KR20090031243A - Colored curable resin composition, method for forming colored pattern, colored pattern, method for manufacturing color filter, color filter and liquid crystal display element - Google Patents

Abstract

A colored curable resin composition is provided to ensure excellent plate shape due to no stripe in coating, and to obtain a color filter by forming a good coating film without pinholes(whitening). A colored curable resin composition comprise (a) a coloring material; (b) solvent; (c) at least one selected from the group consisting of a polymerizable monomer and binder resin; (d) photopolymerization initiator; and (f) at least one selected from the group consisting of a fluoroaliphatic group-containing polymer represented by the chemical formula (1). In the chemical formula (1), i and j show an integer of 1 or more; M is derived from ethylenically unsaturated monomer; k is a repeating unit and an integer of 1 or more; the polymerization ratio of a, b and c is the mass percentage; Sigmaai is numerical value of 1~98 mass %; Sigmabj is numerical value of 1~98 mass %; R^11 and R^12 are respective hydrogen atom or methyl radical; X^1 and X^2 show respective oxygen atom sulfur atom or -N(R^13)-; R^13 shows hydrogen atom or C1-4 alkyl group; m1 and m2 are an integer of 1~6; and n1 is an integer of 0~3.

Description

Colored curable resin composition, colored pattern formation method, colored pattern, manufacturing method of color filter, color filter, and liquid crystal display element {COLORED CURABLE RESIN COMPOSITION, METHOD FOR FORMING COLORED PATTERN, COLORED PATTERN, METHOD FOR MANUFACTURING COLOR FILTER, COLOR FILTER AND LIQUID CRYSTAL DISPLAY ELEMENT}

This invention relates to a colored curable resin composition, the coloring pattern formation method, the coloring pattern, the manufacturing method of a color filter, a color filter, and a liquid crystal display element.

A color filter constituting a liquid crystal display (LCD), a color image tube device (CCD), or the like contains a binder resin and / or a monomer, a photopolymerization initiator, and other components in a solvent dispersion composition of a colorant such as an organic pigment and an inorganic pigment, and thus coloring photosensitivity. It is manufactured by the photolithographic method etc. which include the process of making into a composition and apply | coating and drying this on a transparent substrate and forming the coating film whose thickness is about 1-3 micrometers.

As a coating method on a board | substrate, there exist a spin coating method, the die coating method, etc., and it is used suitably according to the characteristic.

The spin coating method is a widely used method for forming a thin film into a relatively small sized substrate. The coating liquid is dropped on the center of the transparent substrate while the transparent substrate is rotated at a constant rotational speed, and the coating liquid is spread thinly by centrifugal force. It is a coating method of forming the coating film of a desired film thickness on the surface of a transparent substrate by controlling the rotation speed, rotation time, etc. of a suitable transparent substrate. However, due to the principle of thinning the coating film using the centrifugal force by rotation, there is a drawback that the thickness of the coating film of the rotation center portion and the peripheral portion of the transparent substrate becomes too thick as compared to the middle portion thereof.

The die coating method is a method suitable for forming a thin film on a large-size substrate, and is a coating method in which a coating film having a desired film thickness is formed on the surface of a transparent substrate while discharging the coating liquid from the slit to move the slit. However, there is a drawback that stripe irregularities (stripe smears) are likely to occur in the direction perpendicular to the traveling direction of the slits on the mechanism, and the outer periphery of the coating film swells and becomes thicker than the center of the substrate.

Moreover, a problem arises that a pinhole (whitening) occurs if the drying property or surface tension of the coating liquid is 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, Japanese Patent Laid-Open No. 2007-10992 discloses a technique in which a problem is solved by adjusting the contact angle of a composition, and a fluorine-based surfactant is suitably used. In addition, Japanese Patent Application Laid-Open No. 2007-61886 discloses a technique for solving the problem by a composition having polysiloxane as an antistatic agent.

An object of the present invention is to provide a colored curable resin composition that improves the surface shape resulting from application and has fewer defects. Moreover, another object of this invention is to provide the favorable coloring pattern which uses the colored curable resin composition of this invention, and the method of forming this. Moreover, another 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 the liquid crystal display element provided with this color filter.

Means for solving the above problems are as follows.

<1> At least one selected from the group containing (a) a colorant, (b) a solvent, (c) a polymerizable monomer and a binder resin, (d) a photoinitiator, and (f) with the following general formula (1) Colored curable resin composition containing at least 1 sort (s) chosen from the fluoro aliphatic group containing polymer shown:

In general formula (1), i and j represent the integer of 1 or more, respectively, and it means that each repeating unit contains i and j kinds respectively; M is a repeating unit derived from an ethylenically unsaturated monomer and containing k (k is an integer of 1 or more) type; a, b and c are the mass percentages representing the polymerization ratio, ∑ai represents the numerical value of 1 to 98 mass%, ∑bj represents the numerical value of 1 to 98 mass%, and ∑ck is the numerical value of 1 to 98 mass% Represents; 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 an alkyl group having 1 to 4 carbon atoms; m1 and m2 represent the integer of 1-6, respectively, and n1 represents the integer of 0-3.

<2> In the formula ^(1), X 1 and X ² are colored curable resin composition according to <1>, characterized in that 0, respectively.

In <3> General formula (1), m1 and m2 are 1-4, respectively, The colored curable resin composition as described in <1> characterized by the above-mentioned.

<4> ∑ai / (∑ai + ∑bj) is 0.2 to 0.8, wherein the colored curable resin composition according to <1>.

<5> ∑ai + ∑bj is 20 to 50% by mass, wherein the colored curable resin composition according to <1>.

<6> Colored curable resin composition as described in <1> whose n1 is 0 in the said General formula (1).

Content of the <7> above-mentioned fluoro aliphatic group containing polymer is 0.01-20 mass% of solid content in a composition, The colored curable resin composition in any one of <1>-<6> characterized by the above-mentioned.

<8> The product (C x F) of the concentration (C) mass% of the fluoroaliphatic group-containing polymer and the fluorine content (F)% in the fluoroaliphatic group-containing polymer is 0.05 to 0.12 < The colored curable resin composition as described in 1>.

<9> The colored curable resin composition according to <1>, wherein the color material contains a green pigment.

<10> The coloring pattern formed from the composition in any one of <1>-<9>.

<11> The manufacturing method of the color filter characterized by including the process of forming a coloring pattern by apply | coating the colored curable resin composition in any one of <1>-<9> by a spin coating method or the slit-and-spin method. .

<12> The color filter manufactured by the manufacturing method as described in <11>.

<13> Liquid crystal display element using the color filter as described in <12>.

According to this invention, the surface shape resulting from application | coating can be improved, and the coloring curable resin composition with few defects can be provided. Moreover, according to this invention, the favorable coloring pattern which uses the colored curable resin composition of this invention, and the method of forming this can be provided. Moreover, according to this invention, the color filter provided with the said favorable coloring pattern, the manufacturing method of a color filter, and the liquid crystal display element provided with this color filter can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. In addition, it is used by the meaning which includes with "-" the numerical value described before and after that as a lower limit and an upper limit in this specification.

[Coloring curable resin composition]

The colored curable resin composition of this invention is at least 1 sort (s) chosen from the group which consists of (a) a coloring material, (b) solvent, (c) polymerizable monomer, and binder resin, (d) photoinitiator, and (f) predetermined At least 1 sort (s) of a fluoro aliphatic group containing polymer is contained.

Fluoro aliphatic group-containing polymer

The fluoro aliphatic group containing polymer used for this invention is represented by following General formula (1).

In general formula (1), i and j represent the integer of 1 or more, respectively, and it means that each repeating unit contains i and j kinds respectively; M is a repeating unit derived from an ethylenically unsaturated monomer and containing k (k is an integer of 1 or more) type; a, b and c are the mass percentages representing the polymerization ratio, ∑ai represents the numerical value of 1 to 98 mass%, ∑bj represents the numerical value of 1 to 98 mass%, and ∑ck is the numerical value of 1 to 98 mass% Represents; 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 an alkyl group having 1 to 4 carbon atoms; m1 and m2 each represent an integer of 1 to 6; n1 represents the integer of 0-3.

In the formula (1), the following repeating units (A and B) are each a fluoro aliphatic group-containing monomer A having a terminal of-(CF ₂ CF ₂ ) ₃ F and a fluoro terminal of-(CF ₂ CF ₂ ) ₂ F It is a repeating unit derived from aliphatic group containing monomer B.

In the repeating units (A and B), X ¹ and X ² are each preferably 0. That is, it is preferable that the said repeating unit (A and B) is a repeating unit derived from a (meth) acrylic-type monomer, respectively.

It is preferable that it is 1-4, respectively, and, as for m1 and m2, it is more preferable that it is 1-2.

n1 is preferably 0 to 2, more preferably 0 or 1, and most preferably 0.

Although the example of the fluoro aliphatic group containing monomer which induces the said repeating unit (A) is listed below, it is not limited to these. Especially, exemplary compound (A1-1-6 and A2-1-6) which is a (meth) acrylic-type monomer is preferable. In addition, although the following exemplary compound lists the compound of n1 = 0 in Formula (1), the compound whose n1 is 1-3 is included in the example of the fluoro aliphatic group containing monomer which induces the said repeating unit (A), of course. do.

