not be specifically limited if it dissolves the monomer which comprises the acrylic copolymer which has a specific functional group, and the acrylic copolymer which has a specific functional group. As a specific example, the solvent described in (E) solvent mentioned later is mentioned.

  The acrylic copolymer having a specific functional group thus obtained is usually in a solution state dissolved in a solvent.

  In addition, the copolymer solution obtained as described above is re-precipitated by stirring with stirring such as diethyl ether or water, and the produced precipitate is filtered and washed, and then under normal pressure or reduced pressure. The copolymer powder can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the copolymer can be removed, and as a result, a purified copolymer powder can be obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

  In the present invention, the polymerization solution of the acrylic copolymer may be used as it is, or the powder thereof may be used as a solution by re-dissolving in, for example, a solvent (E) described later.

  In the present invention, the copolymer of component (A) may be a mixture of a plurality of types of specific copolymers (copolymers having the specific functional group).

  The copolymerization ratio of the monomers is preferably N-alkoxymethyl (meth) acrylate / alkali-soluble monomer / others = 10 to 60/10 to 40/0 to 80 parts by mass. When there are too few alkali-soluble monomers, an unexposed part does not melt | dissolve in a developing solution, and tends to cause a residual film and a residue. If it is too much, the curability of the exposed area is insufficient and a pattern may not be formed. When there is too little N-alkoxymethyl (meth) acrylate, there exists a possibility that photocurability may be insufficient and an exposed part may melt | dissolve at the time of image development. If the amount is too large, the solubility of the unexposed area is insufficient, which may cause a residual film or residue.

<(B) component>
The component (B) is a compound having two or more polymerizable groups. As used herein, a compound having two or more polymerizable groups means a compound having two or more polymerizable groups in one molecule and having those polymerizable groups at the molecular ends. The polymerizable group means at least one polymerizable group selected from the group consisting of an acrylate group, a methacrylate group, a vinyl group, and an allyl group.
The compound having two or more polymerizable groups as the component (B) has good compatibility with each component in the solution of the negative photosensitive resin composition of the present invention and does not affect the developability. From the viewpoint, a compound having a molecular weight (when the compound is a polymer, a weight average molecular weight) of 1,000 or less is preferable.

Specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, penta Erythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylo Rupropane trimethacrylate, 1,3,5-triacryloyl hexahydro-S-triazine, 1,3,5-trimethacryloyl hexahydro-S-triazine, tris (hydroxyethylacryloyl) isocyanurate, tris (hydroxyethylmethacryloyl) Isocyanurate, triacryloyl formal, trimethacryloyl formal, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethanediol diacrylate, ethanediol dimethacrylate, 2 -Hydroxypropanediol diacrylate, 2-hydroxypropanediol dimethacrylate, diethylene glycol diacrylate , Diethylene glycol dimethacrylate, isopropylene glycol diacrylate, isopropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N, N′-bis (acryloyl) cysteine, N, N′-bis (methacryloyl) cysteine Thiodiglycol diacrylate, thiodiglycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate, bisphenol S dimethacrylate, bisphenoxyethanol full orange acrylate, bis Phenoxyethanol full orange methacrylate,
Examples include diallyl ether bisphenol A, o-diallyl bisphenol A, diallyl maleate, and triallyl trimellitate.

The above-mentioned polyfunctional acrylate compound can be easily obtained as a commercial product, and specific examples thereof include, for example, KYARAD T-1420, DPHA, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R-167, HX -220, HX620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040 (above, Nippon Kayaku Co., Ltd.), Aronix M-210, M-240, M-6200, M-309, Same M-400, Same M-402, Same M-405, Same M-450, Same M-7100, Same M-8030, Same M-8060, Same M-1310, Same M-1600, Same M-1960, M-8100, M-8530, M-8560, M-8560, M-9050 (Made by Toagosei Co., Ltd.), Biscote 295, 300, 360, GPT, 3PA, 400, 260 312 and 335HP (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), A-9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM -3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, TMPT, 9PG, 701, 1206PE, NPG, NOD-N, HD-N, DOD-N , DCP, BP -1300N, BPE-900, BPE-200, BPE-100, BPE-80N, 23G, 14G, 9G, 4G, 3G, 2G, 1G (above, manufactured by Shin-Nakamura Chemical Co., Ltd.) .
These compounds having two or more polymerizable groups can be used alone or in combination of two or more.

