JP2007101997A - Color filter and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter for which arrangement of a partition wall layer is unnecessary because resist processing is not conducted, and of which the tint is not lowered and in which turbidity is not produced, and a method for manufacturing the same. <P>SOLUTION: The color filter has a fine pore structure on a substrate and has any one coloring agent of red, green, and blue coloring agents in each of the fine pores. The manner in which the fine pore structure corresponds to a honeycomb-like porous structure fabricated by self-assembly is preferable. The method for manufacturing the color filter includes steps of forming the fine pore structure, by applying a coating liquid containing an organic solvent and a polymer compound to the substrate, forming liquid drops in the obtained film, and vaporizing the organic solvent and the liquid drops so as to form the fine pore structure having pores in the film; and to make the red, green, and blue coloring agents contained inside the pores of the obtained fine pore structure. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a color filter to which a honeycomb-like porous structure produced by self-organization is applied and a method for producing the same.

  In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays, particularly color liquid crystal displays, has been increasing. However, cost reduction is necessary for further dissemination, and there is an increasing demand for cost reduction of color filters that are particularly heavy in terms of cost.

Conventionally, various methods have been tried to meet the above requirements while satisfying the characteristics required for color filters, and dyeing methods and pigment dispersion methods are mainly used.
The staining method is the most frequently used method. In the dyeing method, first, a layer of a water-soluble polymer material that is a dyeing material is formed on a glass substrate (support), and this is patterned into a desired shape by a photolithography process, and then the obtained pattern is obtained. Is immersed in a dyeing bath to obtain a colored pattern. By repeating this three times, red, green and blue color filter layers are formed.
The pigment dispersion method is a method that has recently been changed from the dyeing method. In this method, first, a photosensitive resin layer in which a pigment is dispersed is formed on a support, and this is patterned to obtain a monochromatic pattern. Further, this process is repeated three times to form red, green and blue color filter layers.
However, these methods need to be exposed and developed, and the same process needs to be repeated three times in order to color the three colors of red, green, and blue, resulting in high costs. Moreover, there is a problem that the yield decreases as the number of processes increases.

In order to make up for these problems, a method of manufacturing a color filter using an ink jet has been proposed (see Patent Documents 1 to 4). However, this method requires a partition wall layer by resist treatment between each color, and is improved. Was desired.
In addition, in order to perform the resist treatment, the color layer requires a polymerizable compound such as a monomer component, an initiator component for initiating polymerization thereof, and so on, in the resulting color filter, the color tone is reduced. There was a problem that the optical density was lowered due to the fogging.

  On the other hand, in recent years, a technique for producing a film having an ordered structure by utilizing a self-organization phenomenon has been studied. For example, in Non-Patent Document 1 and Non-Patent Document 2, a honeycomb-like porous structure can be produced by self-accumulating droplets condensing from the air and a polymer precipitated at the solvent interface in a three-phase boundary region. It is disclosed. The methods described in these documents use droplets that condense from the air and a polymer that precipitates at the solvent interface, and therefore do not require a complicated manufacturing apparatus.

  However, these documents do not disclose or suggest a specific use of the produced honeycomb porous structure or a specific condition control method according to the use, and the honeycomb porous structure is not a color filter. As a result, further research and development are necessary to utilize it as

JP 59-75205 A JP-A 63-235901 JP-A-1-217320 Japanese Patent Laid-Open No. 10-104416 Thin Solid Films, 327-329 (1998) 854-856. Chaos, 9-2 (1999), 308-314

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, it is an object of the present invention to provide a color filter that does not require a partition layer by not performing a resist treatment, and that does not cause a decrease in color or turbidity, and a method for manufacturing the same. To do.

Means for solving the above problems are as follows. That is,
<1> The support has a fine pore structure, and at least one pore in the fine pore structure has any one of a red colorant, a green colorant, and a blue colorant. It is a color filter characterized by this.
<2> The color filter according to <1>, wherein the fine pore structure is a honeycomb-like porous structure produced by self-organization.
<3> The color filter according to any one of <1> to <2>, wherein the fine pore structure material is at least one selected from a hydrophobic polymer and an amphiphilic polymer.
<4> The color filter according to any one of <1> to <3>, wherein the fine pore structure material contains a black colorant.
<5> A coating liquid containing an organic solvent and a polymer compound is applied onto a support, droplets are formed in the obtained film, and the organic solvent and the droplets are evaporated to empty the film. A microporous structure manufacturing process for manufacturing a microporous structure having holes;
It is a manufacturing method of a color filter characterized by including the accommodation process which accommodates a red coloring agent, a green coloring agent, and a blue coloring agent in the void | hole of the obtained fine pore structure.
<6> The method for producing a color filter according to <5>, wherein the coating liquid contains a black colorant.

The color filter of the present invention has a fine pore structure on a support, and any one of a red colorant, a green colorant, and a blue colorant is contained in at least one pore in the fine pore structure. Have. As a result, there is no reduction in color and no blurring, so that a high-definition color filter having a high optical density and excellent durability can be provided. In the color filter, the fine pore structure is preferably a honeycomb-like porous structure produced by self-organization.
Further, the mechanism for forming the fine pore structure is estimated as follows. When the hydrophobic organic solvent evaporates, water condenses on the surface of the solvent whose temperature is lowered due to the removal of latent heat, and becomes fine droplets and adheres to the polymer solution surface. The action of the hydrophilic portion in the polymer solution reduces the surface tension between water and the hydrophobic organic solvent and prevents water droplets from aggregating and coalescing into one mass. The droplets are transferred and collected by the solvent flow based on solvent evaporation and filling from the surroundings, and are further closely packed by the transverse capillary force. Finally, the water evaporates and the polymer remains in a regular and honeycomb form.

In the method for producing a color filter of the present invention, a coating liquid containing an organic solvent and a polymer compound is coated on a support, droplets are formed in the obtained film, and the organic solvent and the droplets are evaporated. A fine pore structure production step of producing a fine pore structure having pores in the film,
A containing step of containing a red colorant, a green colorant, and a blue colorant in the pores of the obtained fine pore structure. As a result, since the resist treatment is not performed, it is possible to manufacture a color filter that does not require the provision of a partition wall layer and that does not cause a decrease in tint or generation of fog.

  According to the present invention, it is possible to solve the conventional problems, and by not performing the resist treatment, it is not necessary to provide a partition wall layer, and the color filter that does not cause a decrease in color or a blur, and its A manufacturing method can be provided.

(Color filter)
The color filter of the present invention has a fine pore structure on a support, and any one of a red colorant, a green colorant, and a blue colorant is contained in at least one pore in the fine pore structure. And other configurations as necessary.
The fine pore structure is preferably a honeycomb-like porous structure produced by self-organization.
The fine pore structure only needs to have any one of the color coloring agents in at least one pore, but has any one of the color coloring agents in as many pores as possible. It is preferable to have any one of the above-mentioned colorants in all the pores. Moreover, although the said micropore structure should just have either a red coloring agent, a green coloring agent, and a blue coloring agent, it is preferable to have all the said color coloring agents.

-Colorant-
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, For example, an organic pigment, an inorganic pigment, dye, etc. are mentioned.
Any one selected from dendritic branched molecules in which metal ions are coordinated as coloring agents, and dendritic branched molecules containing at least one metal particle of metal particles and alloy particles, separately or in combination with these colorants It is also possible to contain the following dendritic branched molecules.
Here, the colorant may be provided in a mosaic shape in the pores included in the fine pore structure, or may be provided in stripes by dividing the color for each predetermined region. It is also possible to determine the sections of each colorant and to repeat this regularly.

  Examples of the colorant include a red dye, a red pigment, and an orange pigment in a red colorant, a green dye, a green pigment, and a yellow pigment in a green colorant, and a blue dye in a blue colorant, A blue pigment and a violet pigment are each preferably used. Further, in the red colorant, a red dye or a red pigment, in a green colorant, a green dye or a green pigment, and in a blue colorant, a blue dye or a blue pigment directly corresponds to each color. In particular, it is preferably used.