Although the example of the fluoro aliphatic group containing monomer which induces the said repeating unit (B) is listed below, it is not limited to these. Especially, exemplary compounds (B1-1-6 and B2-1-6) which are (meth) acrylic-type monomers are preferable.

The said fluoro aliphatic group containing monomer can be manufactured by the telomerization method (also called a telomer method) or the oligomerization method (also called an oligomer method). Regarding the method for producing these fluoroaliphatic compounds, for example, pages 117 to 118 of "Synthesis and Function of Fluorine Compounds" (Survey: Nobuo Ishikawa, Published: CMC, 1987), or "Chemistry of Organic Fluorine Compounds II". (Monograph 187, Ed by Milos Hudlicky and Attila E. Pavlath, American Chemical Society 1995), pages 747-752. The telomerization method is a method of synthesizing telomers by radical polymerization of fluorine-containing vinyl compounds such as tetrafluoroethylene using alkyl halides having a large chain transfer constant such as iodide as telogen (Scheme-1). Example).

The terminal iodide telomers obtained are usually subjected to appropriate terminal chemical modifications, such as, for example, [Scheme 2], to lead to fluoro aliphatic compounds.

In said formula (1), M is a repeating unit derived from an ethylenically unsaturated monomer. Although it does not restrict | limit especially about M, It is preferable that it is a repeating unit which has a polar group which has hydrogen bondability in a side chain. It is preferable that M is a repeating unit represented by following General formula (2).

In the said General formula (2), R <^1> , R <^2> and R <^3> respectively independently represent the group represented by a hydrogen atom, an alkyl group, a halogen atom, or -LQ. L represents a divalent linking group, and Q represents a polar group having hydrogen bonding.

L is preferably an arbitrary group selected from the following linking group, or a divalent linking group formed by combining two or more thereof.

(Connector group)

Single bond, -O-, -CO-, -NR ^4- , -S-, -SO _2- , -P (= O) (OR ⁵ )-, alkylene group, arylene group (R ⁴ is hydrogen atom, alkyl group , An aryl group, or an aralkyl group, R ⁵ represents an alkyl group, an aryl group, or an aralkyl group.)

In more detail, 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, or the like), or It is group represented by -LQ mentioned later, Preferably it is a hydrogen atom, a C1-C6 alkyl group, a chlorine atom, the group represented by -LQ, More preferably, it is a hydrogen atom and a C1-C4 alkyl group, Especially Preferred are hydrogen atoms and alkyl groups having 1 to 2 carbon atoms. As a specific example of the alkyl group which R <^1> , R <^2> and R <^3> can take, a methyl group, an ethyl group, n-propyl group, n-butyl group, sec-butyl group, etc. are mentioned. The alkyl group may have one or more substituents. Examples of the substituent include a halogen atom, an aryl group, a heterocyclic group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a hydroxyl group, an acyloxy group, an amino group, an alkoxycarbonyl group, an acylamino group, an oxycarbonyl group, Carbamoyl group, sulfonyl group, sulfamoyl group, sulfonamide group, sulforyl group, carboxyl group and the like.

In addition, carbon number of an alkyl group does not contain the carbon atom of a substituent. Hereinafter, it is the same also about carbon number of another group.

L is a single bond, -O-, -CO-, -NR ^4- , -S-, -SO _2- , -PO (OR ⁵ )-, an alkylene group, an arylene group or a divalent linking group formed by combining them Indicates. 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.

As L, it is preferable to contain a single bond, -O-, -CO-, -NR ^4- , -S-, -SO _2- , an alkylene group, an arylene group, and -CO-, -O-, -NR ⁴ It is especially preferable to contain an alkylene group or an arylene group. Also. It is also preferable to contain the alkyleneoxy group containing both -O- and an alkylene group, and it is also preferable to contain the polyalkyleneoxy group containing repetition of an alkyleneoxy group.

When L contains an alkylene group, carbon number of an alkylene group becomes like this. Preferably it is 1-10, More preferably, it is 1-8, Especially preferably, it is 1-6. As a specific example of especially preferable alkylene group, a methylene group, ethylene group, trimethylene group, tetrabutylene group, hexamethylene group, etc. are mentioned. Moreover, the alkylene group (meaning that the alkylene group contained in the alkyleneoxy group is included) may have a branched structure, and it is preferable that carbon number of the alkylene chain of a branch part is 1-3.

When L contains an arylene group, carbon number of an arylene group becomes like this. Preferably it is 6-24, More preferably, it is 6-18, Especially preferably, it is 6-12. As a specific example of an especially preferable arylene group, a phenylene group, a naphthalene group, etc. are mentioned.

When L contains a divalent linking group (ie aralkylene group) obtained by combining an alkylene group and an arylene group, the aralkylene group preferably has 7 to 34 carbon atoms, more preferably 7 to 26 carbon atoms, and particularly preferably 7 to 16. As a specific example of an especially preferable aralkylene group, a phenylene methylene group, a phenylene ethylene group, a methylene phenylene group, etc. are mentioned.

The group illustrated as L may have a suitable substituent. As such a substituent, the same thing as the substituent mentioned previously as a substituent in R <^1> -R <^3> is mentioned.

Although the specific structure of L is illustrated below, this invention is not limited to these specific examples.

Provided that R ⁵¹ to R ⁵⁸ each represent a hydrogen atom or an alkyl group (preferably having 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms), and n is 1 to 12 (preferably 2 to 10 carbon atoms). Integer). It is preferable that any one of R ⁵³ and R ⁵⁴ , R ⁵⁵ and R ⁵⁶ , and R ⁵⁷ and R ⁵⁸ is 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 bondability. Preferably, the salt of hydroxyl group, carboxyl group, and carboxyl group (for example, lithium salt, sodium salt, potassium salt, ammonium salt (for example ammonium, tetramethylammonium, trimethyl-2-hydroxyethylammonium, tetrabutylammonium, trimethylbenzylammonium) , Dimethylphenylammonium, etc.), pyridinium salts, etc.), amides of carboxylic acids (N unsubstituted or N-mono lower alkyl substituents such as -CONH ₂ , -CONHCH _3, etc.) sulfo groups, salts of sulfo groups ( Examples of cations forming salts are as described in the above carboxyl groups), sulfonamide groups (N unsubstituted or N-mono lower alkyl substituents, -SO ₂ NH ₂ , -SO ₂ NHCH _3, etc.), phosphoric acid groups, salts of phosphoric acid groups (Examples of cations forming salts are as described in the above carboxyl groups), phosphonamides (N unsubstituted or N-mono lower alkyl substituents, for example -OP (= O) (NH ₂ ) ₂ , -OP ( = O) (NHCH ₃ ) ₂ etc.), ureido group (-NHCONH ₂ ), N position is unsubstituted or A no-substituted amino group (-NH ₂ , -NHCH ₃ ) or the like (lower alkyl group represents a methyl group or an ethyl group).

More preferably, it is a hydroxyl group, a carboxyl group, a sulfo group, and a phosphoric acid group, More preferably, it is a hydroxyl group or a carboxyl group, Especially preferably, it is a hydroxyl group.

It is preferable that the repeating unit represented by the said General formula (2) is a repeating unit derived from a (meth) acrylic-type monomer.

Although the specific example of the ethylenically unsaturated monomer which induces a repeating unit (M) below is shown below, it is not limited to these.

The fluoroaliphatic group polymer represented by the general formula (1) contains at least one repeating unit (A, B, and M), respectively. That is, i, j, and k which represent the number of types of each repeating unit in said Formula (1) are each an integer of 1 or more. The fluoroaliphatic group polymer represented by the said General formula (1) may contain 2 or more types of each repeating unit, and may also contain repeating units other than repeating unit (A, B, and M).

For example, the said fluoro aliphatic group containing polymer may contain 1 type of repeating units derived from the monomer chosen from the following monomer groups, and may contain 2 or more types.

