JPH1020490A - Color photosensitive resin composition, color image forming material, production of color filter and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter in which excellent adhesion with a substrate is obtd., blurs are suppressed to such a level that causes no problem, and high contrast display is possible, and to provide a production method of this color filter, and a color photosensitive resin compsn. and color image forming material from which the color filter can be produced. SOLUTION: This compsn. consists of a polymer prepared by polymn. of unsatd. carboxylic acid and unsatd. monomers copolymerizable with the carboxylic acid, at least one kind of monomer having at least one unsatd. bond in one molecule, a photopolymn. initiator, a dye having >=200 deg.C thermal decomposition temp. and a thermosetting agent which causes crosslinking reaction at 130 to 250 deg.C. The compsn. contains, by weight, 20 to 77% polymer, 20 to 60% to monomer, 0.01 to 20% photopolymn. initiator, 1 to 30% dye and 1 to 40% thermosetting agent of the sum weight of the polymer, monomers, photopolymn. initiator, dye and thermosetting agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art In recent years, home video cameras have been required to be smaller and lighter, and their image pickup devices are being replaced with solid-state image pickup devices from existing image pickup tubes. In such a situation, a color solid-state imaging device is manufactured by forming a color filter in which patterns colored in each color are accurately arranged on a photodiode, and obtains a high-resolution full-color image. On the other hand, a liquid crystal color display has a first multilayer structure (having a color filter, a protective film, a transparent electrode having a matrix pattern, an insulating film, and an alignment film in this order on a transparent substrate such as glass) and a second multilayer structure. A multilayer structure (having a transparent electrode, insulating film, and alignment film in this order on a transparent substrate such as glass or the like on a transparent substrate) is opposed to each other with the alignment film surface inside, and a spacer is interposed therebetween. In this structure, a cell in which liquid crystal is sealed is sandwiched between two polarizing plates. In the first multilayer structure, a transparent electrode having a matrix-like pattern may be provided on a transparent substrate under a color filter. A color filter used in such an application has a structure in which red, blue, and green striped images or dot images are respectively arranged on a substrate, and in some cases, each boundary is divided by a black matrix.

Conventionally, various materials such as a colored photosensitive resin composition, a color filter using the same, and a method for producing the same have been known for producing a color filter. Have the advantages and disadvantages.
For example, a natural protein (gelatin, casein, etc.) is sensitized with dichromate or the like, exposed and developed through a desired mask pattern, and the layer to be dyed is dyed with a red dye to form a red filter component. , Then, after applying an anti-staining film, forming a layer to be dyed, forming a green filter component with a green dye, and forming a blue filter component in the same manner to produce a color filter. In such a method, a color filter having features such as high definition of a pattern and excellent color characteristics is manufactured. However, in such a method, since three-color pixels are repeatedly formed, anti-dyeing treatment is required for each color, which complicates the manufacturing process, increases the cost, and furthermore, smoothes the surface and weather resistance of the dye. Is bad.

On the other hand, one method for forming a colored image on a substrate using a colored photosensitive resin composition is disclosed in Japanese Patent Laid-Open No. 3-282.
No. 404. In general, image formation using a photosensitive resin composition is used in a wide range of fields such as printed wiring boards, printed boards, IC circuits, and color proofing, and there are various methods depending on the application and form. In any case, the method generally includes a step of providing a photosensitive resin layer on a substrate, a step of pattern exposure, and a step of developing. Among these steps, a typical developer used in the developing step is an organic solvent-based developer,
They are broadly classified into alkaline aqueous solutions or aqueous systems, and in recent years, from the viewpoints of working environment, air and water pollution, the transition to photosensitive resin compositions that can be developed with alkaline aqueous solutions or water is in progress.

In this method, a colored photosensitive resin layer is provided on an ultraviolet-transparent temporary support, and the photosensitive resin layer of the image forming material is provided on a support which may have an adhesive layer. The photosensitive resin layer is exposed to a pattern through the temporary support, and after the temporary support is peeled off, it is developed with an alkaline aqueous solution to form a pattern. If necessary, the pattern is applied to the adhesive layer. After embedding in the image, an image forming material having a color different from the first color is brought into close contact and exposure and development are repeated to obtain a multicolor colored image. This method has advantages such as high alignment accuracy, easy control of the concentration of each color by adjusting the thickness of the colored photosensitive resin layer, and development with an alkaline aqueous solution. Can be However, after image formation with the colored photosensitive resin layer, it is necessary to remove unnecessary portions,
Conventionally, most of unnecessary portions have been removed by dissolving in an organic solvent. However, many organic solvents are flammable, and even if they are nonflammable, they are toxic.
A method for removing unnecessary components without using an organic solvent has been desired. As one of the methods, it is conceivable to layer a photosensitive resin composition developable with an alkaline aqueous solution. However, in order to repeat the development using an alkaline aqueous solution, the properties of each composition must be changed. Generally, it is the binder component of the photosensitive resin composition that determines properties such as solubility and thermal softening property of the photosensitive resin composition.

[0006] As a representative document relating to a photosensitive resin composition developable with an aqueous alkali solution, there is Japanese Patent Publication No. 35-14 / 1973.
No. 065 (the binder is a polymer containing a side-chain oxyacid), and JP-B-46-32714 (the binder is, for example, a methyl methacrylate / methacrylic acid copolymer), and JP-B-54. JP-A-34327 (the binder is, for example, a terpolymer of methyl methacrylate / 2-ethylhexyl methacrylate / methacrylic acid), and JP-B-55-38961 (the binder is, for example, Styrene / maleic acid mono-n-butyl ester copolymer, etc., and JP-B-56-33413 (the binder is, for example, a terpolymer of methyl methacrylate / ethyl acrylate / methacrylic acid). Yes), Japanese Patent Publication No. 55-3896
No. 1 (the binder is, for example, a styrene / methyl methacrylate / ethyl acrylate / methacrylic acid quaternary copolymer), and JP-A-52-99810 (the binder is, for example, methacrylic acid). Benzyl / methacrylic acid copolymer), and JP-B-58-12577 (the binder is, for example, a terpolymer of acrylonitrile / 2-ethylhexyl methacrylate / methacrylic acid). JP-B-55-6210 (Binders include, for example, two kinds of methacrylate / ethyl acrylate / acrylate terpolymer and styrene / maleic anhydride copolymer partially esterified with isopropanol). ) And JP-A-58-1142 (the binder is, for example, methyl methacrylate / methacrylic acid / acrylic acid 2).
-Ethylhexyl terpolymer, methyl methacrylate /
Methacrylic acid / 2-ethylhexyl acrylate / n-butyl methacrylate quaternary copolymer). However, the photosensitive resin compositions listed in these documents are excellent, but in order to be used as a color filter, it is necessary to further color the photosensitive resin composition. Or, it is roughly classified into a method of coloring with a pigment. It is presumed that the dye exists in a molecular order in the color filter, but the pigment is insoluble in the solvent, and therefore differs greatly in that it is dispersed as particles of about 0.1 μm. Although pigment-based color filters have many merits, they have a depolarizing effect, and therefore have a problem that display contrast ratio is remarkably inferior. Applications such as solid-state imaging devices that require high resolution and fine patterns Not suitable for Further, since high contrast display is required in the TFT-LCD, this is a serious problem.

When a dye is used in combination with a photosensitive resin composition, high contrast display can be achieved, and full color,
A multi-tone color filter can be realized. When a dye is used in combination with a photosensitive resin composition, a method of forming a color image by dyeing a film formed using the colorless photosensitive resin composition in a dye solution and dissolving the dye to form a colored image There is a method for producing a colored image using a photosensitive resin composition. Among them, the method of dyeing a film formed using a colorless photosensitive resin composition with a dyeing solution, like the conventional dyeing method described above, involves a complicated manufacturing process and high costs. Can not solve the point. On the other hand, when a colored photosensitive resin composition formed by dissolving a dye is used, the dye is uniformly compatible with the polymer / monomer / solvent at the molecular level, but is coated and dried on a support. In the process, the dye molecules are segregated on the surface, so that the adhesion to the transparent substrate is reduced, and the colored photosensitive resin layer is separated from the substrate in the step of separating or developing the support. The degree of segregation of the dye on the surface is affected by the amount and polarity of the dye, polymer, monomer, solvent, etc., but changing only one of these components significantly changes the degree of segregation, and therefore the adhesion. It changes significantly. As a method for improving the adhesion between the substrate and the colored photosensitive resin layer, Japanese Patent Publication No. 4-77282 discloses a method using a substrate having a pressure-sensitive or heat-sensitive adhesive surface, Japanese Patent Application Laid-Open No. 3-282404, and Japanese Patent Application Laid-Open No. 143704, JP-A-3-28
No. 2404 and Japanese Patent Application Laid-Open No. 5-80213,
Method using a substrate having a photosensitive adhesive layer.
JP-A-212623 discloses a method of providing a transparent adhesive layer using various adhesives, JP-A-63-155127, JP-A-63-155105, and JP-A-2-1614.
Japanese Patent Application Laid-Open No. 02-317001 discloses a method in which a silane coupling agent is coated on a substrate or a silane coupling agent is added to a colored resin. A method of treating a substrate with a ring agent is disclosed. The method of improving adhesion by providing an adhesive layer is liable to cause fogging (bleeding) in the non-image area after development due to mixing at the interface between the adhesive layer and the colored photosensitive layer. It is necessary to provide an intermediate layer (which may contain a photosensitive composition) between the layer and the colored photosensitive layer. On the other hand, when an adhesive which does not easily cause fogging (bleeding) is selected, there are disadvantages such as insufficient adhesion to the material to be transferred. Further, the method of providing the adhesive layer and the method of performing the silane coupling treatment have a drawback that the cost of producing a color filter is increased. Therefore, the depolarizing effect is small and the contrast is high.
In addition, a colored image forming material and a color filter having good adhesion without providing an adhesive layer or treating with a silane coupling agent are desired.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a colored photosensitive resin composition capable of forming a colored image forming material for producing a color filter having good adhesion.

Another object of the present invention is to provide a colored photosensitive resin composition capable of forming a colored image forming material for producing a color filter having better adhesion.

Another object of the present invention is to provide a colored image forming material for producing a color filter having good adhesion to a substrate.

Another object of the present invention is to provide a method for producing a color filter which has good adhesion during production, has general performance as a color filter, and is capable of high-contrast display with a small depolarizing effect. And

Another object of the present invention is to provide a color filter which has good adhesion at the time of production, has general performance as a color filter, and is capable of high contrast display with a small depolarizing effect. I do.

[0013]

Means for Solving the Problems The inventors of the present invention have studied to solve the above-mentioned problems, and as a result, have found that a colored photosensitive resin composition having a specific composition containing a dye has a specific surface tension characteristic. When forming a colored image forming material having, the colored image forming material is less segregated on the surface of the dye molecules,
The inventors have found that they have excellent adhesion to a transparent substrate, and have completed the present invention based on this finding.

That is, the present invention relates to a polymer (A) obtained by polymerizing an unsaturated carboxylic acid and another unsaturated monomer copolymerizable therewith with at least one unsaturated carboxylic acid per molecule. At least one monomer having a bond (B), a photopolymerization initiator (C), a dye (D) having a thermal decomposition temperature of 200 ° C. or higher, and a thermosetting agent that causes a crosslinking reaction at 130 ° C. to 250 ° C. E), the polymer (A) being 20 to 77 in the total amount of the polymer (A), the monomer (B), the photopolymerization initiator (C), the dye (D) and the thermosetting agent (E). % By weight, 20 to 60% by weight of the monomer (B), and 0.01 to 2% of the photopolymerization initiator (C).
A colored photosensitive resin composition containing 0% by weight, a dye (D) of 1 to 30% by weight, and a thermosetting agent (E) of 1 to 40% by weight, wherein the colored photosensitive resin composition is dissolved in a solvent. The dissolved solution is applied on a support, and heated at a temperature lower than a temperature at which a crosslinking reaction of the thermosetting agent (E) is caused to remove the solvent to form a film having a thickness of 2 μm.
m, the surface tension dispersing force component γ _sd and the surface tension polarity component γ _{sp of} the obtained film are 12.5 mN / m <γ _sp <35 mN / m, 12.5 mN / m <γ _sd < An object of the present invention is to provide a colored photosensitive resin composition characterized by satisfying 35 mN / m, 30 mN / m <γ _sd + γ _sp <55 mN / m.

The present invention also relates to a colored image forming material formed by applying a solution obtained by dissolving the colored photosensitive resin composition of the present invention in a solvent on a transparent support and drying the same. The component γ _sd and the surface tension polarity component γ _sp are 12.5 mN / m <γ _sp <35 mN / m, 12.5 mN / m <γ _sd <35 mN / m, 30 mN / m <γ _sd + γ _sp <55 mN / m. The present invention provides a colored image forming material characterized in that:

The present invention also relates to a step (a) of laminating the colored image forming material of the present invention such that the colored photosensitive resin layer is in contact with the transparent substrate, (B), exposing the support (c), and removing the unexposed portion of the colored photosensitive resin layer on the substrate using a developing solution (d). And a step (e) of heating a colored image formed by development using a plurality of different colored image forming materials each time for the same substrate, and sequentially repeating the process a plurality of times. It provides the law.

The present invention also provides a color filter obtained by the method of the present invention.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The polymer (A) in the colored photosensitive resin composition of the present invention is a polymer obtained by polymerizing an unsaturated carboxylic acid and another unsaturated monomer copolymerizable therewith. The unsaturated carboxylic acid used in the synthesis of this polymer includes, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and half-esterified products thereof. These unsaturated carboxylic acids are used alone or in combination of two or more. The proportion of unsaturated carboxylic acid used in the synthesis of this polymer is
The total amount of monomers used for the synthesis of the polymer (A), that is,
It is preferably from 1 to 95 mol%, more preferably from 10 to 70 mol%, based on the total amount of unsaturated carboxylic acid and other unsaturated monomers. When the use ratio is less than 1 mol%, a colored photosensitive resin composition exhibiting sufficient developability tends not to be obtained, and when it exceeds 95 mol%, it tends to adversely affect the formation of a colored image.

Other unsaturated monomers copolymerizable with the unsaturated carboxylic acid used in the synthesis of the polymer (A) include, for example, ester monomers (methyl ester, ethyl ester) of acrylic acid or methacrylic acid. , N-propyl ester, iso-propyl ester, n-butyl ester, iso-butyl ester, sec-butyl ester, tert-butyl ester, pentyl ester, hexyl ester, heptyl ester, 2-ethylhexyl ester, octyl ester, nonyl ester , Decyl ester, dodecyl ester, tridecyl ester,
Tetradecyl ester, hexadecyl ester, octadecyl ester, eicosyl ester, docosyl ester, cyclopentyl ester, cyclohexyl ester, cycloheptyl ester, benzyl ester, phenyl ester, methoxyethyl ester, dimethylaminoethyl ester, dimethylaminopropyl ester,
2-chloroethyl ester, 2-fluoroethyl ester, 2-cyanoethyl ester, methoxydiethylene glycol ester, methoxydipropylene glycol ester, methoxytriethylene glycol ester, etc., styrene monomers (styrene, α-methylstyrene, pt- Butylstyrene, etc.), polyolefin monomers (butadiene, isoprene, chloroprene, etc.), vinyl monomers (vinyl chloride, vinyl acetate, etc.), nitrile monomers (acrylonitrile, methacrylonitrile, etc.)
And the like. These unsaturated monomers are used alone or in combination of two or more.

The polymer (A) used in the present invention can be synthesized, for example, by polymerizing a solution containing an unsaturated carboxylic acid, other monomers and a radical polymerization catalyst dropwise in an organic solvent. . The reaction temperature at the time of polymerization is preferably 0 to 180 ° C, and 40 to 1 ° C.
More preferably, the temperature is set to 70 ° C. The reaction temperature is 0 ° C
If it is less than 1, the polymerization reaction tends to be insufficient, and
When the temperature exceeds ℃, the radical polymerization catalyst tends to be deactivated before the polymerization reaction is caused. The dropping time during the polymerization is preferably from 1 to 10 hours, more preferably from 2 to 6 hours. If the dropping time is less than 1 hour, the polymerization reaction tends not to proceed sufficiently, and if it exceeds 10 hours, the molecular weight of the resulting polymer tends to be too high.

The organic solvent used in the polymerization is not particularly limited as long as it has no reactivity with the unsaturated carboxylic acid and dissolves the copolymer formed during the copolymerization reaction. Examples of these organic solvents include alcohol solvents (ethanol, propanol, isopropanol, butanol, isobutanol, benzyl alcohol, etc.), polyalkylene glycol solvents (methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene Glycol dimethyl ether, ethylene glycol monoacetate, etc.), aromatic hydrocarbon solvents (toluene, xylene, etc.), ester solvents (ethyl acetate,
Butyl acetate), ketone solvents (cyclohexanone, methyl isobutyl ketone, etc.), halogen solvents (carbon tetrachloride, trichloroethane, etc.) and the like. These organic solvents are used alone or in combination of two or more. Further, water having no problem of environmental pollution can be used as one kind of the solvent. The use ratio of these solvents is preferably 2 to 4 times the weight of the total amount of the monomers used for the synthesis of the polymer (A). If the use ratio of the organic solvent is less than 2 times, the polymerization reaction tends to not proceed smoothly, and if it exceeds 4 times, the reaction time tends to be long.

As the radical polymerization catalyst used in the polymerization, an initiator such as an azo compound and a peroxide compound used in a usual radical polymerization can be used.
For example, 2,2'-azobis (4-methoxy-2,4-
Dimethylvaleronitrile), 2,2'-azobis (cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile), 2, 2'-azobis (2
-Methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, benzoyl peroxide, di-tert-butylperoxybenzoate And the like. The proportion of the radical polymerization catalyst used is preferably from 0.1 to 5% by weight, and more preferably from 0.2 to 4% by weight, based on the total amount of the monomers used for the synthesis of the polymer (A). Is more preferable.
If the use ratio is less than 0.1% by weight, the polymerization reaction tends not to be completed, and if it exceeds 5% by weight, only a polymer having a small molecular weight tends to be obtained. The weight average molecular weight of the obtained polymer is preferably from 5,000 to 200,000, more preferably from 10,000 to 100,000. This weight average molecular weight is 5,000
If it is less than 0, it tends to be difficult to form a film as a resin, and if it exceeds 200,000, it tends to be high in viscosity and difficult to handle. The weight average molecular weight in the present invention is a value measured by a gel permeation chromatography method and converted using a standard polystyrene calibration curve.

Further, a chain transfer agent can be blended during polymerization for the purpose of controlling the molecular weight. Examples of usable chain transfer agents include, for example, methanethiol, ethanethiol, n-propanethiol, iso-propanethiol, n-butanethiol, 2-methylpropanethiol, 3-methylpropanethiol, 1,1-dimethylethanethiol , 1-hexanethiol, 1-octanethiol, 1-decanethiol, benzenethiol, 2-
Methylbenzenethiol, 3-methylbenzenethiol, 4-methylbenzenethiol, 2-ethylbenzenethiol, 3-ethylbenzenethiol, 4-ethylbenzenethiol, bis (4-hydroxydimethylphenyl) disulfide, bis (2-chloromethylphenyl)
Disulfide, bis (2-bromomethylphenyl) disulfide, dinaphthyl disulfide, di-2-benzothiazodisulfide, α-methylstyrene dimer, carbon tetrachloride, carbon tetrabromide, chloroform and the like. The amount of the chain transfer agent can be appropriately selected depending on the molecular weight of the target polymer (A).

The monomer (B) having one or more unsaturated bonds used in the present invention includes, for example, the following general formula (I)

[0025]

Embedded image [Wherein, R ¹ represents a hydrogen atom or a methyl group, Y represents a saturated or unsaturated hydrocarbon group which may have a substituent, a heterocyclic residue, a polyalkylene glycol residue, or

[0026]

Embedded image (Wherein R ² each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or a trifluoromethyl group, m and n each independently represent an integer of 1 to 20), and k is 1 And an integer of from 10 to 10].

Examples of the optionally substituted saturated or unsaturated hydrocarbon residue and heterocyclic residue represented by Y in the general formula (I) include, for example, those having 1 to 22 carbon atoms. Linear, branched or alicyclic alkane residues (methane residue, ethane residue, propane residue, cyclopropane residue, butane residue, isobutane residue, cyclobutane residue, pentane residue, isopentane residue, Neopentane residue, cyclopentane residue, hexane residue, cyclohexane residue, heptane residue, cycloheptane residue, octane residue, nonane residue, decane residue, etc.), and an aromatic ring residue having 6 to 22 carbon atoms. Groups (benzene, naphthalene, anthracene, biphenyl,
A heterocyclic residue having 4 to 22 carbon atoms (furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyridine, pyrimidine, pyrazine,
Triazine, quinoline, quinoxalin and the like). In addition, examples of the substituent which these hydrocarbon residue and heterocyclic residue may have include a halogen atom, a hydroxyl group, an amino group, a carboxyl group and the like.

Specifically, examples of the monomer having one unsaturated bond include, for example, ester monomers of acrylic acid or methacrylic acid (methyl ester, ethyl ester,
n-propyl ester, iso-propyl ester, n
-Butyl ester, iso-butyl ester, sec-
Butyl ester, tert-butyl ester, pentyl ester, hexyl ester, heptyl ester, 2-
Ethylhexyl ester, octyl ester, nonyl ester, decyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, hexadecyl ester, octadecyl ester, eicosyl ester, docosyl ester, cyclopentyl ester, cyclohexyl ester, cycloheptyl ester, benzyl ester Phenyl ester, methoxyethyl ester, dimethylaminoethyl ester, dimethylaminopropyl ester, 2-chloroethyl ester, 2-fluoroethyl ester, 2-cyanoethyl ester, methoxydiethylene glycol ester, methoxydipropylene glycol ester, methoxytriethylene glycol ester Styrene-based monomers (styrene, α-methylstyrene, pt Butyl styrene, etc.), polyolefin-based monomer (butadiene, isoprene, chloroprene, etc.), vinyl monomers (vinyl chloride, vinyl acetate, etc.),
Nitrile monomers (acrylonitrile, methacrylonitrile, etc.), 1- (methacryloxyethoxycarbonyl)
-2- (3'-chloro-2'-hydroxypropoxycarbonyl) benzene and the like. Examples of the monomer having two unsaturated bonds include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene. Glycol di (meta)
Acrylate, hexapropylene glycol di (meth)
Acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
1,3-butanediol di (meth) acrylate, 1,
4-butanediol di (meth) acrylate, 1,5-
Pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane di (meth) acrylate, bisphenol A di (meth) acrylate, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4
-(Meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane (in the above general formula (I), Y is

[0029]

Embedded image (Wherein, m and n are each independently an integer of 1 to 20)
Is)

[0030]

Embedded image Bisphenol A diglycidyl ether di (meth) acrylate, urethane diacrylate compound, and the like.

Examples of the monomer having three unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, and trimethylolpropane. Triglycidyl ether tri (meth) acrylate,

[0032]

Embedded image And the like.

Examples of the monomer having four unsaturated bonds include, for example, tetramethylolpropanetetra (meth)
Acrylate, pentaerythritol tetra (meth) acrylate and the like can be mentioned.

Examples of the monomer having five unsaturated bonds include dipentaerythritol penta (meth) acrylate, and examples of the monomer having six unsaturated bonds include dipentaerythritol Erythritol hexa (meth) acrylate and the like.
Any material can be used as long as it undergoes radical polymerization by light irradiation.

The monomer (B) used in the present invention
Are used alone or in combination of two or more.
When only one type of monomer is used, a compound having at least one —OH group is used. When two or more types are used in combination, at least one type of at least one —OH group is used. It is preferable to use one having an —OH group.

Examples of the photopolymerization initiator (C) used in the present invention include benzophenone derivatives (benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'- Tetraethyl-4,4'-diaminobenzophenone, 4,4'-dichlorobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, methyl o-benzoylbenzoate, etc., quinone derivatives (4-ethylanthraquinone, phenanthrenequinone, etc.) , Benzoin derivatives (benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n
-Butyl ether, benzoin isobutyl ether, benzoin phenyl ether, etc.), benzyl derivatives (benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, etc.), 2,4,5-triarylimidazole dimer [2- (o- Chlorophenyl)-
4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl)
Imidazole dimer, 2- (o-fluorophenyl)-
4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2, 4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2
4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, etc.), acridine derivatives (9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, etc.), xanthone derivatives (thioxanthone, 2-
Methylthioxanthone, 2-chlorothioxanthone, 2
-Isopropylthioxanthone, 2,4-diethylthioxanthone, etc.). These photopolymerization initiators are used alone or in combination of two or more.

The thermal decomposition temperature used in the present invention is 200 ° C.
Examples of the dye (D) include acid dyes, direct dyes, disperse dyes, oil-soluble dyes, and cationic dyes. The thermal decomposition temperature of the dye (D) used in the present invention is 2
The temperature is at least 00 ° C, preferably at least 250 ° C, more preferably at least 300 ° C. Those having a thermal decomposition temperature of less than 200 ° C. have low heat resistance and decolorize upon heating. It is preferable to use a dye having light fastness as the dye (D). Usually, the light fastness indication (light fastness indication described in CI) described in the color index is 5 or more, preferably 6 or more, more preferably It is desirable to use seven or more. C. I. When the light resistance display is less than 5, the light resistance is low, and the color may be decolored when used as a color filter.

Dyes sold by dye manufacturers not listed in the color index can also be used. As a dye satisfying all of these conditions, for example, a dye classified as a cationic dye (basic dye), an oil-soluble dye, or a disperse dye in a color index is preferable, and is classified as a solvent-soluble dye. Are more preferred.

Examples of such preferred dyes include, for example, AizenSpiron Y manufactured by Hodogaya Chemical Co., Ltd.
yellow 3RH, Orange GRH extr
aconc. , Orange 2RH, Pink
BH, Red GEH, Violet RH, Br
own BH conc. , Brown RH, M
ahogany RH, Black BNH, Bla
ck MH, Black RLH, Yellow
GRLH special, Yellow 3RH
special, Orange 2RH special
al, Orange GRH conc. spec
ial, Red GEH special, Red
GRLH special, Red BEH sp
electrical, Blue GLSH special,
Violet RH specialty, Blue G
NH, Blue 2BNH, Green 3GNH
special, Black RLH special
al, BlackBH special, Blac
k MH special, BlackNPH ne
w Black-1UR, Yellow C-2G
H, Yellow C-GNH, S.H. P. T.
Orange-6, Red C-GH, Red
C-BH, Violet C-RH, S.C. B.
N. Violet 510, Blue C-RH,
S. P. T. Blue-111, Black
GMH special, Aizen SOT Ye
llow-1, Aizen SOT Yellow-
3, Aizen SOT Yellow-4, Ai
Zen SOT Yellow-6, Aizen S
OT Orange-1, Aizen SOT Or
angel-2, Aizen SOT Orange-
3. Aizen SOT Scarlet-1, A
izen SOT Red-1, Aizen SOT
Red-2, Aizen SOT Red-3,
Aizen SOT Blue-1, Aizen S
OT Blue-2, Aizen SOT Blue
-3, Aizen SOT Blue-4, Aiz
solvent-soluble dyes such as en SOT Violet-1;
Mitsui Toatsu Dye Co., Ltd. PS Yellow GG, PS
Yellow S-3G, PS Yellow S
-G, PS Yellow SK, PS Ora
nge GG, PS Orange HG, PS
Red HGG, PS Red GG, PS Re
d G, PS Brilliant Red FG,
PS Brilliant Red HEY, PS
Red BB, PS Red EB, PS Bri
llian Pink FFR, PS Violet
t RR, PS Violet RC, PS Bl
ue 3R, PS Blue RR, PS Blue
e BN, PS Green B, SPR Yel
low 1, SPR Yellow 2, SPR
Red 1, SPR Red 2, SPR Blu
e2, TON Yellow 101, TON
Yellow102, TON Magenta 20
1. TON Cyan 201, MS Yellow
VP, MS Magenta VP, MS Cy
an VP, MS Cyan VPG, CF Ye
low 110, CFRed 226, CF G
reen 303, CF Blue 120, CF
Cyan 123, Yellow EX-551, Nippon Kayaku Co., Ltd. B-38s new pure and the like. These dyes are used alone or in combination of two or more.

The thermosetting agent (E) which causes a crosslinking reaction at 130 to 250 ° C. used in the present invention includes, for example, polymethylol compounds, polyisocyanate compounds, polyepoxy compounds and the like.

These thermosetting agents cause a crosslinking reaction at 130 to 250 ° C., preferably those which cause a crosslinking reaction at 150 to 200 ° C. Those which cause a cross-linking reaction at a temperature lower than 130 ° C. cause a cross-linking reaction at the time of heating and drying or laminating the colored image forming material, making it difficult to develop.
On the other hand, those which cause a crosslinking reaction at a temperature higher than 250 ° C. are liable to cause decomposition of the dye.

As the polymethylol compound, for example,
Polymethylolated aromatic compounds (polymethylolbenzene, polymethylolated phenol, polymethylolated melamine, polymethylolated benzoguanamine, etc.), dimethylolated urea,

[0043]

Embedded image And the like.

Examples of the polyisocyanate compound include tolylene diisocyanate, 2,4-toluylene diisocyanate, naphthylene-1,5-diisocyanate, dimethyl biphenylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, tris- (p-isocyanate Phenyl) thiophosphite, polymethylene polyphenylisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate and the like.

Examples of the polyepoxy compound include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, polyethylene glycol glycidyl ether, tripropylene glycol glycidyl ether, Examples include polypropylene glycol glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, and diglycidyl phthalate.

These compounds are used alone or in combination of two or more.

The compounding amount of the polymer (A) in the colored photosensitive resin composition of the present invention depends on the amount of the polymer (A), monomer (B),
The total amount of the photopolymerization initiator (C), the dye (D) and the thermosetting agent (E) is 20 to 77% by weight, preferably 20 to 6% by weight.
0% by weight, particularly preferably 25 to 45% by weight. If the amount of the polymer (A) is less than 20% by weight, the photocured product tends to become brittle, and if it exceeds 77% by weight, the photosensitivity tends to be insufficient. In the present invention, the amount of the monomer (B) is the total amount of the polymer (A), the monomer (B), the photopolymerization initiator (C), the dye (D), and the thermosetting agent (E). 20 to 60% by weight, preferably 25 to
45% by weight. 20% by weight of monomer (B)
If it is less than 60%, the photosensitivity tends to be insufficient, and if it exceeds 60% by weight, the photocured product tends to be brittle. Also,
The compounding amount of the photopolymerization initiator (C) in the present invention is based on the total amount of the polymer (A), the monomer (B), the photopolymerization initiator (C), the dye (D) and the thermosetting agent (E). , 0.01 to 20% by weight, preferably 1 to 5% by weight. When the amount of the photopolymerization initiator (C) is less than 0.01% by weight, the photosensitivity tends to be insufficient, and when the amount exceeds 20% by weight, the surface of the colored photosensitive resin composition during exposure may be insufficient. Absorption tends to increase and the internal light curing tends to be insufficient. Further, the compounding amount of the dye (D) in the present invention is based on the total amount of the polymer (A), the monomer (B), the photopolymerization initiator (C), the dye (D), and the thermosetting agent (E). 1 to 30% by weight, preferably 10 to 2%
0% by weight. If the amount of the dye (D) is less than 1% by weight, the color tends to be insufficient, and if it exceeds 30% by weight, the light transmittance tends to decrease. Further, the compounding amount of the thermosetting agent (E) in the present invention is as follows:
1 to 40% by weight, preferably 3% by weight based on the total amount of the monomer (B), the photopolymerization initiator (C), the dye (D) and the thermosetting agent (E)
１５15% by weight. If the amount of the thermosetting agent (E) is less than 1% by weight, “bleeding” tends to occur,
If it exceeds 0% by weight, the photocured product tends to become brittle.

In addition to the components (A) to (E), the colored photosensitive resin composition of the present invention contains a color former, a plasticizer, a pigment, a flame retardant, a stabilizer, a thermal polymerization inhibitor, A film property modifier and the like can be added as needed. In particular, a thermal polymerization inhibitor such as methylene bis (5-ethyl-4-t-butyl-2-hydroxybenzene) may be added to a polymer (A), a monomer (B), a photopolymerization initiator (C), a dye ( Usually 0.01 to 100 parts by weight of the total amount of D) and thermosetting agent (E)
It is desirable to add 0.5 parts by weight, preferably 0.1 to 0.3 parts by weight.

The colored photosensitive resin composition of the present invention has the above-mentioned composition, and is further dissolved in a solvent, and the solution is coated on a support, and the temperature at which a crosslinking reaction of the thermosetting agent (E) occurs. When the film is heated at a temperature of less than 2 ° C. to remove the solvent and form a film having a thickness of 2 μm, the resulting film has a surface tension dispersing force component γ _sd and a surface tension polar component γ _sp of 12.5 mN / m <γ _sp <35 mN / m, 12.5 mN / m <γ _sd <35 mN / m, 30 mN / m <γ _sd + γ _sp <55 mN / m, preferably 15 mN / m <γ _sp <25 mN / m, 20 mN / m <γ _sd <35 mN / m, 35 mN / m <γ _sd + γ _sp <50 mN / m. Of course, the colored image forming material of the present invention also requires that the colored photosensitive resin composition layer satisfy the above-mentioned surface tension characteristics. Γ that does not satisfy the above range
Colored image forming materials exhibiting _sd and γ _sp are not preferred because the colored resin layer is likely to be peeled off in the step of peeling off the support or in the developing step, or the developer resistance is reduced. Surface tension dispersion force component γ _sd and surface tension polarity component γ _sp
For example, refer to the literature [Surface Treatment Technology Overview, P81-83
(1988), Industrial Technology Service Center], the contact angle between two kinds of liquids having known surface tensions, for example, water and diiodomethane, and the surface of the colored image forming material is measured and calculated.

When a colored image forming material or a color filter is produced using the colored photosensitive resin composition of the present invention, the colored photosensitive resin composition of the present invention is usually dissolved in a solvent which dissolves all components. It is used as a uniform colored photosensitive resin composition solution obtained by mixing.

As a solvent for dissolving all the above-mentioned components, for example, toluene, acetone, methyl ethyl ketone (ME
K), methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, methyl alcohol, ethyl alcohol and the like. These solvents are used alone or in combination of two or more. The amount of the solvent used includes the polymer (A), the monomer (B), the photopolymerization initiator (C), the dye (D), and the thermosetting agent (including the synthetic solvent for the polymer (A)). The amount is preferably 200 to 800 parts by weight, more preferably 300 to 600 parts by weight, based on 100 parts by weight of the total solid content of E). If the amount of the solvent is less than 200 parts by weight, it is difficult to form a uniform colored photosensitive resin composition film, and if it exceeds 800 parts by weight, the thickness of the colored photosensitive resin composition film becomes thin. Tends to be too much.

The colored image forming material of the present invention is formed by applying a solution obtained by dissolving the colored photosensitive resin composition of the present invention in a solvent on a transparent support and drying.

As the transparent support, a polymer film (for example, a film made of polyethylene terephthalate, polypropylene, polyethylene or the like) is usually used.
Polyethylene terephthalate films are preferred. Since these polymer films must be removed from the colored photosensitive resin composition layer later, they may be subjected to a surface treatment that makes removal impossible, or may be a material. No. The thickness of these polymer films is
5 to 100 μm, preferably 10 to 80 μm
Is more preferable. If the thickness of the polymer film is less than 5 μm, the film strength tends to be insufficient, and if it exceeds 100 μm, the film tends to lack flexibility. These polymer films are
One sheet is used as a transparent support (transparent support film) for the colored photosensitive resin composition layer, and the other polymer film is formed on the surface of the colored photosensitive resin composition layer after the colored photosensitive resin composition layer is formed. They can be laminated to form a protective film.

The drying after applying the colored photosensitive resin composition solution on the transparent support is performed to remove the solvent,
Usually, it is performed by heating. Heating temperature is 40-12
The temperature is preferably 0 ° C, more preferably 60 to 10 ° C.
0 ° C. The heating time is preferably from 1 to 15 minutes, more preferably from 3 to 10 minutes. However, the heating during this drying is preferably lower than the thermal decomposition temperature of the dye (D) and lower than the temperature at which the crosslinking reaction of the thermosetting agent (E) occurs.

The thickness of the colored photosensitive resin composition layer in the colored image forming material of the present invention varies depending on the use of the colored image forming material, but is usually preferably 0.5 to 5 μm.
1 to 2.5 μm is more preferred.

The method of manufacturing a color filter according to the present invention is a method of manufacturing a color filter in which a multicolor image is formed on a substrate using a color image forming material. Since the step (b), the support stripping step (c), the developing step (d) and the thermosetting step (e) are repeated using a plurality of colored image forming materials having different colors on one transparent substrate. Become.

(A) Laminating the colored image forming material such that the colored photosensitive resin composition layer is in contact with the transparent substrate. In this laminating step, when the colored image forming material is provided with the above protective film, After removing the protective film, the colored image forming material of the first color is laminated by being pressed against the substrate while heating, thereby forming a colored photosensitive resin composition layer on the substrate. The heating temperature at the time of laminating the image forming material is preferably from 80 to 120 ° C, more preferably from 85 to 105 ° C. If the heating temperature is lower than 80 ° C., lamination tends to be insufficient, and if it exceeds 120 ° C., the resin tends to be cured. Crimping pressure during lamination of the colored image forming material is preferably in a 1~5kgf / cm ^2, more preferably 1.5~3.5kfg / cm ^2. If the pressing pressure is less than 1 kgf / cm ² , lamination tends to be insufficient, and if it exceeds 5 kgf / cm ² , the colored photosensitive resin composition layer tends to squeeze out during lamination. If the colored image forming material is heated as described above, it is not necessary to pre-heat the substrate in advance, but the substrate may be pre-heated to further improve the followability. In the case where this heat compression bonding is performed using a roll, the roll temperature is preferably set to the above-described heating temperature, and the roll speed is preferably set to 0.1 to 5 m / min.
More preferably, it is 0.5 to 3 m / min.

As a substrate used for manufacturing a color filter, a glass plate, a synthetic resin plate, a synthetic resin film, or the like which is usually transparent and may be subjected to a surface treatment for bonding can be used.

(B) Step of Exposing Active Light to the Laminated Substrate via a Predetermined Photomask After completion of the lamination, the colored photosensitive resin composition layer of the first color is activated through a photomask. Exposure is performed by irradiating a light beam. In the method of the present invention, from the viewpoint of protection of the colored photosensitive resin composition layer, exposure is performed through a transparent support existing on the colored photosensitive resin composition layer while the transparent support is kept on. If necessary, exposure may be performed after the transparent support is peeled off. When an opaque support is used, exposure is performed after the support is peeled off.
As the actinic ray, a known actinic light source, for example, light generated from a carbon arc, a mercury vapor arc, a xenon arc, a flood lamp for photography, a sun lamp, or the like is used. Since the sensitivity of the photopolymerization initiator contained in the colored photosensitive resin composition layer is usually maximum in the ultraviolet to visible light region, the active light source in that case is preferably one that effectively emits ultraviolet to visible light. . The amount of actinic rays is 10 to 5
00 mJ / cm ² , preferably 50 to 300 mJ / cm ²
Is more preferred.

(C) Step of peeling off the support After the exposure, the support such as a polymer film on the colored photosensitive resin composition layer is peeled off and removed.

(D) Step of Removing Unexposed Area of Colored Photosensitive Resin Composition Layer on Transparent Substrate with Developer After the support is peeled off, a known aqueous solution such as an aqueous alkali solution, aqueous developer or organic solvent is used. Using a developer, for example, spray,
The unexposed portion is removed and developed by a known method such as rocking immersion, brushing, and scrubbing to form a colored image of the first color.

As the base of the aqueous alkali solution, for example,
Alkali hydroxides (such as lithium, sodium or potassium hydroxide), alkali carbonates (such as lithium, sodium or potassium carbonate or bicarbonate), alkali metal phosphates (such as potassium phosphate and sodium phosphate),
Examples thereof include alkali metal pyrophosphates (eg, sodium pyrophosphate and potassium pyrophosphate), and among them, an aqueous solution of sodium carbonate is preferable. These bases are used alone or in combination of two or more. The pH of the alkaline aqueous solution used for development is preferably 9 to 11. If the pH of the alkaline aqueous solution is less than 9, the development tends to be insufficient, and if it exceeds 11, the quality tends to change to the exposed part. Further, the temperature of the alkaline aqueous solution is adjusted according to the developability of the photosensitive layer. In addition, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like can be mixed in the alkali solution.

The aqueous developer is composed of water or an aqueous alkali solution and 1
And at least one organic solvent. Examples of the alkaline substance in the aqueous alkaline solution include, in addition to the above base, borax, sodium metasilicate, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-amine
Hydroxymethyl-1,3-propanediol, 1,3
-Diaminopropanol-2, morpholine and the like. Examples of the organic solvent include triacetone alcohol, acetone, ethyl acetate, alkoxyethanol having an alkoxyl group having 1 to 4 carbon atoms, ethyl alcohol,
Examples include isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and the like. These organic solvents are used alone or in combination of two or more. The concentration of the organic solvent in the aqueous solvent is preferably 2 to 90% by volume, more preferably 5 to 80% by volume. The pH of the aqueous developer is preferably from 8 to 12, and more preferably from 9 to 10. If the pH of the aqueous developer is less than 8, development tends to be insufficient, and if it exceeds 12, the exposed part tends to deteriorate. The temperature of the developer can be adjusted according to the developing property. Note that a small amount of a surfactant, an antifoaming agent, or the like can be mixed in the developer.

The organic solvent developer used alone includes:
For example, 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone and the like can be mentioned. These organic solvents contain 1 to 10% by volume to prevent ignition.
Water may be added within the range described above.

(E) Step of heating the colored image formed by development The post-curing is performed by removing the unexposed portion by the development and heating the remaining colored image. After this curing,
The colored image becomes stronger, and the solvent resistance and the like are improved. The heating temperature at the time of this post-curing is in a temperature range in which the thermosetting agent causes a crosslinking reaction, that is, 130 to 250 ° C, preferably 150 to 220 ° C. The heating time is usually 10 to
It is 100 minutes, more preferably 15 to 30 minutes. If the heating time is less than 10 minutes, the crosslinking reaction tends to be insufficient, and if it exceeds 100 minutes, the film tends to peel.

By repeating the above steps (a) to (e) a plurality of times using a plurality of colored image forming materials having different colors, a color filter having a multicolor image having different hues formed on a substrate is obtained. be able to.

The color filter of the present invention is obtained by the above-described method of the present invention and has excellent adhesion between the substrate and the colored pixels. Further, the color filter of the present invention can be manufactured at a low cost because it does not require a complicated process for preventing the colored image forming material from peeling off during the manufacturing process or an expensive material.

[0068]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention and Comparative Examples thereof, but the present invention is not limited to these Examples.

Examples 1 to 15 The materials shown in Tables 1 and 2 were blended to prepare red colored photosensitive resin composition solutions R-1 to R-12 and green colored photosensitive resin composition solution G-1. Manufactured.

The details of the materials used in the examples and comparative examples are as follows. A1: Weight average molecular weight about 80,000 A2: Weight average molecular weight about 80,000

[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

Embedded image Aizen Spiron Red BEH spec
ial: red dye (trade name, manufactured by Hodogaya Chemical Co., Ltd.) Yellow EX-551: yellow dye (trade name, manufactured by Mitsui Toatsu Dye Co., Ltd.) Aezen Spiron Blue GLSH sp
Ecial: Blue dye (trade name, manufactured by Hodogaya Chemical Co., Ltd.) B-38s new pure: Blue dye (trade name, manufactured by Nippon Kayaku Co., Ltd.)

[0084]

[Table 1]

[0085]

[Table 2] Examples 16 to 30 (Preparation of colored image forming material) The colored photosensitive resin composition solutions R-1 to R-12, G-1, produced in Examples 1 to 15,
Each of G-2 and B-1 was applied on a 19 μm-thick polyethylene terephthalate (PET) film using a film coater, dried at 80 ° C. for 5 minutes, and formed on a polyethylene terephthalate film support. Image forming materials R-1F to R-12F, G-1F, G-2F and B comprising a colored photosensitive resin layer having a thickness of 2 μm.
-1F was produced.

Colored photosensitivity of each of the obtained colored image forming materials
Surface tension dispersion force component γ of resin layer_sdAnd surface tension polar component
γ_spWas measured, γ of each colored photosensitive resin layer_sdPassing
And γ _spIs 12.5 mN / m <γ_sp<35 mN / m, 12.5 mN / m <γ_sp<35 mN / m, 30 mN / m <γ_sd+ Γ_spIt was found that the condition of <55 mN / m 2 was satisfied. Table 3 shows the measurement results.
It is shown in Table 4.

The measurement and calculation of γ _sd and γ _sp were performed as follows. Measuring device: CA-D type contact angle meter manufactured by Kyowa Interface Science Co., Ltd. Measuring condition: 23 ° C, 50 ± 5% RH Measurement liquid: water, diiodomethane

[0088]

(Equation 1) W _sl = γ ^l (1 + cos θ) θ: contact angle γ _ld , γ _lp , γ ^l : surface tension of each liquid Examples 31 to 45 (Evaluation of Adhesion) Each of the colored image forming materials prepared in Examples 16 to 30 was applied to a transparent glass substrate (Corning # 70).
59, a product name of Corning Co., Ltd.), the colored photosensitive resin layer was in contact with the glass substrate, and the roll temperature was 1
Lamination was performed using a roll under the conditions of 10 ° C., a roll pressure of 4 kgf / cm ² , and a roll speed of 1.0 m / min. Subsequently, exposure (150 mJ / cm ² ) was performed using an ultra-high pressure mercury lamp (3 kw) through a predetermined photomask to prepare a test piece for evaluating adhesion. First, the support PE
The adhesion of the colored photosensitive resin layer to the glass substrate when the T film was peeled off (the adhesion at the time of PET peeling) was evaluated. The evaluation criteria are as follows. ：: There is no peeling of the colored photosensitive resin layer. Δ: The peeled area of the colored photosensitive resin layer is less than 3% of the whole. ×: The peeled area of the colored photosensitive resin layer is 3% or more.

Next, spray development (developing solution: 0.15% by weight aqueous sodium borate solution, developing temperature: 25 ° C., developing time: 75 seconds) was performed to obtain a line width and space width of 5 μm each.
m, line width and space width each 7.5 μm, line width and space width each 10 μm, line width and space width each 12.5 μm, line width and space width each 15 μm
m, a line width and a space width are each 17.5 μm, and a line width and a space width are each 20 μm.
The presence or absence of peeling (adhesion during development) in each pattern was examined using an optical microscope. The evaluation criteria are as follows. ：: There is no stripped portion in each line / space width pattern. Unevaluable: Since the colored photosensitive resin layer peeled off when the PET film was peeled off, accurate adhesion during development could not be evaluated. ×: A peeled portion was observed in any of the patterns of each line / space width.

Tables 3 and 4 show the above evaluation results.

[0091]

[Table 3]

[0092]

[Table 4] As is clear from Tables 3 and 4, γ _sd and γ _sp of the colored photosensitive resin layer are 12.5 mN / m <γ _sp <35 mN / m, 12.5 mN / m <γ _sd <35 mN / m, 30 mN / M <γ _sd + γ _sp <55 mN / m.
12F, G-1F, G-2F, and B-1F are PET
No peeling of the dye resin layer was observed at the time of peeling and development, and the obtained colored image pattern was also good.

Comparative Examples 1 to 6 Red-colored photosensitive resin composition solutions RR-1 to RR-5 and blue-colored photosensitive resin composition solution RB-1 were prepared by mixing the materials shown in Table 5.

[0094]

[Table 5] Comparative Examples 7 to 12 (Production of Colored Image Forming Material) Colored Photosensitive Resin Composition Solutions RR-1 to RR-5 and RB- Produced in Comparative Examples 1 to 6
1 was coated on a 19 μm-thick polyethylene terephthalate (PET) film using a film coater and dried at 80 ° C. for 5 minutes to form a polyethylene terephthalate film support and a 2 μm-thick colored film formed thereon. Colored image forming material RR-1F comprising photosensitive resin layer
To RR-5F and RB-1F.

