JPH0894827A - Production of color filter - Google Patents

Abstract

PURPOSE: To produce a color filter having high accuracy and high reliability without color defects and having a color pattern of desired arrangement in a simple production process. CONSTITUTION: The production method includes the following processes [1] to [5]. [1]: A transparent conductive layer is formed on a transparent substrate. [2]: A photosensitive compsn. containing (a) a polymer or a polymer mixture having carboxyl groups and hydroxyphenyl groups, (b) a compd. having two or more vinylether groups, and (c) a compd. which produces acid by irradiation of active energy rays is applied on the conductive layer and heated to form a positive photosensitive coating film layer. [3]: The photosensitive resin layer is exposed to light into a desired shape, heated at need, and then developed to expose a part of the transparent conductive layer. [4]: A color part of a desired color is formed by electrodeposition on the exposed conductive layer. [5]: The processes [3] and [4] are repeated required times.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a color filter used for multicoloring a display device such as a liquid crystal display.

[0002]

2. Description of the Related Art Conventionally, various proposals have been made as a method for forming a color filter, but a method for forming a color filter by using electrodeposition has been attracting attention. For example, JP-A-61-272720
In JP-A-61-279803 and JP-A-61-279803, a conductive layer is formed on a substrate, a positive photosensitive film is formed thereon, and the photosensitive film is exposed and developed into a desired shape. , A method of partially exposing a conductive layer and forming a colored layer of a required color on the exposed conductive layer by electrodeposition.

In this method, since a positive type photosensitive film is used, ideally only the exposed part is solubilized in the developing solution, and the unexposed part retains the photosensitivity, so that the exposure and development are performed. It can be repeated. However, the positive type photosensitive coating film using quinonediazide is modified by contact with the first developing solution or electrodeposition solution, heat, etc., and the function as the second or subsequent positive type photosensitive coating film cannot be exhibited. Therefore, in the case of this method, it is actually necessary to apply the positive photosensitive film a plurality of times, and the process becomes complicated.

Further, JP-A-4-247402 and JP-A-5-93807 disclose, as a method for solving the above-mentioned disadvantages, an acid consisting of tert-butyl ester of carboxylic acid or tert-butyl carbonate of phenol. Discloses a method of using a positive photosensitive resin composition containing a polymer having a stable and unstable branched group and a photopolymerization initiator that generates an acid upon exposure. In this method, the tert-butyl ester decomposes into isobutene and a carboxyl group by the attack of acid. As a result, a hydrophilic functional group is formed on the exposed portion of the positive photosensitive film, and development with an alkali developing solution becomes possible.

In the above method, the photon yield is higher than that using quinonediazide as a photosensitizer, and the photosensitivity is improved, but the principle of development is that exposed areas and unexposed areas are the same as those using quinonediazide. The difference in solubility in the developing solution is used. Since the unexposed area is not completely insoluble in the developing solution, the developing conditions are delicate, and strict developing conditions are required to obtain good reproducibility. Control is required. Particularly when the developing step is repeated a plurality of times, the photosensitive film in the unexposed area is also partially dissolved or swollen by the developing solution, and the accuracy of the formed pattern is likely to decrease,
There are drawbacks such as pattern defects.

The object of the present invention is to eliminate the above-mentioned drawbacks.
It is an object of the present invention to provide a method for manufacturing a color filter having a highly reliable colored pattern with high pattern accuracy and no coloring defects in a simple production process.

[0007]

The inventors of the present invention, as a result of earnest research, have found that the above object can be achieved by using a specific positive type photosensitive resin composition, and have completed the present invention. I arrived.

That is, the present invention is as follows. [1] a step of forming a transparent conductive layer on a transparent substrate, [2] (a) a polymer (a-1) having a carboxyl group and a hydroxyphenyl group in one molecule, or a polymer having a carboxyl group ( a-2) and a polymer mixture (a-3) having a hydroxyphenyl group, (b) a compound containing two or more vinyl ether groups in one molecule, and (c) by irradiation with active energy rays. A step of coating a positive photosensitive composition containing an acid generating compound as an essential component on the transparent conductive layer and heating to form a positive photosensitive coating layer, [3] the photosensitive coating layer To expose a part of the transparent conductive layer by exposing it to a desired shape, heating it if necessary, and then developing, [4] coloring the exposed transparent conductive layer with a desired color by electrodeposition. Of forming a part, and [5] The present invention provides a method for manufacturing a color filter, which comprises a step of repeating the above steps [3] and [4] a required number of times.

The present invention also relates to 2. The polymer (a) is the polymer (a-1) and the polymer (a-1) is the polymer (a
-1) A method for producing a color filter according to item 1, which contains a carboxyl group in the range of 0.5 to 10 equivalents and a hydroxyphenyl group in the range of 1.0 to 10 equivalents per kg. is there.

Further, the present invention relates to 3. The polymer (a) is a polymer mixture of the polymer (a-2) and the polymer (a-3), and the polymer (a-2) is 0.1% per 1 kg of the polymer (a-2). Contains a carboxyl group in the range of 5 to 10 equivalents,
The amount of the polymer (a-3) was 1. per 1 kg of the polymer (a-3).
The present invention provides a method for producing a color filter according to item 1, which contains a hydroxyphenyl group in the range of 0 to 10 equivalents.

The present invention also relates to 4. After the steps [1] to [5], [6] there is provided a method for producing a color filter according to the above item 1, which has a step of removing the remaining photosensitive coating layer and exposing the conductive layer.

The present invention also relates to 5. After the step [6], the method for producing a color filter according to the above item 4 is provided, which comprises a step of forming a desired colored portion on the exposed conductive layer by electrodeposition.

The present invention also relates to 6. After the step [6], the method for producing a color filter according to the above item 4 has a step of forming a desired colored portion on the exposed conductive layer by a coating method.

The present invention also relates to 7. The method for producing a color filter according to the above item 4, which comprises a step of forming a metal layer on the exposed conductive layer by a plating method after the step [6].

The present invention also relates to 8. The method for producing a color filter according to item 4 above, which comprises a step of coloring the exposed conductive layer by oxidation or reduction after the step [6].

