JP2001235856A - Photosensitive resin composition and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition so excellent in shelf stability as not to cause image defects due to the crystallization of a UV absorbent precursor even when the composition is held in an environment at a high temperature. SOLUTION: The photosensitive resin composition contains a UV absorbent precursor of formula 1 (where R1-R6 are each alkyl or aryl and R7-R9 are each H or alkyl) convertible to a UV absorbent when a group protected by a protective group is deprotected by heating, a crystallization inhibitor of the UV absorbent precursor, a photopolymerization initiator, a polymerizable monomer and a binder. The crystallization inhibitor is preferably at least one of triazine type, benzotriazole type and hindered amine type UV absorbents.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition and an image forming method useful for producing a color filter used in a liquid crystal display or the like, and more particularly, to color unevenness caused by crystallization of a precursor of an ultraviolet absorbent. The present invention relates to a photosensitive resin composition free from image defects and an image forming method using the same.

[0002]

2. Description of the Related Art Generally, a color filter used in a full-color liquid crystal display is provided between red (R), green (G), and blue (B) pixels for the purpose of preventing light leakage and improving contrast. A pattern pixel having a light shielding property is provided. The pattern pixel having the light-shielding property is formed using a metal film of chromium or the like, a material in which a black coloring agent or the like is dispersed in a photosensitive resin, or the like. However, in the case of a metal film such as chromium, it is performed by forming a metal film on the entire surface of the glass substrate by means such as vapor deposition, then applying a resist, patterning, and etching the metal film. Therefore, in this method, the process is very complicated, the yield is low, and there is a problem in cost.

[0003] In order to solve the above problem, there is known a method of forming a pattern pixel having a light-shielding property using a photosensitive black resin obtained by combining a photosensitive resin and carbon or the like. In this method, the film thickness is several μ
m. However, in the production of a normal color filter, pattern pixels having light-shielding properties and R, G, and B pixels need to have a certain degree of overlap due to problems such as alignment errors. Is inevitable, and in order to obtain a surface with good smoothness, a smoothing layer is further provided thereon or the surface is polished.

As methods for improving the smoothness of the surface of a color filter, Japanese Patent Application Laid-Open Nos. 3-209203 and 4-6
Japanese Patent No. 9602 discloses that after forming R, G, and B pixels, a black photosensitive resin layer is applied to the entire surface and exposed from the back surface to expose R, G, and B pixels.
A so-called self-alignment method of forming a pattern pixel having a light-shielding property in a gap between these pixels using the B pixel itself as an exposure mask is disclosed. However, since the commonly used RGB colorant has a large transmittance in the ultraviolet region for curing the black photosensitive resin composition, even the photosensitive resin composition on the pixel partially cures and hardens on the pixel. There was a problem that it would remain in the device.

To solve the problem, Japanese Patent Laid-Open No. 62-25410
No. 3, JP-A-62-9301, JP-A-1-145562
No. 6, JP-A-2-77014 and the like disclose a technique of adding or impregnating an ultraviolet absorber, and JP-A-9-25360 discloses a technique of reducing the exposure energy by the addition of the ultraviolet absorber. A technique using an ultraviolet absorber precursor is disclosed in consideration of exposure failure at a deep portion of the film. That is, the use of the ultraviolet absorber precursor does not hinder the exposure energy irradiated imagewise before reaching the deep part of the film, and can also avoid a failure in the RGB pixel portion.

However, when the photosensitive resin composition contains an ultraviolet absorber precursor, the ultraviolet absorber precursor tends to form crystals over time, particularly in a high-temperature environment. Crystallization may occur in the photosensitive resin composition, causing defects such as color unevenness in a final product such as a color filter formed using the photosensitive resin composition,
There has been a problem that high-quality products cannot be stably manufactured.

As described above, a photosensitive resin composition which contains an ultraviolet absorber precursor and which does not crystallize even when kept under a high temperature condition for a certain period of time and which has excellent storage stability is provided by: It has not been provided yet.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, an object of the present invention is to provide a photosensitive resin composition having excellent storage stability without accompanying image defects due to crystallization of a UV absorber precursor even when kept under a high temperature environment. And Further, the present invention provides an image forming method capable of stably forming an image free from image defects such as color unevenness using a recording material containing an ultraviolet absorbent precursor, which can form an image by utilizing heat. The purpose is to:

[0009]

Means for solving the above problems are as follows. That is, <1> an ultraviolet absorber precursor represented by the following general formula (1), a crystallization inhibitor of the ultraviolet absorber precursor, and photopolymerization, wherein the protective group is deprotected by heating to become an ultraviolet absorber. A photosensitive resin composition comprising an initiator, a polymerizable monomer, and a binder.

[0010]

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[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R
⁶ each independently represents an alkyl group or an aryl group,
R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or an alkyl group. ]

<2> The photosensitive resin composition according to <1>, wherein the crystallization inhibitor is at least one selected from a triazine-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, and a hindered amine-based compound. .

Preferably, the photosensitive resin composition described in <3> or <4> below. <3> The photosensitive resin composition according to <2>, wherein the crystallization inhibitor has a melting point of 250 ° C. or less. The melting point is more preferably 200 ° C. or lower, and most preferably 150 ° C. or lower. <4> The photosensitive resin composition according to <2> or <3>, wherein the crystallization inhibitor is oily.

<5> Further, the above <1.
> The photosensitive resin composition according to any one of <4>. <6> The photosensitive resin composition according to <5>, wherein the colorant is a pigment.

<7> A step of providing the photosensitive resin composition according to any one of the above <1> to <6> on a substrate, a step of exposing the photosensitive resin composition on the substrate, and an unnecessary photosensitive step. An image forming method comprising: a step of forming a pixel on a substrate by removing a conductive resin composition by a developing treatment; and a step of heating a pixel formed on the substrate.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive resin composition of the present invention is characterized in that it contains, together with a precursor of an ultraviolet absorber, a crystallization inhibitor which prevents precipitation of the precursor by crystallization. Further, the image forming method of the present invention is characterized in that an image is recorded using a material having the photosensitive resin composition of the present invention. Hereinafter, the photosensitive resin composition of the present invention will be described in detail, and the details of the image forming method will be clarified through the description.

<Photosensitive resin composition> The photosensitive resin composition of the present invention is a precursor of an ultraviolet absorber represented by the following general formula (1), wherein a protective group is deprotected by heating to become an ultraviolet absorber. And a crystallization inhibitor of the ultraviolet absorber precursor, a photopolymerization initiator, a polymerizable monomer, and a binder, and if necessary, other components.

(Ultraviolet absorber precursor) As the ultraviolet absorber precursor, an ultraviolet absorber precursor represented by the following general formula (1) is used. The ultraviolet absorber precursor is excellent in the ability to deprotect protective groups by heating.

[0019]

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In the general formula (1), R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group or an aryl group. The alkyl group may have a linear, branched or cyclic structure, and may be unsubstituted or have a substituent. Examples of the substituent of the substituted alkyl group having a substituent include a halogen atom (a fluorine atom, a chlorine atom, and a bromine atom), a cyano group, a nitro group, an aryl group,
Examples include a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group.

Among the above alkyl groups, those having 1 to 1 carbon atoms
8 alkyl groups are preferred, and 1-4 alkyl groups are more preferred. For example, a methyl group, an ethyl group, a propyl group,
Preferred examples include an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, and a cyclohexyl group.

The aryl group represented by R ^{1 to} R ⁶ includes
It may be a single ring or a condensed ring, and may be a substituted aryl group having a substituent or an unsubstituted aryl group. Examples of the substituent of the substituted aryl group having a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a halogen atom, an acylamino group, an acyl group, an alkylthio group, an arylthio group, a hydroxy group, a cyano group, Alkyloxycarbonyl group,
Examples include an aryloxycarbonyl group, a substituted carbamoyl group, a substituted sulfamoyl group, a nitro group, a substituted amino group, an alkylsulfonyl group, and an arylsulfonyl group. Among them, a substituted or unsubstituted phenyl group, 1-naphthyl group and 2-naphthyl group are preferred.