Colored photosensitivity of each obtained colored image forming material
Surface tension dispersion force component γ of resin layer_sdAnd surface tension polar component
γ_spWas measured, and the results shown in Table 6 were obtained. What
Oh, γ _sdAnd γ_spMeasurement and calculation are the same as in the above embodiment.
I went.

Comparative Examples 13 to 18 (Evaluation of Adhesion) Each of the colored image forming materials prepared in Comparative Examples 7 to 12 was applied to a transparent glass substrate (Corning # 705).
9, on one side of Corning Co., Ltd.), the colored photosensitive resin layer was in contact with the glass substrate, and the roll temperature was 11
Lamination was performed using a roll under the conditions of 0 ° C., a roll pressure of 4 kgf / cm ² , and a roll speed of 1.0 m / min. Subsequently, exposure (150 mJ / cm ² ) was performed using an ultra-high pressure mercury lamp (3 kw) through a predetermined photomask to prepare a test piece for evaluating adhesion. First, the support PE
The adhesion of the colored photosensitive resin layer to the glass substrate when the T film was peeled off (the adhesion at the time of PET peeling) was evaluated. Evaluation criteria are as described above.

Next, spray development (developer: 0.15% by weight aqueous sodium borate solution, development temperature: 25 ° C., development time: 75 seconds) was carried out, and line / space = 5, 7.5, 1
Patterns of 0, 12.5, 15, 17.5, and 20 μm were formed, and the presence or absence of peeling (adhesion during development) in each pattern was examined using an optical microscope. Evaluation criteria are as described above.

Table 6 shows the above evaluation results.

[0099]

[Table 6] As is clear from Table 6, γ _sd and γ _sp of the colored photosensitive resin layer are 12.5 mN / m <γ _sp <35 mN / m, 12.5 mN / m <γ _sd <35 mN / m, 30 mN / m < Colored image forming materials RR-1F to RR-5F not in the range of γ _sd + γ _sp <55 mN / m
For RB-1F and RB-1F, peeling of the dye resin layer occurred at the time of PET peeling or development, and a good colored image pattern was not formed.

Example 46 The colored image-forming material R-1F produced in Example 16 was transparent.
Bright glass substrate (Corning # 7059, manufactured by Corning Incorporated)
A colored photosensitive resin layer is in contact with the glass substrate on one side
So that the roll temperature is 110 ° C and the roll pressure is
4kgf / cm ^TwoAnd a roll speed of 1.0 m / min.
In this case, lamination was performed using a roll. Then,
Exposure using an ultra-high pressure mercury lamp (3 kw) through a photomask
Light (150mJ / cm^Two)did. Next, PET film
After peeling off, spray development (developer: 0.15% by weight)
Sodium borate aqueous solution, development temperature: 25 ° C, during development
(Interval: 75 seconds), line width 92 μm, repetition width 300
to form a stripe pattern consisting of μm red pixels.
Was. Then, heating at 200 ° C. for 10 minutes, the red pixel is
Post cured. Next, the red pixel is formed on the layer on which it is formed.
Using the colored image forming material G-2F produced in Example 23
Repeat the same operation as above to add a green pixel next to the red pixel.
Formed. Next, the layer composed of the red and green pixels
Image forming material B-1F prepared in Example 24 on
The same operation is repeated using red and green pixels.
A color filter consisting of three color pixels with blue pixels formed between
Was fabricated. Smell at both PET peeling and development
Even when the dye resin layer was not peeled off, the resulting colored image was obtained.
The pattern was also good.

[0101]

The colored photosensitive resin composition of the present invention provides a colored image forming material for producing a color filter having good adhesion. The colored photosensitive resin composition is also suitable for color hard copy ink, instant photographic ink, liquid crystal printer ink, lens coat varnish, glass coat varnish, and the like.

The colored image forming material of the present invention has good adhesion to a substrate during the production of a color filter. This colored image forming material is also suitable as a film for lens coating, a film for glass coating, and the like.

The method of manufacturing a color filter according to the present invention can easily apply the colored image forming material to a substrate for a color filter and can provide a high-quality fine pattern (pixel). Adhesion is obtained.

The color filter of the present invention manufactured by the manufacturing method of the present invention has good adhesion at the time of manufacturing, has general performance as a color filter, and can perform high-contrast display with a small depolarizing effect. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location G03F 7/004 505 G03F 7/004 505 7/40 501 7/40 501

Claims (5)

[Claims] 1. A polymer (A) obtained by polymerizing an unsaturated carboxylic acid and another unsaturated monomer copolymerizable therewith,
At least one monomer having at least one unsaturated bond in one molecule (B), a photopolymerization initiator (C), a dye (D) having a thermal decomposition temperature of 200 ° C or higher, 130 ° C to 25 ° C
Consists of a thermosetting agent (E) that causes a crosslinking reaction at 0 ° C., and the total amount of the polymer (A), monomer (B), photopolymerization initiator (C), dye (D), and thermosetting agent (E) Medium, polymer (A) is 2
0 to 77% by weight, monomer (B) 20 to 60% by weight, photopolymerization initiator (C) 0.01 to 20% by weight, dye (D)
Is 1 to 30% by weight and the thermosetting agent (E) is 1 to 40% by weight, and a solution obtained by dissolving the colored photosensitive resin composition in a solvent is provided on a support. coated, when formed into a film layer having a thickness of 2μm thermosetting agent by heating at a temperature below the temperature which causes the crosslinking reaction of (E) to remove the solvent, the surface tension dispersion force component gamma _sd and film obtained The surface tension polarity component γ _sp is 12.5 mN / m <γ _sp <35 mN / m, 12.5 mN / m <γ _sd <35 mN / m, and 30 mN / m <γ _sd + γ _sp <55 mN / m. A colored photosensitive resin composition. 2. The colored photosensitive resin composition according to claim 1, wherein at least one of the monomers (B) having at least one unsaturated bond has an —OH group. 3. A colored image-forming material formed by applying a solution obtained by dissolving the colored photosensitive resin composition according to claim 1 in a solvent onto a transparent support and drying the same, wherein the surface tension dispersing force is obtained. The component γ _sd and the surface tension polarity component γ _sp are 12.5 mN / m <γ _sp <35 mN / m, 12.5 mN / m <γ _sd <35 mN / m, 30 mN / m <γ _sd + γ _sp <55 mN / m. A colored image forming material comprising: 4. A step (a) of laminating the colored image forming material according to claim 3 such that the colored photosensitive resin layer is in contact with the transparent substrate, wherein a predetermined photo is applied to the colored photosensitive resin layer laminated on the substrate. A step (b) of exposing an actinic ray through a mask, a step (c) of peeling off the support, a step (d) of removing an unexposed portion of the colored photosensitive resin layer on the substrate using a developer, and A method for producing a color filter, wherein the step (e) of heating a colored image formed by development is sequentially repeated a plurality of times on the same substrate using a plurality of different colored image forming materials each time. 5. A color filter obtained by using the production method according to claim 4.