  The content of the component (B) in the negative photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass with respect to 100 parts by mass of the component (A). And particularly preferably 20 to 70 parts by mass. If this ratio is too small, the exposed area will be insufficiently cured, and pattern formation may not be possible, or even if possible, the film may be unreliable. Moreover, when this ratio is excessive, tack may generate | occur | produce in the coating film after a prebaking, or an unexposed part may become a melt | dissolution defect at the time of image development.

<(C) component>
(C) A component is a photoinitiator. The photopolymerization initiator is not particularly limited as long as it generates radicals upon exposure. Specific examples include aromatic ketones such as benzophenone, Michler ketone, 4,4′-bisdiethylaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrene, benzoin methyl ether, benzoin ethyl ether, Benzoin ethers such as benzoinphenyl ether, benzoin such as methylbenzoin and ethylbenzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di ( m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2, 4,5-triaryl Dazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methylphenyl) imidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- Halomethyloxadiazole compounds such as (p-methoxystyryl) -1,3,4-oxadiazole, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, 2,4- Bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -S-triazine, 2-trichloromethyl-4-amino-6-p -Methoxystyryl-S-triazine, 2- (naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis Halomethyl-S-triazine compounds such as trichloromethyl-S-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy- 1,2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4′- Methyl diphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethyl Thioxanthone, isopropylthioxanthone, 1- (4-phenylthiophenyl) -1,2-octanedione-2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] -1- (O-acetyloxime), 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl Phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-phenyl Acetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone and the like can be mentioned.
The above photopolymerization initiator can be easily obtained as a commercial product. Specific examples thereof include IRGACURE 173, IRGACURE 500, IRGACURE 2959, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 1300, IRGACURE U19, IRGACURE 819, 819DW, IRGACURE 1880, IRGACURE 1870, DAROCURE TPO, DAROCURE 4265, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE OXE02, IRGACURE 250 (above, manufactured by BASF Corp.), KAYACURE DEKT ,Japan (Manufactured by Yakuhin Co., Ltd.), TAZ-101, TAZ-102, TAZ-103, TAZ-104, TAZ-106, TAZ-107, TAZ-108, TAZ-110, TAZ-113, TAZ-114, TAZ-118 , TAZ-122, TAZ-123, TAZ-140, TAZ-204 (manufactured by Midori Chemical Co., Ltd.) and the like.
These photopolymerization initiators can be used alone or in combination of two or more.

  The content of the component (C) in the negative photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 100 parts by mass of the component (A). It is -20 mass parts, Most preferably, it is 1-15 mass parts. If this ratio is too small, the exposed portion may be insufficiently cured, and pattern formation may not be possible, or even if it is possible, a film with low reliability may be formed. Moreover, when this ratio is excessive, the transmittance | permeability of a coating film may fall or the development defect of an unexposed part may arise.

<(D) component>
The component (D) is a polymer having a hydroxy group. Examples of the polymer having a hydroxy group include a polymer obtained by polymerizing a monomer having a hydroxy group, cellulose, hydroxypropyl cellulose, a polymer obtained by copolymerizing a diepoxy compound and a dicarboxylic acid, and a copolymer obtained by copolymerizing a diepoxy compound and a diphenol. Examples thereof include polymers obtained, polyester polyols, polyether polyols, polycaprolactone polyols, and the like, preferably a polymer obtained by polymerizing a monomer having a hydroxy group, or hydroxypropyl cellulose.

As the polymer obtained by polymerizing the above-mentioned monomer having a hydroxy group, a polymer obtained by copolymerizing a monomer having a hydroxy group alone or a copolymerizable monomer among the copolymerizable monomers mentioned in the component (A) described above. Can be mentioned.
Among the copolymerizable monomers listed in the component (A), monomers having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl. Examples include acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, and 5-acryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone.

  As a monomer copolymerizable with the monomer which has a hydroxyl group, the monomer copolymerizable with the monomer which has a specific functional group which can be used together with the monomer of (A) component is mentioned, for example.

  These polymers having a hydroxy group can be used alone or in combination of two or more.

