JP2009093153A - Colored curable composition, coloring pattern, color filter manufacturing method, color filter, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored curable composition improving the planar shape resulting from application and having less defects, and to provide a color filter of superior application properties, and to provide a liquid crystal display. <P>SOLUTION: The colored curable composition contains (a) a coloring material, (b) a solvent, (c) at least one kind selected from among a group comprising a polymerizable monomer and binder resin, (d) a photopolymerization initiator, and (f) at least one kind selected from among polymers containing a fluoroaliphatic group represented by a general formula (1). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a colored curable composition, a colored pattern, a method for producing a color filter, a color filter, and a liquid crystal display device.

  A color filter constituting a liquid crystal display (LCD), a color image pickup tube element (CCD), etc. is composed of a solvent dispersion composition of a colorant such as an organic pigment and an inorganic pigment, a binder resin and / or a monomer, and a photopolymerization initiator. And a curable composition containing other components, which are produced by a photolithographic method including a step of coating and drying on a transparent substrate to form a coating film having a thickness of about 1 to 3 μm. .

As a coating method on the transparent substrate, there are a spin coating method, a die coating method, and the like, which are appropriately used according to the characteristics.
The spin coating method is widely used for forming a thin film on a relatively small-sized substrate. While rotating the transparent substrate at a constant rotational speed, the coating solution is dropped onto the central portion of the transparent substrate and centrifugal force is applied. Is a coating method in which a coating film having a desired film thickness is formed on the surface of the transparent substrate by extending the coating solution thinly and controlling the number of revolutions and the rotation time of the transparent substrate suitable for the coating solution. However, due to the principle of extending the coating film thinly by utilizing the centrifugal force due to rotation, there is a drawback that the coating film thickness at the rotation center portion and the peripheral portion of the transparent substrate becomes too thick compared to the intermediate portion.

  The die coating method is a method suitable for forming a thin film on a large-sized substrate, and a coating liquid having a desired film thickness is formed on a transparent substrate while discharging a coating liquid from the slit and moving the slit relative to the substrate. It is the coating method formed on the surface. However, due to the mechanism, stripe-like unevenness (straight unevenness) is likely to occur in a direction perpendicular to the direction of movement of the slit, and the outer peripheral portion of the coating film rises and the film thickness becomes thicker than the central portion of the substrate.

  Further, there is a problem that pinholes (white spots) occur if the drying property and surface tension of the coating solution are not appropriate regardless of the coating method.

Various attempts have been made to solve the problem of non-uniformity of the coating film in the spin coating method and the die coating method. For example, Patent Document 1 discloses a technique for solving the problem by adjusting the contact angle of the composition, and a fluorine-based surfactant is preferably used. Patent Document 2 discloses a technique for solving the problem by using a composition having polysiloxane as an antistatic agent.
JP 2007-10992 A JP 2007-61886 A

  An object of the present invention is to provide a colored curable composition that improves the surface state of a coating film resulting from coating and has few defects. Moreover, the other object of this invention is to provide the favorable coloring pattern which uses the colored curable composition of this invention, and the method of forming this. Furthermore, the other object of this invention is to provide the color filter provided with the said favorable coloring pattern, the manufacturing method of a color filter, and a liquid crystal display device provided with this color filter.

Means for solving the above-mentioned problems are as follows.
<1> (a) Colorant, (b) Solvent, (c) At least one selected from the group consisting of a polymerizable monomer and a binder resin, (d) a photopolymerization initiator, and (f) the following general formula ( A colored curable composition containing at least one selected from the fluoroaliphatic group-containing polymer represented by 1) (hereinafter sometimes referred to as a specific fluoroaliphatic group-containing polymer).

In the general formula (1), i and j each represent an integer of 1 or more, meaning that each repeating unit includes i and j types respectively; M is derived from an ethylenically unsaturated monomer, and k ( k is an integer of 1 or more) a repeating unit included; a, b, and c represent a copolymerization ratio. When [Σai], [Σbj], and [Σck] are mass percentages in the fluoroaliphatic group-containing polymer of the first term component, the second term component, and the third term component of the general formula (1), respectively. , [Σai] is in the range of 1 to 98 mass%, [Σbj] is in the range of 1 to 98 mass%, and [Σck] is in the range of 1 to 98 mass%. R ¹¹ and R ¹² each represent a hydrogen atom or a methyl group; X ¹ and X ² each represent an oxygen atom, a sulfur atom or —N (R ¹³ ) —, and R ¹³ represents a hydrogen atom or a carbon number of 1 to 4 represents an alkyl group; m1 and m2 each represent an integer of 1 to 6, and n1 represents an integer of 0 to 3.

<2> The polymer according to <1>, wherein [Σai] / ([Σai] + [Σbj]) in the general formula (1) is a fluoroaliphatic group-containing polymer in the range of 0.2 to 0.8. Colored curable composition.
<3> In the general formula (1), ([Σai] + [Σbj]) is a fluoroaliphatic group-containing polymer in the range of 20 to 50% by mass of the (f) fluoroaliphatic group-containing polymer <1 >, Or the colored curable composition as described in <2>.

<4> The colored curable composition according to any one of <1> to <3>, which is a fluoroaliphatic group-containing polymer in which n1 is 0 in the general formula (1).
<5> Any one of <1> to <4>, wherein the content of the fluoroaliphatic group-containing polymer is in the range of 0.01 to 20% by mass with respect to the solid content in the colored curable composition. The colored curable composition described in 1.

<6> The product C × F of C mass% of the fluoroaliphatic group-containing polymer with respect to the solid content of the colored curable composition and fluorine atom content F mass% in the fluoroaliphatic group-containing polymer is 0. The colored curable composition according to any one of <1> to <5>, which is in a range of 0.05 to 0.12.
<7> The colored curable composition according to any one of <1> to <6>, wherein the color material (a) includes a green pigment.

<8> A colored pattern formed from the colored curable composition according to any one of <1> to <7>.
<9> A step of applying the colored curable composition according to any one of <1> to <7> onto a substrate by a spin coating method or a slit and spin coating method, and a step of forming a colored pattern. A manufacturing method of a color filter including the same.
<10> A color filter manufactured by the manufacturing method according to <9>.
<11> A liquid crystal display device using the color filter according to <10>.

  According to the present invention, it is possible to improve the surface state of a coating film resulting from coating and provide a colored curable composition with few defects. Moreover, according to this invention, the favorable coloring pattern which uses the colored curable composition of this invention and the method of forming this can be provided. Furthermore, according to the present invention, it is possible to provide a color filter having the above-described favorable coloring pattern, a method for manufacturing the color filter, and a liquid crystal display device including the color filter.

Hereinafter, the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In this specification, an acrylic compound and a methacrylic compound may be collectively referred to as a (meth) acrylic compound.
[Colored curable composition]
The colored curable composition of the present invention comprises (a) a color material, (b) a solvent, (c) a polymerizable monomer, and at least one selected from the group consisting of a binder resin, (d) a photopolymerization initiator, and (F) Contains at least one specific fluoroaliphatic group-containing polymer.

<Fluoroaliphatic group-containing polymer>
The specific fluoroaliphatic group-containing polymer used in the present invention is a compound represented by the following general formula (1).

In the general formula (1), i and j each represent an integer of 1 or more, meaning that each repeating unit includes i and j types respectively; M is derived from an ethylenically unsaturated monomer, and k ( k is an integer of 1 or more) a repeating unit included; a, b, and c represent a copolymerization ratio. When [Σai], [Σbj], and [Σck] are mass percentages in the fluoroaliphatic group-containing polymer of the first term component, the second term component, and the third term component of the general formula (1), respectively. , [Σai] is in the range of 1 to 98 mass%, [Σbj] is in the range of 1 to 98 mass%, and [Σck] is in the range of 1 to 98 mass%. R ¹¹ and R ¹² each represent a hydrogen atom or a methyl group; X ¹ and X ² each represent an oxygen atom, a sulfur atom or —N (R ¹³ ) —, and R ¹³ represents a hydrogen atom or a carbon number of 1 to 4 represents an alkyl group; m1 and m2 each represent an integer of 1 to 6, and n1 represents an integer of 0 to 3.

