JP2007333880A - Manufacturing method of pixel separation wall for ink jet method, substrate with pixel separation wall for ink jet method, color filter, its manufacturing method and liquid crystal display apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a pixel separation wall for an ink jet method which has a cross-sectional shape suitable for manufacturing RGB pixels of a color filter by the ink jet method and to provide a substrate with the pixel separation wall for the ink jet method manufactured by the method, the color filter using the same and having no color mixing, its manufacturing method and a liquid crystal display apparatus. <P>SOLUTION: The manufacturing method of the pixel separation wall for the ink jet method has at least a photosensitive resin layer formation process of forming a photosensitive resin layer which contains at least an optically acid generating agent, a bridging agent of bridging by an action of the optically acid generation agent, an alkali-soluble binder, a basic compound and a color material at least on one surface of the substrate, an exposure process of exposing the photosensitive resin layer to harden an exposed region and a development process of forming the pixel separation wall by removing the photosensitive resin layer of a non-exposed part. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a separation wall for an ink jet method, a substrate with a separation wall for an ink jet method, a color filter, a method for producing the same, and a liquid crystal display device.

  A color filter for a display device has a structure in which red, green, and blue dot-like images are arranged in a matrix on a substrate such as glass, and the boundary is divided by a dark color separation wall such as a black matrix. As a manufacturing method of such a color filter, conventionally, a substrate such as glass is used as a support, 1) a dyeing method, 2) a printing method, 3) application of a colored photosensitive resin solution, and repeated exposure and development. Colored photosensitive resin liquid method (colored resist method) (see, for example, Patent Document 1) 4) Method of sequentially transferring images formed on a temporary support onto the final or temporary support 5) Pre-coloring A method in which a colored layer is formed by applying the photosensitive resin liquid on a temporary support, and the photosensitive colored layer is sequentially transferred directly onto the substrate, exposed, and developed for the number of colors. There is known a method (transfer method) for forming a multicolor image by the above (see, for example, Patent Document 2). A method using an ink jet method (see Patent Document 3) is also known.

Among these methods, although the color resist method can produce a color filter with high positional accuracy, it is not advantageous in terms of cost due to a large loss in application of the photosensitive resin solution. On the other hand, the ink-jet method has a problem that the positional accuracy of the pixels is poor, although the loss of the resin liquid is small and advantageous in terms of cost.
In order to overcome these problems, a color filter manufacturing method has been proposed in which a separation wall is formed by a colored resist method and an RGB pixel is produced by an inkjet method. In addition, since the edge of each color is easily rounded and each of the ink droplets that have been ejected later easily crosses the image separation wall, color mixing occurs with adjacent pixels, thereby degrading display quality.

  Conventionally, the exposed portion is cured by photoradical polymerization to form a separation wall. However, in this conventional method, the edge of the upper part of the separation wall has already been formed into a gentle shape at the stage after development, and the optimum shape as the separation wall has not been achieved.

Further, a method of forming a cured resin pattern such as a photo spacer by cationic polymerization is disclosed (for example, see Patent Document 4). However, there is no mention of a separation wall used when an RGB pixel is produced by an inkjet method.
Further, a transfer type photosensitive resin composition using chemical amplification useful for forming a color image layer such as a color filter, and a photosensitive transfer sheet using the same are disclosed (for example, Patent Document 5). However, there is no description regarding the shape of the cured resist, although it is sought to reduce the side edge and increase the development latitude.
Japanese Patent Laid-Open No. 1-152449 JP-A-61-99102 JP-A-8-227010 JP 2004-184441 A Japanese Patent Laid-Open No. 2002-351075

The present invention has been made in view of the above-described conventional problems, and a method for manufacturing a separation wall for an inkjet method having a suitable cross-sectional shape when an RGB pixel of a color filter is manufactured by an inkjet method, and the method. It is an object of the present invention to provide a substrate with a separation wall for an inkjet method.
It is another object of the present invention to provide a color filter having high resolution without color mixing using the substrate with a separation wall for the ink jet method, a method for manufacturing the color filter, and a liquid crystal display device using the color filter.

In view of the above circumstances, the present inventors have conducted extensive research and found that the above problems can be solved, thereby completing the present invention.
That is, the present invention is achieved by the following means.

That is, the present invention
<1> A photosensitive resin comprising at least one surface of a substrate containing at least a photoacid generator, a crosslinking agent that crosslinks by the action of the photoacid generator, an alkali-soluble binder, a basic compound, and a coloring material. A photosensitive resin layer forming step of forming a layer; an exposure step of exposing the photosensitive resin layer to cure an exposed region; and removing the photosensitive resin layer in an unexposed portion to form a separation wall. And a developing step.

<2> A photosensitive resin comprising at least one surface of a substrate containing at least a photoacid generator, a crosslinking agent that crosslinks by the action of the photoacid generator, an alkali-soluble binder, a basic compound, and a coloring material. A photosensitive resin layer forming step of forming a layer; an exposure step of exposing the photosensitive resin layer to cure an exposed region; and removing the photosensitive resin layer in an unexposed portion to form a separation wall. A substrate with a separation wall for an ink jet method manufactured through at least a development step.

<3> A photosensitive resin comprising at least one surface of a substrate containing at least a photoacid generator, a crosslinking agent that crosslinks by the action of the photoacid generator, an alkali-soluble binder, a basic compound, and a coloring material. A photosensitive resin layer forming step of forming a layer; an exposure step of exposing the photosensitive resin layer to cure an exposed region; and removing the photosensitive resin layer in an unexposed portion to form a separation wall. A pixel that forms a pixel by applying a droplet of a colored liquid composition to a region separated by the separation wall by the inkjet method using a substrate with a separation wall for an inkjet method manufactured through at least a development step A method for producing a color filter having a forming step.

<4> A color filter manufactured by the method for manufacturing a color filter according to <3>.
<5> A liquid crystal display device having the color filter according to <4>.

According to the present invention, there is provided a method for producing a separation wall for an inkjet method having a cross-sectional shape suitable for producing RGB pixels of a color filter by the inkjet method, and a substrate with a separation wall for an inkjet method produced by the method. Can be provided.
Furthermore, according to the present invention, it is possible to provide a high-resolution color filter without color mixing using the substrate with a separation wall for the ink jet method, a method for manufacturing the color filter, and a liquid crystal display device using the color filter.

The present invention will be described below. In the present invention, the “separation wall for inkjet method” refers to a separation wall used when pixels are formed by inkjet method in the production of a color filter.
<Method for producing separation wall for inkjet method and substrate with separation wall for inkjet method>
The method for producing a separation wall for ink jet method of the present invention (hereinafter sometimes simply referred to as “separation wall”) includes a photoacid generator on at least one surface of a substrate, and the photoacid generator. A photosensitive resin layer forming step of forming a photosensitive resin layer including at least a crosslinking agent that crosslinks by an action, an alkali-soluble binder, a basic compound, and a coloring material; and exposing the photosensitive resin layer to an exposed area At least an exposure process for curing the image forming layer and a developing process for forming a separation wall by removing the photosensitive resin layer in the unexposed area.
The board | substrate with the separation wall for inkjet methods of this invention can be manufactured with the manufacturing method of the separation wall for inkjet methods of this invention.

The separation wall for inkjet method of the present invention comprises a photoacid generator that absorbs light to generate an acid, a crosslinking agent that crosslinks by the action of the photoacid generator, an alkali-soluble binder, a basic compound, a color It manufactures by carrying out the crosslinking reaction of the photosensitive resin layer containing a material.
According to the crosslinking reaction in the present invention, it is not necessary to take measures against insufficient curing due to oxygen inhibition (polymerization in a poor oxygen atmosphere, etc.) as compared with conventional radical polymerization, and separation is performed even at the stage after development. The upper end of the wall and its edge are not rounded, and an optimum shape can be formed for the steep inkjet method.

Hanarega wall in the present invention, the intersection of cross-section that is preferably (1) a substrate and Hanarega wall meets the following conditions (1) and (2) and A ₁ and A _2. Let H be the highest point of the separation wall, G be a leg of a perpendicular line from H to the substrate, and L ₀ be a straight line passing through H and parallel to the substrate surface. A point that internally divides H and G into HP: PG = 1: 3 is defined as P, a straight line passing through P and parallel to the substrate surface is defined as L ₁ , and a point where L ₁ intersects the cross section of the separation wall is represented by B ₁ , B ₂ . When the distance between A ₁ and A ₂ is a and the distance between B ₁ and B ₂ is b, the value of b / a is 0.8 or more and 1.2 or less.
(2) The ratio A ₆₀₀ / A ₅₀₀ of the absorbance A _{600 at 600} nm and the absorbance A ₅₀₀ at ₅₀₀ nm is 0.7 to 1.4.

In order to obtain a color filter with good image quality, the color tone of the separating wall is important in addition to preventing the color mixture between the pixels. Since the side of the image separation wall is usually not vertical (b / a value is less than 1), a color obtained by adding the color of the pixel such as red, blue and green and the color of the image separation wall is displayed around the pixel. Become. In other words, no matter how pure the color of pixels such as red, blue, and green, if the color of the image separation wall is not achromatic, the color tone will not be good when viewed on the entire screen.
The color of the image separation wall is preferably jet black. Therefore, it is preferable to use a black color material such as carbon black, titanium black, graphite, or a metal compound (for example, iron oxide or titanium oxide) as the color material for the separation wall. However, what is generally called a black color material (black pigment or black dye) is not strictly black (absorbance of visible light is equal over the entire wavelength range). For example, even in the case of carbon black, which is a typical black pigment, the color tone varies depending on the preparation method, the particle size, the structure, and the like, but the particle size greatly contributes to this color tone. The particle diameter is preferably 10 to 75 nm, more preferably 12 to 50 nm, and further preferably 15 to 40 nm. If the particle size is less than 10 nm or exceeds 75 nm, the value of A ₆₀₀ / A ₅₀₀ is not preferable because it is out of the range of 0.7 to 1.4.
The “particle diameter” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle diameter” is the above-mentioned particle diameter for a number of particles, This 100 average value is said.

The photosensitive resin layer in the present invention is a method (coating method) for applying a photosensitive resin composition containing at least a photoacid generator, a crosslinking agent, an alkali-soluble binder, a basic compound, and a coloring material, or the photosensitive resin composition. It is formed by a method (transfer method) of transferring a photosensitive transfer material having a photosensitive resin layer formed of an object.
Hereinafter, the photosensitive resin composition and the photosensitive transfer material will be described.

[Photosensitive resin composition]
A separation wall for an inkjet method on a substrate is a photosensitive resin comprising at least a photoacid generator, a crosslinking agent that crosslinks by the action of the photoacid generator, an alkali-soluble binder, a basic compound, and a coloring material. It is formed from a composition (also referred to as “dark color photosensitive resin composition” or “dark color composition”).
Here, the dark color composition is a composition having a high optical density at 555 nm, and its value is preferably 2.5 or more, more preferably 2.5 to 10.0, and more preferably 2.5 to 6 0.0 is more preferable, and 3.0 to 5.0 is particularly preferable.
In addition, since the dark color composition is cured by causing a crosslinking reaction by the catalytic action of an acid generated from a photoacid generator as will be described later, the optical density with respect to the exposure wavelength (generally the ultraviolet region) is also important. That is, the value is 2.0 to 10.0, preferably 2.5 to 6.0, and most preferably 3.0 to 5.0. If it is less than 2.0, the shape of the separation wall may not be as desired, and if it exceeds 10.0, the crosslinking reaction cannot be started and it is difficult to produce the separation wall itself.
Hereinafter, the components in the composition will be described.

(Photoacid generator)
Examples of the photoacid generator that generates an acid by light irradiation include organic halogen compounds, onium salts, and sulfonic acid esters. Among these, organic halogen compounds are preferable, and halomethylated triazine and halomethylated oxadiazole compounds are particularly preferable. Specifically, the halomethylated triazine compound is represented by the general formula (1).