  Examples of the red dye include C.I. I. Acid Red 118, C.I. I. Acid Red 254 and the like.

  Examples of the red pigment include C.I. I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 217, C.I. I. Pigment red 220, C.I. I. Pigment red 223, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 227, C.I. I. Pigment red 228, C.I. I. Pigment red 240, C.I. I. Pigment Red 48: 1, Permanent Carmine FBB (CI Pigment Red 146), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Supra (CI Pigment Red 81), etc. Is mentioned.

  Examples of the orange pigment include C.I. I. Pigment orange 36, C.I. I. Pigment orange 43, C.I. I. Pigment orange 51, C.I. I. Pigment orange 55, C.I. I. Pigment orange 59, C.I. I. Pigment orange 61 and the like.

  Examples of the green dye include C.I. I. Acid Green 25 and the like.

  Examples of the green pigment include C.I. I. Pigment green 7, C.I. I. And CI Pigment Green 36.

  Examples of the yellow pigment include C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 86, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 125, C.I. I. Pigment yellow 137, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. Pigment Yellow 168, Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), and the like.

  Examples of the blue dye include C.I. I. Acid Blue 113, C.I. I. Acid Blue 185, C.I. I. Acid Blue 7 and so on.

  Examples of the blue pigment include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment Blue 64, Victoria Pure Blue BO (C.I. 42595), and the like.

  Examples of the violet pigment include C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 30, C.I. I. Pigment violet 37, C.I. I. Pigment violet 40, C.I. I. And CI Pigment Violet 50.

  In addition, the said colorant, such as an organic pigment, an inorganic pigment, or dye, may be used individually by 1 type, or can also be used in combination of 2 or more type.

The content of the colorant is red colorant, a green colorant, and none of the blue colorant is preferably 0.01 to 10 g / ^{m 2,} more preferably 0.1-5 g / ^{m 2,} 0.1 ˜2 g / m ² is particularly preferred.

When using the colorant as described above, the particle diameter of the pigment or dye is preferably 1 to 10 ⁴ nm, more preferably 10 to 80 nm, and further preferably 20 to 70 nm. Preferably, the thickness is 30 to 60 nm. When the particle size of the pigment or the like is not in the above range, it cannot be uniformly contained in the pores, and it is difficult to produce a high-quality color filter, which is not preferable.

--Binder--
The pores preferably have a binder from the viewpoint of retaining the colorant.
The binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, natural wax such as whale wax, carnauba wax, candelilla wax, wood wax, beeswax, montan wax, lanolin, paraffin wax, micron Crystalline wax, ester wax, oxidized wax, low molecular weight polyethylene wax, synthetic wax such as chlorinated paraffin, higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, furomenic acid, behenic acid, stearyl alcohol, behenine alcohol Fatty alcohols such as sucrose fatty acid esters, fatty acid esters such as sulfitan fatty acid esters, amides such as stearamide and oleinamide, lactones, lactams, aromatic alcohols, ethers, Vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, vinyl chloride-polyvinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid, ethylene-vinyl acetate copolymer, Copolymers such as styrene-butadiene-acrylonitrile copolymer, ethylene-α-olefin copolymer elastomer, saponified ethylene-vinyl acetate copolymer, cellulose resins such as ethyl cellulose and cellulose acetate, polyethylene, polypropylene, acid-modified Examples include polyolefin, polystyrene, polyvinyl butyral, polyacrylonitrile, polyamide, polycarbonate, polysulfone, polyacetal, polymethyl methacrylate, and the like. These may be used alone or in combination of two or more.

As the binder, for example, it is preferable that the binder is swellable with an alkaline aqueous solution, and a binder that is soluble in an alkaline aqueous solution can also be used.
As the binder exhibiting swellability or solubility with respect to the alkaline aqueous solution, for example, those having an acidic group are preferably exemplified.

There is no restriction | limiting in particular as said acidic group, According to the objective, it can select suitably, For example, a carboxyl group, a sulfonic acid group, a phosphoric acid group etc. are mentioned, Among these, a carboxyl group is preferable.
Examples of the binder having a carboxyl group include a vinyl copolymer having a carboxyl group, a polyurethane resin, a polyamic acid resin, and a modified epoxy resin. Among these, the solubility in a coating solvent, the solubility in an alkali developer, and the like. From the viewpoints of solubility, suitability for synthesis, ease of preparation of film properties, etc., a vinyl copolymer having a carboxyl group is preferred.

  The vinyl copolymer having a carboxyl group can be obtained by copolymerization of at least (1) a vinyl monomer having a carboxyl group, and (2) a monomer copolymerizable therewith.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and hydroxyl group. An addition reaction product of a monomer (for example, 2-hydroxyethyl (meth) acrylate) and a cyclic anhydride (for example, maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride), ω-carboxy-polycaprolactone mono Examples include (meth) acrylate. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.
Moreover, you may use the monomer which has anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.

  The copolymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, Fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (eg, vinylpyridine, vinylpyrrolidone) , Vinyl carbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, 2-acrylamido-2-methylpropanesulfonic acid, monophosphate (2-acryloyloxyethyl ester), monophosphate (1-methyl- - acryloyloxyethyl ester), functional groups (e.g., a urethane group, a urea group, a sulfonamide group, a phenol group and a vinyl monomer and the like having an imide group).

  Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, Dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meta ) Acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate , Polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, Nylphenoxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) Examples thereof include acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, and tribromophenyloxyethyl (meth) acrylate.

  Examples of the crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

  Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

  Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloro Examples include methylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, α-methylstyrene, and the like.

  Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  Examples of the method for synthesizing the vinyl monomer having a functional group include an addition reaction of an isocyanate group and a hydroxyl group or an amino group, specifically, a monomer having an isocyanate group and a compound containing one hydroxyl group. Alternatively, an addition reaction with a compound having one primary or secondary amino group, an addition reaction between a monomer having a hydroxyl group or a monomer having a primary or secondary amino group, and a monoisocyanate can be given.

  Examples of the monomer having an isocyanate group include compounds represented by the following structural formulas (1) to (3).

However, in the structural formulas (1) to (3), R ¹ represents a hydrogen atom or a methyl group.

  Examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, and phenyl isocyanate.

  Examples of the monomer having a hydroxyl group include compounds represented by the following structural formulas (4) to (12).

However, in the structural formulas (4) to (12), R ₁ represents a hydrogen atom or a methyl group, and n, n1, and n2 represent an integer of 1 or more.

  Examples of the compound containing one hydroxyl group include alcohols (for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, 2-ethylhexanol). , N-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, etc.), phenols (eg, phenol, cresol, naphthol, etc.), and further containing substituents Examples thereof include fluoroethanol, trifluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, acetoxyphenol, and the like.

  Examples of the monomer having a primary or secondary amino group include vinylbenzylamine.

  Examples of the compound containing one primary or secondary amino group include alkylamines (methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, hexyl). Amine, 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine), cyclic alkylamine (cyclopentylamine, cyclohexylamine, etc.), aralkylamine (benzylamine, phenethylamine, etc.), Arylamines (aniline, toluylamine, xylylamine, naphthylamine, etc.), combinations thereof (N-methyl-N-benzylamine, etc.), and amines containing further substituents (trifluoroethylamino) , Hexafluoro isopropyl amine, methoxyaniline, methoxypropylamine and the like) and the like.

  Examples of the other copolymerizable monomers other than those described above include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylic. Preferable examples include 2-ethylhexyl acid, styrene, chlorostyrene, bromostyrene, and hydroxystyrene.

  The said other copolymerizable monomer may be used individually by 1 type, and may use 2 or more types together.

  The vinyl copolymer can be prepared by copolymerizing the corresponding monomers by a known method according to a conventional method. For example, it can be prepared by using a method (solution polymerization method) in which the monomer is dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Moreover, it can prepare by utilizing superposition | polymerization by what is called emulsion polymerization etc. in the state which disperse | distributed the said monomer in the aqueous medium.

