JP2009025783A - Pigment dispersed resist composition for color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment dispersed resist composition for color filter excellent in developing characteristic in addition to high transparency and high contrast. <P>SOLUTION: The pigment dispersed resist composition for color filter contains an organic pigment, a pigment dispersant, a film forming resin, a photopolymerizable compound, a photopolymerizable initiator and a solvent, the pigment dispersant including two components of (A) an acrylic block copolymer having amine value of 20-40 mgKOH/g and acid value of 15-25 mgKOH/g, which is obtained by living anionic polymerization, and (B) a carbodiimide-based compound having no acidic group within the molecule, and (A) and (B) being included in a mass ratio of 90/10-50/50. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a pigment-dispersed resist composition for a color filter having high transparency, high contrast, and excellent development characteristics.

In manufacturing a color filter using a pigment-dispersed resist composition for color filters, a photosensitive resist film is usually applied to a substrate and then exposed to ultraviolet rays through a mask having a desired pattern. It is obtained by a method of creating a pattern by curing, removing the unexposed coating film with a developer, and then post-baking. In order to form the pattern, a pigment-dispersed resist composition for color filters in which a photosensitive material is added to the pigment composition is used.

The color filter liquid crystal device having the color filter thus obtained has high transparency and high contrast due to intensifying competition with various electronic image display devices such as plasma display methods and organic EL methods. However, it is required to have excellent development characteristics.

In order to obtain the above high transparency and high contrast, it is known that it is effective to make the pigment fine particles. However, as the pigment becomes finer, the pigment tends to aggregate due to an increase in the particle surface area.

In order to prevent the aggregation of the pigment, a method of adding a surfactant or a polymer resin having an absorptivity to the pigment as a pigment dispersant has been proposed (for example, see Patent Document 1). However, when an acrylic copolymer having an amine value and an acid value is used as a pigment dispersant, it is effective in preventing the aggregation of the pigment, but the development margin (the unexposed portion is removed with a developer). And the time until the exposed portion is removed) is shortened, and the edge portion is inversely tapered, resulting in a lack of sharpness.
JP 2004-272219 A

An object of the present invention is to provide a pigment-dispersed resist composition for a color filter having high transparency, high contrast, and excellent development characteristics.

As a result of intensive studies to solve the above problems, the present inventors have found that when an acrylic block copolymer having an amine value and an acid value is used as a pigment dispersant, an acidic group is present in the molecule as the pigment dispersant. The present inventors have found that the above-mentioned problems can be solved by using a carbodiimide-based compound that does not contain any of the above in combination at a specific ratio, thereby completing the present invention.

That is, the present invention is (1) a pigment-dispersed resist composition for a color filter containing an organic pigment, a pigment dispersant, a film-forming resin, a photopolymerizable compound, a photopolymerizable initiator, and a solvent, The pigment dispersant is (A) an acrylic block copolymer having an amine value of 20 to 40 mg KOH / g and an acid value of 15 to 25 mg KOH / g obtained by living anionic polymerization, and (B) a carbodiimide having no acidic group in the molecule. The present invention relates to a pigment-dispersed resist composition for a color filter, which comprises two components of a system compound and (A) and (B) in a mass ratio of 90/10 to 50/50.
Hereinafter, the present invention will be described in more detail.

The organic pigment constituting the pigment-dispersed resist composition for color filters of the present invention has a clear hue and high fastness, C.I. I. Pigment Red 19, 38, 43, 88, 122, 123, 144, 149, 166, 168, 177, 178, 179, 188, 190, 207, 208, 209, 216, 224, 226, 242, 254, 264, etc. Red pigments of C.I. I. Pigment Blue 15: 1, 15: 3, 15: 4, 15: 6, 16, 22, 29, 60, 64, and the like; C.I. I. Pigment Green 7, 10, 36, etc. green pigments; C.I. I. Pigment Yellow 24, 81, 83, 93, 95, 97, 108, 109, 110, 117, 123, 128, 137, 138, 139, 150, 153, 154, 166, 168, 180, 185, etc. C. I. Pigment Violet 19, 23, 29, 30, 31, 37, 88, and other purple pigments; C.I. I. Orange pigments such as Pigment Orange 31, 38, 40, 43, 61, 71 can be used.

In order to obtain a clearer hue, the organic pigment is preferably premixed and salt milled by a conventionally known method.
Particularly preferably, a kneading apparatus (trimix) that revolves a mixture containing an organic pigment, a water-soluble inorganic salt, and a water-soluble dispersion medium that does not substantially dissolve the inorganic salt while rotating three stirring blades. And an organic pigment subjected to salt milling treatment obtained by removing the inorganic salt and the water-soluble dispersion medium.

As the water-soluble inorganic salt, sodium chloride (sodium chloride) is preferable.
The particle size of the inorganic salt is preferably 200 μm or less, more preferably 50 μm or less. Thereby, the particle diameter of the pigment can be made finer and uniform than the primary particle diameter.
In the present invention, the particle size of the inorganic salt was measured by a laser diffraction particle size measurement method and a measuring device: Nanotrac (UPA-EX150, manufactured by Nikkiso Co., Ltd.).

As the water-soluble dispersion medium, a water-soluble organic solvent that does not substantially dissolve the inorganic salt used as the dispersion medium can be used, and has both conditions of being water-soluble and not dissolving the inorganic salt. If it is a thing, it will not specifically limit. Among them, a high boiling point solvent having a boiling point of 120 ° C. or more is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent easily evaporates. Examples of such water-soluble organic solvents include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, 1-methoxy-2-propanol, and 1-ethoxy. Alkoxy alcohols such as 2-propanol; glycols such as diethylene glycol, triethylene glycol, liquid polyethylene glycol, dipropylene glycol, and low molecular weight polypropylene glycol; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl Used ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, etc. It is.

In the present invention, the amount of the organic pigment used is preferably 1 to 40% by mass in the color filter pigment dispersion resist composition of the present invention.

As the pigment dispersant constituting the pigment dispersion resist composition for color filters of the present invention, (A) an acrylic block copolymer having an amine value of 20 to 40 mgKOH / g and an acid value of 15 to 25 mgKOH / g obtained by living anion polymerization And (B) two components of a carbodiimide compound having no acidic group in the molecule are used in combination. When only an acrylic block copolymer is used as a pigment dispersant, it is difficult to obtain all the performances of transparency, contrast, and development characteristics. However, in the present invention, a specific acrylic block copolymer is used as a pigment dispersant. Since a polymer and a carbodiimide-based compound having no acidic group are used in combination, all these performances can be ensured. The reason why such an effect can be obtained is presumed to be that a specific synergistic effect is produced when the above two components are used in combination.