(Wherein R ¹ and R ² are halomethyl groups, and Y is an organic group having 5 or more carbon atoms.)
Examples of the halomethyl group include a trichloromethyl group, a tribromomethyl group, a dichloromethyl group, and a dibromomethyl group. Examples of the organic group having 5 or more carbon atoms include a phenyl group that may have a substituent, Examples include naphthyl group, styryl group, styrylphenyl group, furylvinyl group, quaternized aminoethylamino group. Specific examples of the halomethylated triazine compound include compounds represented by the following formulas (2) to (23).

  Among the halomethylated triazine compounds represented by the general formula (1), preferred are compounds represented by the following general formulas (24) to (26).

In the formula, R ¹ and R ² are halomethyl groups, R is independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 0 to 3.

In the formula, R ¹ and R ² are halomethyl groups, R is independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 0 to 3.

In the formula, R ¹ and R ² are halomethyl groups, R is independently an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 1. Among the compounds represented by the general formulas (24) to (26), R ¹ and R ² are trichloromethyl groups, R has 1 to 2 carbon atoms, and the general formulas (24) and (25 ), N is an integer of 0 to 2, and the general formula (26) is a compound of 0 to 1.
The halomethylated oxadiazole compound is represented by the general formula (27).

In the formula, R ³ is a halomethyl group, and Z is a benzofuryl group or a benzofurylvinyl group which may have a substituent. Specific examples of the halomethylated oxadiazole compound include compounds represented by the following formulas (28) to (45).

  Among the halomethylated oxadiazole compounds represented by the general formula (27), a compound represented by the following general formula (46) is preferable.

In the formula, R ³ is a halomethyl group, each R is independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 0 to 2. Further preferred are compounds in which R ³ is a trichloromethyl group, each R is independently an alkyl group or alkoxy group having 1 to 2 carbon atoms, and n is an integer of 0 to 1.

  A photo-acid generator is 0.05-15 mass% with respect to solid content in the photosensitive resin layer, Preferably it is 5-15 mass%. When the content of the photoacid generator exceeds 15% by mass, the pattern swells, and when it is less than 0.05% by mass, a sufficient amount of acid is not generated by exposure. In some cases, the crosslinking between the binder) and the crosslinking agent becomes insufficient, resulting in a decrease in the remaining film ratio after development, and the heat resistance and chemical resistance of the image are likely to be decreased.

(Crosslinking agent)
The photosensitive resin composition in the present invention contains a crosslinking agent because it cures by causing a crosslinking reaction with an alkali-soluble binder.
The crosslinking agent has a curing action due to the action of an acid. Examples of the crosslinking agent include compounds having a substituent having at least one or more crosslinking substituents (hereinafter referred to as “crosslinkable substituent”).

Specific examples of such a crosslinkable substituent include, for example, (i) a hydroxyalkyl group such as a hydroxyalkyl group, an alkoxyalkyl group, an acetoxyalkyl group, or a derivative thereof;
(Ii) a carbonyl group such as a formyl group, a carboxyalkyl group or a derivative thereof;
(Iii) nitrogen-containing group-containing substituents such as dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group, morpholinomethyl group;
(Iv) Glycidyl group-containing substituents such as glycidyl ether group, glycidyl ester group, glycidylamino group;
(V) Aromatic derivatives such as allyloxyalkyl groups such as benzyloxymethyl group and benzoyloxymethyl group, and aralkyloxyalkyl groups;
(Vi) Substituents containing polymerizable multiple bonds such as vinyl groups and isopropenyl groups.
As the crosslinkable substituent of the crosslinking agent of the present invention, a hydroxyalkyl group, an alkoxyalkyl group or the like is preferable, and an alkoxymethyl group is particularly preferable.

Examples of the crosslinking agent having a crosslinkable substituent include (i) methylol groups such as (i) methylol group-containing melamine compounds, methylol group-containing benzoguanamine compounds, methylol group-containing urea compounds, methylol group-containing glycoluril compounds, and methylol group-containing phenol compounds. Containing compounds;
(Ii) alkoxyalkyl group-containing compounds such as alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing glycoluril compounds, alkoxyalkyl group-containing phenol compounds;
(Iii) Carboxymethyl group-containing compounds such as carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, carboxymethyl group-containing glycoluril compounds, carboxymethyl group-containing phenol compounds;
(Iv) Examples include bisphenol A-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, novolac resin-based epoxy compounds, resol resin-based epoxy compounds, and epoxy compounds such as poly (hydroxystyrene) -based epoxy compounds. it can.

  The crosslinking agent in the present invention is preferably an alkoxymethylated melamine compound or a resin thereof, or an alkoxymethylated glycoluril compound or a resin thereof. Particularly preferred crosslinking agents include alkoxymethylated urea compounds represented by the following formula (47) or alkoxymethylated glycoluril compounds represented by the formula (48).

Here, R ³ is an alkyl group having 1 to 4 carbon atoms.

Here, R ⁴ is an alkyl group having 1 to 4 carbon atoms.

In the formula (47) and formula (48), examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
The cross-linking agent is, for example, after condensing a melamine compound or glycoluril compound and formalin to introduce a methylol group, and then etherifying with a lower alcohol such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, etc. It is obtained by recovering the compound or its resin which cools and precipitates. The crosslinking agent can also be obtained as a commercial product such as CYMEL (trade name, manufactured by Mitsui Cyanamid) or Nicarad (manufactured by Sanwa Chemical).

  As the cross-linking agent, melamine, benzoguanamine, glycoluril, urea, a compound in which formaldehyde is allowed to act, or an alkyl-modified compound thereof, an epoxy compound, a resole compound, and the like are effective. Specific examples thereof are as follows.

Specifically, Mitsui Cyanamid's Cymel (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141,272,254,202,1156,1158 and Nikarad (registered trademark) MW-30M, MW-30, MW-22, MS-11, MS-001, MX-730, MX-750 manufactured by Sanwa Chemical, MX-706 and MX-035 are examples of compounds in which formaldehyde is allowed to act on melamine or alkyl-modified products thereof. Cymel (registered trademark) 1123, 1125, and 1128 are examples of a compound obtained by allowing formaldehyde to act on benzoguanamine or an alkyl-modified product thereof. Cymel (registered trademark) 1170, 1171, 1174, and 1172 are examples of compounds obtained by allowing formaldehyde to act on glycoluril or alkyl-modified products thereof.
UFR (registered trademark) 65, 300 of Mitsui Cyanamid Co., Ltd. can be given as an example of a compound obtained by reacting urea with formaldehyde or an alkyl modified product thereof.

  Examples of epoxy compounds include novolak epoxy resins (VDPN-638, 701, 702, 703, 704, etc. manufactured by Tohto Kasei), amine epoxy resins (YH-434, manufactured by Tohto Kasei), bisphenol A epoxy resin, sorbitol (poly ) Glycidyl ether, (poly) glycerol (poly) glycidyl ether, pentaerythritol (poly) glycidyl ether, triglycidyl trishydroxyethyl isocyanurate, allyl glycidyl ether, ethyl hexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, lauryl alcohol glycidyl ether Glycidyl ether adipate, glycidyl phthalate, dibromophenyl glycidyl ether, dibromoneopentyl glycol Glycidyl ether, glycidyl phthalimide, may be mentioned (poly) ethylene glycol glycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, butyl glycidyl ether.

Among these, particularly preferred compounds include compounds having a —N (CH ₂ OR) ₂ group in the molecule (wherein R represents a hydrogen atom or an alkyl group).
Specifically, a compound obtained by reacting formaldehyde with urea or melamine or an alkyl-modified product thereof is particularly preferable.
Examples of the resol compound include PP-3000s, PP-3000A, RP-2978, SP-1974, SP-1975, SP-1976, SP-1977, and RP-3972 manufactured by Gunei Chemical Co., Ltd.
These crosslinking agents may be used alone or in combination of two or more.

  As content in the photosensitive resin composition (photosensitive resin layer) of a crosslinking agent, Preferably it is 5-70 mass% with respect to the quantity of an alkali-soluble binder, More preferably, it is 10-40 mass%. If the content of the crosslinking agent exceeds 70% by mass, the surface of the photosensitive resin composition may become sticky, resulting in difficulty in handling, and if the content of the crosslinking agent is less than 5% by mass, Cross-linking between the soluble binder and the cross-linking agent becomes insufficient, resulting in a decrease in the remaining film ratio after development, and the separation wall formed using the photosensitive resin composition for forming the separation wall is rounded at the top and its edges. In some cases, a sharp separation wall for the ink jet method cannot be formed.

(Basic compound)
The photosensitive resin composition in the present invention contains a basic compound in order to make the crosslinking reaction between the crosslinking agent and the alkali-soluble binder (photosensitive resin) sufficient.
As the basic compound, known primary to tertiary amine compounds can be used without any particular limitation.
For example, the following compounds can be mentioned.

-Primary amine compound-
Examples of the primary amine compound include benzylamine, phenethylamine, 3-phenyl-1-propylamine, 4-phenyl-1-butylamine, 5-phenyl-1-pentylamine, 6-phenyl-1-hexylamine, α-methylbenzylamine, 2-methylbenzylamine, 3-methylbenzylamine, 4-methylbenzylamine, 2- (p-tolyl) ethylamine, β-methylphenethylamine, 1-methyl-3-phenylpropylamine, 2-chloro Benzylamine, 3-chlorobenzylamine, 4-chlorobenzylamine, 2-fluorobenzylamine, 3-fluorobenzylamine, 4-fluorobenzylamine, 4-bromophenethylamine, 2- (2-chlorophenyl) ethylamine, 2- ( 3-Chlorophenyl) ethyla Min, 2- (4-chlorophenyl) ethylamine, 2- (2-fluorophenyl) ethylamine, 2- (3-fluorophenyl) ethylamine, 2- (4-fluorophenyl) ethylamine, 4-fluoro-α, α-dimethyl Phenethylamine, 2-methoxybenzylamine, 3-methoxybenzylamine, 4-methoxybenzylamine, 2-ethoxybenzylamine, 2-methoxyphenethylamine, 3-methoxyphenethylamine, 4-methoxyphenethylamine, methylamine, ethylamine, propylamine, 2 -Propylamine, allylamine, butylamine, t-butylamine, sec-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, laurylamine, aniline, octylua Nilin, anisidine, 4-chloroaniline, 1-naphthylamine, methoxymethylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 2-butoxyethylamine, 2-cyclohexyloxyethylamine, 3-ethoxypropylamine, Examples include 3-propoxypropylamine and 3-isopropoxypropylamine.

-Secondary amine compound-
Examples of the secondary amine compound include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dibenzylamine, dioctylamine, diallylamine, N-methylbenzylamine, N-methyloctadecylamine, and N-methyl. Aniline, piperidine, pyrrolidine, morpholine, piperazine, methylpiperazine and the like can be mentioned.

-Tertiary amine compound-
Examples of the tertiary amine compound include morpholinoacetophenone, nitrodimethylphenylmorpholine, triethylamine, diazabicyclo [2.2.2] octane, cyclohexylmorpholinothiourea, and the like.

  The basic compound in the present invention is preferably strongly basic. Among them, from the viewpoint of basicity, an aliphatic amine compound, specifically, butylamine, 2-methoxyethylamine, α-methylbenzylamine, diisopropyl is preferred. Amine, methylpiperazine, piperidine, morpholine, triethylamine and morpholinoacetophenone are preferable, and methylpiperazine, triethylamine and morpholinoacetophenone are more preferable.

  These basic compounds may be used alone or in combination of two or more.

The basic compound is preferably 0.1 to 0.5% by mass, more preferably 0.2 to 0.4% by mass, based on the solid content in the photosensitive resin composition (photosensitive resin layer). Especially preferably, it is 0.25-0.35 mass%.
When the content of the basic compound is less than 0.1% by mass in the above range, the effects of the present invention may not be sufficiently obtained. May deteriorate.

(Alkali-soluble binder)
The photosensitive resin composition in the present invention contains at least one alkali-soluble binder (hereinafter also simply referred to as “binder”).
This binder is cured by forming a cross-linked body (polymer) by cross-linking reaction with the cross-linking agent by the catalytic action of an acid generated from the photoacid generator in pattern exposure.

