KR101472867B1 - Pigment dispersion composition, photocurable composition, color filter manufatured by using the same, method for manufacturing color filter - Google Patents

Abstract

A pigment dispersion composition for a color filter, which comprises a pigment in an organic solvent and a polymer having a structural unit represented by the following general formula (1) as a pigment dispersant.

[In the above general formula (1), R ¹ represents hydrogen or a methyl group, R ² represents an alkylene group, and Z represents a nitrogen-containing heterocyclic structure.]

Description

TECHNICAL FIELD [0001] The present invention relates to a pigment dispersion composition, a photo-curable composition, a color filter manufactured using the same, and a method of manufacturing a color filter. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a pigment dispersion composition, a photocurable composition containing the same, a color filter manufactured using the photocurable composition, and a method of manufacturing the color filter.

The color filter contains a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, and a photo-curable composition containing a polyfunctional monomer, a photopolymerization initiator, an alkali-soluble resin and other components to form a photo-curable composition. .

In recent years, the color filter tends to be used not only as a monitor but also as a television (TV) for use in a liquid crystal display device (LCD), and a high color characteristic is required in chromaticity, contrast, It is coming. In addition, in the use of an image sensor (solid-state image pickup device), similarly, color characteristics are required to be high.

For such a demand, it is required to disperse the pigment in a finer state (good dispersibility) and disperse it in a stable state (good dispersion stability). When the dispersibility is insufficient, there is a problem that the formed color resist film is fringed (edge like a saw blade) or surface irregularities, resulting in a decrease in chromaticity and dimensional accuracy of the produced color filter or deterioration of contrast remarkably. In addition, when the dispersion stability is insufficient, the uniformity of the film thickness in the step of coating the photo-curing composition, particularly in the production process of the color filter, may deteriorate, the sensitivity to light in the exposure step may decrease, Is likely to occur. When the dispersion stability of the pigment is poor, the components of the photocurable composition are agglomerated with the lapse of time, resulting in an increase in the viscosity, resulting in an extremely short pot life.

However, when the particle diameter of the pigment is made finer, the surface area of the pigment particle becomes larger, so that the cohesive force between the pigment particles becomes stronger. Therefore, it is often difficult to achieve both dispersion and dispersion stability at an elevation level.

In addition, with respect to the above-mentioned requirement, it is required that the heat resistance of the color filter is good, that is, the discoloration due to heat is suppressed. If the heat resistance is poor, there is a problem that the color filter is discolored by heat and high color characteristics can not be satisfied.

Even in the case of using the pigment dispersion composition as a photo-curable composition, it is possible to obtain a pigment dispersion composition which is capable of satisfying both the dispersibility of the pigment and the dispersion stability, The coating properties of the coating layer may deteriorate.

To solve this problem, various pigment dispersants have been developed. Among these dispersants, a copolymer containing a macromonomer (an oligomer having an ethylenic unsaturated group at the terminal) is useful, and by using a copolymer containing the macromonomer (oligomer having an ethylenic unsaturated group at the terminal) at the end, (See, for example, Patent Documents 1 and 2) that a pigment dispersion having a small size and excellent dispersion stability can be obtained. However, since the copolymer containing the macromonomer described in the above publication does not have a functional group that promotes adsorption to the pigment, it does not function solely as a dispersant, but has a problem that it is required to be used in combination with other dispersants. In addition, when the above-mentioned macromonomer-containing copolymer is used as a dispersing agent, there is a problem that the thickening effect seen in the polymer dispersing agent can be suppressed but the pigment is insufficient in fineness and the dispersibility is insufficient.

In order to improve the dispersion stability, a graft having a partial structure of an organic dye (see, for example, Patent Document 3), a nitrogen containing heterocycle (see, for example, Patent Document 4), a cyclic imide group Polymer. However, a pigment dispersant excellent in dispersibility and fluidity of a pigment and excellent in alkali developability, a pigment dispersion composition containing the pigment dispersant, and a photo-curable composition excellent in heat resistance and applicability have not yet been provided .

Patent Document 1: JP-A-8-259876

Patent Document 2: JP-A-10-339949

Patent Document 3: JP-A-2003-26950

Patent Document 4: JP-A-2003-26949

Patent Document 5: JP-A-2003-277673

It is an object of the present invention to provide a pigment dispersion composition having high pigment dispersibility and dispersion stability by using a polymer which imparts excellent dispersibility and dispersion stability to a pigment, It is an object of the present invention to provide a photocurable composition which has dispersibility and dispersion stability, is excellent in coating properties, is cured by exposure to light, has excellent developability, is excellent in light transmittance and contrast, and can form a colored coating with good heat resistance have.

Another object of the present invention is to provide a color filter having good color characteristics, excellent light transmittance and contrast, and a method of manufacturing such a color filter.

 As a result of intensive studies, the present inventors have found that the above problems can be solved by using a specific graft polymer having a nitrogen-containing heterocyclic structure as a pigment dispersant and have completed the present invention.

That is, the present invention has the following configuration.

≪ 1 > A pigment dispersion composition for a color filter, comprising a pigment and a polymer having a structural unit represented by the following general formula (1) as a pigment dispersant in an organic solvent.

[In the above general formula (1), R ¹ represents hydrogen or a methyl group, R ² represents an alkylene group, and Z represents a nitrogen-containing heterocyclic structure.]

<2> The pigment according to <1>, wherein the nitrogen-containing heterocyclic structure represented by Z in the general formula (1) has a structure selected from the following general formula (2) or general formula (3) Gt;

[In the general formulas (2) and (3), X is a group selected from the group consisting of a single bond, an alkylene group, -O-, -S-, -NR- and -C And R represents a hydrogen atom or an alkyl group. Ring A, ring B, and ring C each independently represent an aromatic ring.

<3> The pigment dispersion composition for a color filter according to <1> or <2>, wherein the pigment dispersant is a graft copolymer further comprising a polymerizable oligomer having an ethylenic unsaturated bond at a terminal thereof as a copolymer unit.

<4> The pigment dispersion composition for a color filter according to any one of <1> to <3>, wherein the pigment dispersant is a copolymer further comprising a monomer having an acid group as a copolymer unit.

<5> The pigment dispersion composition for a color filter according to any one of <1> to <4>, wherein the acid value of the pigment dispersant is 10 to 150 mgKOH / g.

<6> The pigment dispersion composition for a color filter according to any one of <1> to <5>, which further contains an alkali-soluble resin.

<7> The pigment according to any one of <1> to <7>, wherein the pigment contains at least one selected from CIPigment Yellow 139, CIPigment Yellow 150, CIPigment Green 36, CIPigment Red 177, CIPigment Red 254, CIPigment Blue 15: The pigment dispersion composition for a color filter according to any one of &lt; 1 &gt; to &lt; 6 &gt;

<8> A photocurable composition for a color filter, which comprises the pigment dispersion composition according to any one of <1> to <7>, a photopolymerizable compound, and a photopolymerization initiator.

<9> The photocurable composition for a color filter according to <8>, wherein the photopolymerization initiator comprises at least one selected from the group consisting of a triazine-based compound, a ropin dimer-based compound, and an oxime-based compound.

<10> The color filter according to <8> or <9>, which has a coloring pattern formed by using a photo-curing composition for a color filter.

<11> A photosensitive film forming process for forming a photosensitive film by applying the photocurable composition for a color filter described in <8> or <9> directly or through another layer on a substrate, and a step of forming a photosensitive film by pattern exposure and development And a coloring pattern forming step of forming a coloring pattern by performing a coloring pattern forming process.