The general formula (1) includes the following repeating units A and B. Following repeating units A, and each repeating unit B, terminal _- (CF 2 _{CF 2) 3} F and is fluoro aliphatic group-containing monomer A, and terminal _- (CF 2 _{CF 2)} fluoroaliphatic is ₂ F It is a repeating unit derived from the group B-containing monomer B.

In the repeating units A and B, X ¹ and X ² are each independently an oxygen atom, a sulfur atom, —NH—, —N (CH ₃ ) —, —N (CH ₂ CH ₃ ) —, —N (CH ₂ CH ₂ CH ₃ ) — and —N (CH ₂ CH ₂ CH ₂ CH ₃ ) —, and among them, an oxygen atom is preferable. That is, the repeating units A and B are each preferably a repeating unit derived from a (meth) acrylic monomer.
m1 and m2 are each independently preferably an integer of 1 to 4, and more preferably an integer of 1 to 2.
n1 is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 0.

  Examples of the fluoroaliphatic group-containing monomer for deriving the repeating unit A are listed below, but are not limited thereto. Especially, exemplary compound A1-1-6 and A2-1-6 which are (meth) acrylic-type monomers are preferable. In addition, although the following exemplary compound lists the compound of n1 = 0 in General formula (1), Of course, the compound whose n1 is the range of 1-3 WHEREIN: The fluoro fat which derives the said repeating unit A It is contained in the example of a group containing monomer.

  Examples of the fluoroaliphatic group-containing monomer for deriving the repeating unit B are listed below, but are not limited thereto. Especially, exemplary compound B1-1-6 and B2-1-6 which are (meth) acrylic-type monomers are preferable.

  The aforementioned fluoroaliphatic group-containing monomers A and B can be produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). Regarding the production method of these fluoroaliphatic compounds, for example, “Synthesis and Function of Fluorine Compounds” (Supervision: Nobuo Ishikawa, published by CMC Co., Ltd., 1987), “Chemistry of Organic Fluorines Compounds”. II "(Monograph 187, Ed by Milos Hudricky and Attila E. Pavlath, American Chemical Society 1995). The telomerization method is a method of synthesizing a telomer by radical polymerization of a fluorine-containing vinyl compound such as tetrafluoroethylene using an alkyl halide having a large chain transfer constant such as iodide as a telogen (example in Scheme-1). showed that).

  The obtained terminal iodinated telomer is usually subjected to appropriate terminal chemical modification such as [Scheme 2], and led to a fluoroaliphatic compound.

  In the general formula (1), M is a repeating unit derived from an ethylenically unsaturated monomer. M is not particularly limited, but is preferably a repeating unit having a polar group having hydrogen bonding properties in the side chain. M is preferably a repeating unit represented by the following general formula (2).

In the general formula (2), R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group, a halogen atom, or a group represented by -LQ. L represents a divalent linking group, and Q represents a polar group having hydrogen bonding properties.

L is preferably an arbitrary group selected from the following linking group group, or a divalent linking group formed by combining two or more thereof.
(Linked group group)
Single bond, —O—, —CO—, —NR ⁴ —, —S—, —SO ₂ —, —P (═O) (OR ⁵ ) —, alkylene group, arylene group (R ⁴ is hydrogen atom, alkyl A group, an aryl group, or an aralkyl group, and R ⁵ represents an alkyl group, an aryl group, or an aralkyl group.)

More specifically, in general formula (2), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.) ) Or a group represented by -LQ described later, preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a chlorine atom, or a group represented by -LQ, more preferably hydrogen. An atom and an alkyl group having 1 to 4 carbon atoms are preferable, and a hydrogen atom and an alkyl group having 1 to 2 carbon atoms are particularly preferable. Specific examples of the alkyl group that R ¹ , R ² and R ³ can take include a methyl group, an ethyl group, an n-propyl group, an n-butyl group and a sec-butyl group. The alkyl group may have one or more substituents. Examples of the substituent include a halogen atom, aryl group, heterocyclic group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxyl group, acyloxy group, amino group, alkoxycarbonyl group, acylamino group, oxycarbonyl Group, carbamoyl group, sulfonyl group, sulfamoyl group, sulfonamido group, sulfolyl group, carboxyl group and the like.

  The carbon number of the alkyl group does not include the carbon atom of the substituent. The same applies to the carbon number of other groups.

L is a single bond, —O—, —CO—, —NR ⁴ —, —S—, —SO ₂ —, —PO (OR ⁵ ) —, an alkylene group, an arylene group, or a combination thereof. Represents a valent linking group. Here, R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. R ⁵ represents an alkyl group, an aryl group, or an aralkyl group.
L preferably includes a single bond, —O—, —CO—, —NR ⁴ —, —S—, —SO ₂ —, an alkylene group, or an arylene group, and —CO—, —O—, —NR ⁴ - it is particularly preferred that contain an alkylene group or an arylene group. Further, it preferably contains an alkyleneoxy group containing both —O— and an alkylene group, and preferably contains a polyalkyleneoxy group containing a repeating alkyleneoxy group.
When L contains an alkylene group, the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Specific examples of particularly preferable alkylene groups include a methylene group, an ethylene group, a trimethylene group, a tetrabutylene group, and a hexamethylene group. Moreover, the alkylene group (meaning also including the alkylene group contained in an alkyleneoxy group) may have a branched structure, and it is preferable that carbon number of the alkylene chain of a branched part is 1-3.

When L contains an arylene group, the carbon number of the arylene group is preferably 6 to 24, more preferably 6 to 18, and particularly preferably 6 to 12. Specific examples of particularly preferred arylene groups include phenylene groups and naphthalene groups.
When L contains a divalent linking group (that is, an aralkylene group) obtained by combining an alkylene group and an arylene group, the carbon number of the aralkylene group is preferably 7 to 34, more preferably 7 to 26, and particularly preferably. 7-16. Specific examples of particularly preferred aralkylene groups include a phenylenemethylene group, a phenyleneethylene group, and a methylenephenylene group.
The group listed as L may have an appropriate substituent. Examples of such a substituent include the same substituents as those described above as the substituents for R ^{1 to} R ³ .
Although the specific structure of L is illustrated below, this invention is not limited to these specific examples.

However, in L-28, R ^{51 to} R ⁵⁸ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and n is 1 to 12 (preferably 2 to 10). ). One of R ⁵³ and R ⁵⁴ , R ⁵⁵ and R ⁵⁶ , and R ⁵⁷ and R ⁵⁸ is preferably a hydrogen atom and the other is an alkyl group.

Q is not particularly limited as long as it is a polar group having hydrogen bonding properties. Preferably, hydroxyl group, carboxyl group, salt of carboxyl group (for example, lithium salt, sodium salt, potassium salt, ammonium salt (for example, ammonium, tetramethylammonium, trimethyl-2-hydroxyethylammonium, tetrabutylammonium, trimethylbenzylammonium, dimethylphenyl) Ammonium, etc.), pyridinium salts, etc.), amides of carboxylic acids (N unsubstituted or N-mono lower alkyl substituted, such as —CONH ₂ , —CONHCH ₃ etc.) sulfo groups, sulfo group salts (cations forming salts) examples of are the same as those described in the above carboxyl group), a sulfonamido group (N unsubstituted, or N- mono-lower-alkyl _{substituents,} -SO ₂ NH _2, such as -SO 2 NHCH _3), phospho group, phospho group Salt of the salt Examples of thione are the same as those described in the above carboxyl group), phosphonamides (N unsubstituted, or N- mono-lower-alkyl substituents, for example, _{-OP (= O) (NH 2} ) 2, -OP (= O) (NHCH ₃ ) ₂ ), a ureido group (—NHCONH ₂ ), an amino group (—NH ₂ , —NHCH ₃ ) which is unsubstituted or monosubstituted at the N-position (wherein the lower alkyl group is a methyl group or Represents an ethyl group).
A hydroxyl group, a carboxyl group, a sulfo group and a phospho group are more preferred, a hydroxyl group or a carboxyl group is more preferred, and a hydroxyl group is particularly preferred.