[0016]

The present invention will be described in more detail below. First, in step [1], a transparent conductive layer 2 is formed on a transparent substrate 1 as shown in FIG. The transparent substrate 1 may be any substrate as long as it is a transparent substrate normally used for color filters, and examples thereof include a glass substrate and a plastic substrate. For the transparent conductive layer 2, for example, one containing tin oxide, indium oxide, or antimony oxide as a main component is preferably used. This transparent conductive layer can be formed by a method such as a vapor deposition method, a sputtering method or a sol-gel method.

Then, in step [2], a positive photosensitive composition is applied onto the transparent conductive layer and heated to form a positive photosensitive coating layer. The positive photosensitive composition to be applied is a polymer (a-1) having a carboxyl group and a hydroxyphenyl group in one molecule, and a compound (b) [containing two or more vinyl ether groups in one molecule [b]. Hereinafter, abbreviated as "polyvinyl ether compound (b)"] and a compound (c) that generates an acid upon irradiation with active energy rays [hereinafter,
Abbreviated as "photo-acid generating compound (c)"] as an essential component; and a polymer (a-2) having a carboxyl group and a polymer (a-3) having a hydroxyphenyl group. It is one of the compositions selected from the composition containing the combined mixture, the poly (vinyl ether) compound (b) and the photoacid generating compound (c) as essential components. As the above-mentioned positive-type photosensitive composition, Japanese Patent Application Nos. 5-125500 and 5-125, which are applications by the present applicant.
The photosensitive compositions described in Japanese Patent Application No. 501 and Japanese Patent Application No. 6-99139 can be used.

When the film formed by applying the positive type photosensitive composition is heated, the positive type photosensitive composition is crosslinked by an addition reaction of a carboxyl group and / or a hydroxyphenyl group and a vinyl ether group, and is crosslinked with a solvent or an alkaline aqueous solution. Becomes insoluble, and is further irradiated with active energy rays and, if necessary, heated after irradiation, the cross-linked structure is cleaved by the catalytic action of the acid generated in the irradiated part, and the irradiated part becomes soluble again in the solvent or alkaline aqueous solution. It works by the new mechanism. That is, the unexposed area is insolubilized in the solvent or aqueous alkaline solution used for development due to the cross-linking structure, and the unexposed area is not dissolved or swelled during development, so that it is found in the conventional positive photosensitive composition. It does not cause such a problem.

Further, the positive-type photosensitive composition of the present invention does not need to use a large amount of functional groups having a high absorption coefficient, as compared with the positive-type photosensitive composition using quinonediazide as a photosensitizer. The transparency of the acid can be increased, and the acid generated in the irradiated part acts as a catalyst by heating and cuts the cross-linking structure in a chain to enhance the sensitivity as a positive type composition. You can

Each component of the positive photosensitive composition used in the present invention will be described. The component (a) is a polymer component and is the polymer (a-1) or the polymer (a-
It is a polymer mixture of 2) and the polymer (a-3).

Polymer (a-1) is a film-forming polymer containing at least one carboxyl group and a hydroxyphenyl group in one molecule, for example, hydroxystyrene such as p-hydroxystyrene and a carboxyl group. A copolymer with a polymer unsaturated monomer contained therein; a copolymer with hydroxystyrene and another monomer copolymerizable with the carboxyl group-containing monomer, and the like can be mentioned.

Examples of the polymerizable unsaturated monomer containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and the like. Is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
Propyl acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
C ₁ -C ₁₂ alkyl esters of (meth) acrylic acid such as nonyl acrylate and decyl (meth) acrylate; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (meth) acrylic acid 3 - hydroxypropyl, (meth) C ₂ -C ₆ hydroxyalkyl esters of (meth) acrylic acid such as hydroxyethyl acrylate-butyl; styrene, alpha-methyl styrene, p-tert
-Vinyl aromatic compounds such as butyl styrene; vinyl acetate, (meth) acrylonitrile, (meth) acrylamide, vinylpyrrolidone, etc., and these monomers may be used alone or in combination of two or more kinds. can do.

Further, as the polymer (a-1), phenolcarboxylic acids such as hydroxybenzoic acid, gallic acid, resorcinic acid, etc., or these and phenol, carbon number 1 to 1
It is also possible to use a polymer obtained by condensing formaldehyde with a mixture of mono- or di-alkylphenol of 8 or naphthols, and one or more phenols selected from resorcin, catechol and the like.

The polymer (a-1) is generally about 500 to
It is preferred to have a number average molecular weight in the range of 100,000, especially in the range of about 1,500 to 30,000. On the other hand, the content of the carboxyl group is generally in the range of 0.5 to 10 equivalents, particularly 0.5 to 5.0 equivalents per 1 kg of the polymer, and the hydroxyphenyl group is at least 1.0 equivalent per 1 kg of the polymer. , Particularly preferably in the range of 2.0 to 8.0 equivalents. Further, the polymer (a-1)
Has a glass transition temperature (Tg) of 0 ° C. or higher, especially 5 to
It is preferably in the range of 70 ° C.

Polymer (a-2) The polymer (a-2) is a film-forming polymer containing at least one carboxyl group in one molecule.
A homopolymer of a polymerizable unsaturated monomer containing a carboxyl group; a copolymer of the carboxyl group-containing monomer with another copolymerizable monomer; a carboxyl group in the molecular chain or at the terminal of the molecule. Examples thereof include polyester resins, polyurethane resins, polyamide resins, and the like.

Examples of the polymerizable unsaturated monomer containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and the like, which are copolymerizable with these carboxyl group-containing monomers. As the other monomer, the other copolymerizable monomers similar to those exemplified for the copolymer in the polymer (a-1) can be used. These monomers may be used alone or in combination of two or more. In particular, as the other monomer, styrene, α-methylstyrene, C ₁ -C ₆ alkyl substituted styrene (for example p
It is preferable to use a vinyl aromatic compound such as -tert-butylstyrene) in terms of the accuracy of the image pattern formed.

The polymer (a-2) is generally about 3,000.
0 to about 100,000, especially about 5,000 to about 30,0
It is preferable to have a number average molecular weight in the range of 00, and the content of the carboxyl group is generally in the range of 0.5 to 10 equivalents, particularly 0.5 to 5.0 equivalents per 1 kg of the polymer. Is desirable. Further, the polymer (a-2)
Has a glass transition temperature (Tg) of 0 ° C. or higher, especially 5 to
It is preferably in the range of 70 ° C.

Polymer (a-3) The polymer (a-3) is a polymer containing at least one hydroxyphenyl group in one molecule, and is, for example, a monofunctional or polyfunctional phenol compound, an alkylphenol compound or Condensates of their mixtures with carbonyl compounds such as formaldehyde and acetone; homopolymers of vinyl aromatic compounds containing hydroxy groups such as p-hydroxystyrene; vinyl aromatic compounds containing hydroxyl groups and other copolymers. Examples thereof include copolymers with possible monomers.

Examples of the monofunctional or polyfunctional phenol compound include phenol, o-cresol and m.
-Cresol, p-cresol, 3,5-xylenol, 2,6-xylenol, 2,4-xylenol, catechol, resorcin, pyrogallol, bisphenol A, etc., a compound having 1 to 3 hydroxyl groups on the benzene ring Examples of the alkylphenol compound include p-isopropylphenol and p-isopropylphenol.
Examples thereof include alkylphenol compounds having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms in the alkyl moiety such as -tert-butylphenol, p-tert-amylphenol and p-tert-octylphenol.

The condensation reaction of these compounds with a carbonyl compound such as formaldehyde or acetone can be carried out by a method known per se. Generally, when the condensation reaction is carried out with an alkali catalyst, it becomes insoluble and infusible as the condensation proceeds. And a soluble and fusible novolak type is obtained by condensation with an acid catalyst. In the present invention, the latter novolak type phenolic resin can usually be used. The molecular weight of the novolac type phenol resin increases as the condensation proceeds, but it is generally preferable that the molecular weight obtained by the condensation in the reaction time of 1 to 3 hours is in the range of 500 to 2,000. As the other monomer copolymerizable with the hydroxy group-containing vinyl aromatic compound, the other copolymerizable monomers similar to those exemplified for the copolymer in the polymer (a-1) may be used. Can be used,

The polymer (a-3) is generally about 500
To about 100,000, especially about 1,000 to about 30,000
It preferably has a number average molecular weight in the range of 0.

The content of hydroxyphenyl group in the polymer (a-3) is generally 1.0 to 1 per 1 kg of the polymer.
Conveniently it is in the range of 0 equivalents, especially 2.0 to 8.0 equivalents. The glass transition temperature (Tg) of the polymer (a-3) is preferably 0 ° C. or higher, and particularly preferably in the range of 5 to 70 ° C. When the component (a) is a polymer mixture of the polymer (a-2) and the polymer (a-3), the mixing ratio of both is (a-2) / (a-3) solid content weight. 90 by ratio
It is preferably in the range of / 10 to 10/90, particularly 70/30 to 30/70.

Polyvinyl ether compound (b) The polyvinyl ether compound (b) has the formula -R in one molecule.
At least two vinyl ether groups represented by —O—CH═CH ₂ [wherein R represents a linear or branched alkylene group having 1 to 6 carbon atoms such as ethylene, propylene and butylene], and preferably Is a low molecular weight or high molecular weight compound containing 2 to 4, for example, polyphenol compounds such as bisphenol A, bisphenol F, bisphenol S, and phenol resin, ethylene glycol, propylene glycol, trimethylolpropane, trimethylolethane, Condensation products of polyols such as pentaerythritol and halogenated alkyl vinyl ethers such as chloroethyl vinyl ether; tolylene diisocyanate, xylylene diisocyanate,
Examples thereof include reaction products of a polyisocyanate compound such as hexamethylene diisocyanate and isophorone diisocyanate with a hydroxyalkyl vinyl ether such as hydroxyethyl vinyl ether. In particular, a condensate of the above polyphenol compound and a halogenated alkyl vinyl ether and a reaction product of a polyisocyanate compound having an aromatic ring and a hydroxyalkyl vinyl ether,
It is suitable from the viewpoint of etching resistance, accuracy of the formed pattern, and the like.

The poly (vinyl ether) compound (b) having a melting point or a softening point of 150 ° C. or lower, particularly 130 ° C. or lower, is a liquid at ordinary temperature, and the polymer (a- 1) Medium or polymer (a
-2) and / or easily migrates into the polymer (a-3),
Addition reaction easily occurs between the carboxyl group and / or phenolic hydroxyl group in the polymer (a-1) or the polymer (a-2) and / or (a-3) and the vinyl ether group of the polyvinyl ether compound (b). preferable.

Photoacid- generating compound (c) The photoacid-generating compound (c) is decomposed by irradiation with an active energy ray described below to give the polymer (a-1) or polymer (a-2) and / or A compound that generates an acid having sufficient strength to cleave the cross-linked structure formed between (a-3) and the polyvinyl ether compound (b), and includes, for example, one represented by the following formula. . Of these (IX)
Compounds of formula are particularly preferred.

Ar ₂ I ⁺ · X ⁻ (I) [wherein Ar represents an aryl group, for example, a phenyl group,
X ^- is PF ₆ ^-, SbF ₆ ^- or AsF ₆ ^- represents a]

Ar ₂ S ⁺ · X ⁻ (II) [wherein, Ar and X ⁻ have the same meanings as above]

[0038]

[Chemical 1] [In the formula, R is an alkyl group having 1 to 12 carbon atoms or 1 carbon atom.
It represents 12 alkoxy group, n represents 0 to 3, X ^-
Has the same meaning as above]

[0039]

[Chemical 2] [In the formula, X ⁻ has the same meaning as above]

[0040]

[Chemical 3] [In the formula, X ⁻ has the same meaning as above]

[0041]

[Chemical 4] [In the formula, X ⁻ has the same meaning as above]

[0042]

[Chemical 5] [In the formula, X ⁻ has the same meaning as above]

[0043]

[Chemical 6] [In the formula, R ₁ and R ₂ each independently have 1 to 12 carbon atoms.
Represents an alkyl group or an alkoxy group having 1 to 12 carbon atoms]

[0044]

[Chemical 7] [In the formula, R ₁ and R ₂ have the same meanings as described above.]

[0045]

[Chemical 8]

Positive-Type Photosensitive Composition The positive-type photosensitive composition used in the present invention comprises the above-mentioned polymer component (a) component, polyvinyl ether compound (b) and photo-acid generating compound (c). The above-mentioned three components are contained as essential components, and the mixing ratio thereof can be varied over a wide range according to the use of the composition, etc., but the poly (vinyl ether) compound (b) is 100 parts by weight of the component (a). It is preferable to use 5 to 150 parts by weight, particularly 10 to 100 parts by weight, relative to the parts, and the photoacid-generating compound (c) is the component (a) and the poly (vinyl ether) compound (b). It is suitable to use in the range of generally 0.1 to 40 parts by weight, particularly 0.2 to 20 parts by weight, based on 100 parts by weight of the total amount.

If desired, a sensitizing dye may be added to the above-mentioned photosensitive composition. Examples of the sensitizing dye that can be used include phenothiazine-based, anthracene-based, coronene-based, benzanthracene-based, and perylene-based. Examples thereof include pyrene-based, merocyanine-based, and ketocoumarin-based dyes.
An appropriate amount of these sensitizing dyes to be compounded is 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, per 100 parts by weight of component (a).

In addition, for the purpose of imparting appropriate flexibility, non-adhesiveness, etc. to the coating film formed in the above-mentioned photosensitive composition, a plasticizer such as phthalate ester, a polyester resin,
You may add acrylic resin etc. The addition amount thereof is usually 50 per 100 parts by weight of the total amount of the component (a), the poly (vinyl ether) compound (b) and the photoacid generating compound (c).
It is preferably not more than 1 part by weight, more preferably 0.1 to 40 parts by weight.

Furthermore, if necessary, a fluidity modifier, a dye, a colorant such as a pigment, or the like may be added to the photosensitive composition.

The above-mentioned photosensitive composition can be prepared by mixing the above-mentioned components as they are or in a solvent if necessary. The solvent that can be used in that case is not particularly limited as long as it can dissolve each component of the composition, and examples thereof include ketone-based, ester-based, alcohol-based, glycol-based, glycol ether-based, cyclic ether-based or aliphatic or Examples thereof include aromatic hydrocarbon solvents. These solvents may be used alone or in combination of two or more, if necessary.

In the above photosensitive composition, the content of the carboxyl group in the mixture is 0 per 1 kg of the total of the mixture of the component (a) which is a polymer, the poly (vinyl ether compound) (b) and the photoacid generating compound (c). The aqueous photosensitive composition can be dissolved or dispersed in water by neutralizing the carboxyl group with a basic compound in an amount of 0.5 to 5.0 equivalents. Examples of the basic compound used for neutralization include amines such as triethylamine, diethylamine, dimethylethanolamine and diethanolamine; inorganic alkalis such as caustic soda and caustic potash. You may use these individually or in mixture of 2 or more types. Normal,
These basic compounds have a carboxyl group of 0.1
Used in the range of to 1.0 equivalent.

In the step [2] of the present invention, the positive photosensitive composition is coated on the transparent conductive layer and heated to form a positive photosensitive coating layer 3 as shown in FIG. 1 (B). To be done. The positive photosensitive composition is coated by a spin coating method, a spray method, a bar coater coating method, a printing method, or the like, and when the positive photosensitive composition is an anionic or other ionic aqueous composition, it is electrodeposited. It can also be done by law.

The thickness of the positive type photosensitive coating layer is not particularly limited, but is usually 0.5 to 10 μm. By heating after coating, carboxyl groups in the photosensitive film and /
Alternatively, an addition reaction between a hydroxyphenyl group and a vinyl ether group occurs and crosslinks, so that the coating becomes insoluble in a solvent or an alkaline aqueous solution. The heating after coating is performed under the temperature and time conditions in which the crosslinking reaction substantially occurs, for example, about 60 to about 150.
It can be carried out at a temperature of ° C for about 1 to about 30 minutes.

In step [3], the positive photosensitive film layer obtained in step [2] is exposed to a desired shape. For example, as shown in FIG. 1C, a mask 4 having a predetermined pattern is set on the positive photosensitive film layer 3, and active energy rays are exposed from above the mask 4. As the exposure method, other than the method using a mask, a method of selectively irradiating an active energy ray with a reduction projection exposure machine, a direct drawing machine or the like may be used. The active energy ray is selected according to the kind of the photo-acid generating compound (c) contained in the photosensitive composition, and the like. For example, an electron beam, a monochromatic ray having a wavelength of 200 to 600 nm or a mixed ray thereof, A laser beam etc. are mentioned.

In the exposed area, the photoacid generating compound (c) is decomposed to generate a strong acid, and the catalytic action of this acid breaks the crosslinked structure of the positive photosensitive film, so that the exposed area is exposed to a solvent or an alkaline aqueous solution. Again becomes soluble. In order to enhance the catalytic action of this acid, it may be heated after exposure if necessary. This heating is performed under temperature and time conditions that promote the cleavage of the crosslinked structure of the photosensitive film, for example, about 60 to about 1.
It can be performed at a temperature of 50 ° C. for about 1 to about 30 minutes.

In the step [3], after the above exposure and, if necessary, heating, the photosensitive film layer is developed with a developing solution to form a pattern on the substrate as shown in FIG. 1 (D). A part of the transparent conductive layer can be exposed. Figure 1
In (D), the conductive layer is exposed at the location where the first coloring is required. As the developing solution, a polymer (a-
1) or a liquid capable of dissolving the polymer (a-2),
For example, a water-soluble organic base such as an alkanolamine,
Hydroxyammonium salts such as tetraethylammonium hydroxide; inorganic alkalis, for example, aqueous solutions of caustic soda, sodium carbonate, sodium metasilicate and the like can be used. You may use these basic substances individually or in mixture of 2 or more types. The concentration of the basic substance in the developer is usually preferably in the range of 0.05 to 10% by weight. In addition, an organic solvent may be mixed in the developing solution, if necessary, within a range in which it can be mixed.

The development can be carried out by a method known per se, such as immersing the substrate to be treated in a developing solution or spraying the developing solution on the substrate. After forming the pattern, the substrate may be washed with water and / or dried by heating, if necessary.

In the step [4], as shown in FIG. 1E, the colored portion 5 of a desired color is formed by electrodeposition on the transparent conductive layer exposed by forming a pattern on the substrate.
(First colored portion, for example, blue) is formed.

As the film-forming component of the electrodeposition paint used for this electrodeposition, a synthetic polymer resin is usually used, and the resin may be anionic, cationic or amphoteric, but is anionic. Those are particularly preferable. Examples of the synthetic polymer resin include various conventionally known resins such as acrylic resin, epoxy resin, urethane resin, polybutadiene resin, polyamide resin, carboxyl-containing polybutadiene resin, and carboxyl-containing alkyd resin.
This electrocoating material may be either photo-curable or thermo-curable, and after forming the colored portion, the colored portion may be cured by irradiation with active energy rays or heating, if necessary.

In step [5], the above steps [3] and [4] are repeated as many times as necessary. That is, the positive photosensitive film layer of the substrate obtained in the step [4] is exposed to a desired shape as in the step [3]. Figure 1
As shown in (F), the positive photosensitive film layer 3 and the colored portion 5
A mask having a predetermined pattern is set on the above, and active energy rays are exposed from the above. After the exposure, the transparent conductive layer is exposed at a portion where the second coloring is required as shown in FIG. 1G by heating as needed and then developing. Further, by performing electrodeposition on the obtained substrate in the same manner as in the step [4], a colored portion 6 (second colored portion, for example, red) of a desired color is formed as shown in FIG. 1 (H). To do.
The number of repetitions of the steps [3] and [4] may be determined according to the number of colors of the colored portion required. 1 (I), (J) and (K) show a third colored portion 7 (third colored portion, eg green).
The steps [3] and [4] for forming the are shown.

If necessary, the substrate having multicolored colored portions obtained by the above steps [1] to [5] further has another colored portion (for example, black) on the portion other than the colored portion on the conductive layer. Matrix) may be formed. In that case, first, the step [6] of removing the remaining photosensitive coating layer is required. For example, by using a remover which does not dissolve the colored portions 5, 6 and 7 shown in FIG. 1 (K) and preferentially or selectively removes the remaining photosensitive coating layer to dissolve the remaining photosensitive coating layer. By performing the removal, the remaining photosensitive coating layer can be removed as shown in FIG. In this case, before removing the photosensitive film layer, irradiation with an active energy ray may be applied to generate a strong acid to destroy the crosslinked structure of the photosensitive film, and then the solution may be removed with a removing solution. In this case, the developing solution used in step [3] can be used as the removing solution.

After the above step [6], another colored portion (eg, black matrix) is formed on the exposed conductive layer to obtain a color filter as shown in FIG. 1M, for example. You can As a method for forming another colored portion such as a black matrix on the conductive layer, a colored paint is applied by an electrodeposition coating method or a coating method such as a spin coating method, a spray method, a bar coater coating method, or a printing method. Examples thereof include a method of coating by a method and then curing; a method of forming a metal layer on the conductive layer by a plating method; a method of coloring the exposed conductive layer by oxidation or reduction.

[0063]

According to the method of manufacturing a color filter of the present invention, a simple production process provides high accuracy, no coloring defects, high reliability, and an arbitrary array shape without being affected by the shape of the conductive layer. It is possible to manufacture a color filter having a colored pattern of.

[0064]

EXAMPLES The present invention will be described in more detail below with reference to examples. In addition, "part" and "%" are based on weight.

Production Example 1 : Synthesis of carboxyl group- and hydroxyphenyl group-containing polymer (a-1-1) 600 parts of o-hydroxybenzoic acid, 90 parts of o-cresol
0 parts, 30% formalin 1,145 parts, deionized water 1
30 parts and 6.5 parts of oxalic acid were placed in a flask and heated under reflux for 60 minutes. Thereafter, 13.5 parts of 15% hydrochloric acid was added and the mixture was heated under reflux for 40 minutes. Then 400 parts of deionized water at about 15 ° C was added to keep the contents at about 50 ° C to precipitate the resin.
After further adding 400 parts of deionized water to wash the resin at 50 ° C., the water layer was removed, and the same washing operation was repeated 3 times, followed by drying under reduced pressure at about 120 ° C. Polymer (a-1-1)] was obtained. This resin has a molecular weight of about 650 and a carboxyl group content of 2.8 mol / k.
g Polymer, hydroxyphenyl group content 5.4mol / kg
It was a polymer.

Production Example 2 : Synthesis of carboxyl group- and hydroxyphenyl group-containing polymer (a-1-2) 200 parts of tetrahydrofuran, 65 parts of p-hydroxystyrene, 28 parts of n-butyl acrylate, 1 acrylic acid
1 part and 3 parts of azobisisobutyronitrile were placed in a flask and the inside of the container was replaced with nitrogen, and then heated at 100 ° C. for 2 hours while stirring. The product was poured into 1,500 parts of toluene, the formed precipitate was separated, dissolved in 300 parts of acetone, and then poured again into 1,500 parts of toluene. The precipitate was dried under reduced pressure at 60 ° C to obtain a polymer (a-1-2).
This polymer has a molecular weight of about 5,200, and the composition ratio is acrylic acid / n-butyl acrylate / p-hydroxystyrene =
The ratio was 17/37/50 (weight ratio), and the carboxyl group content was 1.8 mol / kg polymer and the hydroxyphenyl group content was 4.6 mol / kg polymer.

Production Example 3 : Synthesis of carboxyl group-containing polymer (a-2-1) A mixture of acrylic acid 216 parts styrene 500 parts n-butyl methacrylate 284 parts azobisisobutyronitrile (AIBN) 50 parts was prepared. After adding dropwise to 600 parts of methyl isobutyl ketone heated to 80 ° C. and stirring for 2 hours, the temperature of the polymer (a-2-
A resin solution of 1) was obtained. This resin solution has a solid content of about 62.
5%, the content of carboxyl group in the solid content is 3 mol / k
The content was g and the aromatic ring content was 34.6%.