Hereinafter, the present invention will be described in detail.

<Pigment dispersion composition>

The pigment dispersion composition of the present invention is characterized in that it contains a pigment and a polymer having a structural unit represented by the following general formula (1) as a pigment dispersant in an organic solvent (hereinafter appropriately referred to as a specific pigment dispersant) And is useful for forming a coloring pattern.

That is, it is important to use a pigment dispersant having the specific structure of the pigment dispersing composition of the present invention.

First, a specific pigment dispersant which is an important component of the present invention will be described.

[Polymer having a structural unit represented by the general formula (1) (specific pigment dispersant)]

In the general formula (1), R ¹ represents hydrogen or a methyl group, R ² represents an alkylene group, and Z represents a nitrogen-containing heterocyclic structure.

Examples of the alkylene group represented by R ² include, but not limited to, methylene, ethylene, trimethylene, tetramethylene, hexamethylene, 2-hydroxypropylene, methyleneoxy, A methylene group, a methylene group, a methylene oxycarbonyl group and a methylene thio group are more preferable.

In the general formula (1), Z represents a nitrogen-containing heterocyclic structure, and specific examples thereof include pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, quinoline A benzothiazole structure, a benzothiazole structure, a cyclic amide structure, a cyclic urea structure, and a cyclic imide structure may be substituted with at least one substituent selected from the group consisting of a hydrogen atom, .

Among them, the heterocyclic structure represented by Z is preferably a structure represented by the following general formula (2) or (3).

X represents a single bond, an alkylene group (e.g., a methylene group, an ethylene group, a propylene group, a trimethylene group or a tetramethylene group), -O-, -S-, -NR- and - C (= O) -. Examples of the alkyl group when R represents a hydrogen atom or an alkyl group and R represents an alkyl group include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.

Among them, X is preferably a single bond, a methylene group, -O- or -C (= O) -, and particularly preferably -C (= O) -.

In Formulas (2) and (3), Ring A, Ring B, and Ring C each independently represent an aromatic ring. Examples of the aromatic ring include aromatic rings such as benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, A naphthalene ring, an anthracene ring, a pyridine ring, a phenoxazine ring, an acridine ring, a phenothiazine ring, a pyrazine ring, a pyrazine ring, A phenoxazine ring, an acridine ring and an anthraquinone ring are preferable, and a benzene ring, a naphthalene ring and a pyridine ring are particularly preferable.

In the pigment dispersant of the present invention, preferred specific examples (Exemplary Monomers (M-1) to (M-8)) of the structural unit represented by the general formula (1) But is not limited to.

The structural unit represented by the general formula (1) is preferably contained in an amount of 2 to 50 mass%, more preferably 4 to 30 mass%, and particularly preferably 5 to 20 mass% in a specific pigment dispersant Do.

The pigment dispersant in the present invention is particularly preferably a graft copolymer comprising, in addition to the structural unit represented by the general formula (1), a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal thereof as a copolymerized unit.

The polymerizable oligomer having an ethylenically unsaturated double bond at such a terminal is also referred to as a macromonomer since it is a compound having a predetermined molecular weight.

In the present invention, the polymerizable oligomer used in the present invention is composed of a polymer chain portion and a polymerizable functional group portion having an ethylenically unsaturated double bond at the terminal thereof. It is preferable from the viewpoint of obtaining a desired graft polymer that the group having an ethylenically unsaturated double bond at only one end of the polymer chain is obtained. As the group having an ethylenically unsaturated double bond, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is particularly preferable.

The number average molecular weight (Mn) of the macromonomer and the polystyrene standard is preferably in the range of 1,000 to 10,000, more preferably in the range of 2,000 to 9,000.

The portion of the polymer chain may be a homopolymer or copolymer formed of at least one monomer selected from the group consisting of alkyl (meth) acrylate, styrene and derivatives thereof, acrylonitrile, vinyl acetate and butadiene, Polypropylene oxide, and polycaprolactone.

 The polymerizable oligomer is preferably an oligomer represented by the following general formula (4).

In the general formula (4), R ¹¹ and R ¹³ each independently represent a hydrogen atom or a methyl group.

R ¹² represents an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms. The alkylene group may further have a substituent (e.g., a hydroxyl group), and R ¹² may be a plurality of alkylene groups connected through an ester bond, an ether bond, an amide bond or the like.

Y represents a phenyl group having no substituent, a phenyl group having one alkyl group having 1 to 4 carbon atoms or -COOR ¹⁴ . Here, R ¹⁴ represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, or an arylalkyl group having 7 to 10 carbon atoms. Y is preferably a phenyl group or -COOR ¹⁴ , wherein R ¹⁴ represents an alkyl group having 1 to 12 carbon atoms.

and q represents an integer of 20 to 200.

Preferable examples of the polymerizable oligomer (macromonomer) usable in the synthesis of the pigment dispersant in the present invention include polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and poly- Acrylate, and (meth) acryloyl group bonded to one of the molecular terminals of polystyrene. Examples of such polymerizable oligomers available on the market include mono-terminated methacryloylated polystyrene oligomers (Mn = 6000, trade name: AS-6, manufactured by Toagosei Chemical Industry Co., Ltd.), polymethyl methacrylate (Manufactured by Toagosei Chemical Industry Co., Ltd.) and an end-capped methacryloyl poly-n-butyl acrylate oligomer (Mn = 6000, trade name: AB-6 , Manufactured by Toagosei Chemical Industry Co., Ltd.).

The pigment dispersant in the present invention preferably further contains a monomer (structural unit) having an acid group as a copolymerization component.

Examples of the monomer having an acid group include (meth) acrylic acid, p-vinylbenzoic acid, maleic acid, fumaric acid, itaconic acid, adduct of succinic anhydride of 2-hydroxyethyl (meth) Phthalic acid adducts, and the like.

The pigment dispersant in the present invention may contain a copolymerizable vinyl monomer as a copolymerizable component within a range that does not impair the effect thereof.

Examples of the vinyl monomer that can be used herein include, but are not limited to, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, Acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable. Specific examples of such vinyl monomers include the following compounds.

Examples of the (meth) acrylic esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl Propyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (Meth) acrylate, octadecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethoxyethyl Acrylic acid diethylene glycol monomethyl ether, (meth) acrylic acid diethylene glycol monoethyl ether, (metha) (Meth) acrylate, triethylene glycol monomethyl ether of (meth) acrylic acid, triethylene glycol monoethyl ether of (meth) acrylic acid, polyethylene glycol monomethyl ether of (meth) acrylic acid, polyethylene glycol monoethyl ether of Ethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (Meth) acrylate, tribromohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, and tribromophenyloxyethyl (meth) acrylate.

In the present specification, the term &quot; (meth) acrylic &quot; may be sometimes referred to as &quot; acrylic or methacrylic &quot;

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

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

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

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

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

(Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N- (Meth) acrylamide, N, N-butyl (meth) acrylamide, N-cyclohexyl (Meth) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, .

Examples of the styrene include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromo Styrene, chloromethylstyrene, hydroxystyrene protected with a group capable of being deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate and? -Methylstyrene.

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

In the pigment dispersant in the present invention, the acid value is preferably 10 to 150 mgKOH / g, more preferably 20 to 140 mgKOH / g, and particularly preferably 30 to 120 mgKOH / g. When the acid value is in the range of 10 to 150 mgKOH / g, the alkali solubility of the resist solution is suitably maintained to achieve good developability and excellent dispersion stability of the pigment is achieved.