The acrylic block copolymer [component (A)] includes a pigment adsorption block containing a basic group as a pigment adsorption group, a pigment adsorption block containing an acid group as a pigment adsorption group, and a block not containing a pigment adsorption group It is preferable to use a block copolymer having:

As the pigment adsorption group, a pigment adsorption block further containing an acid group in addition to a pigment adsorption block containing a basic group is constituted by using a monomer having an acidic group together with a monomer having a basic group. Can be mentioned.

The monomer having a basic group is a monomer having a primary amino group, a secondary amino group or a tertiary amino group, specifically, N, N-dimethylaminoethyl (meth). Acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylacrylamide, diethylacrylamide, dimethylaminopropylmethacrylamide, acryloylmorpholine, vinylimidazole, 2-vinylpyridine, monomer having amino group and caprolactone skeleton , A reaction product of a monomer having a glycidyl group such as glycidyl (meth) acrylate and a compound having one secondary amino group in the molecule, a (meth) acryloylalkyl isocyanate compound and 4- (2-aminomethyl) -Pyridine, 4- (2-aminoethyl) -pyridine, 4- (2-H Roxyethyl) pyridine, 1- (2-aminoethyl) -piperazine, 2-amino-6-methoxybenzothiazole, 1- (2-hydroxyethylimidazole), N, N-diallylmelamine, N, N-dimethyl-1, Examples include a reaction product with 3-propanediamine.

As the monomer having an acidic group, a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group, specifically, as a monomer having a carboxyl group, acrylic acid, methacrylic acid, As monomers having a sulfonic acid group, such as unsaturated monocarboxylic acid compounds such as crotonic acid, unsaturated dicarboxylic acid compounds such as maleic acid, fumaric acid and itaconic acid, and half esters thereof, 2-acrylamido-2-methyl- As monomers having a phosphate group, such as 1-propanesulfonic acid, 2-methacrylamide-2-methyl-1-propanesulfonic acid, styrenesulfonic acid, acid phosphonyl (meth) acrylate, acid phosphonylethyl (meta ) Acrylate and the like.

Constituent components of the block not containing the pigment adsorbing group include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and benzyl chloride, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate. And unsaturated carboxylic acid alkyl esters such as benzyl (meth) acrylate, polycaprolactone-containing monomers, polyalkylene glycol monoester monomers, and the like.
The acrylic block copolymer is obtained by living anion polymerization or the like, and a conventionally known polymerization method can be used.

The amine value of the acrylic block copolymer is 20 to 40 mgKOH / g.
In the specification of the present application, the amine value means an amine value per 1 g of solid content, and a 0.1N hydrochloric acid aqueous solution is used, and potentiometric titration (for example, COMMITITE (AUTO TITRATOR COM-900, BURET B-900, TITSTATIONK) -900), manufactured by Hiranuma Sangyo Co., Ltd., and then converted into an equivalent of potassium hydroxide.

The acid value of the acrylic block copolymer is 15 to 25 mgKOH / g.
In addition, in this specification, an acid value means the acid value per 1g of solid content, and it is potentiometric titration method (For example, COMMITITE (AUTO TITRATOR COM-900, BURET B-900, TITSTATION K-900) according to JISK0070. ), A value measured by Hiranuma Sangyo Co., Ltd.).

Examples of commercially available products of the acrylic block copolymer (A) include Disperbyk-2001 (amine value 29 mgKOH / g, acid value 19 mgKOH / g, manufactured by Big Chemie) and the like.

Moreover, it does not specifically limit as said (B) carbodiimide type compound which does not have an acidic group in a molecule | numerator, The following can be mentioned as a suitable example.
(B) -1: a carbodiimide compound described in JP-A Nos. 2003-344996 and 2004-038772,
(B) -2: A carbodiimide-based compound having a carbodiimide group having at least one of a polyester side chain, a polyether side chain, and a polyacryl side chain (International Publication WO 03/075527, JP 2006-225431 A)
(B) -3: Basic group-containing carbodiimide compound (International Publication WO 04/000950)
(B) -4: A carbodiimide compound into which at least one selected from a colorant intermediate chain and a colorant derivative chain has been introduced (International Publication WO04 / 003085)
(B) -5: A carbodiimide compound into which a polybutadiene chain is introduced (Japanese Patent Laid-Open No. 2006-257243)
(B) -6: A carbodiimide compound into which a chain containing an amide group is introduced (Japanese Patent Laid-Open No. 2006-176657)

Among the above, a basic group-containing carbodiimide compound, among them, at least one side chain selected from the group consisting of a polyester side chain, a polyether side chain, a polyacryl side chain, and a polybutadiene side chain, and at least 1 A basic group-containing carbodiimide compound having a basic nitrogen-containing group in the molecule is preferred.
This compound can be obtained, for example, by the following method.

In addition, the “basic group-containing carbodiimide compound” in the present specification can include a compound obtained by introducing the above side chain and a basic nitrogen-containing group based on a compound having a carbodiimide group. Of course, those having a carbodiimide group in the molecule of the finally obtained compound are also included.

The “side chain” refers to a chain that is branched from the main chain when the carbodiimide compound is used as the main chain.
The “basic nitrogen-containing group” includes not only a group containing nitrogen that forms a quaternary ammonium ion in water but also a group containing nitrogen that acts as a Lewis base. As an amino group or a nitrogen-containing heterocyclic group.

In the present invention, at least one selected from the group consisting of a polyester chain, a polyether chain, a polyacryl chain, and a polybutadiene chain by utilizing the reaction between such a carbodiimide group and a functional group capable of reacting with the carbodiimide group. When seeds are introduced into the molecule, the reaction between the carbodiimide group and the functional group is sometimes referred to as a grafting reaction. The side chain introduced by the method is grafted and the introduced polyester side chain is grafted. Polyester side chain, polyether side chain may be called grafted polyether side chain, polyacryl side chain may be called grafted polyacryl side chain, and polybutadiene side chain may be called grafted polybutadiene side chain.

Preferred examples of the basic group-containing carbodiimide compound include a basic nitrogen-containing compound such as an amino group or a nitrogen-containing heterocyclic group in the isocyanate group based on a compound having at least one isocyanate group and carbodiimide group in the molecule. A method of reacting a compound, and a method of adding at least one side chain selected from the group consisting of a polyester side chain, a polyether side chain, a polyacryl side chain, and a polybutadiene side chain by grafting reaction At least one selected from the group consisting of a polyester side chain, a polyether side chain, a polyacryl side chain, and a polybutadiene side chain by grafting reaction to the side chain in the main chain obtained in And a basic group-containing carbodiimide compound having a side chain.