  Content of the polymer which polymerized the monomer which has the hydroxyl group of (D) component in the negative photosensitive resin composition of this invention is 5-100 mass parts based on 100 mass parts of copolymer of (A) component. It is preferably 10 to 80 parts by mass. If this ratio is too small, the curability may be insufficient and solvent resistance may not be obtained. If this ratio is excessive, the developability of the unexposed area may be reduced, resulting in a residual film or residue.

<(E) Solvent>
What dissolves (A) component, (B) component, (C) component, and (D) component used in the present invention and dissolves (F) component, (G) component, etc., which will be added as required, as desired As long as the solvent has such solubility, the type and structure thereof are not particularly limited.

  Examples of such a solvent (E) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol. Monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, 2-hydroxypropion Ethyl acetate, ethyl 2-hydroxy-2-methylpropionate, ethoxy vinegar Ethyl, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, pyruvate Examples include ethyl, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

  These solvents can be used singly or in combination of two or more.

  Among these (E) solvents, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate and the like are preferable from the viewpoint of good coating properties and high safety. These solvents are generally used as solvents for photoresist materials.

<(F) component>
Component (F) is a thermal acid generator. The film formed from the negative photosensitive resin composition of the present invention can be formed into a highly reliable film by thermosetting by post-baking after forming a pattern, but the acid generated by the thermal acid generator is It becomes a catalyst and can accelerate curing. That is, it is not particularly limited as long as it is a compound that does not thermally decompose at a pre-baking temperature of 80 ° C. to 120 ° C. and generates an acid at 120 ° C. or higher. As a specific example of such a thermal acid generator,
For example, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 1H, 2H, 2H-perfluorooctanesulfonic acid, Pyridine salts of sulfonic acids such as fluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, salts such as morpholine salt, triethylamine salt, trimethylamine salt, Sus (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylenetris (methylsulfonate), p-toluenesulfonic acid Ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2 , 2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl-p-toluenesulfonamide,

等が挙げられる。

Etc.

  The content of the component (F) in the cured film forming composition of the present embodiment is preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass with respect to 100 parts by mass of the component (A). Part to 10 parts by weight, more preferably 0.5 part to 8 parts by weight. By setting the content of the component (F) to 0.01 parts by mass or more, sufficient thermosetting and solvent resistance can be imparted. However, when it is more than 20 parts by mass, the unexposed part may be poorly developed or the storage stability of the composition may be lowered.

<(G) component>
The crosslinking agent that is the component (G) of the present invention may be any crosslinking agent that can react with the component (A) or the component (D) by the acid generated from the component (F). Examples of such a crosslinking agent include compounds such as an epoxy compound and a methylol compound, and a methylol compound is preferred.

  Specific examples of the methylol compound described above include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

  Specific examples of the alkoxymethylated glycoluril include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4 , 6-Tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. As commercially available products, compounds such as glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resins (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin (high condensation type, commercial product) manufactured by Dainippon Ink & Chemicals, Inc. Name: Becamine (registered trademark) J-300S, P-955, N) and the like.

  Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethyl benzoguanamine. As commercial products, Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade names: Nikarac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.

  Specific examples of alkoxymethylated melamine include, for example, hexamethoxymethylmelamine. As commercially available products, methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compounds (trade name: My Coat (registered trademark)) 506, 508), methoxymethyl type melamine compound manufactured by Sanwa Chemical Co., Ltd. (trade names: Nicalac (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compounds (trade names: Nicalac (registered trademark) MX-45, MX-410, MX-302) and the like.

  Moreover, the compound obtained by condensing the melamine compound by which the hydrogen atom of such an amino group was substituted by the methylol group or the alkoxymethyl group, the urea compound, the glycoluril compound, and the benzoguanamine compound may be sufficient. For example, the high molecular weight compound manufactured from the melamine compound and the benzoguanamine compound which are described in US Patent 6,323,310 is mentioned. Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.). Examples of commercially available products of the benzoguanamine compound include product name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.).

  These crosslinking agents can be used alone or in combination of two or more.

  The content of the crosslinking agent as the component (G) in the negative photosensitive resin composition of the present invention is preferably 100 parts by mass or less, more preferably based on 100 parts by mass of the copolymer as the component (A). 80 parts by mass or less. If this ratio is excessive, the developability of the unexposed area may be reduced, resulting in a residual film or residue.

