JP2010084021A - Resin, method for producing the resin, pigment dispersion, colored curable composition, method for preparing the colored curable composition, color filter and method for producing the color filter - Google Patents

Abstract

【選択図】なしDisclosed is a novel resin useful as a dispersant for fine pigments, a method for producing the same, and a pigment dispersion containing the resin and excellent in dispersibility and dispersion stability of fine pigments. In addition, it contains the above resin and is excellent in dispersibility and dispersion stability of fine pigments, as well as excellent in coating properties and developability, and can form a colored cured film with good color characteristics such as contrast and color unevenness. Providing a sex composition.
(A) a compound represented by the following general formula (I); (b-1) at least one compound selected from a lactone and a hydroxyl group-containing carboxylic acid; or (b-2) a polyester; , A resin represented by the following general formula (II) (in the general formulas (I) and (II), V represents an organic group containing a group having a pKa of less than 4, and W represents a nucleophilic property. A group, W ′ represents a residue of W, and n represents an integer of 1 or more), a pigment dispersion containing this resin, and a colored curable composition.

[Selection figure] None

Description

  The present invention is used for a novel resin useful as a pigment dispersant, a method for producing the resin, a pigment dispersion containing the resin, a liquid crystal display device (LCD), a solid-state imaging device (CCD, CMOS, etc.), and the like. The present invention relates to a colored curable composition suitable for producing a color filter, a color filter having a colored region formed by the colored curable composition, and a method for producing the same.

  The color filter is an essential component for liquid crystal displays and solid-state image sensors. The color filter is usually produced by a photolithography method using a curable composition containing a colorant (pigment or dye). When the colorant is a pigment, it is necessary to use the dispersant in order to ensure the dispersibility and dispersion stability of the pigment.

By the way, in recent years, liquid crystal displays are required to have higher image quality and improved contrast and color purity compared to conventional TV and monitor applications. Regarding curable compositions for color filter production, attempts have been made to improve contrast by using finer particle sizes of pigments to be used (see, for example, Patent Document 1).
In addition, in color filters for solid-state imaging devices, it is necessary to reduce color unevenness in order to achieve high resolution. For this reason, secondary aggregates can be formed using fine pigments having a small particle size. It is important to disperse it in the absence.

  However, when the particle size of the pigment is made finer, the specific surface area of the pigment increases, the stability of the dispersion state deteriorates, and it is difficult to achieve both contrast or color unevenness and dispersion stability. If a large amount of a dispersant is used to improve dispersion stability, problems such as inability to form a pattern by a photolithographic method, insufficient curability, and deterioration of substrate adhesion occur.

In order to overcome these problems, various dispersing agents have been proposed, but still insufficient.
For example, Patent Documents 2 to 4 have developed a dispersant containing a phosphate group at the end of a polymer. However, in the method for producing a dispersant disclosed in Patent Documents 2 to 4, it is difficult to completely convert the terminal hydroxyl group, and in order to completely convert, the phosphate esterifying agent is excessively used. Unreacted reactant remains in the resin. When these resins are used as a dispersant, there has been a problem that developability and dispersion stability deteriorate.

In recent years, particularly in color filters for liquid crystal display elements, improvement in color purity is required, and for this reason, it is necessary to increase the filling amount of the pigment in the colored layer. In addition, in color filters for solid-state image sensors, it is necessary to reduce stray light due to scattering as one of the means for improving the resolving power. For this reason, there is a strong demand for thin colored layers. In the production of the color filter, it is necessary to increase the filling amount of the pigment in the colored layer.
In order to increase the filling amount of the pigment, it is necessary to increase the pigment concentration in the curable composition. However, when the pigment concentration is increased, the content of the dispersion resin and curable components (monomer, polymerization initiator, etc.) in the curable composition is inevitably lowered, so that the developability and dispersion stability are deteriorated. There was a problem of poor formability.
JP 2006-30541 A JP 2007-231107 A Special table 2003-533455 gazette US Pat. No. 5,151,218

Accordingly, a first object of the present invention is to provide a novel resin useful as a fine pigment dispersant and a method for producing the same, and a pigment containing the resin and having excellent dispersibility and dispersion stability of the fine pigment. It is to provide a dispersion.
In addition, the second object of the present invention contains the above resin, and is excellent in the dispersibility and dispersion stability of fine pigments, is excellent in coating properties and developability, and has good color characteristics such as contrast and color unevenness. The object is to provide a colored curable composition capable of forming a colored cured film.
A third object of the present invention is to provide a color filter having a color pattern with good color characteristics such as contrast and color unevenness, formed using the above colored curable composition, and a method for producing the same. .

In view of the above circumstances, the present inventors conducted extensive research and found that by using a novel resin having a specific structure, the dispersibility of fine pigments in a pigment dispersion containing the same and a colored curable composition・ We found that dispersion stability improved unexpectedly. Furthermore, this invention was completed by using the color filter created with the colored curable composition containing resin of this invention.
That is, the object of the present invention is achieved by the following means.

  The novel resin of the present invention comprises (a) a compound represented by the following general formula (I), (b-1) at least one compound selected from lactones and hydroxyl group-containing carboxylic acids, or (b- 2) A resin represented by the following general formula (II) obtained by reacting polyester.

  In the general formula (I), V represents an organic group containing a group having a pKa of less than 4. W represents a nucleophilic group. n represents an integer of 1 or more.

  In the general formula (II), V has the same meaning as V in the general formula (I). W 'represents a residue of W in the general formula (I). Y represents a polyester chain. n is synonymous with n in the general formula (I).

  In the novel resin of the present invention, the group having a pKa of less than 4 contained in V in the general formula (I) is preferably a phosphate group or a sulfonate group.

  Moreover, the method for producing the resin of the present invention comprises (a) at least one compound selected from (a) a compound represented by the general formula (I) and (b-1) a lactone and a hydroxyl group-containing carboxylic acid, or (B-2) A method for producing a resin represented by the general formula (II) in which polyester is reacted.

The pigment dispersion of the present invention is characterized by containing (A) the novel resin of the present invention, (B) a pigment, and (C) a solvent.
The colored curable composition of the present invention comprises (A) the novel resin of the present invention, (B) a pigment, (C) a solvent, (D) a photopolymerization initiator, and (E) an ethylenically unsaturated double. It contains a compound containing a bond. In particular, (D) the photopolymerization initiator is preferably an oxime initiator.
Further, the method for preparing the colored curable composition of the present invention comprises (A) a photopolymerization initiator in a pigment dispersion containing (A) the novel resin of the present invention, (B) a pigment, and (C) a solvent. And (E) a compound containing an ethylenically unsaturated double bond is added.

The color filter of the present invention is characterized by having a colored pattern formed using the colored curable composition of the present invention on a support. Among these, this color filter is preferably used for color separation.
The method for producing a color filter of the present invention comprises a colored layer forming step of forming the colored layer by applying the colored curable composition of the present invention on a support, and the colored layer is patterned through a mask. It includes an exposure step of exposing and a developing step of developing a colored layer after exposure to form a colored pattern.

According to the present invention, a novel resin useful as a dispersant for fine pigments and a method for producing the same, and a pigment dispersion containing the resin and excellent in dispersibility and dispersion stability of fine pigments are provided. be able to.
In addition, according to the present invention, a colored cured film containing the above resin, excellent in dispersibility and dispersion stability of fine pigments, excellent in coatability and developability, and excellent in color characteristics such as contrast and color unevenness. The coloring curable composition which can form can be provided.
According to the third aspect of the present invention, it is possible to provide a color filter having a color pattern with good color characteristics such as contrast and color unevenness formed using the above colored curable composition, and a method for producing the same. .

Hereinafter, the best mode for carrying out the invention will be described in detail.
The colored region in the present invention includes a colored pixel (colored pattern) region and a light shielding film forming region in the color filter. Moreover, in the notation of group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted means that what has a substituent is included with the thing which does not have a substituent. For example, the expression “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

[New resin (resin represented by formula (II)) and its production method]
The novel resin of the present invention includes (a) a compound represented by the general formula (I), (b-1) at least one compound selected from a lactone and a hydroxyl group-containing carboxylic acid, or (b-2). ) A resin represented by the general formula (II) obtained by reacting polyester.
In addition, the method for producing the novel resin (resin represented by the general formula (II)) of the present invention includes (a) a compound represented by the general formula (I), (b-1) a lactone and a hydroxyl group-containing carboxyl. It is characterized by reacting at least one compound selected from acids or (b-2) polyester.
Hereinafter, the novel resin of the present invention (resin represented by the general formula (II)) will be described in detail together with its production method.

<(A) Compound represented by formula (I)>
First, the compound represented by the following general formula (I) used for obtaining the resin represented by the general formula (II) of the present invention will be described.

In the general formula (I), V represents an organic group containing a group having a pKa of less than 4.
“PKa” as used herein is pKa measured at 25 ° C. in water and has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.) It is.
The “functional group whose pKa is less than 4” is not particularly limited as long as its physical properties satisfy this condition, and examples thereof include known functional groups whose pKa satisfies the above range. Specifically, phosphoric acid groups (pKa: about 1 to 3), sulfonic acid groups (pKa: about −3 to −2), and fluoroalkylcarboxylic acids (pKa: about 1 to 2) are mentioned. -From the viewpoint of developability, a phosphoric acid group (pKa: about 1 to 3) and a sulfonic acid group (pKa: about -3 to -2) are most preferable.

  In the general formula (I), the “organic group” in V is a functional group having a carbon atom as a main constituent, and specifically includes an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group. Group, an alkynyl group, an aryl group, or a heterocyclic group may be mentioned, and an alkyl group, a cycloalkyl group, an alkenyl group, or a cycloalkenyl group is particularly preferable, and an alkyl group is most preferable.