Monomer group

(1) alkenes

Ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-dodecene, 1-octadecene, 1-icocene, hexafluoropropene, vinylidene fluoride, chlorotrifluoroethylene, 3,3, 3-trifluoropropylene, tetrafluoroethylene, vinyl chloride, vinylidene chloride and the like;

(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 acids

(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 acryl Latex, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, tert-octyl acrylate, dodecyl acrylate, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 2-bromo Ethyl acrylate, 4-chlorobutyl acrylate, 2-cyanoethyl acrylate, 2-acetoxyethyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl Acrylate, 2-methoxyethyl acrylate, ω-methoxy polyethylene glycol acrylate (addition mole number of polyoxyethylene: n = 2 to 1 00), 3-methoxybutyl 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, etc.);

(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 (addition mole number of polyoxyethylene: n = 2 to 100), 2-acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-butoxide Ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, glycidyl methacrylate, 3-trimethoxysilylpropyl methacrylate, allyl methacrylate, 2-isocyanatoethyl meth Acrylates and the like;

(3c) diesters of unsaturated polyhydric carboxylic acids

Dimethyl maleate, dibutyl maleate, dimethyl itaconic acid, dibutyl itaconic acid, dibutyl crotonate, dihexyl crotonate, diethyl fumarate, dimethyl fumarate and the like;

(3d) Amides of α, β-unsaturated carboxylic acids

N, N-dimethyl acrylamide, N, N-diethyl acrylamide, Nn-propyl acrylamide, N-tert butyl acrylamide, N-tert octyl methacrylamide, N-cyclohexyl acrylamide, N-phenyl acrylamide N- (2-acetoacetoxyethyl) acrylamide, N-benzyl acrylamide, N-acryloyl morpholine, diacetone acrylamide, N-methyl maleimide, and the like;

(4) unsaturated nitriles

Acrylonitrile, methacrylonitrile and the like;

(5) styrene and its derivatives

Styrene, vinyltoluene, ethylstyrene, p-tert butylstyrene, methyl p-vinylbenzoate, α-methylstyrene, p-chloromethylstyrene, vinylnaphthalene, p-methoxystyrene, p-hydroxymethylstyrene, p-ace Oxy styrene and the like;

(6) vinyl esters

Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl benzoate, vinyl salicylate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acetate, and the like;

(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-vinylpyrrolidone, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, 2-vinyl oxazoline, 2-isopropenyloxazoline and the like.

A, b, and c in the general formula (1) are mass percentages indicating the polymerization ratio of monomers for inducing each repeating unit, ∑ai represents a numerical value of 1 to 98 mass%, and ∑bj is 1 to 98 mass% Represents the numerical value of, and? Ck represents the numerical value of 1-98 mass%. It is preferable that ∑ai is 5-40 mass%, ∑bj is 5-40 mass%, ∑ck is 20-90 mass%, ∑ai is 10-35 mass%, and ∑bj is 10-35 mass It is%, and it is more preferable that (sigma) ck is 30-80 mass%. The fluoroaliphatic group-containing polymer represented by the general formula (1) may contain repeating units other than the repeating units (A, B, and M), that is, ∑ai + ∑bj + ∑ck <100% by mass, It is preferable not to contain repeating units other than the said repeating unit (A, B, and M), ie, it is preferable that it is ∑ai + ∑bj + ∑ck = 100 mass%.

In addition, if 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, the planar shape can be improved, which is preferable. Specifically, it is preferable that the sum (∑ai + ∑bj) of the total mass (Σai) of the i-type repeating units (A) and the total mass of the j-type repeating units (B) is 20 to 50 mass%, It is more preferable that it is 25-45 mass%, and it is still more preferable that it is 25-40 mass%. If (∑ai + ∑bj) is within the above range, the surface shape of the coating film can be further improved.

Furthermore, from the same point of view, it is preferable that ratio (∑ai / (∑ai + ∑bj)) of ∑ai to ∑ai + ∑bj is 0.2 to 0.8, more preferably 0.3 to 0.6, still more preferably 0.35 to 0.55. Do. It is preferable that Σai / (∑ai + ∑bj) be in the above range because the surface shape of the coating film can be further improved.

Although the specific example of the fluoro aliphatic group containing polymer which can be used for this invention is put together in following Table 1, it is not limited to the following specific example. In addition, the repeating unit (A, B, and M) in following Table 1 is specified by the exemplary compound No. of the monomer which guide | induces each repeating unit.

The colored curable resin composition of this invention should just contain at least 1 sort (s) of the said fluoro aliphatic group containing polymer, and of course may contain 2 or more sorts. In the said composition, as an addition amount of the said fluoro aliphatic group containing polymer, 0.01-20 mass% of the solid content mass of a colored curable composition is preferable, 0.1-10 mass% is more preferable, 1-5 mass% is further more preferable. .

Moreover, the preferable range of the concentration (C) mass% of the said fluoro aliphatic group containing polymer in solid content of the said composition changes with the fluorine content (F)% in the said fluoro aliphatic group containing polymer. In order to further improve the coated surface shape, the product of the concentration (C) mass% of the fluoroaliphatic group-containing polymer and the fluorine content (F)% in the fluoroaliphatic group-containing polymer is preferably 0.05 to 0.12, and is 0.06 to 0.09. It is more preferable, and it is still more preferable that it is 0.06-0.08. If CxF is the said range, the surface shape of a coating film can be improved more.

Second fluoro aliphatic group containing polymer

In the colored curable resin composition of this invention, the fluoro aliphatic group containing polymer (henceforth "the 1st fluoro aliphatic group containing polymer") outside the range of the said fluoro aliphatic group containing polymer (henceforth "second fluoro aliphatic group"). Containing polymers) may be added. First and at least one carboxyl group (-COOH) or its salt of the repeating unit derived from a monomer having a fluoro-aliphatic group-containing aliphatic polymer with 2-fluoro, sulfo (-SO ₃ H) or a salt thereof, or phosphono It is preferable to contain at least 1 sort (s) of the repeating unit derived from the monomer which has acidic groups, such as oxy {-OP (= O) (OH) ₂ } or its salt.

As a preferable example of the said 2nd fluoro aliphatic group containing polymer, the following polymer A (repeat unit derived from a fluoro aliphatic group containing monomer and the repeat represented by following General formula (1a)) described in the international publication 2006/001504 pamphlet It is a copolymer containing a unit).

In the formula, R ^1a , R ^2a and R ^3a each represent a hydrogen atom or a substituent; L ^a represents a divalent linking group selected from the following linking group or a divalent linking group formed by combining two or more selected from the following linking group.

(Linking 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;

VII ^a represents a carboxyl group (-COOH) or a salt thereof, a sulfo group (-SO ₃ H) or a salt thereof, or a phosphonooxy {-OP (= 0) (OH) ₂ } or a salt thereof.

In formula, R <^1a> , R <^2a> , R <^3a> and L ^<a> are synonymous with the preferable range of R <^1> , R <^2> , R <^3> and L in the said General formula (2), respectively.

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

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 group having 1 to 4 carbon atoms. Z represents a hydrogen atom or a fluorine atom, m5 represents an integer of 1 ~ 6, n ₅ is an integer of 2-4.

Moreover, the said 2nd fluoro aliphatic group containing polymer may contain the repeating unit which has a hydrogen bondable group represented by the said General formula (2), and is at least 1 sort (s) chosen from the said monomer group (1)-(7). The repeating unit derived from the monomer of may be contained. Although the exemplary compound of the polymer which can be used as a 2nd fluoro aliphatic group containing polymer for the colored curable resin composition of this invention is listed below, it is not limited to the following specific example.

In the form which adds the said 2nd fluoroaliphatic group containing polymer, it is preferable that the addition amount (mass%) of the said 2nd fluoroaliphatic group containing polymer is the addition amount (mass%) of the said 1st fluoroaliphatic group containing polymer.

It is preferable that the weight average molecular weight of the said 1 fluoro aliphatic group containing polymer (and the 2nd fluoro aliphatic group containing polymer added as desired) is 1,000,000 or less. More preferably, the weight average molecular weight is 500,000 or less, Especially preferably, the weight average molecular weight is 100,000 or less.

A weight average molecular weight can be measured as a value of polyethylene oxide (PEO) conversion using gel permeation chromatography (GPC).

In addition, a weight average molecular weight can also be calculated | required as a value of polystyrene (PST) conversion using gel permeation chromatography (GPC). The physical property value of the fluoro aliphatic group containing polymer described in this invention can be determined using the same method unless it mentions specially.

(Weight average molecular weight and number average molecular weight)

It carried out by polystyrene conversion by the GPC (gel permeation chromatography) measurement of the following conditions.

Column used: TSKgel superHZM-H, TSKgel superHZ4000, TSKgel superHZ2000

Eluent: THF

Flow rate: 0.35ml / min

Temperature: 40 ℃

Detection condition: RI

System: High speed GPC device (Toso HLC-8220)

There is no restriction | limiting in particular about the manufacturing method of the said 1 fluoro aliphatic group containing polymer (and the 2nd fluoro aliphatic group containing polymer added as desired). For example, it can manufacture by polymerization methods, such as cation polymerization, radical polymerization, or anionic polymerization using a vinyl group, and among these, a radical polymerization method is especially preferable at the point which can be used for general use.

As a polymerization initiator of radical polymerization, although well-known compounds, such as a radical thermal polymerization initiator and a radical photoinitiator, can be used, it is especially preferable to use a radical thermal polymerization initiator. Here, a radical thermal polymerization initiator is a compound which generate | occur | produces a radical by heating above decomposition temperature. As such a radical thermal polymerization initiator, for example, diacyl peroxide (acetyl peroxide, benzoyl peroxide, etc.), ketone peroxide (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), hydroperoxide (hydrogen peroxide, tert-butyl, for example) Hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxide (di-tert-butylperoxide, dicumylperoxide, dilauroyl peroxide, etc.), peroxy esters (tert-butylperoxyacetate, tert- Butyl peroxy pivalate, etc.), an azo compound (azobisisobutyronitrile, azobisisovaleronitrile, etc.), persulfates (ammonium persulfate, sodium persulfate, potassium persulfate, etc.) are mentioned. These radical thermal polymerization initiators may be used individually by 1 type, or may be used in combination of 2 or more type.