As a means for keeping the acid value of the pigment dispersant in the appropriate range, for example, means for containing 1% or more of a copolymerizable component having an acid group, or adding a acid anhydride, for example, by a polymer reaction are listed.

A preferred embodiment of the specific pigment dispersant according to the present invention includes a polymerizable oligomer containing 2 to 50 mass% of the structural unit represented by the general formula (1) and having an ethylenically unsaturated double bond at the terminal thereof, 10 to 90% by mass, a structural unit containing an acid group of 1 to 30% by mass, and a vinyl monomer of 0 to 20% by mass.

The specific molecular weight of the specific pigment dispersant according to the present invention is preferably 15000 to 200000 in weight average molecular weight (Mw) and 8000 to 100000 in number average molecular weight (Mn). The molecular weight can be measured by GPC.

Specific examples of the pigment dispersant (Exemplary Compounds (1) to (22)) which can be suitably used in the pigment dispersion composition of the present invention are listed below together with their weight average molecular weight, but the present invention is not limited thereto .

[Exemplary Compound (1)] The exemplified monomer (M-1) / the terminal methacryloylated polymethyl methacrylate copolymer (copolymerization ratio = 10/90 mass%, weight average molecular weight: 50000)

[Exemplary Compound (2)] The above exemplified monomer (M-1) / methacrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 35000)

[Exemplary Compound (3)] The above exemplified monomer (M-1) / 2-hydroxyethyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (5/10/85 mass%, weight average molecular weight 40000 )

[Exemplary Compound (4)] The above-mentioned exemplary monomer (M-1) / methacrylic acid / benzyl methacrylate copolymer / terminal methacryloylated polymethyl methacrylate copolymer (15/5/10/70 mass% Weight average molecular weight: 60000)

(Exemplary Compound (5)) The exemplified monomer (M-5) / the terminal methacryloylated polymethyl methacrylate copolymer (20/80 mass%, weight average molecular weight 80000)

(Exemplary Compound (6)) The above exemplified monomer (M-5) / methacrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 30000)

[Exemplary Compound (7)] The above exemplified monomer (M-5) / acrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (25/15/60 mass%, weight average molecular weight:

(Exemplary Compound (8)) The exemplified monomer (M-5) / terminal methacryloylated polybutyl acrylate copolymer (15/85 mass%, weight average molecular weight: 40000)

[Exemplary Compound (9)] The above exemplified monomer (M-5) / 2-hydroxyethyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (15/10/75 mass%, weight average molecular weight 80000 )

(Exemplary Compound (10)) The exemplified monomer (M-6) / terminal methacryloylated polymethyl methacrylate copolymer (12/88 mass%, weight average molecular weight: 50000)

(Exemplary Compound (11)) The exemplified monomer (M-6) / methacrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 35000)

[Exemplary Compound (12)] The above exemplified monomer (M-6) / methacrylic acid / benzyl methacrylate / methoxypolyethylene glycol methacrylate copolymer (10/10/50/30 mass%, weight average molecular weight 40000)

[Exemplary Compound (13)] The above exemplified monomer (M-6) / 2-hydroxyethyl methacrylate / terminal methacryloylated polystyrene copolymer (5/10/85 mass%, weight average molecular weight 20000)

[Exemplary Compound (14)] The above exemplified monomer (M-6) / methacrylic acid / methyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (8/12/10/70 mass% Molecular weight 60000)

(Exemplary Compound (15)) The above-mentioned Exemplary Monomer (M-6) / methoxypolyethylene glycol methacrylate copolymer (15:85 mass%, weight average molecular weight 15000)

(Exemplary Compound (16)) The above exemplified monomer (M-1) / methacrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (copolymerization ratio = 10 / 7.5 / 82.5 mass%, weight average molecular weight 25000)

[Exemplary Compound (17)] The above-mentioned exemplary monomer (M-1) / terminal methacryloylated polymethyl methacrylate copolymer (copolymerization ratio = 10/90 mass%, weight average molecular weight: 27000)

(Exemplary Compound (18)) The above-mentioned exemplary monomer (M-6) / terminal methacryloylated polymethyl methacrylate copolymer (copolymerization ratio = 10/90 mass%, weight average molecular weight 25000)

(Exemplary Compound (19)) The above-mentioned exemplary monomer (M-6) / methacrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (copolymerization ratio = 10/12/78 mass%

[Exemplary Compound (20)] The adduct / terminal methacryloylated polymethyl methacrylate copolymer (copolymerization ratio = 10/2) of the above-mentioned exemplary monomer (M-6) / 2-hydroxyethyl methacrylate / 20/70 mass%, weight average molecular weight 26000)

[Exemplary Compound (21)] The above exemplified monomer (M-6) / acrylic acid / benzyl methacrylate / terminal methacryloylated polystyrene copolymer (copolymerization ratio = 10/10/10/70 mass%, weight average molecular weight 25000)

[Exemplary Compound (22)] The above-mentioned exemplary monomer (M-8) / methacrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (copolymerization ratio = 10/12/78 mass%, weight average molecular weight 25000)

The pigment dispersion composition of the present invention comprises a polymer compound having the specific structural unit as a pigment dispersant. The pigment dispersion composition of the present invention may contain, in addition to the above-mentioned specific polymer compound, a dispersant such as a pigment dispersant or a surfactant conventionally known for the purpose of further improving the dispersibility of the pigment, It may be added as long as it is not.

These known dispersants can be used in the range of 1 to 50% by mass with respect to the specific pigment dispersant according to the present invention.

A variety of commercially available dispersants can be used as known dispersants that can be used in combination with the above-mentioned specific pigment dispersants. For example, phthalocyanine derivatives (commercially available product EFKA-745 (manufactured by EFKA Chemicals BV), SOLSPERSE 5000 (Manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 90, No. 95 (product of Zeneka Co., Ltd.); organosiloxane polymer KP341 (A product of Kyoeisha Chemical Co., Ltd.) and W001 (product of Yusho KK); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether , Nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate and sorbitan fatty acid ester; W004, W005, W017 (product of Yusho KK) Anionic surfactants EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401 and EFKA polymer 450 (available from Sangyo KK), Disperse Aid 6, Disperse Aid 8, Disperse Aid (Manufactured by Zeneka Co., Ltd.), such as SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, ; Adeka Pluronic 131, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, Fl08, L121, P-123 (manufactured by Asahi Denka Kogyo KK) (Sanyo Chemical Industries, Ltd.). Products).

The pigment dispersion composition of the present invention comprises at least one kind of pigment in the organic solvent and the above-mentioned specific pigment dispersant of the present invention, and can be constituted by using other components such as a resin component as required. This pigment dispersion composition contains at least one kind of the polymer compound of the present invention described above as a pigment dispersant, so that the dispersion state of the pigment in the organic solvent becomes favorable and good color characteristics can be obtained. In addition, when the color filter is constituted High contrast can be obtained. In particular, it exhibits an excellent dispersing effect on the organic pigment.

[Pigment]

The pigment dispersion composition of the present invention can be appropriately selected from various inorganic pigments or organic pigments known in the art.

Considering that the pigment is preferably an inorganic pigment or an organic pigment and has a high transmittance, it is preferable to use one having a small particle size as much as possible, and considering the handling property, the average particle diameter of the pigment is preferably 0.01 to 0.1 mu m, More preferably 0.05 mu m.

Examples of the inorganic pigment include metal compounds represented by metal oxides and metal complex salts. Specific examples thereof include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, , Complex oxides of the above metals, and the like.