Further, the “organic group” in V may be substituted with a functional group other than “a functional group having a pKa of less than 4”.
Examples of the substituent that V may have include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably carbon An alkyl group of 1 to 30, for example, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group ), A cycloalkyl group [preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as a cyclohexyl group or a cyclopentyl group, and a cycloalkyl group having a polycyclic structure, such as a bicycloalkyl group. (Preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms such as bicyclo [1,2,2] heptane-2. Yl group, a bicyclo [2,2,2] octan-3-yl group) or tricycloalkyl group, and the like. Among these, a monocyclic cycloalkyl group and a bicycloalkyl group are preferable, and a monocyclic cycloalkyl group is particularly preferable. ],

An alkenyl group (a linear or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl Group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, such as 2-cyclopenten-1-yl group and 2-cyclohexen-1-yl group; A cycloalkenyl group such as a bicycloalkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms such as a bicyclo [2,2,1] hept-2-en-1-yl group, Bicyclo [2,2,2] oct-2-en-4-yl group) and tricycloalkenyl groups, and monocyclic cycloalkenyl groups are particularly preferred. There.) Alkynyl group (preferably, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl group, propargyl group, trimethylsilyl ethynyl group),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl group, p-tolyl group, naphthyl group, m-chlorophenyl group, o-hexadecanoylaminophenyl group), heterocyclic ring Group (preferably a substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed 5- to 7-membered heterocyclic group, more preferably a ring atom is a carbon atom, A heterocyclic group selected from a nitrogen atom and a sulfur atom and having at least one hetero atom of any one of a nitrogen atom, an oxygen atom and a sulfur atom, particularly preferably a 2-furyl group, 2- A thienyl group, a 2-pyridyl group, a 4-pyridyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group), a cyano group, a carboxyl group,

Alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy group, ethoxy group, isopropoxy group, t-butoxy group, n-octyloxy group, 2-methoxyethoxy group) An aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms such as phenoxy group, 2-methylphenoxy group, 2,4-di-t-amylphenoxy group, 4-t -Butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group),

An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as a formyloxy group, An acetyloxy group, a pivaloyloxy group, a stearoyloxy group, a benzoyloxy group, a p-methoxyphenylcarbonyloxy group), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N , N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group), alkoxycarbonyloxy group (Preferably A substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, an n-octylcarbonyloxy group), an aryloxycarbonyloxy group (preferably Is a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group),

An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group or an n-hexadecylthio group), an arylthio group (preferably a substituted or unsubstituted group having 6 to 30 carbon atoms); A substituted arylthio group, for example, a phenylthio group, a p-chlorophenylthio group, an m-methoxyphenylthio group, a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, The heterocyclic moiety is preferably the heterocyclic moiety described above for the heterocyclic group, for example, 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group), acyl group (preferably formyl group, carbon A substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms For example, an acetyl group, a pivaloyl group, a 2-chloroacetyl group, a stearoyl group, a benzoyl group, a pn-octyloxyphenylcarbonyl group), an aryloxycarbonyl group (preferably a C7-30 substituent). Or an unsubstituted aryloxycarbonyl group, for example, a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group, a pt-butylphenoxycarbonyl group),

An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, n-octadecyloxycarbonyl group), carbamoyl group (preferably Is a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methyl Sulfonyl) carbamoyl group) and the like.
Among the above functional groups, those having a hydrogen atom may be substituted with any of the above groups after removing this.

  The molecular weight of the organic group containing a group having a pKa of less than 4 represented by V is 100 to 2,000, preferably 100 to 1,000, and most preferably 100 to 500. Within this range, the pigment dispersion stability deteriorates.

Preferable examples of the organic group containing a group having a pKa of less than 4 represented by V include —R ^a —PO ₃ H ₂ , —R ^a —PO ₂ H ₂ , —R ^a —SO ₃ H, or — R ^a -CF ₂ CO ₂ H and the like. Here, R ^a represents an alkylene group, a cycloalkylene group, or an arylene group, respectively.

W in the general formula (I) represents a nucleophilic group.
The nucleophilic group represented by W means a group that can undergo a condensation reaction with an ester or a carboxylic acid, and specifically includes a hydroxyl group, an amino group, a mercapto group, etc., but a hydroxyl group or an amino group And an amino group is most preferred. The “amino group” here means a primary or secondary amino group.
The reason why the amino group is most preferable is that when W is an amino group, an amide group having basicity is introduced into the resin represented by the general formula (II), so that the adsorptive power with the pigment is increased and the pigment dispersion is further increased. This is due to the improvement in performance.

  N in the general formula (I) represents an integer of 1 or more, but 1 to 10 is preferable and 1 to 5 is most preferable from the viewpoint of raw material availability and dispersion stability.

  Although the specific example of a compound represented by general formula (I) below is shown, this invention is not limited to this.

<(B-1) Lactone and hydroxyl group-containing carboxylic acid>
Next, the lactone and hydroxyl group-containing carboxylic acid used for obtaining the resin represented by the general formula (II) of the present invention will be described.
As the lactone, known ones can be used without limitation. For example, β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-hexanolactone, γ-octanolactone, δ-valerolactone, δ -Hexalanolactone, δ-octanolactone, ε-caprolactone, δ-dodecanolactone, α-methyl-γ-butyrolactone and the like.

  Further, as the hydroxyl group-containing carboxylic acid, known compounds can be used without limitation as long as they have a hydroxyl group and a carboxyl group in the molecule, for example, glycolic acid, lactic acid, 3-hydroxypropionic acid. 4-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, ricinoleic acid, 12-hydroxydodecanoic acid, 12-hydroxystearic acid, 2,2-bis (hydroxymethyl) butyric acid and the like.

  Among the lactones and hydroxyl group-containing carboxylic acids described above, a lactone having 6 to 30 carbon atoms or a hydroxyl group-containing carboxylic acid is particularly preferable, and γ-hexanolactone is most preferable from the viewpoint of dispersion stability.

  The above-mentioned lactone and hydroxyl group-containing carboxylic acid may be used alone or in combination of two or more.

<(B-2) Polyester>
Here, the polyester used for obtaining the resin represented by the general formula (II) of the present invention will be described.
The polyester in the present invention includes (1) polycondensation of carboxylic acid and lactone, (2) polycondensation of hydroxy group-containing carboxylic acid, and (3) dihydric alcohol and divalent carboxylic acid (or cyclic acid anhydride). Polyester synthesized by a known method such as polycondensation can be used.
Hereinafter, the methods (1) to (3) will be described.

(1) As the carboxylic acid used for the polycondensation reaction between the carboxylic acid and the lactone, an aliphatic carboxylic acid (a linear or branched carboxylic acid having 1 to 30 carbon atoms is preferable. For example, formic acid, acetic acid, propionic acid, butyric acid, Valeric acid, n-hexanoic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, palmitic acid, 2-ethylhexanoic acid, cyclohexane acid, etc.), hydroxy group-containing carboxylic acid (C1-C30 direct) A chain or branched hydroxy group-containing carboxylic acid is preferable, for example, glycolic acid, lactic acid, 3-hydroxypropionic acid, 4-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, ricinoleic acid, 12-hydroxydodecanoic acid, 12-hydroxystearic acid. Acid, 2,2-bis (hydroxymethyl) butyric acid, etc.), in particular, straight chain fat having 6 to 20 carbon atoms. Carboxylic acid, or a hydroxy group-containing carboxylic acids having 1-20 carbon atoms preferred.
These carboxylic acids may be used as a mixture.

Moreover, (1) As lactone used for the polycondensation reaction of carboxylic acid and lactone, known lactones can be used, for example, β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-hexanolactone, γ-octanolactone, δ-valerolactone, δ-hexalanolactone, δ-octanolactone, ε-caprolactone, δ-dodecanolactone, α-methyl-γ-butyrolactone, etc. -Caprolactone is preferred from the viewpoint of reactivity and availability.
These lactones may be used as a mixture of plural kinds.

  (1) In the polycondensation reaction of carboxylic acid and lactone, the charging ratio (molar ratio) at the time of reaction between carboxylic acid and lactone cannot be uniquely determined because it depends on the molecular weight of the target polyester chain, but carboxylic acid: lactone = 1: 1 to 1: 1,000 are preferred, and 1: 3 to 1: 500 are most preferred.

  (2) The hydroxy group-containing carboxylic acid used for the polycondensation of the hydroxy group-containing carboxylic acid is the same as the hydroxy group-containing carboxylic acid mentioned as the carboxylic acid used in (1), and the preferred range is also the same.

  (3) As the dihydric alcohol used in the polycondensation reaction of the dihydric alcohol and the divalent carboxylic acid (or cyclic acid anhydride), a linear or branched aliphatic diol (a diol having 2 to 30 carbon atoms is preferable, , Ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, etc.) In particular, aliphatic diols having 2 to 20 carbon atoms are preferable.

(3) The divalent carboxylic acid used for the polycondensation reaction of the dihydric alcohol and the divalent carboxylic acid is a linear or branched divalent aliphatic carboxylic acid (a divalent aliphatic carboxylic acid having 1 to 30 carbon atoms). For example, succinic acid, maleic acid, adipic acid, sebacic acid, dodecanedioic acid, glutaric acid, suberic acid, tartaric acid, oxalic acid, malonic acid and the like. Acid is preferred.
Instead of these divalent carboxylic acids, acid anhydrides equivalent to these divalent carboxylic acids (for example, succinic anhydride, glutaric anhydride, etc.) may be used.

(3) In a polycondensation reaction of a dihydric alcohol and a divalent carboxylic acid (or cyclic acid anhydride), the divalent carboxylic acid and the dihydric alcohol (or cyclic acid anhydride) are charged at a molar ratio of 1: 1. Is preferred.
This makes it possible to introduce a carboxylic acid at the terminal.

  The methods (1) to (3) may be performed by a method in which all of the raw materials are mixed and heated to react, and a part of the raw materials are heated and reacted, and the remaining raw materials are added thereto. You may carry out by the method of making it react, adding.

The polycondensation in producing the polyester is preferably performed by adding a catalyst.
As a catalyst, the catalyst used when making it react with the at least 1 sort (s) chosen from the compound (a) general formula (I) mentioned later and (b-1) lactone and a hydroxyl-group containing carboxylic acid mentioned later is mentioned. The preferred range is also the same.
The catalytic reaction temperature is preferably 80 ° C to 250 ° C, and most preferably 100 ° C to 180 ° C. Moreover, although reaction time changes with reaction conditions, it is 1 to 24 hours in general.

The number average molecular weight of the polyester used for obtaining the resin represented by the general formula (II) of the present invention can be measured as a polystyrene equivalent value by GPC method.
The number average molecular weight of this polyester is preferably 1,000 to 50,000, more preferably 3,000 to 30,000, and most preferably 4,000 to 20,000. When the molecular weight is in this range, both dispersibility and developability can be achieved.