The radical polymerization method is not particularly limited, and an emulsion polymerization method, suspension polymerization method, block polymerization method, solution polymerization method and the like can be adopted. More specifically, solution polymerization which is a typical radical polymerization method is demonstrated. The outlines of the other polymerization methods are the same, and the details thereof are described in, for example, the Polymer Science Experiment Method, Polymer Society Edition (Tokyo Kagakudojin, 1981).

In order to perform solution polymerization, an organic solvent is used. These organic solvents can be arbitrarily selected within the range of not impairing the object and effect of the present invention. These organic solvents are normally organic compounds which have a boiling point under atmospheric pressure within the range of 50-200 degreeC, and the organic compound which melt | dissolves each component uniformly is preferable. Examples of preferred organic solvents include alcohols such as isopropanol and butanol, dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and ethers such as dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Ketones, ethyl acetate, butyl acetate, esters, such as amyl acetate and (gamma) -butyrolactone, and aromatic hydrocarbons, such as benzene, toluene, and xylene, are mentioned. In addition, these organic solvents can be used individually by 1 type or in combination of 2 or more types. Moreover, the water mixed organic solvent which used water together with the said organic solvent from the viewpoint of the solubility of a monomer and the produced polymer can also be applied.

Moreover, although solution polymerization conditions are not specifically limited, For example, it is preferable to heat for 10 minutes-30 hours within the temperature range of 50-200 degreeC. In addition, it is preferable to perform an inert gas purge not only during solution polymerization but also before the start of solution polymerization so that the generated radicals are not deactivated. As an inert gas, nitrogen gas is normally used suitably.

A radical polymerization method using a chain transfer agent is particularly effective in order to obtain the first fluoro aliphatic group-containing polymer (and the second fluoro aliphatic group-containing polymer added as desired) in a preferable molecular weight range.

As a chain transfer agent, mercaptans (for example, octyl mercaptan, decyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, octadecyl mercaptan, thiophenol, p-nonylthiophenol, etc.), polyhalogenated alkyl ( For example, carbon tetrachloride, chloroform, 1,1,1-trichloroethane, 1,1,1-tribromooctane, and the like, and low-active monomers (α-methylstyrene, α-methylstyrene dimer, etc.) can be used. However, Preferably, they are C4-C16 mercaptans. The amount of use of these chain transfer agents is significantly influenced by the activity of the chain transfer agent, the combination of the monomers, the polymerization conditions, and the like, and precise control is necessary, but is usually about 0.01 mol% to 50 mol% based on the total moles of the monomers used, Preferably it is 0.05 mol%-30 mol%, Especially preferably, it is 0.08 mol%-25 mol%. These chain transfer agents should just exist in a system simultaneously with the monomer which should be controlled the degree of polymerization in a superposition | polymerization process, and it does not have a problem especially about the addition method. It may melt | dissolve and add to a monomer, and can also add separately from a monomer.

The viscosity in 25 degreeC of the said fluoro aliphatic group containing polymer is 200 Pa.s-10000Pa * s, It also relates to the colored curable resin composition characterized by the above-mentioned. If the viscosity at 25 degrees C of the said fluoro aliphatic group containing polymer is 200 Pa.s-10000 Pa.s, a favorable surface shape can be obtained. It is more preferable that it is 250-5000 Pa.s, and, as for the viscosity of the said fluoro aliphatic group containing polymer, it is still more preferable that it is 300-1000 Pa.s. In addition, in this specification, the "viscosity" of a fluoro aliphatic group containing polymer uses the rheology case VAR-100 type rheometer, the gap-gap distance 1.5 mm, frequency 1 Hz, strain 0.005, temperature increase rate 5 degreeC / min, nitrogen atmosphere The value measured by oscillation mode under the following conditions.

In this embodiment, it is preferable that the said fluoro aliphatic group containing polymer is selected from the fluoro aliphatic group containing polymer represented by the said General formula (1). In particular, in said general formula (1), the polymer in which both R11 and R12 is a fluoro aliphatic group containing a methyl group is preferable. In the colored curable resin composition of this aspect, it is preferable that content of the said fluoro aliphatic group containing polymer is 0.02-0.50 mass% with respect to the gross mass of a colored curable resin composition (solid content, when prepared as a coating liquid), and it is 0.03 from a viewpoint. It is more preferable that it is -0.30 mass%, and it is still more preferable that it is 0.05-0.20 mass%.

Colored curable resin composition

Next, at least 1 sort (s) chosen from the group which consists of (a) color material, (b) solvent, (c) polymerizable monomer, and binder resin used for the colored curable resin composition of this invention, (d) photoinitiator Explain.

(a) color material

As a coloring material in this invention, a pigment or dye can be used. In addition, in this invention, a coloring agent and a coloring material are synonymous with a coloring material.

Pigments

As a pigment which can be used for the pigment dispersion composition of this invention, various conventionally well-known inorganic pigments or organic pigments can be used. In addition, considering that it is preferable that the pigment has a high transmittance regardless of the inorganic pigment or the organic pigment, it is preferable to use a pigment having a small particle size and a small particle size as much as possible. Primary particle diameter 0.01-0.3 micrometer, More preferably, it is a pigment of 0.01-0.15 micrometer. When the particle diameter is in the above range, the transmittance is high, the color characteristics are good, and it is effective to form a high contrast color filter.

The average primary particle diameter is observed by SEM or TEM, and is calculated | required by measuring 100 particle size in the part which particle | grains 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, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and The complex oxide of the said metal is mentioned.

As said organic pigment, for example

CIPigment 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,

CIPigment 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, 174, 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

Cl substituents of CIPigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Thing, 80

C.I.Pigment Violet 1, 19, 23, 27, 32, 37, 42

C.I.Pigment Brown 25, 28

C.I. Pigment Black 1, 7 etc. are mentioned.

Among these, the following can be mentioned as a pigment which can be used preferably. However, in this invention, it 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

Pigment Refinement

In the present invention, an organic pigment fine and sized as needed can be used. The refinement of the pigment is a process of grinding it as a high viscosity liquid composition together with the pigment, the water-soluble organic solvent and the water-soluble inorganic salts.

As a water-soluble organic solvent, 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 monomethyl ether acetate, and the like. However, if it is adsorbed to the pigment by a small amount and is not lost in the waste water, 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, methylcyclohexane, halogenated hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or the like may be used, or two or more solvents may be mixed and used as necessary.

In this invention, sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate etc. are mentioned as a water-soluble inorganic salt.

Although the usage-amount of water-soluble inorganic salt is 1-50 times mass of a pigment and many have a grinding effect, it is preferable that a more preferable quantity is 1-10 times mass, and moisture is 1 mass% or less from a viewpoint of productivity.

The usage-amount of a water-soluble organic solvent is the range of 50 mass%-300 mass% with respect to a pigment, Preferably it is the range of 100 mass%-200 mass%. There is no restriction | limiting in particular about the operating conditions of the wet grinding apparatus in this invention, In order to operate the grinding | pulverization by grinding media effectively, the operating conditions when the apparatus is a kneader, The rotation speed of the blade in an apparatus is 10-200 rpm, It is also preferable that the larger the rotation ratio of the two axes is, the larger the grinding effect is. 1 hour-8 hours are preferable with dry grinding time, and 50-150 degreeC of internal temperature of an apparatus is preferable. Moreover, the water-soluble inorganic salt which is a grinding media has a grinding particle size of 5-50 micrometers, the distribution of particle diameter is sharp, and spherical shape is preferable.

-Combination of Pigments-(Color Matching)

These organic pigments can be used alone or in various combinations to improve color purity. The specific example of the said combination is shown below. For example, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them as a red pigment, a disazo yellow pigment, an isoindolin yellow pigment, a quinophthalone yellow pigment or peryl A mixture of a len red pigment, an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, and the like can be used. For example, CI pigment red 177 is mentioned as an anthraquinone pigment, CI pigment red 155 and CI pigment red 224 are mentioned as a perylene pigment, CI pigment red as a diketopyrrolopyrrole pigment. CI pigment yellow 83, CI from a viewpoint of color reproducibility Preference is given to mixing with Pigment Yellow 139 or C.I. Pigment Red 177. In addition, the mass ratio of the red pigment and the other pigment is preferably 100: 5 to 100: 80. In 100: 4 or less, it is difficult to suppress the light transmittance of 400 nm-500 nm, and color purity may not be improved. Moreover, the coloring power may fall at 100: 81 or more. Especially as said mass ratio, the range of 100: 10-100: 65 is optimal. In addition, in the case of the combination of red pigments, it can adjust to chromaticity.

Moreover, as a green pigment, the halogenated phthalocyanine type pigment can be used individually by 1 type, or the mixture of this and a disazo yellow pigment, a quinophthalone type yellow pigment, an azomethine type yellow pigment, or an isoindolin type yellow pigment can be used. For example, CI Pigment Green 7, 36, 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180 or CI Pigment Yellow Mixing of 185 is preferred. As for the mass ratio of a green pigment and a yellow pigment, 100: 5-100: 200 are preferable. When the said mass ratio is less than 100: 5, it may become difficult to suppress the light transmittance of 400-450 nm, and color purity may not be improved. If the wavelength exceeds 100: 200, the main wavelength may be near the long wavelength, which may cause a large deviation from the NTSC target color. As said mass ratio, the range of 100: 20-100: 150 is especially preferable.

As a blue pigment, a phthalocyanine type pigment can be used individually by 1 type, or the mixture of this and a dioxadine type purple pigment can be used. Particularly preferred examples include a mixture of C.I. Pigment Blue 15: 6 and C.I.Pigment Violet 23.

As for the mass ratio of a blue pigment and a purple pigment, 100: 0-100: 100 are preferable, More preferably, it is 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 can be used, and the combination of carbon black and titanium black is preferable.

In addition, the mass ratio of carbon black and titanium black is preferably in the range of 100: 0 to 100: 60. If it is 100: 61 or more, dispersion stability may fall.

-dyes-

In this invention, when using dye as a coloring agent, the colored curable resin composition melt | dissolved uniformly 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 Laid-Open No. 64-90403, Japanese Patent Laid-Open No. 64-91102, Japanese Patent Laid-Open No. 1-94301, Japanese Patent Laid-Open No. 6-11614, Japanese Patent Registration 2592207, U.S. Patent 4,808,501, U.S. Patent 5,667,920, U.S. Patent 5,059,500, Japanese Patent Application Laid-Open No. 5-333207, Japanese Patent Application Laid-Open No. 6-35183, Japanese Patent Application Laid-Open No. 6-51115 Japanese Patent Application Laid-Open No. Hei 6-194828, Japanese Patent Application Laid-Open No. Hei 8-211599, Japanese Patent Application Laid-Open No. Hei 4-249549, Japanese Patent Application Laid-Open No. Hei 10-123316, Japanese Patent Application Laid-Open No. 11-302283 Japanese Patent Laid-Open No. 7-286107, Japanese Patent Laid-Open No. 2001-4823, Japanese Patent Laid-Open No. 8-15522, Japanese Patent Laid-Open No. 8-29771, Japanese Patent Laid-Open No. 8-146215, Japanese Patent Laid-Open No. 11-343437, Japanese Patent Laid-Open No. 8-62416, Japanese Patent Publication 2002-14220, Japanese Patent Publication 2002-14221, Japanese Patent Publication 2002-14222, Japanese Patent Publication 2002-14223, Japanese Patent Application Laid-Open No. 8-302224, Japanese Patent Application Laid-Open No. 8- It is a pigment | dye as described in Unexamined-Japanese-Patent No. 73758, Unexamined-Japanese-Patent No. 8-179120, Unexamined-Japanese-Patent No. 8-151531.

Examples of the chemical structure include pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridoneazo, cyanine, phenothiazine and pyrrolo. Dyestuffs, such as a pyrazole azomethine type, a xanthene type, a phthalocyanine type, a benzopyran type, an indigo type, 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 the said composition, and 15-50 mass% is more preferable. When content of a pigment is in the said range, color concentration is enough and it is effective for ensuring the outstanding color characteristic.

Dispersant

The pigment dispersion composition of the present invention contains at least one kind of dispersant. By containing this dispersing agent, the dispersibility of a pigment can be improved.

As a dispersing agent, a well-known pigment dispersing agent and surfactant can be selected suitably, for example.

Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer polyflow Nos. 75, No. 90 , Cationic surfactants such as No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Corporation); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid Nonionic surfactants such as esters; Anionic surfactants such as W004, W005, and W017 (manufactured by Yusho Corporation); EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (all manufactured by Chiba Specialty Chemical Co., Ltd.), Disperse Ade 6, Disperse Ade 8, Disperse Ade 15, Polymer dispersing agents such as Disperse Aid 9100 (all of which are manufactured by Sanofoko Corp.); Various Solsper dispersants (manufactured by Nihon Lubrizol Co., Ltd.) such as Solsper's 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; Adekaplanic 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 iso Net S-20 (product made in Sanyo-Kase 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 (made by Big Chemie Co., Ltd.) is mentioned. In addition, the oligomer or polymer which has a polar group in a molecular terminal or a side chain, such as an acryl-type copolymer, is mentioned.

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

Pigment Derivatives

Pigment derivative is added to the pigment dispersion composition of this invention as needed. By adsorbing a pigment derivative having affinity to the dispersant or a polar group introduced thereon onto the surface of the pigment and using this as the adsorption point of the dispersant, the pigment can be dispersed into the colored curable resin composition as fine particles to prevent its reagglomeration. It is effective in forming a color filter having high contrast and excellent transparency.

The pigment derivative is a compound in which an organic pigment is used as a mother skeleton, and an acidic group, a basic group, and an aromatic group are introduced into the side chain as a substituent. The organic pigments specifically include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindolin type pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments and benzoimidazolones. Pigments; and the like. Generally, pale yellow aromatic polycyclic compounds, such as naphthalene system, anthraquinone system, triazine system, and quinoline system, which are not called dyes, are also included. As a pigment derivative, Unexamined-Japanese-Patent No. 11-49974, Unexamined-Japanese-Patent No. 11-189732, Unexamined-Japanese-Patent No. 10-245501, Unexamined-Japanese-Patent No. 2006-265528, Unexamined-Japanese-Patent No. 8-295810 What is described in Unexamined-Japanese-Patent No. 11-199796, Unexamined-Japanese-Patent No. 2005-234478, Unexamined-Japanese-Patent No. 2003-240938, Unexamined-Japanese-Patent No. 2001-356210, etc. can be used.

As content in the pigment dispersion composition of the pigment derivative which concerns 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, the dispersion can be satisfactorily carried out while the viscosity is kept low, and the dispersion stability after dispersion can be improved, and excellent color characteristics are obtained with high transmittance, and thus have good color characteristics when producing a color filter. It can be configured with high contrast.

Method of dispersion

The dispersion method is, for example, a microdispersion using, for example, a bead disperser (eg, a dispermat made by GETZMANN) using zirconium oxide beads or the like, in which a pigment and a dispersant are mixed in advance and dispersed in a homogenizer or the like. This can be done by doing so. As dispersion time, about 3 to 6 hours are suitable.

(b) solvent

The pigment dispersion composition and colored curable composition of this invention can be prepared generally using a solvent with the said component.

Examples of the solvent 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, and lactic acid Methyl, ethyl lactate, methyl oxyacetic acid, ethyl oxyacetic acid, butyl oxyacetic acid, methyl methoxyacetate, methoxyacetic acid ethyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, 3-oxypropionate methyl, 3- 3-oxypropionic acid alkyl esters, such as ethyl oxypropionate; Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate , 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetic acid, methyl 2-oxobutanoate, 2-oxo Ethyl butane and the like; Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 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 and the like; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; 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, and 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 type other than using independently.

(c) polymerizable monomer and binder resin

The polymerizable monomer and binder resin in the present invention are described below. In addition, in this invention, a polymeric monomer and a photopolymerizable compound are synonymous, and binder resin and alkali-soluble resin are synonymous.

Photopolymerizable Compound

As a photopolymerizable compound, the compound which has at least 1 addition-polymerizable ethylenically unsaturated group, and whose boiling point is 100 degreeC or more at normal pressure is preferable, and the tetrafunctional or more than 4 functional acrylate compound is especially preferable.

As a compound which has the said at least 1 addition-polymerizable ethylenically unsaturated group and whose boiling point is 100 degreeC or more at normal pressure, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) Monofunctional acrylates and methacrylates such as acrylate; Polyethylene glycol di (meth) acrylate, trimethol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimetholethane, etc. (Meth) acrylated after addition of ethylene oxide or propylene oxide to polyfunctional alcohols; poly (meth) acrylated of pentaerythritol or dipentaerythritol, Japanese Patent Publication No. 48-41708, Japan Urethane acrylates described in Japanese Patent Application Publication No. 50-6034, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 48-64183, and Japanese Patent Publication Polyfunctional acrylates and methacrylates, such as the polyester acrylates of 49-43191 and Unexamined-Japanese-Patent No. 52-30490, and epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid, are mentioned. have.

Moreover, the thing introduce | transduced as a photocurable monomer and oligomer can also be used by Japanese adhesive association Vol.20, N. 7, pp. 300-308.

Further, (meth) acrylated is added after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in Japanese Patent Application Laid-open No. Hei 10-62986 together with the specific examples as general formulas (1) and (2). Compounds can also be used.

Especially, the structure in which dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and these acryloyl groups via ethylene glycol and a propylene glycol residue are preferable. These oligomer types can also be used.

Also, the urethane acrylates described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. Hei 2-16765, and Japanese Patent Publication No. 58 Also suitable are urethane compounds having an ethylene oxide-based skeleton described in -49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. Furthermore, by using addition polymerizable compounds having an amino structure or sulfide structure in the molecules described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-open No. Hei 1-105238, The photopolymerizable composition which is very excellent in speed can be obtained. As a commercial item, urethane oligomer UAS-10, UAB-140 (made by San-Yogoku Saku Pulp Co., Ltd.), UA-7200 (made by Shin-Nakamura Kagaku Co., Ltd.), DPHA-40H (made by Nihon Kayaku Co., Ltd.), UA-306H, UA-306T, UA- 306I, AH-600, T-600, AI-600 (made by Kyoe company), etc. are mentioned.

Moreover, ethylenically unsaturated compounds which have an acid group are also suitable, As a commercial item, TO-756 which is a carboxyl group-containing trifunctional acrylate made by Toagosei Co., Ltd., and TO-1382 which is a carboxyl group-containing 5-functional acrylate, for example. Etc. can be mentioned.

A photopolymerizable compound can be used in combination of 2 or more type other than using individually by 1 type.

As content in the colored curable resin composition of a photopolymerizable compound, 20-200 parts are preferable with respect to 100 parts of total solids of the said composition, More preferably, it is 50-120 parts. If content of a photopolymerizable compound exists in the said range, hardening reaction can fully be performed.

Alkali-soluble resin

As alkali-soluble resin, it is a linear organic polymer polymer, group which promotes at least 1 alkali solubility (for example, carboxyl group, phosphoric acid group, sulfonic acid group etc.) in a molecule | numerator (preferably an acryl-type copolymer, the molecule which has a styrene-type copolymer as a main chain). It can select suitably from alkali-soluble resin which has). Among these, More preferably, it can develop with a weak alkali aqueous solution soluble in an organic solvent.

For the production of alkali-soluble resin, for example, a method by a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, and the like when preparing alkali-soluble resin by the radical polymerization method can be easily set by those skilled in the art, and conditions can be determined experimentally. .

As said linear organic polymer, the polymer which has a carboxylic acid in a side chain is preferable. For example, Japanese Patent Publication No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 59-53836, and Japanese Patent Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, etc. described in each publication of Japanese Patent Application Laid-Open No. 59-71048 Acidic anhydride is added to the acidic cellulose derivative which has an acid, the polymer which has a hydroxyl group, etc., and the high molecular polymer which has a (meth) acryloyl group in a side chain is mentioned as a preferable thing.

Among these, a multipart copolymer consisting of benzyl (meth) acrylate / (meth) acrylic acid copolymer and benzyl (meth) acrylate / (meth) acrylic acid / other monomers is particularly suitable.

In addition, what copolymerized 2-hydroxyethyl methacrylate etc. can also be mentioned as useful. The said polymer can be mixed and used in arbitrary quantity.

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

About the specific structural unit of alkali-soluble resin, the copolymer of (meth) acrylic acid and another monomer copolymerizable with this is suitable especially. Here, (meth) acrylic acid is a general term which combined acrylic acid and methacrylic acid, and (meth) acrylate is also a general term of acrylate and methacrylate similarly below.

As another monomer copolymerizable with the said (meth) acrylic acid, an alkyl (meth) acrylate, an aryl (meth) acrylate, a vinyl compound, etc. are mentioned. Here, the hydrogen atom of an alkyl group and an aryl group may be substituted by the 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, and isobutyl (meth). Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) Acrylate, cyclohexyl (meth) acrylate, etc. are mentioned.

Moreover, as said vinyl compound, styrene, (alpha) -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene, for example Macromonomer, polymethylmethacrylate macromonomer, 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, R <^32> represents a C6-C10 aromatic hydrocarbon ring, R <^33> represents a C1-C8 alkyl group or a C6-C12 aralkyl group.], Etc. are mentioned.

These copolymerizable other monomers can be used individually by 1 type or in combination of 2 or more types. Preferred copolymerizable other monomers are at least one selected from CH ₂ = CR ³¹ R ³² , CH ₂ = C (R ³¹ ) (COOR ³³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene, Especially preferred are CH ₂ = CR ³¹ R ³² and / or CH ₂ = C (R ³¹ ) (COOR ³³ ).

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

(d) photopolymerization initiator

As a photoinitiator, halomethyl-sadiazole described in Unexamined-Japanese-Patent No. 57-6096, Unexamined-Japanese-Patent No. 59-1281, Unexamined-Japanese-Patent No. 53-133428, etc. are mentioned, for example. Active halogen compounds such as triazine, aromatic carbonyl compounds such as ketal, acetal, or benzoin alkyl ethers described in the specifications of US Patent No. 4318791 and European Patent Application Publication No. 88050, and the benzos described in US Patent No. 4199420 Aromatic ketone compounds such as phenones, (thio) xanthones or acridine compounds described in French Patent Invention No. 2456741, compounds such as coumarins or ropin dimers described in JP-A-10-62986, Japan Sulfonium organoboron complexes, such as Unexamined-Japanese-Patent No. 8-015521, etc. are mentioned.

Examples of the photopolymerization initiator include acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, triazine series, halomethyloxadiazole series, acridine series, coumarin series, ropin dimer series, biimidazole series, An oxime ester system etc. are preferable.

As said acetophenone type photoinitiator, 2, 2- diethoxy acetophenone, p-dimethylamino acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylamino, for example Acetophenone, 4'-isopropyl-2-hydroxy-2-methyl- propiophenone, etc. are mentioned suitably.

As said ketal type photoinitiator, benzyl dimethyl ketal, benzyl- (beta)-methoxyethyl acetal, etc. are mentioned suitably, for example.

As said benzophenone type photoinitiator, For example, benzophenone, 4,4'- (bisdimethylamino) benzophenone, 4,4'- (bisdiethylamino) benzophenone, 4,4'- dichloro benzophenone, 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, etc. are mentioned suitably.

As said benzoin type or benzoyl type photoinitiator, benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl benzoate, etc. are mentioned suitably, for example.

As said xanthone type photoinitiator, diethyl thioxanthone, diisopropyl thioxanthone, monoisopropyl thioxanthone, chloro thioxanthone, etc. are mentioned suitably, for example.

As said triazine type photoinitiator, it is 2, 4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2, 4-bis (trichloromethyl) -6-p-meth, for example. Oxystyryl-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-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxy Carbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, etc. are mentioned suitably.

As said halomethyloxadiazole type photoinitiator, 2-trichloromethyl-5-styryl-1,3,4- oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1, 3,4-oxodiazole, 2-trichloromethyl-5- (naphtho-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) sty Reel-1,3,4-oxodiazole etc. are mentioned suitably.

As said acridine type photoinitiator, 9-phenyl acridine, 1, 7-bis (9-acridinyl) heptane, etc. are mentioned suitably, for example.

As said coumarin-type photoinitiator, it is 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino- ((s -Triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, etc. are mentioned suitably. .

As said lophine dimer type photoinitiator, it is 2- (o-chlorophenyl) -4,5-diphenyl imidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenyl imida, for example. Zolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenyl imidazolyl dimer, etc. are mentioned suitably.

As said biimidazole type photoinitiator, 2-mercapto benzimidazole, 2,2'- benzothiazolyl disulfide, etc. are mentioned suitably, for example.

In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6- Trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophosphoro-trialkylphenylphosphonium salt, and the like.

In this invention, it is not limited to the above photoinitiator, Another well-known thing can also be used. For example, the bisinalpolyketolaldonyl compounds described in US Pat. No. 2,367,660, the α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670, and the acyl inether described in US Pat. No. 2,448,828. , Aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, and triallylimidazole described in US Pat. No. 3,549,367. Combination of dimer / p-aminophenyl ketone, benzothiazole compound / trihalomethyl-s-triazine compound described in Japanese Patent Publication No. 51-48516, JCSPerkin II (1979) 1653-1660, JCS Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and the oxime ester compound of Unexamined-Japanese-Patent No. 2000-66385.

Moreover, these photoinitiators can also be used together.

As content in the colored curable resin composition of a photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of the said composition, More preferably, it is 0.5-5.0 mass%. If content of a photoinitiator is in the said range, a polymerization reaction will advance favorably and film formation with favorable intensity | strength is possible.

Other Ingredients

To the colored curable resin composition of the present invention, various additives such as a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, other fillers, polymer compounds other than the alkali-soluble resin, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-agglomerating agents, as necessary It can be contained.

Thermal polymerization initiator

It is also effective to contain a thermal polymerization initiator in the pigment dispersion composition of the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds, and examples of the azo compounds include bis azo compounds, and ketone peroxide, peroxy ketal, and hydroper as the peroxide compounds. Oxide, dialkyl peroxide, diacyl peroxide, peroxy ester, peroxydicarbonate and the like.

Thermal polymerization component

It is also effective to contain a thermal-polymerization component in the pigment dispersion composition of this invention. If necessary, an epoxy compound can be added to improve the strength of the coating film. As an epoxy compound, it is a compound which has 2 or more epoxy rings in a molecule | numerator, such as a bisphenol A type, a cresol novolak type, a biphenyl type, and an alicyclic epoxy compound. For example, as bisphenol A type, Efototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 These include in addition to (from Totokase Co., Ltd.), Denacol EX-1101, EX-1102, and EX-1103 (from Nagase Kaze Co., Ltd.), Fraxel GL-61, GL-62, G101, G102 (above Daiselkagaku). Similar bisphenol F type and bisphenol S type are also mentioned. In addition, epoxy acrylates, such as Ebecryl 3700, 3701, and 600 (above-DICEL), can also be used. As the cresol novolac type, Efototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above tocecase), Denacol EM-125, etc. (above Nagase casee), biphenyl As an alicyclic epoxy compound, such as 3,5,3 ', 5'- tetramethyl-4,4' diglycidyl biphenyl as a type, it is ceoxide 2021, 2081, 2083, 2085, epoxide GT-301, GT- 302, GT-401, GT-403, EHPE-3150 (above Daiselkagaku), Santoto ST-3000, ST-4000, ST-5080, ST-5100, etc. (above Totokase) etc. are mentioned. . In addition, 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o- Phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and other glycidyl esters in which dimer acid is modified in the skeleton of an amine epoxy resin, efototo YH-434, YH-434L, and a bisphenol A epoxy resin. Can be used.