In order to obtain a basic group-containing carbodiimide compound by the production method of the present invention, the carbodiimide compound used as a starting material has at least one carbodiimide group in the molecule, that is, a group represented by -N = C = N-. And a compound having at least one isocyanate group, and will be described in more detail with the following preferable examples (a) to (c). It is appropriately selected and used depending on the form.

(A) A carbodiimide compound having an isocyanate group obtained by decarboxylation of a diisocyanate compound.
A carbodiimide compound can be produced by carbodiimidizing an isocyanate compound by a decarboxylation reaction in an organic solvent in the presence of a carbodiimidization catalyst, and when the material is a diisocyanate compound, an isocyanate is present at both ends of the molecule. A carbodiimide compound having a group will be obtained.

In the above production method, the diisocyanate compound to be decarboxylated includes, for example, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, tetramethylxylylene diisocyanate. And aliphatic, alicyclic, aromatic or araliphatic diisocyanate compounds.

As said organic solvent, it is preferable to use what has a high boiling point and does not have active hydrogen which reacts with an isocyanate compound and the carbodiimide compound to produce | generate, For example, aromatic hydrocarbons, such as toluene, xylene, diethylbenzene; Glycol ether esters such as diethylene glycol diacetate, dipropylene glycol dibutyrate, hexylene glycol diacetate, glycol diacetate, methyl glycol acetate, ethyl glycol acetate, butyl glycol acetate, ethyl diglycol acetate, butyl diglycol acetate; Ketones such as ketones, acetophenone, propiophenone, diisobutylketone, cyclohexanone; amyl acetate, propyl propionate, ethyl butyrate Fatty acid esters and the like can be mentioned.

As the carbodiimidization catalyst, phospholenes and phospholene oxides are preferably used. For example, 1-ethyl-3-methyl-3-phospholene oxide, 1-phenyl-3-methyl-3-phospholene oxide 1-phenyl-3-methyl-2-phospholene oxide and the like.

As a method of performing a decarboxylation reaction of an isocyanate group using these materials, a known method can be used. For example, the reaction can be performed at a reaction temperature of 100 to 200 ° C. in a nitrogen atmosphere. Examples of other methods for obtaining the above compound having a carbodiimide group include methods such as US Pat. No. 2,941,956, Japanese Patent Publication No. 47-33279, Japanese Patent Application Laid-Open No. 5-178954, and Japanese Patent Application Laid-Open No. 6-56950. Is mentioned.

With respect to the carbodiimide compound having an isocyanate group obtained by using such a production method, for example, a compound obtained by decarboxylation of K mol (wherein K ≧ 2) diisocyanate compound is represented by the following general formula (1- Shown in 1).
OCN- (A-N = C = N) _K-1 -A-NCO (1-1)
In the general formula (1-1), A represents a residue excluding the isocyanate group of the diisocyanate compound used for the synthesis of the carbodiimide compound having an isocyanate group.

Examples of commercially available carbodiimide compounds having an isocyanate group represented by the general formula (1-1) include carbodiimide compounds using tetramethylxylylene diisocyanate as raw materials, such as carbodilite V-03, V-05, etc. Product name, manufactured by Nisshinbo Co., Ltd.).

(B) A carbodiimide compound obtained by further extending the carbodiimide compound of (a) with a chain extender.
The carbodiimide compound of the above (a) is made high in molecular weight using a chain extender capable of reacting with an isocyanate group, and can be a compound containing more carbodiimide groups in the molecule. The chain extender that can be used at this time is preferably a compound that has low reactivity with a carbodiimide group and that selectively reacts with an isocyanate group first, and examples thereof include a diol compound, a diamine compound, and hydrazine. .

(C) A compound obtained by decarboxylation of 1 mol of a monoisocyanate compound and K mol (where K is an integer of 1).
As an intermediate compound between those having an isocyanate group at both ends of the molecule and those having no isocyanate group, the reaction is stopped with a monoisocyanate compound at only one end, and a carbodiimide compound having an isocyanate group at the other end is also obtained. Can do. A carbodiimide compound in which one end of such a molecule is stopped with a monoisocyanate compound can be represented by the following general formula (1-2).
OCN- (A-N = CN) _k- B (1-2)
In the general formula (1-2), B represents a residue other than the isocyanate group of the monoisocyanate compound used for the synthesis of the carbodiimide compound having an isocyanate group. A is as described above.

Here, examples of the diisocyanate compound that can be used include the same synthetic materials as in the above (a), and examples of the monoisocyanate compound include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octadecyl isocyanate, and phenyl. Examples thereof include aliphatic, alicyclic, aromatic or araliphatic monoisocyanate compounds such as isocyanate.
As mentioned above, the said carbodiimide compound (a)-(c) may be used independently as a starting material of a carbodiimide type compound, and may use 2 or more types together.

And in said carbodiimide compound, the thing of carbodiimide equivalent is 100-50000 is utilized. Here, the carbodiimide equivalent means a number represented by (molecular weight of carbodiimide compound) / (number of carbodiimide groups in carbodiimide compound molecule). If the carbodiimide equivalent of the compound is too high, the weight ratio of the polyester side chain, the polyether side chain, the polyacryl side chain, and the polybutadiene side chain to the whole molecule of the carbodiimide compound is reduced, and the dispersion stability of the pigment is reduced. May decrease. On the other hand, a compound having a low carbodiimide equivalent can increase the weight ratio of a side chain having a polyester side chain, a polyether side chain, a polyacryl side chain, and a polybutadiene side chain to the entire molecule of the carbodiimide compound. However, it is difficult to control the synthesis of the carbodiimide compound itself and the reaction for introducing the side chain. Therefore, a more preferable carbodiimide equivalent is 200 or more and 10,000 or less.

The basic group-containing carbodiimide compound of the present invention has a basic nitrogen-containing group in the molecule. As a method for obtaining such a carbodiimide compound, for example, a reaction with the above isocyanate group is used. First, a basic nitrogen-containing group is also introduced into the main chain of the carbodiimide group-containing compound (in addition, after the introduction of the side chain, the reaction with the isocyanate group is used). Thus, a method of introducing a basic nitrogen-containing group into the main chain of the carbodiimide group-containing compound can also be used because the final compound is the same). And when introducing a basic nitrogen-containing group into the main chain of the carbodiimide group-containing compound, from the above conditions, a hydroxyl group suitable as a functional group capable of selectively reacting with an isocyanate group, a carbodiimide group or an isocyanate group It is preferable to use a compound having a tertiary amino group or a basic nitrogen-containing heterocyclic group that does not participate in the reaction.