  From the viewpoint of production stability, the polyester used for obtaining the resin represented by the general formula (II) of the present invention is particularly (1) polycondensation of carboxylic acid and lactone, or (2) hydroxy group-containing carboxyl. Polyesters synthesized by acid polycondensation are preferred, and (1) polyesters synthesized by polycondensation of carboxylic acid and lactone are most preferred.

<Resin represented by general formula (II)>
Next, (a) the compound represented by the general formula (I), (b-1) at least one compound selected from a lactone and a hydroxyl group-containing carboxylic acid, or (b-2) a polyester, A resin represented by the following general formula (II) (resin of the present invention) obtained by reacting and will be described.

  In said general formula (II), V is synonymous with V in general formula (I), and its preferable example is also the same. W 'represents a residue of W in the general formula (I). Y represents a polyester chain. n is synonymous with n in the general formula (I), and preferred examples are also the same.

In the polyester represented by Y, at least one selected from (b-1) a lactone or a hydroxyl group-containing carboxylic acid is condensed, or (b-2) the polyester and W in the general formula (I) are reacted. It is formed by doing.
The number average molecular weight of the polyester represented by Y is preferably 1,000 to 50,000, more preferably 3,000 to 30,000, and most preferably 4,000 to 20,000. The number average molecular weight of Y can be determined by a terminal group quantification method (a method for calculating and calculating the ratio of the number of moles of terminal groups to the repeating unit of polyester by NMR or titration).

The resin represented by the general formula (II) has a weight average molecular weight of preferably 1,000 to 50,000, more preferably 3,000 to 30,000, and more preferably 4,000 to 20,000 in terms of polystyrene converted by GPC. 000 is most preferred.
The acid value of the resin represented by the general formula (II) is preferably 2 mgKOH / g to 200 mgKOH / g, more preferably 10 mgKOH / g to 150 mgKOH / g, and most preferably 20 mgKOH / g to 100 mgKOH / g.

Specific examples of the resin represented by the general formula (II) are shown below, but the present invention is not limited thereto.
In the following specific examples, “x” represents an integer of 1 to 150.

Furthermore, although the specific structure of resin represented by general formula (II) of this invention is shown with a weight average molecular weight and a number average molecular weight, this invention is not limited to this.

<Method for producing resin represented by formula (II)>
The method for producing the resin represented by the general formula (II) of the present invention (the resin of the present invention) includes (a) a compound represented by the general formula (I), (b-1) a lactone and a hydroxyl group-containing carboxylic acid. It is characterized by reacting at least one compound selected from the above or (b-2) polyester.
Here, (a) the compound represented by the general formula (I), (b-1) lactone and hydroxyl group-containing carboxylic acid, and (b-2) polyester used in the method for producing the resin of the present invention, As described above.

In the method for producing a resin of the present invention, when (a) the compound represented by the general formula (I) is reacted with (b-1) at least one selected from a lactone and a hydroxyl group-containing carboxylic acid, a catalyst is used. Is preferably added. Thereby, productivity improves.
As the catalyst, a catalyst that functions as a Lewis acid is preferable. For example, a Ti compound (for example, Ti (OBu) ₄ , Ti (O—Pr) _4, etc.), a Sn compound (for example, tin octylate, dibutyltin oxide, dibutyltin laurate). Rate, monobutyltin hydroxybutyl oxide, stannic chloride, etc.), protonic acids (for example, sulfuric acid, paratoluenesulfonic acid, etc.) and the like.
The catalyst amount is preferably 0.01 mol% to 10 mol%, most preferably 0.1 mol% to 5 mol%, based on the number of moles of (b-1) lactone and / or hydroxyl group-containing carboxylic acid used. .

  (A) The reaction of the compound represented by the general formula (I) and at least one selected from (b-1) lactone or hydroxyl group-containing carboxylic acid is performed by mixing all of these raw materials at once and heating. Alternatively, the reaction may be carried out by a method, or a part of the raw material may be heated and reacted, and the reaction may be carried out while the remaining raw material is added thereto.

  In the method for producing a resin of the present invention, at least one selected from (a) a compound represented by the general formula (I) and (b-1) a lactone and a hydroxyl group-containing carboxylic acid, or (b- 2) When reacting with polyester, the reaction temperature is preferably 50 ° C to 250 ° C, and most preferably 80 ° C to 180 ° C. The reaction time varies depending on the reaction conditions, but is generally 1 hour to 24 hours.

(Pigment dispersion)
The pigment dispersion liquid of the present invention contains (A) the resin of the present invention, (B) a pigment, and (C) a solvent.
By adding the resin of the present invention to the pigment dispersion, the dispersibility and dispersion stability of the pigment in the pigment dispersion can be dramatically improved.

<(A) Resin of the Present Invention>
The content of the resin of the present invention (A) in the pigment dispersion of the present invention is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and more preferably 30% by mass to the pigment. 50 mass% is still more preferable.

  Next, the (B) pigment and (C) solvent used in the pigment dispersion of the present invention will be described.

<(B) Pigment>
As the pigment that the pigment dispersion of the present invention has, conventionally known various inorganic pigments or organic pigments can be used.
Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a fine one as much as possible, and considering the handling properties, the average particle diameter of the pigment is 0.005 μm to 0.1 μm is preferable, and 0.005 μm to 0.05 μm is more preferable.

  Examples of the inorganic pigment used in the pigment dispersion of the present invention include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, Mention may be made of metal oxides such as magnesium, chromium, zinc and antimony, and composite oxides of the above metals.

Examples of organic pigments that can be used in the pigment dispersion of the present invention include:
C. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142,147,148,150,151,153,154,155,157,158,159,160,161,162,163,164,165,166,167,168,169,170,172,17 , 174,175,176,180,181,182,183,184,185,188,189,190,191,191: 1,192,193,194,195,196,197,198,199,200,202 , 203, 204, 205, 206, 207, 208;

C. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79;
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235 , 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 , 268, 269, 270, 271, 272, 273, 274, 275, 276;

C. I. Pigment violet 1, 1: 1,2,2: 2,3,3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50; I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, 79 Changed to OH;
C. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55;
C. I. Pigment brown 23, 25, 26;
C. I. Pigment black 1, 7;
Examples thereof include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black.

  In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These pigments having a basic N atom exhibit good dispersibility in a colored curable composition containing the pigment dispersion of the present invention (colored curable composition of the present invention). Although the cause is not fully elucidated, it is presumed that the good affinity between the photosensitive polymerization component and the pigment has an effect.

  Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

C. I. Pigment yellow 11,24,108,109,110,138,139,150,151,154,167,180,185;
C. I. Pigment orange 36, 71;
C. I. Pigment Red 122,150,171,175,177,209,224,242,254,255,264;
C. I. Pigment violet 19, 23, 32;
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment green 7, 36, 37, 55;
C. I. Pigment Black 1

These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of preferred usage modes and combinations of organic pigments are shown below.
For example, as a red pigment, an anthraquinone pigment, perylene pigment, diketopyrrolopyrrole pigment alone, or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment Or a mixture with a perylene-based red pigment can be used. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred.
The mass ratio between the red pigment and the yellow pigment is preferably 100: 5 to 100: 50, and most preferably in the range of 100: 10 to 100: 30, from the relationship between the light transmittance and the color resolution.
In the case of a combination of red pigments, the mass ratio of the pigment can be adjusted in accordance with the desired spectrum.

Further, as the green pigment, a halogenated phthalocyanine pigment alone or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment may be used. it can. For example, C.I. I. Pigment green 7, 36, 37, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, or C.I. I. Mixture with CI Pigment Yellow 185 is preferred.
The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150, particularly preferably in the range of 100: 30 to 100: 120.

As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred.
The mass ratio of the blue pigment and the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 10 or less.

Further, as the pigment for the black matrix, carbon, titanium black, iron oxide and titanium oxide are used alone or in combination, and a combination of carbon and titanium black is preferable.
Here, the mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60.

  As the pigment used in the present invention, it is preferable to use a pigment which has been subjected to a refinement treatment in advance. The primary particles of the pigment are made fine by mechanically kneading, using a kneader or the like, i) an organic pigment, ii) a water-soluble inorganic salt, and iii) a water-soluble organic solvent that does not substantially dissolve the inorganic salt. Is well known (salt milling method). In this step, if necessary, iv) a polymer compound for pigment coating may be used at the same time.

i) Organic pigment Examples of the organic pigment include the same organic pigments as described above.

ii) Water-soluble inorganic salt The water-soluble inorganic salt is not particularly limited as long as it is soluble in water, and sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used. Sodium chloride or sodium sulfate is preferably used.
The amount of the water-soluble inorganic salt used in the salt milling is preferably 1 to 30 times, particularly 5 to 25 times the weight of the organic pigment from the viewpoint of both processing efficiency and production efficiency. This is because the finer efficiency is higher as the amount ratio of the inorganic salt to the organic pigment is larger, but the amount of treatment of one pigment is reduced.

iii) ii) Water-soluble organic solvents that do not substantially dissolve water-soluble inorganic salts
iii) The water-soluble organic solvent functions to wet i) organic pigments, ii) water-soluble inorganic salts, dissolves (mixes) in water, and uses ii) water-soluble inorganic salts. It will not be specifically limited if it does not melt | dissolve substantially. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent easily evaporates.
Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monoethyl. Ether acetate, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene Glycol monoethyl ether, liquid polypropylene glycol, or the like is used.
These water-soluble organic solvents may be used alone or in combination of two or more.

The amount of the water-soluble organic solvent added is ii) a water-soluble inorganic salt from the viewpoint of uniform kneading, uniform particle size, good shear on the kneaded composition, and sufficient effect of refining. The content is preferably 5% by mass to 50% by mass. More preferably, it is 10 mass%-40 mass% with respect to an inorganic salt, and optimally it is 15 mass%-35 mass% with respect to an inorganic salt. When the addition amount is less than 5% by mass,
All of the water-soluble organic solvent may be added at the initial stage of salt milling, or may be added separately.

iv) Pigment-coating polymer compound The pigment-coating polymer compound that can be added during the above-mentioned salt milling is preferably a solid at room temperature, water-insoluble, and a water-soluble compound used as a wetting agent during salt milling. It must be at least partially soluble in the organic solvent. For such a polymer compound, a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like is used.
In the case of obtaining a dried fine pigment after salt milling, the polymer compound for coating iv) is preferably solid at room temperature.
The natural resin is typically rosin, and the modified natural resin includes rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof.
Examples of the synthetic resin include an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin.
Examples of synthetic resins modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins.
Synthetic resins include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, polyurethane, polyester, poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin Condensates and the like can also be used.
The timing of adding these resins may be added all at the beginning of salt milling, or may be added separately.