Thermal polymerization inhibitor

It is preferable to further add a thermal polymerization inhibitor to the pigment dispersion composition of the present invention, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl Catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercapto Benzoimidazole and the like are useful.

Manufacturing method ... of ... color curable resin composition and color filter using this

The colored curable resin composition of this invention contains alkali-soluble resin, a photopolymerizable compound, and a photoinitiator (preferably with a solvent) in the pigment dispersion composition of this invention mentioned above, and additives, such as surfactant, as needed for this, The mixture can be prepared by going through a mixed dispersion step of mixing and dispersing the mixture using various mixers and dispersers.

In addition, although the mixing-dispersion process preferably consists of kneading dispersion and subsequent non-dispersion treatment, the kneading dispersion can be omitted.

An example of the manufacturing method of the colored curable resin composition of this invention is shown below.

The mixture of the pigment, the water-soluble organic solvent, and the water-soluble inorganic salt is mixed with a kneader such as two rolls, three rolls, a ball mill, a trommill, a disper, a kneader, a kneader, a homogenizer, a blender, a single screw or a twin screw extruder. After grinding a pigment while giving strong shearing force, this mixture is put into water, and it becomes a slurry form with an agitator etc. Subsequently, this slurry is filtered, washed with water, and after removing a water-soluble organic solvent and a water-soluble inorganic salt, it is dried and a micronized pigment is obtained.

Bead dispersion is performed with a pigment, a dispersing agent, and / or a pigment derivative and a solvent. Mainly or vertically using sand grinders, pin mills, slit mills, ultrasonic dispersers, and the like, and finely dispersed with beads formed of glass, zirconia, or the like having a particle diameter of 0.01 to 1 mm to obtain a pigment dispersion composition. In addition, the process which refine | miniaturizes a pigment can also be abbreviate | omitted.

Further details on kneading and dispersion are described in T.C. Patton's "Paint Flo® and Pigment Dispersion" (1964 John Johnley and Sons).

And the photocurable compound, a photoinitiator, alkali-soluble resin, etc. are added to the pigment dispersion composition obtained as mentioned above, and the coloring curable resin composition of this invention is obtained.

The colored curable resin composition of this invention is apply | coated to a board | substrate directly or through another layer by the apply | coating methods, such as rotational coating, slit coating, casting | coating, roll coating, and bar coating, and forms a photocurable coating film, and through a predetermined | prescribed mask pattern By exposing and developing and removing an unhardened part with a developing solution after exposure, the patterned film which consists of pixels of each color (3 or 4 colors) can be formed and it can be set as a color filter.

At this time, as radiation to be used, ultraviolet rays such as g-ray, h-ray, i-ray, and j-ray are particularly preferable. As for the color filter for liquid crystal display devices, exposure using mainly h line | wire and i line | wire is preferable with a proximity exposure machine and a mirror projection exposure machine.

In order to further improve the surface shape of the coating film, the surface tension ratio (10 m sec / 1000 m sec) of 10 m sec and 1000 m sec, measured by the maximum shell pressure method of the coating liquid of the colored curable resin composition, is 1.00 to 1.20. It is preferable, it is more preferable that it is 1.00-1.15, and it is still more preferable that it is 1.00-1.10. If surface tension ratio is the said range, the surface shape of a coating film can be improved more.

In addition, the measurement of the surface tension by the maximum pressure method is described in detail in "Chemical Handbook Revised 5th Edition" Chapter 8 Interfaces and Colloids, page 90, 8.2 Surface Tension and Wetting, and "ASTM D3825-90". The surface tension of a colored curable resin composition can also be measured with reference to the method described in such a publication. In addition, in order to measure surface tension continuously with time change, the surface tension meter, such as "MPT2" by LAUDA, can be used, for example.

The color filter of this invention is formed on board | substrates, such as glass, using the colored curable resin composition of this invention mentioned above, For example, the slit application | coating of the colored curable resin composition of this invention on a board | substrate directly or through another layer is carried out. After forming a coating film by this, this coating film is dried, pattern exposure is performed, and it can produce suitably by performing the image development process using a developing solution sequentially. Thereby, the color filter used for a liquid crystal display element or a solid-state image sensor can be manufactured with little difficulty in a process, high quality, and low cost.

Examples of the substrate include alkali-free glass, soda glass, pyrex (registered trademark) glass, quartz glass, and a transparent conductive film attached thereto, and photoelectric conversion element substrates used in solid-state imaging devices and the like. Examples thereof include silicon substrates and plastic substrates. On these substrates, a black matrix is usually formed to isolate each pixel, or a transparent resin layer is formed to promote adhesion or the like.

It is preferable that the plastic substrate has a gas barrier layer and / or a solvent-resistant layer on its surface. In addition to the colored curable resin composition of the present invention on a driving substrate (hereinafter referred to as a "TFT system liquid crystal drive substrate") on which a thin film transistor (TFT) of a thin film transistor (TFT) system color liquid crystal display device is disposed. A color filter can be prepared by forming a patterned film formed thereon. In the photomask used at that time, a pattern for forming a through hole or a U-shaped depression is formed in addition to the pattern for forming a pixel. As a board | substrate in a TFT system liquid crystal drive board | substrate, glass, silicon, a polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. are mentioned, for example. 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, vapor phase reaction, vacuum deposition, or the like as desired. For example, the board | substrate etc. which formed the passivation film, such as a silicon nitride film, on the surface of a TFT system liquid crystal drive substrate or the surface of the said drive substrate are mentioned.

Although it does not specifically limit as a method of apply | coating the colored curable resin composition of this invention to a board | substrate, The method of using slit nozzles, such as a slit-and-spin method and a spinless coating method (henceforth a slit nozzle coating method), is preferable. 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 coating substrate. For example, the fifth generation glass substrate (1100 mm x 1250 mm) is applied by the spinless coating method. In this case, the discharge amount of the colored curable resin composition from the slit nozzle is usually 500 to 2000 microliters / second, preferably 800 to 1500 microliters / second, and the coating speed is usually 50 to 300 mm / second, preferably 100-200 mm / sec. As solid content of colored curable resin composition, it is 10 to 20% normally, Preferably it is 13 to 18%. When forming the coating film by the colored curable resin composition of this invention on a board | substrate, as thickness (after prebaking process) of the said coating film, it is generally 0.3-5.0 micrometers, Preferably it is 0.5-4.0 micrometers, Most preferably, 0.8 ˜3.0 μm.

Usually, a prebaking process is performed after application | coating. If necessary, vacuum treatment may be performed before prebaking. The conditions of vacuum drying are the degree of vacuum normally 0.1-1.0 torr, Preferably it is about 0.2-0.5 torr.

Prebaking process is 50-140 degreeC using a hotplate, oven, etc., Preferably it is about 70-110 degreeC, and can be performed on 10-300 second conditions. You may use a high frequency process etc. together. The high frequency treatment can be used alone.

Since it forms by apply | coating to a surface, the interface of the said surface and an air interface exist in the opposite side. The fluorine atoms present in the fluoroaliphatic group-containing polymer contribute to the improvement of the planar shape, and therefore are preferably localized at the air interface. On the other hand, the air interface is set at 0 nm and ranges from 0 nm to 10 nm in the depth direction. The presence of fluorine atoms to some extent is also important for improving the planar shape. From this point of view, when the fluorine atom abundance ratio (ESCA: F / C) at the air interface is 100, the fluorine atom abundance (ESCA: F / C) at the position of 10 nm from the air interface is 2 to 10. desirable.

In the development treatment, the uncured portion after exposure is eluted to the developer to leave only the hardened powder. As image development temperature, it is 20-30 degreeC normally, and as image development time, it is 20 to 90 second.

As the developing solution, any one can be used as long as it dissolves the coating film of the photocurable colored curable resin composition in the uncured portion and does not dissolve the cured portion. Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used.

The above-mentioned solvent which can be used when preparing the pigment dispersion composition or colored curable resin composition of this invention is mentioned as said organic solvent.

As said alkaline aqueous solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium, for example. The concentration of the alkaline compounds such as hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001-10% by mass, preferably 0.01- The alkaline aqueous solution melt | dissolved so that it may become 1 mass% is mentioned. A suitable amount of water-soluble organic solvents, such as methanol and ethanol, surfactant, etc. can also be added to alkaline aqueous solution.