The repeating unit represented by the general formula (2) is preferably a repeating unit derived from a (meth) acrylic monomer.
Specific examples of the ethylenically unsaturated monomer for deriving the repeating unit M are shown below, but are not limited thereto.

The (f) fluoroaliphatic group-containing polymer represented by the general formula (1) includes at least one repeating unit A, repeating unit B, and M. That is, in the above general formula (1), i, j, and k represent the number of types of each repeating unit, and are each an integer of 1 or 2. The fluoroaliphatic group-containing polymer represented by the general formula (1) may contain two or more kinds of each repeating unit, and also contains repeating units other than the repeating unit A, the repeating unit B, and M. You may go out.
For example, the fluoroaliphatic group-containing polymer may contain one type of repeating unit derived from a monomer selected from the following monomer group, or may contain two or more types.

Monomer group (1) Alkenes ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-dodecene, 1-octadecene, 1-eicosene, hexafluoropropene, vinylidene fluoride, chlorotrifluoroethylene, 3, 3, 3-trifluoropropylene, tetrafluoroethylene, vinyl chloride, vinylidene chloride, etc .;
(2) Dienes 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2-n-propyl-1,3-butadiene, 2,3-dimethyl-1,3 -Butadiene, 2-methyl-1,3-pentadiene, 1-phenyl-1,3-butadiene, 1-α-naphthyl-1,3-butadiene, 1-β-naphthyl-1,3-butadiene, 2-chloro -1,3-butadiene, 1-bromo-1,3-butadiene, 1-chlorobutadiene, 2-fluoro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1,1,2- Trichloro-1,3-butadiene and 2-cyano-1,3-butadiene, 1,4-divinylcyclohexane and the like;

(3) Derivatives of α, β-unsaturated carboxylic acid (3a) Alkyl acrylates Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate , Amyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, tert-octyl acrylate, dodecyl acrylate, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, 2-cyanoethyl acrylate, 2-acetoxyethyl acrylate, methoxybenzyl Chryrate, 2-chlorocyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, 2-methoxyethyl acrylate, ω-methoxypolyethylene glycol acrylate (number of added polyoxyethylene: n = 2 to 100), 3-methoxy Butyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, glycidyl acrylate Such);

(3b) Alkyl methacrylates Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2 -Ethylhexyl methacrylate, n-octyl methacrylate, stearyl methacrylate, benzyl methacrylate, phenyl methacrylate, allyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, ω Methoxypolyethylene glycol methacrylate (number of added polyoxyethylene: n = 2 to 100), 2-acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate Glycidyl methacrylate, 3-trimethoxysilylpropyl methacrylate, allyl methacrylate, 2-isocyanatoethyl methacrylate, etc .;

(3c) Diesters of unsaturated polycarboxylic acids Dimethyl maleate, dibutyl maleate, dimethyl itaconate, dibutyl taconate, dibutyl crotonate, dihexyl crotonate, diethyl fumarate, dimethyl fumarate, etc .;
(3d) Amides of α, β-unsaturated carboxylic acids N, N-dimethylacrylamide, N, N-diethylacrylamide, Nn-propylacrylamide, N-tertbutylacrylamide, N-tertoctylmethacrylamide, N- Cyclohexylacrylamide, N-phenylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, N-benzylacrylamide, N-acryloylmorpholine, diacetone acrylamide, N-methylmaleimide and the like;

(4) Unsaturated nitriles Acrylonitrile, methacrylonitrile, etc .;
(5) Styrene and its derivatives Styrene, vinyl toluene, ethyl styrene, p-tert butyl styrene, methyl p-vinyl benzoate, α-methyl styrene, p-chloromethyl styrene, vinyl naphthalene, p-methoxy styrene, p-hydroxy Methyl styrene, p-acetoxy styrene, etc .;
(6) Vinyl esters Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl benzoate, vinyl salicylate, vinyl chloroacetate, vinyl methoxyacetate, vinyl vinyl acetate, etc .;

(7) Vinyl ethers Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl Vinyl ether, n-eicosyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, fluorobutyl vinyl ether, fluorobutoxyethyl vinyl ether, etc .; and (8) other polymerizable monomers N-vinyl pyrrolidone, methyl vinyl ketone, phenyl vinyl ketone, Methoxyethyl vinyl ketone, 2-vinyl oxazoline, 2-isopropenyl oxazoline .

  In the general formula (1), a, b and c represent the copolymerization ratio of the monomer for deriving each repeating unit. When [Σai], [Σbj], and [Σck] are mass percentages in the fluoroaliphatic group-containing polymer of the first term component, the second term component, and the third term component of the general formula (1), respectively. , [Σai] represents a numerical value in the range of 1 to 98 mass%, [Σbj] represents a numerical value in the range of 1 to 98 mass%, and [Σck] represents a numerical value in the range of 1 to 98 mass%. [Σai] is preferably in the range of 5 to 40% by mass, [Σbj] is preferably in the range of 5 to 40% by mass, and [Σck] is preferably in the range of 20 to 90% by mass. [Σai] is more preferably in the range of 10 to 35 mass%, [Σbj] is more preferably in the range of 10 to 35 mass%, and Σck is more preferably in the range of 30 to 80 mass%. The fluoroaliphatic group-containing polymer represented by the general formula (1) may contain a repeating unit other than the repeating units A, B and M, that is, [Σai] + [Σbj] + [Σck] <100% by mass may be included, but it is preferable not to include a repeating unit other than the repeating units A, B and M, that is, [Σai] + [Σbj] + [Σck] = 100% by mass. Is preferred.

Further, it is preferable that the ratio of the repeating units A and B derived from the fluoroaliphatic group-containing monomer contained in the fluoroaliphatic group-containing polymer is in a predetermined range because the surface shape can be improved. Specifically, the mass percentage [Σai] of the i-type repeating unit A that is the first term component of the general formula (1) in the fluoroaliphatic group-containing polymer, and the second term component of the general formula (1) It is preferable that the sum ([Σai] + [Σbj]) of the mass percentage [Σbj] of the j-type repeating unit B which is is in the range of 20 to 50% by mass, The range is more preferably 25 to 45% by mass, and further preferably 25 to 40% by mass. When ([Σai] + [Σbj]) is in the above range, the surface shape of the coating film can be further improved.
From the same viewpoint, the ratio of [Σai] to ([Σai] + [Σbj]) ([Σai] / ([Σai] + [Σbj])) is in the range of 0.2 to 0.8. Is more preferable, and the range of 0.3 to 0.6 is more preferable, and the range of 0.35 to 0.55 is more preferable. It is preferable that ([Σai] / ([Σai] + [Σbj])) is in the above-mentioned range since the surface shape of the coating film can be improved.

  Specific examples of the fluoroaliphatic group-containing polymer that can be used in the present invention are summarized in Table 1 below, but are not limited to the following specific examples. In Table 1 below, repeating units A, B, and M are monomeric compound Nos. Derived from the respective repeating units. It is specified by.