As the organic pigment, for example,

CI Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;

C. I. Pigment Orange 36, 38, 43, 71;

CI Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;

C. I. Pigment Violet 19, 23, 32, 37, 39;

C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C. I. Pigment Green 7, 36, 37;

C. I. Pigment Brown 25, 28;

C. I. Pigment Black 1,7;

And so on.

In the present invention, although not particularly limited, the following pigments are more preferable.

CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,

C. I. Pigment Orange 36, 71,

CI Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,

C. I. Pigment Violet 19, 23, 37,

CI Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,

C.I.Pigment Green 36

C.I.Pigment Black 7

Among these, the following pigments are particularly preferable.

C. I. Pigment Yellow 139, 150

C. I. Pigment Red 177, 254

C. I. Pigment Violet 23

C. I. Pigment Blue 15: 6

C.I.Pigment Green 36

These organic pigments may be used alone or in combination of several to enhance color purity. Specific examples of combinations are shown below.

Examples of the red pigments include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone, or at least one of them, a bisazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a peryl A mixture of a red pigment and a red pigment may be used. Examples of the anthraquinone pigments include CIPigment Red 177, the perylene pigments include CIPigment Red 155 and CIPigment Red 224, the diketopyrrolopyrrole pigments include CIPigment Red 254, In view of color reproducibility, mixing with CIPigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. When the ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 nm to 500 nm, and the color purity may not be increased. On the other hand, if the ratio exceeds 100: 50, the dominant wavelength becomes longer than the short wavelength, and the deviation from the NTSC target color may become large. Particularly, the mass ratio is most preferably in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted to the chromaticity.

As the green pigment, a halogenated phthalocyanine pigment may be used singly or in combination with a bisazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindolin yellow pigment. For example, it is preferable to mix CI Pigment Green 7, 36, 37 with CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, or CI Pigment Yellow 185. The mass ratio of the green pigment to the yellow pigment is preferably from 100: 5 to 100: 150. When the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 nm to 450 nm, and the color purity may not be increased. On the other hand, if the ratio exceeds 100: 150, the dominant wavelength becomes longer than the longer wavelength, and the deviation from the NTSC target color may become large. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

As the blue pigment, a phthalocyanine-based pigment may be used alone, or a mixture of the phthalocyanine-based pigment and a dioxazine-based purple pigment may be used. For example, a mixture of CI Pigment Blue 15: 6 and CI Pigment Violet 23 is preferable. The mass ratio of the blue pigment to the purple pigment is preferably 100: 0 to 100: 50, more preferably 100: 5 to 100: 30.

As the pigment for the black matrix, carbon, titanium black, iron oxide, titanium oxide alone or a mixture thereof is exemplified, and a combination of carbon and titanium black is preferable. The mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60. If it exceeds 100: 60, dispersion stability may be lowered.

The content of the pigment in the pigment dispersion composition is preferably from 40 to 90% by mass, and more preferably from 50 to 80% by mass, based on the total solid content (mass) of the composition. When the content of the pigment is within the above range, it is effective to ensure sufficient color density and to secure excellent color characteristics.

 The content of the specific pigment dispersant according to the present invention in the pigment dispersion composition is preferably 0.5 to 100 mass%, more preferably 3 to 70 mass%, with respect to the mass of the pigment. When the amount of the pigment dispersant is within the above range, a sufficient pigment dispersion effect can be obtained. Further, even when the pigment dispersant is added in an amount of more than 100 parts by mass, the effect of further improving the pigment dispersion effect may not be expected.

When a known dispersing agent which can be used in combination is used, the content thereof is preferably 0.05 to 50% by mass with respect to the mass of the pigment, and is preferably 1 to 50% by mass with respect to the mass of the specific pigment dispersant .

[solvent]

The pigment dispersion composition of the present invention contains the above-mentioned pigment and a specific pigment dispersant in an organic solvent. Examples of the solvent (organic solvent) used for preparing the pigment dispersant composition include 2-acetoxy-1-methoxypropane, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, xylene and the like can be enumerated, for example, can do. The amount of the solvent to be added is appropriately selected depending on the use of the pigment dispersion composition, etc. However, when used in the preparation of the photo-curing composition described later, the concentration of the solid content containing the pigment and the pigment dispersant is preferably 5 to 50 mass% Can be added.

In the pigment dispersion composition of the present invention, various additives may be used in combination as long as the effect of the present invention is not impaired.

For example, for the purpose of imparting film-forming properties to the pigment dispersion composition of the present invention and adjusting the viscosity of the composition, the alkali-soluble resin and the like described below may be added as desired.

The preparation of the pigment dispersion composition of the present invention is not particularly limited, but may be carried out by using a pigment, a pigment dispersant, and a solvent, for example, by using a vertical or horizontal sand grinder, a pin mill, a slit mill or an ultrasonic disperser, , Zirconia, and the like.

Further, before the bead dispersion is carried out, a strong shearing force is exerted by using two rolls, three rolls, a ball mill, a throm mill, a drum mill, a dispenser, a kneader, a coneizer, a homogenizer, a blender, It is also possible to carry out the kneading dispersion treatment.

Further, details of kneading and dispersing are described in T.C. Patton "Paint Flow and Pigment Dispersion" (published in 1964 by John Wiley and Son).

&Lt; Photocurable composition >

The photocurable composition of the present invention contains at least the above-described pigment dispersion composition of the present invention, an alkali-soluble resin, a photopolymerizable compound and a photopolymerization initiator, and may contain other components as required. Since this photo-curing composition contains the above-described specific pigment dispersant according to the present invention, the pigment is maintained in a good dispersed state in the composition to obtain good color characteristics, and a high contrast can be obtained, for example, when a color filter is constituted.

Each component contained in the photocurable composition of the present invention will be described in detail below.

[Pigment dispersion composition]

The photocurable composition of the present invention comprises at least one of the pigment dispersion compositions of the present invention. Details of the pigment dispersion composition of the present invention constituting the photocurable composition are as described above.

The content of the pigment dispersion composition in the photocurable composition of the present invention is preferably such that the content of the pigment is in the range of 5 to 70% by mass, preferably 15 to 60% by mass, based on the total solid content (mass) Is more preferable. When the content of the pigment dispersion composition is within the above range, the color density is sufficient and it is effective in securing excellent color characteristics.

[Alkali-soluble resin]

The photocurable composition of the present invention contains at least one alkali-soluble resin.

The alkali-soluble resin is preferably a linear organic polymer polymer, and includes at least one group capable of promoting alkali solubility (for example, a carboxyl group, a phosphoric acid group and a sulfonic acid group) in a molecule (preferably, And the like). Of these, more preferably, it is soluble in an organic solvent and can be developed by a weakly alkaline aqueous solution.

The alkali-soluble resin can be produced, for example, by a known radical polymerization method. Polymerization conditions such as the temperature, pressure, kind and amount of the radical initiator and the kind of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art and can be determined experimentally.

The linear organic polymer is preferably a polymer having a carboxylic acid in the side chain. For example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Application Laid-open No. 59-53836, Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like as described in the respective publications of JP-A-59-71048, Acidic cellulose derivatives having a carboxylic acid, acid anhydrides added to a polymer having a hydroxyl group, and the like, and polymer polymers having a (meth) acryloyl group in the side chain are also preferable.

Among these, polyisoprene copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid copolymer and benzyl (meth) acrylate / (meth) acrylic acid / other monomers are preferable.

In addition to these, copolymers of 2-hydroxyethyl methacrylate and the like are also listed as useful. The polymers may be mixed in any amount and used.

In addition to the above, there may be mentioned 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A No. 7-140654, 2-hydroxy- Acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydro Hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, and the like.