The developing method may be a dip method, a shower method, a spray method, or the like, and a swing method, a spin method, an ultrasonic method, or the like may be combined therewith. Before the contact with the developer, the surface to be developed may be wetted with water or the like beforehand to prevent development deviation. Further, the substrate may be inclined and developed.

After the development treatment, a rinse step of washing and removing the excess developer is carried out, followed by heat treatment (post-baking) in order to complete curing after drying.

The rinse step is usually performed with pure water, but in order to save the developer, pure water may be used in the final cleaning, and the pure water used at first may be used, the substrate may be inclined to be washed, or ultrasonic irradiation may be used in combination.

After rinsing, water is removed, and after drying, heat treatment is usually performed at about 200 ° C to 250 ° C. This heat treatment (post-baking) can be carried out continuously or collectively using heating means such as a hot plate, a convection oven (hot air circulation dryer), a high frequency heater, or the like so that the coating film after development becomes the above conditions.

By repeating the above operation sequentially for each color in accordance with the desired number of colors, it is possible to produce a color filter in which a cured film in which a plurality of colors are colored is formed.

Although the use of the pigment dispersion composition and colored curable resin composition of this invention was demonstrated mainly centering on the use to a color filter, it is applicable also to formation of the black matrix which isolate | separates each colored pixel which comprises a color filter.

The said black matrix can be formed by exposing and developing the pigment dispersion composition of this invention using black pigments, such as carbon black and titanium black, as a pigment, and then post-baking further as needed, and promoting hardening of a film | membrane.

Example

An Example is given to the following and this invention is demonstrated to it further more concretely. Materials, reagents, amounts of substances, proportions thereof, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. In addition, in the following, all parts and% shall be a mass reference | standard unless there is particular notice.

The physical property determination method of benzyl methacrylate / methacrylate and benzyl methacrylate / methacrylic acid in the following resin is as showing below.

(Weight average molecular weight and number average molecular weight)

It carried out by polystyrene (PST) conversion by GPC (gel permeation chromatography) measurement of the following conditions.

Column: TSKgel MultiporeHXL-M (porous polydisperse linear column)

Eluent: THF

Flow rate: 1.0ml / min

Temperature: 40 ℃

Detection condition: RI

System: High speed GPC device (Toso HLC-8220)

(Example 1)

200 parts of green pigment C.I.Pigment Green 36, 1600 parts of sodium chloride, and 360 parts of diethylene glycol were put into a 1-gallon kneader made by stainless (manufactured by Inouese Corporation) and kneaded at 50 ° C for 8 hours. Next, the kneaded product was 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, followed by drying at 60 ° C. for 1 day to 190 parts. A green pigment was obtained.

Subsequently, 200 parts of yellow pigment C.I.Pigment Yellow 138, 2000 parts of sodium chloride, and 360 parts of diethylene glycol were put in a stainless first gellan kneader (manufactured by Inouese Corporation) and kneaded at 50 ° C for 8 hours. Next, the kneaded product was 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, followed by drying at 60 ° C. for 1 day to 190 parts. A yellow pigment was obtained.

The mixture was stirred and mixed at a rotational speed of 3,000 r.p.m. for 3 hours using a homogenizer with the following composition to prepare a mixed solution.

〔Furtherance〕

Pigment Green 36 (average primary particle diameter 25 nm)... Part 66

Pigment Yellow 138 (average primary particle diameter 25 nm)... Part 68

Phthalocyanine derivative (manufactured by Solsperth 5000 Nippon Lubrizol Corporation). Part 10

Benzyl methacrylate / methyl methacrylate (= 70/30 [molar ratio]) copolymer

        (Weight average molecular weight: 30,000) Part 32

Dispersant (BYK-161, manufactured by BYK). Part 10

Propylene glycol monomethyl ether acetate... 720 copies

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 mm phi zirconia beads.

The component of the following composition was further added to the obtained pigment dispersion liquid, and it stirred and mixed, and prepared the colored curable resin composition (color resist liquid) of this invention.

〔Furtherance〕

· Dipentaerythritol penta / hexaacrylate... Part 72

Photoinitiator A: 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime)... Part 4.5

Photoinitiator B: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1

                                                 … Part 15

Photoinitiator C: diethyl thioxanthone... Part 4.5

Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 30,000). Part 172

Propylene glycol monomethyl ether acetate... 106 copies

Epoxy Resin: (trade name EHPE3150 Daisel Kagaku). Part 11

Example polymer P-17 (MW = 15000). Part 1.8

(1st fluoro aliphatic group containing polymer of general formula (1))

3-ethoxyethyl propionate. Part 814

(Examples 2-10)

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 thereof was changed in the same manner as in Example 1 except that Colored curable resin composition (color resist liquid) was prepared.

(Comparative Example 1)

In Example 1, as shown in Table 2 below, the fluoroaliphatic group-containing polymer (P-17) was changed to various polymers, and the same amount as that of Example 1 was changed except that the amount of addition was changed. Curable resin composition (color resist liquid) was prepared.

(Manufacturing, measuring and evaluating measuring boards)

-One. Evaluation of radiation stripe and pinhole (whitening)

About each of the colored curable resin composition (color resist liquid) prepared in each Example and each comparative example, it spin-coated at the rotation speed of 740-850 rpm on the glass substrate (1737, a Corning company) of 550 mm x 650 mm, and was 1.3 micrometers. The coating film of the film thickness was obtained.

The surface shape of the coating film was observed by visual observation and optical microscope, and the radiation stripe and pinhole (whitening) were evaluated.

Radiation stripe

   1 no radiation stripe

   2 slightly at the end

   3 little at the end

   4 at end and center

Pinhole (White)

   1 not observed at all

   2 slightly observed but permissible

   4 Observed and out of tolerance

The practical ranges here are all 1 to 3.

-2. Production-of colored filter board

The y-values of the photocurable compositions (color resist liquids) prepared in the examples and the comparative examples were sequentially indexed for the color concentration on another 100 mm x 100 mm glass substrate 1735 (manufactured by Corning). It was applied as possible and dried in an oven at 90 ° C. for 60 seconds (prebaking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm 2 (roughness 20 mW / cm 2), and the exposed coating film was covered with a 1% aqueous solution of alkaline developer CDK-1 (manufactured by FUJIFILM Materials), for 60 seconds. It stopped. After stopping, pure water was spread out in the shower to wash off the developer. Then, the coating film subjected to the photocuring treatment and the developing treatment as described above is heat treated in an oven at 220 ° C. for 1 hour (post-baking), and a colored resin film for color filter composition is formed on the glass substrate to form a colored filter substrate (color Filter).

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

As shown in Table 2, the colored curable resin composition using the fluoroaliphatic group-containing polymer represented by the general formula (1) has no spinning stripe at the time of its application and has a good surface shape and a pinhole (whitening) It was found that an excellent color filter can be produced by forming a good coating film without a film.

Claims (13)

at least one selected from the group containing (a) a colorant, (b) a solvent, (c) a polymerizable monomer and a binder resin, (d) a photoinitiator, and (f) a fluorine represented by the following general formula (1): Color curable resin composition characterized by containing 1 or more types chosen from the aliphatic group containing polymer.

In general formula (1), i and j represent the integer of 1 or more, respectively, and it means that each repeating unit contains i and j types, respectively; M is a repeating unit derived from an ethylenically unsaturated monomer and containing k (k is an integer of 1 or more); a, b and c are the mass percentages indicating the polymerization ratio, ∑ai represents the numerical value of 1 to 98 mass%, ∑bj represents the numerical value of 1 to 98 mass%, and ∑ck is the numerical value of 1 to 98 mass% Represents; 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 an alkyl group having 1 to 4 carbon atoms; m1 and m2 represent the integer of 1-6, respectively, and n1 represents the integer of 0-3. The colored curable resin composition according to claim 1, wherein in Formula (1), X ¹ and X ² are each O. The colored curable resin composition according to claim 1, wherein m1 and m2 in the general formula (1) are 1 to 4, respectively. The colored curable resin composition according to claim 1, wherein ∑ai / (∑ai + ∑bj) is 0.2 to 0.8. The colored curable resin composition according to claim 1, wherein Σai + ∑bj is 20 to 50 mass%. The colored curable resin composition according to claim 1, wherein n1 in General Formula (1) is zero. The colored curable resin composition according to claim 1, wherein the content of the fluoroaliphatic group-containing polymer is 0.01 to 20% by mass of the solid content in the composition. The product (C x F) of the concentration (C) mass% of the fluoroaliphatic group-containing polymer and the fluorine content (F)% in the fluoroaliphatic group-containing polymer is 0.05 to 0.12. Colored curable resin composition to be used. The colored curable resin composition according to claim 1, wherein the color material contains a green pigment. It is formed with the composition of any one of Claims 1-9, The coloring pattern characterized by the above-mentioned. A method of producing a color filter, comprising the step of forming a colored pattern by applying the colored curable resin composition according to any one of claims 1 to 9 by a spin coating method or a slit and spin method. It is manufactured by the manufacturing method of Claim 11, The color filter characterized by the above-mentioned. The color filter of Claim 12 was used, The liquid crystal display element characterized by the above-mentioned.