JP5576091B2 - Photosensitive resin composition and substrate - Google Patents

Description

  The present invention relates to a photosensitive resin composition suitably used for forming a light shielding film such as a black matrix, and a substrate having a light shielding film formed using the photosensitive resin composition.

  A display body such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates on which a pair of electrodes facing each other is formed. A color filter including pixel regions of red (R), green (G), and blue (B) is formed inside one substrate. In this color filter, a black matrix is usually formed so as to partition red, green, and blue pixel regions.

  Generally, a color filter is manufactured by a lithography method. That is, first, a black photosensitive resin composition is applied onto a substrate, dried, then exposed to light and developed to form a black matrix. Next, for each of the photosensitive resin compositions of red, green, and blue, application, drying, exposure, and development are repeated to form a pixel region of each color at a specific position to manufacture a color filter.

  In recent years, in the manufacture of a liquid crystal display, an attempt has been made to improve the contrast of an image displayed on the liquid crystal display by improving the light shielding property by the black matrix. Further, in order to reduce the polishing process, the black matrix is becoming thinner. Accordingly, the black matrix is required to have higher light shielding properties.

  In order to improve the light blocking property of the black matrix, it is necessary to use a light blocking agent having a high blackness. Conventionally, carbon black is generally used as such a light-shielding agent. Recently, fine particles mainly composed of a silver-tin alloy have been proposed as a light-shielding agent having higher blackness (Patent Document 1). reference). Further, Patent Document 1 discloses a photosensitive resin composition containing such a light shielding agent.

JP 2006-225503 A

  However, as a result of investigations by the present inventors, the photosensitive resin composition disclosed in Patent Document 1 has low sensitivity, and the cured resin pattern may be peeled off from the substrate during development. There is a problem that the straightness of the machine is reduced.

  The present invention has been made in view of the above problems, and has high sensitivity while using fine particles mainly composed of a silver-tin alloy as a light-shielding agent, causing problems such as peeling of a cured resin pattern and a decrease in straightness. An object of the present invention is to provide a non-photosensitive resin composition and a substrate having a light-shielding film formed using the photosensitive resin composition.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above problem can be solved by combining a specific photopolymerization initiator with a light shielding agent that is a fine particle mainly composed of a silver tin alloy. The headline and the present invention were completed. Specifically, the present invention provides the following.

  The first aspect of the present invention comprises (A) a photopolymerizable compound, (B) an oxime-based photopolymerization initiator, and (C) a light-shielding agent, and the (C) light-shielding agent mainly comprises a silver-tin alloy. It is a photosensitive resin composition that is a fine particle as a component.

  The 2nd aspect of this invention is a base material which has the light shielding film formed using the photosensitive resin composition which concerns on this invention.

  According to the present invention, there is provided a photosensitive resin composition that has high sensitivity while using fine particles mainly composed of a silver-tin alloy as a light-shielding agent, and does not cause problems such as peeling of a cured resin pattern and deterioration of straightness, and The base material which has the light shielding film formed using the photosensitive resin composition can be provided.

≪Photosensitive resin composition≫
The photosensitive resin composition according to the present invention contains at least (A) a photopolymerizable compound, (B) an oxime photopolymerization initiator, and (C) a light-shielding agent. Hereinafter, each component contained in the photosensitive resin composition will be described in detail.

<(A) Photopolymerizable compound>
The (A) photopolymerizable compound contained in the photosensitive resin composition according to the present invention is not particularly limited, and a conventionally known photopolymerizable compound can be used. Among them, a resin or monomer having an ethylenically unsaturated group is preferable, and it is more preferable to combine these. By combining a resin having an ethylenically unsaturated group and a monomer having an ethylenically unsaturated group, curability can be improved and pattern formation can be facilitated.