When the colored curable composition using the pigment dispersion of the present invention (colored curable composition of the present invention) is used for forming a colored region of a color filter, the primary color of the pigment from the viewpoint of color unevenness and contrast. The particle diameter is preferably 5 nm to 100 nm, more preferably 5 nm to 70 nm, still more preferably 5 nm to 50 nm, and most preferably 5 nm to 40 nm. The above-described resin of the present invention can exert an effect particularly on pigments in the range of 5 nm to 40 nm.
The primary particle diameter of the pigment can be measured by a known method such as an electron microscope.

  Among these, the pigment is preferably a pigment selected from anthraquinone, azomethine, benzylidene, cyanine, diketopyrrolopyrrole, and phthalocyanine.

The pigment content in the pigment dispersion of the present invention is preferably 30% by mass or more, more preferably 35% by mass or more and 80% by mass or less, based on the total solid content of the pigment dispersion. Most preferably, it is at least 70% by mass.
When the resin of the present invention is used as a pigment dispersant, it can be said that the effect is particularly remarkable under a high content condition of 40% by mass or more, in which stable uniform dispersion is difficult with a known dispersant.

(C) Solvent The pigment dispersion of the present invention has at least one (C) solvent.
(C) As a solvent, the liquid selected from the organic solvent shown below is mentioned, The solubility of each component contained in a pigment dispersion liquid, the applicability | paintability at the time of applying to a curable composition, etc. are considered. Basically, it is not particularly limited as long as these desired physical properties are satisfied. However, it is preferably selected in consideration of safety.
Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl oxyacetate, and ethyl oxyacetate. , Butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, 3-methoxypropion Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2-methoxypropion Ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2 -Methyl methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate (ethylene glycol monomethyl ether acetate), ethyl cellosolve acetate (ethylene glycol monoethyl ether acetate), diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, pro Etc. glycol propyl ether acetate;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Aromatic hydrocarbons such as toluene, xylene and the like;
Is preferred.

  Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate (PGMEA) and the like are more preferable.

As content of the (C) solvent in the pigment dispersion liquid of this invention, 50 mass%-90 mass% are preferable, 60 mass%-95 mass% are more preferable, 70 mass%-90 mass% are the most preferable.
When the content of the solvent is within the above range, it is advantageous in terms of suppressing the generation of foreign matter.

<Other ingredients>
In addition to the essential components (A) to (C) described above, the pigment dispersion of the present invention contains other components depending on the purpose, such as the use of the pigment dispersion, as long as the effects of the present invention are not impaired. be able to.

(Pigment derivative)
The pigment dispersion of the present invention preferably further contains a pigment derivative. In particular, by containing a pigment derivative having a basic group, dispersibility and dispersion stability are dramatically improved.
The pigment derivative preferably has a structure in which a part of an organic pigment, anthraquinones or acridones is substituted with an acidic group, a basic group or a phthalimidomethyl group.
Examples of the organic pigment constituting the pigment derivative include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine, aminoanthraquinone, diaminodi Anthraquinone pigments such as anthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindoline pigment, isoindoline Examples thereof include linone pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.

  Examples of the basic group possessed by the pigment derivative include an amino group (a linear or branched alkyl group, a primary, secondary or tertiary amino group having a cycloalkyl group or an aryl group), or a nitrogen-containing heterocyclic group (for example, pyridyl, Pyrimidyl, pyridazyl, triazyl, imidazolyl, pyrazolyl and the like are preferable, and a tertiary amino group having a linear or branched alkyl group is most preferable.

  The amount of the pigment derivative used in the pigment dispersion of the present invention is not particularly limited, but it is preferably 1% by mass to 50% by mass and more preferably 5% by mass to 30% by mass with respect to the pigment.

  Specific examples of the pigment derivative used in the pigment dispersion of the present invention are listed below, but the present invention is not limited to this.

(Other polymer materials)
From the viewpoint of improving dispersion stability, controlling developability, etc., the pigment dispersion of the present invention includes, for example, a polyamidoamine and salt thereof, a polycarboxylic acid and salt thereof, Molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl Polymer dispersing agents such as amines and alkanolamines can be further added.
Such other polymer dispersants can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.

The polymer dispersant that can be used in combination is adsorbed on the surface of the pigment and acts to prevent reaggregation.
Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.
Specific examples of other polymer dispersants that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group)” manufactured by BYK Chemie, 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050 ”manufactured by EFKA Corporation. 4010, 4165 (polyurethane type), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 ( Azo Pigment Derivative) ”,“ Ajispur PB821, PB822 ”manufactured by Ajinomoto Fine Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha,“ Polyflow No. 50E, No. 300 (acrylic copolymer) ”, Enomoto “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725” manufactured by Kasei Corporation, manufactured by Kao “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," Acetami 86 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft-type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical Co., Ltd. Alternatively, (meth) acrylic acid / (meth) acrylic acid alkyl copolymer, preferably (meth) acrylic acid / (meth) acrylic acid alkyl having an acid value of 20 to 150 mgKOH (alkyl having 1 to 10 carbon atoms is most preferred) ) Copolymers It is.

These polymer dispersants may be used alone or in combination of two or more.
(A) When using together the resin of this invention and a polymer dispersing agent, as content of the polymeric material in this invention, it is 1 mass%-100 mass% with respect to the resin of (A) this invention. It is preferably 3% by mass to 80% by mass, more preferably 5% by mass to 50% by mass.

<Preparation of pigment dispersion composition>
The pigment dispersion composition of the present invention can be made of, for example, a mixed solution containing (A) the resin of the present invention, (B) a pigment, and (C) a solvent with glass having a particle diameter of 0.01 mm to 1 mm, zirconia, or the like. It can be obtained by carrying out fine dispersion treatment with the beads.
In addition, before carrying out fine dispersion with beads, use a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single or twin screw extruder, etc. It is also possible to carry out the kneading and dispersing process while giving.

  For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like, and the method described herein can also be applied to the present invention.

  Since the pigment dispersion of the present invention uses (A) the resin of the present invention as a pigment dispersant, it is excellent in the dispersibility and dispersion stability of the pigment even when it contains a fine pigment at a high concentration.

[Colored curable composition and preparation method thereof]
The colored curable composition of the present invention contains (A) the resin of the present invention, (B) a pigment, (C) a solvent, (D) a photopolymerization initiator, and (E) an ethylenically unsaturated double bond. It is characterized by containing a compound.
By containing these components (A) to (E), the colored curable composition of the present invention has excellent dispersibility and dispersion stability of fine pigments, as well as excellent coating properties and developability, and contrast and color. A colored cured film having good color characteristics such as unevenness can be formed.
Hereinafter, each component which comprises the colored curable composition of this invention is demonstrated.

<(A) Resin of the Present Invention, (B) Pigment, and (C) Solvent>
(A) Resin of the present invention, (B) Pigment, and (C) Solvent constituting the colored curable composition of the present invention are the components (A) to (C) constituting the above-described pigment dispersion of the present invention. And preferred examples are also the same.
In the colored curable composition of the present invention, (A) the content of the resin of the present invention is preferably in the range of 5% by mass to 50% by mass with respect to the total solid content in the colored curable composition, and 10% by mass. The range of% -40 mass% is more preferable, and the range of 15 mass% -30 mass% is still more preferable.
Further, in the colored curable composition of the present invention, the content of the (B) pigment is preferably in the range of 30% by mass to 80% by mass, and 35% by mass with respect to the total solid content in the colored curable composition. The range of -70 mass% is more preferable, and the range of 40 mass%-65 mass% is still more preferable.
Furthermore, in the colored curable composition of the present invention, the content of the solvent (C) is preferably in the range of 60% by mass to 95% by mass, and 70% by mass to 90% by mass with respect to all components of the colored curable composition. The range of mass% is more preferable, and the range of 75 mass% to 85 mass% is still more preferable.

<(D) Photopolymerization initiator>
The colored curable composition of the present invention contains (D) a photopolymerization initiator in order to improve sensitivity and pattern formation.
The photopolymerization initiator in the present invention is a compound that is decomposed by light and initiates and accelerates the polymerization of a polymerizable component such as a compound containing (E) an ethylenically unsaturated double bond, which will be described later. A compound having absorption in a region of 300 nm to 500 nm is preferable.
Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

Examples of the photopolymerization initiator used in the present invention include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, Examples thereof include metallocene compounds, hexaarylbiimidazole compounds, organic borate compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, acylphosphine (oxide) compounds, and alkylamino compounds.
Hereinafter, each of these compounds will be described in detail.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP 48-36281, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62 -212401, JP-A-63-70243, JP-A-63-298339, M.S. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and in particular, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

  Examples of the oxodiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) , Acetophenone derivatives such as 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone derivatives such as 2,4-diisopropylthioxanthone, and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

Examples of the ketal compound include benzyl methyl ketal and benzyl-β-methoxyethyl ethyl acetal.
Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, and methyl-o-benzoylbenzoate.

  Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 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, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di -Cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentaful Lophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5 5'-tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 In Japanese Patent Laid-Open No. 6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfonic acid compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compounds and the like.

  In the present invention, the compound represented by the following general formula (3) is more preferable as the oxime ester compound from the viewpoints of sensitivity, time stability, and coloring during post-heating.

  In the general formula (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 1-5.

  R is preferably an acyl group from the viewpoint of increasing sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable.

  A is an alkylene group substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heat aging, An alkylene group substituted with an alkenyl group (for example, vinyl group, allyl group), an aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) A substituted alkylene group is preferred.

  Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloring due to heating. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

X is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl that may have a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. Group, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, a substituent An arylthioxy group which may have an amino group and an amino group which may have a substituent are preferable.
Moreover, n in General formula (3) has a preferable integer of 1-2.