  The colored curable composition of this invention should just contain at least 1 type of the said fluoro aliphatic group containing polymer, and of course may contain 2 or more types. In the composition, the addition amount of the fluoroaliphatic group-containing polymer is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass with respect to the solid content of the colored curable composition. 1 to 5% by mass is more preferable.

  Moreover, the preferable range of C mass% of the fluoroaliphatic group-containing polymer with respect to the solid content of the composition varies depending on the fluorine atom content F% in the fluoroaliphatic group-containing polymer. In order to further improve the coated surface state, the product of C mass% of the fluoroaliphatic group-containing polymer with respect to the solid content of the composition and fluorine content F% in the fluoroaliphatic group-containing polymer is It is preferably from 05 to 0.12, more preferably from 0.06 to 0.09, and even more preferably from 0.06 to 0.08. When C × F is within the above range, the surface shape of the coating film can be further improved.

Second fluoroaliphatic group-containing polymer The colored curable composition of the present invention includes a fluorocarbon outside the range of the fluoroaliphatic group-containing polymer (hereinafter referred to as “first fluoroaliphatic group-containing polymer”). One or more aliphatic group-containing polymers (hereinafter sometimes referred to as “second fluoroaliphatic group-containing polymer”) may be added. The second fluoroaliphatic group-containing polymer includes at least one repeating unit derived from a monomer having a fluoroaliphatic group, a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a It preferably contains a salt, or at least one repeating unit derived from a monomer having an acidic group such as phosphonoxy {—OP (═O) (OH) ₂ } or a salt thereof.

  Preferable examples of the second fluoroaliphatic group-containing polymer include the following polymer A (repeating unit derived from a fluoroaliphatic group-containing monomer described in International Publication No. 2006/001504, and the following general formula (1a And a repeating unit represented by formula (1)).

In the formula, each of R ^1a , R ^2a and R ^3a represents a hydrogen atom or a substituent; La is ^a divalent linking group selected from the following linking group group or two or more selected from the following linking group group Represents a divalent linking group formed by combining.
(Linking group group) Single bond, —O—, —CO—, —NR ^4a — (R ^4a represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group), —S—, —SO ₂ —, — P (═O) (OR ^5a ) — (R ^5a represents an alkyl group, an aryl group, or an aralkyl group), an alkylene group, and an arylene group;
Q ^a represents a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, or phosphonoxy {—OP (═O) (OH) ₂ } or a salt thereof.
^{Wherein, R 1a, R 2a, R} 3a, and ^{L a} are each, in the general formula ^(2), respectively as the preferred ranges of R ^1, R 2, ^{R 3} and L synonymous.

  The repeating unit derived from the fluoroaliphatic group-containing monomer of the second fluoroaliphatic group-containing polymer may be any one of the repeating units A and B. A repeating unit derived from a fluoroaliphatic group-containing monomer represented by the following formula (3) is also preferable.

一般式（３）中、Ｒ^５は水素原子またはメチル基を表し、Ｘ^５は酸素原子、イオウ原子または−Ｎ（Ｒ^１５）−を表し、Ｒ^１５は水素原子または炭素数１〜４のアルキル基を表す。Ｚは水素原子又はフッ素原子を表し、ｍ５は１〜６の整数を表し、ｎ_５は２〜４の整数を表す。

In general formula (3), R ⁵ represents a hydrogen atom or a methyl group, X ⁵ represents an oxygen atom, a sulfur atom or —N (R ¹⁵ ) —, and R ¹⁵ represents a hydrogen atom or an alkyl having 1 to 4 carbon atoms. Represents a group. Z represents a hydrogen atom or a fluorine atom, m5 represents an integer of 1 to 6, and n ₅ represents an integer of 2 to 4.

  The second fluoroaliphatic group-containing polymer may contain a repeating unit having a hydrogen bonding group represented by the general formula (2), or the monomer groups (1) to (7). It may contain a repeating unit derived from at least one monomer selected from: Hereinafter, exemplary compounds of the polymer that can be used as the second fluoroaliphatic-containing polymer are listed in the colored curable composition of the present invention, but the present invention is not limited to the following specific examples.

  In the embodiment in which the second fluoroaliphatic group-containing polymer is added, the addition amount (% by mass) of the second fluoroaliphatic group-containing polymer is the addition amount (% by mass) of the first fluoroaliphatic group-containing polymer. It is preferable that:

The weight average molecular weight of the first fluoroaliphatic group-containing polymer (and optionally added second fluoroaliphatic group-containing polymer) is preferably 1,000,000 or less. More preferred is a weight average molecular weight of 500,000 or less, and particularly preferred is a weight average molecular weight of 100,000 or less.
The weight average molecular weight can be measured as a value in terms of polyethylene oxide (PEO) using gel permeation chromatography (GPC).

Moreover, a weight average molecular weight can be calculated | required also as a value of polystyrene (PST) conversion using a gel permeation chromatography (GPC). The physical property values of the fluoroaliphatic group-containing polymer described in the present invention can be determined using the same method unless otherwise specified.
(Weight average molecular weight and number average molecular weight)
The measurement was performed in terms of polystyrene by GPC (gel permeation chromatography) measurement under the following conditions.
Column used: TSKgel superHZM-H, TSKgel superHZ4000, TSKgel superHZ2000 manufactured by Tosoh Eluent: THF
Flow rate: 0.35 ml / min
Temperature: 40 ° C
Detection condition: RI
System: High-speed GPC equipment set (Tosoh HLC-8220)

  There are no particular restrictions on the method for producing the first fluoroaliphatic group-containing polymer (and the second fluoroaliphatic group-containing polymer that is optionally added). For example, it can be produced by a polymerization method such as cationic polymerization using a vinyl group, radical polymerization, or anionic polymerization, and among these, the radical polymerization method is particularly preferred because it can be used for general purposes.

  As the polymerization initiator for radical polymerization, known compounds such as radical thermal polymerization initiators and radical photopolymerization initiators can be used, and it is particularly preferable to use radical thermal polymerization initiators. Here, the radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include diacyl peroxide (acetyl peroxide, benzoyl peroxide, etc.), ketone peroxide (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), hydroperoxide (hydrogen peroxide, tert. -Butyl hydroxide, cumene hydroperoxide, etc.), dialkyl peroxide (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyesters (tert-butyl peroxyacetate, tert) -Butyl peroxypivalate, etc.), azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.), persulfates (ammonium persulfate, sodium persulfate) And potassium persulfate) and the like. Such radical thermal polymerization initiators can be used singly or in combination of two or more.

  The radical polymerization method is not particularly limited, and an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method, and the like can be adopted. The solution polymerization, which is a typical radical polymerization method, will be described more specifically. The outlines of other polymerization methods are the same, and details thereof are described, for example, in “Polymer Science Experimental Method” edited by Polymer Society (Tokyo Kagaku Dojin, 1981).

  An organic solvent is used for solution polymerization. These organic solvents can be arbitrarily selected as long as the objects and effects of the present invention are not impaired. These organic solvents are usually organic compounds having boiling points under atmospheric pressure in the range of 50 to 200 ° C., and organic compounds that uniformly dissolve each component are preferred. Examples of preferable organic solvents include alcohols such as isopropanol and butanol, ethers such as dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethyl acetate and acetic acid. Examples thereof include esters such as butyl, amyl acetate and γ-butyrolactone, and aromatic hydrocarbons such as benzene, toluene and xylene. These organic solvents can be used alone or in combination of two or more. Furthermore, a water-mixed organic solvent in which water is used in combination with the above organic solvent is also applicable from the viewpoint of the solubility of the monomer and the polymer to be produced.

  Also, the solution polymerization conditions are not particularly limited, but for example, it is preferable to heat within a temperature range of 50 to 200 ° C. for 10 minutes to 30 hours. Furthermore, in order not to deactivate the generated radicals, it is preferable to perform an inert gas purge not only during solution polymerization but also before the start of solution polymerization. Usually, nitrogen gas is suitably used as the inert gas.