  The binder can be appropriately selected from known binders such as (meth) acrylic resin, polyester resin, vinyl resin, novolac resin (phenol novolac resin, cresol novolac resin, etc.), polyhydroxystyrene, and the like. .

In the present invention, a vinyl copolymer obtained by copolymerization of a (meth) acrylic monomer is particularly preferable, and a copolymer containing a methacrylic acid alkyl ester, an acrylic acid alkyl ester, or a carboxyl group-containing monomer as a constituent unit is preferable. More preferred. A (meth) acrylic type is preferable in terms of imparting flexibility, and a carboxyl group is preferably contained in terms of imparting appropriate weak alkali development.
In addition, (meth) acryl shows that it can take both acryl or methacryl. The same applies hereinafter.

  Among the above, a copolymer containing at least one of methyl methacrylate and benzyl methacrylate is particularly preferable. Examples of the copolymer containing at least one of methyl methacrylate and benzyl methacrylate include a copolymer containing methyl methacrylate, a copolymer containing benzyl methacrylate, and a copolymer containing methyl methacrylate and benzyl methacrylate. .

  Examples of the copolymer containing methyl methacrylate include a methacrylic acid / methyl methacrylate copolymer (copolymerization ratio: 14 to 17.6 mol% / 82.4 to 86 mol%, weight average molecular weight 20,000 to 140). , 000), methacrylic acid / methyl methacrylate / ethyl acrylate copolymer (copolymerization ratio: 5 to 10 mol% / 70 to 60 mol% / 25 to 30 mol%, weight average molecular weight 20,000 to 140,000) Etc.

  Examples of the copolymer containing benzyl methacrylate include methacrylic acid / benzyl methacrylate copolymer (copolymerization ratio: 25 to 37 mol% / 75 to 63 mol%, weight average molecular weight 20,000 to 150,000), methacrylic acid. / Benzyl methacrylate / styrene copolymer (copolymerization ratio: 20 mol% / 17.8 mol% / 62.2 mol%, weight average molecular weight 20,000 to 140,000).

  The copolymer containing methyl methacrylate and benzyl methacrylate includes a methacrylic acid / methyl methacrylate / benzyl methacrylate copolymer (copolymerization ratio: 14.6 to 27.2 mol% / 79.1 to 32.7 mol). % / 16.3 to 40 mol%, weight average molecular weight 20,000 to 150,000), methacrylic acid / methyl methacrylate / benzyl methacrylate / 2-ethylhexyl acrylate copolymer (copolymerization ratio: 10 to 15 mol% / 70-65 mol% / 10 mol% / 10 mol%, weight average molecular weight 20,000-150,000) and the like.

  The cresol novolac resin and polyhydroxystyrene and derivatives thereof that are conventionally used in commercially available negative resist compositions are colored after exposure and after baking, but after such exposure, coloring during baking is not possible. The above-mentioned methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / methyl methacrylate / benzyl methacrylate copolymer and the like are particularly preferable in that they are small and the light transmittance does not decrease.

  Said alkali-soluble binder may be used individually by 1 type, or may use 2 or more types together.

  As content in the photosensitive resin composition of the said alkali-soluble binder, 10-90 mass% is preferable with respect to the total solid of this composition, and 20-70 mass% is more preferable.

  When the content of the alkali-soluble binder exceeds 90% by mass, or when the content is less than 10% by mass, the crosslinking between the alkali-soluble binder and the crosslinking agent becomes insufficient, and the remaining film ratio after development decreases. In some cases, the separation wall formed by using the photosensitive resin composition for forming the separation wall is rounded at the upper part and the edge thereof, so that a sharp separation wall for the ink jet method may not be formed.

(Color material)
Specific examples of the color material used in the present invention include those given the color index (CI) numbers described in the following dyes and pigments.
For the photosensitive resin composition in the present invention, organic pigments, inorganic pigments, dyes, and the like can be suitably used. When the photosensitive resin layer is required to have light shielding properties, carbon black, titanium oxide, tetraoxide In addition to a light-shielding agent such as metal oxide powder such as iron, metal sulfide powder, and metal powder, a mixture of pigments such as red, blue, and green can be used. Moreover, a well-known color material (dye, pigment) can be used. When using a pigment among the known coloring materials, it is preferable that the pigment is uniformly dispersed in the photosensitive resin composition.
The ratio of the color material in the solid content of the photosensitive resin composition is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, from the viewpoint of sufficiently shortening the development time. More preferably, it is 50-55 mass%.

  Specific examples of the known dyes or pigments include the color materials described in JP-A-2005-17716 [0038] to [0040] and JP-A-2005-361447 [0068] to [0072]. The coloring materials described in JP-A-2005-17521 and the color materials described in [0080] to [0088] can be suitably used.

  The pigment is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a photosensitive resin composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle) described later. The vehicle refers to a portion of a medium in which a pigment is dispersed when the paint is in a liquid state, and is a liquid portion that binds to the pigment and hardens the coating film (binder), and a component that dissolves and dilutes the portion. (Organic solvent). The disperser used for dispersing the pigment is not particularly limited. For example, the kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, 438, Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described in Item 310 of the document.

(solvent)
In the photosensitive resin composition in the present invention, an organic solvent may be further used in addition to the above components. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like.

(Surfactant)
In the image separation wall or the photosensitive transfer material in the present invention, the photosensitive resin composition can be applied to a substrate or a temporary support by using a slit-like nozzle described later. By containing an appropriate surfactant therein, the film thickness can be controlled to be uniform, and coating unevenness can be effectively prevented.
Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.
The surfactant content relative to the total solid content of the photosensitive resin composition is generally 0.001 to 1%, preferably 0.01 to 0.5%, and preferably 0.03 to 0.3. % Is particularly preferred.

(UV absorber)
The photosensitive resin composition in the present invention may contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include salicylate series, benzophenone series, benzotriazole series, cyanoacrylate series, nickel chelate series, hindered amine series and the like in addition to the compounds described in JP-A-5-72724.
Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-di-phenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone , Nickel dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -Sebake 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4- Piperidenyl) -ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5-triazine -2-yl] amino} -3-phenylcoumarin and the like.
In addition, as for content of the ultraviolet absorber with respect to the total solid of the photosensitive resin composition, 0.5 to 15% is common, 1 to 12% is preferable, and 1.2 to 10% is especially preferable.

(Sensitizer)
The photosensitive resin composition in the present invention may contain a sensitizer as necessary. By using a sensitizer, the sensitivity of the photosensitive resin composition in the visible light region can be made sufficient.
Although the specific example of the sensitizer used suitably for this invention below is shown, this invention is not limited to these.

  The content of the sensitizer in the photosensitive resin composition is preferably 0.5 to 3.0% by mass, more preferably 1.0 to 2.0% by mass in terms of solid content. .

  The thickness of the photosensitive resin layer in the present invention is not particularly limited and depends on the solid content of the photosensitive resin composition and the thickness of the separation wall to be formed. To 12 μm is preferable, 1.5 to 12 μm is more preferable, 1.8 to 8 μm is further preferable, and 2.0 to 6.0 μm is particularly preferable.

[Photosensitive transfer material]
In order to realize the shape of the separating wall in the present invention easily and at low cost, it has at least an intermediate layer and a layer made of a photosensitive resin composition in order from the side closer to the temporary support on the temporary support. There is a method (2) described later in which a photosensitive transfer material is used.

(Temporary support)
The temporary support in the photosensitive transfer material can be appropriately selected from those that are chemically and thermally stable and composed of a flexible substance. Specifically, a thin sheet such as Teflon (registered trademark), polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, or a laminate thereof is preferable. As thickness of the said temporary support body, 5-300 micrometers is suitable, Preferably it is 20-150 micrometers. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

(Photosensitive resin composition layer)
The photosensitive resin composition layer in the photosensitive transfer material is formed from the photosensitive resin composition, and the shape and other characteristics, the formation method, and the like are the same as those formed by the coating method, and are preferable. The aspect is also the same.

(Middle layer)
In the photosensitive resin transfer material in the present invention, the photosensitive resin layer formed on the temporary support and other layers (for example, the following thermoplastics) are used for the purpose of preventing the layers from being mixed when forming a multilayer. An intermediate layer is preferably provided between the resin layer and the resin layer.
Specifically, the intermediate layer is preferably a layer mainly composed of polyethylene, polyvinylidene chloride, polyvinyl alcohol or the like, and among them, a layer mainly composed of polyvinyl alcohol is more preferable.
The polyvinyl alcohol preferably has a saponification degree of 80% or more. As content of the said polyvinyl alcohol in the said intermediate | middle layer, 25 mass%-99 mass% are preferable, 50 mass%-90 mass% are more preferable, 50 mass%-80 mass% are especially preferable. Further, polymers such as polyvinyl pyrrolidone and polyacrylamide may be added as necessary, and among them, polyvinyl pyrrolidone is preferable. The addition amount of these polymers is 1-40 mass% of the whole layer, More preferably, it is 10-35 mass%.
Moreover, as an intermediate | middle layer which can be used for this invention, the "separation layer" described in [0014]-[0015] of Unexamined-Japanese-Patent No. 5-72724 is mentioned as a preferable thing. In addition, as a film thickness of an intermediate | middle layer, Preferably it is 0.2-10 micrometers, More preferably, it is 0.5-3.0 micrometers.

(Thermoplastic resin layer)
The photosensitive transfer material may have a thermoplastic resin layer as necessary. Such a thermoplastic resin layer is preferably alkali-soluble and comprises at least a resin component, and the resin component preferably has a substantial softening point of 80 ° C. or less. By providing such a thermoplastic resin layer, good adhesion to the permanent support (substrate) can be exhibited in the separation wall forming method described later.
Examples of alkali-soluble thermoplastic resins having a softening point of 80 ° C. or lower include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meth) acrylic. Examples thereof include saponification products of acid ester copolymers, saponification products such as poly (meth) acrylic acid esters, and (meth) acrylic acid ester copolymers such as butyl (meth) acrylate and vinyl acetate.
For the thermoplastic resin layer, at least one of the above-mentioned thermoplastic resins can be appropriately selected and used. Further, “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Federation, published by the Industrial Research Council, Of those organic polymers having a softening point of about 80 ° C. or lower, issued on October 25, 1968), those soluble in an alkaline aqueous solution can be used.
In addition, for an organic polymer substance having a softening point of 80 ° C. or higher, by adding various plasticizers compatible with the polymer substance to the organic polymer substance, the substantial softening point is 80 ° C. or lower. It can also be used by lowering. In addition, these organic polymer substances include various polymers, supercooling substances, adhesion improvers or interfaces within the range where the substantial softening point does not exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support. Activators, mold release agents, etc. can also be added.
Specific examples of preferable plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, and biphenyl diphenyl phosphate.

(Protective film)
It is preferable to provide a thin protective film on the photosensitive resin composition layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but it must be easily separated from the photosensitive resin composition layer. For example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material. The thickness of the protective film is generally 4 to 40 μm, preferably 5 to 30 μm, and particularly preferably 10 to 25 μm.

(Method for producing photosensitive transfer material)
The photosensitive transfer material according to the present invention is provided with a thermoplastic resin layer by applying a coating liquid (thermoplastic resin layer coating liquid) in which a thermoplastic resin layer additive is dissolved on a temporary support, and drying. Then, a solution of an intermediate layer material composed of a solvent that does not dissolve the thermoplastic resin layer is applied and dried on the thermoplastic resin layer, followed by applying and drying a coating solution for the photosensitive resin composition. it can. When a thermoplastic resin layer is not provided, or when a layer (intermediate layer) made of a solvent that does not mix the two is provided between the thermoplastic resin layer and the photosensitive resin composition layer, the photosensitive resin composition There is no particular restriction on the solvent of the material coating solution.
In addition, a sheet provided with the thermoplastic resin layer and the intermediate layer on the temporary support and a sheet provided with the photosensitive resin layer on the protective film are prepared so that the intermediate layer and the photosensitive resin composition layer are in contact with each other. Further, a sheet provided with a thermoplastic resin layer on the temporary support and a sheet provided with a dark color photosensitive resin composition layer and an intermediate layer on a protective film are also prepared. However, it can also be produced by bonding them together so that the thermoplastic resin layer and the intermediate layer are in contact with each other.
In addition, although application | coating in the said preparation method can be performed with a well-known coating apparatus etc., in this invention, it is preferable to perform with the coating apparatus (slit coater) using a slit-shaped nozzle.