[Resin having an ethylenically unsaturated group]
As the resin having an ethylenically unsaturated group, (meth) acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene Glycol monoethyl ether (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol diacrylate, triethylene glycol di (meth) acrylate, tetrae Lenglycol di (meth) acrylate, butylene glycol dimethacrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra Oligomers in which (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, cardoepoxy diacrylate, etc. are polymerized; polyhydric alcohols (Meth) acrylate obtained by reacting (meth) acrylic acid with polyester prepolymer obtained by condensing monobasic acid or polybasic acid with And polyurethane (meth) acrylate obtained by reacting a polyol and a compound having two isocyanate groups and then reacting with (meth) acrylic acid; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S Type epoxy resin, phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or cycloaliphatic epoxy resin, amine epoxy resin, dihydroxy Examples thereof include an epoxy (meth) acrylate resin obtained by reacting an epoxy resin such as a benzene type epoxy resin with (meth) acrylic acid. Furthermore, a resin obtained by reacting an epoxy (meth) acrylate resin with a polybasic acid anhydride can be suitably used.

  As the resin having an ethylenically unsaturated group, a resin obtained by further reacting a reaction product of an epoxy compound and an unsaturated group-containing carboxylic acid compound with a polybasic acid anhydride can be preferably used. .

Among these, the compound represented by the following formula (a1) is preferable. The compound represented by the formula (a1) itself is preferable in terms of high photocurability.

In the above formula (a1), X represents a group represented by the following formula (a2).

In the formula (a2), R ^1a independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ^2a independently represents a hydrogen atom or a methyl group, and W represents Represents a single bond or a group represented by the following formula (a3).

  Moreover, in said formula (a1), Y represents the residue remove | excluding the acid anhydride group (-CO-O-CO-) from dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride and glutaric anhydride.

In the above formula (a1), Z represents a residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like.
Moreover, in said formula (a1), m represents the integer of 0-20.

  The acid value of the resin having an ethylenically unsaturated group is preferably 10 to 150 mgKOH / g, and more preferably 70 to 110 mgKOH / g, in terms of resin solids. By setting the acid value to 10 mgKOH / g or more, sufficient solubility in the developer can be obtained. Moreover, by making an acid value into 150 mgKOH / g or less, sufficient sclerosis | hardenability can be obtained and surface property can be made favorable.

  Moreover, it is preferable that it is 1000-40000, and, as for the mass mean molecular weight of resin which has an ethylenically unsaturated group, it is more preferable that it is 2000-30000. By setting the mass average molecular weight to 1000 or more, heat resistance and film strength can be improved. Moreover, sufficient solubility with respect to a developing solution can be acquired by making a mass mean molecular weight into 40000 or less.

[Monomer having an ethylenically unsaturated group]
Monomers having an ethylenically unsaturated group include monofunctional monomers and polyfunctional monomers.
Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl ( And (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers may be used alone or in combination of two or more.

  On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meta Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydi Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (Meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene Examples thereof include polyfunctional monomers such as ethers, polyhydric alcohols and N-methylol (meth) acrylamide condensates, and triacryl formal. These polyfunctional monomers may be used alone or in combination of two or more.

  (A) It is preferable that content of a photopolymerizable compound is 50-99.9 mass parts with respect to 100 mass parts of solid content of the photosensitive resin composition. By setting the content to 50 parts by mass or more with respect to 100 parts by mass of the solid content, sufficient heat resistance and chemical resistance can be expected.

<(B) Oxime-based photopolymerization initiator>
It does not specifically limit as an oxime type photoinitiator contained in the photosensitive resin composition concerning this invention, A conventionally well-known oxime type photoinitiator can be used. By using an oxime-based photopolymerization initiator as a photopolymerization initiator, (C) sufficient sensitivity can be maintained even when fine particles mainly composed of a silver-tin alloy are used as a light-shielding agent. Problems such as peeling of the resin pattern and a decrease in straightness do not occur.

Among the oxime photopolymerization initiators, those represented by the following formula (b1) are preferable.

In the above formula (b1), R ^1b represents —NO ₂ or —COR ^5b . R ^5b represents a heterocyclic group, a condensed cyclic aromatic group, or an aromatic group, which may have a substituent. R ^{2b to} R ^4b each independently represent a monovalent organic group.