<Other additives>
Furthermore, as long as the negative photosensitive resin composition of the present invention does not impair the effects of the present invention, the surfactant, rheology modifier, pigment, dye, storage stabilizer, antifoaming agent, or It can contain dissolution promoters such as polyphenols and polycarboxylic acids.

<Negative photosensitive resin composition>
The negative photosensitive resin composition of the present invention comprises (A) a polymer, (B) a compound having two or more polymerizable groups, (C) a photopolymerization initiator, and (D) a component. A polymer having a hydroxy group is dissolved in a solvent (E), and if desired, one or more of a thermal acid generator of component (F), a crosslinking agent of component (G), and other additives are further added. It is a composition that can be contained.

Especially, the preferable example of the negative photosensitive resin composition of this invention is as follows.
[1]: Based on 100 parts by mass of component (A), 5 to 100 parts by mass of component (B), 0.1 to 30 parts by mass of component (C), and 5 to 100 parts by mass of component (D). A negative photosensitive resin composition containing and dissolving these components in the solvent (E).
[2] A negative photosensitive resin composition further comprising 0.01 to 20 parts by mass of the component (F) based on 100 parts by mass of the component (A) in the composition of the above [1].
[3] A negative photosensitive resin composition further comprising 100 parts by mass or less of component (G) based on 100 parts by mass of component (A) in the composition of [1] or [2] above.

  The ratio of the solid content in the negative photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1 to 80% by mass, It is 5 to 60% by mass, or 10 to 50% by mass. Here, solid content means what remove | excluded the (E) solvent from all the components of the negative photosensitive resin composition.

  Although the preparation method of the negative photosensitive resin composition of this invention is not specifically limited, As the preparation method, for example, (A) component (copolymer) is melt | dissolved in (E) solvent, B) component (compound having two or more polymerizable groups), (C) component (photopolymerization initiator), and (D) component (hydroxyl group-containing polymer) are mixed at a predetermined ratio to obtain a uniform solution. Or (F) component (thermal acid generator), (G) component (crosslinking agent) and other additives are added and mixed as necessary at an appropriate stage of the preparation method. Can be mentioned.

  In the preparation of the negative photosensitive resin composition of the present invention, (E) a solution of a specific copolymer obtained by a polymerization reaction in a solvent can be used as it is. In this case, the solution of the component (A) In the same manner as described above, when the (B) component, (C) component, (D) component and the like are added to obtain a uniform solution, (E) a solvent may be further added for the purpose of adjusting the concentration. At this time, the (E) solvent used in the process of forming the specific copolymer and the (E) solvent used for adjusting the concentration when preparing the negative photosensitive resin composition may be the same, May be different.

  Thus, the prepared negative photosensitive resin composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

<Coating film and cured film>
The negative photosensitive resin composition of the present invention is applied to a semiconductor substrate (for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or an ITO substrate. Etc.) and film substrate (for example, triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, acrylic film, polyimide resin film, etc.), etc., spin coating, flow coating, roll coating, slit coating. A coating film can be formed by coating by spin coating or ink jet coating following the slit, followed by preliminary drying in a hot plate or oven. Then, a negative photosensitive resin film is formed by heat-treating this coating film.

  As conditions for this heat treatment, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C. to 150 ° C. and a time of 0.3 to 60 minutes are employed. The heating temperature and heating time are preferably 80 to 120 ° C. and 0.5 to 10 minutes.

  The film thickness of the negative photosensitive resin film formed from the negative photosensitive resin composition is, for example, 0.1 to 50 μm, is, for example, 0.5 to 30 μm, and is, for example, 1 to 25 μm.

When the negative photosensitive resin film formed from the negative photosensitive resin composition of the present invention is exposed to light such as ultraviolet rays, ArF, KrF, and F ₂ laser light using a mask having a predetermined pattern, Due to the action of radicals generated from the photopolymerization initiator (C) contained in the negative photosensitive resin film, the exposed portion of the film becomes insoluble in the alkaline developer.

  Thereafter, development is performed using an alkaline developer. Thereby, the part which is not exposed among negative photosensitive resin films is removed, and a pattern-like relief is formed.

  Examples of the alkaline developer that can be used include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline. Alkaline aqueous solutions such as amine aqueous solutions such as ethanolamine, propylamine, and ethylenediamine. Further, a surfactant or the like can be added to these developers.