Production Example 4 : Synthesis of carboxyl group-containing polymer (a-2-2) Acrylic acid 288 parts Styrene 300 parts n-Butyl acrylate 255 parts 2-Hydroxyethyl acrylate 157 parts t-Butyl peroxybenzoate 100 parts The resulting mixture is heated to 110 ° C. and stirred 2-
After dropping into 1,000 parts of butoxyethanol over 2 hours, the temperature was maintained for 2 hours, and the polymer (a-2
A resin solution of -2) was obtained. This resin solution has a solid content of about 50
%, And the carboxyl group content in the solid content is 4 mol / kg
The aromatic ring content was 20.7%.

Production Example 5 : Synthesis of hydroxyphenyl group-containing polymer (a-3-1) o-cresol 1,490 parts, 30% formalin 1,
145 parts, deionized water 130 parts, and oxalic acid 6.5 parts were put into a flask and heated under reflux for 60 minutes. Then add 15% hydrochloric acid to 1
3.5 parts was added and the mixture was heated to reflux for 40 minutes. Then 400 parts of deionized water at about 15 ° C was added to keep the contents at about 75 ° C to precipitate the resin. Then, a 35% sodium hydroxide solution was added to neutralize and the water layer was removed, 400 parts of deionized water was further added, the resin was washed at 75 ° C., the water layer was removed, and the same washing operation was repeated twice. Then, it is dried under reduced pressure at about 120 ° C. and a novolac phenol resin [polymer (a-3-
1)] was obtained. This resin had a molecular weight of about 600.

Production Example 6 : Synthesis of hydroxyphenyl group-containing polymer (a-3-2) 60 parts of tetrahydrofuran, p-hydroxystyrene 2
1 part, n-butyl acrylate 9 parts, and azobisisobutyronitrile 3 parts were put into a flask, and the inside of the container was replaced with nitrogen and heated at 100 ° C. for 2 hours while stirring. 700 ml of product
Was poured into toluene and the precipitate formed was separated, 100 ml
After dissolving in acetone, 700 ml was poured again into toluene. The precipitate was dried under reduced pressure at 60 ° C. to obtain the polymer (a-3
-2) was obtained. This polymer had a molecular weight of about 14,000.

Production Example 7 : Polyvinyl ether compound (b-
Synthesis of 1) Bisphenol A 45.6 parts, 2-chloroethyl vinyl ether 80 parts, toluene 100 parts were put in a flask,
After purging with nitrogen, add 20 parts of sodium hydroxide, and the temperature is 80 ° C.
Heated for 30 minutes. Then, a solution prepared by dissolving 4.56 parts of tetrabutylammonium bromide in 20 parts of 2-chloroethyl vinyl ether was added, and the mixture was heated and reacted at 95 ° C. for 5 hours. After washing the reaction three times with deionized water, the oil layer was separated. The oil layer was distilled to remove unreacted 2-chloroethyl vinyl ether and toluene to obtain a polyvinyl ether compound (b-1). This compound contained two vinyl ether groups in one molecule.

Production Example 8 : Polyvinyl ether compound (b-
Synthesis of 2) o-cresol 1,490 parts, 30% formalin 1,
145 parts, deionized water 130 parts, and oxalic acid 6.5 parts were put into a flask and heated under reflux for 60 minutes. Then add 15% hydrochloric acid to 1
3.5 parts was added and the mixture was heated to reflux for 40 minutes. Then 400 parts of deionized water at about 15 ° C was added to keep the contents at about 75 ° C to precipitate the resin. Then, a 35% sodium hydroxide solution was added to neutralize and the water layer was removed, 400 parts of deionized water was further added, the resin was washed at 75 ° C., the water layer was removed, and the same washing operation was repeated twice. Then, it was dried under reduced pressure at about 120 ° C. to obtain a novolac phenol resin. Molecular weight about 600
Met. Bisphenol A 45.6 in Production Example 7
Production Example 7 except that 15 parts of the resin is used instead of the part
A poly (vinyl ether) compound (b-2) was obtained in exactly the same manner as. This compound contained an average of about 3.5 vinyl ether groups in one molecule.

Production of Positive Photosensitive Composition Production Example 9 Polymer (a-1-1) 100 parts Polyvinyl ether compound (b-1) 60 parts Photoacid generating compound (c-1) (Note 1) 10 parts The above mixture was dissolved in diethylene glycol dimethyl ether to give a positive photosensitive composition (P-
1) was obtained. (Note 1) Photoacid generating compound (c-1): a compound represented by the following formula.

[0074]

[Chemical 9]

Production Example 10 Polymer (a-2-1) solution (solid content 62.5%) 80 parts Polymer (a-3-1) 65 parts Polyvinyl ether compound (b-1) 60 parts Photo acid generation Compound (c-1) 10 parts The above mixture is dissolved in diethylene glycol dimethyl ether to give a positive photosensitive composition (P-
2) was obtained.

Production Example 11 Polymer (a-1-2) 100 parts Polyvinyl ether compound (b-2) 20 parts Photoacid generating compound (c-2) (Note 2) 7.5 parts Sensitizing dye (Note 3) 1 part Triethylamine 6 parts The above mixture was dissolved in a mixed solvent of 150 parts of 2-butoxyethanol and 25 parts of benzyl alcohol, and this solution was gradually added to 547 parts of deionized water under stirring to obtain a solid content of about 15%. Positive photosensitive composition (P-
3) was obtained. (Note 2) Photoacid generating compound (c-2): a compound represented by the following formula.

[0077]

[Chemical 10] (Note 3) Sensitizing dye: A compound represented by the following formula.

[0078]

[Chemical 11]

Production Example 12 Polymer (a-2-2) solution (solid content 50%) 200 parts Polymer (a-3-2) 50 parts Polyvinyl ether compound (b-2) 25 parts Photo acid generating compound ( c-2) 8 parts Triethylamine 15 parts After dissolving the above mixture in 200 parts of 2-butoxyethanol and 40 parts of benzyl alcohol, this solution was gradually added to 688 parts of stirring deionized water to obtain a solid content of about 15 parts.
% Of an aqueous dispersion to obtain a positive photosensitive composition (P-4).

Production Example 13 of electrodeposition coating material for forming colored portion Production Example 13 Monomer composition is styrene / methyl methacrylate / n-
Butyl acrylate / n-butoxymethyl acrylamide / 2-hydroxyethyl acrylate / acrylic acid =
10/34 / 28.5 / 10/12 / 5.5 (weight ratio)
Acrylic resin having a weight average molecular weight of 15,000 is dissolved in a mixed solvent of isopropyl alcohol / n-butyl alcohol / ethylene glycol monobutyl ether / propylene glycol monomethyl ether = 20/25/15/40 (weight ratio). To 100 parts of a resin solution having a solid content of 51%, 10 parts of propylene glycol monomethyl ether and 2.7 parts of triethylamine (neutralization equivalent 0.6
(Corresponding to 9). This mixed solution was gradually added to stirring deionized water to obtain an anionic electrodeposition resin composition having a solid content of 8.4%. This electrodeposition resin composition 98
16 parts of a blue pigment phthalocyanine blue was mixed with 4 parts of the mixture, and the pigment was dispersed with a paint shaker to obtain a blue anion electrodeposition bath solution.

Production Examples 14 to 16 Production Example 13 was repeated in the same manner as in Production Example 13 except that the electrodeposition resin composition and the pigment were mixed as shown in Table 1 below, and each color was red, green or black. To obtain an anion electrodeposition bath solution. The blending amounts in Table 1 are shown in parts by weight.

[0082]

[Table 1]

Example 1 Obtained in Production Example 9 on the transparent conductive layer 2 of the substrate [FIG. 1 (A)] in which the ITO (indium tin oxide) compound which is the transparent conductive layer 2 was formed on the glass substrate 1. The positive photosensitive composition (P-1) was applied with a spinner and dried by heating at 90 ° C. for 10 minutes to form a crosslinked positive photosensitive coating layer 3 having a film thickness of about 2 μm [FIG. 1 (B )]. Then, a mask 4 having a predetermined pattern is brought into close contact with the positive type photosensitive coating layer 3 [FIG. 1 (C)] and exposed through a mask 4 with an ultra-high pressure mercury lamp to an exposure amount of 20 mj / cm ^2. And 10 more
After heating at 0 ° C. for 3 minutes and developing with an alkaline developer which is an aqueous solution of tetramethylammonium hydroxide having a concentration of 0.75%, the exposed portion forms a salt and is eluted to expose the surface of the transparent conductive layer 2. [FIG. 1 (D)].

The substrate having this exposed portion was dipped in the blue anion electrodeposition bath solution obtained in Production Example 13, and a DC voltage of 5 V was applied for 30 seconds using the transparent conductive layer 2 as an anode. Was thoroughly washed with water. No electrodeposition film was formed at the location where the photosensitive coating layer was present, and an electrodeposition film that was not washed away with water was formed at the location where the transparent conductive layer was exposed.
After washing with water, it was heated and dried at 80 ° C. for 10 minutes to form the first colored portion 5 which was a transparent blue polymer film on the exposed portion of the transparent conductive layer [FIG. 1 (E)].

Then, a mask having a shifted pattern of the mask 4 was brought into close contact with this substrate, exposed through the mask with an ultra-high pressure mercury lamp in the same manner as above, and further heated at 100 ° C. for 3 minutes, and thereafter, the same as above. The surface of the transparent conductive layer 2 was exposed by developing with an alkaline developer [FIG. 1 (G)]. This substrate was dipped in the red anion electrodeposition bath solution obtained in Production Example 14 above, followed by conducting current, washing with water, and drying by heating in the same manner as above to obtain a transparent red layer at a location where the transparent conductive layer was exposed. The second colored portion 6 which is a polymer film was formed [FIG. 1 (H)].

Further, a mask in which the pattern of the mask 4 was shifted was brought into close contact with this substrate, exposed through the mask with an ultra-high pressure mercury lamp in the same manner as above, and further heated at 100 ° C. for 3 minutes, and then the same as above. The surface of the transparent conductive layer 2 was exposed by developing with an alkaline developer [FIG. 1 (J)]. This substrate was immersed in the green anion electrodeposition bath solution obtained in Production Example 15 above, followed by conducting electricity, washing with water, and drying by heating in the same manner as above, whereby a transparent green layer was formed at the location where the transparent conductive layer was exposed. A third colored portion 7 which is a polymer film was formed [FIG. 1 (K)].

Then, the entire surface of the substrate on which the remaining photosensitive film and the colored portions of blue, red and green are formed is exposed to an exposure amount of 20 mj / cm ² with an ultra-high pressure mercury lamp and further exposed at 100 ° C. for 3 minutes. After being dried by heating, by elution with a removing solution which is a sodium carbonate aqueous solution having a concentration of 1.25%, only the photosensitive film portion is eluted while leaving the colored portions of blue, red and green, and the surface of the transparent conductive layer 2 is removed. Was exposed [FIG. 1 (L)], and then heat-dried at 140 ° C. for 10 minutes to obtain a color filter. The thickness of the colored film in each colored portion was about 2 μm. The obtained color filter had high pattern accuracy, no coloring defects, and high reliability.

Example 2 A substrate [FIG. 1 (L)] in which the surface of the transparent conductive layer 2 was exposed by eluting only the photosensitive film portion while leaving the blue, red and green colored portions in Example 1 The sample was immersed in the black anion electrodeposition bath solution obtained in Preparation Example 16, a DC voltage of 3 V was applied for 20 seconds using the transparent conductive layer 2 as an anode, and then the substrate was pulled up and washed with water at 140 ° C. for 10 seconds. Another colored portion 8 is formed on the exposed portion of the transparent conductive layer by heating and drying for 8 minutes.
(Black matrix) was formed, and each colored portion of blue, red and green was sufficiently cured to obtain a color filter [FIG. 1 (M)]. The thickness of the colored film in each colored portion was about 2 μm. The obtained color filter had high pattern accuracy, no coloring defects, and high reliability.

Example 3 In Example 2, instead of the positive photosensitive composition (P-1), the positive photosensitive composition (P-2) obtained in Production Example 10 was used.
A color filter was obtained in the same manner as in Example 2 except that was used. The thickness of the colored film in each colored portion of this color filter was about 2 microns. Further, the obtained color filter had high pattern accuracy, no coloring defects, and high reliability.

Example 4 A substrate (FIG. 1A) in which an ITO (indium tin oxide) compound, which is a transparent conductive layer 2, was formed on a glass substrate 1 was used as a positive photosensitive composition ( P-3) is immersed in the electrodeposition bath, a direct current having a current density of 50 mA / cm ² is applied between the transparent conductive layer 2 as an anode and the counter electrode for 1 minute, and then the substrate is pulled up and washed sufficiently with water, It was heated and dried at 100 ° C. for 10 minutes to form a crosslinked positive photosensitive film layer 3 having a film thickness of about 3 μm [FIG. 1 (B)]. Using the substrate having this positive type photosensitive coating layer, the exposure amount was 5 mj / cm ² by the direct writing method so that the same pattern as that in Example 2 could be obtained by the light of the wavelength of 488 nm of the argon laser. The same procedure as in Example 2 was carried out except that the procedure was performed to obtain a color filter having blue, red, green, and black (black matrix) colored portions. The thickness of the colored film in each colored portion of this color filter was about 2 microns. Further, the obtained color filter had high pattern accuracy, no coloring defects, and high reliability.

Example 5 In Example 4, instead of the positive photosensitive composition (P-3), the positive photosensitive composition (P-4) obtained in Production Example 12 was used.
A color filter was obtained in the same manner as in Example 1 except that was used as the electrodeposition bath. The thickness of the colored film in each colored portion of this color filter was about 2 microns. Further, the obtained color filter had high pattern accuracy, no coloring defects, and high reliability.

Example 6 A substrate (FIG. 1 (L)) in which the surface of the transparent conductive layer 2 was exposed by eluting only the photosensitive film portion while leaving the colored portions of blue, red and green in Example 1 A commercially available black negative resist was applied to the surface of the substrate 1 on which the colored portion was formed by a spin coating method and dried. Then, the glass surface side of the substrate 1 was exposed using a high-pressure mercury lamp, developed using a black resist developing solution, and then heat-dried at 140 ° C. for 10 minutes. As a result, a color filter in which black colored portions (black matrix) were formed in the spaces between the blue, red, and green colored portions [FIG. 1 (M)] was obtained. The thickness of the colored film in each colored portion of this color filter was about 2 microns. Further, the obtained color filter had high pattern accuracy, no coloring defects, and high reliability.

Example 7 The substrate [FIG. 1 (L)] in Example 1 in which only the photosensitive film portion was eluted leaving the blue, red, and green colored portions to expose the surface of the transparent conductive layer 2 [FIG. 1 (L)] As a cathode, 400 g of chromic anhydride and 6 parts of sodium hydroxide per liter of plating bath
Immersion in a chrome plating bath containing 0 g, barium carbonate 7.5 g, and fluorosilicic acid 1 g, and applying a DC voltage of 5 V for 20 seconds between the counter electrode and chrome plating on the exposed transparent conductive layer. Was formed to obtain a color filter. The obtained color filter had high pattern accuracy, no coloring defects, and was highly reliable.

Example 8 A substrate [Example 1 (L)] in Example 1 in which the surface of the transparent conductive layer 2 was exposed by leaving only the blue, red, and green colored portions and eluting only the photosensitive film portion As a cathode, it is immersed in an electrolytic reduction bath of a hydrochloric acid aqueous solution having a concentration of 3.5%, a stainless steel plate is used as an anode, and a direct current voltage of 25 V is applied between both electrodes for 5 seconds,
The exposed transparent conductive layer was electrolytically reduced to blacken it to obtain a color filter. The obtained color filter had high pattern accuracy, no coloring defects, and was highly reliable.

[Brief description of drawings]

FIG. 1 is a process chart showing an example of a manufacturing method of the present invention,
(A)-(M) is the figure seen from the cross section.

[Explanation of symbols]

 1 Glass Substrate 2 Transparent Conductive Layer 3 Photosensitive Film Layer 4 Photomask 5 First Colored Part 6 Second Colored Part 7 Third Colored Part 8 Another Colored Part

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Riki Norimatsu 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Kansai Paint Co., Ltd.

Claims (8)

[Claims] 1. A step of forming a transparent conductive layer on a transparent substrate, [2] (a) a polymer (a-1) having a carboxyl group and a hydroxyphenyl group in one molecule, or a carboxyl group. A mixture of a polymer (a-2) having a hydroxyl group and a polymer (a-3) having a hydroxyphenyl group, (b) a compound having two or more vinyl ether groups in one molecule, and (c) A step of coating a positive photosensitive composition containing, as an essential component, a compound capable of generating an acid upon irradiation with active energy rays, on the transparent conductive layer and heating to form a positive photosensitive coating layer, [3] Exposing the photosensitive coating layer to a desired shape, heating it if necessary, and then developing it to expose a part of the transparent conductive layer; [4] by electrodeposition on the exposed transparent conductive layer. Step of forming a colored part of a desired color And [5] A method of manufacturing a color filter, which comprises repeating the above steps [3] and [4] a required number of times. 2. The polymer (a) is a polymer (a-1), and the polymer (a-1) has a carboxyl content in the range of 0.5 to 10 equivalents per 1 kg of the polymer (a-1). Group and 1.0 ~
The method for producing a color filter according to claim 1, which contains a hydroxyphenyl group in the range of 10 equivalents. 3. The polymer (a) is a polymer mixture of the polymer (a-2) and the polymer (a-3), and the polymer (a-
2) contains a carboxyl group in the range of 0.5 to 10 equivalents per 1 kg of the polymer (a-2), and the polymer (a-3)
Contains a hydroxyphenyl group in the range of 1.0 to 10 equivalents per 1 kg of the polymer (a-3). 4. The method for producing a color filter according to claim 1, further comprising the step of [6] removing the remaining photosensitive coating layer and exposing the conductive layer after the steps [1] to [5]. 5. The method for producing a color filter according to claim 4, further comprising a step of forming a desired colored portion on the exposed conductive layer by electrodeposition after the step [6]. 6. The method for producing a color filter according to claim 4, further comprising a step of forming a desired colored portion on the exposed conductive layer after the step [6] by a coating method. 7. The method for manufacturing a color filter according to claim 4, further comprising a step of forming a metal layer on the exposed conductive layer after the step [6] by a plating method. 8. The method for producing a color filter according to claim 4, further comprising a step of coloring the exposed conductive layer by oxidation or reduction after the step [6].