[substrate]
As the substrate (permanent support), a metallic support, a metal bonded support, glass, ceramic, a synthetic resin film, or the like can be used. Particularly preferred is a glass or a transparent synthetic resin film having transparency and good dimensional stability.

The image separation wall in the present invention is formed using the photosensitive resin composition, and is preferably produced by the following coating method (1) and the following transfer method (2).
That is, (1) the separation wall is formed by applying and drying a photosensitive resin composition on a substrate, and then exposing and developing.
(2) A photosensitive transfer material having a photosensitive transfer layer (photosensitive resin composition layer) formed on a temporary support with a photosensitive resin composition is transferred onto the substrate, and then exposed and developed. Form.

In the present invention, as shown in FIG. 1, the cross-sectional shape of the separation wall formed on the substrate is defined as A ₁ and A _{2 at} the intersection of the cross-section of the separation wall and the highest height of the separation wall. The point of the perpendicular line from the point H to H and the substrate to the substrate is G, the straight line passing through H and parallel to the substrate surface is L ₀ , and the point that internally divides H and G into HP: PG = 1: 3 is P and P A straight line parallel to the substrate surface is L ₁ , the point where L ₁ intersects the cross section of the separation wall is B ₁ and B ₂ , the distance between A ₁ and A ₂ is a, and the distance between B ₁ and B ₂ is b When doing so, the value of b / a is preferably 0.8 or more and 1.2 or less.

In the present invention, in the cross-sectional shape of the separation wall formed on the substrate, the intersections of the cross-section of the separation wall and the substrate are A ₁ and A ₂ , and the highest point of the separation wall is H, H The line of the perpendicular drawn from the substrate to the substrate passes through G and H, the straight line parallel to the substrate surface is L ₀ , and the point dividing H and G into HP: PG = 1: 3 is P and passes through P and is parallel to the substrate surface. When the straight line is L ₁ , the point where L ₁ intersects the cross section of the separation wall is B ₁ and B ₂ , the distance between A ₁ and A ₂ is a, and the distance between B ₁ and B ₂ is b, oxygen inhibition The value of b / a can be adjusted to 0.8 or more and 1.2 or less without using an oxygen-poor atmosphere in which no oxygen occurs or without providing an oxygen blocking layer.
These values are actually measured by cutting the separation wall formed on the substrate vertically with the substrate cut vertically to expose the cross section and directly observing with a microscope or the like. By passing through the step of fixing the shape of the separation wall obtained in this way, for example, when used in a color filter, it is difficult for ink that has once been ejected into the gap to get over the separation wall. As a result, it is possible to obtain a good color filter while preventing color mixing with adjacent pixels. The b / a value is preferably 0.8 or more and 1.2 or less, more preferably 0.85 or more and 1.15 or less, and particularly preferably 0.9 or more and 1.1 or less. .

  In the present invention, the height h of the separation wall (the distance between the highest point of the separation wall H and the foot G of the perpendicular line from the H to the substrate) is 1.0 μm or more. The thickness is preferably 1.5 μm or more and 10 μm or less, more preferably 1.8 μm or more and 7.0 μm or less, and particularly preferably 2.0 μm or more and 5.0 μm or less. Especially, color mixing can be more effectively prevented by setting the thickness to 1.5 μm or more and 10 μm or less. If the height is less than 1.5 μm, color mixing tends to occur, and if it exceeds 10 μm, it is difficult to form a separation wall.

The optical density at 555 nm of the separation wall in the present invention is preferably 2.5 or more, more preferably 2.5 to 10.0, still more preferably 2.5 to 6.0, and more preferably 3.0 to 5.0. Particularly preferred.
By setting the optical density range, a display device having a high contrast is obtained. Further, it is preferable that the color of the separating wall is black from the viewpoint of display quality of the display device.
The separation wall in the present invention preferably has a value of “absorbance at 600 nm ÷ absorbance at 500 nm” in the range of 0.7 to 1.4. Above all, from the viewpoint of display quality of the display device, 0.75 to 1 The range of .2 is more preferable, and the range of 0.77 to 1.15 is more preferable.
If the absorbance ratio is outside the above preferred range, the separation wall appears to be colored, which is not preferred.
In order to make the ratio of the absorbance within a preferable range, it can be achieved by adjusting the color material type.

(Manufacturing method of separation wall for inkjet method)
The method for producing a separation wall for an inkjet method of the present invention (hereinafter also referred to as “formation of a separation wall”) includes at least the photoacid generator, a crosslinking agent, an alkali-soluble binder, a basic compound, and a coloring material. The photosensitive resin layer forming step for forming the photosensitive resin layer, the exposure step for exposing the photosensitive resin layer to cure the exposed region, and removing the photosensitive resin layer in the unexposed area are separated. At least a developing step for forming a wall.
With the above-described configuration, a method for producing a separation wall for an inkjet method having a cross-sectional shape suitable for producing RGB pixels of a color filter by the inkjet method, and a substrate with a separation wall for an inkjet method produced by the method Can be provided.
The method for producing a separation wall for an ink jet method of the present invention will be specifically described below, but is not limited thereto.

-Formation of separation wall using photosensitive resin composition-
(Photosensitive resin layer forming step)
First, after cleaning the substrate, the substrate is heat-treated to stabilize the surface state. After the temperature of the substrate is adjusted, the photosensitive resin composition is applied. Subsequently, after part of the solvent is dried to eliminate the fluidity of the coating layer, pre-baking is performed to obtain a photosensitive resin layer. In addition, after part of the solvent is dried to eliminate the fluidity of the coating layer, unnecessary coating liquid around the substrate is removed with an EBR (edge bead remover) or the like, and then pre-baked to form a photosensitive resin. A layer may be obtained.
The coating is not particularly limited, and is a glass substrate coater having a known slit nozzle (for example, product name: MH-1600 manufactured by FAS Asia) or glass having a slit nozzle. A substrate coater (manufactured by Hirata Kiko Co., Ltd.) can be used.
The drying can be performed using a known drying apparatus (for example, VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.)).
Although it does not specifically limit as prebaking, For example, it can achieve by making 120 degreeC 3 minutes. The film thickness of the obtained photosensitive resin layer is as described above.

(Exposure process)
Subsequently, in a state where a substrate and a mask having an image pattern (for example, quartz exposure mask) are set up vertically, the distance between the exposure mask surface and the photosensitive resin layer is appropriately set (for example, 200 μm) and exposed. (Exposure process). By exposure, the region (exposure region) irradiated with light of the photosensitive resin layer is cured.
The exposure is performed, for example, with a proximity type exposure machine (for example, manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp, and the exposure amount may be appropriately selected (for example, 300 mJ / cm ² ). it can.

(Development process)
Next, it develops with a developing solution and removes the photosensitive resin layer of an unexposed part, and a patterning image is obtained (development process), and if necessary, it is washed with water and a separation wall is obtained.
Prior to the development, it is preferable to spray pure water with a shower nozzle or the like to uniformly wet the surface of the photosensitive resin layer.
As the developer used in the development process, a dilute aqueous solution of an alkaline substance is used, but it may be further added with a small amount of an organic solvent miscible with water.
Examples of the light source used for the light irradiation include medium to ultrahigh pressure mercury lamps, xenon lamps, metal halide lamps, and the like.

  Examples of the alkaline substance in the method using the photosensitive resin composition and the method using the photosensitive transfer material described below include alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal carbonates ( For example, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate, potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, , Sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like. The concentration of the alkaline substance is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14.

  Examples of the “water-miscible organic solvent” include, for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether. Benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like are preferable. . The concentration of the organic solvent miscible with water is preferably 0.1 to 30% by mass. Furthermore, a known surfactant can be added, and the concentration of the surfactant is preferably 0.01 to 10% by mass.

  The developer can be used as a bath solution or a spray solution. When removing the uncured portion of the photosensitive resin layer, it is possible to combine methods such as rubbing with a rotating brush or wet sponge in the developer. The liquid temperature of the developer is usually preferably from about room temperature to 40 ° C. The development time is usually about 10 seconds to 2 minutes, depending on the composition of the photosensitive resin layer, the alkalinity and temperature of the developer, and the type and concentration when an organic solvent is added. If it is too short, the development of the non-exposed area may be insufficient, and the absorbance of ultraviolet rays may be insufficient, and if it is too long, the exposed area may be etched. In either case, it is difficult to make the separation wall shape suitable. In this developing step, the separating wall shape is formed as described above.

-Formation of separation walls using photosensitive transfer materials-
(Photosensitive resin layer forming step)
First, after peeling off and removing the protective film of the photosensitive transfer material described above, the surface of the exposed photosensitive resin layer is bonded onto a permanent support (substrate) and laminated by heating and pressing through a laminator or the like (laminate) ). As the laminator, those appropriately selected from conventionally known laminators, vacuum laminators and the like can be used, and an auto-cut laminator can also be used in order to increase productivity.

(Exposure and development process)
Next, the temporary support is removed. Subsequently, a desired photomask is disposed above the removal surface after removal of the temporary support, irradiated with ultraviolet rays from a light source, and developed using a predetermined processing liquid after irradiation to obtain a patterning image. If necessary, it is washed with water to obtain a separation wall.
As the developer used for the development process and the light source used for the light irradiation, the developer and the light source in the formation using the coating method are similarly used.

(Water repellent treatment)
In the method for producing a color filter of the present invention, it is preferable that at least a part of the separation wall is made water-repellent by subjecting the separation wall to water repellency treatment. This eliminates inconveniences such as when the droplets of the colored liquid composition are subsequently applied between the separation walls by a method such as ink jet, the ink gets over the separation walls and mixes with the adjacent color. Because of that.
As the water repellent treatment, a method of applying a water repellent material on the upper surface of the separation wall, a method of newly providing a water repellent layer, a method of imparting water repellency by plasma treatment, and a method of kneading a water repellent substance on the separation wall And a method of imparting water repellency with a photocatalyst.
Hereinafter, the water repellent treatment will be described in detail.

(1) <Method of kneading a water-repellent substance into the separation wall>
As a means for preventing “color mixing”, there is a method for producing a separation wall using a photoresist obtained from the photosensitive resin composition (dark color photosensitive resin composition) of the present invention containing the fluororesin (A). is there.
The fluorine-containing resin of the present invention has an Rf group (a) having a polyfluoroether structure represented by the following formula 1 and an acidic group (b), and has an acid value of 1 to 300 mgKOH / g.
-(X-O) _n -Y Formula 1
In Formula 1, X is a C1-C10 divalent saturated hydrocarbon group or a C1-C10 fluorinated divalent saturated hydrocarbon group, and is the same for each unit surrounded by n Y represents a hydrogen atom (only when a fluorine atom is not bonded to a carbon atom adjacent to an oxygen atom adjacent to Y), a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or A fluorinated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is shown, and n is an integer of 2 to 50.
However, the total number of fluorine atoms in Formula 1 is 2 or more.

  As an aspect of X and Y in Formula 1, Preferably, X is a C1-C10 hydrogen atom remove | excluded alkylene group or a C1-C10 perfluorinated alkylene group. Each of the units enclosed by n represents the same group or a different group, and Y represents a fluorinated alkyl group or a par group having 1 to 20 carbon atoms except for one hydrogen atom having 1 to 20 carbon atoms. The thing which shows the fluorinated alkyl group is mentioned.

  As an embodiment of X and Y in Formula 1, more preferably, X is a C 1-10 perfluorinated alkylene group, and represents the same group or different groups for each unit enclosed by n. , Y may be a perfluorinated alkyl group having 1 to 20 carbon atoms.

  When the aspect of X and Y is the above, the fluorine-containing resin exhibits good ink repellency.

  In Formula 1, n represents an integer of 2 to 50. n is preferably from 2 to 30, and more preferably from 2 to 15. When n is 2 or more, the ink falling property is good. When n is 50 or less, when the fluorine-containing resin is synthesized by copolymerization of a monomer having an Rf group (a) with a monomer having an acidic group (b) or another monomer, The monomer compatibility is improved.

  Moreover, 2-50 are preferable and, as for the total number of the carbon atoms in Rf group (a) which consists of a polyfluoroether structure represented by Formula 1, 2-30 are more preferable. Within this range, the fluorine-containing resin exhibits good ink repellency, particularly organic repellency. In addition, when the fluororesin is synthesized by copolymerization with a monomer having an Rf group (a), a monomer having an acidic group (b), and other monomers, the compatibility of the monomers is good. It becomes.

Examples of _{X, -CF 2 -, - CF} 2 CF 2 -, - CF 2 CF 2 CF 2 -, - CF 2 CF (CF 3) -, - CF 2 CF 2 CF 2 CF 2 -, - _{CF 2 CF 2 CF (CF 3} ) -, and _{CF 2 CF (CF 3) CF} 2 - and the like.

Specific examples of _{Y, -CF 3, -CF 2 CF} 3, -CF 2 CHF 2, - (CF 2) 2 CF 3, - (CF 2) 3 CF 3, - (CF 2) 4 CF 3, _{- (CF 2) 5 CF 3} , - (CF 2) 6 CF 3, - (CF 2) 7 CF 3, - (CF 2) 8 CF 3, - (CF 2) 9 CF 3 and, _(CF 2) ₁₁ CF ₃ , — (CF ₂ ) ₁₅ CF ₃ may be mentioned.

A preferred embodiment of the Rf group (a) having a polyfluoroether structure represented by Formula 1 includes the Rf group (a) represented by Formula 2.
_{-C p-1 F 2 (p} -1) -O- (C p F 2p -O) n-1 -C q F 2q + 1 ··· Equation 2
In Formula 2, p represents an integer of 2 or 3, and is the same group for each unit enclosed by n, q represents an integer of 1 to 20, and n represents an integer of 2 to 50.

As Rf group (a) represented by Formula 2, specifically,
_{-CF 2 O (CF 2 CF 2} O) n-1 CF 3 (n is 2-9),
_{-CF (CF 3) O (CF} 2 CF (CF 3) O) n-1 C 6 F 13 (n is 2-6),
_{-CF (CF 3) O (CF} 2 CF (CF 3) O) n-1 C 3 F 7 (n is 2-6)
Is preferable from the viewpoint of ease of synthesis.

  The Rf groups (a) in the fluororesin may all be the same or different.

  The content of fluorine atoms in the fluorine-containing resin is preferably 1 to 60%, more preferably 5 to 40%. Within such a range, the fluororesin exhibits good ink repellency and the developability of the photosensitive resin composition of the present invention is good.

The fluorine-containing resin has an acidic group (b).
As the acidic group (b), at least one acidic group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group or a salt thereof is preferable.

  The acid value of the fluororesin is preferably 1 to 300 mgKOH / g, more preferably 5 to 200 mgKOH / g, and particularly preferably 10 to 150 mgKOH / g. Within this range, the developability of the photosensitive resin composition of the present invention will be good. In addition, an acid value is the mass (unit mg) of potassium hydroxide required in order to neutralize 1 g of resin, and a unit is described in this specification as mgKOH / g.

  The number average molecular weight of the fluororesin is preferably 500 or more and less than 20000, and more preferably 2000 or more and less than 15000. Within this range, the developability of the photosensitive resin composition of the present invention is good. The number average molecular weight is measured using polystyrene as a standard substance by gel permeation chromatography.

  The fluorine-containing resin includes a monomer unit based on a monomer having an ethylenic double bond and an Rf group (a), and a single unit based on a monomer having an ethylenic double bond and an acidic group (b). It is a copolymer containing a monomer unit, and it is preferable that an acid value is 1-300 mgKOH / g.

Examples of the ethylenic double bond include a (meth) acryloyl group, a vinyl group, and an allyl group.

As a monomer having an ethylenic double bond and an Rf group (a),
CH ₂ = CR ¹ COOQ ² Rf, CH ₂ = CR ¹ OCOQ ¹ Rf, CH ₂ = CR ¹ OQ ¹ Rf, CH ₂ = CR ¹ CH ₂ OQ ¹ Rf, CH ₂ = CR ¹ COOQ ² NR ¹ SO ₂ Rf CH ₂ = CR ¹ COOQ ² NR ¹ CORf, CH ₂ = CR ¹ COOQ ² NR ¹ COOQ ² Rf, CH ₂ = CR ¹ COOQ ² OQ ¹ Rf, and the like. However, R ¹ represents a hydrogen atom or a methyl group, Q ¹ represents a single bond or a divalent organic group having 1 to 6 carbon atoms, and Q ² represents a divalent organic group having 1 to 6 carbon atoms. Q ¹ and Q ² may have a cyclic structure.

As specific examples of Q ¹ and Q ² ,
_{-CH 2 -, - CH 2 CH} 2 -, - CH (CH 3) -, - CH 2 CH 2 CH 2 -, - C (CH 3) 2 -, - CH (CH 2 CH 3) -, - CH ₂ CH ₂ CH ₂ CH ₂ —, —CH (CH ₂ CH ₂ CH ₃ ) —, —CH ₂ (CH ₂ ) ₃ CH ₂ —, —CH (CH ₂ CH (CH ₃ ) ₂ ) —, —CH _{2 CH (OH) CH 2 -,} - CH 2 CH 2 NHCOOCH 2 -, - CH 2 CH (OH) CH 2 OCH 2 - and the like. Q ¹ may be a single bond.
From the viewpoint of ease of _{synthesis, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH (OH) CH 2 - is preferred.

Specific examples of the monomer having an ethylenic double bond and an Rf group (a) include the following.
_{CH 2 = CHCOOCH 2 CF 2 O} (CF 2 CF 2 O) n-1 CF 3 (n is _{3~9), CH 2 = CHCOOCH 2} CF (CF 3) O (CF 2 CF (CF 3) O) n _-1 C ₆ F ₁₃ (n is _{2~6), CH 2 = CHCOOCH 2} CF (CF 3) O (CF 2 CF (CF 3) O) n-1 C 3 F 7 (n is 2-6).
_{CH 2 = C (CH 3)} COOCH 2 CH 2 NHCOOCH 2 CF 2 O (CF 2 CF 2 O) n-1 CF 3 (n is _{3~9), CH 2 = C (} CH 3) COOCH 2 CH 2 NHCOOCH _{2 CF (CF 3) O (} CF 2 CF (CF 3) O) n-1 C 3 F 7 (n is _{2~6), CH 2 = C (} CH 3) COOCH 2 CH 2 NHCOOCH 2 CF (CF 3 _{) O (CF 2 CF (CF} 3) O) n-1 C 6 F 13 (n is 2-6).
_{CH 2 = C (CH 3)} COOCH 2 CH (OH) CH 2 OCH 2 CF 2 O (CF 2 CF 2 O) n-1 CF 3 (n is _{3~9), CH 2 = C (} CH 3) COOCH _{2 CH (OH) CH 2 OCH} 2 CF (CF 3) O (CF 2 CF (CF 3) O) n-1 C 6 F 13 (n is _{2~6), CH 2 = C (} CH 3) COOCH 2 _{CH (OH) CH 2 OCH 2} CF (CF 3) O (CF 2 CF (CF 3) O) n-1 C 3 F 7 (n is 2-6).

  The content of the monomer unit based on the monomer having an ethylenic double bond and Rf group (a) in the fluororesin is preferably 1 to 95%, more preferably 5 to 80%, and more preferably 20 to 20%. 60% is more preferable. Within such a range, the fluororesin exhibits good ink repellency and the developability of the photosensitive resin composition of the present invention is good.

  Examples of the monomer having an acidic group (b) include a monomer having a carboxyl group, a monomer having a phenolic hydroxyl group, and a monomer having a sulfonic acid group.

  Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof. These may be used alone or in combination of two or more.

  Examples of the monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. In addition, one or more hydrogen atoms of these benzene rings are an alkyl group such as a methyl group, an ethyl group or an n-butyl group, an alkoxy group such as a methoxy group, an ethoxy group or an n-butoxy group, a halogen atom or an alkyl group. Examples thereof include compounds in which one or more hydrogen atoms are substituted with a halogen atom, a haloalkyl group, a nitro group, a cyano group, or an amide group. These may be used alone or in combination of two or more.

  Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-hydroxy-3- (meth) allyloxypropane sulfonic acid, and (meth) acrylic acid-2-sulfoethyl. , (Meth) acrylic acid-2-sulfopropyl, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, or salts thereof. These may be used alone or in combination of two or more.

  The content of the monomer unit based on the monomer having an acidic group (b) in the fluororesin is preferably 0.1 to 40%, more preferably 0.5 to 30%, and 1 to 20%. Further preferred. Within such a range, the fluorine-containing resin exhibits good ink repellency and the developability of the photosensitive resin composition becomes good.

  Monomer based on monomer unit based on monomer having fluorine-containing resin having ethylenic double bond and Rf group (a), and monomer having ethylenic double bond and acidic group (b) In the case of a copolymer having a body unit, it has a monomer unit based on a monomer having no Rf group (a) and acidic group (b) (hereinafter referred to as “other monomer”). You may do it.

  Other monomers include hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylic esters, (meth) acrylamides, aromatic Examples include vinyl compounds, chloroolefins, fluoroolefins, and conjugated dienes. These compounds may contain a functional group, and examples thereof include a hydroxyl group, a carbonyl group, an alkoxy group, and an amide group. Moreover, you may have group which has a polysiloxane structure. However, monomer units based on these other monomers do not have an Rf group (a) and an acidic group (b). These may be used alone or in combination of two or more. In particular, (meth) acrylic acid esters and (meth) acrylamides are preferable because they are excellent in heat resistance of a coating film formed from the photosensitive resin composition of the present invention.

  In the fluororesin, the proportion of monomer units based on other monomers is preferably 80% or less, and more preferably 70% or less. Within this range, the developability of the photosensitive resin composition of the present invention will be good.

  The fluororesin in the present invention is a monomer unit based on a monomer having the above ethylenic double bond and Rf group (a), and a single unit having an ethylenic double bond and an acidic group (b). In addition to being obtained by synthesizing a copolymer containing monomer units based on a monomer, a compound having an Rf group (a) and / or a compound having an acidic group (b) in a polymer having a reactive site It can also be obtained by various modification methods to be reacted.

  As various modification methods for reacting a compound having an Rf group (a) with a polymer having a reactive site, for example, a monomer having an epoxy group is copolymerized in advance, and then an Rf group (a) and a carboxyl group are later included. Examples thereof include a method of reacting a compound and a method of previously copolymerizing an epoxy group-containing monomer and then reacting a compound having an Rf group (a) and a hydroxyl group.

  Specific examples of the monomer having an epoxy group include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate.

Examples of the compound having an Rf group (a) and a carboxyl group include compounds represented by the following formula 3.

_{HOOC-C p-1 F 2} (p-1) -O- (C p F 2p -O) n-1 -C q F 2q + 1 ··· Equation 3
In Formula 3, p is an integer of 2 or 3, q is an integer of 1 to 20, and n is an integer of 2 to 50.

Examples of the compound having an Rf group (a) and a hydroxyl group include compounds represented by the following formula 4.

_{HOCH 2 -C p-1 F 2} (p-1) -O- (C p F 2p -O) n-1 -C q F 2q + 1 ··· Equation 4
In Formula 4, p represents an integer of 2 or 3, q represents an integer of 1 to 20, and n represents an integer of 2 to 50.

  Examples of various modification methods for reacting a polymer having a reactive site with a compound having an acidic group (b) include a method in which a monomer having a hydroxyl group is copolymerized in advance and then an acid anhydride is reacted. Moreover, the method of making the acid anhydride which has an ethylenic double bond copolymerize previously, and making the compound which has a hydroxyl group react later is mentioned.