  The suitable solvent used in the solution polymerization method is not particularly limited and may be appropriately selected depending on the monomer used and the solubility of the copolymer to be produced. For example, methanol, ethanol, propanol, Examples include isopropanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene and the like. These solvents may be used alone or in combination of two or more.

  The radical polymerization initiator is not particularly limited, and examples thereof include 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile). Examples thereof include peroxides such as azo compounds and benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate.

  The content of the polymerizable compound having a carboxyl group in the vinyl copolymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 5 to 50 mol%, and preferably 10 to 40 mol%. Is more preferable, and 15 to 35 mol% is particularly preferable.

The molecular weight of the binder having a carboxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the weight average molecular weight is preferably 2,000 to 300,000, and 4,000 to 150, 000 is more preferable.
When the weight average molecular weight is less than 2,000, the film forming property may be deteriorated, and when it exceeds 300,000, the surface state of the film may be deteriorated.

  The binder which has the said carboxyl group may be used individually by 1 type, and may use 2 or more types together. When two or more binders are used in combination, for example, a combination of two or more binders composed of different copolymerization components, two or more binders having different weight average molecular weights, two or more binders having different degrees of dispersion, etc. Is mentioned.

  The binder having a carboxyl group may be partially or entirely neutralized with a basic substance. The binder may be used in combination with resins having different structures such as polyester resin, polyamide resin, polyurethane resin, epoxy resin, polyvinyl alcohol, and gelatin.

  Moreover, as the binder, a resin soluble in an alkaline aqueous solution described in Japanese Patent No. 2873889 can be used.

  The content of the binder in all components of the pores is not particularly limited and can be appropriately selected according to the purpose. For example, 5 to 80% by mass is preferable, and 10 to 70% by mass is more preferable. 15-50 mass% is especially preferable.

  The acid value of the binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 70 to 250 mgKOH / g, more preferably 90 to 200 mgKOH / g, and particularly preferably 100 to 180 mgKOH / g. preferable.

The binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, JP-A Nos. 51-131706, 52-94388, 64-62375, and JP-A-2 -97513, JP-A-3-289656, JP-A-61-2243869, JP-A-2002-296776, and the like. Specifically, phenol novolac type epoxy acrylate monotetrahydrophthalate, cresol novolac epoxy acrylate monotetrahydrophthalate, bisphenol A type epoxy acrylate monotetrahydrophthalate, etc., for example, (meth) acrylic to epoxy resin or polyfunctional epoxy compound This is obtained by reacting a carboxyl group-containing monomer such as an acid and further adding a dibasic acid anhydride such as phthalic anhydride.
The molecular weight of the epoxy acrylate compound is preferably 1,000 to 200,000, and more preferably 2,000 to 100,000. When the molecular weight is less than 1,000, the film-forming property may be deteriorated, and when it exceeds 200,000, the surface condition during film formation may be deteriorated.

An acrylic resin having at least one polymerizable group such as an acidic group and a double bond described in JP-A-6-295060 can also be used. Specifically, at least one polymerizable double bond in the molecule, for example, an acrylic group such as a (meth) acrylate group or (meth) acrylamide group, various polymerizations such as vinyl ester of carboxylic acid, vinyl ether, allyl ether Sex double bonds can be used. More specifically, acrylic resins containing carboxyl groups as acidic groups, glycidyl esters of unsaturated fatty acids such as glycidyl acrylate, glycidyl methacrylate, cinnamic acid, and epoxy groups such as cyclohexene oxide in the same molecule (meth) Examples thereof include compounds obtained by adding an epoxy group-containing polymerizable compound such as a compound having an acryloyl group. In addition, a compound obtained by adding an isocyanate group-containing polymerizable compound such as isocyanate ethyl (meth) acrylate to an acrylic resin containing an acidic group and a hydroxyl group, an acrylic resin containing an anhydride group, a hydroxyalkyl ( Examples thereof include compounds obtained by adding a polymerizable compound containing a hydroxyl group such as (meth) acrylate. As these commercially available products, for example, “Kaneka Resin AX; manufactured by Kaneka Chemical Co., Ltd.”, “Cyclomer (CYCLOMER) A-200; manufactured by Daicel Chemical Industries, Ltd.”, “CYCLOMER (M)” 200; manufactured by Daicel Chemical Industries, Ltd. "can be used.
Furthermore, a reaction product of hydroxyalkyl acrylate or hydroxyalkyl methacrylate described in JP-A No. 50-59315 and any of polycarboxylic acid anhydride and epihalohydrin can be used.

  Further, a compound obtained by adding an acid anhydride to an epoxy acrylate having a fluorene skeleton described in JP-A-5-70528, a polyamide (imide) resin described in JP-A-11-288087, and JP-A-2-097502 And styrene-containing styrene derivatives and acid anhydride copolymers described in JP-A No. 2003-203310 and polyimide precursors described in JP-A No. 11-282155 can be used. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The molecular weight of the acrylic resin, epoxy acrylate having a fluorene skeleton, polyamide (imide), amide group-containing styrene / acid anhydride copolymer, or polyimide precursor is preferably 3,000 to 500,000, 5,000-100,000 are more preferable. The molecular weight may be less than 3,000.

  10-60 mass% is preferable, as for solid content in all the components which the void | hole of the said binder has, 10-55 mass% is more preferable, and 15-40 mass% is especially preferable.

-Fine pore structure-
The fine pore structure material in the fine pore structure is not particularly limited and may be appropriately selected depending on the intended purpose. For example, at least one selected from a hydrophobic polymer and an amphiphilic polymer is suitable. is there.
The fine pore structure preferably contains a black colorant in the fine pore structure material from the viewpoint of functioning as a black matrix.

<Polymer>
--Hydrophobic polymer--
There is no restriction | limiting in particular as said hydrophobic polymer, According to the objective, it can select suitably according to the objective, For example, vinyl polymer (For example, polyethylene, polypropylene, polystyrene, polyacrylate, polymethacrylate, polyacrylamide) , Polymethacrylamide, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyhexafluoropropene, polyvinyl ether, polyvinyl carbazole, polyvinyl acetate, polyvinyl carbazole, polytetrafluoroethylene, etc., polyester (eg, polyethylene terephthalate, polyethylene) Naphthalate, polyethylene succinate, polybutylene succinate, polylactic acid, etc.), polylactone (eg polycaprolactone, etc.), polyamide or poly Imides (eg, nylon or polyamide acid), polyurethanes, polyureas, polycarbonates, polyaromatics, polysulfones, polyethersulfones, polysiloxane derivatives, and the like. From the viewpoints of solubility, optical physical properties, electrical physical properties, film strength, elasticity, and the like, these may be homopolymers as necessary, or may take the form of copolymers or polymer blends. In addition, you may use these polymers as a mixture of 2 or more types of polymers as needed.

-Amphiphilic polymer-
The amphiphilic polymer is not particularly limited and may be appropriately selected depending on the intended purpose.For example, polyacrylamide is a main chain skeleton, a dodecyl group is a hydrophobic side chain, and a carboxyl group is a hydrophilic side chain. Examples thereof include an amphiphilic polymer and a polyethylene glycol / polypropylene glycol block copolymer.
The hydrophobic side chain is a non-polar linear group such as an alkylene group or a phenylene group, and has a hydrophilic group such as a polar group or an ionic dissociation group up to the terminal except for a linking group such as an ester group or an amide group. It is preferable that the structure does not branch. As the hydrophobic side chain, for example, when an alkylene group is used, it is preferably composed of 5 or more methylene units.
The hydrophilic side chain preferably has a structure having a polar part, an ionic dissociation group, or a hydrophilic part such as an oxyethylene group at the end via a linking part such as an alkylene group.