Specifically, examples of the compound having one hydroxyl group and a tertiary amino group include N, N-dialkylalkanolamine compounds such as N, N-dimethylethanolamine and N, N-diethylethanolamine, and secondary amines. Examples thereof include an ethylene oxide adduct of a compound, a reaction product of a secondary amine compound and an epoxy compound, and the like. Examples of the compound having two hydroxyl groups and a tertiary amino group include N-alkyl dialkanolamine compounds such as N-methyldiethanolamine and N-ethyldiethanolamine, ethylene oxide adducts of primary amine compounds, primary amine compounds, and the like. The reaction material with an epoxy compound etc. can be mentioned.

Further, examples of the compound having a hydroxyl group and a basic nitrogen-containing heterocyclic group include, for example, a heterocyclic ring containing tertiary basic nitrogen such as hydroxypyridine, pyridinemethanol, pyridineethanol, pyridine, pyrazine, triazine, quinoline and the like. And a compound having a hydroxyl group can be used. Moreover, even a heterocyclic compound containing secondary basic nitrogen such as piperidine or piperazine can be used by alkylating and tertiaryizing to contain a hydroxyl group.

Then, 2 mol of the compound having one hydroxyl group may be reacted with 1 mol of the compound represented by the general formula (1-1) to introduce a basic nitrogen-containing group at the end of the main chain. Is reacted with the compound represented by the general formula (1-1) in an amount such that the isocyanate group is in excess of the hydroxyl group, and a basic nitrogen-containing group is introduced into the main chain. Alternatively, 2 mol of a compound having one hydroxyl group may be reacted with 1 mol of the compound described in (b) to introduce a basic nitrogen-containing group at the end of the main chain, or a compound having two hydroxyl groups May be reacted with the compound described in (b) in an amount in which the isocyanate group is in excess of the hydroxyl group to introduce a basic nitrogen-containing group in the main chain, and 1 mol of the compound having one hydroxyl group Reacting with 1 mol of the compound represented by the above general formula (1-2) In addition, a basic nitrogen-containing group may be introduced at the end of the main chain, and 1 mol of a compound having two hydroxyl groups is reacted with 2 mol of the compound represented by the general formula (1-2). A basic nitrogen-containing group may be introduced into the main chain. A compound in which a basic nitrogen-containing group is introduced into such a main chain is a more preferable compound.

Further, a compound having no basic nitrogen-containing group can also be used in the reaction. For example, a low-molecular monoalcohol compound such as methanol or ethanol, a monoalkyl ester compound of (poly) alkylene glycol, a polyester compound containing one hydroxyl group , Polyether compounds, polyacryl compounds and the like.

A compound having a basic nitrogen-containing group in the main chain and having one or more carbodiimide groups in the molecule obtained by the above method is further grafted to a polyester side chain, a polyether side chain, a poly At least one graft selected from the group consisting of a grafted polyester side chain, a grafted polyether side chain, a grafted polyacryl side chain, and a grafted polybutadiene side chain by introducing an acrylic side chain or a polybutadiene chain A basic group-containing carbodiimide compound containing at least one side chain may be used.

As a typical method for introducing these side chains into the molecule by grafting reaction, a functional group capable of reacting with a carbodiimide group, for example, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, an amino group, etc. A method of reacting a polyester compound, a polyether compound, a polyacryl compound, or a polybutadiene compound having a carbodiimide group of a carbodiimide compound can be used.

As the polyester compound having the functional group, first,
(1) Ring-opening polymerization compound of cyclic ester compound using oxycarboxylic acid, monoalcohol, low molecular diol compound or the like as an initiator (for example, lactic acid, caproic acid, 12-hydroxystearic acid, dimethylolpropionic acid, dimethylolbutane) Mono- or polyoxycarboxylic acid such as acid is used as an initiator, and ε-caprolactone, γ-butyrolactone, 2-methylcaprolactone, 4-methylcaprolactone, β-propiolactone, δ-valerolactone, β-methyl-δ- A polyester compound containing a carboxyl group and a hydroxyl group obtained by ring-opening polymerization of a cyclic ester compound such as valerolactone; a ring-opening polymerization of the cyclic ester compound using a low-molecular monool compound such as methanol or ethanol as an initiator. Polyester monoester containing hydroxyl groups Lumpur compounds, ethylene glycol, used as the initiator of low molecular weight diol compounds such as propylene glycol, and polyester diol compounds) having a hydroxyl group obtained by ring-opening polymerization of the cyclic ester compound.

(2) Self-polycondensation compound of oxycarboxylic acid (for example, polyester compound containing carboxyl group and hydroxyl group obtained by polycondensation of monooxycarboxylic acid such as lactic acid, caproic acid, 12-hydroxystearic acid, etc.) Can be mentioned.

(3) Compounds obtained by polycondensation of low molecular diol compounds and low molecular dicarboxylic acid compounds (for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol) Low molecular weight diol compound components such as linear glycols such as 1,2-propanediol, neopentyl glycol, branched glycols such as 3-methyl-1,5-pentanediol, ethylbutylpropanediol, and succinic acid A low molecular weight diol compound in the presence of an excess of a low molecular weight diol compound such as adipic acid, azelaic acid, sebacic acid, maleic acid and other saturated and unsaturated aliphatic dicarboxylic acids, and aromatic dicarboxylic acid such as phthalic acid. And polyester diol compounds containing a hydroxyl group obtained by reaction with

And (4) a phosphate ester compound of a ring-opening polymer of a cyclic ester compound using a monoalcohol as an initiator (for example, containing a phosphate group obtained by esterifying the polyester monool compound with phosphoric acid). Polyester diol compounds),
(5) A ring-opening polymerization compound of a cyclic ester compound using an amino group-containing sulfonic acid compound as an initiator (for example, obtained by ring-opening polymerization of the cyclic ester compound using an amino group-containing sulfonic acid compound such as taurine as an initiator) And a polyester diol compound containing a sulfonic acid group).

(6) A sulfurous acid gas adduct of a ring-opening polymer of a cyclic ester compound using a monoalcohol as an initiator (for example, a polyester diol containing a sulfonic acid group obtained by adding sulfurous acid gas to the polyester monool compound) Compounds). The polyester compound having a phosphoric acid group or a sulfonic acid group is preferably a compound having a polyester chain obtained by ring-opening polymerization of polycaprolactone.

Next, as the polyether compound having the functional group, first,
(1) Ring-opening polymerization compounds of cyclic ether compounds using monoalcohols, low molecular diol compounds and the like as initiators (for example, monoesters such as lactic acid, caproic acid, 12-hydroxystearic acid, dimethylolpropionic acid, dimethylolbutanoic acid, etc.) Alternatively, a polyether compound containing a carboxyl group and a hydroxyl group obtained by ring-opening polymerization of a cyclic ether compound such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran using polyoxycarboxylic acid as an initiator; methanol Polyether monool compounds containing hydroxyl groups obtained by ring-opening polymerization of the above cyclic ether compounds using low molecular monool compounds such as ethanol as initiators; low molecular diols such as ethylene glycol and propylene glycol Object was used as the initiator, mention may be made of polyether diol compounds) having a hydroxyl group obtained by ring-opening polymerization of the cyclic ether compound.

And (2) a phosphate ester compound of a ring-opening polymer of a cyclic ether compound using a monoalcohol as an initiator (for example, containing a phosphate group obtained by esterifying the polyether monool compound with phosphoric acid) Polyether compound).

(3) Ring-opening polymerization compound of a cyclic ether compound using an amino group-containing sulfonic acid compound as an initiator (for example, ring-opening polymerization of the cyclic ether compound using an amino group-containing sulfonic acid compound such as taurine as an initiator) And polyether compounds containing sulfonic acid groups obtained in this way).

(4) A sulfurous acid gas adduct of a ring-opening polymer of a cyclic ether compound using a monoalcohol as an initiator (for example, a polysulfuric acid group-containing polysulfide group obtained by adding sulfurous acid gas to the polyether monool compound) Ether compounds).

Next, as the polyacryl compound having the above functional group, an acid group-free radical polymerizable unsaturated monomer containing at least one acid group-free (meth) acrylic monomer is transferred to an acid group-containing chain. Examples thereof include a polyacryl compound which is polymerized in the presence of an agent and contains an acid group at one end of the molecule.

Examples of the acid group-containing chain transfer agent include chain transfer agents having a carboxyl group such as mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, O-mercaptobenzoic acid; 2-chloroethanesulfonic acid, 2-chloroethanesulfonic acid Sulfonic acid group-containing chains such as sodium, 4-chlorophenyl sulfoxide, 4-chlorobenzenesulfonamide, p-chlorobenzenesulfonic acid, sodium p-chlorobenzenesulfonate, sodium 2-bromoethanesulfonate, sodium 4- (bromomethyl) benzenesulfonate A transfer agent etc. are mentioned. Among these acid group-containing chain transfer agents, thiol-based acid group-containing chain transfer agents are preferable, and mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, and O-mercaptobenzoic acid are more preferable.

Examples of the acid group-free (meth) acrylic monomer include alkyl (meth) acrylate compounds (for example, methyl methacrylate), (meth) acrylate compounds having an aromatic ring (for example, allyl acrylate, allyl methacrylate, Acrylic acid ester compounds such as benzyl acrylate and benzyl methacrylate). Examples of the non-acrylic acid group-containing radical-polymerizable unsaturated monomer other than acrylic are styrene monomers such as styrene and α-methylstyrene. Can be mentioned.

When polymerizing a polyacryl compound using such a monomer component, a commonly used initiator, for example, an azo-nitrile compound: 2,2'-azo-bis-isobutyronitrile, 1,1'- Azo-bis-1-cyclobutanenitrile, 2,2'-azo-bis-2methylbutyronitrile, etc., azo compounds: 2,3-diaza-bicyclo [2,2,1] heptene, 2,2,2 ' -Azo-bis-propane, 1,1'-azo-bis-1-phenylethane, peroxide compounds: t-butyl peroxide, benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, etc. it can.

The polyacrylic compound having an acid group at one end is obtained by using a polymerization method such as bulk polymerization, solution polymerization, and suspension polymerization if necessary, and using a total charge method, an initiator dropping method or a monomer dropping method as an initiator. It can be synthesized by reacting for 1 to 8 hours at a reaction temperature of 70 to 170 ° C. or higher. In this polymerization, a polyacrylic compound having an acid group at one end can be obtained by using an acid group-containing chain transfer agent as the chain transfer agent.
In the synthesis of the polyacrylic compound, the amount of the acid group-containing chain transfer agent is such that the amount of the monomer to be used and the amount of the acid group-containing chain transfer agent are the desired number average molecular weight. To be determined as appropriate.

Next, as the polybutadiene compound having the functional group, first,
(1) A compound obtained by reacting a polybutadiene polyol with an acid anhydride such as phthalic anhydride, maleic anhydride, succinic anhydride, benzoic anhydride, or styrene-maleic anhydride resin.

(2) Moreover, the compound which prepared the use ratio for polybutadiene and carried out addition polymerization of maleic acid or maleic anhydride can be mentioned.
As a method for reacting an acid anhydride with the above polybutadiene polyol, a method for addition polymerization of maleic acid or maleic anhydride to polybutadiene, etc., conventional methods can be used.
In addition, these polyester compounds, polyether compounds, polyacrylic compounds, and polybutadiene compounds are particularly preferred to have a carboxyl group, a sulfonic acid group, and a phosphoric acid group from the viewpoint of reactivity with a carbodiimide group.

Further, when the compound having a carbodiimide group for introducing a side chain further has an isocyanate group, the compound having a hydroxyl group undergoes a reaction with the isocyanate group prior to the carbodiimide group, making it difficult to control the reaction. A compound having two or more hydroxyl groups may be cross-linked during the grafting reaction to cause gelation.
Therefore, for a compound having only a hydroxyl group as a functional group, a polyester compound containing one carboxyl group, a polyether compound, a polyhydric acid compound such as phthalic anhydride, maleic anhydride, and succinic anhydride is further reacted. It is desirable to carry out a grafting reaction after obtaining an acrylic compound or a polybutadiene compound.

The compound in which at least one polyester compound, polyether compound, polyacryl compound, or polybutadiene compound exemplified above is introduced into the molecule by grafting may have 0 carbodiimide groups or 1 or more carbodiimide groups. Good.

For example, a basic nitrogen-containing group in the main chain is obtained by reacting the polycarbodiimide compound represented by the general formula (1-1) with an isocyanate group, one hydroxyl group, and at least one basic nitrogen-containing compound of the polycarbodiimide compound. And a side chain is introduced by a reaction with at least one selected from the group consisting of a polyester chain, a polyether chain, a polyacrylic chain, and a polybutadiene chain having a functional group capable of reacting with a carbodiimide group of a carbodiimide compound. If it is, basic group-containing carbodiimide compounds represented by the following general formulas (2) and (3) can be obtained.

Z ¹ —OCHN— (A—N═C═N) ₁ — (A—X (—Y)) _m —NHCO—Z ² (2)
_{^{Z 1 -OCHN- (A-X (}} -Y)) n -A-NHCO-Z 2 (3)
In the general formula, Z ¹ and Z ² each independently represent a residue of a compound having a functional group capable of reacting with an isocyanate group, which may have a different structure, excluding the functional group. A is a residue excluding the isocyanate group of the diisocyanate compound used for the synthesis of the polycarbodiimide compound. X is the same or different, and a trivalent linking group obtained by reacting a carbodiimide group and a functional group capable of reacting with it, Y is the same or different, polyester chain, polyether chain, polyacryl chain, polybutadiene chain And l, m, and n represent an integer of 1 or more. And when using with the compound of General formula (2) as it is, and the compound of General formula (3), it is necessary to have at least 1 basic nitrogen-containing group in either Z < ¹ > or Z < ² >. Those having a basic nitrogen-containing group as Z ¹ and Z ² have a basic nitrogen-containing group introduced into the main chain.

In addition, as a trivalent coupling group represented by said X, for example, the coupling group formed from the reaction of a carbodiimide group and a carboxyl group includes the following general formulas (4) and (5), carbodiimide group and hydroxyl group: The linking group formed from the reaction of the following general formulas (6) and (7), the linking group formed from the reaction of the carbodiimide group and the amino group is the following general formula (8), carbodiimide group and sulfone The linking group formed from the reaction with the acid group is represented by the following general formula (9), and the linking group formed from the reaction between the carbodiimide group and the phosphoric acid group is represented by the following general formula (10).

In addition, the reactions listed above, that is, the ring-opening reaction of the cyclic ester compound using the hydroxyl group-containing compound as an initiator, the polycondensation reaction of oxycarboxylic acid, the polycondensation reaction of the low-molecular diol compound and the low-molecular dicarboxylic acid compound A ring-opening reaction of a hydroxyl group-containing ester compound and an acid anhydride, a ring-opening reaction of a cyclic ether compound, a ring-opening reaction of a hydroxyl group-containing ether compound and an acid anhydride, a reaction between a carbodiimide group, a carboxyl group, a hydroxyl group, and the like, A conventional method can be used for the reaction of an isocyanate group and a hydroxyl group.

The carbodiimide compound having at least one side chain selected from the group consisting of a polyester side chain, a polyether side chain, a polyacryl side chain, and a polybutadiene chain and a basic nitrogen-containing group in the molecule is a carbodiimide type. The amount of basic nitrogen-containing group per 1 g of compound is preferably 0.02 to 4 mmol, more preferably 0.05 to 3 mmol. When the amount of the basic nitrogen-containing group per 1 g of the carbodiimide compound is within the above range, good pigment dispersion stability can be obtained.

In the basic group-containing carbodiimide compound, the polyester chain, the polyether chain, the polyacryl chain, and the polybutadiene chain introduced as side chains have an effect of improving the dispersion stability of the pigment in the dispersion medium. Although not particularly limited, the formula weight is preferably 200 or more and 10,000 or less. More preferably, it is 300 or more and 5000 or less.
The number average molecular weight of the basic group-containing carbodiimide compound is preferably 1000 or more and 100000 or less, more preferably 1000 or more and 50000 or less. If the number average molecular weight of the carbodiimide compound is too high, when a pigment having a functional group capable of reacting with a carbodiimide group is dispersed in a dispersion medium and when a pigment-dispersed resist composition is obtained, an appropriate viscosity is obtained. Is difficult to obtain, particularly when a high concentration pigment dispersion composition is required. On the other hand, if the number average molecular weight is too low, the dispersion stability of the pigment in the dispersion medium is undesirably lowered.
Therefore, according to each required performance, the amount of basic nitrogen-containing group of the carbodiimide-based compound, the number and formula weight of side chains such as polyester side chain, polyether side chain, polyacryl side chain present in the molecule, It is preferable to adjust carbodiimide equivalent etc. suitably.

The basic group-containing carbodiimide-based compound does not have an acidic group in the molecule.
In the present invention, the component (A) and the component (B) are used so that the mass ratio [(A) / (B)] is 90/10 to 50/50. When the mass ratio of (A) is larger than 90, the development margin becomes fast, and when it is smaller than 50, the development behavior of the uncured portion at the time of development is lowered, which is not preferable.

In the present invention, the pigment dispersant is a combination of two components of the acrylic block copolymer of the component (A) and the carbodiimide compound of the component (B). Other pigment dispersants can also be used in combination.

In the present invention, the amount of the pigment dispersant obtained by totaling the (A) acrylic block copolymer, the (B) carbodiimide compound having no acidic group in the molecule, and other dispersant is 100 masses of organic pigment. It is preferably 1 to 100 parts by mass, more preferably 1 to 60 parts by mass with respect to parts (total of organic pigments).

Examples of the film forming resin constituting the pigment-dispersed resist composition for color filters of the present invention include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, monoalkyl maleate, cytosolanic acid, and cytosolanic anhydride. Carboxyl group-containing unsaturated monomers such as cytoalkylan monoalkyl ester, styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol methacrylate , N-phenylmaleimide, polystyrene macromonomer, and polymethylmethacrylate macromonomer, obtained by reacting with at least one selected from the group consisting of Alkali-soluble resins having carboxyl groups is a polymer can be exemplified.

The film-forming resin preferably has an acid value of 50 to 300 mgKOH / g and a weight average molecular weight of 1,000 to 200,000 from the viewpoint of film-forming properties and alkali developability.
In the present invention, the weight average molecular weight is a polystyrene equivalent weight average molecular weight obtained based on GPC. In the present invention, Water 2690 (manufactured by Waters) is used as the GPC apparatus, and PLgel 5μ MIXED-D (manufactured by Polymer Laboratories) is used as the column.
In this invention, the usage-amount of the said film formation resin becomes like this. Preferably it is 10-1,000 mass parts with respect to 100 mass parts (total of organic pigments) of an organic pigment, More preferably, it is 20-100 mass parts.

Examples of the photopolymerizable compound constituting the pigment-dispersed resist composition for color filters of the present invention include monomers and oligomers having a photopolymerizable unsaturated bond.
Specifically, examples of the monomer having one photopolymerizable unsaturated bond in the molecule include alkyls such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Methacrylate or acrylate; Aralkyl methacrylate or acrylate such as benzyl methacrylate or benzyl acrylate; Alkoxyalkyl methacrylate or acrylate such as butoxyethyl methacrylate or butoxyethyl acrylate; N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate or the like Aminoalkyl methacrylate or acrylate; diethylene glycol monoethyl ether, triethylene glycol Methacrylic acid ester or acrylic acid ester of polyalkylene glycol monoalkyl ether such as monobutyl ether and dipropylene glycol monomethyl ether; Methacrylic acid ester or acrylic acid ester of polyalkylene glycol monoaryl ether such as hexaethylene glycol monophenyl ether; Isobonyl Examples include methacrylate or acrylate; glycerol methacrylate or acrylate; 2-hydroxyethyl methacrylate or acrylate.

Examples of monomers having two or more photopolymerizable unsaturated bonds in the molecule include bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol dimethacrylate, and glycerol dimethacrylate. , Neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate Dipentaerythritol pentamethacrylic Bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, Examples include tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate.
As the oligomer having a photopolymerizable unsaturated bond, one obtained by appropriately polymerizing the monomer can be used.

These photopolymerizable compounds can be used alone or in combination of two or more.
In this invention, the usage-amount of the said photopolymerizable compound becomes like this. Preferably it is the range of 3-50 mass% based on the total solid in the pigment dispersion resist composition for color filters of this invention.

Although it does not specifically limit as a photoinitiator which comprises the pigment dispersion resist composition for color filters of this invention, For example, a benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4, for example. '-Dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2 Benzo anthraquinone, 1,4-dimethyl anthraquinone, 2-phenyl-anthraquinone, triazine photopolymerization initiators, and the like. These photoinitiators are used individually or in combination of 2 or more types.

In this invention, the usage-amount of the said photoinitiator becomes like this. Preferably it is the range of 1-20 mass% based on the total solid in the pigment dispersion resist composition for color filters of this invention.

The solvent (solvent) constituting the pigment-dispersed resist composition for a color filter of the present invention is preferably an ester organic solvent or ether type having a boiling point of 100 to 220 ° C. at normal pressure (1.013 × 10 ² kPa). Organic solvents, ether ester organic solvents, ketone organic solvents, aromatic hydrocarbon solvents, nitrogen-containing organic solvents, and the like.

Specific examples of such organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene Ether organic solvents such as glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether Ether ester organic solvents such as rubacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ketone organic solvents such as methyl isobutyl ketone, cyclohexanone, 2-heptanone, δ-butyrolactone; methyl 2-hydroxypropionate, Ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate Ester organic solvents such as ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, n-amyl formate; N-methylpyrrolidone, N, N-dimethylformamide, N, Nitrogen-containing organic solvents such as N-dimethylacetamide can be exemplified, and these can be used alone or in admixture of two or more.

Among these organic solvents, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 2 in terms of solubility, dispersibility, coatability, etc. -Heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl formate, and the like, more preferably propylene glycol Monomethyl ether acetate.

Further, when two or more kinds of these organic solvents are used, 50 of all the solvents used in the pigment-dispersed resist composition for a color filter of the present invention due to the solubility of the alkali-soluble resin, the pigment dispersibility, the coating property and the like. The content is preferably at least mass%, more preferably at least 70 mass%.

If a large amount of an organic solvent having a boiling point exceeding 220 ° C. is contained, the organic solvent does not sufficiently evaporate when pre-baked on the coated film, and remains in the dried film. There is a risk that the heat resistance of the will be reduced. In addition, when a large amount of an organic solvent having a boiling point of less than 100 ° C. is contained, it becomes difficult to apply uniformly without unevenness, and a coating film excellent in surface smoothness may not be obtained.

Furthermore, in the pigment dispersion resist composition for color filters of the present invention, various additives such as other photopolymerizable compounds, thermal polymerization inhibitors, ultraviolet absorbers, antioxidants and the like other than those described above are included as necessary. Can be used as appropriate.

Examples of the method for producing the pigment dispersion resist composition for a color filter of the present invention using the constituent materials constituting the above color dispersion pigment dispersion resist composition include organic pigments and (A) acrylic block copolymer. (B) a carbodiimide compound, a dispersion medium, and a mixture composed of other additives as required, using a roll mill, a high-speed stirrer, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, a high-pressure disperser, etc. A pigment dispersion composition is obtained by kneading and dispersing, and then a photopolymerizable compound, a photopolymerization initiator, a film-forming resin, an organic solvent, and other additives are added according to the purpose, and a stirrer or the like is used. However, this production method is an example of a preferred embodiment of the present invention, and the present invention is not limited thereto. Not.

Since the pigment-dispersed resist composition for a color filter of the present invention has the above-described configuration, it has high transparency, high contrast, and excellent development characteristics.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” means “% by mass”, and “part” means “part by mass”.

<Organic pigment>
(Trimix treated pigment red 254 (PR254))
In the tank of Trimix TX-15 (trade name, manufactured by Inoue Seisakusho Co., Ltd.) I. 750 parts by mass of Pigment Red 254, 7500 parts by mass of sodium chloride, and 1800 parts by mass of diethylene glycol were added, and the mixture was kneaded at 45 ° C. for 3 hours within a range of 70% of the rated current value of 9.3 A, and subjected to salt milling. . Next, 1300 parts by mass of the obtained kneaded material was put into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then to 40 ° C. And dried for a whole day and night to obtain 95 parts by mass of trimix-treated pigment red 254.
(Pigment Green 36 (PG36))
Product name: Lionol Green 6YK (Toyo Ink Co., Ltd.)
(Pigment Yellow 150 (PY150))
Product name: E4GN-GT (manufactured by LANXESS)

<Pigment dispersant>
(Acrylic block copolymer having amine value and acid value, component (A))
Disperbyk-2001 (DB-2001, manufactured by Big Chemie)
(Carbodiimide pigment dispersant having no acidic group, component (B))
A four-necked flask equipped with a reflux condenser, a nitrogen gas inlet tube, a stirring rod, and a thermometer was charged with 76 parts by mass of a polycarbodiimide compound having an carbodiimide equivalent of 316 having an isocyanate group and 22.2 parts by mass of N-methyldiethanolamine. The isocyanate group and the hydroxyl group were reacted by maintaining at about 100 ° C. for 2 hours. Next, 246.3 parts by mass of a polycaprolactone having a carboxyl group and having a molecular weight of 2000 and 516.8 parts by mass of propylene glycol monomethyl ether acetate are charged and held at about 80 ° C. for 2 hours to react the carbodiimide group with the carboxyl group to obtain a solid. A 40% by mass carbodiimide compound (carbodiimide compound having a carbodiimide group having a polyester side chain, acid value 0 mgKOH / g) was obtained.