  Specific examples of the monomer having a hydroxyl group include vinylphenol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, Glycerin mono (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydro Shimechiru (meth) acrylamide, N, N-bis (hydroxymethyl), and the like.

Furthermore, the monomer having a hydroxyl group may be a monomer having a polyoxyalkylene chain whose terminal is a hydroxyl group. For example, CH ₂ = CHOCH ₂ C ₆ H ₁₀ CH ₂ O (C ₂ H ₄ O) _g H (where g is an integer of 1 to 100, the same shall apply hereinafter), CH ₂ = CHOC ₄ H ₈ O (C _{2 H 4 O) g H,} CH 2 = CHCOOC 2 H 4 O (C 2 H 4 O) g H, CH 2 = C (CH 3) COOC 2 H 4 O (C 2 H 4 O) g H, CH ₂ = CHCOOC ₂ H ₄ O (C ₂ H ₄ O) _h (C
₃ H ₆ O) _k H (where h is 0 or an integer of 1 to 100, k is an integer of 1 to 100, and h + k is 1 to 100. The same shall apply hereinafter), CH ₂ = C _{(CH 3) COOC 2 H 4} O (C 2 H 4 O) h (C 3 H 6 O) k H and the like. These may be used alone or in combination of two or more.

  Specific examples of the acid anhydride include phthalic anhydride, 3-methylphthalic anhydride, trimellitic anhydride, and the like.

  Specific examples of the acid anhydride having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6 anhydride -Tetrahydrophthalic acid, cis-1,2,3,6-tetrahydrophthalic anhydride, 2-buten-1-yl succinic anhydride, etc. are mentioned.

  The compound having a hydroxyl group may be a compound having one or more hydroxyl groups. Specific examples of the monomer having a hydroxyl group shown above, ethanol, 1-propanol, 2-propanol, 1- Alcohols such as butanol and ethylene glycol; cellsolves such as 2-methoxyethanol, 2-ethoxyethanol and 2-butoxyethanol; 2- (2-methoxyethoxy) ethanol; 2- (2-ethoxyethoxy) ethanol; And carbitols such as (2-butoxyethoxy) ethanol. A compound having one hydroxyl group in the molecule is preferred. These may be used alone or in combination of two or more.

  The polymer having the reactive site, which is a fluorine-containing resin or a precursor of the fluorine-containing resin, is reacted by dissolving the monomer in a solvent together with a chain transfer agent as necessary and heating, and adding a polymerization initiator. It can be synthesized by the method.

  The blending amount of the fluororesin (A) is preferably 0.01 to 50%, more preferably 0.1 to 30%, and particularly preferably 0.2 to 10% with respect to the solid content in the photosensitive resin composition. preferable. Within such a range, the photosensitive resin composition exhibits good ink repellency and ink tumbling properties and good developability.

(2) <Method of providing a water repellent layer>
As a means for preventing “color mixing”, there is a method of producing a partition wall having ink repellency at a position matching the separation wall on the substrate on which the separation wall is formed.

  A silicone rubber layer is preferably used as the partition wall having ink repellency. The silicone rubber layer coated on the surface layer is required to have a repulsive effect on the solution and ink used for coloring, and is not limited to this, but is repeated as in the following general formula (1). The main component is a linear organic polysiloxane having a molecular weight of several thousands to several hundreds of thousands.

In general formula (1), n is an integer of 2 or more, and R is an alkyl group, alkenyl group, or phenyl group having 1 to 10 carbon atoms.

  Silicone rubber can be obtained by sparsely cross-linking such a linear organic polysiloxane. Cross-linking agents are acetoxy silane, ketoxime silane, alkoxy silane, amino silane, amido silane, alkenoxy silane, etc., used for so-called room temperature (low temperature) curable silicone rubber, and usually have a terminal hydroxyl group as a linear organic polysiloxane. In combination with these, a deacetic acid type, a deoxime type, a dealcohol type, a deamine type, a deamide type, and a deketone type silicone rubber are obtained. In addition, a small amount of an organic tin compound or the like is added to the silicone rubber as a catalyst. Various layers may be used as an adhesive layer between the photosensitive resin layer and the silicone rubber layer, and aminosilane compounds and organic titanate compounds are particularly preferable. Instead of providing an adhesive layer between the photosensitive resin layer and the silicone rubber layer, an adhesive component may be added to the silicone rubber layer. An aminosilane compound or an organic titanate compound can also be used as this additional adhesive component.

  The exposure for producing the partition wall is performed from the back side of the substrate using the separation wall as a mask, and further, the irradiation UV light is scattered to expand the incident light from the size of the transmission part and to act on the photosensitive resin. The portion of the resin that is solubilized by reaction is made larger on the surface side of the silicone rubber. After exposure in this manner, a partition wall having a silicone rubber surface layer can be produced by developing with an n-heptane / ethanol mixture.

(3) <Method of imparting water repellency by plasma treatment>
As a means for preventing “color mixing”, there is a method of performing water repellency treatment by plasma on a substrate on which a separation wall is formed.

As the gas containing at least fluorine atoms introduced in this step, one or more halogen gases selected from CF ₄ , CHF ₃ , C ₂ F ₆ , SF ₆ , C ₃ F ₈ , and C ₅ F ₈ are used. It is preferable. In particular, C ₅ F ₈ (octafluorocyclopentene) has an ozone depletion ability of 0, and at the same time, has an atmospheric life (CF ₄ : 50,000 years, C ₄ F ₈ : 3200 years) as compared with conventional gases. It is very short with 98 years. Therefore, the global warming potential is 90 (100-year integrated value assuming CO ₂ = 2), which is very small (CF ₄ : 6500, C ₄ F ₈ : 8700) compared to conventional gases, and the ozone layer and the global environment It is extremely effective for protection and is desirable for use in the present invention.

Further, as the introduced gas, a gas such as oxygen, argon, or helium may be used in combination as necessary. In this step, when a mixed gas of at least one halogen gas selected from CF ₄ , CHF ₃ , C ₂ F ₆ , SF ₆ , C ₃ F ₈ , and C ₅ F ₈ and O ₂ is used, It is possible to control the degree of ink repellency on the surface of the image separation wall processed in this step. However, in the mixed gas, the oxidation reaction mixture ratio by O ₂ exceeds 30% of O ₂ is dominant, because the ink repellency enhancing effect is prevented, also, O ₂ mixing ratio is more than 30% When the mixed gas is used, it is necessary to use O ₂ in a range where the mixing ratio of O ₂ is 30% or less.

  As a method for generating plasma, methods such as low frequency discharge, high frequency discharge, and microwave discharge can be used. Conditions such as a pressure, a gas flow rate, an output, and a processing time during plasma processing can be arbitrarily set, but in order to achieve the effects of the present invention, the following conditions are more preferable.

  The pressure during the plasma treatment is preferably 10 to 100 Pa, more preferably 20 to 80 Pa, and further preferably 30 to 50 Pa. The gas flow rate is preferably 40 to 300 sccm, more preferably 50 to 200 sccm, and still more preferably 60 to 100 sccm. The output is preferably 10 to 100 W, more preferably 20 to 90 W, and even more preferably 30 to 80 W. The treatment time depends on the pressure and output, is preferably 20 to 200 sec, more preferably 20 to 100 sec, and further preferably 10 to 50 sec.

(4) <Method of applying a water repellent material to the upper surface of the separation wall>
As means for preventing “color mixing”, there is a method in which a water repellent material is applied to the entire surface of a substrate on which a separation wall is formed.
Water repellent materials such as fluoropolymers such as polytetrafluoroethylene, silicone rubber, perfluoroalkyl acrylate, hydrocarbon acrylate, methyl siloxane, etc. are generally considered water repellent materials and have a contact angle of 60 ° or more with color materials If it is a thing, it will not specifically limit.

  As a method for applying the water repellent material, it is possible to select the most suitable method for each material such as slit coat, spin coat, dip coat, roll coat, etc., as long as it does not affect the substrate, separation wall, etc. is there.

Next, UVO ₃ treatment is performed from the back side of the substrate through the separation wall, and the water-repellent film other than the separation wall is selectively removed or hydrophilized (contact angle with the colorant is 30 ° before and after the treatment). (There is an opening above).

  If the water repellent material can be removed or hydrophilized, the patterning method can be selected according to the material, such as laser ablation, plasma ashing, dry treatment such as corona discharge treatment, and wet treatment using alkali. Is possible. In addition, if it is possible to form a pattern of a water repellent material on the separation wall, a lift-off method or the like is also effective.

  Among the water repellent treatment methods (1) to (4) above, (3) the water repellent treatment method using plasma is particularly preferable from the viewpoint of “simpleness of the process”.

<Color Filter Manufacturing Method, Color Filter, and Liquid Crystal Display>
The method for producing a color filter of the present invention uses a substrate with a separation wall for an inkjet method of the present invention, and a colored liquid composition (hereinafter sometimes referred to as “ink”) in a region separated by the separation wall. A pixel forming step of forming a pixel by applying the liquid droplets by an inkjet method. The color filter of this invention can be manufactured with the manufacturing method of the color filter of this invention.

As an ink jet recording apparatus for carrying out the ink jet method, a method in which charged ink is continuously ejected and controlled by an electric field, a method in which ink is intermittently ejected using a piezoelectric element, a method in which ink is heated and foamed is used. Then, various methods such as a method of intermittent injection can be employed.
The ink used may be oily or water-based. The coloring material contained in the ink can be used for both dyes and pigments, and the use of pigments is more preferable from the viewpoint of durability. In addition, a coating-type colored ink (colored resin composition, for example, described in JP-A No. 2005-3861 [0034] to [0063]) or JP-A No. 10-195358 [0009] is used for producing a known color filter. ]-[0026] The inkjet composition as described above can also be used.
In consideration of the process after coloring, a component that is cured by heating or that is cured by energy rays such as ultraviolet rays can be added to the ink in the present invention. Various thermosetting resins are widely used as components that are cured by heating, and examples of components that are cured by energy rays include those obtained by adding a photoinitiator to an acrylate derivative or a methacrylate derivative. In particular, in view of heat resistance, those having a plurality of acryloyl groups and methacryloyl groups in the molecule are more preferable. These acrylate derivatives and methacrylate derivatives are preferably water-soluble, and even those that are sparingly soluble in water can be used after being emulsified.
In this case, the photosensitive resin composition containing a coloring material such as a pigment described in the above section <Photosensitive resin composition> can be used as a preferable one.

  Further, as the ink that can be used in the present invention, a thermosetting ink for a color filter containing at least a binder and a bifunctional to trifunctional epoxy group-containing monomer can also be used as a suitable ink.

The color filter of the present invention is a color filter in which pixels are formed by an inkjet method, but it is preferable to form three color filters by spraying RGB three color inks.
This color filter is used as a display element in combination with a liquid crystal display element, an electrophoretic display element, an electrochromic display element, PLZT, or the like. It can also be used for applications using color cameras and other color filters.

  The pattern shape of the color filter thus formed is not particularly limited, and may be a general black matrix shape such as a stripe shape, a lattice shape, or a delta arrangement. May be.

(Overcoat layer)
After the color filter is manufactured, an overcoat layer may be provided on the entire surface to improve resistance. The overcoat layer can protect the solidified layers of the inks R, G, and B and can flatten the surface, but it is preferably not provided from the viewpoint of increasing the number of steps.

Examples of the resin (OC agent) that forms the overcoat layer include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition. Above all, it is excellent in transparency in the visible light region, and the resin component of the photocurable composition for color filters is usually mainly composed of an acrylic resin, so that the acrylic resin composition is excellent in adhesion. Things are desirable.
Examples of the overcoat layer include those described in JP-A No. 2003-287618, paragraphs 0018 to 0028, and commercially available overcoat agents such as “Optomer SS6699G” manufactured by JSR.

The color filter of the present invention is suitably used for display devices such as liquid crystal display devices, plasma display display devices, EL display devices, and CRT display devices. For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issue)).
Of these display devices, application to a liquid crystal display device is particularly preferable. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention can be applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".

  In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC Co., Ltd., 1994)”, “2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)” (Table Yoshiyoshi) Fuji Chimera Research Institute, published in 2003) ”.