  Hereinafter, although the specific example of the novel oxime compound of this invention is shown below, this invention is not limited to these.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, No. 055, No. 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP Examples include iodonium salts described in JP-A No. -150848 and JP-A-2-296514.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability. . In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability and sensitivity. It is preferably substituted with. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello
et al, J. et al. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt, C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  Examples of the alkylamino compound include compounds having a dialkylaminophenyl group described in paragraph No. [0047] of JP-A-9-281698, JP-A-6-19240, JP-A-6-19249, and the like. An amine compound is mentioned. Specifically, compounds having a dialkylaminophenyl group include compounds such as ethyl p-dimethylaminobenzoate, and dialkylaminophenyl carbaldehydes such as p-diethylaminobenzcarbaldehyde and 9-julolidylcarbaldehyde. Examples of the amine compound include triethanolamine, diethanolamine, and triethylamine.

  As the photopolymerization initiator (D) used in the present invention, from the viewpoint of exposure sensitivity, a triazine compound, an alkylamino compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, Phosphine oxide compounds, metallocene compounds, oxime compounds, biimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halo A compound selected from the group consisting of a methyloxadiazole compound and a 3-aryl-substituted coumarin compound is preferred.

  More preferably, they are triazine compounds, alkylamino compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, biimidazole compounds, onium compounds, benzophenone compounds, acetophenone compounds. At least one compound selected from the group consisting of triazine compounds, alkylamino compounds, oxime compounds and biimidazole compounds is more preferred, and oxime compounds are most preferred.

  In particular, when the colored curable composition of the present invention is used for forming colored pixels in a color filter of a solid-state imaging device, the amount of the photopolymerization initiator added is reduced because the pigment concentration in the composition is high due to the formulation. Sensitivity will decrease. Further, when exposure is performed with a stepper, if an initiator that generates a halogen-containing compound at the time of exposure, such as a triazine compound, is used, it causes corrosion of equipment and is difficult to use. Considering these, as the photopolymerization initiator that satisfies the sensitivity and various performances, an oxime compound is preferable, and an oxime compound having absorption at 365 nm is most preferable.

  (D) It is preferable that content of a photoinitiator is 0.1 mass%-50 mass% with respect to the total solid of the colored curable composition of this invention, More preferably, it is 0.5 mass%. -30% by mass, particularly preferably 1% by mass to 20% by mass. Within this range, good sensitivity and pattern formability can be obtained.

<(E) Compound containing ethylenically unsaturated double bond>
The colored curable composition of the present invention can contain a compound containing an ethylenically unsaturated double bond.

  The compound containing an ethylenically unsaturated double bond that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond, Preferably, it is selected from compounds having two or more. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate Sorbitol tetritaconate, etc. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include, for example, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. Those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Furthermore, monomers containing acid groups can also be used, such as (meth) acrylic acid, pentaerythritol triacrylate succinic acid monoester, dipentaerythritol pentaacrylate succinic acid monoester, pentaerythritol triacrylate maleic acid monoester, dipenta Erythritol pentaacrylate maleic acid monoester, pentaerythritol triacrylate phthalic acid monoester, dipentaerythritol pentaacrylate phthalic acid monoester, pentaerythritol triacrylate tetrahydrophthalic acid monoester, dipentaerythritol pentaacrylate tetrahydrophthalic acid monoester, etc. It is done. In these, pentaerythritol triacrylate succinic acid monoester etc. are mentioned.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. It contains two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group in the compound represented by the following general formula (a) to a polyisocyanate compound having two or more isocyanate groups. A vinyl urethane compound etc. are mentioned.

Formula ^{_{(a) CH 2 = C (}} R 10) COOCH 2 CH (R 11) OH
(However, R ¹⁰ and R ¹¹ represent H or CH _3. )

  Further, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56-17654 Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Furthermore, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, JP-A-1-105238 Can obtain a photopolymerizable composition having an excellent photosensitive speed.

  Other examples include reacting polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. And polyfunctional acrylates and methacrylates such as epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 are also included. be able to. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these addition polymerizable compounds, the details of usage, such as the structure, single use or combined use, and addition amount can be arbitrarily set according to the performance design of the colored curable composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image portion, that is, the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether type). A method of adjusting both sensitivity and strength by using a compound) is also effective. From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably a compound containing three or more, and most preferably a compound containing four or more. preferable. Moreover, it is preferable to contain an EO modified body from a viewpoint of hardening sensitivity and developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.

  In addition, addition polymerization is also performed with respect to compatibility and dispersibility with other components (for example, (A) resin, (D) photopolymerization initiator, (B) pigment) in the colored curable composition of the present invention. The selection and use method of the compound is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more compounds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesion to a solid surface such as a substrate.

  From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. are mentioned as preferable ones. Also, commercially available products include urethane oligomers UAS-10 and UAB-140 (Sanyo Kokusaku Pulp Co. Manufactured), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha), UA-7200 (Shin Nakamura Chemical Co., Ltd.) Product).

  Among them, bisphenol A diacrylate EO modified, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, di Examples of commercially available modified products such as pentaerythritol hexaacrylate EO include DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 ( Kyoeisha) is more preferable.

  The content of the compound containing (E) an ethylenically unsaturated double bond in the present invention is preferably 1% by mass to 90% by mass in the solid content of the colored curable composition of the present invention. It is more preferably from 80% by mass to 80% by mass, and further preferably from 10% by mass to 70% by mass.

  In particular, when the colored curable composition of the present invention is used for forming a colored pattern of a color filter, the content of the compound (E) containing an ethylenically unsaturated double bond is 5% by mass to 50% in the above range. The mass is preferably 7% by mass, more preferably 7% by mass to 40% by mass, and still more preferably 10% by mass to 35% by mass.

The colored curable composition of the present invention preferably further contains (F) an alkali-soluble resin in addition to the components (A) to (E) described above.
By containing an alkali-soluble resin, developability and pattern formation are improved.

<(F) Alkali-soluble resin>
The (F) alkali-soluble resin that can be used in the present invention is a linear organic high molecular polymer, preferably in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as the main chain). Can be appropriately selected from alkali-soluble resins having at least one group that promotes alkali solubility (for example, carboxyl group, phosphoric acid group, sulfonic acid group, hydroxyl group, etc.).
More preferable as the alkali-soluble resin is a polymer having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid, as described in Japanese Unexamined Patent Publication Nos. 59-53836 and 59-71048. Acrylic copolymers such as acid copolymers, partially esterified maleic acid copolymers, etc., acidic cellulose derivatives having carboxylic acids in the side chains, and polymers having hydroxyl groups with acid anhydrides added. Can be mentioned.
The acid value is preferably in the range of 20 mgKOH / g to 200 mgKOH / g, preferably 30 mgKOH / g to 150 mgKOH / g, more preferably 35 mgKOH / g to 120 mgKOH / g.

As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
As the alkyl (meth) acrylate and aryl (meth) acrylate, CH ₂ ═C (R ¹ ) (COOR ² ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; ² represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 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, hydroxyalkyl (meth) acrylate (alkyl is an alkyl group having 1 to 8 carbon atoms) ), Hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate and the like.

A resin having a polyalkylene oxide chain in the molecular side chain is also preferred.
The polyalkylene oxide chain may be a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or a combination thereof, and the terminal is a hydrogen atom or a linear or branched alkyl group.
1-20 are preferable and, as for the repeating unit of a polyethylene oxide chain and a polypropylene oxide chain, 2-12 are more preferable. Acrylic copolymers having a polyalkylene oxide chain in these side chains are, for example, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate , Poly (ethylene glycol-propylene glycol) mono (meth) acrylate and the like and compounds in which these terminal OH groups are alkyl-blocked, such as methoxypolyethylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, methoxypoly (ethylene glycol) -An acrylic copolymer having propylene glycol) mono (meth) acrylate or the like as a copolymerization component.

Further, as the vinyl compound, CH ₂ = CR ¹ R ² [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. To express. Specific examples include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like.
These other copolymerizable monomers can be used singly or in combination of two or more. Other preferable copolymerizable monomers are alkyl (meth) acrylate (alkyl is an alkyl group having 2 to 4 carbon atoms), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene.
Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.

As described above, the acrylic resin has an acid value in the range of 20 mgKOH / g to 200 mgKOH / g. When the acid value exceeds 200 mgKOH / g, the acrylic resin becomes too soluble in alkali and the appropriate development range (development latitude) becomes narrow. On the other hand, if it is too small, less than 20 mgKOH / g, the solubility in alkali is small and it takes too much time for development, which is not preferable.
Also, the mass average molecular weight Mw (polystyrene conversion value measured by GPC method) of the acrylic resin is used to realize a viscosity range that is easy to use in the process of applying a color resist, etc., and to secure film strength. , Preferably from 2,000 to 100,000, more preferably from 3,000 to 50,000.
In order to make the acid value of acrylic resin into the range specified above, it can be easily performed by appropriately adjusting the copolymerization ratio of each monomer. Further, the range of the mass average molecular weight can be easily set by using an appropriate amount of a chain transfer agent according to the polymerization method when the monomers are copolymerized.
The acrylic resin can be produced, for example, by a known radical polymerization method. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an acrylic resin by radical polymerization can be easily set by those skilled in the art. Is possible.

  The addition amount when adding the alkali-soluble resin to the colored curable composition of the present invention is preferably 5 to 90% by mass, more preferably 10 to 60% by mass, based on the total solid content of the composition. . When the amount of the alkali-soluble resin is within this range, the film strength is sufficient and the solubility can be easily controlled. Further, when the amount of the alkali-soluble resin is within this range, the pigment concentration is sufficient, and a coating film having a sufficient thickness is easily obtained. As a result, when forming a colored pattern of a color filter using the colored curable composition of the present invention, a high yield is obtained when slit coating suitable for coating on a wide and large substrate is used. A film can be obtained, and sufficient color density can be obtained with the obtained colored pattern.

Moreover, in order to improve the crosslinking efficiency of the colored curable composition in the present invention, an alkali-soluble resin having a polymerizable group may be used alone or in combination with an alkali-soluble resin having no polymerizable group.
As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin or the like containing a group containing a carbon-carbon unsaturated bond such as an allyl group, a (meth) acryl group, or an allyloxyalkyl group in the side chain is useful. .
Such an alkali-soluble resin having a group containing a carbon-carbon unsaturated bond can be developed with an alkali developer, and further has photocurability and thermosetting properties.