  Among the above, a tetraethylammonium hydroxide 0.1 to 2.38 mass% aqueous solution is generally used as a photoresist developer, and the alkaline developer is also used in the photosensitive resin composition of the present invention. It can be developed satisfactorily without causing problems such as swelling.

  Further, as a developing method, any of a liquid piling method, a dipping method, a rocking dipping method, and the like can be used. The development time at that time is usually 15 to 180 seconds.

  After development, the negative photosensitive resin film is washed with running water, for example, for 20 to 90 seconds, and then air-dried with compressed air or compressed nitrogen or by spinning to remove moisture on the substrate, and A patterned film is obtained.

  Subsequently, the pattern forming film is subjected to post-baking for thermosetting, specifically by heating using a hot plate, an oven, etc., thereby providing heat resistance, transparency, and flatness. In addition, a film having a good relief pattern with excellent water absorption and chemical resistance can be obtained.

  The post-bake is generally processed at a heating temperature selected from the range of 120 ° C. to 250 ° C. for 1 to 30 minutes when on a hot plate and 1 to 90 minutes when in an oven. The method is taken.

  Thus, by such post-baking, a target cured film having a good pattern shape can be obtained.

  As described above, the negative photosensitive resin composition of the present invention can be made thicker (the coating film thickness becomes thicker when compared with the same solid content), has no tack before exposure, is alkaline Development is possible, and even a film thickness of about 10 μm has sufficiently high sensitivity, and the film thickness at the exposed portion is very small during development, and a coating film having a fine pattern can be formed. Furthermore, the cured film is excellent in transparency, reliability such as heat resistance and solvent resistance, and has a small shrinkage at the time of post-baking and can form a thick film. (In addition to the vertical and horizontal directions, it indicates the shrinkage of dimensions including the thickness direction). Therefore, it can be suitably used for various films in liquid crystal displays, organic EL displays, touch panel elements, etc., for example, interlayer insulating films, protective films, insulating films, optical films and the like.

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

[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
MAA: methacrylic acid MI: maleimide MMA: methyl methacrylate BMAA: N-butoxymethylacrylamide HEMA: 2-hydroxyethyl methacrylate ST: styrene AIBN: azobisisobutyronitrile PRG1: 1- (4-phenylthiophenyl) -1 , 2-Octanedione-2- (O-benzoyloxime)
PRG2: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide HPC: Hydroxypropyl cellulose DPHA: Dipentaerythritol penta / hexaacrylate PETA: Pentaerythritol triacrylate PTSM: Paratoluenesulfonic acid morpholine salt PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate CYM: Cymel 303 (manufactured by Mitsui Cytec Co., Ltd.)

[Measurement of number average molecular weight and weight average molecular weight]
The number average molecular weight and the weight average molecular weight of the specific copolymer and the specific cross-linked product obtained according to the following synthesis example were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation. Tetrahydrofuran was flowed through the column at a flow rate of 1 ml / min (column temperature: 40 ° C.) for elution. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

<Synthesis Example 1>
MI (20.0 g), BMAA (34.6 g), and ST (22.3 g) are used as monomer components constituting the copolymer, and AIBN (4 g) is used as a radical polymerization initiator. By carrying out a polymerization reaction in PGME (150 g), a copolymer solution (copolymer concentration: 35 mass%) having Mn 5,200 and Mw 12,000 was obtained (P1). The polymerization temperature was adjusted to a temperature of 60 ° C to 90 ° C.

<Synthesis Example 2>
MAA (6.5 g), BMAA (16.3 g), ST (9.8 g) were used as monomer components constituting the copolymer, and AIBN (1.8 g) was used as a radical polymerization initiator. Was subjected to a polymerization reaction in a solvent PGME (64 g) to obtain a copolymer solution (copolymer concentration: 30% by mass) of Mn 6,000 and Mw 12,000 (P2). The polymerization temperature was adjusted to a temperature of 60 ° C to 90 ° C.

<Comparative Synthesis Example 1>
MAA (20.0 g), HEMA (40.0 g), and MMA (40.0 g) are used as monomer components constituting the copolymer, and AIBN (5 g) is used as a radical polymerization initiator. By carrying out a polymerization reaction in PGME (247 g), a copolymer solution (copolymer concentration: 30% by mass) as Mn 4,900 and Mw 8,700 was obtained (P3). The polymerization temperature was adjusted to a temperature of 60 ° C to 90 ° C.