  The ratio between the hydrophobic side chain and the hydrophilic side chain differs depending on the size, nonpolarity, polarity strength, hydrophobic strength of the hydrophobic organic solvent, etc. The ratio (hydrophobic side chain / hydrophilic side chain) is preferably 3/1 to 1/3. In the case of a copolymer, a block copolymer in which a hydrophobic side chain and a hydrophilic side chain form a block as long as it does not affect the solubility in a hydrophobic solvent, rather than an alternating polymer of hydrophilic side chains of hydrophobic side chains. It is preferable that

  The number average molecular weight (Mn) of the hydrophobic polymer and the amphiphilic polymer is preferably 1,000 to 10,000,000, and more preferably 5,000 to 1,000,000.

Although the honeycomb structure film can be formed with only the hydrophobic polymer, it is preferably used together with the amphiphilic polymer.
The composition ratio (mass ratio) between the hydrophobic polymer and the amphiphilic polymer is preferably 99: 1 to 50:50, and more preferably 90:10 to 80:20. When the ratio of the amphiphilic polymer is less than 1% by mass, a uniform honeycomb structure may not be obtained. On the other hand, when the ratio of the amphiphilic polymer exceeds 50% by mass, the stability of the film, particularly the mechanical stability may not be sufficiently obtained.

  The hydrophobic polymer and the amphiphilic polymer are also preferably polymerizable (crosslinkable) polymers having a polymerizable group in the molecule. In addition, a polymerizable polyfunctional monomer is blended together with the hydrophobic polymer and / or the amphiphilic polymer, and after forming a honeycomb film with the blend, a thermosetting method, an ultraviolet curing method, an electron beam curing method, etc. It is also preferable to perform a curing treatment by a known method.

The polyfunctional monomer used in combination with the hydrophobic polymer and / or the amphiphilic polymer is preferably a polyfunctional (meth) acrylate from the viewpoint of reactivity. Examples of the polyfunctional (meth) acrylate include dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol caprolactone adduct hexaacrylate or a modified product thereof, epoxy acrylate oligomer, polyester acrylate oligomer, Urethane acrylate oligomer, N-vinyl-2-pyrrolidone, tripropylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or a modified product thereof can be used. These polyfunctional monomers are used singly or in combination of two or more from the balance of scratch resistance and flexibility.
When the hydrophobic polymer and the amphiphilic polymer are a polymerizable (crosslinkable) polymer having a polymerizable group in the molecule, they react with the polymerizable group of the hydrophobic polymer and the amphiphilic polymer. It is also preferable to use a polymerizable polyfunctional monomer in combination.

Polymerization of the monomer having an ethylenically unsaturated group can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, mat particles and an inorganic filler is prepared, and the coating liquid is applied on a transparent support and then ionizing radiation or heat is applied. It can be cured by a polymerization reaction to form an antireflection film.

Examples of the radical photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-alkyldione compounds, Examples include disulfide compounds, fluoroamine compounds, and aromatic sulfoniums.
Examples of the acetophenones include 2,2-ethoxyacetophenone, p-methylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone and the like.
Examples of the benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
Examples of the benzophenones include benzophenone, 2,4-chlorobenzophenone, 4,4-dichlorobenzophenone, p-chlorobenzophenone, and the like.
Examples of the phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Various examples of the radical photopolymerization initiator are also described in the latest UV curing technology (P.159, issuer; Kazuhiro Takasawa, publisher; Technical Information Association, Inc., published in 1991).
Further, as a commercially available photocleavable photoradical polymerization initiator, Irgacure (651, 184, 907) manufactured by Ciba Specialty Chemicals Co., Ltd. and the like are preferable examples.
It is preferable to use the said photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, and it is more preferable to use it in the range of 1-10 mass parts.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the external photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone, and thioxanthone.

As said thermal radical initiator, an organic peroxide, an inorganic peroxide, an organic azo compound, an organic diazo compound, etc. can be used, for example.
Specific examples of the organic peroxide include benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, and butyl hydroperoxide. Examples of the inorganic peroxide include hydrogen peroxide, ammonium persulfate, and potassium persulfate. Examples of the azo compound include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile), and the like. Examples of the diazo compound include diazoaminobenzene, p-nitrobenzenediazonium, and the like.

  The polymer concentration of both the hydrophobic polymer and the amphiphilic polymer to be dissolved is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass. If the polymer concentration is less than 0.01% by mass, the obtained film may have insufficient mechanical strength, or the pore size and arrangement may be disturbed. If it exceeds, it may be difficult to obtain a sufficient honeycomb structure.

<Black colorant>
There is no restriction | limiting in particular as said black coloring agent, Although it can select suitably according to the objective, For example, a black pigment, a black dye, etc. are mentioned suitably.
Examples of the black pigment include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), titanium oxide, and the like. And organic pigments such as aniline black (CI Pigment Black 1).
Examples of the black dye include C.I. I. Reactive Black 3, C.I. I. Reactive Black 4, C.I. I. Reactive Black 7, C.I. I. Reactive Black 11, C.I. I. Reactive Black 12, C.I. I. Reactive Black 17; C.I. I. Basic Black 2, C.I. I. B. Basic Black 8; I. Direct Black 19, C.I. I. Direct Black 22, C.I. I. Direct Black 32, C.I. I. Direct Black 38, C.I. I. Direct Black 51, C.I. I. Direct Black 56, C.I. I. Direct Black 71, C.I. I. Direct Black 74, C.I. I. Direct Black 75, C.I. I. Direct Black 77, C.I. I. Direct Black 154, C.I. I. Direct Black 168, C.I. I. Direct black 171; I. Food Black 1, C.I. I. Food black 2 etc. are mentioned.
Among these black colorants, carbon black is particularly preferable from the viewpoints of availability and durability.

  The content of the black colorant in the fine pore structure is not particularly limited and may be appropriately selected depending on the purpose. It is preferably 0.01 to 50% by mass with respect to the fine pore structure material, and 0 0.01 to 10% by mass is more preferable, and 0.1 to 5% by mass is most preferable. If the content is less than 0.01% by mass, the concentration may be insufficient and the contrast may be lowered. If the content exceeds 50% by mass, the contrast performance may be saturated and the film quality may be deteriorated.

  The honeycomb structure in the honeycomb-shaped porous film produced by the self-organization means a structure in which pores having a fixed shape and a fixed size are continuously and regularly arranged. This regular arrangement is two-dimensional in the case of a single layer and regular in three dimensions in the case of a multilayer. This regularity is arranged so that a plurality of (for example, six) holes surround one hole in a two-dimensional manner, and three-dimensionally like a face-centered cubic or hexagonal crystal structure. However, depending on the manufacturing conditions, other regularity may be exhibited.

  In producing the honeycomb structure, since it is essential to form fine water droplet particles on the polymer solution, the solvent to be used is preferably water-insoluble. Examples of the water-insoluble solvent include halogen-based organic solvents such as chloroform and methylene chloride; aromatic hydrocarbons such as benzene, toluene and xylene; esters such as ethyl acetate and butyl acetate; water-insoluble such as methyl isobutyl ketone Ketones; ethers such as diethyl ether; carbon disulfide; and the like. These may be used singly or as a mixed solvent in which these solvents are combined.

The pore diameter in the fine pore structure is preferably 1,000 nm or less, more preferably 50 nm or more and 1,000 nm or less, and particularly preferably 20 nm or more and 1,000 nm or less. When the diameter of the pores exceeds 1,000 nm, each strength is lowered, and it may be easily broken during the stretching process.
Here, in order to reduce the pore diameter of the fine pore structure, it is effective to promote rapid drying. For example, it is effective to use a low-boiling point solvent as the solvent used, raise the support temperature, or increase the developing speed to reduce the initial developing liquid thickness.

  Although the thickness of the fine pore structure is approximately the pore size size to 200 μm, it is possible to provide a thick layer without pores on the support side by increasing the concentration of the developed polymer. In this case, the thickness of the thick layer without voids can be controlled within a range of 0 to 500 μm.