<Pigment dispersion aid>
Anthraquinone sulfonic acid derivative copper phthalocyanine sulfonic acid derivative

<Alkali-soluble resin>
BMM / MAA copolymer (benzyl methacrylate / methacrylic acid copolymer, theoretical acid value: 120 mgKOH / g, weight average molecular weight: 25,000)
<Photopolymerizable compound>
DPEHA (dipentaerythritol hexaacrylate)

<Photopolymerization initiator>
Irgacure 907 (Ciba Specialty Chemicals, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one <organic solvent>
PGMEA (propylene glycol monomethyl ether acetate)

Examples 1-7 and Comparative Examples 1-7
<Pigment dispersion composition>
The composition of Table 1 was kneaded in a bead mill at a temperature of 60 ° C. all day and night to obtain pigment dispersion compositions 1 to 14. In addition, the unit of the numerical value showing a composition is a mass part.

<Red pigment dispersion resist composition for color filter>
The pigment dispersion compositions 1 to 14 and other materials were mixed uniformly using a high-speed stirrer so as to have the composition shown in Table 1, and then filtered with a filter having a pore diameter of 3 μm. Examples 1 to 7 and Comparative Example 1 The pigment dispersion resist composition for color filters of -7 was obtained.
In addition, the unit of the numerical value showing a composition is a mass part.

[Evaluation]
<Contrast of pigment dispersed resist composition for color filter>
The pigment-dispersed resist compositions for color filters of Examples 1 to 7 and Comparative Examples 1 to 7 were applied onto a glass substrate using a spin coater so that the film thickness was 1.2 μm, and prebaked at 100 ° C. for 3 minutes. Then, it exposed with the high pressure mercury lamp, and also post-baked for 30 minutes at 230 degreeC.
Next, the glass substrate coated with the resist composition is sandwiched between two polarizing plates (manufactured by Nitto Denko Corporation, model number: SEG1224Du), and the polarizing plate on the front side is rotated while being irradiated with a fluorescent lamp (wavelength range: 380 to 780 nm). The intensity of light transmitted when the polarization planes of the front-side polarizing plate and the rear-side polarizing plate were parallel and at right angles was measured with a color luminance meter (BM-5A, manufactured by Topcon). Contrast ratio is the ratio of the luminance when the polarization planes of the front and rear polarizing plates are parallel to the luminance when the polarization planes of the front and rear polarizing plates are perpendicular to each other. As evaluated.
Contrast ratio = (luminance when the polarization planes of the front and rear polarizing plates are parallel / luminance when the polarization planes of the front and rear polarizing plates are perpendicular).

<Evaluation of color characteristics of pigment dispersed resist composition for color filter>
The color characteristics (x, y, Y) of the resists of Examples 1 to 7 and Comparative Examples 1 to 7 having a film thickness of 1.2 μm were measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2500PC, C light source 2 °). Field of view). For Examples 1 to 4 and Comparative Examples 1 to 3, brightness Y at red chromaticity (x, y) = (0.600, 0.320) was determined. For Examples 5 and 6 and Comparative Examples 4 and 5, lightness Y at green chromaticity (x, y) = (0.239, 0.420) was obtained. For Example 7 and Comparative Examples 6 and 7, brightness Y at yellow chromaticity (x, y) = (0.421, 0.500) was determined.

<Development behavior of resist pattern>
The pigment-dispersed resist compositions for color filters of Examples 1 to 7 and Comparative Examples 1 to 7 were applied onto a glass substrate with a spin coater so as to have a film thickness of 1 μm, and prebaked at 100 ° C. for 3 minutes. The resulting coating film was developed using a pH 12 aqueous KOH solution, and the development behavior when the uncured resist composition was completely removed was visually evaluated.

<Development margin of resist pattern>
The pigment-dispersed resist compositions for color filters of Examples 1 to 7 and Comparative Examples 1 to 7 were applied onto a glass substrate with a spin coater so as to have a film thickness of 1 μm, and prebaked at 100 ° C. for 3 minutes. The obtained coating film was developed using a pH 12 aqueous KOH solution, and the time from the time when the uncured resist composition was completely removed to the time when the cured composition was also removed was measured.

<Development residue of resist pattern>
The pigment dispersion resist compositions for color filters of Examples 1 to 7 and Comparative Examples 1 to 7 were applied on a glass substrate with a spin coater so as to have a film thickness of 1 μm, prebaked at 100 ° C. for 3 minutes, and then cured. And a mask capable of obtaining a grid pattern with a line width of 25 μm in which the area ratio of the uncured portion is 20:80, was exposed using a high-pressure mercury lamp at a UV integrated light amount of 270 mJ / cm ² . The obtained coating film was developed using 0.016% potassium hydroxide aqueous solution, and the glass substrate on which the pattern was formed was observed with a microscope (model VHS-500, magnification 450, manufactured by Keyence Corporation). Then, the evaluation was made based on the removed state of the resist composition in the uncured portion.

<Coating state after development of resist pattern>
The pigment dispersion resist compositions for color filters of Examples 1 to 7 and Comparative Examples 1 to 7 were applied on a glass substrate with a spin coater so as to have a film thickness of 1 μm, prebaked at 100 ° C. for 3 minutes, and then cured. And a mask capable of obtaining a grid pattern with a line width of 25 μm in which the area ratio of the uncured portion is 20:80, was exposed using a high-pressure mercury lamp at a UV integrated light amount of 270 mJ / cm ² . The obtained coating film was developed using 0.016% potassium hydroxide aqueous solution, and the glass substrate on which the pattern was formed was observed with a microscope (model VHS-500, magnification 450, manufactured by Keyence Corporation). Evaluation was made based on the surface state of the cured portion of the coating film.

From Table 1, the resist composition of the Example which used together the acrylic block copolymer and the carbodiimide type compound by the specific ratio as a pigment dispersant was excellent in all the characteristics of transparency, contrast, and development characteristics. On the other hand, the comparative example was inferior in development characteristics.

The pigment-dispersed resist composition for a color filter of the present invention can be applied to a color filter such as a liquid crystal display device.

Claims (1)

A pigment dispersion resist composition for a color filter containing an organic pigment, a pigment dispersant, a film-forming resin, a photopolymerizable compound, a photopolymerizable initiator, and a solvent,
The pigment dispersant is (A) an acrylic block copolymer having an amine value of 20 to 40 mgKOH / g and an acid value of 15 to 25 mgKOH / g obtained by living anion polymerization, and (B) having no acidic group in the molecule. A pigment-dispersed resist composition for color filters, comprising two components of a carbodiimide compound and containing (A) and (B) in a mass ratio of 90/10 to 50/50.