In order to obtain the first fluoroaliphatic group-containing polymer (and optionally added second fluoroaliphatic group-containing polymer) in a preferable molecular weight range, a radical polymerization method using a chain transfer agent is particularly effective. is there.
As chain transfer agents, mercaptans (for example, octyl mercaptan, decyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, octadecyl mercaptan, thiophenol, p-nonylthiophenol, etc.), polyhalogenated alkyls (for example, carbon tetrachloride, chloroform, etc.) , 1,1,1-trichloroethane, 1,1,1-tribromooctane, etc.) and low-activity monomers (α-methylstyrene, α-methylstyrene dimer, etc.) can be used, preferably carbon These are mercaptans of 4-16. The amount of these chain transfer agents used is remarkably influenced by the activity of the chain transfer agent, the combination of the monomers, the polymerization conditions and the like, and must be precisely controlled. It is about 01 mol% to 50 mol%, preferably 0.05 mol% to 30 mol%, particularly preferably 0.08 mol% to 25 mol%. These chain transfer agents may be present in the system simultaneously with the target monomer whose degree of polymerization is to be controlled in the polymerization process, and the addition method is not particularly limited. It may be added after being dissolved in the monomer, or may be added separately from the monomer.

  The present invention also relates to a colored curable composition characterized in that the fluoroaliphatic group-containing polymer has a viscosity at 25 ° C. of 200 Pa · s to 10,000 Pa · s. When the viscosity at 25 ° C. of the fluoroaliphatic group-containing polymer is 200 Pa · s to 10,000 Pa · s, a good surface shape can be obtained. The viscosity of the fluoroaliphatic group-containing polymer is more preferably 250 to 5000 Pa · s, and further preferably 300 to 1000 Pa · s. In this specification, the “viscosity” of the fluoroaliphatic group-containing polymer is determined by using a VAR-100 rheometer manufactured by Rheology, a distance between gaps of 1.5 mm, a frequency of 1 Hz, a strain of 0.005, and a heating rate of 5 ° C./min. The value measured by the oscillation mode under the condition of nitrogen atmosphere.

In this embodiment, the fluoroaliphatic group-containing polymer is preferably selected from the fluoroaliphatic group-containing polymer represented by the general formula (1). In particular, in the general formula (1), a fluoroaliphatic group-containing polymer in which both R ¹¹ and R ¹² are methyl groups is preferable. In the colored curable composition of this embodiment, the content of the fluoroaliphatic group-containing polymer is 0.02 to the total mass of the colored curable composition (solid content when prepared as a coating liquid). The amount is preferably 0.50% by mass, more preferably 0.03 to 0.30% by mass, and more preferably 0.05 to 0.20% by mass from the viewpoint of further improving the surface shape of the coating film. Further preferred.

Colored curable composition Next, at least one selected from the group consisting of (a) a color material, (b) a solvent, (c) a polymerizable monomer, and a binder resin used in the colored curable composition of the present invention. (D) The photopolymerization initiator will be described.

(A) Coloring material The coloring material in the present invention may be a pigment or a dye. In the present invention, the colorant and the colorant are synonymous with the colorant.

-Pigment-
As the pigment that can be used in the pigment dispersion composition of the present invention, conventionally known various inorganic pigments or organic pigments can be used. Moreover, considering that it is preferable that the pigment has a high transmittance regardless of whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having a particle size as small as possible, and considering handling properties. Then, it is preferably a pigment having an average primary particle diameter of 0.01 to 0.3 μm, more preferably 0.01 to 0.15 μm. When the particle size is within the above range, the transmittance is high, the color characteristics are good, and it is effective for forming a color filter with high contrast.
The average primary particle diameter is obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.

  Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as the above, and complex oxides of the above metals.

Examples of the organic pigment include:
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73
C. I. Pigment Green 7, 10, 36, 37
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl substituent was changed to OH Stuff, 80
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42
C. I. Pigment Brown 25, 28
C. I. Pigment Black 1, 7 and the like.

Among these, the pigments that can be preferably used include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37;
C. I. Pigment Black 1, 7
-Finer pigments-

  In the present invention, if necessary, a fine and sized organic pigment can be used. The refinement of the pigment is a step of grinding it as a highly viscous liquid composition together with the pigment, the water-soluble organic solvent, and the water-soluble inorganic salts.

  Water-soluble organic solvents include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol A monomethyl ether acetate etc. can be mentioned. However, if it is adsorbed to the pigment by using a small amount and does not flow away into the wastewater, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane , Heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohesasan, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. Two or more kinds of solvents may be mixed and used as necessary.

  In the present invention, examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.

The amount of the water-soluble inorganic salt used is 1 to 50 times the mass of the pigment, and a larger amount has a grinding effect, but a more preferable amount is 1 to 10 times the mass in terms of productivity, and further moisture is 1% or less. It is preferable that
The amount of the water-soluble organic solvent used is in the range of 50% by mass to 300% by mass and preferably in the range of 100% by mass to 200% by mass with respect to the pigment. Although there is no particular limitation on the operating conditions of the wet pulverizing apparatus in the present invention, the operating conditions in the case where the apparatus is a kneader are as follows. 200 rpm is preferable, and a relatively large biaxial rotation ratio is preferable because the grinding effect is large. The operation time is preferably 1 to 8 hours in combination with the dry grinding time, and the internal temperature of the apparatus is preferably 50 to 150 ° C. Further, the water-soluble inorganic salt that is a pulverization medium preferably has a pulverization particle size of 5 to 50 μm, a sharp particle size distribution, and a spherical shape.

-Preparation of pigment-(Color matching)
These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment , A mixture with an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, or the like can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139 or C.I. I. Mixing with Pigment Red 177 is preferred. The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80 from the viewpoints of color purity and coloring power. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  Further, as the green pigment, one kind of halogenated phthalocyanine pigment can be used alone or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. . For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200 from the viewpoint of color purity and NTSC target hue. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

As the blue pigment, a single phthalocyanine pigment or a mixture of this and a dioxazine purple pigment can be used. As a particularly preferred example, C.I. I. Pigment blue 15: 6 and C.I. I. A mixture with pigment violet 23 can be mentioned.
The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.

Moreover, as a pigment suitable for black matrix use, carbon black, graphite, titanium black, iron oxide, titanium oxide alone or a mixture thereof can be used, and a combination of carbon black and titanium black is preferable.
The mass ratio of carbon black to titanium black is preferably in the range of 100: 0 to 100: 60. If it is 100: 61 or more, the dispersion stability may decrease.

-Dye-
In the present invention, when a dye is used as the colorant, a uniformly curable colored curable composition is obtained.
There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.
The chemical structure is pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

-Pigment concentration-
As content in the pigment dispersion composition of a pigment, 10-60 mass% is preferable with respect to the total solid (mass) of this composition, and 15-50 mass% is more preferable. When the pigment content is within the above range, the color density is sufficient and it is effective to ensure excellent color characteristics.

-Dispersant-
The pigment dispersion composition of the present invention contains at least one dispersant. By containing this dispersant, the dispersibility of the pigment can be improved.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many types of compounds can be used. For example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Nonionic surfactants such as octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic systems such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) Surfactant: EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals) Polymer dispersants such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, Various Solsperse dispersants such as 26000, 28000 (manufactured by Nippon Lubrizol Corp.); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co., Ltd.) and Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (by Big Chemie). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer.

  As content in the pigment dispersion composition of a dispersing agent, 1-100 mass% is preferable with respect to the mass of the above-mentioned pigment, and 3-70 mass% is more preferable.