Examples of alkali-soluble resins having groups containing these carbon-carbon unsaturated bonds are shown below, but alkali-soluble groups such as COOH groups and OH groups and carbon-carbon unsaturated bonds may be included. For example, it is not limited to the following.
(1) It is obtained by reacting an isocyanate group and an OH group in advance, leaving one unreacted isocyanate group and at least one (meth) acryloyl group and an acrylic resin containing a carboxyl group. Urethane modified acrylic resin,
(2) an acrylic resin obtained by a reaction between an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule;
(3) Acid pendant type epoxy acrylate resin,
(4) An acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a carbon-carbon unsaturated bond.
Among the above, the resins (1) and (2) are particularly preferable.

More specific examples include a copolymer of 2-hydroxyethyl acrylate having an OH group, for example, methacrylic acid having a COOH group, and a monomer such as an acrylic or vinyl compound copolymerizable therewith. Further, a compound obtained by reacting a compound having an epoxy ring reactive with an OH group and a group containing a carbon-carbon unsaturated bond (for example, a compound such as glycidyl acrylate) can be used.
In the reaction with the OH group, a compound having an acid anhydride, an isocyanate group, or an acryloyl group can be used in addition to the epoxy ring.
Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polyunsaturated. A reaction product obtained by reacting a basic acid anhydride can also be used.
Furthermore, as a compound having both an alkali-soluble group such as a COOH group and a group containing a carbon-carbon unsaturated bond, for example, Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (COOH group-containing Polyethane acrylic) oligomer, Diamond Shamrock Co. Ltd .; biscort R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); cyclomer P series, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.) Ebecryl 3800 (manufactured by Daicel UC Corporation), and the like.

  The acid value of the alkali-soluble resin having a polymerizable group in the present invention is preferably 30 mgKOH / g to 150 mgKOH / g, more preferably 35 mgKOH / g to 120 mgKOH / g, and the mass average molecular weight Mw is preferably Is 2,000 to 50,000, more preferably 3,000 to 30,000.

  The colored curable composition of this invention may further contain the component explained in full detail as needed.

<Sensitizer>
The colored curable composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the photosensitive wavelength.
As the sensitizer that can be used in the present invention, those that are sensitized by the electron transfer mechanism or the energy transfer mechanism with respect to the above-mentioned (D) photopolymerization initiator are preferable.

Examples of the sensitizer that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (Isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, toluidine blue) , Acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg Squalium), acridine orange, coumarins (eg 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazole , Porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, and other aromatics Examples include ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.
Further, European Patent No. 568,993, US Patent No. 4,508,811, No. 5,227,227, Japanese Patent Application Laid-Open No. 2001-125255, Japanese Patent Application Laid-Open No. 11-271969, etc. And the like.

<Polymerization inhibitor>
In the present invention, a small amount of a thermal polymerization inhibitor is used to prevent unnecessary thermal polymerization of a compound having an (EE) ethylenically unsaturated double bond, which can be polymerized during the production or storage of a colored curable composition. It is desirable to add.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the colored curable composition.
If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to prevent polymerization inhibition due to oxygen, and the coating film is coated in the drying process after the colored curable composition is applied. It may be unevenly distributed on the surface.
The amount of the higher fatty acid derivative added is preferably from about 0.5% to about 10% by weight of the colored curable composition.

<Other additives>
Furthermore, in order to improve the physical properties of the cured film, the colored curable composition of the present invention may be added with an inorganic filler, a known additive such as a plasticizer, or a substrate adhesive that can improve the substrate adhesion. Good.
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like.

When the colored curable composition of the present invention is applied to the surface of a hard material such as a substrate, an additive (hereinafter referred to as “substrate adhesion agent”) for improving the adhesion to the surface of the hard material. May be added.
As the substrate adhesion agent, known materials can be used, but it is particularly preferable to use a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane is most preferable.

  Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite). ) Titanate, tetra (2,2-diallyloxymethyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldi Methacrylic isostearoyl titanate, isopropyl isostearoyl diacryl titanate, Li isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- amidoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.

  The content of the substrate adhesive is from 0.1% by mass to 30% by mass with respect to the total solid content of the colored curable composition from the viewpoint of leaving no residue in the unexposed portions of the colored curable composition. Or less, more preferably 0.5% by mass or more and 20% by mass or less, and particularly preferably 1% by mass or more and 10% by mass or less.

The colored curable composition of the present invention can be preferably used in the fields of image forming materials such as three-dimensional stereolithography, holography, and color filters, and inks, paints, adhesives, and coating agents.
In addition, the colored curable composition of the present invention can form a colored region having excellent pigment dispersion stability and developability, high definition and good color characteristics even when containing a fine pigment at a high concentration. . Therefore, when producing a color filter for a solid-state imaging device, particularly when forming a pixel having a film thickness of 0.8 μm or less, preferably in a range of 0.1 μm to 0.5 μm, the color curable property of the present invention. Compositions are particularly preferred.

<Preparation method of colored curable composition>
The method for preparing the colored curable composition of the present invention comprises (A) a pigment dispersion containing the resin of the present invention, (B) a pigment, and (C) a solvent, (D) a photopolymerization initiator, and (E ) A compound containing an ethylenically unsaturated double bond is added.
That is, the method for preparing the colored curable composition of the present invention comprises (D) a photopolymerization initiator and (E) a compound containing an ethylenically unsaturated double bond in the pigment dispersion of the present invention. It is performed by adding the arbitrary component of.

[Color filter and manufacturing method thereof]
Next, the color filter of the present invention and the manufacturing method thereof will be described.
The color filter of the present invention has a colored pattern formed on the support using the colored curable composition of the present invention.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

The method for producing a color filter of the present invention includes a colored layer forming step of forming the colored layer by applying the colored curable composition of the present invention on a support, and an exposure step of exposing the colored layer through a mask. And a developing step of developing the colored layer after exposure to form a colored pattern.
Hereafter, each process in the manufacturing method of this invention is demonstrated.

<Colored layer forming step>
In the colored layer forming step, the colored curable composition of the present invention is applied to form a colored layer on the support.

As the support that can be used in this step, for example, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these glasses, imaging elements, etc. Examples of the photoelectric conversion element substrate include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

As a coating method of the colored curable composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied. .
The film thickness immediately after application of the colored curable composition of the present invention may be any film according to the film thickness (dry film thickness) after drying of the colored layer to be described later. From the viewpoint of easy drying of the solvent, 0.1 μm to 10 μm is preferable, 0.2 μm to 5 μm is more preferable, and 0.2 μm to 3 μm is still more preferable.

  The colored layer applied on the substrate can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, oven, or the like.

As the film thickness after drying of the colored layer (hereinafter referred to as “dry film thickness” as appropriate), in order to use it as a color filter for liquid crystal display elements, it is possible to cope with LCD thinning, from the viewpoint of ensuring color density, The thickness is preferably 0.1 μm or more and 2.0 μm or less, more preferably 0.2 μm or more and 1.8 μm or less, and particularly preferably 0.3 μm or more and 1.75 μm or less.
In addition, in order to use as a color filter for a solid-state imaging device such as a CCD image sensor, the light in the oblique direction does not reach the light receiving unit from the viewpoint of securing the color density, and the light collection rate at the end and center of the device is low. From the viewpoint of reducing inconveniences such as significant difference, it is preferably 0.05 μm or more and 1.0 μm or less, more preferably 0.1 μm or more and 0.8 μm or less, particularly preferably 0.2 μm or more and 0.7 μm or less.

<Exposure process>
In the exposure step, the colored layer formed in the colored layer forming step is exposed through a mask having a predetermined mask pattern.
That is, in this step, pattern exposure to the colored layer is performed, but only the colored layer portion irradiated with light is cured.

As radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are particularly preferably used.
Irradiation dose is more preferably ^5mJ / cm ^{2 ~1500mJ} / cm 2 is preferably ^{10mJ / cm 2 ~1000mJ / cm 2} , 10mJ / cm 2 ~500mJ / cm 2 being most preferred.

When manufacturing a color filter for a liquid crystal display device, the irradiation amount in the exposure of preferably ^5mJ / cm ^{2 ~200mJ} / cm 2 within the above ^{range, 10mJ / cm 2 ~150mJ / cm} 2 Gayori 10 mJ / cm ^{2 to} 100 mJ / cm ² is most preferable.
Further, when manufacturing a color filter for a solid-state imaging device, the irradiation amount in the ^{exposure, 30mJ / cm 2 ~1500mJ / cm} 2 within the above range is preferably 50mJ ^/ cm ² ~1000mJ ^/ cm 2 More preferably, 80 mJ / cm ^{2 to} 500 mJ / cm ² is most preferable.

<Development process>
Next, in the development step, the colored layer after being exposed in the exposure step is developed to form a colored pattern.
By performing this development step, the unexposed portion (uncured portion) of the colored layer is removed, and only the cured portion of the colored layer remains on the support.
As the developer used in this development step, an alkali developer is used, and among them, an alkali developer containing an organic alkaline compound is desirable from the viewpoint of not causing damage to the underlying circuit.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 seconds to 90 seconds.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4, And organic alkaline compounds such as 0] -7-undecene, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like.
An alkaline aqueous solution obtained by diluting these alkaline agents with pure water so as to have a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass is preferably used as the developer.

  When the colored curable composition of the present invention is used, since it contains the resin of the present invention, it has excellent pigment dispersibility and dispersion stability, and has a functional group having a pKa of less than 14 in the molecule. Therefore, it is excellent in developability. Therefore, even when a fine pattern is formed, a residual film of an uncured portion hardly occurs. Therefore, it is used for forming a colored pattern of a color filter for a solid-state image sensor such as a CCD image sensor that requires fine pattern formation. Is preferred.

In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.
Next, excess developer is washed away and dried.

  In the method for producing a color filter of the present invention, after the colored layer forming step, the exposure step, and the development step described above, the formed colored pattern is cured by heating (post-baking) and / or exposure as necessary. A curing step may be included.

<Curing process (Portobake)>
The post-baking in the curing step in the present invention is a heat treatment after development for complete curing of the colored pattern, and usually a heat curing treatment at 100 ° C. to 240 ° C. is performed.
When a support body is a glass substrate or a silicon substrate, 200 to 240 degreeC is preferable among the said temperature range.
In this post-baking, the coloring pattern obtained after development is continuously or batch-wise used by heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so as to satisfy the above conditions. It can be carried out.