^Examples of the heterocyclic group represented by R ^5b include a 5- or more-membered heterocyclic group containing at least one atom of a nitrogen atom, a sulfur atom, and an oxygen atom, preferably a 5-membered or 6-membered heterocyclic group. Examples of heterocyclic groups include nitrogen-containing 5-membered ring groups such as pyrrolyl, imidazolyl and pyrazolyl groups; nitrogen-containing 6-membered ring groups such as pyridyl, pyrazinyl, pyrimidyl and pyridazinyl groups; thiazolyl and isothiazolyl groups Nitrogen-containing sulfur groups such as oxazolyl groups and isoxazolyl groups; sulfur-containing groups such as thienyl groups and thiopyranyl groups; oxygen-containing groups such as furyl groups and pyranyl groups; Among these, those containing one nitrogen atom or one sulfur atom are preferable. This heterocyclic ring may contain a condensed ring. Examples of the heterocyclic group containing a condensed ring include a benzothienyl group.

^Examples of the condensed cyclic aromatic group represented by R ^5b include a naphthyl group, an anthryl group, and a phenanthryl group. Moreover, a phenyl group is mentioned as an aromatic group represented by R ^<1b> .

The heterocyclic group, the condensed cyclic aromatic group, or the aromatic group may have a substituent. In particular, when R ^5b is an aromatic group, it preferably has a substituent. Examples of such _{^{substituents, -NO 2, -CN, -SO 2}} R 6b, -COR 6b, -NR 7b R 8b, -R 9b, -OR 9b, -O-R 10b -O-R 11b , etc. Is mentioned.

R ^6b independently represents an alkyl group, which may be substituted with a halogen atom, and may be interrupted by an ether bond, a thioether bond, or an ester bond. The alkyl group for R ^6b preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.

R ^7b and R ^8b each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, which may be substituted with a halogen atom, and among these, the alkylene part of the alkyl group and the alkoxy group is an ether bond, It may be interrupted by a thioether bond or an ester bond. R ^7b and R ^8b may be bonded to form a ring structure. The alkyl group or alkoxy group in R ^7b and R ^8b preferably has 1 to 5 carbon atoms. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, methoxy group, ethoxy group, A propoxy group etc. are mentioned.

A ring structure that can be formed by combining R ^7b and R ^8b includes a heterocyclic ring. Examples of the heterocyclic ring include 5-membered or more, preferably 5 to 7-membered heterocyclic rings containing at least a nitrogen atom. This heterocyclic ring may contain a condensed ring. Examples of the heterocyclic ring include piperidine ring, morpholine ring, thiomorpholine ring and the like. Among these, a morpholine ring is preferable.

R ^9b represents an alkyl group in which part or all of the hydrogen atoms may be substituted with a halogen atom. The alkyl group for R ^9b preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.

R ^10b and R ^11b each independently represent an alkyl group, which may be substituted with a halogen atom, and may be interrupted by an ether bond, a thioether bond, or an ester bond. Preferred carbon numbers and specific examples thereof are the same as those described for R ^6b above.

Among these, preferred examples of R ^5b include a pyrrolyl group, a pyridyl group, a thienyl group, a thiopyralyl group, a benzothienyl group, a naphthyl group, and a phenyl group having a substituent.

In the above formula (b1), R ^2b represents a monovalent organic group. As ^the organic ^{group, -R 12b, -OR 12b, -COR} 12b, -SR 12b, preferably a group represented by -NR ^{12b R 13b.} R ^12b and R ^13b each independently represent an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these may be substituted with a halogen atom, an alkyl group, or a heterocyclic group, Among them, the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond. R ^12b and R ^13b may be bonded to form a ring structure with the nitrogen atom.

As an alkyl group represented by R ^{< 12b>} , R ^<13b> , a C1-C20 thing is preferable and a C1-C5 thing is more preferable. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl. Group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group And a straight chain or branched chain group such as Moreover, this alkyl group may have a substituent. Examples of those having a substituent include a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

As an alkenyl group represented by R ^12b and R ^13b , those having 1 to 20 carbon atoms are preferable, and those having 1 to 5 carbon atoms are more preferable. Examples of alkenyl groups include linear or branched groups such as vinyl, allyl, butenyl, ethenyl, and propynyl groups. Moreover, this alkenyl group may have a substituent. Examples of those having a substituent include 2- (benzoxazol-2-yl) ethenyl group and the like.