-Support-
The support is not particularly limited as long as it is transparent and has a certain degree of strength, and can be appropriately selected according to the purpose. For example, an inorganic material such as glass, metal, silicon wafer; polyethylene terephthalate, Polyester such as polyethylene naphthalate; Polyolefin such as polyethylene and polypropylene; Polyamide, Polyether, Polystyrene, Polyesteramide, Polycarbonate, Polyphenylene sulfide, Polyetherester, Polyvinyl chloride, Polyacrylic ester, Polymethacrylic ester, Polyetherketone And organic materials excellent in organic solvent resistance such as polyfluorinated ethylene; liquids such as water, liquid paraffin, and liquid polyether.
The thickness of the support is not particularly limited as long as it is a thickness in a range usually employed, and can be appropriately selected according to the purpose. For example, it is preferably 0.02 to 4.0 mm.

  Here, FIG. 1 shows an example of the color filter of the present invention. A black honeycomb porous structure 2 is formed on a support 1, and a colorant 4 is formed in the pores 3 of the honeycomb porous structure. Is filled.

-Application-
The color filter of the present invention is intended to be formed on the counter substrate of the liquid crystal display device (the substrate on the side where there is no active element such as a TFT). The BOA method for forming the layer or the HA method having a high aperture structure on the TFT substrate can also be targeted.

  An overcoat film or a transparent conductive film can be further formed on the color filter as necessary. Thereafter, liquid crystal is sealed between the color filter and the counter substrate, and a liquid crystal display device is manufactured. The liquid crystal display method is not particularly limited and may be appropriately selected depending on the purpose. HAN (Hybrid Aligned Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), GH (Guest Host), FLC (ferroelectric liquid crystal), AFLC (antiferroelectric liquid crystal), PDLC (polymer dispersion) Applicable to display methods such as liquid crystal display).

In particular, the color filter of the present invention does not require a polymerizable compound such as a monomer or a polymerization initiator in the color layer, that is, the pores. When used as a plate, it is highly fine and durable and is preferably used.
In addition, from the same viewpoint, it is durable and suitable for use in electric decorations such as displays and CCD cameras.

(Color filter manufacturing method)
The method for producing a color filter of the present invention includes a fine pore structure manufacturing process, and further includes an accommodating process and, if necessary, other processes.

-Microporous structure fabrication process-
The fine pore structure preparation step includes an organic solvent and a polymer compound, preferably a liquid containing a black colorant is cast on a support to form a film, and droplets are formed in the film. The step of evaporating the organic solvent and the droplets to produce a film having pores in the film.

  There is no restriction | limiting in particular as said casting method, According to the objective, it can select suitably, For example, a slide method, an extrusion method, a bar method, a gravure method etc. are mentioned.

  As an environment in which the film is formed, it is preferable that the relative humidity is in the range of 50 to 95%. If the relative humidity is less than 50%, water condensation on the solvent surface may be insufficient, and if it exceeds 95%, it may be difficult to control the environment and maintain uniform film formation. is there.

Further, as the environment for forming the film, it is preferable to apply a steady air with a constant air flow in addition to the relative humidity. The relative wind speed with respect to the film is preferably 0.1 to 20 m / s. If the wind speed is less than 0.1 m / s, it may be difficult to control the environment, and if it exceeds 20 m / s, the solvent surface may be disturbed and a uniform film may be difficult to obtain.
In addition, the direction in which the steady wind is applied can be produced in any direction of 0 to 90 ° with respect to the support surface, but 0 to 60 ° is preferable in order to improve the uniformity of the honeycomb structure.

  As the gas whose humidity and flow rate are controlled during the film formation, for example, an inert gas such as nitrogen gas or argon gas can be used in addition to air, but dust removal treatment such as passing through a filter in advance is possible. It is preferable to apply. Since dust in the atmosphere acts as a condensation nucleus of water vapor and affects film formation, it is preferable to install a dust removal facility or the like at the manufacturing site.

  The environment in which the film is formed is preferably strictly controlled by using a commercially available constant dew point humidity generator or the like. The air volume is preferably controlled with a blower or the like, and it is preferable to use a closed space in order to prevent the influence of outside air. In addition, it is preferable to set a gas introduction / extraction path and a film formation environment so that the gas is replaced by a laminar flow. Furthermore, it is preferable to monitor the temperature, humidity, flow rate and the like with a measuring instrument in order to control the film formation quality. In order to control the hole diameter and film thickness with high accuracy, it is essential to strictly manage these parameters (especially humidity and flow rate).

-Containment process-
The accommodation step is a step of accommodating a red colorant, a green colorant, and a blue colorant in the pores of the obtained fine pore structure.
The method for accommodating the red colorant, the green colorant, and the blue colorant in the pores is not particularly limited and may be appropriately selected depending on the intended purpose. Preferably, for example, a method of filling the pores with a molten red colorant, a green colorant, and a blue colorant, a method of filling the pores with a solution prepared with a solvent that does not dissolve the honeycomb-like porous structure, and pores Examples thereof include a method of polymerizing by heating or light irradiation after the monomer is filled therein.
Here, the respective colorants may be accommodated in the holes in a mosaic shape, or may be color-coded for each predetermined region and accommodated in a stripe shape, or each color colorant may be contained in the predetermined region. You may define a division and accommodate it so that this may be repeated regularly.

  Here, the manufacturing process diagram of the color filter according to the present invention is shown in FIG. Preferably, a polymer solution containing a black colorant is cast on a support by the casting step 10 to form a film (hereinafter sometimes referred to as “polymer film”). Thereafter, in the condensation drying step 11, water is condensed and contained as droplets in the polymer film. The condensation drying process 11 will be described in detail later. The solvent and droplets of the polymer solution are evaporated to obtain the honeycomb structure film 12. A filling step 13 for filling the pores of the honeycomb structure film 12 with a red colorant, a green colorant, and a blue colorant is performed to obtain a color filter 14. In addition, the irradiation process 15 can also be performed while obtaining the color filter 14 from a polymer film. In that case, ultraviolet rays or electron beams can be used as irradiation light. Although not shown, a stretching process of stretching a film filled with a red colorant, a green colorant, and a blue colorant in the pores can also be performed.

As the material of the honeycomb structure film 12, a polymer compound that can be dissolved in a water-insoluble solvent as described above (hereinafter also referred to as “hydrophobic polymer compound”) can be preferably used.
Moreover, although the honeycomb structure film 12 can be formed with only the hydrophobic polymer, it is preferable to add an amphiphilic material. As the amphiphilic material, those described above can be appropriately selected and used.
In addition, as the solvent for preparing the polymer solution by dissolving each of the polymer compounds, those described above can be appropriately selected and used.

  Next, FIG. 3 shows a schematic diagram of a film manufacturing facility 20 for manufacturing the honeycomb structure film 12. The polymer solution 21 is placed in a tank 22. The tank 22 is provided with a stirring blade 23, and the polymer solution 21 is uniformly mixed by rotating the stirring blade 23. The polymer solution 21 is sent to the casting die 25 by the pump 24. The casting die 25 is provided on the casting belt 26. Further, the casting belt 26 is stretched around rotating rollers 27 and 28. The rotation belts 27 and 28 are rotated by a driving device (not shown), so that the casting belt 26 travels endlessly. Further, a temperature controller 29 is attached to the rotary rollers 27 and 28. The temperature of the casting belt 26 can be adjusted by adjusting the temperature of the rotating rollers 27 and 28. Further, when the polymer film 40 on the casting belt 26 is peeled off, a peeling roller 30 that supports the polymer film 40 and a winder 31 that winds the polymer film 40 as a film are also provided.

  In the casting step 10, the polymer solution 21 is cast (cast) from the casting die 25 onto the casting belt 26. Subsequently, a condensation drying step 11 is performed. The condensation drying step 11 will be described in conjunction with FIGS. 4A to 4D. As shown in FIG. 4A, a polymer film 40 is formed on the casting belt 26. The surface temperature of the polymer film 40 (hereinafter sometimes referred to as “film surface temperature”) is TL (° C.). In the present invention, the film surface temperature TL is preferably 0 ° C. or higher. If the film surface temperature TL is less than 0 ° C., the droplets in the polymer film 40 may solidify and a desired hole may not be formed.