As concrete constituent units of the alkali-soluble resin, copolymers of (meth) acrylic acid and other monomers copolymerizable therewith are particularly preferable.

Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.

Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (Meth) acrylate, benzyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl And so on.

Examples of the vinyl compound include styrene,? -Methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromolecule A monomer, a polymethyl methacrylate macromonomer, 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. (Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms), CH ₂ ═C (R ¹ ) (COOR ³ ) And the like).

These copolymerizable other monomers may be used singly or in combination of two or more. Preferred other copolymerizable monomers are at least one member selected from CH ₂ ═CR ¹ R ² , CH ₂ ═C (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene, Particularly preferably, CH ₂ = CR ¹ R ² and / or CH ₂ = C (R ¹ ) (COOR ³ ). Of these, R ¹ , R ² and R ³ are each as defined above.

The content of the alkali-soluble resin in the photocurable composition is preferably from 1 to 20% by mass, more preferably from 2 to 15% by mass, and particularly preferably from 3 to 12% by mass, based on the total solid content of the composition.

[Photopolymerizable compound]

The photocurable composition of the present invention contains at least one photopolymerizable compound.

As the photopolymerizable compound, a compound having at least one addition-polymerizable ethylenic unsaturated group and having a boiling point of 100 DEG C or higher at normal pressure is preferable, and among these, an acrylate compound having four or more functionalities is more preferable.

(Meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. Examples of the compound having at least one addition polymerizable ethylenic unsaturated group and having a boiling point of 100 deg. Monofunctional acrylate or methacrylate such as acrylate; (Meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Acryloyloxyethyl) isocyanurate, glycerin, trimetholol ethane, and the like, and the like, such as ethyleneglycol monomethacrylate, erythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohol of poly (meth) acrylate, pentaerythritol or dipentaerythritol obtained by poly (meth) acrylate, Japanese Patent Publication No. 48-41708, Japan JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-A- Polyfunctional acrylates or methacrylates such as epoxy acrylates, which are reaction products of epoxy resin with (meth) acrylic acid, epoxy acrylates, and the like, as disclosed in Japanese Patent Application Laid-Open No. 49-43191, Japanese Patent Publication Can be listed.

Further, those which have been introduced as photo-curable monomers and oligomers in Japan Adhesion Society, Vol. 20, No. 7, pages 300 to 308 can also be used.

Further, in Japanese Patent Application Laid-Open No. 10-62986, it is also possible to add ethylene oxide or propylene oxide to the above polyfunctional alcohol represented by general formulas (1) and (2) together with specific examples thereof and then to (meth) Compounds can also be used.

Among them, a structure in which dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (metha) acrylate, and acryloyl groups thereof are interposed between ethylene glycol and propylene glycol residue is preferable. These oligomer types can also be used.

The photopolymerizable compound may be used singly or in combination of two or more kinds.

The content of the photopolymerizable compound in the photocurable composition is preferably from 15 to 80 mass%, more preferably from 30 to 70 mass%, based on the total solid content of the composition. When the content of the photopolymerizable compound is within the above range, the curing reaction is sufficiently carried out.

[Photopolymerization initiator]

The photocurable composition of the present invention contains at least one photopolymerization initiator.

Examples of the photopolymerization initiator include halomethyl oxadiazole described in Japanese Patent Application Laid-Open No. 57-6096, halomethyl-s-triazine disclosed in Japanese Patent Publication Nos. 59-1281 and 53-133428, Aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in each specification such as US patent USP-4318791 and EP-88050A, benzoin compounds described in USP-4199420, (Thio) xanthones or acridine compounds described in Fr-2456741, compounds such as coumarins or ropin dimers described in JP-A No. 10-62986, And sulfonium organic boron complexes such as those described in JP-A-8-015521.

Among them, as the photopolymerization initiator, there may be mentioned an acetophenone compound, a ketal compound, a benzophenone compound, a benzoin compound, a benzoyl compound, a xanthone compound, a triazine compound, a halomethyloxadiazole compound, an acridine compound, More preferably a coumarin-based compound, a ropin dimer-based compound, a nonimidazole-based compound, an oxime-based compound or the like, and more preferably a triazine-based compound, a ropinimumerogether compound or an oxime-based compound.

Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl- Phenone, 4'-isopropyl-2-hydroxy-2-methyl-propiophenone, and the like.

As the ketal type photopolymerization initiator, for example, benzyl dimethyl ketal, benzyl- beta -methoxy ethyl acetal and the like can be preferably exemplified.

Examples of the benzophenone-based photopolymerization initiator include benzophenone, 4,4'- (bisdimethylamino) benzophenone, 4,4 '- (bisdiethylamino) benzophenone, 4,4'-dichlorobenzophenone, (4-morpholinophenyl) -butanone-1,2-tolyl-2-dimethylamino-1- (4- 1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoprofenone-1 can be preferably exemplified.

Examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl-o-benzoyl benzoate and the like.

Examples of the xanton-based photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, and chlorothioxanthone.

Examples of the triazine-based photopolymerization initiator include 2,4-bis (trichloromethyl) -6- p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (Trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (Trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl- Tri (trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl) -s-triazine, 3,4-dimethoxystyryl-2,6- Di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o- (Chloromethyl) - phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) s-triazine, and the like.

Examples of the halomethyloxadiazole photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) , 4-oxodiazole, 2-trichloromethyl-5- (naphtho-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl- -1,3,4-oxodiazole, and the like can be preferably exemplified.

As the above-mentioned acrylic-based photopolymerization initiator, for example, 9-phenylacridine, 1,7-bis (9-acridinyl) heptane and the like can be preferably exemplified.

Examples of the photopolymerization initiator of the coumarin system include 3-methyl-5-amino- ((s-triazin-2-yl) amino) 3-phenylcoumarin, 3-butyl-5-dimethylamino- ((s-triazin-2-yl) amino) -3-phenyl coumarin and the like have.

Examples of the photopolymerization initiator of the roffin dimer system include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5- Dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, and the like can be preferably exemplified.

As the imidazole-based photopolymerization initiator, for example, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide and the like can be preferably exemplified.

Examples of the oxime-based photopolymerization initiator include 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, o-benzoyl-4 '- (benzmercapto) benzoyl- , And JCS Perkin II (1979), pp. 1653-1660, J.C.S. Perkin II (1979), p.156 to 162, Journal of Photopolymer Science and Technology (1995), p.202 to 232, JP-A 2000-66385, JP-A 2000-80068, And the compounds described in Publication 2004-534797.

Examples of the photopolymerization initiator other than the above include 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyloxide, hexafluorophosphorothio-trialkylphenylphosphonium salt, and the like.

In the present invention, not only the above-mentioned photopolymerization initiator but also other known ones can be used. For example, bisphenol polyketal aldonyl compounds described in U.S. Patent No. 2,367,660, α-carbonyl compounds described in U.S. Patent Nos. 2,367,661 and 2,367,670, acyloin ethers described in U.S. Patent No. 2,448,828, Aromatic acyloin compounds substituted with a-hydrocarbons described in U.S. Patent No. 2,722,512, polynuclear quinone compounds described in U.S. Patent Nos. 3,046,127 and 2,951,758, triallylimidazole dimers described in U.S. Patent No. 3,549,367 / p-aminophenyl ketone, and benzothiazole-based compounds / trihalomethyl-s-triazine-based compounds described in JP-B-51-48516.

These photopolymerization initiators may also be used in combination.

The content of the photopolymerization initiator in the photocurable composition is preferably from 0.1 to 15.0% by mass, more preferably from 0.5 to 10.0% by mass, based on the total solid content of the composition. When the content of the photopolymerization initiator is within the above range, the polymerization reaction proceeds satisfactorily, and a film having good strength can be formed.