As an aryl group represented by R ^12b and R ^13b , those having 6 to 20 carbon atoms are preferable, and those having 6 to 10 carbon atoms are more preferable. Examples of the aryl group include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, anthryl group, phenanthryl group and the like.

As the aralkyl group represented by R ^12b and R ^13b , those having 7 to 20 carbon atoms are preferable, and those having 7 to 12 carbon atoms are more preferable. Examples of the aralkyl group include benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group, phenylethyl group, phenylethenyl group and the like.

^Examples of the heterocyclic group represented by R ^12b and R ^13b include a 5- or more-membered heterocyclic group containing at least one atom of a nitrogen atom, a sulfur atom, and an oxygen atom, preferably a 5- to 7-membered heterocyclic group. . This heterocyclic group may contain a condensed ring. Examples of the heterocyclic group include pyrrolyl, pyridyl, pyrimidyl, furyl, and thienyl groups.

Among these R ^12b and R ^13b , the alkylene part of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond.

A ring structure that can be formed by combining R ^12b and R ^13b includes a heterocyclic ring. Examples of the heterocyclic ring include 5-membered or more, preferably 5 to 7-membered heterocyclic rings containing at least a nitrogen atom. This heterocyclic ring may contain a condensed ring. Examples of the heterocyclic ring include piperidine ring, morpholine ring, thiomorpholine ring and the like.

Among these, R ^2b is most preferably a methyl group, an ethyl group, a propyl group, or a phenyl group.

In the above formula (b1), R ^3b represents a monovalent organic group. As this organic group, it has a C1-C5 alkyl group, the C6-C12 aryl group which may have a substituent, the group represented by a following formula (b2), or a substituent. An optionally substituted heterocyclic group is preferred. Examples of the substituent include the same groups as those for R ^5b . Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

In the above formula (b2), R ^14b represents an alkylene group having 1 to 5 carbon atoms which may be interrupted by an oxygen atom. Examples of such an alkylene group include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, n-pentylene group, isopentylene group, sec-pentylene group and the like. A linear or branched group is mentioned. Among these, R ^14b is most preferably an isopropylene group.

In the formula (b2), R ^15b represents a monovalent organic group represented by —NR ^16b R ^17b (R ^16b and R ^17b each independently represents a monovalent organic group). Among such organic groups, the structure of R ^15b represented by the following formula (b3) is preferable in that the solubility of the oxime photopolymerization initiator can be improved.

In said formula (b3), R ^<18b> , R ^<19b> is a C1-C5 alkyl group each independently. Examples of such an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec- Examples thereof include a pentyl group and a tert-pentyl group. Among these, R ^18b and R ^19b are most preferably a methyl group.

^Examples of the heterocyclic group represented by R ^3b include 5-membered or more, preferably 5-membered or 6-membered heterocyclic groups containing at least one of a nitrogen atom, a sulfur atom, and an oxygen atom. Examples of heterocyclic groups include nitrogen-containing 5-membered ring groups such as pyrrolyl, imidazolyl and pyrazolyl groups; nitrogen-containing 6-membered ring groups such as pyridyl, pyrazinyl, pyrimidyl and pyridazinyl groups; thiazolyl and isothiazolyl groups Nitrogen-containing sulfur groups such as oxazolyl groups and isoxazolyl groups; sulfur-containing groups such as thienyl groups and thiopyranyl groups; oxygen-containing groups such as furyl groups and pyranyl groups; Among these, those containing one nitrogen atom or one sulfur atom are preferable. This heterocyclic ring may contain a condensed ring. Examples of the heterocyclic group containing a condensed ring include a benzothienyl group.

Moreover, the heterocyclic group may have a substituent. Examples of the substituent include the same groups as those for R ^5b .