<Examples 1 to 4, 6, Reference Example 5, and Comparative Examples 1 to 2>
In accordance with the composition shown in the following Table 1, (B), (C), (D), and (E) solvent, and (F) and (G) components are added to the solution of component (A). By mixing at a ratio and stirring at room temperature for 5 hours to obtain a uniform solution, negative photosensitive resin compositions of Examples , Reference Examples and Comparative Examples were prepared.

Obtained in Examples 1 to 4, reference example 5 and the negative photosensitive resin composition of Comparative Example 1及beauty 2, respectively, were measured prebaked KomakuAtsu, presence or absence of tack, solvent resistance, patterning sensitivity, the .

[Evaluation of film thickness after pre-baking]
The negative photosensitive resin composition was applied onto a silicon wafer using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film. The film thickness of this coating film was measured using F20 manufactured by FILMETRICS. Furthermore, the presence or absence of tack was evaluated.

[Evaluation of solvent resistance (residual film rate)]
The negative photosensitive resin composition was applied onto a silicon wafer using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film. This coating film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5.5 mW / cm ² for 33 seconds using an Canon ultraviolet irradiation device PLA-600FA. Thereafter, development was performed by immersing in an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, followed by post-baking in an oven at a temperature of 140 ° C. for 5 minutes to form a cured film. Formed. The film remaining rate was measured for the cured film immersed in N-methylpyrrolidone (hereinafter referred to as NMP) for 3 minutes.

[Evaluation of patterning sensitivity]
The negative photosensitive resin composition was applied onto alkali-free glass using a spin coater, and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film. This coating film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5.5 mW / cm ² at intervals of 50 mJ / cm ² through a 20 μm line & space pattern mask by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. Thereafter, development was performed by immersing in a 2.38 mass% TMAH aqueous solution for 60 seconds, and then washing was performed with ultrapure water for 20 seconds to form a pattern. The minimum exposure amount at which a 20 μm pattern was formed was defined as sensitivity.

[Evaluation results]
The results of the above evaluation are shown in Table 2 below.

As can be seen from the results shown in Table 2, each of the negative photosensitive resin compositions of Examples 1 to 4 was capable of coating with a thick film of 15 μm or more and alkali development, and maintained high solvent resistance. .
In Comparative Example 1, the coating film cannot be thickened, and the remaining film ratio after post-baking (after the solvent resistance test) is as low as 49% or less, and the cured film cannot maintain the thickness of the coating film. It was. In Comparative Example 2, tacking occurred after pre-baking, and patterning could not be performed.

  The negative photosensitive resin composition according to the present invention is a material for forming a cured film such as a protective film, a planarizing film, and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element, an organic EL element, and a touch panel element. Particularly suitable as an interlayer insulating film of a TFT type liquid crystal element, a protective film of a color filter, an array flattening film, an interlayer insulating film of a capacitive touch panel, an insulating film of an organic EL element, a display surface antireflection layer It is also suitable as a material for forming a structure sheet or the like.

Claims (6)

The photosensitive resin composition containing the following (A) component, (B) component, (C) component, (D) component, and (E) solvent.
Component (A): a copolymer obtained by copolymerizing a monomer mixture containing at least (i) N-alkoxymethyl (meth) acrylamide and (ii) maleimide ,
(B) component: a compound having two or more polymerizable groups,
Component (C): photopolymerization initiator,
(D) component: a polymer containing a hydroxy group,
(E) Solvent. The photosensitive resin composition according to claim 1, further comprising 0.1 to 10 parts by mass of a thermal acid generator as a component (F) with respect to 100 parts by mass of the component (A) in the photosensitive resin composition. object. (A) component, in addition to said (i) and (ii), a copolymer of a monomer mixture containing a monomer having a further hydroxy group, the photosensitive resin composition of claim 1. The photosensitive resin composition as described in any one of Claims 1 thru | or 3 which contains a crosslinking agent further as (G) component. The cured film obtained using the photosensitive resin composition as described in any one of Claims 1 thru | or 4 . An interlayer insulating film for a liquid crystal display comprising the cured film according to claim 5 .