Next, components other than those described above will be described.

[solvent]

The photocurable composition of the present invention can be preferably prepared by using a solvent together with the above components.

Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, butyl esters, alkyl esters, Methoxyacetate, methyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate and methyl 3- methoxyacetate, methyl methoxyacetate, methyl methoxyacetate, methyl methoxyacetate, 3-oxypropionate alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate, and methyl 2-oxypropionate , 2-oxypropionic acid alkyl esters such as ethyl 2-oxypropionate and propyl 2-oxypropionate (examples Examples of the solvent include methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Methyl propionate, methyl 2-ethoxy-2-methylpropionate, ethyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2- Methyl 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, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (also referred to herein as 2-acetoxy-1-methoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like;

Aromatic hydrocarbons such as toluene, xylene and the like.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, , Ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate and the like.

The solvent may be used alone or in combination of two or more.

[Other ingredients]

The photo-curing composition of the present invention may further contain a fluorinated organic compound, a thermal polymerization inhibitor, a colorant, a photopolymerization initiator, and other fillers, as represented by the general formula (1) or (2) described in JP-A No. 10-62986 , A polymer compound other than the alkali-soluble resin, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent.

&Lt; Fluorine organic compound &

By containing the fluorine-based organic compound, it is possible to improve the liquid property (in particular, the fluidity) as a coating liquid and to improve the uniformity of the coating thickness and the liquid skip property. That is, the interfacial tension between the substrate and the coating liquid is lowered to improve the wettability to the substrate, and the coating property to the substrate is improved. Thus, even when a thin film of about several micrometers is formed in a small amount of liquid, Is effective in that a film of

The fluorine-containing organic compound preferably has a fluorine content of 3 to 40 mass%, more preferably 5 to 30 mass%, and particularly preferably 7 to 25 mass%. When the fluorine content is within the above range, it is effective from the viewpoint of coating thickness uniformity and liquid skewness, and also has good solubility in the composition.

Examples of the fluorinated organic compounds include MEGAFAC F171, F172, F173, F177, F141, F142, F143, F144, R30 and F437 (manufactured by DAINIPPON INK AND CHEMICALS, INCORPORATED) Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, and FC-311 (manufactured by SUMITOMO 3M LIMITED) SC-383, S393 and KH-40 (manufactured by Asahi Glass Co., Ltd.).

The fluorine-based organic compound is particularly effective, for example, in preventing coating unevenness and unevenness in thickness when a coated film to be applied is thinned. It is also effective in applying a slit which tends to cause liquid dropping.

The amount of the fluorine-based organic compound to be added is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass of the pigment dispersion composition or photo-curable composition.

<Thermal polymerization initiator>

It is also effective to include a thermal polymerization initiator in the photocurable composition of the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compound include azobis compounds. Examples of the peroxide compounds include ketone peroxides, peroxyketals, Hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxy esters, peroxydicarbonates, and the like.

<Surfactant>

The photocurable composition of the present invention is preferably composed of various kinds of surfactants from the viewpoint of improving the applicability, and various nonionic, cationic and anionic surfactants can be used. Among them, a fluorine-based surfactant having a nonionic surfactant and a perfluoroalkyl group is preferable.

Specific examples of the fluorochemical surfactant include MEGAFAC (registered trademark) series of DAINIPPON INK AND CHEMICALS, INCORPORATED product, FLUORAD (registered trademark) series of 3M Limited product, and the like.

Other than the above, examples of the additive include fillers such as glass and alumina; Itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives, acidic anhydrides added to polymers having hydroxyl groups, alcohol-soluble nylons, bisphenol A and epichlorohydrin An alkali-soluble resin such as a phenoxy resin; Surfactants such as nonionic, cationic and anionic surfactants, specifically phthalocyanine derivatives (commercially available product EFKA-745 (product of Morishita Sangyo K.K.)); (Manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid type (co) polymer Polyflow No. 75, No. 90, No. 95 (product of Kyoeisha Chemical Co., Ltd.) , W001 (manufactured by Yusho KK);

Examples of other additives include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol diisole, (Nonionic surfactants such as Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904 and 150R1 manufactured by BASF Corporation; W004, W005, W017 EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (available from Morishita Sangyo KK), Disperse Aid 6 (manufactured by Yusho KK), and other anionic surfactants such as EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, , Disperse Aid 8, Disperse Aid 15 and Disperse Aid 9100 (manufactured by San Nopko Limited); and various dispersants such as SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000 and 28000 Co., Ltd. (Manufactured by Asahi Denka Kogyo KK) and Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, An ultraviolet absorber such as Isonet S-20 (manufactured by Sanyo Chemical Industries, Ltd.), 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5- chlorobenzotriazole, And anti-aggregation agents such as sodium polyacrylate.

In order to further improve the developability of the photo-curable composition by promoting the alkali solubility of the uncured portion, it is preferable to add an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less, to the photo- . Specific examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, sebacic acid, capric acid, diethylacetic acid, enanthic acid and caprylic acid; There may be mentioned oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, succinic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, , Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconic acid and camphoric acid; Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemellitic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melotropic acid and pyromellitic acid; Other carboxylic acids such as phenylacetic acid, hydratrophic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atrophic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylmyridene acetic acid, do.

<Thermal polymerization inhibitor>

The photo-curable composition of the present invention is preferably further added with a thermal polymerization inhibitor, and examples thereof include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, (4-methyl-6-t-butylphenol), 2-mercaptobenzoimidazole, and the like are useful. Do.

The photo-curing composition of the present invention is obtained by incorporating (preferably together with a solvent) an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator into the above-described pigment dispersion composition of the present invention and adding additives such as a surfactant And the like.

&Lt; Color filter and manufacturing method thereof &

The color filter of the present invention is produced by forming a colored film (coloring pattern) on a substrate such as glass using the photocurable composition of the present invention described above. For example, the color filter of the present invention can be directly or alternatively (Preferably, applied by spin coating, slit coating, soft coating, roll coating or the like) to form a photosensitive film, exposing the formed photosensitive film through a predetermined mask pattern, It is most preferable to fabricate a color filter by forming a coloring pattern of each color (for example, three colors or four colors) (for example, a coloring pixel) by developing and removing the uncured portions with a developing solution.

This makes it possible to manufacture a color filter for use in a liquid crystal display element or a solid-state image pickup element with little difficulty in process, high quality and low cost.

At this time, ultraviolet rays such as g-ray, h-ray, i-ray and j-ray are preferable as the radiation used for exposure.

Drying (prebaking) of the film with the photo-curing composition of the present invention applied (preferably applied) on the substrate can be carried out in a temperature range of 50 to 140 ° C for 10 to 300 seconds using a hot plate, an oven or the like have.

In the development, the uncured portions after exposure are eluted into the developer to leave only the hardened portions. The development temperature is usually 20 to 30 ° C, and the development time is 20 to 90 seconds.

Any solution may be used as long as it dissolves the film of the photo-curable composition in the uncured portion and does not dissolve the cured portion. Concretely, a combination of various organic solvents or an alkaline aqueous solution can be used.

Examples of the organic solvent include the above-mentioned solvents that can be used in preparing the pigment dispersion composition or photocurable composition of the present invention.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide Alkaline compounds such as benzoyl peroxide, benzoyl peroxide, benzoyl peroxide, benzoyl peroxide, benzoyl peroxide, benzoyl peroxide, benzoyl peroxide, % By mass of the alkaline aqueous solution.