R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or an alkyl group. Here, the alkyl group has the same meaning as the alkyl groups represented by R ^{1 to} R ⁶ .

The ultraviolet absorbent precursor represented by the general formula (1) has a high R ¹ deprotection ability by heat and is particularly excellent in stability of the ultraviolet absorbent precursor.
Preferred are compounds in which -R ⁶ is a methyl group and R ⁷ -R ⁹ are hydrogen atoms.

The ultraviolet absorbent precursor has a relatively low ultraviolet absorbing ability in a normal state, but by performing a heat treatment, the protective group is deprotected and exhibits a function as an ultraviolet absorbent. Here, the temperature at which deprotection can be performed is 10
0-400 degreeC is preferable, and 140-300 degreeC is more preferable.

The content of the ultraviolet absorbent precursor in the photosensitive resin composition of the present invention is preferably 0.1 to 30% by weight based on the total solid weight of the photosensitive resin composition. 0.1-20% by weight is more preferred. When the content is less than 0.1% by weight, the amount of the ultraviolet absorbent generated after the heat treatment is small, and the function as a self-alignment type photomask may be reduced, and the content may be 30% by weight.
If it exceeds 300, the absorption of the ultraviolet absorbent precursor itself becomes a problem, and it may not be possible to sufficiently expose the film to a deep portion during exposure. The ultraviolet absorber precursor may be used alone or in combination of two or more.

(Crystallization inhibitor) The crystallization inhibitor is not particularly limited as long as it is a material that prevents the ultraviolet absorber precursor from being precipitated from the photosensitive resin composition. The skeleton can be appropriately selected, and the skeleton may be similar to or different from the skeleton of the ultraviolet absorbent precursor described above. Above all, particularly preferred are ultraviolet absorbers and / or hindered amine compounds,
As the ultraviolet absorber, a triazine-based ultraviolet absorber,
Benzotriazole UV absorbers are more preferred. For example, 2- (2′-hydroxyphenyl) benzotriazole-based compound, 2-hydroxybenzophenone-based compound, salicylic acid ester-based compound, mono-tris (2-
UV absorbers such as (hydroxyphenyl) -1,3,5-triazine-based compounds and 2-hydroxyphenyldiazine-based compounds, and known hindered amine-based compounds can be suitably used. In order to improve the ability of the ultraviolet absorber precursor to prevent crystallization, it is particularly preferable to use a triazine-based ultraviolet absorber having a nucleus similar to the skeleton of the ultraviolet absorber precursor.

The melting point of the crystallization inhibitor is 250
C. or less, more preferably 200.degree. C. or less, and most preferably 150.degree. C. or less. When the melting point exceeds 250 ° C., the ability to prevent crystallization is reduced, and the above-mentioned ultraviolet absorbent precursor may be crystallized from the photosensitive resin composition. Further, the crystallization inhibitor may be solid or oily, but is preferably oily in that it has a high crystallization preventing effect.

Specific examples of the ultraviolet absorber as the crystallization inhibitor include JP-B-56-13933, US Pat. No. 3,118,872, US Pat. No. 3,242,175, US Pat. No. 3,244,708, GB1321561, and EP434.
No. 608, U.S. Pat. No. 4,619,956, U.S. Pat.
No. 4749, U.S. Pat. No. 5,461,151, EP7044
No. 37, WO96128431, JP-A-5-1172
No. 82, No. 7-233154, No. 6-211813
Nos. 7-109274, 8-259545, 8-337574, 10-45729, 10-
No. 147577, No. 10-182621, Tokuheihei 8-
No. 501291, JP-T-11-503112, JP-A-7-258228, JP-A-8-67813, and JP-A-8-29
No. 0112, No. 10-140089, No. 11-310
No. 576, etc. (benzotriazole-based, triazine-based). Further, specific examples of the hindered amine compound as the crystallization inhibitor include paragraph [010] of JP-A-11-269210.
2] and the like.

Further, in addition to the above-mentioned ultraviolet absorber, as a crystallization inhibitor, [0098] of JP-A-10-182621 is used.
79] to [0097], and various compound groups (antioxidants, light stabilizers, phosphites, phosphonites, basic co-stabilizers, etc.) described in [0101] to [0118] can also be used. These compounds may be used alone or in combination of two or more, and may be used together with the ultraviolet absorber. In addition, it is also preferable that the various compound groups be used in combination with the ultraviolet absorber in that the crystallization preventing effect of the ultraviolet absorber precursor can be more effectively improved.

In particular, when a benzotriazole-based ultraviolet absorber precursor having 16 or more carbon atoms or a triazine-based ultraviolet absorber precursor having 21 or more carbon atoms is used as the ultraviolet absorber, The ultraviolet absorber precursor is preferably used because it is excellent in heat resistance and its crystallinity is higher, so that the use of the crystallization inhibitor in combination is particularly useful in that a higher crystallization inhibitory effect is obtained. It is.

The content of the crystallization inhibitor in the photosensitive resin composition of the present invention is preferably 1 to 300% by weight, more preferably 5 to 1% by weight, based on the content of the ultraviolet absorbent precursor.
00% by weight is more preferred. If the content is less than 1% by weight, the ability to prevent crystallization may decrease,
When the content exceeds 0% by weight, the solid content in the photosensitive resin composition increases and the film thickness increases, which may lead to a decrease in photosensitivity. The crystallization inhibitor may be used alone or in combination of two or more.

(Binder) As the binder,
There is no particular limitation, and ordinary film-forming polymers can be used. Among them, while having excellent pigment dispersibility, good compatibility with a polymerizable monomer and a photopolymerization initiator, alkali developer solubility, organic solvent solubility during coating solution preparation, strength,
Those having an appropriate softening temperature and the like are preferable.

Specifically, JP-A-59-44615, JP-A-11-269210, and JP-A-10-4
No. 5816, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-7.
No. 1048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer; (meth) acryl Copolymer of acid and (meth) acrylic acid ester: styrene / maleic anhydride copolymer; reaction products of these copolymers with alcohols; Further, a cellulose derivative having a carboxylic acid group in a side chain is also included.

In addition to the above, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group can also be suitably used. In particular, a copolymer of benzyl (meth) acrylate and (meth) acrylic acid or a multi-component copolymer of benzyl (meth) acrylate, (meth) acrylic acid and another monomer described in US Pat. No. 4,139,391. Polymers may be mentioned. Among them, a copolymer of (meth) acrylic acid and (meth) acrylic acid ester is preferable.

The molecular weight of the binder is 500
0 to 200,000 is preferred. The binder may be used alone, or may be used in the form of a composition in combination with a usual film-forming polymer. The content of the binder in the photosensitive resin composition is 1 to 8 with respect to the total solid weight of the photosensitive resin composition.
0% by weight is preferred.

(Polymerizable monomer) Examples of the polymerizable monomer include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or more at normal pressure. . Specific examples thereof include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di ( (Meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanedio Rudi (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Examples thereof include polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding propylene oxide to ethylene oxide to an alcohol and then (meth) acrylated.

Furthermore, known (meth) acrylic acid esters, urethane (meth) acrylates, (meth) acrylic amides described in JP-A-60-258538
Allyl compounds, vinyl esters, etc .;
08, JP-B-50-6034, JP-A-51
-Urethane acrylates described in -37193;
JP-A-48-64183, JP-B-49-4319
Polyester acrylates and methacrylates such as polyester acrylates described in JP-A No. 1 and JP-B-52-30490; epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid;

Among them, (meth) acrylic acid such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate Esters are preferred.

The above polymerizable monomers may be used alone or in combination of two or more. The content of the polymerizable monomer is preferably from 5 to 80% by weight, and more preferably from 10 to 6% by weight based on the total solid weight of the photopolymerizable resin composition.
0% by weight is more preferred.