  By repeating the color layer forming step, the exposure step, and the developing step (and the curing step if necessary) as described above for a desired number of hues, a color filter having a desired hue (3 colors or 4 colors) is produced. The

  As the application of the colored curable composition of the present invention, the application mainly to the pixel of the color filter has been mainly described, but it goes without saying that it can also be applied to a black matrix provided between the pixels of the color filter. The black matrix was subjected to pattern exposure in the same manner as in the above pixel production method except that the colored curable composition of the present invention was added with a black pigment such as carbon black or titanium black as a colorant. Then, it can form by performing alkali image development, and also post-baking as needed after that, and hardening of a film | membrane is accelerated | stimulated.

The color filter of the present invention is excellent in the dispersibility and dispersion stability of the pigment, and further, since the colored pattern is produced using the colored curable composition of the present invention which is also excellent in coatability and developability, the desired shape In addition, a high-resolution colored pattern can be easily formed, and color characteristics such as contrast and color unevenness of the formed colored pattern are excellent.
Therefore, the color filter of the present invention can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD. In particular, since the color filter of the present invention can have a high-resolution and thin colored pattern, it is effective to be used for color separation, and in particular, a high-resolution CCD element exceeding 1 million pixels. And a color filter such as a CMOS.
The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD element and a microlens for condensing light.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these. Unless otherwise specified, “part” is based on mass. Moreover, a weight average molecular weight and a number average molecular weight are the polystyrene conversion values by GPC measurement, and an acid value is calculated | required with the potentiometric method.

[Synthesis Example 1: Synthesis of Resin (A-1-1)]
114 g (1.0 mol) of 6-hexanolactone, 15.5 g (0.10 mol) of compound (I-11), and 0.10 g of monobutyltin oxide were mixed and heated at an internal temperature of 100 ° C. for 24 hours. After completion of the reaction, the solution was transferred to a petri dish and cooled to obtain 120 g of the resin (A-1-1) of the present invention.
The obtained resin (A-1-1) had a weight average molecular weight of 4,000, a number average molecular weight of 2,500, and an acid value of 86 mgKOH / g.

[Synthesis Examples 2 to 6: Synthesis of Resins (A-1-2) to (A-1-6)]
Except having changed the preparation amount of the compound (I-11) used in the said synthesis example 1 into the preparation amount of the following Table 1, operation similar to the synthesis example 1 is performed, and resin (A-1-2)-( A-1-6) was synthesized.

[Synthesis Example 7: Synthesis of Resin (A-2)]
114 g (1.0 mol) of 6-hexanolactone, 3.4 g (0.020 mol) of compound (I-7) and 0.10 g of monobutyltin oxide were mixed and heated at an internal temperature of 100 ° C. for 24 hours. After completion of the reaction, the solution was transferred to a petri dish and cooled to obtain 110 g of the resin (A-2) of the present invention.
The obtained resin (A-2) had a weight average molecular weight of 19,000, a number average molecular weight of 13,000, and an acid value of 29 mgKOH / g.

[Synthesis Example 8: Synthesis of Resin (A-3)]
114 g (1.0 mol) of 6-hexanolactone, 21.3 g (0.10 mol) of compound (I-16), and 0.10 g of monobutyltin oxide were mixed and heated at an internal temperature of 100 ° C. for 24 hours. After completion of the reaction, the solution was transferred to a petri dish and cooled to obtain 120 g of the resin (A-3) of the present invention.
The obtained resin (A-3) had a weight average molecular weight of 5,000, a number average molecular weight of 3,000, and an acid value of 42 mgKOH / g.

[Synthesis Example 9: Synthesis of Resin (A-4)]
300 g (1.0 mol) of 12-hydroxystearic acid, 15.4 g (0.033 mol) of a 30% by weight aqueous solution of compound (I-28), and 1 L of toluene are mixed, and water is added through a Dean-Stark tube at an external temperature of 140 ° C. The reaction was carried out for 48 hours while removing. After the reaction was completed, toluene was removed by reducing the pressure to an external temperature of 100 ° C. and an internal pressure of 1 mmHg to obtain 300 g of the resin (A-4) of the present invention.
The obtained resin (A-4) had a weight average molecular weight of 13,000, a number average molecular weight of 7,000, and an acid value of 6 mgKOH / g.

[Synthesis Example 10: Synthesis of Resin (A-5)]
114 g (1.0 mol) of 6-hexanolactone, 8.6 g (0.050 mol) of decanoic acid and 0.10 g of monobutyltin oxide were mixed and heated at an internal temperature of 160 ° C. for 24 hours. The reaction temperature was raised to 120 ° C., 7.0 g (0.050 mol) of compound (I-5) was added thereto, and the mixture was heated for 24 hours. After completion of the reaction, the solution was transferred to a petri dish and cooled to obtain 110 g of the resin (A-5) of the present invention.
The weight average molecular weight of the obtained resin (A-5) was 9,000, the number average molecular weight was 6,000, and the acid value was 43 mgKOH / g.

[Synthesis Example 11: Synthesis of Comparative Resin (B-1)]
6-hexanolactone (114 g, 1.0 mol), octanol (13.0 g, 0.10 mol), and monobutyltin oxide (0.10 g) were mixed and heated at an internal temperature of 160 ° C. for 24 hours. Synthesized. Next, the reaction temperature was raised to 120 ° C., 4.7 g (0.033 mol) of phosphorus oxide was added, and the mixture was heated for 24 hours. After completion of the reaction, the solution was transferred to a petri dish and cooled to obtain 110 g of a comparative resin (B-1).
The mixture of the obtained comparative resin (B-1) had a weight average molecular weight of 8,000, a number average molecular weight of 6,000, and an acid value of 42 mgKOH / g.
From the MASS measurement, phosphorus oxide was completely lost, but ¹ H NMR showed that 10 mol% of the intermediate (B ′) remained.

[Synthesis Example 12: Synthesis of Resin for Comparison (B-2)]
Except having changed the usage-amount of the phosphorus oxide used in the synthesis example 11 into 0.050 mmol, operation similar to the synthesis example 11 was performed, and 110g of comparative resin (B-2) was obtained.
The mixture of the obtained comparative resin (B-2) had a weight average molecular weight of 8,000, a number average molecular weight of 6,000, and an acid value of 85 mgKOH / g.
Further, from ¹ H NMR, the intermediate (B ′) completely disappeared, but from MASS measurement, it was found that phosphorus oxide remained.

[Examples 1 to 15, Comparative Examples 1 and 2]
A1-1. Preparation of Pigment Dispersion Liquid Pigment (40 parts by mass) described in Table 2 below, resin of the present invention or comparative resin (20 parts by mass) described in Table 2 below, propylene glycol 2-monomethyl ether 1-acetate ( Hereinafter, a mixed solution composed of 140 parts by mass of PGMEA) and pigment derivatives (0.2 parts by mass) described in Table 2 below only in Examples 7 to 15 was mixed with a bead mill (0.3 mm diameter of zirconia beads). The pigment dispersions (X-1) to (X-17) were prepared by mixing and dispersing for 3 hours.

<Primary particle diameter of pigment>
The prepared pigment dispersion was applied, and 50 primary particle sizes of the pigment in the coating film were observed with an SEM, and an average value was calculated. The results are shown in Table 2.

<Dispersibility and dispersion stability>
Further, the viscosities of one day after the preparation of the pigment dispersion and one month after the preparation were measured. For measuring the viscosity, a TV-22 viscometer cone plate type (Toki Sangyo Co., Ltd.) was used. The results are shown in Table 2.
It can be seen that the smaller the viscosity value, the better the dispersibility of the pigment, and the smaller the viscosity and the smaller the increase in viscosity over time, the better the dispersion stability of the pigment.

  The structures of the pigment derivatives (C-1) and (C-2) described in Table 2 are as follows.

[Examples 16 to 31, Comparative Examples 3 and 4]
Here, an example in which a colored curable composition for forming a color filter for a liquid crystal display element is prepared will be described.

1-2. Preparation of colored curable composition (coating liquid) Using the pigment dispersion liquids (X-1) to (X-17), the colored curable composition was prepared by stirring and mixing so that the following composition ratio was obtained.
-600 parts of the pigment dispersion described in Table 3-30 parts of the photopolymerization initiator described in Table 3-50 parts of pentaerythritol tetraacrylate-Alkali-soluble resin (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, Molar ratio: 80/10/10, Mw: 10,000) 5 parts Solvent: 900 parts of propylene glycol monomethyl ether acetate 1 part of substrate adhesion agent (3-methacryloxypropyltrimethoxysilane)

1-3. Formation of Colored Layer Using the above-mentioned colored curable composition as a resist solution, slit-applied to a glass substrate of 550 mm × 650 mm under the following conditions, and then waiting for 10 minutes as it is, followed by vacuum drying and prebaking (100 ° C. 80 Seconds) to form a coating film (colored layer) of the colored curable composition.

(Slit application conditions)
・ Gap of the opening at the tip of the coating head: 50 μm
・ Application speed: 100 mm / second ・ Clearance between substrate and application head: 150 μm
・ Dry film thickness 1.75μm
・ Application temperature: 23 ℃

1-4. Exposure and development Thereafter, using a 2.5 kW ultra-high pressure mercury lamp, a coating film (colored layer) of the colored curable composition was applied with a LE4000A manufactured by Hitachi High-Technology Corporation using a test photomask having a line width of 20 μm. The pattern was exposed with an exposure amount corresponding to “exposure sensitivity” evaluated by the method described later. After the exposure, the entire surface of the coating film was covered with a 1% aqueous solution of an inorganic developer (trade name: CDK-1, manufactured by FUJIFILM Electronics Materials Co., Ltd.) and allowed to stand for 60 seconds.

1-5. Heat treatment After stationary, pure water was sprayed in a shower to wash away the developer, and the coating film subjected to the exposure (photocuring) treatment and development treatment was heated in an oven at 220 ° C. for 1 hour (post-baking).
Thereby, the color filter which has the coloring pattern formed using the colored curable composition on the glass substrate was obtained.