When an alkaline aqueous solution is used as a developing solution, cleaning (rinsing) is generally performed with water after development.

After the development, the surplus developer is washed away, dried, and then heat-treated (post-baking) is generally performed at a temperature of 100 to 240 캜.

The post-baking is post-development heating to complete curing, and heating (hard baking) is usually performed at about 200 ° C to 250 ° C. In this post-baking treatment, the coated film after development can be carried out continuously or collectively by using a heating means such as a hot plate, a convection oven (hot-air circulation type drier), high-frequency induction heating or the like.

By repeating the above operations sequentially for each color in accordance with the desired number of colors, a color filter in which colored cured films of a plurality of colors are formed can be manufactured.

When the photocurable composition of the present invention is applied on a substrate to form a film, the dry thickness of the film is generally from 0.3 to 5.0 mu m, preferably from 0.5 to 3.5 mu m, and most preferably from 1.0 to 2.5 mu m.

Examples of the substrate include a non-alkali glass, a soda glass, a Pyrex (registered trademark) glass, a quartz glass, and a photoelectric conversion element substrate used for a solid-state image pickup device or the like, A silicon substrate, and the like, and a plastic substrate. On these substrates, a black stripe for isolating each pixel is usually formed.

It is preferable that the plastic substrate has a gas barrier layer and / or a solvent-resistant layer on its surface.

Other layers in the case where the photocurable composition is provided on the substrate through another layer include a gas barrier layer, a solvent-resistant layer, and the like.

In the above description, the use of the pigment dispersion composition and the photo-curing composition of the present invention has been mainly described, but the present invention can also be applied to the formation of a black matrix for isolating each coloring pixel constituting a color filter.

The black matrix is subjected to pattern exposure and development using the photocurable composition (pigment dispersion composition) of the present invention using a black pigment such as carbon black or titanium black as a pigment, and then post baking is further performed if necessary, And the like.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it is beyond the scope of the present invention. Unless specifically stated below, &quot; part &quot; means &quot; part by mass &quot;.

(Synthesis Example 1)

(Synthesis of monomer 1)

 9.76 parts of 9 (10H) acridone and 5.94 parts of t-butoxy potassium were dissolved in 30 parts of dimethyl sulfoxide and heated to 45 占 폚. 15.26 parts of chloromethylstyrene was added dropwise thereto, and the mixture was heated and stirred at 50 캜 for further 5 hours. This reaction solution was poured into 200 parts of distilled water with stirring, and the resulting precipitate was collected by filtration and washed to obtain 11.9 parts of monomer 1.

&Lt; Synthesis of Polymer 1 >

5.0 parts of the monomer 1, 37.5 parts of polymethyl methacrylate (AA-6, manufactured by Toagosei Chemical Industry Co., Ltd.) having a methacryloyl group at the terminal, 7.5 parts of methacrylic acid, and 1-methoxy- 50 parts by mass of 2-propanol was introduced into a nitrogen-purged three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Three-One Motor), heated to 78 ° C while heating while flowing nitrogen into the flask. 0.1 part of 2,2-azobis (2,4-dimethylvaleronitrile) (product of Wako Pure Chemical Industries, V-65) was added thereto, and the mixture was heated and stirred at 78 占 폚 for 2 hours. After 2 hours, 0.1 part of V-65 was further added and the mixture was heated and stirred for 3 hours. 66.7 parts of 2-acetoxy-1-methoxypropanol was added to the reaction solution to obtain a solution of 30 parts of polymer 1 % Solution.

(Synthesis Example 2)

&Lt; Synthesis of monomer 2 >

 Monomer 2 was obtained in the same manner as in Synthesis Example of Monomer 1 except that 9.76 parts of 9 (10H) acridone used in the synthesis of Monomer 1 in Synthesis Example 1 was changed to 7.8 parts of phthalimide.

&Lt; Synthesis of Polymer 2 >

A 30% solution of the polymer 2 (the exemplified compound (6)) was obtained in the same manner as in the synthesis example of the polymer 1, except that the monomer 1 was changed to the monomer 2.

(Synthesis Example 3)

&Lt; Synthesis of monomer 3 >

Synthesis Example 1: Synthesis of Monomer 1 Monomer 3 was obtained in the same manner as in Synthesis Example of Monomer 1 except that 9.76 parts of 9 (10H) acridone used in Synthesis of Monomer 1 was changed to 9.52 parts of 1,8-naphthalimide.

&Lt; Synthesis of Polymer 3 >

A 30% solution of Polymer 3 (Exemplified Compound (11)) was obtained in the same manner as in Synthesis Example of Polymer 1, except that the monomer 1 was changed to Monomer 3.

(Synthesis Example 4)

&Lt; Synthesis of Polymer 4 >

5.0 parts of the monomer 1, 41.3 parts of polymethylmethacrylate (AA-6: manufactured by Toagosei Chemical Industry Co., Ltd.) having a methacryloyl group at the terminal, 3.7 parts of methacrylic acid, And 50 parts by mass of 1-methoxy-2-propanol were introduced into a nitrogen-purged three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Three-One Motor), heated while flowing nitrogen into the flask, Lt; 0 &gt; C.

0.15 parts of dimethyl 2,2'-azobisisobutyrate (product of Wako Pure Chemical Industries, V-601) was added, and the mixture was heated and stirred at 75 占 폚 for 3 hours. 0.15 parts of V-601 was further added, and the mixture was heated and stirred for 3 hours, then 0.15 parts of V-601 was added again, and the mixture was heated and stirred for 3 hours. 66.7 parts of 2-acetoxy-1-methoxypropane was added to the reaction solution to obtain a 30% solution of Polymer 4 (Exemplary Compound (16)).

(Synthesis Example 5)

&Lt; Synthesis of Polymer 5 >

5.0 parts of the above monomer 1, 45.0 parts of polymethyl methacrylate (AA-6: manufactured by Toagosei Chemical Industry Co., Ltd.) having a methacryloyl group at the terminal, 0.19 parts of n-dodecyl mercaptan, 2-propanol were introduced into a nitrogen-purged three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Three-One Motor), heated while flowing nitrogen into the flask, and heated to 75 ° C.

0.05 part of dimethyl 2,2'-azobisisobutyrate (product of Wako Pure Chemical Industries, V-601) was added, and the mixture was heated and stirred at 75 ° C for 3 hours. 0.05 part of V-601 was further added, and the mixture was heated and stirred for 3 hours. After that, 0.05 part of V-601 was added again and the mixture was heated and stirred for 3 hours. 66.7 parts of 2-acetoxy-1-methoxypropane was added to the reaction solution to obtain a 30% solution of Polymer 5 (Exemplified Compound (17)).

(Synthesis Example 6)

&Lt; Synthesis of Polymer 6 >

5.0 parts of the monomer 3, 45.0 parts of polymethylmethacrylate (AA-6: manufactured by Toagosei Chemical Industry Co., Ltd.) having a methacryloyl group at the terminal, 0.19 parts of n-dodecylmercaptan, 2-propanol were introduced into a nitrogen-purged three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Three-One Motor), heated while flowing nitrogen into the flask, and heated to 75 ° C.

0.05 part of dimethyl 2,2'-azobisisobutyrate (product of Wako Pure Chemical Industries, V-601) was added, and the mixture was heated and stirred at 75 占 폚 for 3 hours. 0.05 part of V-601 was further added, and the mixture was heated and stirred for 3 hours. After that, 0.05 part of V-601 was added again and the mixture was heated and stirred for 3 hours. 66.7 parts of 2-acetoxy-1-methoxypropane was added to the reaction solution to obtain a 30% solution of Polymer 6 (Exemplified Compound (18)).