(Photopolymerization Initiator) Examples of the photopolymerization initiator include a vicinal polyketaldonyl compound described in US Pat. No. 2,367,660 and US Pat. No. 2,448,828.
No. 2,027,512, an acyloin ether compound described in US Pat. No. 2,722,512, an α-hydrocarbon-substituted aromatic acyloin compound described in US Pat.
27 and 2951758, a combination of a triarylimidazole dimer and a p-aminoketone described in U.S. Pat. No. 3,549,367, and JP-B-51-48516. Benzothiazole compounds and trihalomethyl-s-triazine compounds, trihalomethyl-s-triazine compounds described in U.S. Pat. No. 4,239,850, and trihalomethyl oxadiazole compounds described in U.S. Pat. No. 4,221,976. be able to.

Examples of the photopolymerization initiator include benzophenone, camphorquinone, 4,4-bis (dimethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, and 4-dimethylaminobenzophenone. , 4-dimethylaminoacetophenone, benzylanthraquinone, 2
Bisacyl such as -tert-butylanthraquinone, 2-methylanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorenone, acridone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Phosphine oxides, Lucirin TP
Aromatic ketones such as acylphosphine oxides such as O, α-hydroxy or α-aminoacetophenones, α-hydroxycycloalkylphenyl ketones, and dialkoxyacetophenones;

Benzoin and benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin phenyl ether; 2- (o-chlorophenyl) -4,5-diphenylimidazole 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-
2,4,6-triarylimidazole dimers such as (p-methoxyphenyl) -4,5-diphenylimidazole dimer, and other U.S. Patent Nos. 3,784,557 and 42.
Nos. 52887, 4311783, 4459349
Nos. 4,410,621 and 4,622,286;

Polyhalogen compounds such as carbon tetrabromide, phenyltribromomethylsulfone and phenyltrichloromethylketone; JP-A-59-133428, JP-B-57
No.-1819, JP-B-57-6096, U.S. Pat.
A compound described in 615455;

2,4,6-tris (trichloromethyl)
-S-triazine, 2-methoxy-4,6-bis (trichloromethyl) -S-triazine, 2-amino-4,6
-Bis (trichloromethyl) -S-triazine, 2-
JP-A-58-29803 such as (P-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine
S-triazine derivatives having a trihalogen-substituted methyl group described in (1);

Methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, benzoyl peroxide, di-tert-butyldiperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) ) Hexane, tert-butylperoxybenzoate, a, a'-bis (tert-butylperoxyisopropyl) benzene, dicumyl peroxide, 3,3 ', 4,4'-tetra- (tert-butylperoxycarbonyl) ) Japanese Patent Application Laid-Open No.
Organic peroxides described in No. 9-189340;

Azinium salts described in US Pat. No. 4,743,530; organoboron compounds; phenylglyoxalic esters such as methyl phenylglyoxalate; bis (η ^{5, 2} -cyclopentadien-1-yl) ) -Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium and the like; η ⁵ -cyclopentadienyl-η ⁶ -cumenyl-iron (1 +)-hexafluoro Iron arylene complexes such as phosphate (1-); diaryliodonium salts such as diphenyliodonium salts; and triarylsulfonium salts such as triphenylsulfonium salts.

More detailed examples of the above photopolymerization initiator,
Examples of other types of photopolymerization initiators include paragraphs [0067] to [01] of JP-A-10-45816.
32].

Further, as the photopolymerization initiator, a material comprising a combination of two or more compounds can be used. For example, a combination of 2,4,5-triarylimidazole dimer and mercaptobenzoxazole or the like,
4,4'- described in U.S. Pat. No. 3,427,161.
Combination of bis (dimethylamino) benzophenone, benzophenone and benzoin methyl ether, benzoyl-N-methylnaphthothiazoline and 2,4-bis (trichloromethyl) -6- (4'-) described in U.S. Pat. No. 4,239,850. Methoxyphenyl) -triazole, a combination of a dialkylaminobenzoic acid ester described in JP-A-57-23602 and dimethylthioxanthone, and a 4,4′-bis (JP-A-59-78339) described in JP-A-59-78339. Dimethylamino) benzophenone, benzophenone, and a polymethyl halide compound.

In the case of a photopolymerization initiator obtained by combining two or more kinds, a combination of 4,4'-bis (diethylamino) benzophenone and benzophenone, a combination of 2,4-diethylthioxanthone and ethyl 4-dimethylaminobenzoate Or a combination of 4,4'-bis (diethylamino) benzophenone and 2,4,5-triarylimidazole dimer.

The organic boron compound is described in
2-143044, JP-A-9-188865, JP-A-9-188686, JP-A-9-188710, and the like, or an organic boron compound described in each publication or a spectral sensitizing dye-based boron compound obtained from a cationic dye And the like.

Of the above, trihalomethyl-s-triazine, trihalomethyloxadiazole and triarylimidazole dimer are preferred. The content of the photopolymerization initiator is generally 0.01 to 20% by weight based on the total solid weight of the photosensitive resin composition, and 0.1 to 20% by weight.
15% by weight is preferred.

(Other Components) The photosensitive resin composition of the present invention contains a colorant, a solvent, a thermal polymerization inhibitor, a dispersing aid, a plasticizer,
Other components such as a surfactant and an adhesion promoter can also be contained. -Colorant- Examples of the colorant include known dyes and pigments, and pigments are particularly preferable from the viewpoints of light resistance, heat resistance, chemical resistance, and the like. The pigment is used by being uniformly dispersed in the photosensitive resin composition. The particle size is preferably 5 μm or less, particularly preferably 1 μm or less. Further, when the pigment is used for producing a color filter, the particle diameter of the pigment is preferably 0.5 μm or less.

As the pigment, a red pigment, a green pigment,
Use blue pigment. As the red pigment, for example,
C. I. Pigment Red 9, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 14
9, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180,
C. I. Pigment Red 192, C.I. I. Pigment Red 215, C.I. I. Pigment Red 216, C.I.
I. Pigment Red 217, C.I. I. Pigment Red 220, C.I. I. Pigment Red 223, C.I. I. Pigment Red 224, C.I. I. Pigment Red 22
6, C.I. I. Pigment Red 227, C.I. I. Pigment Red 228, C.I. I. Pigment Red 240,
C. I. Pigment Red 48: 1, C.I. I. Pigment Red 242, C.I. I. Pigment Red 209,
C. I. Pigment Red 146, C.I. I. Pigment Red 11, C.I. I. Pigment Red 81, C.I. I.
Pigment Red 213, C.I. I. Pigment Red 2
72, C.I. I. Pigment Red 270, C.I. I. Pigment Red 255, C.I. I. Pigment Red 26
4, C.I. I. Pigment Red 254 and the like.

Examples of the green pigment include C.I. I.
Pigment Green 7, C.I. I. Pigment Green 3
6 and the like. As the blue pigment, for example,
C. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 22, C,
I. Pigment Blue 60, C.I. I. Pigment Blue 64 and the like.

In addition to the above pigments, yellow pigments, orange pigments, violet pigments, brown pigments, and black pigments can be used, if necessary. Examples of the yellow pigment include C.I. I. Pigment Yellow 20,
C. I. Pigment Yellow 24, C.I. I. Pigment Yellow 12, C.I. Pigment Yellow 17, C.I.
I. Pigment Yellow 83, C.I. I. Pigment Yellow 86, C.I. I. Pigment Yellow 93, C.I. I.
Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment Yellow 117, C.I.
I. Pigment yellow 125, C.I. I. Pigment yellow 137, C.I. I. Pigment Yellow 138,
C. I. Pigment Yellow 139, C.I. I. Pigment yellow 147, C.I. I. Pigment Yellow 14
8, C.I. I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. I. Pigment yellow,
C. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. Pigment Yellow 16
8, C.I. I. Pigment Yellow 185 and the like.

Examples of the orange pigment include C.I.
I. Pigment Orange 36, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I.
Pigment Orange 55, C.I. I. Pigment Orange 59, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 71 and the like. Examples of the violet pigment include C.I. I. Pigment Violet 19, C.I. I. Pigment Violet 23, C.I.
I. Pigment Violet 29, C.I. I. Pigment Violet 30, C.I. I. Pigment Violet 3
7, C.I. I. Pigmented Violet 40, C.I. I. Pigment Violet 50 and the like.

Examples of the brown pigment include C.I.
I. Pigment Brown 23, C.I. I. Pigment Brown 25, C.I. I. Pigment Brown 26 and the like. Examples of the black pigment include C.I. I. Pigment Black 7 and the like.