-Pigment derivative-
A pigment derivative is added to the pigment dispersion composition of the present invention as necessary. The pigment is dispersed in the colored curable composition as fine particles by adsorbing the pigment derivative with a part having affinity with the dispersant or a polar group introduced onto the pigment surface and using this as the adsorption point of the dispersant. Therefore, the reaggregation can be prevented, and it is effective in constructing a color filter having high contrast and excellent transparency.

  Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included. Examples of the dye derivative include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the pigment dispersion composition of the pigment derivative based on this invention, 1-30 mass% is preferable with respect to the mass of a pigment, and 3-20 mass% is more preferable. When the content is within the above range, while maintaining the viscosity low, the dispersion can be performed well and the dispersion stability after the dispersion can be improved, and the color characteristics with high transmittance can be obtained. When producing a filter, it can be configured to have high contrast with good color characteristics.

-Method of dispersion-
The dispersion method is, for example, using a bead disperser using zirconia beads or the like (for example, a disperse mat manufactured by GETZMANN Co., Ltd.) that has been previously mixed with a pigment and a dispersant and previously dispersed with a homogenizer or the like. This can be done by fine dispersion. The dispersion time is preferably about 3 to 6 hours.

(B) Solvent The pigment dispersion composition and colored curable composition of the present invention can be generally prepared using a solvent together with the above components.
Solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, lactic acid 3 such as ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate -Oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropion Ethyl, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2- Methyl methyl propionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Ter, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons such as toluene, xylene and the like.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using it independently.

(C) Polymerizable monomer and binder resin The polymerizable monomer and binder resin in the present invention are described below. In the present invention, the polymerizable monomer and the photopolymerizable compound have the same meaning, and the binder resin and the alkali-soluble resin have the same meaning.

-Photopolymerizable compound-
As the photopolymerizable compound, a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure is preferable, and a tetrafunctional or higher functional acrylate compound is more preferable.

Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Monofunctional acrylates and methacrylates such as phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) Ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and the addition of ethylene oxide and propylene oxide followed by (meth) acrylate conversion, poly (pentaerythritol or dipentaerythritol poly ( (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 Polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-B-52-30490 and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid can be mentioned.
Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be used.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used.

Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are via ethylene glycol and propylene glycol residues are preferable. These oligomer types can also be used.
Also, urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, Urethane compounds having an ethylene oxide skeleton described in JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition having a very high photosensitive speed. Commercially available products include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
Further, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned.

The photopolymerizable compound can be used in combination of two or more, in addition to being used alone.
The content of the photopolymerizable compound in the colored curable composition is preferably 20 to 200 parts, more preferably 50 to 120 parts, relative to 100 parts of the total solid content of the composition. When the content of the photopolymerizable compound is within the above range, the curing reaction can be sufficiently performed.

-Alkali-soluble resin-
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

  For example, a known radical polymerization method can be applied to the production of the alkali-soluble resin. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As said linear organic high molecular polymer, the polymer which has carboxylic acid in a side chain is preferable. For example, it is described in JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-71048. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., as well as in the side chain Preferred examples include acidic cellulose derivatives having a carboxylic acid, polymers having a hydroxyl group, an acid anhydride added to the polymer, and a polymer having a (meth) acryloyl group in the side chain.

Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are preferable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. The polymer can be used by mixing in an arbitrary amount.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Etc.

  As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. Here, (meth) acrylic acid is a general term that combines acrylic acid and methacrylic acid, and (meth) acrylate is also a general term for acrylate and methacrylate.

Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. it can.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and CH _2. = CR ³¹ R ³² , CH ₂ = C (R ³¹ ) (COOR ³³ ) [wherein R ³¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³² is an aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon ring, and R ³³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. ], Etc. can be mentioned.

These other copolymerizable monomers can be used singly or in combination of two or more. Preferred other copolymerizable monomers are selected from CH ₂ ═CR ³¹ R ³² , CH ₂ ═C (R ³¹ ) (COOR ³³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. It is at least one, and particularly preferably CH ₂ = CR ³¹ R ³² and / or CH ₂ = C (R ³¹ ) (COOR ³³ ).

  As content in the colored curable composition of alkali-soluble resin, 1-15 mass% is preferable with respect to the total solid of this composition, More preferably, it is 2-12 mass%, Most preferably 3 to 10% by mass.

(D) Photopolymerization initiator Examples of the photopolymerization initiator include halomethyl oxadiazole described in JP-A-57-6096, JP-B-59-1281, JP-A-53-133428, and the like. Active halogen compounds such as halomethyl-s-triazine as described, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in US Pat. No. 4,318,791 and European Patent Application No. 88050, US patents Aromatic ketone compounds such as benzophenones described in No. 4199420, (thio) xanthones or acridine compounds described in French Patent Invention No. 2456741, and coumarins described in JP-A-10-62986 Or compounds such as lophine dimers, and compounds such as JP-A-8-015521 And the like, and the like.

  Examples of the photopolymerization initiator include acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, triazine, halomethyloxadiazole, acridine, coumarins, lophine dimers, biphenyl Imidazole type, oxime ester type and the like are preferable.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, Preferable examples include 4′-isopropyl-2-hydroxy-2-methyl-propiophenone.

  Preferable examples of the ketal photopolymerization initiator include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.

  Examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and 1-hydroxy-cyclohexyl. -Phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 and the like can be preferably exemplified.

  Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the triazine photopolymerization initiator include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl- s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (trichloromethyl) -6-biphenyl- s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl- 2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxystyryl-2,6-di (trichloromethyl) -s-to Azine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (Chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine and the like can be preferably exemplified.

  Examples of the halomethyloxadiazole-based photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3. , 4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3 A preferred example is 4-oxodiazole.

  Preferred examples of the acridine-based photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the coumarin-based photopolymerization initiator include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s Preferred examples include -triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the lophine dimer-based photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer. And 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer and the like can be preferably exemplified.

  Preferable examples of the biimidazole photopolymerization initiator include 2-mercaptobenzimidazole, 2,2′-benzothiazolyl disulfide and the like.

  In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl Examples thereof include carbonyl-diphenyl phosphonyl oxide and hexafluorophospho-trialkylphenyl phosphonium salt.

In this invention, it is not limited to the above photoinitiator, Other well-known things can also be used. For example, vicinal polykettle aldonyl compounds described in US Pat. No. 2,367,660, and α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, the triarylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, Benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516; C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Examples include Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and oxime ester compounds described in JP-A No. 2000-66385.
Moreover, these photoinitiators can also be used together.

  As content in the colored curable composition of a photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of this composition, More preferably, it is 0.5-5.0. % By mass. When the content of the photopolymerization initiator is within the above range, the polymerization reaction can proceed well to form a film with good strength.

-Other components-
In the colored curable composition of the present invention, if necessary, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, other fillers, a polymer compound other than the above alkali-soluble resin, an adhesion promoter, an oxidation agent Various additives such as an inhibitor, an ultraviolet absorber and an aggregation inhibitor can be contained.

-Thermal polymerization initiator-
It is also effective to contain a thermal polymerization initiator in the colored curable composition of the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

-Thermal polymerization component-
It is also effective to contain a thermal polymerization component in the colored curable composition of the present invention. If necessary, an epoxy compound can be added to increase the strength of the coating film. The epoxy compound is a compound having two or more epoxy rings in the molecule, such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound. For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103 and the like (manufactured by Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (manufactured by Daicel Chemical) and their similar The bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UCB) can also be used. As cresol novolak type, Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above manufactured by Tohto Kasei Co., Ltd.), Denacol EM-125, etc. (above manufactured by Nagase Kasei), Examples of cycloaliphatic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT- 401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100 (manufactured by Toto Kasei) and the like. 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid diester In addition, glycidyl esters such as Epototo YH-434 and YH-434L, which are amine-type epoxy resins, and glycidyl esters obtained by modifying dimer acid in the skeleton of bisphenol A-type epoxy resins can also be used.