1-6. Performance Evaluation The dispersibility, dispersion stability, exposure sensitivity, coatability, and developability of the colored curable composition prepared as described above were evaluated as shown below. Table 3 shows the results.
Further, the contrast of the color filter obtained as described above was also evaluated as follows, and the results are shown in Table 3.

1-6-1. Dispersibility, dispersion stability 1-2. The viscosity of the colored curable composition obtained in the above section was measured for one day after the preparation and one month after the preparation. For measuring the viscosity, a TV-22 viscometer cone plate type (Toki Sangyo Co., Ltd.) was used.
It can be seen that the smaller the viscosity value, the better the dispersibility of the pigment, and the smaller the viscosity and the smaller the increase in viscosity over time, the better the dispersion stability of the pigment.

1-6-2. Exposure sensitivity 1-4. In ^terms, exposure is performed by changing the various exposure amounts in the range of ^{10mJ / cm 2 ~500mJ / cm 2} , the exposure amount of the pattern line width after post-baking becomes 20μm was evaluated as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity.

1-6-3. Application property 1-3. The coating film (colored layer) of the colored curable composition obtained in the above section was observed with the naked eye to observe whether there was any coating unevenness represented by striation or the like.
A sample having no unevenness was marked with ◯, and a sample with unevenness was marked with ×.

1-6-4. Developability 1-4. In the section, after development, 20 development parts (unexposed parts) were observed with an SEM, and the number of residues was counted.
The smaller the residue, the better the developability.

1-6-5. Contrast of color filter 1-5. The color filter obtained in the above section is sandwiched between two polarizing plates, and the luminance of transmitted light when the polarizing axis of the polarizing plate is parallel and vertical is measured with a color luminance meter (color luminance meter BM-7 manufactured by Topcon Corporation). ) To determine the contrast.
The higher the contrast, the better the performance as a color filter for a liquid crystal display element.

The photopolymerization initiators (Z-1) to (Z-7) described in Table 3 are as follows.
In addition, the photoinitiator (Z-1) shown below is a mixture of (Z-1-a) :( Z-1-b) = 20: 10 (parts by mass).

[Examples 32-45, Comparative Examples 5 and 6]
Hereinafter, the example which prepared the colored curable composition for forming the color filter for solid-state image sensors is given and demonstrated.

2-1. Preparation of resist solution Components of the following composition were mixed and dissolved to prepare a resist solution.
<Composition of resist solution>
Solvent: propylene glycol monomethyl ether acetate 19.20 parts Solvent: ethyl lactate 36.67 parts Alkali-soluble resin: benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate copolymer (molar ratio = 60/22 / 18, 40% PGMEA solution with a weight average molecular weight of 15,000 number average molecular weight) 30.51 parts ・ Compound containing ethylenically unsaturated double bond: dipentaerythritol hexaacrylate
12.20 parts ・ Polymerization inhibitor: p-methoxyphenol 0.0061 parts ・ Fluorosurfactant: F-475, Dainippon Ink & Chemicals, Inc. 0.83 part ・ Photopolymerization initiator: trihalomethyltriazine -Based photopolymerization initiator 0.586 parts (TAZ-107, manufactured by Midori Chemical Co., Ltd.)

2-2. Production of silicon substrate with undercoat layer A 6-inch silicon wafer was heated in an oven at 200 ° C. for 30 minutes. Next, the resist solution is applied onto the silicon wafer so as to have a dry film thickness of 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. Got.

2-3. Preparation of colored curable composition (coating liquid) Using the pigment dispersion liquids (X-1) to (X-17), the colored curable composition was prepared by stirring and mixing so that the following composition ratio was obtained.
-600 parts of pigment dispersion described in Table 4-30 parts of photopolymerization initiator described in Table 4-Compound containing ethylenically unsaturated double bond (TO-1382 manufactured by Toagosei Co., Ltd.) 25 parts ( Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate and succinic acid derivative of dipentaerythritol pentaacrylate)
・ Compound containing ethylenically unsaturated double bond 30 parts (dipentaerythritol hexaacrylate)
・ 900 parts of propylene glycol monomethyl ether acetate

2-4. Preparation of color filter by colored curable composition and evaluation of exposure sensitivity The colored curable composition prepared as described above was prepared according to 2-1. The colored layer (coating film) was formed by coating on the undercoat layer of the silicon wafer with the undercoat layer obtained in (1). And the heat processing (prebaking) were performed for 120 second using a 100 degreeC hotplate so that the dry film thickness of this coating film might be set to 0.5 micrometer.

Then, various exposure amount of i-line stepper exposure apparatus FPA-3000i5 + (Canon (Ltd.)) 50 mJ using a pattern at a wavelength of 365nm through 1.5μm square Island pattern mask ^/ cm ^{2 ~1200mJ /} cm 2 And exposed.
Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (Fuji Film). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.

The silicon wafer on which the colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotational speed of 50 r. p. m. While being rotated, pure water was supplied from the upper part of the rotation center in the form of a shower through a spray nozzle, followed by rinsing treatment, and then spray drying.
Thereafter, the size of the colored pattern was measured using a length measuring SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation). The exposure amount at which the pattern size was 2 μm was evaluated as the exposure sensitivity.

2-5. Performance Evaluation The dispersibility, dispersion stability, exposure sensitivity, coating property, and developability of the colored curable composition prepared as described above were evaluated as shown below. Table 4 shows the results.
Further, the contrast and color unevenness of the color filter obtained as described above were also evaluated as follows, and Table 4 shows the results.

2-5-1. Dispersibility, dispersion stability 2-3. The viscosity of the colored curable composition obtained in the above section was measured for one day after the preparation and one month after the preparation. For measuring the viscosity, a TV-22 viscometer cone plate type (Toki Sangyo Co., Ltd.) was used.
It can be seen that the smaller the viscosity value, the better the dispersibility of the pigment, and the smaller the viscosity and the smaller the increase in viscosity over time, the better the dispersion stability of the pigment.

2-5-2. Exposure sensitivity 2-4. As described in the section, the exposure amount at which the pattern size was 2 μm was evaluated as the exposure sensitivity. The smaller the exposure value, the higher the sensitivity.

2-5-3. Application property 2-4. The coating film of the colored curable composition obtained in the item (1) was observed with the naked eye to observe whether there was any coating unevenness represented by striation or the like.
A sample having no unevenness was marked with ◯, and a sample with unevenness was marked with ×.

2-5-4. Developability 2-4. In the section, after development, 20 development parts (unexposed parts) were observed with an SEM, and the number of residues was counted.

2-5-6. Color filter color unevenness 2-4. The color unevenness of the color filter obtained in the section was evaluated by analyzing the luminance distribution by the following method and based on the ratio of the pixels whose deviation from the average is within ± 5% to the total number of pixels. The evaluation criteria are as follows.
A method for measuring the luminance distribution will be described. First, 2-3. The colored curable composition obtained in the above section 2-2. The colored layer (coating film) was formed by coating on the undercoat layer of the glass plate with the undercoat layer produced by the method described in the section.
Heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of this coating film was 0.7 μm.
The luminance distribution of the coated glass plate was analyzed by analyzing an image taken with a microscope MX-50 (manufactured by Olympus), and the ratio (percentage) of pixels having a deviation from the average within ± 5% was calculated. The higher this value, the smaller the color unevenness and the better.

  Photopolymerization initiators (Z-1) to (Z-5) described in Table 4 are the same as those described above.

From the results of Tables 3 and 4, it can be seen that the colored curable compositions of Examples are excellent in pigment dispersibility and dispersion stability. In addition, when the colored curable composition of this example is coated on a support and then subjected to exposure and development to form a colored pattern, the coating property, exposure sensitivity, and developability may be excellent. I understand.
Furthermore, it turns out that the color filter provided with the coloring pattern formed using the colored curable composition of an Example is excellent in contrast and a color nonuniformity compared with a comparative example.

  From these results, even when the colored curable composition of the example is a case of producing a color filter for use in a solid-state imaging device or a case of producing a color filter for use in a liquid crystal display device, It was found that excellent pattern formability was realized and a colored pattern having excellent color characteristics could be formed.

Claims (10)

(A) A compound represented by the following general formula (I) is reacted with (b-1) at least one compound selected from a lactone and a hydroxyl group-containing carboxylic acid, or (b-2) a polyester. A resin represented by the following general formula (II).

(In the above general formula (I), V represents an organic group containing a group having a pKa of less than 4. W represents a nucleophilic group. N represents an integer of 1 or more.)

(In the general formula (II), V has the same meaning as V in the general formula (I). W ′ represents the residue of W in the general formula (I). Y represents a polyester chain. N represents the general formula. (It is synonymous with n in (I).)   The resin according to claim 1, wherein the group having a pKa of less than 4 contained in V in the general formula (I) is a phosphate group or a sulfonate group. (A) A compound represented by the following general formula (I) is reacted with (b-1) at least one compound selected from a lactone and a hydroxyl group-containing carboxylic acid, or (b-2) a polyester. The manufacturing method of resin represented by the following general formula (II).

(In the above general formula (I), V represents an organic group containing a group having a pKa of less than 4. W represents a nucleophilic group. N represents an integer of 1 or more.)

(In the general formula (II), V has the same meaning as V in the general formula (I). W ′ represents the residue of W in the general formula (I). Y represents a polyester chain. N represents the general formula. (It is synonymous with n in (I).)   (A) A pigment dispersion containing the resin according to claim 1, (B) a pigment, and (C) a solvent.   (A) The resin according to claim 1 or 2, (B) a pigment, (C) a solvent, (D) a photopolymerization initiator, and (E) a compound containing an ethylenically unsaturated double bond. Colored curable composition.   The colored curable composition according to claim 5, wherein the photopolymerization initiator (D) is an oxime initiator.   (A) A pigment dispersion containing the resin according to claim 1 or 2, (B) a pigment, and (C) a solvent, (D) a photopolymerization initiator, and (E) an ethylenically unsaturated diester. A method for preparing a colored curable composition comprising adding a compound containing a heavy bond.   A color filter having a colored pattern formed using the colored curable composition according to claim 5 or 6 on a support.   The color filter according to claim 8, which is used for color separation. A colored layer forming step of applying the colored curable composition according to claim 5 or 6 on a support to form a colored layer;
An exposure step of pattern-exposing the colored layer through a mask;
A development step of developing the colored layer after exposure to form a colored pattern;
A method for producing a color filter comprising: