JP2007072412A - Colored composition, photosensitive colored resin composition, photosensitive solution for forming colored image, method for producing colored image, method for producing color filter and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high heat-resistance colored composition which is used in a photosensitive solution for forming a colored image that uses Pigment Red 254 as a pigment in production of a color filter, and which suppresses generation of foreign substances by a heating step and eliminates defects. <P>SOLUTION: The colored composition contains a pigment containing Pigment Red 254 and a resin, wherein the resin is a resin synthesized by making an ethylenically unsaturated group-containing isocyanate (B) represented by Formula (1): CH<SB>2</SB>=C(R<SB>1</SB>)-COO-X-NCO added to a polymer (A) obtained by polymerizing monomer components, containing a monomer having a dicyclo ring or a tricyclo ring, a monomer having a hydroxyl group and a monomer having an N-substituted maleimide group, wherein R<SB>1</SB>denotes H or methyl; and X represents alkylene or -R<SB>2</SB>-OCONH-R<SB>3</SB>- (R<SB>2</SB>is alkylene and R<SB>3</SB>is a divalent residue in a diisocyanate compound). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a colored composition, a photosensitive colored resin composition, a photosensitive liquid for forming a colored image, a method for producing a colored image, a method for producing a color filter, and a color filter.

In recent years, color filters are frequently used in liquid crystal display devices, sensors, color separation devices, and the like. In this color filter manufacturing method, there is a heating step during pixel formation, ITO film formation, and the like. In the colored pixel using Pigment Red 254 in this heating step, there is a problem that foreign matters are generated due to thermal deposits and become defective. As a method for solving this problem, for example, C.I. I. It has been proposed to use Pigment Red 254 as a pigment in a radiation-sensitive composition for forming colored pixels (see, for example, Patent Document 1).
JP 2003-248115 A

  The present invention eliminates the problems that occur in the conventional color filter manufacturing process, that is, a highly heat-resistant colored composition, a photosensitive colored resin composition, and a colored image forming product that suppresses the generation of foreign matters by the heating process and eliminates defects. A photosensitive solution, a method for producing a colored image using the same, a method for producing a color filter, and a color filter are provided.

The present invention relates to a pigment characterized by containing 5 to 100% by weight of Pigment Red 254 under the name of the color index, and a molecular weight having a weight average molecular weight (Mw) of 3,000 to 200,000. In the coloring composition containing a resin having a monomer component containing a monomer (a1) having a dicyclo ring or a tricyclo ring, a monomer (a2) having a hydroxyl group, and a monomer (a3) having an N-substituted maleimide group ( A resin synthesized by adding an ethylenically unsaturated group-containing isocyanate (B) represented by the following general formula (1) to a polymer (A) obtained by polymerizing a), and a monomer component (a ) And ethylenically unsaturated group-containing isocyanate (B), the amount of monomer (a1) used is 3 to 70% by weight, the amount of monomer (a2) used is 5 to 50% by weight, monomer (a3) 5 to 50 heavy %, Related to the coloring compositions the amount of the ethylenically unsaturated group-containing isocyanate (B) is characterized in that 1 to 30 wt%.
_{CH 2 = C (R 1)} -COO-X-NCO (1)
[Wherein, R ₁ represents a hydrogen atom or a methyl group, X represents a linear or branched alkylene group having 2 to 6 carbon atoms, or —R ₂ —OCONH—R ₃ — (R ₂ represents carbon the number represents 2-6 linear or branched alkylene group, R ₃ is represented.) the divalent R ₃ groups of the diisocyanate compound represented by CON-R ₃ -NCO. ]

  In the present invention, the monomer component (a) further contains a monomer (a4) having a carboxyl group, and the monomer (a) and the ethylenically unsaturated group-containing isocyanate (B) The use amount of a4) is 5 to 50% by weight.

  The present invention also relates to a photosensitive colored resin composition comprising the above colored composition, a monomer containing one or more photopolymerizable unsaturated bonds in the molecule, and a photoinitiator.

  The present invention also relates to a colored image forming photosensitive solution comprising the above-described photosensitive colored resin composition and an organic solvent.

  The present invention also relates to a method for producing a colored image, wherein a photosensitive layer comprising the above-described photosensitive colored resin composition is formed on a substrate and exposed and developed.

  According to another aspect of the present invention, a colored image is characterized in that the above-described colored image forming photosensitive solution is applied on a substrate and dried to form a photosensitive layer made of a photosensitive colored resin composition on the substrate, and then exposed and developed. Relates to the manufacturing method.

  The present invention also relates to a method for producing a color filter including a step of forming a colored image by the above-described method for producing a colored image.

  The present invention also relates to a color filter made by the above manufacturing method.

  The colored composition, photosensitive resin composition, and colored image forming photosensitive solution of the present invention have no generation of precipitates during the course of the thermal process, and according to the method for producing a colored image according to the present invention, coloring excellent in heat resistance characteristics Images can be produced.

According to the method for producing a color filter of the present invention, a color filter having excellent heat resistance and free from defects due to precipitates can be produced.
Moreover, the color filter produced by the manufacturing method of the color filter which concerns on this invention is excellent in a heat resistant characteristic.

Hereinafter, the present invention will be described in detail.
Resin used in the colored composition of the present invention is a monomer component containing a monomer (a1) having a dicyclo ring or a tricyclo ring, a monomer (a2) having a hydroxyl group, and a monomer (a3) having an N-substituted maleimide group (a The above-mentioned ethylenically unsaturated group-containing isocyanate (B) is added to the polymer (A) obtained by polymerizing the polymer (A).

Among the monomer components (a), the monomer (a1) having a dicyclo ring or a tricyclo ring in the monomer molecule is preferably a vinyl monomer capable of vinyl polymerization, for example, dicyclopentenyl (meth) acrylate, dicyclopentenyl. Oxyethyl (meth) acrylate, (meth) acrylic acid ester having a tricyclo [5.2.1.0 ^2,6 ] decyl group (for example, methacryloyloxytricyclo [5.2.1.0 ^2,6 Decane). In particular, tricyclo [5.2.1.0 ^{2, 6]} methacrylic acid with decyl ester, or tricyclo [5.2.1.0 ^{2, 6]} Methacrylic acid ester resin having a decyl group is valid . These monomers (a1) may be used alone or in combination of two or more. The amount of monomer (a1) used is 3 to 70% by weight, preferably 5 to 65% by weight, based on the total of monomer component (a) and ethylenically unsaturated group-containing isocyanate (B). Preferably it is 10 to 60% by weight. In the case of less than 3% by weight, the transparency of the resulting copolymer resin is lowered, and in the case of exceeding 70% by weight, the resulting resin has a high viscosity, so that the handling property is not good, and in a system containing a pigment, , Dispersion stability may be reduced.

  Among the monomer components (a), the monomer (a2) having a hydroxyl group is preferably a vinyl monomer capable of vinyl polymerization, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy Examples thereof include butyl (meth) acrylate and parahydroxystyrene. These monomers (a2) may be used alone or in combination of two or more. The amount of monomer (a2) used is 5 to 50% by weight, preferably 10 to 40% by weight, based on the total of monomer component (a) and ethylenically unsaturated group-containing isocyanate (B). Weight percent is more preferred. If it is less than 5% by weight, the pattern formation time is delayed, and the characteristics of the present invention cannot be obtained. When it exceeds 50% by weight, the resulting resin has a high viscosity, and the obtained resin tends to become cloudy with respect to a solvent having a low polarity.

  Among the monomer components (a), the monomer (a3) having an N-substituted maleimide group in the monomer molecule includes N-cyclohexylmaleimide, N-2-methylhexylmaleimide, N-2-ethylcyclohexylmaleimide, N-2 -Chlorocyclohexylmaleimide, N-phenylmaleimide, N-2-methylphenylmaleimide, N-2-ethylphenylmaleimide, N-2-chlorophenylmaleimide and the like. Among these, N-cyclohexylmaleimide and N-2-methylcyclohexylmaleimide are particularly preferable in terms of transparency and solubility. These N-substituted maleimides may be used alone or in combination of two or more. The amount of the monomer (a3) used is 5 to 50% by weight, preferably 10 to 40% by weight, based on the total of the monomer component (a) and the ethylenically unsaturated group-containing isocyanate (B). Weight percent is more preferred. When the amount is less than 5% by weight, sufficient adhesion of the coating film cannot be obtained with respect to adhesion during alkali development and adhesion due to thermal history. In addition, when the amount exceeds 50% by weight, the transparency may be lowered, and when a pigment or other pigment-dispersed coloring material is dispersed to form a coating film, the coating film becomes brittle and the resulting pixels are not chipped. May occur.

  In addition, when the resin composition of the present invention can be alkali-developed, a monomer (a4) further having a carboxyl group is used as the monomer component (a). As the monomer (a4), for example, vinyl monomers capable of vinyl polymerization are preferable, and examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, citraconic acid, mesaconic acid, and α-chloroacrylic acid. Can be mentioned. These monomers (a4) may be used alone or in combination of two or more. The amount of monomer (a4) used is 5 to 50% by weight, more preferably 8 to 40% by weight, based on the total of monomer component (a) and ethylenically unsaturated group-containing isocyanate (B). 10 to 30% by weight is more preferable. If it is less than 5% by weight, alkali development failure occurs when alkali development is performed, and a fine pixel pattern cannot be obtained. Further, when the pigment is dispersed, aggregation occurs in a short time, and sufficient storage stability cannot be obtained. On the other hand, if it exceeds 50% by weight, the viscosity of the resulting resin is too high to be suitable for handling, the moisture resistance of the cured coating film is lowered, and the developer resistance of the cured coating film may be lowered.

  By adding the ethylenically unsaturated group-containing isocyanate (B) to the polymer (A) obtained as described above, the resin used in the present invention is synthesized.

Specific examples of the ethylenically unsaturated group-containing isocyanate (B) represented by the general formula (1) include 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, and 2-isocyanate. Examples include -1-methylethyl (meth) acrylate, 2-isocyanate-1,1-dimethylethyl (meth) acrylate, and 4-isocyanatocyclohexyl (meth) acrylate.
Moreover, the reaction product of about 1: 1 molar ratio of the hydroxyalkyl (meth) acrylate represented by following formula (2) and the diisocyanate compound represented by following formula (3) is also mentioned.
_{CH 2 = C (R 1)} -COOR 2 OH (2)
CON-R ₃ -NCO (3)
(Here, R ₁ , R ₂ and R ₃ have the same meaning as described above, and R ₂ is preferably an ethylene group or a propylene group, more preferably a dimethylene group or a trimethylene group, and particularly preferably a dimethylene group.)

Examples of the diisocyanate compound represented by the formula (3) include hexamethylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (commonly called TDI), 4,4'-diphenylmethane diisocyanate (same MDI), 3, 5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (same IPDI), m- or p-xylylene diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, lysine diisocyanate, pyridinediyl isocyanate Etc.
Among these, industrially useful 2-isocyanatoethyl (meth) acrylate is particularly preferable.

  These ethylenically unsaturated group-containing isocyanates (B) may be used alone or in combination of two or more. The amount of the ethylenically unsaturated group-containing isocyanate (B) used in the addition reaction is 1 to 30% by weight based on the total of the monomer component (a) and the ethylenically unsaturated group-containing isocyanate (B). 3 to 20 weight% is more preferable, and 5 to 18 weight% is still more preferable. If the amount is less than 1% by weight, the heat resistance is not improved. If the amount exceeds 30% by weight, the addition reaction does not proceed, the residual monomer increases, and the dispersion stability of the dye decreases.

The weight average molecular weight of the resin used in the present invention thus obtained is in the range of 3,000 to 200,000, preferably in the range of 3,000 to 100,000, and 5,000 to 50, A range of 000 is more preferred. If the weight average molecular weight is less than 3,000, the alkali resistance decreases, and if it exceeds 200,000, the viscosity increases when used as a photosensitive solution, and the coating property tends to decrease when spin coating is performed. .
In the present specification, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

Examples of the dye used in the coloring composition of the present invention include C.I. I. Pigment Red 254 (color index name) is used as an essential component in an amount of 5 to 100% by weight based on the total amount of the pigment. If necessary, other pigments such as other pigments and dyes may be used in an amount of 95% by weight or less based on the total amount of the pigment for adjusting the chromaticity. These C.I. I. As the coloring matter other than Pigment Red 254, either a dye or a pigment can be used, but a pigment is preferable in consideration of heat resistance and light resistance.
For example, when the coloring composition of the present invention is used for forming a red image, C.I. I. Pigment Red 254 includes C.I. I. Other pigments or dyes other than CI Pigment Red 254 may be used in combination. Usually, at least one of other red pigments, yellow pigments and orange pigments is used. The amount of these chromaticity adjusting dyes is changed according to the required chromaticity. When using them, it is preferably 5 to 95% by weight based on the total pigment component.

Examples of these pigments used for chromaticity adjustment include C.I. I. Pigment Red 9, 57, 123, 155, 166, 168, 177, 180, 209, 217, 220, 224, C.I. I. Pigment Yellow 20, 24, 83, 93, 109, 110, 117, 125, 138, 139, 147, 150, 154, C.I. I. Pigment orange 38, 43, 71 and the like.
These red pigment, yellow pigment, and orange pigment for adjusting chromaticity may be used alone or in combination of two or more.

  The colored composition may contain a monomer having one or more photopolymerizable unsaturated bonds in the molecule, a photoinitiator, or the like to form a photosensitive colored resin composition, and further contains an organic solvent. Thus, a colored image forming photosensitive solution can be obtained.

  Examples of monomers having one or more photopolymerizable unsaturated bonds in the molecule include methyl methacrylate, benzyl methacrylate, butoxyethyl methacrylate, butoxytriethylene glycol acrylate, ECH (epichlorohydrin) -modified butyl acrylate, and dicyclopentanyl. Acrylate, EO (ethylene oxide) modified dicyclopentenyl acrylate, N, N-dimethylaminoethyl methacrylate, ethyl diethylene glycol acrylate, 2-ethylhexyl acrylate, glycerol methacrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl methacrylate, caprolactone modified-2- Hydroxyethyl acrylate, isobornyl acrylate, methoxydipropylene glycol Relate, methoxylated cyclodecatriene acrylate, phenoxyhexaethylene glycol acrylate, EO modified phosphoric acid acrylate, caprolactone modified tetrahydrofurfuryl acrylate, EO modified bisphenol A diacrylate, ECH modified bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4 -Butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, EO-modified phosphate diacrylate, ECH-modified phthalate diacrylate, polyethylene glycol 400 diacrylate, polypropylene Glycol 400 dimethacrylate, tetraethylene glycol Acrylate, ECH-modified 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, EO-modified phosphoric acid triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate (PO is propylene) Oxide, the same applies hereinafter), tris (methacryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, acrylates such as dipentaerythritol pentaacrylate, methacrylates corresponding to these, etc. Is mentioned. These monomers can be used alone or in combination of two or more.

Examples of the photoinitiator include benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, and benzoin methyl. Ether, benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1 -Propane, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10- 2,4,5-triarylimidazole dimers such as enanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer Examples include masses.
These photoinitiators are used individually or in combination of 2 or more types.

  Examples of the organic solvent include ketone compounds, alkylene glycol ether compounds, alcohol compounds, and aromatic compounds. Specifically, the ketone compound includes acetone, methyl ethyl ketone, cyclohexanone, and the like, and the alkylene glycol ether compound includes methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ethylene glycol monopropyl ether, ethylene Glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene Glycol monomethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol isopropyl ether acetate, diethylene glycol butyl ether acetate, diethylene glycol-t-butyl ether acetate, triethylene glycol methyl ether acetate, triethylene glycol ethyl ether acetate, There are triethylene glycol propyl ether acetate, triethylene glycol isopropyl ether acetate, triethylene glycol butyl ether acetate, triethylene glycol-t-butyl ether acetate, etc. There are til alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, 3-methyl-3-methoxybutanol, etc., and aromatic compounds such as benzene, toluene, xylene, N-methyl-2-pyrrolidone, N-hydroxymethyl- Examples thereof include 2-pyrrolidone, and other examples include organic solvents such as 3-methyl-3-methoxybutyl acetate, ethyl acetate, tetrahydrofuran, and dioxane. These can be used alone or in combination of two or more.

  The blending ratio of the resin, the dye, the monomer having one or more photopolymerizable unsaturated bonds in the molecule and the photoinitiator used in the photosensitive colored resin composition or the photosensitive solution for colored image formation is based on the total amount of these. The total resin amount is preferably 10 to 85% by weight, more preferably 20 to 60% by weight, particularly preferably 25 to 50% by weight, and the dye is preferably 5 to 70% by weight, more preferably 10 to 40%. % By weight, particularly preferably 15 to 30% by weight, and the monomer having at least one photopolymerizable unsaturated bond in the molecule is preferably 2 to 50% by weight, more preferably 5 to 45% by weight, and particularly preferably 10%. The photoinitiator is preferably 0.01 to 20% by weight, more preferably 2 to 15% by weight, and particularly preferably 5 to 10% by weight.

If the resin is too small in the photosensitive colored resin composition or the photosensitive liquid for forming a colored image, the dispersion stability of the dye tends to be lowered. There exists a tendency for the applicability | paintability at the time of spin coat to fall.
If the amount of the dye is too small, the color density of the image tends to be low, and if the amount is too large, the photosensitivity tends to decrease.

Further, if the monomer having one or more photopolymerizable unsaturated bonds in the molecule is too small, the photosensitivity tends to be low, and if too large, the dispersion stability of the dye tends to be lowered.
Furthermore, when there is too little photoinitiator, there exists a tendency for photosensitivity to become low, and when too much, there exists a tendency for adhesiveness to fall.

  The organic solvent has a total solid content of 5 to 40% by weight including a resin, a dye, a monomer containing one or more photopolymerizable unsaturated bonds in the molecule and a photoinitiator in the colored image forming photosensitive solution. It is preferable to be used. When the total solid content exceeds 40% by weight, the viscosity tends to be high and the coating property tends to be poor. If the total solid content is less than 5% by weight, the viscosity tends to be low and the applicability tends to be poor.

  In the photosensitive coloring resin composition or colored image forming photosensitive solution of the present invention, a thermal polymerization inhibitor (hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, etc.) for suppressing dark reaction, and adhesion to the substrate Of titanate coupling agents (such as silane coupling agents having vinyl group, epoxy group, amino group, mercapto group, isopropyltrimethacryloyl titanate, diisopropylisostearoyl-4-aminobenzoyl titanate) Surfactants (fluorine-based, silicon-based, hydrocarbon-based, etc.) for improving smoothness and various additives such as ultraviolet absorbers and antioxidants can be used as necessary.

Next, the manufacturing method of the coloring composition of this invention, the photosensitive coloring resin composition, and the photosensitive liquid for colored image formation is demonstrated.
The dye is mixed with a resin and an organic solvent and, if necessary, a dispersant and dispersed. At this time, the mixture is preferably subjected to a dispersion treatment by kneading using a dispersion / kneading apparatus such as an ultrasonic disperser, a triple roll, a ball mill, a sand mill, a bead mill, a homogenizer, or a kneader. At this time, it is preferable to use at least 20 parts by weight of the resin with respect to 100 parts by weight of the dye. When the amount of the resin is too small, the dispersion stability of the dye tends to decrease. The organic solvent is preferably used at least 100 parts by weight at the time of dispersion with respect to 100 parts by weight of the total amount of the dye and the resin at the time of dispersion. If the amount is less than 100 parts by weight, the viscosity at the time of dispersion is too high, and dispersion may be difficult particularly when dispersed by a ball mill, a sand mill, a bead mill or the like. As described above, a colored composition can be produced.

In order to obtain a photosensitive colored resin composition or a colored image-forming photosensitive solution, a monomer having one or more photopolymerizable unsaturated bonds in the molecule and a photoinitiator are further mixed. Mixing may be performed before or after the dispersion treatment. The whole amount of the resin may not be used at the time of dispersion, and the remainder may be mixed later, particularly at the time of producing a colored image forming photosensitive solution.
The amount of each component used is adjusted from the time of production of the colored composition so that the final blending ratio in the photosensitive colored resin composition or colored image forming photosensitive solution is obtained.

  Dispersants include anionic dispersants such as polycarboxylic acid type polymer surfactants, polysulfonic acid type polymer surfactants, nonionic dispersants such as polyoxyethylene / polyoxypropylene block polymers, anthraquinone type, perylene. Organic pigment derivatives such as carboxyl groups, sulfonate groups, carboxylic acid amide groups, and hydroxyl groups introduced into organic pigments such as phthalocyanines, phthalocyanines, and quinacridones. The dispersibility and dispersion stability of the pigment are improved, which is preferable. These pigment dispersants and organic dye derivatives are preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the dye. If it exceeds 50 parts by weight, the chromaticity tends to shift.

  In the dispersion treatment, the entire amount of the resin may be used together with the pigment during the dispersion treatment, or a part of the resin may be added after the dispersion treatment. However, it is preferable to use at least 20 parts by weight of the resin for 100 parts by weight of the dye during the dispersion treatment. If it is less than 20 parts by weight, the dispersion stability of the dye tends to decrease.

  Similarly, the entire amount of the organic solvent may be used together with the pigment during the dispersion treatment, or a part of the organic solvent may be added after the dispersion treatment. However, it is preferable to use at least 100 parts by weight of the organic solvent at the time of the dispersion treatment with respect to 100 parts by weight of the total amount of the dye and the resin at the time of the dispersion treatment. If it is less than 100 parts by weight, the viscosity at the time of dispersion treatment is too high, and dispersion may be difficult particularly when dispersed by a ball mill, sand mill, bead mill or the like.

  When manufacturing the color filter of this invention, the photosensitive coloring resin composition suitable for colored images, such as red, green, blue, and black, is used. Usually, the photosensitive colored resin composition and the colored image forming photosensitive solution of the present invention are used for the production of a red colored image. The photosensitive colored resin composition and the colored image forming photosensitive solution used for forming colored images of other colors are suitable for each colored image in the photosensitive colored resin composition and the colored image forming photosensitive solution of the present invention. You may use what changed into the thing. Further, the resin may be appropriately changed to other resins usually used in the photosensitive colored resin composition and the colored image forming photosensitive solution.

  As dyes used for forming colored images such as blue, green and black, both dyes and pigments can be used, but pigments are preferred in view of heat resistance and light resistance. There are inorganic and organic pigments, and both can be used.

  For a blue colored image, a single blue pigment system may be used, or toning may be performed by mixing a violet pigment system with a blue pigment system. Examples of the blue pigment system include Pigment Blue 15, 15: 3, 15: 4, 15: 6, 22, 60, 76 and the like by color index name. Moreover, as a purple pigment type | system | group, pigment violet 10, 19, 23, 29, 37, 50 etc. are mentioned by the color index name, for example. These blue and purple pigments can be used in combination of two or more. When a blue pigment system and a violet pigment system are used in combination, the violet pigment system is preferably used in an amount of 90 parts by weight or less based on 100 parts by weight of the total amount of the blue pigment system and the violet pigment system.

  For a green colored image, a single green pigment system may be used, or a yellow pigment system may be mixed with a green pigment system to perform toning. Examples of the green pigment system include pigment green 7, 36, and 37 as color index names. Examples of the yellow pigment system include pigment yellow 17, 20, 24, 83, 93, 109, 110, 117, 125, 128, 129, 183, 139, 147, 154, etc. . Two or more of these green and yellow pigments can be mixed and used. When a green pigment system and a yellow pigment system are mixed and used, it is preferable to use the yellow pigment system at 90 parts by weight or less with respect to 100 parts by weight of the total amount of the green pigment system and the yellow pigment system.

  For black colored images, for example, black pigments such as carbon black, graphite, titanium carbon, black iron oxide, and manganese dioxide are used.

  In order to form a photosensitive layer on a substrate using the photosensitive colored resin composition, a colored image forming solution is directly applied to the substrate, or the photosensitive solution is once applied to a support and formed into a film. It can be carried out by forming it on a substrate.

  The substrate is selected depending on the application, for example, a transparent glass plate such as white plate glass, blue plate glass, silica-coated blue plate glass, a synthetic resin sheet such as polyester resin, polycarbonate resin, acrylic resin, vinyl chloride resin, Examples include a film or plate, a metal plate such as an aluminum plate, a copper plate, a nickel plate, and a stainless steel plate, other ceramic plates, and a semiconductor substrate having a photoelectric conversion element. These substrates may be previously formed with a black matrix by chromium vapor deposition or the like.

Examples of the method for applying the photosensitive solution to the substrate include roll coater coating, spin coater coating, spray coating, whaler coating, dip coater coating, curtain flow coater coating, wire bar coater coating, gravure coater coating, and air knife coater coating. After application, it is preferable to dry at a temperature of 50 to 130 ° C. for 1 to 30 minutes. In this way, a film made of a colored image forming material can be obtained.
The thickness of the photosensitive layer thus formed is appropriately determined depending on the application, but is preferably in the range of 0.1 to 300 μm. Moreover, when using for a color filter, it is preferable to be set as the range of 0.2-5 micrometers.

  A photosensitive layer can be formed on the support in the same manner as described above. In order to form the photosensitive layer on the substrate, there is a method in which a film is stacked on the substrate and pressure-bonded through a roller. At this time, it is preferable to slightly heat the roller. Moreover, it is preferable to perform pressure bonding under reduced pressure. The support is preferably peeled off after forming a photosensitive layer on the substrate. As the support, a polyethylene film, an acrylic resin film, a polyester film, or the like can be used.

  The photosensitive layer formed on the substrate can be exposed by irradiating the photosensitive layer with an actinic ray in an image form. Thereby, the film | membrane of an exposure part can be hardened. At the time of exposure, an oxygen barrier film such as polyvinyl alcohol may be formed on the surface of the film with a thickness of 0.5 to 30 μm and exposed from above.

As the actinic ray light source, for example, a carbon arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a visible light laser, and the like are suitable. Actinic rays are irradiated in an image form by performing pattern exposure through a photomask or direct drawing by scanning using these light sources.
Following the exposure, a development process is performed.

  An aqueous solution containing an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate or sodium metasilicate, an organic base such as monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, triethylamine or n-butylamine, or a salt. A colored image pattern of a cured film corresponding to an image can be obtained by removing a non-exposed portion by spraying a developer such as (alkaline developer) or an organic solvent or immersing the developer in a developer.

  After development, post-baking is preferably performed in order to further harden the colored image pattern. The post-baking temperature is preferably 60 to 280 ° C., and the heating time is preferably about 1 to 60 minutes.

  A colored image can be obtained by such a colored image forming step. In particular, in the method for producing a color filter, the colored image forming step is repeated for different colored images of 3 to 4 colors including the green image forming step. Is preferred. For example, colored images of red, green, and blue are formed on a black matrix previously formed by chromium vapor deposition or the like. Moreover, after forming a black matrix using a black colored image forming material, red, green and blue colored images are formed. Further, after forming red, green, and blue colored images, a black matrix is formed using a black image forming material in the gaps between these colored images. The order of forming red, green and blue colored images is arbitrary. The colored image is made to form pixels for each color.

EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not restrict | limited by these.
A blending table of materials used for synthesizing the resins used in Examples and Comparative Examples is shown in Table 1, and a method for synthesizing the resins is shown below.
Table 2 shows the color image-forming photosensitive solution compositions used in the examples and comparative examples.
Table 3 shows the heat resistance evaluation of the color image forming photosensitive solutions of Examples and Comparative Examples.

<Synthesis of Resin A>
(A) 320 g of propylene glycol monomethyl ether acetate was weighed in a 1-liter four-necked flask, and the liquid temperature was kept at 90 ° C. while bubbling with N ₂ . (B) 275 g of propylene glycol monomethyl ether acetate, methacryloyloxytricyclo [5.2.1.0 ^2,6 ] decane (manufactured by Hitachi Chemical Co., Ltd., FANCYL FA-513M) in a 1 liter beaker, 45 g of N-cyclohexylmaleimide and 45 g of 2-hydroxyethyl methacrylate were mixed and dissolved while bubbling with N ₂ . After confirming the dissolution of N-cyclohexylmaleimide, 3 g of 2,2′-azobisisobutyronitrile was dissolved. The solution obtained in (B) was continuously added dropwise to propylene glycol monomethyl ether acetate at 90 ° C. in the four-necked flask of (A) over 3 hours, and then kept at 90 ° C. for 3 hours.
While maintaining at 90 ° C. for 3 hours, 0.6 g of 2,2′-azobisisobutyronitrile previously dissolved in 40 g of propylene glycol monomethyl ether acetate was divided into several times to reduce the residual monomer. Added. After performing the reaction at 90 ° C. for a total of 6 hours, the liquid temperature was raised to 120 ° C., and then kept at 120 ° C. for 1 hour and naturally cooled. Furthermore, 31 g of 2-isocyanatoethyl methacrylate and 0.3 g of dibutyltin laurate were added and stirred at 70 ° C. for 4 hours to obtain Resin A shown in Table 1. The weight average molecular weight of the resin was 25,000.

<Synthesis of Resin B>
(A) 320 g of propylene glycol monomethyl ether acetate was weighed in a 1-liter four-necked flask, and the liquid temperature was kept at 90 ° C. while bubbling with N ₂ . (B) 275 g of propylene glycol monomethyl ether acetate, methacryloyloxytricyclo [5.2.1.0 ^2,6 ] decane (manufactured by Hitachi Chemical Co., Ltd., FANCYL FA-513M) in a 1 liter beaker, 45 g of N-cyclohexylmaleimide, 45 g of 2-hydroxyethyl methacrylate, and 34 g of methacrylic acid were mixed and dissolved while bubbling with N ₂ . After confirming the dissolution of N-cyclohexylmaleimide, 3 g of 2,2′-azobisisobutyronitrile was dissolved. The solution obtained in (B) was continuously added dropwise to propylene glycol monomethyl ether acetate at 90 ° C. in the four-necked flask of (A) over 3 hours, and then kept at 90 ° C. for 3 hours.
While maintaining at 90 ° C. for 3 hours, 0.6 g of 2,2′-azobisisobutyronitrile previously dissolved in 40 g of propylene glycol monomethyl ether acetate was divided into several times to reduce the residual monomer. Added. After performing the reaction at 90 ° C. for a total of 6 hours, the liquid temperature was raised to 120 ° C., and then kept at 120 ° C. for 1 hour, followed by natural cooling. Furthermore, 31 g of 2-isocyanatoethyl methacrylate and 0.3 g of dibutyltin laurate were added, and the mixture was stirred at 70 ° C. for 4 hours to obtain a resin B described in Table 1. The weight average molecular weight of the resin was 25,000.

<Synthesis of Resin C>
(A) 340 g of propylene glycol monomethyl ether acetate was weighed in a 1-liter four-necked flask, and the liquid temperature was kept at 90 ° C. while bubbling with N ₂ . (B) In a 1 liter beaker, 295 g of propylene glycol monomethyl ether acetate, 160 g of benzyl methacrylate, 34 g of 2-hydroxyethyl methacrylate and 34 g of methacrylic acid were mixed and dissolved while bubbling with N ₂ . After confirming the dissolution, 3 g of 2,2′-azobisisobutyronitrile was dissolved. The solution obtained in (B) was continuously added dropwise to propylene glycol monomethyl ether acetate at 90 ° C. in the four-necked flask of (A) over 3 hours, and then kept at 90 ° C. for 3 hours.
While maintaining at 90 ° C. for 3 hours, 0.6 g of 2,2′-azobisisobutyronitrile previously dissolved in 40 g of propylene glycol monomethyl ether acetate was divided into several times to reduce the residual monomer. Added. After performing the reaction at 90 ° C. for a total of 6 hours, the liquid temperature was raised to 120 ° C., and then kept at 120 ° C. for 1 hour and naturally cooled to obtain Resin C shown in Table 1. The weight average molecular weight of the resin was 23,000.

Example 1
(1) Production of colored image forming sensitizing solution: 250 g of diethylene glycol dimethyl ether, 60 g of resin A, C.I. I. Pigment Red 254: 36 g was added and dispersed for 2 hours using a bead mill.
To this dispersion (220 g), dipentaerythritol hexaacrylate (35 g) as a monomer, benzophenone (6 g), N, N′-tetraethyl-4,4′-diaminobenzophenone (3 g) and diethylene glycol dimethyl ether (125 g) as a photoinitiator were added and mixed. A photosensitive solution containing a photosensitive colored resin composition having the composition shown in Table 2 was obtained.

(2) Evaluation of heat resistance of colored image forming photosensitive solution The photosensitive solution of (1) is applied on a glass substrate (Corning, product name 7059) by spin coating, and further dried at 110 ° C. for 5 minutes. A film having a thickness of 2.0 μm was formed.
The obtained film was exposed to 100 mJ / cm ² with an ultrahigh pressure mercury lamp.
The exposed film was post-baked at 200 ° C. for 30 minutes, and the chromaticity was measured.
The film after chromaticity measurement was post-baked at 200 ° C. for 60 minutes, and then post-baked at 280 ° C. for 60 minutes, and the presence or absence of precipitates was observed with an optical microscope. The evaluation results are shown in Table 3.

Example 2
A colored image forming photosensitive solution was prepared in the same manner as in Example 1 except that the resin used was changed to resin B in the production of the colored image forming photosensitive solution. This composition is shown in Table 2.
With this photosensitive solution, the heat resistance of the colored image forming photosensitive solution was evaluated in the same manner as in Example 1 (2). The evaluation results are shown in Table 3.

Comparative Example 1
A colored image forming photosensitive solution was prepared in the same manner as in Example 1 except that the resin used was changed to resin C in the production of the colored image forming photosensitive solution. This composition is shown in Table 2.
With this photosensitive solution, the heat resistance of the colored image forming photosensitive solution was evaluated in the same manner as in Example 1 (2). The evaluation results are shown in Table 3.

Claims (8)

Pigment Red 254 with a color index name of 5 to 100% by weight based on the total amount of the dye, and a resin having a molecular weight of 3,000 to 200,000 in weight average molecular weight (Mw) In the colored composition, the resin polymerizes a monomer component (a) containing a monomer (a1) having a dicyclo ring or a tricyclo ring, a monomer (a2) having a hydroxyl group and a monomer (a3) having an N-substituted maleimide group. A resin synthesized by adding an ethylenically unsaturated group-containing isocyanate (B) represented by the following general formula (1) to the polymer (A) obtained as described above, and the monomer component (a) and the ethylenic component The amount of monomer (a1) used is 3 to 70% by weight, the amount of monomer (a2) used is 5 to 50% by weight, and the amount of monomer (a3) used is the total of unsaturated group-containing isocyanate (B). 5-50% by weight, Eth Coloring composition amount of emissions unsaturated group-containing isocyanate (B) is characterized in that 1 to 30 wt%.
_{CH 2 = C (R 1)} -COO-X-NCO (1)
[Wherein, R ₁ represents a hydrogen atom or a methyl group, X represents a linear or branched alkylene group having 2 to 6 carbon atoms, or —R ₂ —OCONH—R ₃ — (R ₂ represents carbon the number represents 2-6 linear or branched alkylene group, R ₃ is represented.) the divalent R ₃ groups of the diisocyanate compound represented by CON-R ₃ -NCO. ]   The monomer component (a) further contains a monomer (a4) having a carboxyl group, and the amount of the monomer (a4) used is relative to the total of the monomer component (a) and the ethylenically unsaturated group-containing isocyanate (B). The coloring composition according to claim 1, wherein the coloring composition is 5 to 50% by weight.   A photosensitive colored resin composition comprising the colored composition according to claim 1 or 2, a monomer containing one or more photopolymerizable unsaturated bonds in the molecule, and a photoinitiator.   A photosensitive liquid for colored image formation comprising the photosensitive colored resin composition according to claim 3 and an organic solvent.   A method for producing a colored image, comprising forming a photosensitive layer comprising the photosensitive colored resin composition according to claim 3 on a substrate, and performing exposure and development.   A method for producing a colored image, comprising: applying a photosensitive solution for forming a colored image according to claim 4 on a substrate; drying the photosensitive layer to form a photosensitive layer made of a photosensitive colored resin composition; and exposing and developing the photosensitive layer. .   A method for producing a color filter, comprising a step of forming a colored image by the method for producing a colored image according to claim 5.   A color filter made by the production method according to claim 7.