  The casting chamber in which casting is performed is partitioned into a condensation zone 32 and a drying zone 33 as shown in FIG. The condensation zone 32 is provided with a blower 34. The air 35 adjusted for condensation is blown from the blower 34 to the polymer film 40 on the casting belt 26. The blower 34 is preferably composed of a plurality of blower units including blower ports 34a, 34c, 34e and suction ports 34b, 34d, 34f. Thereby, it becomes easy to adjust the dew condensation conditions of the polymer film 40. Note that FIG. 3 shows a structure composed of three units, but the present invention is not limited to the illustrated form.

  A dryer 36 is provided in the drying zone 33. Drying air 37 is blown from the dryer 36 to the polymer film 40. As shown in FIG. 3, it is preferable that the dryer 36 also includes a plurality of air blowing units including air blowing ports 36a, 36c, 36e, and 36g and suction ports 36b, 36d, 36f, and 36h. Thereby, it becomes easy to adjust the drying conditions of the polymer film 40. Although FIG. 3 shows a configuration including four units, the present invention is not limited to the illustrated form.

  It is more preferable to adjust the temperature of the casting belt 26 through the rotary rollers 27 and 28 using the temperature controller 29. Examples of the method for adjusting the temperature include a method in which a liquid flow path is provided inside the rotary rollers 27 and 28 and the heat transfer medium is fed into the liquid flow path for adjustment. In adjusting the temperature, it is preferable that the lower limit value is 0 ° C. or higher. Moreover, it is preferable to set it as the solvent boiling point or less of the polymer solution 21, and, more preferably, to set it as (solvent boiling point -3 degreeC). As a result, the condensed moisture does not solidify and the solvent of the polymer solution 21 is suppressed from rapidly evaporating, so that the honeycomb structure film 12 having an excellent shape can be obtained. Furthermore, in the temperature adjustment, the distribution of the film surface temperature is also within ± 3 ° C. by making the temperature distribution within ± 3 ° C. across the width direction of the polymer film 40. By reducing the temperature distribution in the width direction of the polymer film 40, anisotropy is suppressed in the formation of pores in the honeycomb structure film 12, so that the commercial value is improved.

  Further, it is preferable that the conveying direction of the casting belt 26 is within ± 10 ° with respect to the horizontal direction. By adjusting the transport direction, the form of the droplets 44 can be adjusted as shown in FIGS. By adjusting the form of the droplet 44, the form of the hole can be adjusted.

  Wind 35 is blown from the blower 34. The dew point TD1 (° C.) of the wind 35 is preferably 0 ° C. ≦ (TD1-TL) ° C. with respect to the surface temperature TL (° C.) of the polymer film 40 passing through the condensation zone 32, and 0 ° C. ≦ (TD1-TL) More preferably, the temperature is more preferably from 5 ° C. to 60 ° C., and particularly preferably from 10 ° C. to 40 ° C. When the (TD1-TL) ° C. is less than 0 ° C., condensation may be difficult to occur, and when it exceeds 80 ° C., condensation and drying become steep, and it is difficult to control the pore size and make it uniform. May be. The temperature of the wind 35 is not particularly limited and can be appropriately selected according to the purpose. When the temperature of the wind is less than 5 ° C., the liquid, particularly water, hardly evaporates and the honeycomb structure film 12 having a good shape may not be obtained. Moreover, when it exceeds 100 degreeC, before the droplet 44 arises in the polymer film 40, there exists a possibility of volatilizing as water vapor | steam.

  As shown in FIG. 4A, moisture (modeled) 43 in the wind 35 in the condensation zone 32 is condensed on the polymer film 40 into droplets 44. Then, as shown in FIG. 4B, the moisture 43 is condensed using the droplet 44 as a nucleus to grow the droplet 44. As shown in FIG. 4C, when the drying air 37 is blown to the polymer film 40 in the drying zone 33, the organic solvent 42 is volatilized from the polymer film 40. At this time, water is volatilized also from the droplets 44, but the volatilization rate of the organic solvent 42 is faster. Therefore, the droplets 44 have a substantially uniform shape due to surface tension as the organic solvent 42 volatilizes. Further, as the drying proceeds, moisture evaporates as water vapor 48 from the droplets 44 of the polymer film 40 as shown in FIG. 4D. When the droplets 44 evaporate from the polymer film 40, the portions where the droplets 44 were formed become holes 47, and the honeycomb structure film 12 as shown in FIG. 4 is obtained. In the present invention, the form of the honeycomb structure film 12 is not particularly limited. Specifically, as shown in FIG. 5, the distance L2 between the adjacent holes 47 is 0.05 μm or more at the center-to-center distance. It can be controlled to 100 μm or less.

  The blowing direction of the wind 35 is parallel to the moving direction of the polymer film 40 (cocurrent flow). When the air is blown as a countercurrent, the film surface of the polymer film 40 may be disturbed, and the growth of the droplets may be hindered. Further, the blowing speed of the wind 35 is preferably 0.1 m / s or more and 20 m / s or less, more preferably 0.5 m / s or more and 15 m / s or less, relative to the moving speed of the polymer film 40, and 2 m / s. More preferably, it is s or more and 10 m / s or less. If the blowing speed is less than 0.1 m / s, the polymer film 40 may be transported to the drying zone 33 without the droplets 44 growing sufficiently in the polymer film 40. Moreover, when it exceeds 20 m / s, there exists a possibility that disorder may arise in the polymer film 40 surface, or condensation may not fully advance.

  The time for the polymer film 40 to pass through the condensation zone 32 is preferably 0.1 seconds or more and 100 seconds or less. If the passage time is less than 0.1 seconds, it may be difficult to form a desired hole because the droplets 44 are formed without being sufficiently grown. There is a possibility that the film becomes too large to obtain a honeycomb structure film.

  The blowing speed of the drying air 37 for drying the polymer film 40 in the drying zone 33 is preferably 0.1 m / s or more and 20 m / s or more, more preferably 0.5 m / s or more and 15 m / s or less, and 2 m / s or more. 10 m / s or less is still more preferable. If the blowing speed is less than 0.1 m / s, the evaporation of moisture from the droplets 44 may not proceed sufficiently, and the productivity may be inferior. If it exceeds 20 m / s, the droplets 44 are inferior. As a result, the evaporation of moisture suddenly occurs and the shape of the formed hole 37 may be disturbed.

  When the dew point of the drying air 37 is TD2 (° C.), the relationship with the film surface temperature TL (° C.) is preferably (TL−TD2) ° C. ≧ 1 ° C. As a result, the growth of the droplet 44 of the polymer film 40 is stopped in the drying zone 33, and the water constituting the droplet can be volatilized as the water vapor 48.

  The air blowing from the blowers 34 and 37 can be dried by a reduced pressure drying method in addition to the method of blowing air with a 2D nozzle. By performing drying under reduced pressure, it is possible to adjust the evaporation rate of the organic solvent 42 and the moisture 43 of the droplets 44. By adjusting this, a droplet 44 is formed in the polymer film 40, the droplet 44 is evaporated while the organic solvent 42 is evaporated, and a hole 47 is formed at a position where the droplet is provided. The size and shape of the holes in the invention can be changed.

  Also, a method of drying by a reduced pressure drying method, or a condenser cooled from the membrane surface and having a groove on the surface at a position about 3 to 20 mm away from the membrane surface, water vapor (volatile organic solvent is also on the surface of the condenser) In addition, a method of condensing and drying can also be applied. By applying any one of the drying methods, the film surface of the polymer film 40 can be dried with less dynamic influence, so that a smoother film surface can be obtained.

  Further, by using a plurality of blower units of the blower 34 and the dryer 36 or by dividing the blower unit into a plurality of zones, different dew point conditions can be set or different drying temperature conditions can be set. By selecting these conditions, it is possible to improve the dimensional controllability of the holes 47 and improve the hole uniformity. The number of blower units and zones is not particularly limited, but an optimal combination is determined in terms of film quality and equipment cost.