The pigments may be used alone or in combination of two or more. Among them, Pigment Yellow 138, Pigment Yellow 139, Pigment Yellow 185, Pigment Red 254, Pigment Green 36, Pigment Blue 15 and the like are preferable.

The colorants may be used alone or in combination of two or more. The content in the photosensitive resin composition is based on the total solid weight of the photosensitive resin composition.
0.1 to 70% by weight is preferable, and 1 to 50% is particularly preferable.

-Solvent- The photosensitive resin composition is prepared by dissolving the photosensitive resin composition containing each component in a solvent, for example, when the photosensitive resin composition is provided on a substrate as in the image forming method of the present invention described below. It is used as an applied coating solution. As the solvent used in this case, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether,
So-called cellosolves such as diethylene glycol monomethyl ether and ethylene glycol monoethyl ether, and their acetates, ethyl acetate and acetic acid n
Acetates such as -propyl, i-propyl acetate, n-butyl acetate, i-butyl acetate, benzene, toluene,
Examples include aromatic hydrocarbons such as xylene, ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone, and alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin.

-Thermal Polymerization Inhibitor-Examples of the thermal polymerization inhibitor include hydroquinone,
p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4 -Methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like. The thermal polymerization inhibitor can be used in a range that does not impair the effects of the present invention.

The dispersing aid, plasticizer, surfactant, adhesion promoter and the like can be appropriately selected from known ones as long as the effects of the present invention are not impaired.

As described below, the photosensitive resin composition of the present invention is useful for producing a color filter, and utilizes a (photosensitive) heat-sensitive recording material to be recorded by a heating element such as a thermal head or a laser conversion heat. Such as a laser thermosensitive recording material, it can be suitably used for the production of a recording material for recording using heat, a resist or a photomask for producing a printed substrate, a black and white or color transfer color-developing sheet or a color-developing sheet, and the like. Other components may be added according to the application.

<Image Forming Method> The image forming method of the present invention includes a step of providing the above-described photosensitive resin composition of the present invention on a substrate (hereinafter sometimes referred to as a “photosensitive resin layer forming step”). A step of exposing the photosensitive resin composition on the substrate (hereinafter, sometimes referred to as an “exposure step”) and a step of removing unnecessary photosensitive resin composition by a development process to form a pixel on the substrate (Hereinafter, sometimes referred to as a “pixel forming step”), and a step of heat-treating the pixels formed on the substrate (hereinafter, sometimes referred to as a “heat treatment step”).
And the above four steps may be repeated a plurality of times. A multicolor image can be formed by repeating the above four steps a plurality of times using a photosensitive resin composition containing a colorant having a different hue.

In the photosensitive resin layer forming step, the present invention comprises at least a UV absorber precursor, a crystallization inhibitor of the UV absorber precursor, a binder, a polymerizable monomer and a photopolymerization initiator on a substrate. A photosensitive resin composition is provided. In this case, as a method of providing the photosensitive resin composition on the substrate, a coating solution prepared by dissolving the photosensitive resin composition in a solvent is prepared, applied on the substrate by a known application method, and dried to form a layer (hereinafter, referred to as “layer”). The photosensitive resin composition may be formed on a temporary support by using a transfer material having a photosensitive resin layer applied on a temporary support by a known coating method, and then transferred onto a substrate by transfer. And the like. In the case of the above method, the photosensitive resin layer can be used as an independent sheet (photosensitive sheet) once peeled off from the temporary support.

Examples of the known coating method include a method using a spinner, a wiper, a roller coater, a curtain coater, a knife coater, a wire bar coater, an extruder, and the like. After the application, the photosensitive resin layer or the photosensitive sheet can be obtained by drying.

As a specific embodiment of the transfer material in the above method, it can be basically constituted in the same manner as a known photosensitive transfer material, and the simplest embodiment thereof is a temporary material made of a flexible plastic film or the like. This is an embodiment in which a thin layer (photosensitive resin layer) made of a photosensitive resin composition is formed on a support, and furthermore, a peeling property at the interface between the support and the photosensitive resin layer is further improved. An undercoat layer, an intermediate layer, a release layer, and the like, which can provide a cushioning property or a cushioning property, can be arbitrarily provided.

Specifically, a transfer material described in JP-A-4-208940 having a separation layer having a small adhesive force to a temporary support and a photosensitive resin layer is disclosed in JP-A-5-173320.
Japanese Patent Application Publication No. JP-A-2003-133873, a photosensitive transfer material having a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer on a temporary support, and having the smallest adhesive force between the temporary support and the thermoplastic resin layer. Kaihei 5-
Japanese Patent Application Laid-Open No. 5-80503, which discloses a transfer material having a thermoplastic resin layer, a separation layer and a photosensitive resin layer and having the smallest adhesive force between the thermoplastic resin layer and the separation layer.
JP-A No. 6-1980, having a thermoplastic resin layer, an intermediate layer and a photosensitive resin layer on a temporary support, a photosensitive transfer material having the smallest adhesive force between the temporary support and the thermoplastic resin layer, And the like. Among them, a photosensitive transfer material in which an alkali-soluble thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer are laminated in this order on a temporary support is preferable. In addition, a protective film can be laminated on the photosensitive resin layer as needed.

When the photosensitive resin composition is provided on the substrate by the above method, first, if necessary, the protective film of the transfer material is removed, and the photosensitive resin layer is applied to the substrate under pressure and heat. After the alignment, the temporary support is peeled off from the substrate. A known laminator and vacuum laminator can be used for lamination, and an auto-cut laminator can be used to further improve productivity.

In the exposing step, the photosensitive resin composition provided on the substrate is imagewise irradiated with light (pattern exposure) with or without a predetermined photomask. As a light source used for light irradiation, a known light source such as an ultra-high pressure mercury lamp or a xenon lamp can be used. The photomask can be appropriately selected from known ones.

In the pixel forming step, an unnecessary photosensitive resin composition (a photosensitive resin layer in an unnecessary area not involved in pixel formation) is removed by a developing process to form a pixel on a substrate. As a developer used for the development process, in the case of a negative photosensitive resin layer, a solvent or an alkali aqueous solution that dissolves an unexposed portion and does not dissolve the exposed portion is used, and in the case of a positive photosensitive resin layer, Use the opposite solvent or the like. From the viewpoint of the impact on the environment in recent years, development processing using an alkaline aqueous solution is preferred for both the negative type and the positive type.For example, a dilute aqueous solution of an alkaline substance or a small amount of an organic solvent having miscibility with water in the dilute aqueous solution is used. Additions may be given.

Examples of the alkaline substance include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (eg, sodium carbonate, potassium carbonate, etc.), and alkali metal bicarbonates (eg, , Sodium bicarbonate, potassium bicarbonate, etc.), alkali metal silicates (eg, sodium silicate, potassium silicate, etc.), alkali metal metasilicates (eg, sodium metasilicate, potassium metasilicate, etc.),
Examples include triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (eg, tetramethylammonium hydroxide), and trisodium phosphate. The concentration of the alkaline substance is preferably 0.01 to 30% by weight, and the pH is preferably 8 to 14.

Suitable organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether. , Benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ
-Butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone. The concentration of the organic solvent miscible with water is 0.1 to 30% by weight.

A known surfactant can be further added to the developer, and the concentration of the surfactant is as follows.
0.01 to 10% by weight is preferred.

The developer can be used as a bath liquid or a spray liquid. When removing an unnecessary area of the photosensitive resin layer, a method such as rubbing with a rotating brush or a wet sponge in a developer can be combined. Usually, the temperature of the developer is preferably from about room temperature to 40 ° C.
After the development processing, a water washing step can be provided.

In the heat treatment step, the pixels formed on the substrate are subjected to a heat treatment to further harden the pixels and to decompose the ultraviolet absorbent precursor contained in the pixels to change them into the ultraviolet absorbent. . As a method of the heat treatment, a convection oven, a hot plate,
Known methods such as an infrared heater can be used. The conditions for the heat treatment are selected so that the ultraviolet absorber precursor can sufficiently exhibit the ultraviolet absorption function at the stage where the precursor is desired to be present as the ultraviolet absorber. The temperature is 120-300
C. is preferred, and 130 to 250 C. is particularly preferred. The heating time is preferably from 1 to 200 minutes.

Further, the thickness of the photosensitive resin layer before exposure was 365 nm.
Is preferably from 1: 0.99 to 1: 0.00001, more preferably from 1: 0.5 to 1: 0.00001. More preferably, 1: 0.1 to 1: 0.000
Most preferably it is 01. After the heat treatment, the transmittance of the finally formed pixel at 365 nm is preferably 2% or less. If the transmittance of the formed pixel exceeds 2%, the function as a photomask in the self-alignment method may be reduced.

Next, as a specific example of the image forming method of the present invention, a case where a color filter is manufactured will be described as an example.
Color filters are red (R), green (G), blue (B)
Can be manufactured by repeating the four steps (the photosensitive resin layer forming step to the heat treatment step) in the image forming method of the present invention in order for each pixel.
The process of (4) may be repeated for each pixel of RGB.

(1) A photosensitive resin composition containing the ultraviolet absorbent precursor represented by the general formula (1), a polymerizable monomer, a photopolymerization initiator and a binder is added to a solvent to form a coating liquid. Further, a coating liquid in which a pigment is dispersed (a coating liquid for a photosensitive resin layer) is applied and dried, or, as described above,
Using a transfer material in which a photosensitive resin layer is previously formed on a temporary support, transferring the transfer material, and providing a colored photosensitive resin layer on the substrate (photosensitive resin layer forming step); (2) coloring Exposing the exposed photosensitive resin layer in a pattern via a photomask (exposure step); (3) After exposure, the photosensitive resin layer is subjected to a development process to form a pixel composed of an exposed portion of the photosensitive resin layer. (Pixel formation step); (4) a step of baking the pixels formed on the substrate by heat treatment and further curing (heat treatment step)

In the above step (1), a pigment having a desired hue is selected as a pigment, and a coating solution of each color of RGB is prepared and used to form RGB pixels on a substrate in order.
After the second color, the layer may be formed so as to cover the pixels of the first color, and only the uncured area is dissolved and removed by the developing treatment.

In the step (1), a transfer material in which a photosensitive resin layer is applied on a temporary support by a known coating method in advance, and a photosensitive resin composition is provided on a substrate by transfer is used. preferable.

The above steps (1) to (4) are general methods in an image forming method for forming an image using a photosensitive transfer material, and are described, for example, in JP-A-5-173320. . As a typical image forming method, a photosensitive resin composition layer of a photosensitive transfer material is overlaid on the surface of a transparent substrate to be installed on a liquid crystal display element, and after removing the support,
A step of exposing the photosensitive resin composition layer on the material to be transferred to the photosensitive resin composition layer via a photomask, a step of heating the photosensitive resin composition layer after the exposure, and a developing treatment to dissolve and remove unexposed portions. A method combining steps and the like can be used.

As described above, it is preferable to provide an alkali-soluble thermoplastic resin layer, an intermediate layer and the like between the substrate and the photosensitive resin layer. -Thermoplastic resin layer-The thermoplastic resin layer is a layer that is easily deformed when stress is applied, and has an effect of improving the adhesion of the photosensitive resin layer to a substrate or the like and improving image quality. Further, when a multi-color image (for example, a color filter or the like) is formed using a plurality of photosensitive transfer materials on the same substrate or the like,
When transferring the second and subsequent colors, since the pixels of the first color are already formed on the substrate and the pixels have irregularities,
In the case where the photosensitive resin layer of the second color is to be transferred and formed so as to cover the pixels of the first color, it is possible to avoid the occurrence of a transfer failure or the like due to the formation of a gap near the foot of the pixel.

Examples of the thermoplastic resin to be used include alkali-soluble thermoplastic resins, for example, a saponified product of ethylene and acrylate copolymer, a saponified product of styrene and (meth) acrylate copolymer, vinyl Saponified products of toluene and (meth) acrylate copolymers, poly (meth) acrylates, saponified products of (meth) acrylate copolymers such as butyl (meth) acrylate and vinyl acetate, etc. No. The layer thickness of the thermoplastic resin layer is preferably from 6 to 100 μm, more preferably from 10 to 50 μm.

—Intermediate Layer— From the viewpoint of improving the photopolymerization efficiency by blocking oxygen, it is preferable to provide an intermediate layer. As the material used for the intermediate layer,
It is necessary to use an alkali-soluble material which is not easily deformed when subjected to stress, and which can be applied to the thermoplastic resin layer. For example, Japanese Patent Application Laid-Open No. Sho 46-2121 and Japanese Patent Publication No. Sho 56-4
No. 0824, polyvinyl ether /
Maleic anhydride polymer, water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, polyvinylpyrrolidone, various polyacrylamides, various water-soluble polyamides, polyacrylic acid A water-soluble salt, gelatin, an ethylene oxide polymer, a water-soluble salt selected from the group consisting of various starches and their analogs, a styrene / maleic acid copolymer, a maleate resin, and a combination of two or more of these. No. Among them, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferred. The polyvinyl alcohol preferably has a saponification ratio of 80% or more, and the content of polyvinylpyrrolidone is preferably 1 to 75% by weight of the solid content of the intermediate layer, and 1 to 6% by weight.
0% by weight is more preferable, and 10 to 50% by weight is most preferable. If the content is less than 1% by weight, sufficient adhesion to the photosensitive resin layer may not be obtained, and if it exceeds 75% by weight, oxygen barrier ability may be reduced.

The intermediate layer is very thin, and the layer thickness is preferably 0.1 to 5.0 μm, and 0.5 to 2.0 μm.
m is more preferred. If the layer thickness is less than 0.1 μm, the oxygen permeability may be too high, and if it exceeds 5.0 μm, it may take too much time during development or when removing the intermediate layer.

The thermoplastic resin layer and the intermediate layer are formed by dissolving each component in a solvent which does not adversely affect an adjacent layer to form a coating liquid as in the case of forming the photosensitive resin layer by coating. It can be formed on a substrate or the like by a coating method.

(Substrate) The substrate is not particularly limited and may be appropriately selected depending on the intended purpose. In the case of producing a color filter, a known glass plate, a soda glass plate having a silicon oxide film formed on the surface, or the like may be used. It is suitable. When the photosensitive resin composition is provided on a temporary support, the temporary support is not particularly limited and can be appropriately selected depending on the purpose. However, a flexible sheet is preferred.

[0090]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the following examples, “%” is used unless otherwise specified.
Means "% by weight", and "parts" means "parts by weight".

Example 1 <Preparation of Photosensitive Transfer Material> First, a compound having the following composition was mixed to prepare a coating solution for a thermoplastic resin layer. [Composition of the coating solution for the thermoplastic resin layer] ・ Benzyl methacrylate / 2-ethylhexyl acrylate / methyl methacrylate / methacrylic acid copolymer: 4.5 parts (copolymerization ratio: 4.5 / 11.7) /55/28.8, weight average molecular weight 80000) ・ Styrene / acrylic acid copolymer ・ ・ ・ 15 parts (copolymerization ratio: 60/40, weight average molecular weight 8000) ・ 2,2-bis [4- (methacrylic acid) Roxypoly 7 parts Ethoxy) phenylpropane] F-176PF 1.5 parts (Fluorine-based surfactant, manufactured by Dainippon Ink Co., Ltd.) Propylene glycol monomethyl ether 28 parts Methyl ethyl ketone ... 27 copies

A polyethylene terephthalate base film (PET base film) having a thickness of 75 μm was prepared as a temporary support, and the thermoplastic resin layer coating liquid obtained above was applied on the film by a spin coater.
After drying in an oven at 0 ° C. for 5 minutes, a thermoplastic resin layer having a thickness of 15 μm was formed on the PET base film.

Next, a compound having the following composition was mixed to prepare a coating solution for the intermediate layer, and the coating solution for the intermediate layer was further laminated and applied on the thermoplastic resin layer by a spin coater. Thereafter, the resultant was dried in an oven at 100 ° C. for 2 minutes to form an intermediate layer having a thickness of 1.6 μm on the thermoplastic resin layer. [Composition of coating solution for intermediate layer] Polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.): 13 parts Polyvinyl pyrrolidone: 6 parts (PVP-K30, manufactured by Gokyo Sangyo Co., Ltd.) Methanol: 173 parts ・ Ion-exchanged water: 211 parts

Next, a compound having the following composition is mixed, and four kinds of coating solutions for the photosensitive resin layer of red, green, blue and black (the red and blue coating solutions are used for the photosensitive resin of the present invention). (Comprising a conductive resin composition). [Composition of coating solution for red photosensitive resin layer] RT-107 ... 48.33 parts (CI PR254 dispersion liquid, manufactured by FUJIFILM Aurin Co., Ltd.) MMPG-AC ... 10. 54 parts (propylene glycol monomethyl ether acetate)-Cyclohexanone ... 0.73 parts-Methyl ethyl ketone ... 31.91 parts-Surfactant ... 0.11 parts (MegaFac F-176, Dainippon Ink & Chemicals, Inc.)・ Phenothiazine: 0.0015 parts ・ Benzyl methacrylate / methacrylic acid copolymer: 0.43 parts (copolymerization ratio: 72:28, molecular weight: 30,000) ・ Dipentaerythritol hexaacrylate -5.11 parts-2-trichloromethyl-5- (p-styryls ... 0.43 parts tyryl) -1,3,4 Oxadiazole-Crystallization inhibitor ... 0.45 parts (oil-like triazine-based ultraviolet absorber; Tinuvin 400, manufactured by Ciba Specialty Chemicals Co., Ltd.)-Precursor of the following ultraviolet absorber (1)- 2.23 parts (2,4,6-tris [2,4-bis (methoxycarbonyloxy) phenyl] -1,3,5-triazine)

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[Composition of green photosensitive resin layer coating solution] GT-2: 15.86 parts (CI. PG36 dispersion, manufactured by FUJIFILM Aurin Co., Ltd.) YT-123・ 11.07 parts (CI PY138 dispersion, manufactured by Fuji Film Orin Co., Ltd.) ・ MMPG-AC ・ ・ ・ 14.67 parts (propylene glycol monomethyl ether acetate) ・ Methyl ethyl ketone ・ ・ ・ 51.60 parts ・Surfactant: 0.13 parts (MegaFac F-176, manufactured by Dainippon Ink Co., Ltd.) Phenothiazine: 0.004 parts Benzyl methacrylate / methacrylic acid copolymer: 1.21 parts (Copolymerization ratio: 72:28, molecular weight 30,000) dipentaerythritol hexaacrylate 4.01 parts 2-trichloromethyl-5- ( -Styryls ... 0.193 parts Tyryl) -1,3,4-oxadiazole 7-[[4- (diethylamino) -6- (3 -... 1.26 parts hydroxymethylpiperidino) -S-triazinyl (2)]-amino] -3-phenylcoumarin

[Composition of Blue Coating Solution for Photosensitive Resin Layer] 7075M 32.93 parts (CI.PB 15: 6 dispersion, manufactured by Mikuni Pigment Co., Ltd.) MMPG-AC 8.45 parts (propylene glycol monomethyl ether acetate) ・ Methyl ethyl ketone ・ ・ ・ 52.50 parts ・ Surfactant ・ ・ ・ 0.17 parts (MegaFac F-176, manufactured by Dainippon Ink & Chemicals, Inc.) ・ Phenothiazine 0.022 parts-benzyl methacrylate / methacrylic acid copolymer-2.18511 parts (copolymerization ratio: 72:28, molecular weight 40000)-dipentaerythritol hexaacrylate-3.95 parts -2 -Trichloromethyl-5- (p-styryls ... 0.202 parts tyryl) -1,3,4-oxadiazole-Crystallizing inhibitor 0.04 parts (oil-like triazine-based ultraviolet absorber; Tinuvin 400, manufactured by Ciba Specialty Chemicals Co., Ltd.)-The ultraviolet absorber precursor (1) 0.25 parts (2 4,6-tris [2,4-bis (methoxycarbonyloxy) phenyl] -1,3,5-triazine

[Composition of Black Coating Solution for Photosensitive Resin Layer] CFP-FF-775B 6.37 parts (CIPB15: 6 dispersion, manufactured by FUJIFILM Aurin Co., Ltd.) CFP -FF-293Y ... 4.78 parts (CI PY139 dispersion liquid, manufactured by FUJIFILM Aurin Co., Ltd.)-CFP-FF-802V ... 5.90 parts (CI PV23 dispersion liquid)・ CFP-FF-949K ・ ・ ・ 16.88 parts (Carbon black dispersion, manufactured by Fuji Film Orin Co., Ltd.) ・ MMPG-AC ・ ・ ・ 27.17 parts (propylene glycol monomethyl) (Ether acetate) ・ Methyl ethyl ketone ・ ・ ・ 74.00 parts ・ Surfactant ・ ・ ・ 0.14 parts (MegaFac F-176, manufactured by Dainippon Ink & Chemicals, Inc.) Hydroquinone monomethyl ether: 0.0032 parts Dipentaerythritol hexaacrylate: 6.89 parts Bis [4- [N- [4- (4,6-bistri ... 0.193 parts chloromethyl- s-Triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate

As described above, four PET base films having the thermoplastic resin layer and the intermediate layer laminated in this order are prepared, and the red, green, blue or black photosensitive layer is formed on the intermediate layer of each PET base film. The coating solution for the resin layer was applied by lamination using a spin coater. Thereafter, the PET base films of the four colors were dried in an oven at 100 ° C. for 2 minutes to form a photosensitive resin layer on each intermediate layer. Then, a protective film is formed by laminating a 12 μm thick polypropylene film at room temperature on each of the red, green, blue and black photosensitive resin layers, and a thermoplastic resin layer and an intermediate layer are formed on a PET base film. , Photosensitive resin layer (red,
Green, blue or black) and a protective film laminated in this order, a red pixel photosensitive transfer material (1), a green pixel photosensitive transfer material (1), a blue pixel photosensitive transfer material (1) And a photosensitive transfer material (1) for black pixels.

Example 2 In Example 1, the amount of the crystallization inhibitor used for preparing the red photosensitive resin layer coating solution was changed to 0.70 part, and the blue photosensitive resin layer coating solution was used. Except that the amount of the crystallization inhibitor used for the preparation was changed to 0.10 parts, a thermoplastic resin layer, an intermediate layer, a photosensitive resin layer (red or Blue) and a protective film were laminated in this order to prepare a photosensitive transfer material for red pixels (2) and a photosensitive transfer material for blue pixels (2).

Example 3 In Example 1, 0.45 parts of the crystallization inhibitor (Tinuvin 400) used for preparing the red photosensitive resin layer coating solution was replaced with Tinuvin 1130 (oil-like benzotriazole-based resin). UV absorber (crystallization inhibitor); Ciba Specialty Chemicals Co., Ltd.)
In place of 0.51 part, 0.04 part of the crystallization inhibitor (Tinuvin 400) used in the preparation of the blue photosensitive resin layer coating solution was replaced with 0.06 part of Tinuvin 1130 (the crystallization inhibitor). Other than that, in the same manner as in Example 1, for a red pixel, a thermoplastic resin layer, an intermediate layer, a photosensitive resin layer (red or blue), and a protective film are laminated in this order on a PET base film. A photosensitive transfer material (3) and a blue pixel photosensitive transfer material (3) were prepared.

Example 4 In Example 1, 0.45 part of the crystallization inhibitor (Tinuvin 400) used for preparing the red photosensitive resin layer coating solution was replaced with the following crystallization inhibitor (1)
(Asymmetric triazole-based ultraviolet absorber) Instead of 0.50 parts, 0.04 part of the crystallization inhibitor (Tinuvin 400) used in the preparation of the blue photosensitive resin layer coating solution was replaced with the following crystallization inhibitor (1) Example 1 except that 0.05 parts were replaced
In the same manner as described above, a thermoplastic resin layer, an intermediate layer, a photosensitive resin layer (red or blue), and a protective film are laminated in this order on a PET base film, and a red pixel photosensitive transfer material (4) And a photosensitive transfer material (4) for a blue pixel.

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(Example 5) In Example 1, 2.23 parts of the ultraviolet absorbent precursor (1) and a crystallization inhibitor (Tinuvin 40) used in preparing the red photosensitive resin layer coating solution were used.
0) 0.45 part, 2.98 parts of the following ultraviolet absorber precursor (2), and 0.10 part of Chimassorb 2020 (hindered amine compound (anti-crystallization agent); Ciba Specialty Chemicals Co., Ltd.) , Tinuvin 123
(Hindered amine compound (anti-crystallization agent); Ciba Specialty Chemicals Co., Ltd.) 0.40 parts, and further, an ultraviolet absorber precursor (used for preparing a blue photosensitive resin layer coating solution) 1) 0.25 part and a crystallization inhibitor (tinuvin 400) 0.04 part, respectively, 0.33 part of the following ultraviolet absorber precursor (2), and Chimassorb 2020 (hindered amine compound (crystallization inhibitor);
Ciba Specialty Chemicals Co., Ltd.) 0.01
Part, Tinuvin 123 (hindered amine compound (anti-crystallization agent); Ciba Specialty Chemicals Co., Ltd.)
Ex.), A thermoplastic resin layer, an intermediate layer, a photosensitive resin layer (red or blue), and a protective film were formed on the PET base film in this order in the same manner as in Example 1. Laminated photosensitive transfer material (5) for red pixel and photosensitive transfer material (5) for blue pixel were prepared.

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Example 6 In Example 1, 0.45 part of the crystallization inhibitor (Tinuvin 400) used for preparing the red photosensitive resin layer coating solution was replaced with Tinuvin 400 (Ciba Specialty Chemicals). 0.20 part, Tinuvin 123 (hindered amine compound (anti-crystallization agent); Ciba Specialty Chemicals Co., Ltd.)
Instead of 0.10 parts, the crystallization inhibitor (Tinuvin 400) 0.0 used in the preparation of the blue photosensitive resin layer coating solution was further added.
4 parts were replaced with 0.02 parts of Tinuvin 400 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and 0.01 parts of Tinuvin 123 (hindered amine compound (anti-crystallization agent); manufactured by Ciba Specialty Chemicals Co., Ltd.) In the same manner as in Example 1, except that the thermoplastic resin layer, the intermediate layer, the photosensitive resin layer (red or blue) and the protective film are laminated in this order on the PET base film, A photosensitive transfer material (6) and a photosensitive transfer material (6) for a blue pixel were produced.

Comparative Example 1 The procedure of Example 1 was repeated except that the crystallization inhibitor used for preparing the red and blue photosensitive resin layer coating solutions was not used.
A photosensitive transfer material (7) for red pixels and a photosensitive material for blue pixels, in which a thermoplastic resin layer, an intermediate layer, a photosensitive resin layer (red or blue), and a protective film are laminated in this order on an ET base film. A transfer material (7) was produced.

<Evaluation 1> A thermo test was performed on the photosensitive transfer materials (1) to (6) and (7) for red pixels obtained above at 30 ° C. for 7 days. On the other hand, a separately prepared glass substrate was treated with a silane coupling agent solution (KBM-603).
(1% diluent), washed with water for 10 seconds, drained with an air gun, and dried in an oven at 110 ° C. for 5 minutes to obtain a silane-coupling-treated glass substrate. Seven silane coupling-treated glass substrates were prepared corresponding to the photosensitive transfer material.

The protective film was removed from each of the red pixel photosensitive transfer materials (1) to (6) and (7) after the thermotest, and the surface of the photosensitive resin layer of each photosensitive transfer material was removed.
The silane-coupling-treated glass substrate is overlapped so as to be in contact with the glass substrate, and a laminator (first laminator 8)
B-550-80, manufactured by Taisei Laminator Co., Ltd.), pressure 2 kg / m ² , roller temperature 130 ° C., 0.2 m
/ Min transport conditions. Next, the temporary support (PET base film) of each photosensitive transfer material was peeled off at the interface with the thermoplastic resin layer, and only the temporary support was removed.
Then, samples (1) to (6) and (7) in which a photosensitive resin layer, an intermediate layer, and a thermoplastic resin layer were laminated in this order on a silane coupling-treated glass substrate were obtained.

For each of the samples (1) to (7), an aligner MAP-1200L (manufactured by Dainippon Screen Co., Ltd.) was used through a photomask for red pixels, and an ultra-high pressure mercury lamp (500 W / cm), the photosensitive resin layer was exposed for 3 seconds from a distance of 60 cm (irradiation energy: 20 mJ / cm ² ). After exposure, a predetermined processing solution (T
The thermoplastic resin layer and the intermediate layer of each sample were dissolved and removed with PD2 (10-fold diluted solution of Fuji Photo Film Co., Ltd.) to form a red colored layer. The presence or absence of a precipitate on the surface of the red colored layer (photosensitive resin layer) formed on each sample was confirmed with a microscope. The results are shown in Table 1 below.
Shown in

[0111]

[Table 1]

From the results in Table 1 above, in the photosensitive transfer materials (1) to (6) for red pixels using the photosensitive resin composition of the present invention containing a crystallization inhibitor, all of the crystals having a symmetric structure Despite the presence of highly absorbent UV absorber precursor, no color unevenness due to precipitation of UV absorber precursor was observed on the surface of the formed pixel, and a red colored layer without image defects was formed stably We were able to. In particular, in the photosensitive transfer materials (1), (2), (4) and (6) for red pixels using a triazine-based ultraviolet absorber as a crystallization inhibitor,
A more sufficient crystallization preventing effect was observed. When a precipitate of the ultraviolet absorbent precursor is present in the layer, for example, when a color filter is used, irregularities are formed along the precipitate on the surface of the color filter, and the cell gap uniformity is impaired and the color is deteriorated. Unevenness or the like is generated, and the quality of the color filter is deteriorated. On the other hand, in the photosensitive transfer material for red pixel (7) in which the crystallization inhibitor was not used together with the ultraviolet absorbent precursor, the ultraviolet absorbent precursor was deposited on the surface of the formed colored layer, and was deposited along the precipitate. As a result, color unevenness or the like occurred, and a colored layer having no image defects could not be formed. The same evaluation as in Evaluation 1 was performed using the photosensitive transfer materials for blue pixels (1) to (7). As a result, the same results as in the case of the photosensitive transfer material for red pixels were obtained.

<Preparation and Evaluation of Color Filter> The photosensitive transfer material for red pixel (1), the photosensitive transfer material for green pixel (1), and the photosensitive transfer material for blue pixel (1) prepared in Example 1 And photosensitive transfer materials for black pixels (1), photosensitive transfer materials for red pixels (2) to (7), and photosensitive transfer materials for blue pixels (2) to which were prepared in Examples 2 to 6 and Comparative Example 1. Using (7), a color filter was produced in the following procedure.

First, a red colored layer was formed on a silane-coupling-treated glass substrate by using the photosensitive transfer material (1) for red pixels prepared in Example 1 and performing the same operation as in Evaluation 1 described above. . Here, the thermoplastic resin layer and the intermediate layer are dissolved and removed, and only a red colored layer made of a photosensitive resin layer is formed on the silane coupling-treated glass substrate.

In this state, the substrate is treated with a predetermined processing solution (TC).
The photosensitive resin layer is developed with D1 (five-fold diluted solution of Fuji Photo Film Co., Ltd.) to dissolve and remove the unnecessary photosensitive resin layer in the unexposed area, and is further treated with a predetermined processing solution (T-SD1).
The developing residual film was removed while brushing with a (10-fold diluted solution of Fuji Photo Film Co., Ltd.) to form a red pixel pattern on the silane coupling-treated glass substrate.
Next, in order to increase the degree of cure of the red pixel, the same aligner as described above was applied to the entire surface of the glass substrate from the rear surface side (the surface of the glass substrate on which the red pixel pattern was not provided) to 20 mJ / cm ^{2 using} an ultrahigh pressure mercury lamp. Post-exposure was performed with irradiation energy, and baked in an oven at 220 ° C. for 20 minutes. By this heating, the protective group of the ultraviolet absorber precursor is deprotected, and an ultraviolet absorber is generated.

Next, the protective film of the green pixel photosensitive transfer material (1) is removed, and the surface of the photosensitive resin layer of the photosensitive transfer material (1) and the red color of the glass substrate on which the red pixel is formed are removed. The layers were overlapped so that the surface on the side where the pixels were provided was in contact with each other, and bonded using a laminator in the same manner as in the case of forming the red pixel pattern as described above. continue,
The PET base film of the green pixel photosensitive transfer material (1) was peeled off at the interface with the thermoplastic resin layer, and only the temporary support (PET base film) was removed from the glass substrate side.

The aligner MAP-1200 was applied to the glass substrate in which a photosensitive resin layer (green), an intermediate layer and a thermoplastic resin layer were laminated in this order on the red pixels of the substrate.
L (manufactured by Dainippon Screen Co., Ltd.) and an ultra-high pressure mercury lamp (500 W / cm) through a photomask for green pixels
Was exposed to the photosensitive resin layer for 3 seconds from a distance of 60 cm (irradiation energy: 20 mJ / cm ² ). After exposure,
A predetermined processing solution (T-PD2 (Fuji Photo Film Co., Ltd.)
), The thermoplastic resin layer and the intermediate layer were dissolved and removed. Further, a predetermined processing solution (T-CD1
Unnecessary photosensitive resin layer in the unexposed area is dissolved and removed with (5 times diluted solution of Fuji Photo Film Co., Ltd.), and then a predetermined processing solution (T-SD1 (Fuji Photo Film Co., Ltd.)) is added. The developing residual film was removed while brushing with a 10-fold diluted solution) to form a green pixel pattern on the glass substrate on which the red pixels were formed.

Next, after using the photosensitive transfer material for blue pixel (1) and removing its protective film, the surface of the photosensitive resin layer of the photosensitive transfer material (1) is removed in the same manner as described above. The glass substrate on which the green pixels are formed is attached so that the surface of the glass substrate on which the pixels are provided is in contact with each other, and the temporary support is removed, exposed and exposed in the same manner as in the case of forming the red and green pixel patterns. Dissolution and removal of the plastic resin layer and the intermediate layer, development / remaining film processing (removal of unexposed areas and development residual film),
And baking to form a blue pixel pattern on the glass substrate on which the red and green pixels were formed.

Further, after using the photosensitive transfer material for black pixels (1) and removing its protective film, the surface of the photosensitive resin layer of the photosensitive transfer material (1) is red,
The glass substrate on which the green and blue pixels were formed was attached so as to be in contact with the surface on the side where the pixels were provided, and the temporary support was removed. No pixel or photosensitive resin layer is provided on the glass substrate in which a photosensitive resin layer (black), an intermediate layer, and a thermoplastic resin layer are laminated in this order on red, green, and blue pixels of the substrate. Using an aligner MAP-1200L (manufactured by Dainippon Screen Co., Ltd.), exposure was performed from the surface of the glass substrate on the side using an ultra-high pressure mercury lamp (500 W / cm) (irradiation energy: 70 mJ / cm ² ). That is, the red, green, and blue pixel patterns already formed contain an ultraviolet absorber, so that irradiation light is not transmitted in the pixel area, and the photosensitive area for the black pixels is only between pixels outside the pixels. The transfer material (1) is exposed.

After the exposure, the dissolution and removal of the thermoplastic resin layer and the intermediate layer and the development / remaining film processing (removal of the unexposed area and the development residual film) are performed in the same manner as in the case of forming the red, green and blue pixel patterns. ) And baking, a black matrix was formed between the pixels on the glass substrate on which the red, green, and blue pixels were formed. As described above, the color filter (1) including the red pixel, the green pixel, the blue pixel, and the black matrix was manufactured.

Further, instead of the red pixel photosensitive transfer material (1) and the blue pixel photosensitive transfer material (1) used above, the red pixel photosensitive transfer materials (2) to (7) are used, respectively.
By using the blue pixel photosensitive transfer materials (2) to (7), the color filter (2)
To (7). The number of each photosensitive transfer material corresponds to the number of a color filter. In the production of the color filter, the photosensitive transfer material for blue pixels and the photosensitive transfer material for black pixels (1) and the photosensitive transfer material for black pixels (1) prepared in Example 1 were used. Was.

<Evaluation 2> For the color filters (1) to (7) produced in the same manner as in Evaluation 1, the presence or absence of precipitates and the color unevenness on the surface of each pixel (photosensitive resin layer) were examined with a microscope. And evaluated visually.

As a result, a color filter (1) produced using the photosensitive resin composition of the present invention containing a crystallization inhibitor was prepared.
In (6) to (6), no irregularities due to the generation of precipitates were observed on the surface of the color filter, and a color filter excellent in surface smoothness without color unevenness was able to be stably produced. on the other hand,
In the color filter (7) produced without containing a crystallization inhibitor in the photosensitive resin composition, color unevenness occurs due to the precipitation of the ultraviolet absorber precursor on the surface of the color filter, and the color filter has a smooth surface and high quality color. No filter could be made.

[0124]

According to the present invention, a photosensitive resin composition having excellent storage stability without causing image defects due to crystallization of the ultraviolet absorbent precursor even when maintained in a high temperature environment. Can be provided. Further, it is possible to provide an image forming method capable of stably forming an image free from image defects such as color unevenness by using a recording material containing an ultraviolet absorbent precursor, which can form an image using heat.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/3435 C08K 5/3435 5/3492 5/3492 5/3495 5/3495 C08L 101/00 C08L 101 / 00 G03F 7/027 G03F 7/027 7/028 7/028 7/032 7/032 7/40 501 7/40 501 (72) Inventor Koji Inoue 200 Onakazato, Fujinomiya City, Shizuoka Prefecture Inside Fuji Photo Film Co., Ltd. F-term (reference) 2H025 AA00 AB13 AC01 AD01 BC31 BC43 CB04 CB10 CB13 CB14 CB43 CC02 CC11 CC12 CC20 FA03 FA17 FA29 FA30 2H096 AA28 BA05 BA20 EA02 GA08 HA01 HA03 4J002 AA001 AB011 BG011 BG031 BH01E EB031 BH01E EB031E EU177 EU186 EU187 EU189 EU198 EU239 EV299 EV319 EW139 EZ009 FD056 FD099 FD149 FD200 FD207 FD208 4J011 PA43 PA69 PA70 PB24 PB25 PB40 PC02 QA03 QA04 QA06 QA08 QA22 QA23 Q A24 QA25 QB16 QB23 SA01 SA04 SA06 SA21 SA22 SA25 SA31 SA34 SA61 SA62 SA63 SA64 SA73 SA76 SA78 SA83 SA84 SA87 TA01 TA03 UA01 VA01 WA01

Claims (5)

[Claims] An ultraviolet absorber precursor represented by the following general formula (1), a crystallization inhibitor for the ultraviolet absorber precursor, and photopolymerization, wherein the protective group is deprotected by heating to become an ultraviolet absorber. A photosensitive resin composition comprising an initiator, a polymerizable monomer, and a binder. Embedded image [Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent an alkyl group or an aryl group, and R ⁷ , R ⁸ , R
⁹ each independently represents a hydrogen atom or an alkyl group. ] 2. The photosensitive resin composition according to claim 1, wherein the crystallization inhibitor is at least one selected from a triazine-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, and a hindered amine compound. 3. The method according to claim 1, further comprising a coloring agent.
3. The photosensitive resin composition according to item 1. 4. The photosensitive resin composition according to claim 3, wherein the colorant is a pigment. 5. A step of providing the photosensitive resin composition according to claim 1 on a substrate, a step of exposing the photosensitive resin composition on the substrate, and a step of developing an unnecessary photosensitive resin composition. An image forming method, comprising: a step of forming a pixel on a substrate by removing the pixel by processing; and a step of subjecting the pixel formed on the substrate to a heat treatment.