In the above formula (b1), R ^4b represents a monovalent organic group. Among these, it is preferable that it is a C1-C5 alkyl group. Examples of such an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec- Examples thereof include a pentyl group and a tert-pentyl group. Of these, R ^4b is most preferably a methyl group.

  (B) 0.1-50 mass% is preferable with respect to solid content of the photosensitive resin composition, and, as for content of an oxime system photoinitiator, 1-45 mass% is more preferable. By setting it within the above range, sufficient heat resistance and chemical resistance can be obtained, coating film forming ability can be improved, and photocuring failure can be suppressed.

<(C) Shading agent>
As the (C) light-shielding agent contained in the photosensitive resin composition according to the present invention, fine particles containing silver tin (AgSn) alloy as a main component (hereinafter referred to as “AgSn alloy fine particles”) are used. The AgSn alloy fine particles may be composed mainly of an AgSn alloy, and may contain, for example, Ni, Pd, Au, etc. as other metal components.
The average particle diameter of the AgSn alloy fine particles is preferably 1 to 300 nm.

When this AgSn alloy is represented by the chemical formula Ag _x Sn, the range of x in which a chemically stable AgSn alloy is obtained is 1 ≦ x ≦ 10, and the chemical stability and the blackness can be obtained simultaneously. The range of 3 ≦ x ≦ 4.
Here, when the mass ratio of Ag in the AgSn alloy is determined in the range of x,
When x = 1, Ag / AgSn = 0.4762
When x = 3, 3 · Ag / Ag ₃ Sn = 0.7317
When x = 4, 4 · Ag / Ag ₄ Sn = 0.7843
When x = 10, 10 · Ag / Ag ₁₀ Sn = 0.008
It becomes. Therefore, this AgSn alloy is chemically stable when Ag is contained in an amount of 47.6 to 90% by mass, and effective when Ag is contained in an amount of 73.17 to 78.43% by mass. Chemical stability and blackness can be obtained.

  The AgSn alloy fine particles can be produced using a normal fine particle synthesis method. Examples of the fine particle synthesis method include a gas phase reaction method, a spray pyrolysis method, an atomization method, a liquid phase reaction method, a freeze drying method, and a hydrothermal synthesis method.

The AgSn alloy fine particles have high insulating properties, but depending on the application of the photosensitive resin composition, the surface may be covered with an insulating film in order to further improve the insulating properties. As a material for such an insulating film, a metal oxide or an organic polymer compound is suitable.
As the metal oxide, an insulating metal oxide such as silicon oxide (silica), aluminum oxide (alumina), zirconium oxide (zirconia), yttrium oxide (yttria), titanium oxide (titania), etc. is preferably used. It is done.
In addition, as the organic polymer compound, an insulating resin such as polyimide, polyether, polyacrylate, polyamine compound, or the like is preferably used.

The thickness of the insulating film is preferably 1 to 100 nm, and more preferably 5 to 50 nm, in order to sufficiently enhance the surface insulation of the AgSn alloy fine particles.
This insulating film can be easily formed by a surface modification technique or a surface coating technique. In particular, use of an alkoxide such as tetraethoxysilane or aluminum triethoxide is preferable because an insulating film having a uniform thickness can be formed at a relatively low temperature.

  The content of the (C) light-shielding agent is preferably 4 to 400% by mass and preferably 20 to 200% by mass with respect to the solid content of the photosensitive resin composition other than the (C) light-shielding agent. By setting it within the above range, it is possible to obtain sufficient light shielding properties and to suppress poor photocuring.

<(S) Organic solvent>
The photosensitive resin composition according to the present invention preferably contains an organic solvent for dilution. Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , Dipropylene glycol monomethyl ether , (Poly) alkylene glycol monoalkyl ethers such as dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; Diethylene glycol Other ethers such as methyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Alkyl 2-lactic acid esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxy Ethyl acetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate , N-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate Other esters such as ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, N -Amides such as dimethylformamide and N, N-dimethylacetamide. These organic solvents may be used alone or in combination of two or more.

  Among these, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, and 3-methoxybutyl acetate are the above-mentioned (A). It is preferable because it exhibits excellent solubility in the photopolymerizable compound and (B) oxime-based photopolymerization initiator, and (C) the dispersibility of insoluble components such as a light-shielding agent can be improved. It is particularly preferable to use butyl acetate, propylene glycol monomethyl ether acetate, or cyclohexanone.

  (S) Content of the organic solvent can be used in 50-500 mass parts with respect to the total of 100 mass parts of solid content contained in the photosensitive resin composition.

<Other ingredients>
The photosensitive resin composition according to the present invention may contain an additive as necessary. Specifically, sensitizers, curing accelerators, crosslinking agents, dispersion aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, thermal polymerization inhibitors, antifoaming agents, surface activity Agents and the like.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition according to the present invention can be obtained by mixing all the above components with a stirrer. In addition, you may filter using a filter so that the obtained mixture may become uniform.

≪Base material≫
The base material which concerns on this invention has a light shielding film formed using the photosensitive resin composition. Although it does not specifically limit as a base material, For example, a glass base material is mentioned.

  In order to form a light-shielding film having a predetermined pattern using the photosensitive resin composition according to the present invention, first, a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, a spinner (rotary coating device), a curtain flow, or the like. The photosensitive resin composition is applied onto the substrate using a non-contact type coating apparatus such as a coater.

  Next, the coated photosensitive resin composition is dried to form a coating film. The drying method is not particularly limited. For example, (1) a method of drying on a hot plate at 80 to 120 ° C., preferably 90 to 100 ° C. for 60 to 120 seconds, and (2) room temperature for several hours to several days. Any of a method of leaving it, and a method of removing the solvent by putting it in a warm air heater or an infrared heater for several tens of minutes to several hours may be used.

Next, this coating film is partially exposed by irradiating active energy rays such as ultraviolet rays and excimer laser light through a negative mask. Although an irradiation amount changes also with compositions of the photosensitive resin composition, about 30-2000 mJ / cm < ² > is preferable, for example.

  Next, the exposed coating film is developed into a desired shape by developing with a developer. The development method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. Examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

  Next, post-baking is performed at about 200 ° C. on the developed coating film. At this time, it is preferable to expose the entire surface of the formed cured resin pattern (light shielding film).

  The light-shielding film formed in this manner is excellent in light-shielding properties and insulating properties, and thus can be suitably used as a black matrix or the like in a liquid crystal display.

  Examples of the present invention will be described below, but the scope of the present invention is not limited to these examples.

<Example 1>
As the photopolymerizable compound, the following resin (A-1) and dipentaerythritol hexaacrylate were prepared.

[Synthesis Method of Resin (A-1)]
First, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid Was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target value. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by the following formula (a4) of colorless and transparent solid.

Next, after adding 600 g of 3-methoxybutyl acetate to 307.0 g of the bisphenolfluorene type epoxy acrylate thus obtained and dissolving, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was gradually heated and reacted at 110 to 115 ° C. for 4 hours. After confirming disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain Resin (A-1). The disappearance of the acid anhydride group was confirmed by IR spectrum.
This resin (A-1) corresponds to the compound represented by the above formula (a1). This resin (A-1) was adjusted to a solid content concentration of 50% by mass with 3-methoxybutyl acetate.

  In addition, IRGACURE OXE-02 (manufactured by Ciba Specialty Chemicals; Oxime 1 described below) was prepared as a photopolymerization initiator.

  Further, as the light-shielding agent, AgSn alloy fine particle dispersion (25% by mass of AgSn alloy fine particles having an average particle size of 200 to 300 nm, dispersant: 3.7% by mass of DPK-164 (manufactured by Big Chemie), solvent: propylene glycol monomethyl ester Tail acetate) was prepared. The AgSn alloy fine particles were prepared with reference to the descriptions in paragraphs [0033] and [0034] of Patent Document 1.

  Each of these components and an organic solvent (3-methoxybutyl acetate / propylene glycol monomethyl ether acetate / cyclohexanone = 50/45/5) were blended in the proportions shown in Table 1, mixed for 2 hours with a stirrer, and then a 5 μm membrane. The mixture was filtered with a filter to prepare a photosensitive resin composition having a solid content concentration of 22% by mass. In addition, the numerical value in Table 1 represents a mass part.

<Examples 2 to 12>
A photosensitive resin composition was prepared in the same manner as in Example 1 except that any of oximes 1 to 10 described later was used as a photopolymerization initiator and the content of the light shielding agent was changed as shown in Table 1.

<Comparative Examples 1-4>
In Comparative Example 1, a low-resistance carbon black dispersion (55% by mass of carbon black, solvent: 3-methoxybutyl acetate, manufactured by Mikuni Dye Co., Ltd.) was prepared as a light-shielding agent. In Comparative Example 2, a high-resistance carbon black dispersion (carbon Black 55% by mass, solvent: 3-methoxybutyl acetate, produced by Mikuni Dye Co., Ltd. was prepared. In Comparative Example 3, a Ti fine particle dispersion (Ti fine particle 55% by mass, solvent: 3-methoxybutyl acetate, produced by Mikuni Dye Co., Ltd.) In Comparative Example 4, an organic pigment dispersion (RGB mixture 55% by mass, solvent: 3-methoxybutyl acetate, manufactured by Mikuni Dye Co., Ltd.) was prepared and used in the proportions shown in Table 1, respectively. In the same manner as in No. 1, a photosensitive resin composition was prepared.

<Comparative Example 5>
As photopolymerization initiators, aminoketone-based triazine PMS (manufactured by PANCHIM; aminoketone 1 described later) and benzophenone-based EAB-F (manufactured by Hodogaya Chemical Co., Ltd .; benzophenone 1 described later) were used in the ratios shown in Table 1, respectively. A photosensitive resin composition was prepared in the same manner as in Example 1 except for the above.

  In addition, the structure of the photoinitiator used in Examples 1-12 and Comparative Examples 1-5 is as follows. In the chemical formula, -Ac represents an acetyl group, and -OAc represents an acetoxy group.

<Evaluation>
[Evaluation of resistance value]
The photosensitive resin compositions of Examples and Comparative Examples were applied on a low resistance silicon wafer using a spin coater and dried at 100 ° C. for 120 seconds to form a coating film. Subsequently, this coating film was irradiated with ghi rays at an irradiation amount of 100 mJ / cm ² . And it post-baked in the circulation type oven for 20 minutes at 230 degreeC. The formed light shielding film had a thickness of 1.0 μm. About this light shielding film, resistance value was measured using Hi-Lester MCP-HT450 (made by Mitsubishi Chemical Corporation). The results are shown in Table 2.

[Evaluation of shrink rate]
A light shielding film was formed in the same manner as in the above [Evaluation of resistance value], and the ratio of film thickness before and after post-baking was calculated as the shrink rate. The results are shown in Table 2.

[OD value evaluation]
The photosensitive resin composition of an Example and a comparative example was apply | coated on 1737 glass (made by Corning) using a spin coater, and it dried at 100 degreeC for 120 second, and formed the coating film. Subsequently, this coating film was irradiated with ghi rays at an irradiation amount of 100 mJ / cm ² . And it post-baked in the circulation type oven for 20 minutes at 230 degreeC. The thickness of the formed light shielding film was three levels of 0.8 μm, 1.0 μm, and 1.2 μm. About this light shielding film, OD value in each film thickness was measured using D200-II (made by Macbeth), and OD value per micrometer was computed with the approximated curve. The results are shown in Table 2.

[Evaluation of sensitivity and development margin]
The photosensitive resin composition of an Example and a comparative example was apply | coated on 1737 glass (made by Corning) using a spin coater, and it dried at 100 degreeC for 120 second, and formed the coating film. Next, this coating film was selectively irradiated with ghi rays through a negative mask while increasing the irradiation amount by 10 mJ from ²⁰ to 100 mJ / cm ² . Then, a light-shielding film including a line pattern having a line width of 20 μm was formed by spray development using a 0.5 mass% sodium carbonate aqueous solution at 26 ° C. for 50 to 100 seconds and increasing the time for 10 seconds. Thereafter, post-baking was performed in a circulation oven at 230 ° C. for 20 minutes. The formed light shielding film had a thickness of 1.0 μm. With respect to this light-shielding film, the sensitivity was evaluated based on the exposure amount on which a line pattern having a line width of 20 μm was formed, and the development margin was developed in 60 seconds. The results are shown in Table 2.

[Evaluation of pattern straightness, pattern peeling, development residue]
About the light shielding film (cured resin pattern) obtained by the above [Evaluation of Sensitivity], pattern straightness, pattern peeling, and development residue were evaluated. Whether the straightness of the pattern is rattled at the edge of the 20 μm line, whether the pattern is peeled off at the 5 μm line, and whether there is any peeling or chipping, or whether the residue of the light-shielding agent remains on the glass. Or evaluated. The results are shown in Table 2.

As can be seen from Table 2, in the photosensitive resin compositions of Examples 1 to 12 using the oxime photopolymerization initiator together with the AgSn alloy fine particles, the resistance value of the obtained light shielding film is high, and the compounding amount of the AgSn alloy fine particles is increased. A corresponding OD value was obtained. Moreover, the development margin was wide, the pattern straightness, the pattern peeling, and the development residue evaluation were good.
On the other hand, in the photosensitive resin compositions of Comparative Examples 1 to 4 using low resistance carbon black, high resistance carbon black, Ti fine particles, or pigment dispersion instead of AgSn alloy fine particles, the amount of the same amount as in Example 1 was used. Although a light-shielding agent was used, the OD value was lower than that in Example 1. Also, pattern formation was poor.
Further, in the photosensitive resin composition of Comparative Example 5 using an aminoketone photopolymerization initiator and a benzophenone photopolymerization initiator instead of the oxime photopolymerization initiator, the pattern straightness is poor and pattern peeling occurs. It was.
From this result, it was shown that by combining the AgSn alloy fine particles and the oxime-based photopolymerization initiator, the sensitivity is increased, and problems such as peeling of the cured resin pattern and a decrease in straightness do not occur.

Claims (7)

(A) a photopolymerizable compound, (B) an oxime-based photopolymerization initiator, and (C) a light-shielding agent,
The (A) photopolymerizable compound includes a resin obtained by further reacting a reaction product of an epoxy compound and an unsaturated group-containing carboxylic acid compound with a polybasic acid anhydride,
(C) A photosensitive resin composition in which the light-shielding agent is fine particles mainly composed of a silver-tin alloy.   The photosensitive resin composition according to claim 1, wherein the (C) light-shielding agent has an average particle diameter of 1 to 300 nm.   The photosensitive resin composition of Claim 1 or 2 with which the surface of said (C) light-shielding agent is coat | covered with the insulating film.   The photosensitive resin composition according to claim 3, wherein the insulating film is made of a metal oxide or an organic polymer compound.   The content of the (C) light-shielding agent is 4 to 400% by mass with respect to the solid content of the photosensitive resin composition other than the (C) light-shielding agent. Photosensitive resin composition. 6. A resin obtained by further reacting a reaction product of the epoxy compound with an unsaturated group-containing carboxylic acid compound with a polybasic acid anhydride is a compound represented by the following formula (a1): The photosensitive resin composition of any one of these.

[In the formula (a1), X represents a group represented by the following formula (a2).

(In formula (a2), R ^1a Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom; ^2a Each independently represents a hydrogen atom or a methyl group, and W represents a single bond or a group represented by the following formula (a3). )

  Y represents a residue obtained by removing an acid anhydride group (—CO—O—CO—) from a dicarboxylic acid anhydride, and Z represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic dianhydride. Represents a group. m represents an integer of 0 to 20. ] The base material which has the light shielding film formed using the photosensitive resin composition of any one of Claim 1 to 6 .