The case where the color filter of the present invention is applied to a liquid crystal display device will be described below with reference to the drawings.
FIG. 2 is a view showing a cross section of one embodiment of the color filter of the present invention. In FIG. 2, 11 is a transparent substrate as a substrate, 12 is a separation wall, 13 is a colored portion which is a pixel, and 14 is a protective layer formed as necessary. When a liquid crystal element is configured using the color filter of the present invention, ITO (indium tin) for driving liquid crystal is further formed on the colored portion 13 or on the protective layer 14 formed on the colored portion 13. A transparent conductive film made of a transparent conductive material such as oxide) may be formed and provided.

The liquid crystal display device of the present invention has the color filter of the present invention. The liquid crystal display element in the present invention is an element having a liquid crystal layer in which a liquid crystal material is sealed between a pair of opposed substrates.
The liquid crystal display device has a color filter on at least one of a pair of substrates facing each other, and a liquid crystal layer is sandwiched between two substrates each having a conductive layer on the surface facing each other. This is a display device in which a voltage is applied to the liquid crystal material and the liquid crystal material sandwiched therebetween changes the alignment state in accordance with the voltage and performs display.

A basic configuration mode of the liquid crystal display device includes: (1) a driving side substrate in which driving elements such as thin film transistors (hereinafter sometimes referred to as “TFTs”) and pixel electrodes (conductive layers) are arranged; A liquid crystal material enclosed between a color filter and a counter substrate (conductive layer) provided with a color filter; (2) a color filter integrated drive in which a color filter is directly formed on the drive substrate; Examples include a liquid crystal material sealed between a substrate and a counter substrate including a counter electrode (conductive layer).
Examples of the conductive layer include an ITO film; a metal film such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; a metal oxide film such as SiO _2. A membrane is particularly preferred. For the drive side substrate, color filter side substrate, and counter substrate, for example, a known glass plate such as a soda glass plate, a low expansion glass plate, a non-alkali glass plate, a quartz glass plate, or a plastic film is used. Configured.
As a driving side substrate in which driving elements such as TFTs and pixel electrodes are arranged, for example, TFTs and TFTs connected to data bus lines and gate bus lines arranged in a matrix so as to cross each other vertically are arranged. For example, a conductive layer connected to the data bus line may be provided.

  FIG. 3 is a cross-sectional view of an embodiment of a liquid crystal display element configured using the color filter of FIG. In FIG. 3, 17 is a common electrode (transparent conductive film), 18 is an alignment film, 19 is a liquid crystal, 21 is a counter substrate, 22 is a pixel electrode, and 23 is an alignment film. A description thereof will be omitted.

The color liquid crystal element is generally formed by combining the substrate 11 on the color filter side and the counter substrate 21 and enclosing the liquid crystal 19. TFTs (not shown) and pixel electrodes 22 are formed in a matrix inside one substrate 21 of the liquid crystal element. In addition, a color filter coloring portion 13 is formed inside the substrate 11 on the color filter side so that R, G, and B are arranged at a position facing the pixel electrode 22, and a transparent common electrode is formed thereon. 17 is formed. Further, alignment films 18 and 23 are formed in the planes of both substrates, and liquid crystal molecules are arranged in a certain direction. These substrates are arranged to face each other via a spacer (not shown), are bonded together by a sealing material (not shown), and a liquid crystal 19 is filled in the gap. When the liquid crystal display element is a transmissive type, the substrate 21 and the pixel electrode 22 are formed of a transparent material, a polarizing plate is bonded to the outside of each substrate, and a back surface generally combining a fluorescent lamp and a scattering plate. Display is performed by using a light and causing the liquid crystal compound to function as an optical shutter that changes the light transmittance of the backlight. In the case of the reflection type, the substrate 21 or the pixel electrode 22 is formed of a material having a reflection function, or a reflective layer is provided on the substrate 21 and a polarizing plate is provided outside the transparent substrate 11 to provide a color. Display is performed by reflecting light incident from the filter side.
Since the liquid crystal display device of the present invention has the color filter of the present invention, it can display a high-resolution image free from mixed colors and white spots.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited by the following Example. Unless otherwise specified, “%” and “part” represent “% by mass” and “part by mass”.

[Production method of photosensitive resin composition]
The photosensitive resin composition is first weighed in the amount of carbon black dispersion and propylene glycol monomethyl ether acetate described in the following photosensitive resin composition formulation, mixed at a temperature of 24 ° C. (± 2 ° C.), and stirred at 150 RPM for 10 minutes. Then, methyl ethyl ketone, binder P-1, crosslinking agent MW-30M (manufactured by Sanwa Chemical Co., Ltd.), 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) ) Amino-3′-bromophenyl] -s-triazine, triethylamine, surfactant 1 are weighed and added in this order at a temperature of 25 ° C. (± 2 ° C.) and 150 RPM for 30 minutes at a temperature of 40 ° C. (± 2 ° C.). It is obtained by stirring.

<Photosensitive resin composition prescription>
・ Carbon black dispersion (carbon black particle size 20 nm) 20.5 parts ・ Propylene glycol monomethyl ether acetate 8.0 parts ・ Methyl ethyl ketone 53 parts ・ Binder P-1 7.3 parts ・ Crosslinking agent MW-30M (Sanwa Chemical) 6.4 parts · 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine 6 parts ・ Triethylamine 0.04 parts ・ Surfactant 1 0.055 parts

<Carbon black dispersion>
・ Carbon black (Nexex 35 manufactured by Degussa) 13.1 parts ・ Dispersant (see below) 0.80 parts

-Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000) 6.72 parts-Propylene glycol monomethyl ether acetate 79.38 parts

<Binder P-1>
-Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27 parts-Propylene glycol monomethyl ether acetate 73 parts

<Surfactant 1>
・ The following structure 1 30 parts ・ Methyl ethyl ketone 70 parts

[Example 1]
(Formation of a separation wall)
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., the photosensitive resin composition was applied with a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. did. Subsequently, 1 part of the solvent was dried for 30 seconds with a VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a photosensitive resin layer.

With a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) with an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask with image pattern) standing vertically, the exposure mask surface and photosensitive resin The distance between the layers was set to 200 μm, and pattern exposure was performed with an exposure amount of 200 mJ / cm ² . One minute after the completion of exposure, heat treatment (post-exposure baking) was performed at 120 ° C. for 30 seconds.

  Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the photosensitive resin layer, and then a KOH developer (KOH, containing a nonionic surfactant, product names: CDK-1, Fuji) The film was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa using a film electronics materials, to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, followed by heat treatment at 220 ° C. for 30 minutes, and a grid pattern separation with a width of 15 μm and a height of 2.0 μm. Got a wall.

[Plasma water repellency treatment]
The substrate on which the separation wall was formed was subjected to plasma water repellency treatment under the following conditions using a cathode coupling parallel plate type plasma treatment apparatus.
Gas used: CF ₄ gas flow rate: 80 sccm
Pressure: 40Pa
RF power: 50W
Processing time: 30 sec

(Pixel formation)
Next, each of R, G, and B inks was applied to the gaps between the black matrix pattern-like separation walls using an inkjet device, and colored.
In this ink, among the following components, first, a pigment, a polymer dispersant and a solvent are mixed, and a pigment dispersion is obtained using a three roll and a bead mill, and the pigment dispersion is sufficiently stirred with a dissolver or the like. While adding other materials little by little, R (red) ink was prepared.
<R ink composition>
・ Pigment (CI Pigment Red 254) 5 parts ・ Polymer dispersant (Solsperse 24000 manufactured by AVECIA) 1 part ・ Binder (glycidyl methacrylate-styrene copolymer) 3 parts ・ First epoxy resin (novolak type epoxy resin) Epicoat 154 manufactured by Yuka Shell
2 parts, 2nd epoxy resin (neopentyl glycol diglycidyl ether) 5 parts, curing agent (trimellitic acid) 4 parts, solvent: 80 parts ethyl 3-ethoxypropionate

Further, C.I. I. In place of Pigment Red 254, C.I. I. G (green) ink was prepared in the same manner as R ink except that the same amount of pigment green 36 was used.
Further, C.I. I. In place of Pigment Red 254, C.I. I. B (blue) ink was prepared in the same manner as in the R ink except that the same amount of Pigment Blue 15: 6 was used.
The color filter after pixel coloring was baked in an oven at 230 ° C. for 30 minutes, whereby both the separation wall (black matrix) and each pixel were completely cured to obtain a color filter.

In the color filter thus obtained, the ink constituting each pixel fits perfectly in the separation wall gap (region separated by the separation wall), and no defect such as a color mixture with adjacent pixels was found.
A transparent electrode of ITO (Indium Tin Oxide) was further formed on the R pixel, G pixel, B pixel and black matrix of the color filter substrate obtained above by sputtering. Separately, a glass substrate was prepared as a counter substrate, and patterning was performed for the PVA mode on the transparent electrode and the counter substrate of the color filter substrate, respectively.
A photospacer was provided in a portion corresponding to the upper part of the separation wall on the ITO transparent electrode, and an alignment film made of polyimide was further provided thereon.
After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to the outer periphery of the black matrix provided around the pixel group of the color filter, and a liquid crystal for PVA mode is dropped and bonded to the counter substrate. After bonding, the bonded substrate was irradiated with UV, and then heat-treated to cure the sealant. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a cold cathode tube was constructed and placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device.

[Evaluation]
(Evaluation of unevenness of substrate with separation wall)
The substrate with the separation wall prepared as described above was evaluated by the number of people who felt unevenness when 10 people visually observed the light from a 45 ° angle with respect to the transmitted light.
-Evaluation criteria-
○: Less than 3 people △: 3 or more and less than 7 people ×: 7 or more people

(Shape evaluation by b / a value: see FIG. 1)
The obtained color filter was cut vertically along with the substrate to expose the cross section, and photographed with a scanning electron microscope (magnification 20000 times). The intersections of the cross section of the substrate and the separation wall are A ₁ and A ₂ , the highest point of the separation wall is H, the perpendicular foot drawn from H to the substrate is G, and passes through H and parallel to the substrate surface. The straight line is L ₀ , the point where H and G are internally divided into HP: PG = 1: 3 is P, the straight line passing through P and parallel to the substrate surface is L ₁ , and the point where L ₁ intersects the section of the separation wall The B / a value was determined by setting B ₁ and B ₂ , and the distance between A ₁ and A ₂ as a and the distance between B ₁ and B ₂ as b. The measurement was performed on 10 points selected at random, and the values obtained by averaging these values are shown in Table 1.

(Evaluation of shape based on d / h value of upper end corner of separation wall: see FIG. 4. Note that the drawing is a schematic view and is different from the actual shape size.)
From the above scanning electron micrograph, the shape of the upper corner of the separation wall was evaluated by the following method. The height from the substrate at the highest height of the separation wall from the substrate is H, the leg of the perpendicular line from the H to the substrate is G, the straight line HG is on the straight line HG, and H and G are HQ: PQ = 1: as Q a point which internally divides 4, a straight line parallel to the street substrate surface Q and L _2. The point where L ₂ intersects the cross section of the separation wall is R, and the tangent line at R is L ₃ . The point of intersection S of L ₃ and _{L 0.} When the height of the separating wall is h and the distance from S to the section of the separating wall is d, the value of d / h is a measure of the shape of the top corner of the separating wall. It can be seen that color mixing is unlikely to occur if the value of d / h is 0.06 or less, and color mixing is less likely to occur if this value is 0.04 or less.