-Thermal polymerization inhibitor-
In addition to the above, it is preferable to add a thermal polymerization inhibitor in addition to the above, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, etc. Useful.

-Colored curable composition and method for producing color filter using the same-
In the colored curable composition of the present invention, the pigment dispersion composition described above includes (c) at least one selected from the group consisting of a polymerizable monomer and a binder resin, (d) a photopolymerization initiator, and (f). A specific fluoroaliphatic group-containing polymer or the like (preferably together with a solvent) is added, and an additive such as a surfactant is mixed therewith as necessary, and then mixed and dispersed using various mixers and dispersers. It can prepare by going through a mixing and dispersing step.
The mixing and dispersing step preferably includes kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

An example of the manufacturing method of the colored curable composition of this invention is shown below.
A mixture of a pigment, a water-soluble organic solvent, and a water-soluble inorganic salt is mixed with a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single- or twin-screw extruder, etc. Is used to grind the pigment while applying a strong shearing force, and the mixture is put into water and made into a slurry with a stirrer or the like. Subsequently, this slurry is filtered and washed with water to remove the water-soluble organic solvent and the water-soluble inorganic salt, and then dried to obtain a refined pigment.

The beads are dispersed with a pigment and a dispersant and / or a pigment derivative and a solvent. Using a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc., fine dispersion with beads made of 0.01 to 1 mm particle size glass, zirconia, etc., pigment dispersion composition Get. It is also possible to omit the process of making the pigment fine.
For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.
Then, (c) a polymerizable monomer and a binder resin, (d) a photopolymerization initiator, (f) a specific fluoroaliphatic group-containing polymer, and the like are added to the pigment dispersion composition obtained as described above. The colored curable composition of the present invention is obtained.

The colored curable composition of the present invention is applied to a substrate directly or through another layer by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, etc., and a photocurable coating film The film is exposed through a predetermined mask pattern, and after the exposure, the uncured portion is developed and removed with a developer to form a pattern film composed of pixels of each color (three colors or four colors), and a color filter It can be.
In this case, ultraviolet rays such as g-line, h-line, i-line and j-line are particularly preferable as the radiation to be used. The color filter for the liquid crystal display device is preferably an exposure using mainly h-line and i-line in a proximity exposure machine and a mirror projection exposure machine.

  In order to further improve the surface state of the coating film, the surface tension ratio (10 ms / 1000 ms) between 10 ms and 1000 ms measured by the maximum bubble pressure method of the coating solution of the colored curable composition is: It is preferably 1.00 to 1.20, more preferably 1.00 to 1.15, and even more preferably 1.00 to 1.10. When the surface tension ratio is in the above range, the surface shape of the coating film can be further improved.

  The measurement of surface tension by the maximum bubble pressure method is described in detail in “Chemical Handbook 5th edition”, Chapter 8, Interfaces and Colloids, page 90, 8.2 Surface tension and wetting, “ASTM D3825-90”, etc. Therefore, the surface tension of the colored curable composition of the present invention can also be measured with reference to the method described in this publication. Further, in order to continuously measure the surface tension with time, a surface tension meter such as “MPT2” manufactured by LAUDA can be used.

  The color filter of the present invention is formed on a substrate such as glass using the colored curable composition of the present invention described above, and the colored curable composition of the present invention is directly or via other layers. Then, after forming a coating film on the substrate by, for example, slit coating, the coating film is dried, subjected to pattern exposure, and development processing using a developer can be sequentially performed. Thereby, the color filter used for a liquid crystal display device or a solid-state image sensor has few process difficulties, and can be manufactured with high quality and low cost.

Examples of the substrate include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these substrates, and solid-state imaging devices. Examples thereof include a photoelectric conversion element substrate such as a silicon substrate, and a plastic substrate. On these substrates, usually, a black matrix for isolating each pixel is formed, or a transparent resin layer is provided for promoting adhesion.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface. In addition, the color curable property of the present invention is also applied to a driving substrate (hereinafter referred to as “TFT type liquid crystal driving substrate”) on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is arranged. A color filter can be prepared by forming a patterned film made of the composition. The photomask used at that time is provided with a pattern for forming a through hole or a U-shaped depression in addition to a pattern for forming a pixel. Examples of the substrate in the TFT liquid crystal driving substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of a TFT liquid crystal driving substrate or a surface of the driving substrate can be used.

  A method for applying the colored curable composition of the present invention to a substrate is not particularly limited, but a method using a slit nozzle such as a slit-and-spin method or a spinless coating method (hereinafter referred to as a slit nozzle coating method). Is preferred. In the slit nozzle coating method, the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, when a fifth generation glass substrate (1100 mm × 1250 mm) is coated by the spinless coating method. The discharge amount of the colored curable composition from the slit nozzle is usually 500 to 2000 microliter / second, preferably 800 to 1500 microliter / second, and the coating speed is usually 50 to 300 mm / second. , Preferably it is 100-200 mm / sec. The solid content of the colored curable composition is usually 10 to 20%, preferably 13 to 18%. When forming a coating film with the colored curable composition of the present invention on a substrate, the thickness of the coating film (after pre-baking treatment) is generally 0.3 to 5.0 μm, preferably 0.5 to 4 0.0 μm, most preferably 0.8 to 3.0 μm.

Usually, a pre-bake treatment is performed after coating. If necessary, vacuum treatment can be performed before pre-baking. As the conditions for vacuum drying, the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr.
The pre-bake treatment is performed in a temperature range of 50 to 140 ° C., preferably about 70 to 110 ° C., using a hot plate, an oven, or the like, and can be performed under conditions of 10 to 300 seconds. High frequency treatment or the like may be used in combination. High frequency processing can be used alone.

  Since it is formed by coating on the surface, there is an interface with the surface and an air interface on the opposite side. The fluorine atom present in the fluoroaliphatic group-containing polymer contributes to the improvement of the planar shape, and is therefore preferably unevenly distributed at the air interface. On the other hand, the air interface is positioned from 0 nm to 0 nm. The presence of fluorine atoms to some extent in the depth direction up to 10 nm is also important for improving the surface shape. From this viewpoint, when the fluorine atom abundance ratio (ESCA: F / C) at the air interface is 100, the fluorine atom abundance ratio (ESCA: F / C) at a position of 10 nm from the air interface is 2 to 10. Is preferred.

In the development process, the uncured portion after the exposure is eluted in the developer, and only the cured portion remains. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
As the developer, any one can be used as long as it dissolves the coating film of the photocurable colored curable composition in the uncured portion while not dissolving the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

Examples of the organic solvent include the solvents described above that can be used when preparing a pigment dispersion composition or a colored curable composition.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentrations of alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene are 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass can be mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

  The development method may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. Before the developer is touched, the surface to be developed can be previously moistened with water or the like to prevent uneven development. In addition, development can be performed with the substrate inclined.

After the development processing, after a rinsing step for washing and removing excess developer, drying is performed, and then heat treatment (post-baking) is performed to complete the curing.
The rinsing process is usually performed with pure water. However, to save liquid, pure water is used in the final cleaning. At the beginning of cleaning, used pure water is used, the substrate is tilted and cleaned, and ultrasonic irradiation is performed. Can be used together.

After rinsing, draining and drying are performed, and then a heat treatment is usually performed at about 200 ° C to 250 ° C. In this heat treatment (post-bake), the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with a formula.
By sequentially repeating the above operation for each color in accordance with the desired number of hues, a color filter formed with a plurality of colored cured films can be produced.

The use of the pigment dispersion composition and the colored curable composition has been described mainly focusing on the use for a color filter, but it can also be applied to the formation of a black matrix that isolates each colored pixel constituting the color filter. .
The black matrix can be formed by exposing and developing a colored curable composition using a black pigment such as carbon black or titanium black as a pigment, and then post-baking as necessary to promote film curing. .

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. In the following, all parts and% are based on mass unless otherwise specified.

Of the following resins, the methods for determining the physical properties of benzyl methacrylate / methyl methacrylate and benzyl methacrylate / methacrylic acid are as follows.
(Weight average molecular weight and number average molecular weight)
The measurement was performed in terms of polystyrene by GPC (gel permeation chromatography) measurement under the following conditions.
Column used: TSKgel Multipore HXL-M (Porous polydisperse linear column) manufactured by Tosoh Eluent: THF
Flow rate: 1.0 ml / min
Temperature: 40 ° C
Detection condition: RI
System: High-speed GPC equipment set (Tosoh HLC-8220)

Example 1
Green pigment C.I. I. 200 parts of Pigment Green 36, 1600 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 8 hours. Next, the kneaded product is poured into 10 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 60 ° C. overnight. 190 parts of a green pigment were obtained.
The yellow pigment C.I. I. 200 parts of Pigment Yellow 138, 2000 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 8 hours. Next, the kneaded product is poured into 10 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 60 ° C. overnight. 190 parts of a yellow pigment were obtained.
With the following composition, the mixture was stirred for 3 hours using a homogenizer at a rotational speed of 3,000 rpm and mixed to prepare a mixed solution.

〔composition〕
Pigment Green 36 (average primary particle size 25 nm) 66 parts Pigment Yellow 138 (average primary particle size 25 nm) 68 parts Phthalocyanine derivative (Solsperse 3000 manufactured by Nippon Lubrizol Co., Ltd.)
... 10 parts benzyl methacrylate / methyl methacrylate (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 30,000) ... 32 parts dispersant (BYK-161, manufactured by BYK) ... 10 parts Propylene glycol monomethyl ether acetate 720 parts

  Subsequently, the mixed solution obtained above was further subjected to co-dispersion treatment for 6 hours in a bead disperser Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.) using 0.1 mmφ zirconia beads.

  Components of the following composition were further added to the obtained pigment dispersion and mixed by stirring to prepare a colored curable composition (color resist solution) of the present invention.

〔composition〕
Dipentaerythritol pentahexaacrylate 72 parts Photoinitiator A: 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) 4.5 parts Photopolymerization initiator B: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 15 parts Photopolymerization initiator C: diethylthioxanthone 4.5 parts benzyl methacrylate / methacrylic Acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 30,000) ... 172 parts · Propylene glycol monomethyl ether acetate · 106 parts · Epoxy resin: (trade name EHPE3150, manufactured by Daicel Chemical Industries) ... 11 parts Exemplified polymer P-17 (MW = 15000): 1.8 parts (first fluoroaliphatic group of the general formula (1) Yes polymer)
・ 3-Ethoxyethyl propionate ... 814 parts

(Examples 2 to 10)
In Example 1, the fluoroaliphatic group-containing polymer P-17 was changed to various polymers as shown in Table 2 below, and the present invention was carried out in the same manner as in Example 1 except that the amount added was changed. A colored curable composition (color resist solution) was prepared.

(Comparative Example 1)
In Example 1, the fluoroaliphatic group-containing polymer P-17 was changed to various polymers as shown in Table 2 below, and the amount of addition was changed in the same manner as in Example 1 except that the comparison was made. A colored curable composition (color resist solution) was prepared.

(Production, measurement, and evaluation of measurement substrate)
-1. Evaluation of radiation streaks and pinholes
For each of the colored curable compositions (color resist solutions) prepared in each Example and each Comparative Example, spin coating was performed on a 550 mm × 650 mm glass substrate (1737, manufactured by Corning) at a rotation speed of 740 to 850 rpm, A coating film having a thickness of 1.3 μm was obtained.
The surface state of the coating film was observed visually and with an optical microscope, and radiation streaks and pinholes (white spots) were evaluated.

Radiation streaks ◎ No radiation streaks ○ Slightly at the end △ Slightly at the end × At the end and center

Pinhole
◎ Not observed at all ○ Slightly observed but acceptable range x Observed and exceeded acceptable range

-2. Fabrication of colored filter substrate
Each of the photocurable compositions (color resist solutions) prepared in each Example and each Comparative Example is sequentially provided on a different 100 mm × 100 mm glass substrate (1737, manufactured by Corning), and y value serving as an index of color density. Was applied to 0.090 and dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been subjected to the photo-curing treatment and the development treatment as described above is heat-treated in a 220 ° C. oven for 1 hour (post-baking), and a colored resin coating for forming a color filter is formed on the glass substrate, A colored filter substrate (color filter) was produced.

Pc-1 and Pc-2 used in Table 2 are shown below.

  As shown in Table 2 above, the colored curable composition using the fluoroaliphatic group-containing polymer represented by the general formula (1) has no radiation streaks when applied, has a good surface shape, and has a pinhole. It was found that a good coating film without white spots can be formed and an excellent color filter can be produced.

Claims (11)

(A) a coloring material, (b) a solvent, (c) at least one selected from the group consisting of a polymerizable monomer and a binder resin, (d) a photopolymerization initiator, and (f) in the following general formula (1) A colored curable composition containing at least one selected from the fluoroaliphatic group-containing polymers represented.

In the general formula (1), i and j each represent an integer of 1 or more, meaning that each repeating unit includes i and j types respectively; M is derived from an ethylenically unsaturated monomer, and k ( k is an integer of 1 or more) a repeating unit included; a, b, and c represent a copolymerization ratio. When [Σai], [Σbj], and [Σck] are mass percentages in the fluoroaliphatic group-containing polymer of the first term component, the second term component, and the third term component of the general formula (1), respectively. , [Σai] is in the range of 1 to 98 mass%, [Σbj] is in the range of 1 to 98 mass%, and [Σck] is in the range of 1 to 98 mass%. R ¹¹ and R ¹² each represent a hydrogen atom or a methyl group; X ¹ and X ² each represent an oxygen atom, a sulfur atom or —N (R ¹³ ) —, and R ¹³ represents a hydrogen atom or a carbon number of 1 to 4 represents an alkyl group; m1 and m2 each represent an integer of 1 to 6, and n1 represents an integer of 0 to 3.   2. The colored curable property according to claim 1, wherein [Σai] / ([Σai] + [Σbj]) in the general formula (1) is a fluoroaliphatic group-containing polymer in the range of 0.2 to 0.8. Composition.   The ([Σai] + [Σbj]) in the general formula (1) is a fluoroaliphatic group-containing polymer in the range of 20 to 50% by mass of the (f) fluoroaliphatic group-containing polymer, or The colored curable composition according to claim 2.   The colored curable composition according to any one of claims 1 to 3, which is a fluoroaliphatic group-containing polymer in which n1 is 0 in the general formula (1).   The content of the fluoroaliphatic group-containing polymer is in the range of 0.01 to 20% by mass with respect to the solid content in the colored curable composition. Colored curable composition.   The product C × F of C mass% of the fluoroaliphatic group-containing polymer with respect to the solid content of the colored curable composition and fluorine atom content F mass% in the fluoroaliphatic group-containing polymer is 0.05 to It is the range of 0.12, The colored curable composition of any one of Claims 1-5.   The colored curable composition according to any one of claims 1 to 6, wherein the color material (a) contains a green pigment.   The coloring pattern formed from the colored curable composition of any one of Claims 1-7.   A color filter comprising: a step of applying the colored curable composition according to any one of claims 1 to 7 onto a substrate by a spin coating method or a slit and spin coating method; and a step of forming a colored pattern. Manufacturing method.   A color filter manufactured by the manufacturing method according to claim 9.   A liquid crystal display device using the color filter according to claim 10.