  The relationship between the film surface temperature TL (° C.) and the dew point temperature TDn (° C.) of the condensation zone or drying zone (n means the n zone number) shall be 0 ° C. ≦ | TDn−TL | ° C. ≦ 80 ° C. Is preferred. By setting the difference to 80 ° C. or less, rapid volatilization of at least one of the organic solvent and moisture can be suppressed, and the honeycomb structured film 12 having a desired form can be obtained. In addition, when impurities are mixed into the polymer film 40, the formation of the honeycomb structure is hindered. Therefore, it is preferable that the dust levels of the air outlets 34a, 34c, 34e, 36a, 36c, 36e, and 36g be class 1000 or less. Therefore, it is preferable to attach an air conditioner 39 to the housing 38 in which the blower 34 and the dryer 36 are installed, thereby performing air conditioning in the housing 38. Thereby, the possibility that impurities are mixed into the polymer film 40 is reduced, and a good honeycomb structure film 12 can be obtained.

  The honeycomb structure film 12 that has been dried is peeled off from the casting belt 26 while being supported by the peeling roller 30, and wound up by the winder 32. In addition, although the conveyance speed of the honeycomb structure film 12 is not specifically limited, It is preferable that they are 0.1 m / min or more and 60 m / min or less. If the conveyance speed is less than 0.1 m / min, the productivity is inferior and the cost is not preferable. On the other hand, if it exceeds 60 m / min, an excessive tension is applied to the honeycomb structure film when it is transported, causing a defect such as a disorder of the honeycomb structure. The honeycomb structured film 12 can be continuously manufactured by the above method.

  FIG. 6 shows a film manufacturing facility 60 according to another embodiment of the present invention. A film 62 serving as a support is conveyed from the delivery device 61. The film 62 is conveyed while being wound around the backup roller 63. A slide coater 64 is provided facing the backup roller 63. The slide coater 64 is provided with a decompression chamber 65. A polymer solution 67 sent from a polymer solution supply device 66 by a liquid feed pump is pushed out from a slide coater 64 and applied onto a film 62 as a support, whereby a polymer film 68 is formed.

  The slide coater 64 is excellent in uniform coating properties in the transport direction of the film 62 and can form the polymer film 68 at a high speed. Further, even when the surface of the film 62 as a support is uneven, the film 62 is smoothed when it is wound around the backup roller 63, so that it is excellent in uniform coatability. Furthermore, since the coating is performed in a non-contact manner on the film 62, uniform coating is possible without damaging the surface of the film 62.

  The polymer film 68 formed on the film 62 is subjected to the condensation drying process 11 by the wind 70 of the blower 69. In addition, the description of the part of the same conditions as the description mentioned above is abbreviate | omitted in the condensation drying process 11. After passing through the condensation drying step 11, the honeycomb structure film 71 is wound around the winding roll 72. Further, the film 62 is also taken up by the take-up roll 73. The transport direction of the film 62 on which the polymer film 68 is formed is preferably within ± 10 ° with respect to the horizontal direction. In addition, it is more preferable to use a film 62 made of a material that easily absorbs the organic solvent of the polymer solution 66. These materials are not particularly limited as long as they absorb an organic solvent. For example, when methyl acetate is used as the main solvent of the polymer solution 67, it is preferable to use cellulose acylate as the material of the film.

  In FIG. 7, the film manufacturing equipment 80 of other embodiment used for the manufacturing method of the film which concerns on this invention is shown. In addition, description of the same location as the film manufacturing equipment 60 is abbreviate | omitted. A film 82 serving as a support is conveyed from the delivery machine 81. The film 82 is conveyed while being wound around the backup roller 83. A multi-layer slide coater 84 is provided opposite to the backup roller 83. The multilayer slide coater 84 is provided with a decompression chamber 85. A polymer solution 87 sent from a polymer solution supply device 86 by a liquid feed pump is pushed out from a multilayer slide coater 84 and applied onto a film 82 as a support to form a polymer film 88. . The polymer film 88 formed on the film 82 is subjected to the condensation drying process 11 by the wind 90 of the blower 89. After passing through the condensation drying step 11, the honeycomb structure film 91 is wound around a winding roll 92. Further, the film 82 is also taken up by the take-up roll 93.

  By casting (applying) the polymer solution 87 composed of multiple layers onto the film 82, it is possible to change the form, physical properties, and the like in the thickness direction of the honeycomb structure film 91.

  In FIG. 8, the film manufacturing equipment 100 of other embodiment used for the manufacturing method of the film which concerns on this invention is shown. In addition, description of the same location as the film manufacturing equipment 60 is abbreviate | omitted. A film 102 serving as a support is conveyed from the delivery machine 101. The film 102 is conveyed while being wound around the backup roller 103. An extrusion coater 104 is provided facing the backup roller 103. The extrusion coater 104 is provided with a decompression chamber 105. The polymer solution 107 sent from the polymer solution supply device 106 by the liquid feed pump is pushed out from the extrusion coater 104 and applied onto the film 102 as the support, thereby forming the polymer film 108. . The polymer film 108 formed on the film 102 is subjected to the condensation drying process 11 by the wind 110 of the blower 109. After passing through the condensation drying step 11, the honeycomb structure film 111 is wound around the winding roll 112. Further, the film 102 is also taken up by the take-up roll 113.

  In FIG. 9, the film manufacturing equipment 120 which manufactures the film which concerns on this invention is shown and demonstrated. The polymer solution 122 is applied to the film 123 using a wire bar applicator 121. The wire bar 124 that rotates in the moving direction of the film 123 that moves at a constant speed pulls the polymer solution 122 from the primary polymer solution tank 125 to the liquid storage portion 126 by the rotation. When the polymer solution 122 in the liquid storage portion 126 comes into contact with the film 123 via the wire bar 124, a polymer film 127 having a uniform thickness is formed. The polymer film 127 is subjected to the condensation drying step 11 with the wind 129 of the blower 128, whereby the honeycomb structure film 130 can be obtained. In the manufacturing method of the honeycomb structure film 130 using the wire bar 124, the liquid storage portion 126 prevents air from entering the contact portion between the polymer solution 122 and the film 123, so that bubbles are mixed into the polymer film 127. There is an advantage that it becomes difficult.

  When the films 62, 82, 102, 123 are used as the support, the honeycomb structure films 71, 91, 111, 130 can be wound as an integral film and used as the base film of the color filter 14.

  FIG. 10 shows a production facility 140 for producing a film according to the present invention. The film 141 is conveyed while being wound around the impression cylinder 142. A plate cylinder 143 is disposed opposite the impression cylinder 142. A desired pattern is formed on the surface of the plate cylinder 143. The polymer solution 145 stored in the polymer solution tank 144 is accumulated in the recess as the plate cylinder 143 rotates. Excess polymer solution 145 is scraped off by the doctor blade 146. Thereafter, a polymer solution 145 is applied on the film 141 that is wound around the impression cylinder 142 and a polymer film 147 is formed.

  The condensation drying process 11 of the polymer film 147 is performed by the blower 148. The wind 149 blown from the blower 148 is a parallel flow in the same direction as the transport direction of the film 141. In the polymer film 147, the honeycomb structure 150 is formed through the condensation drying step 11. The film 141 becomes the honeycomb structure forming film 151 in which the honeycomb structure 150 is formed in a desired pattern.