(Evaluation of blackness of separation wall)
A solid image having the same thickness as the separation wall was created on the glass plate in the same manner as the separation wall except that the entire surface of the sample was exposed without using an exposure mask. The absorbance of this sample in the wavelength region of 450 nm to 650 nm is measured using a spectrophotometer UV-2100. The values of 500 nm and 600 nm are obtained from this chart and calculated by the following formula.
Blackness = absorbance at 600 nm ÷ absorbance at 500 nm

(Evaluation of color mixture between pixels)
The obtained color filter was visually observed with a 200-fold optical microscope from the side opposite to the side on which the pixels were formed to check for color mixing between the pixels. 1000 pixels were observed and divided into the following ranks. The results are shown in Table 1. Allowable are those of A rank and B rank.
Rank A: No color mixing B Rank: Color mixing 1-2 places C Rank: Color mixing 3-10 places D Rank: Color mixing 11 places or more

[Example 2]
(Preparation of photosensitive transfer material-1)
A photosensitive resin composition is applied on a 75 μm-thick polyethylene terephthalate film temporary support using a slit nozzle and dried at 100 ° C. for 3 minutes to provide a photosensitive resin layer, on which a protective film is formed. (Polypropylene film having a thickness of 12 μm) was pressure-bonded to obtain photosensitive transfer material-1.

(Formation of a separation wall)
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% by mass aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes by a substrate preheating apparatus.

After the protective film of the photosensitive transfer material-1 was peeled off, a rubber roller temperature of 130 ° C. and a linear pressure of 100 N were applied to the substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)). / Cm, laminating at a conveyance speed of 2.2 m / min.
After peeling off the temporary support, exposure is performed with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp with the substrate and mask (quartz exposure mask with image pattern) standing vertically. The distance between the mask surface and the photosensitive resin layer was set to 200 μm, and pattern exposure was performed with an exposure amount of 200 mJ / cm ² . One minute after the completion of exposure, heat treatment (post-exposure baking) was performed at 120 ° C. for 30 seconds.

Subsequently, a sodium carbonate developer (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, stabilizer contained, trade name: T -CD1, manufactured by Fuji Photo Film Co., Ltd.), shower development was performed at 29 ° C. for 30 seconds and a cone type nozzle pressure of 0.15 MPa to develop the photosensitive resin layer, thereby obtaining a patterned pixel.
Thereafter, the substrate was further post-exposed with 500 mJ / cm ² light from the side of the photosensitive resin layer with an ultrahigh pressure mercury lamp, and then heat-treated at 220 ° C. for 15 minutes to obtain a separation wall.
Thereafter, a color filter was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 1. Further, a liquid crystal display device was produced in the same manner as in Example 1.

[Example 3]
(Preparation of photosensitive transfer material-2)
In Example 2, the photosensitive transfer material-2 was prepared in the same manner as in Example 2 except that the following thermoplastic resin layer and intermediate layer were provided between the temporary support and the photosensitive resin layer in order from the temporary support. Obtained.

(Formation of thermoplastic resin layer)
The following thermoplastic resin layer coating solution was applied to a 75 μm thick polyethylene terephthalate film temporary support using a slit nozzle so that the dry film thickness was 3 μm and dried at 100 ° C. for 3 minutes.
<Coating liquid formulation for thermoplastic resin layer>
Methanol 11.1 parts Propylene glycol monomethyl ether acetate 6.4 parts Methyl ethyl ketone 52.4 parts Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55) /11.7/4.5/28.8, molecular weight = 100,000, Tg≈70 ° C.) 5.83 parts styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 63/37, molecular weight = 10,000, Tg≈100 ° C.) 13.6 parts · 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd.) 9.1 parts · Surfactant 1 0.54 parts ・ Methyl ethyl ketone 70 parts

(Formation of intermediate layer)
The following intermediate layer coating solution was applied onto the above-mentioned thermoplastic resin layer using a slit nozzle so that the dry film thickness was 1.6 μm, and dried at 100 ° C. for 3 minutes.
<Preparation of coating solution for intermediate layer>
Polyvinyl alcohol 32.2 parts (PVA205 (saponification rate = 88%); manufactured by Kuraray Co., Ltd.)
-14.9 parts of polyvinylpyrrolidone (PVP, K-30; manufactured by ASP Japan)
・ Methanol 429 parts ・ Distilled water 524 parts

(Formation of a separation wall)
Transfer and exposure were performed in the same manner as in Example 2 except that photosensitive transfer material-1 was changed to photosensitive transfer material-2.
Next, 30 ° C. in a triethanolamine developer (containing 2.5% triethanolamine, nonionic surfactant, polypropylene antifoam, trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.) The thermoplastic resin layer and the intermediate layer were removed by shower development with a flat nozzle pressure of 0.04 MPa for 50 seconds.
Subsequently, a sodium carbonate-based developer (0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer, trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd.) was used for shower development at 29 ° C. for 30 seconds and a cone type nozzle pressure of 0.15 MPa to develop the photosensitive resin layer, thereby obtaining a patterned pixel.

Subsequently, using a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer, trade name “T-SD1 (manufactured by Fuji Photo Film)” at 33 ° C. for 20 seconds, cone type nozzle pressure of 0. Residue removal was performed with a rotating brush having a shower and nylon hair at 02 MPa to obtain a black (K) image.
Thereafter, the substrate was further post-exposed with 500 mJ / cm ² light from the side of the photosensitive resin layer with an ultrahigh pressure mercury lamp, and then heat-treated at 220 ° C. for 15 minutes to obtain a separation wall.
Thereafter, a color filter was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 1. Further, a liquid crystal display device was produced in the same manner as in Example 1.

[Example 4]
The evaluation was performed in the same manner as in Example 3 except that the height of the separation wall was 2.7 μm. The results are shown in Table 1.

[Example 5]
The evaluation was performed in the same manner as in Example 3 except that the height of the separation wall was changed to 3.3 μm. The results are shown in Table 1.

[Example 6]
The evaluation was performed in the same manner as in Example 3 except that the height of the separation wall was 4.5 μm. The results are shown in Table 1.

[Example 7]
In Example 1, a photosensitive resin composition was prepared with the same additive / amount except that triethylamine in the additive was changed to morpholinoacetophenone and added, and it was treated in the same manner as in Example 3. A liquid crystal display device was produced. The results are shown in Table 1.

[Comparative Example 1]
[Production Method of Comparative Photosensitive Resin Composition 1]
The comparative photosensitive resin composition 1 was first weighed in the amounts of carbon black dispersion and propylene glycol monomethyl ether acetate described in the following comparative photosensitive resin composition 1 formulation, and mixed at a temperature of 24 ° C. (± 2 ° C.). Stir at 150 RPM for 10 minutes, then methyl ethyl ketone, binder P-1, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3 '-Bromophenyl] -s-triazine and surfactant 1 are weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at a temperature of 40 ° C. (± 2 ° C.) for 150 RPM for 30 minutes. .
A color filter was obtained in the same manner as in Example 1 except that this comparative photosensitive resin composition 1 was used. Moreover, the same evaluation as Example 1 was performed. The results are shown in Table 1. Further, a liquid crystal display device was produced in the same manner as in Example 1.

<Comparison Photosensitive Resin Composition 1 Formulation>
Carbon black dispersion (carbon black particle size 20 nm) 23 parts Propylene glycol monomethyl ether acetate 8.0 parts Methyl ethyl ketone 53 parts Binder P-1 9.1 parts Hydroquinone monomethyl ether (polymerization inhibitor) 0.002 Parts DPHA solution 4.5 parts 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine (photopolymerization) Initiator) 0.16 part ・ Surfactant 1 0.055 part

<DPHA solution>
・ Dipentaerythritol hexaacrylate (containing polymerization inhibitor MEHQ 500 ppm, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76 parts ・ Propylene glycol monomethyl ether acetate 24 parts

[Comparative Example 2]
[Production Method of Comparative Photosensitive Resin Composition 2]
The comparative photosensitive resin composition 2 is first weighed in the amount of carbon black dispersion and propylene glycol monomethyl ether acetate described in the following comparative photosensitive resin composition 2 formulation, and mixed at a temperature of 24 ° C. (± 2 ° C.). The mixture was stirred at 150 RPM for 10 minutes, and then methyl ethyl ketone, binder P-1, crosslinking agent MW-30M (manufactured by Sanwa Chemical Co., Ltd.), 2,4-bis (trichloromethyl) -6- [4 '-(N, N- Weigh out bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine and surfactant 1 and add them in this order at a temperature of 25 ° C. (± 2 ° C.) and at a temperature of 40 ° C. (± 2 ° C.). It is obtained by stirring at 150 RPM for 30 minutes.
A color filter was obtained in the same manner as in Example 1 except that this comparative photosensitive resin composition 2 was used. Moreover, the same evaluation as Example 1 was performed. The results are shown in Table 1. Further, a liquid crystal display device was produced in the same manner as in Example 1.

<Comparison of photosensitive resin composition 2>
・ Carbon black dispersion (carbon black particle size 20 nm) 20.5 parts ・ Propylene glycol monomethyl ether acetate 8.0 parts ・ Methyl ethyl ketone 53 parts ・ Binder P-1 7.3 parts ・ Crosslinking agent MW-30M (Sanwa Chemical) 6.4 parts · 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine 6 parts Surfactant 1 0.055 parts

<Carbon black dispersion>
-Carbon black (Nippex 35 manufactured by Degussa) 13.1 parts-Dispersant (see above) 0.80 parts

-Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000) 6.72 parts-Propylene glycol monomethyl ether acetate 79.38 parts

<Binder P-1>
-Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27 parts-Propylene glycol monomethyl ether acetate 73 parts

<Surfactant 1>
・ 30 parts of the structure 1 ・ 70 parts of methyl ethyl ketone

As is clear from Table 1 above, in any of Examples 1 to 7 having a separation wall subjected to a crosslinking reaction by addition of an amine, there was no color mixing and there was no unevenness (pixel surface shape) of the separation wall substrate. It was.
On the other hand, in Comparative Examples 1 and 2, both color mixing and unevenness of the separation wall substrate (pixel surface shape) were poor.

(Evaluation)
When the liquid crystal display device obtained above was displayed in white and in black, the display quality was visually observed. The results are shown in Table 2.

As is clear from Table 2, the screens of the liquid crystal display devices provided with the color filters prepared in Examples 1 to 7 were all good in color mixing.
On the other hand, the liquid crystal display device provided with the color filter produced in Comparative Examples 1 and 2 was a reddish display with a degree of difference in both white display and black display states, and the display quality was inferior. .

It is an example of the schematic diagram which shows the cross-sectional shape of the separation wall of this invention. It is a figure which shows the cross section of one Embodiment of the color filter of this invention. It is sectional drawing of one Embodiment of a liquid crystal display device comprised using the color filter shown in FIG. It is another example of the schematic diagram which shows the cross-sectional shape of the image separation wall of this invention.

Explanation of symbols

11 Substrate (transparent substrate)
12 Separation Wall 13 Pixel 14 Protective Layer

Claims (5)

A photosensitive resin layer including at least a photoacid generator, a crosslinking agent that crosslinks by the action of the photoacid generator, an alkali-soluble binder, a basic compound, and a coloring material is formed on at least one surface of the substrate. A photosensitive resin layer forming step, an exposure step of exposing the photosensitive resin layer to cure an exposed region, and a developing step of forming a separation wall by removing the photosensitive resin layer in an unexposed portion. A method for producing a separation wall for an ink jet method having at least A photosensitive resin layer including at least a photoacid generator, a crosslinking agent that crosslinks by the action of the photoacid generator, an alkali-soluble binder, a basic compound, and a coloring material is formed on at least one surface of the substrate. A photosensitive resin layer forming step, an exposure step of exposing the photosensitive resin layer to cure an exposed region, and a developing step of forming a separation wall by removing the photosensitive resin layer in an unexposed portion. A substrate with a separating wall for an ink jet method manufactured through at least the above. A photosensitive resin layer including at least a photoacid generator, a crosslinking agent that crosslinks by the action of the photoacid generator, an alkali-soluble binder, a basic compound, and a coloring material is formed on at least one surface of the substrate. A photosensitive resin layer forming step, an exposure step of exposing the photosensitive resin layer to cure an exposed region, and a developing step of forming a separation wall by removing the photosensitive resin layer in an unexposed portion. A pixel forming step of forming a pixel by applying a droplet of a colored liquid composition to a region separated by the separation wall by an inkjet method using a substrate with a separation wall for an inkjet method manufactured through at least A method for producing a color filter. A color filter manufactured by the method for manufacturing a color filter according to claim 3. A liquid crystal display device comprising the color filter according to claim 4.

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