  The color filter of the present invention obtained according to the method of manufacturing the color filter of the present invention may be used as it is by first manufacturing it on a desired support, or manufactured after being immersed in a suitable solvent such as ethanol. After peeling from the support at the time, it may be used on a desired substrate. In the case of use after peeling, an adhesive such as an epoxy resin or a silane coupling agent suitable for the material and the material of the desired substrate may be used for the purpose of improving the adhesion to a new substrate.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

Example 1
PEN (polyethylene naphthalate) having a weight average molecular weight of 45,000 and an amphiphilic polymer represented by the following structural formula having a weight average molecular weight of 50,000 as a fine pore structure material at a mass ratio of 10: 1. A small amount of carbon black (Mitsubishi Carbon Black (# 2770B), manufactured by Mitsubishi Chemical Corporation) as a black colorant is added to 0.5 mL of methylene chloride solution (0.2% by mass as polymer concentration) mixed at a ratio of A coating solution was prepared.
Next, the entire volume is developed on a glass substrate for HDD kept at 2 ° C. in a closed space not affected by outside air, and constant humidity of 70% relative humidity is 45 ° with respect to the substrate surface at a steady flow rate of 2 L / min. A uniform honeycomb structure was obtained by spraying from the direction of and evaporating methylene chloride. The constant humidity air was supplied by connecting a humidity generator manufactured by Yamato Scientific Co., Ltd. to a compressor SC-820 manufactured by Hitachi Koki Co., Ltd., on which a commercially available dust removal air filter (filtration degree 0.3 μm) was installed. Moreover, it was 0.3 m / s when the flow velocity of the air of a spraying part was measured.

  When the structure of the obtained film was observed with a field emission scanning electron microscope (S4300, manufactured by Hitachi, Ltd.), a honeycomb structure in which pores having a pore diameter of 10 μm were regularly arranged in a hexagonal shape could be confirmed. The vacancies formed a single layer from the front surface to the back surface of the film, and the structure was such that the top and bottom of the film penetrated. The vacancies were distributed over almost the entire surface except for a part around the cast area, and had a beautiful spherical shape.

Next, in the pores of the obtained film, C.I. I. Acid Red 118, C.I. I. Acid Green 25, C.I. I. Acid Blue 113 is used to contain 0.85 g of carbana wax, 0.02 g of stearic acid, and 0.13 g of a colorant (a total of a red colorant, a green colorant, and a blue colorant) per gram. The prepared colored composition was filled in a mosaic shape to produce the color filter of Example 1.
When the shape of the color filter was observed with a field emission scanning electron microscope (S4300, manufactured by Hitachi, Ltd.), a very good color filter having no color mixture could be obtained without using a resist.

(Example 2)
In Example 1, C.I. I. Pigment Red 9, C.I. I. Pigment Green 7, C.I. I. A color filter of Example 2 was produced in the same manner as Example 1 except that CI Pigment Blue 15 was used.
When the shape of the color filter was observed with a field emission scanning electron microscope (S4300, manufactured by Hitachi, Ltd.), as in Example 1, a very good color filter having no color mixture was obtained without using a resist. I was able to.

(Example 3)
In Example 1, PEN (polyethylene naphthalate) having a weight average molecular weight of 45,000 and an amphiphilic polymer represented by the following structural formula having a weight average molecular weight of 50,000 were mixed at a mass ratio of 95: 5. A color filter of Example 3 was prepared in the same manner as in Example 1 except that a black colorant was added to 0.5 mL of the methylene chloride solution (0.2% by mass as the polymer concentration) to prepare a coating solution. did.

Example 4
In Example 1, a black colorant was added to 0.5 mL of a methylene chloride solution (0.2% by mass as a polymer concentration) in which only PEN (polyethylene naphthalate) having a weight average molecular weight of 45,000 was dissolved. A color filter of Example 4 was produced in the same manner as Example 1 except that it was prepared.

(Example 5)
In Example 1, a black colorant was added to 0.5 mL of a methylene chloride solution (polymer concentration: 0.2% by mass) in which only an amphiphilic polymer represented by the following structural formula was dissolved to prepare a coating solution. A color filter of Example 5 was produced in the same manner as Example 1 except for the above.

(Comparative Example 1)
According to the method of Example 1 described in JP-A-9-43414, a color filter of Comparative Example 1 was produced.

<Evaluation>
Using the obtained color filters of Examples 1 to 5 and Comparative Example 1, the following evaluation was performed. The results are shown in Table 1.
(1) Evaluation of optical density The optical density of the obtained color filter was measured using a Macbeth density system (trade name: TD-904, manufactured by Macbeth Co., Ltd. At this time, each density of B, G, R was 2 A value of .0 or more was evaluated as .largecircle., A value of 1.5 to 2.0 was evaluated as .DELTA.

(2) Evaluation of durability The density reduction rate after leaving the obtained color filter under a fluorescent lamp (12,000 Lux) for 20,000 hours was measured. At this time, when the concentration reduction rate was less than 10% compared to before leaving, the case of ◯, the case of 30 to 10% as Δ, and the case of over 30% as x.

From the results of Table 1, the color filters of Examples 1 to 5 having the red colorant, the green colorant, and the blue colorant in the pores of the honeycomb structure are compared with the color filter of Comparative Example 1. Thus, it was found that the optical density and durability were excellent. In particular, it was found that the color filters of Examples 1 and 2 in which the composition ratio of the hydrophobic polymer to the amphiphilic polymer is in the range of 90:10 to 80:20 are extremely excellent in optical density and durability.

The color filter of the present invention does not require a polymerizable compound such as a monomer or a polymerization initiator in the color layer, that is, the pores. When used, it has high definition and good durability, and can be suitably used.
In addition, from the same viewpoint, it is durable and suitable for use in electric decorations such as displays and CCD cameras.
Since the color filter manufacturing method of the present invention does not require resist treatment, it is not necessary to provide a partition wall layer, and it is possible to manufacture a color filter that does not cause a decrease in color or turbidity. It is suitably used for producing the color filter of the present invention.

FIG. 1 is a schematic diagram showing an example of the color filter of the present invention. FIG. 2 is a process diagram for explaining an example of a method for producing a color filter according to the present invention. FIG. 3 is a schematic view of a film production facility used in an example of a method for producing a color filter according to the present invention. FIG. 4A is a schematic diagram showing an example of a method for forming a color filter according to the present invention and showing a state in which a polymer film is formed on a casting belt. FIG. 4B is a schematic diagram illustrating an example of a method for forming a color filter according to the present invention, in which droplets are condensed and grow. FIG. 4C is a schematic diagram showing an example of a method for forming a color filter of the present invention, and shows a state in which an organic solvent volatilizes from a polymer film by drying. FIG. 4D is a schematic diagram illustrating an example of a method for forming a color filter according to the present invention, in which moisture is volatilized from a droplet of a polymer film by drying. FIG. 5 is a cross-sectional view showing an example of a color filter according to the present invention. FIG. 6 is a schematic view of a film production facility showing another example used in the method for producing a color filter according to the present invention. FIG. 7 is a schematic view of a film production facility showing still another example used in the method for producing a color filter according to the present invention. FIG. 8 is a schematic view of a film production facility showing still another example used in the method for producing a color filter according to the present invention. FIG. 9 is a schematic view of a film production facility showing still another example used in the method for producing a color filter according to the present invention. FIG. 10 is a schematic view of a film production facility showing still another example used in the method for producing a color filter according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Cast process 11 Condensation drying process 12 Honeycomb structure film 13 Filling process 14 Color filter

Claims (6)

  The support has a fine pore structure, and at least one pore in the fine pore structure has any one of a red colorant, a green colorant, and a blue colorant. Color filter.   The color filter according to claim 1, wherein the fine pore structure is a honeycomb-like porous structure produced by self-organization.   The color filter according to claim 1, wherein the fine pore structure material is at least one selected from a hydrophobic polymer and an amphiphilic polymer.   The color filter according to any one of claims 1 to 3, wherein the fine pore structure material contains a black colorant. A coating liquid containing an organic solvent and a polymer compound is applied onto a support, droplets are formed in the obtained film, and the organic solvent and the droplets are evaporated to have pores in the film. A fine pore structure production process for producing a fine pore structure;
A method for producing a color filter, comprising: containing a red colorant, a green colorant, and a blue colorant in the pores of the obtained fine pore structure. The manufacturing method of the color filter of Claim 5 in which a coating liquid contains a black coloring agent.