(Synthesis Example 7)

&Lt; Synthesis of Polymer 7 >

5.0 parts of the monomer 3, 39.0 parts of polymethyl methacrylate (AA-6: manufactured by Toagosei Chemical Industry Co., Ltd.) having a methacryloyl group at the terminal, 6.0 parts of methacrylic acid, n-dodecyl mercaptan 0.93 part and 1 part methoxy-2-propanol were introduced into a nitrogen-purged three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Three-One Motor), heated while flowing nitrogen into the flask, Lt; 0 &gt; C.

0.21 parts of dimethyl 2,2'-azobisisobutyrate (product of Wako Pure Chemical Industries, V-601) was added, and the mixture was heated and stirred at 75 占 폚 for 3 hours. 0.21 part of V-601 was further added, and the mixture was heated and stirred for 3 hours. Then, 0.21 part of V-601 was added again and the mixture was heated and stirred for 3 hours. 66.7 parts of 2-acetoxy-1-methoxypropane was added to the reaction solution to obtain a 30% solution of Polymer 7 (Exemplified Compound (19)).

(Synthesis Example 8)

&Lt; Synthesis of Polymer 8 >

5.0 parts of the monomer 3, 35.0 parts of polymethylmethacrylate (AA-6: manufactured by Toagosei Chemical Industry Co., Ltd.) having a methacryloyl group at the terminal thereof, 35.0 parts of 2-hydroxyethyl methacrylate anhydrous succinic anhydride 10.0 parts of an adduct (NK ESTER SA: the following structure, manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.66 part of n-dodecylmercaptan and 50 parts by mass of 1-methoxy- , Stirred with a stirrer (Shinto Kagaku Co., Three-One Motor), heated while flowing nitrogen into the flask, and heated to 75 캜.

0.15 parts of dimethyl 2,2'-azobisisobutyrate (product of Wako Pure Chemical Industries, V-601) was added, and the mixture was heated and stirred at 75 占 폚 for 3 hours. 0.15 parts of V-601 was further added, and the mixture was heated and stirred for 3 hours, then 0.15 parts of V-601 was added again, and the mixture was heated and stirred for 3 hours. 66.7 parts of 2-acetoxy-1-methoxypropane was added to the reaction solution to obtain a 30% solution of Polymer 8 (Exemplified Compound (20)).

(Synthesis Example 9)

&Lt; Synthesis of Polymer 9 >

5.0 parts of the monomer 3, 35.0 parts of polymethyl methacrylate (AA-6: manufactured by Toagosei Chemical Industry Co., Ltd.) having a methacryloyl group at the terminal, 5.0 parts of acrylic acid, 5.0 parts of benzyl methacrylate, -Dodecylmercaptan and 50 parts by mass of 1-methoxy-2-propanol were introduced into a nitrogen-purged three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Three-One Motor) And heated to 75 캜.

0.28 parts of dimethyl 2,2'-azobisisobutyrate (product of Wako Pure Chemical Industries, V-601) was added thereto, and the mixture was heated and stirred at 75 ° C for 3 hours. 0.28 parts of V-601 was further added, and the mixture was heated and stirred for 3 hours. Then, 0.28 parts of V-601 was added again and the mixture was heated and stirred for 3 hours. 66.7 parts of 2-acetoxy-1-methoxypropane was added to the reaction solution to obtain a 30% solution of polymer 9 (Exemplary Compound (21)).

(Synthesis Example 10)

&Lt; Synthesis of monomer 4 >

9.52 parts of 1,8-naphthalimide and 5.94 parts of t-butoxy potassium were dissolved in 30 parts of dimethyl sulfoxide and heated to 45 캜. 26.72 parts of 4-bromohexyl styrene (synthesized by the method described in Japanese Patent Application Laid-Open No. 11-60519) was added dropwise thereto, and the mixture was further heated and stirred at 50 캜 for 5 hours. This reaction solution was poured into 200 parts of distilled water with stirring, and the obtained precipitate was collected by filtration and washed, whereby 14.5 parts of monomer 4 was obtained.

&Lt; Synthesis of Polymer 10 >

5.0 parts of the monomer 4, 39.0 parts of polymethyl methacrylate (AA-6: manufactured by Toagosei Chemical Industry Co., Ltd.) having a methacryloyl group at the terminal, 6.0 parts of methacrylic acid, n-dodecyl mercaptan 0.90 part and 1-methoxy-2-propanol were introduced into a nitrogen-purged three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Three-One Motor), heated while flowing nitrogen into the flask, Lt; 0 &gt; C. 0.21 parts of dimethyl 2,2'-azobisisobutyrate (product of Wako Pure Chemical Industries, V-601) was added, and the mixture was heated and stirred at 75 占 폚 for 3 hours. 0.21 part of V-601 was further added, and the mixture was heated and stirred for 3 hours. Then, 0.21 part of V-601 was added again and the mixture was heated and stirred for 3 hours. 66.7 parts of 2-acetoxy-1-methoxypropane was added to the reaction solution to obtain a 30% solution of the polymer 10 (the above exemplified compound (22)).

(Example 1)

&Lt; Preparation of pigment dispersion composition >

The components of the following composition (1) were mixed and stirred with a homogenizer at 3,000 rpm for 3 hours and mixed to prepare a mixed solution containing the pigment.

[Composition (1)]

ㆍ C.I. Pigment Red 254 ... 90 parts

ㆍ C.I. Pigment Red 177 ... 10 copies

A 30% solution of the polymer 1 (pigment dispersant) ... 150 parts

ㆍ 2-Acetoxy-1-methoxypropane ... 750 parts

Subsequently, the mixed solution obtained above was subjected to dispersion treatment for 6 hours with a bead dispersing machine DISPERMAT (manufactured by GETZMANN) using 0.3 mm phi zirconia beads. Thereafter, the pressure-sensitive high-pressure disperser NANO-3000-10 (manufactured by Nihon BEE Co., Ltd. Ltd.) was subjected to dispersion treatment at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3. This dispersion treatment was repeated 10 times to obtain a red pigment dispersion composition (R1).

&Lt; Evaluation of Pigment Dispersion Composition >

The obtained pigment dispersion composition was evaluated in the following manner.

(1) Measurement and evaluation of viscosity

The viscosity η ¹ of the pigment dispersion composition immediately after dispersion and the viscosity η ² of the pigment dispersion composition after one week of dispersion (at room temperature) after the dispersion were measured for the resulting pigment dispersion composition using an E-type viscometer to determine the degree of thickening Respectively. The evaluation results are shown in Table 1 below. Here, a low viscosity indicates good dispersibility and dispersion stability.

(2) Measurement and evaluation of contrast

The obtained pigment dispersion composition was coated on a glass substrate, and a sample was prepared so that the thickness of the coated film after drying was 1 占 퐉. The sample was placed between two polarizing plates, and the amount of transmitted light when the polarization axes were parallel and perpendicular was measured, and the ratio was used as the contrast (the evaluation method is described in "Seventh Color Optics Conference, 1990 The results of the measurement evaluation are shown in Table 1. Here, the high contrast indicates that the pigment is highly dispersed in the high- Which indicates that the transmittance, that is, the tinting strength, is high.

(Examples 2 to 10)

The procedure of Example 1 was repeated except that the pigment dispersant (polymer 1) was changed to the polymer compound (pigment dispersant) (polymer 2 to polymer 10) obtained in Synthesis Examples 2 to 10, respectively, (R2) to (R10) were prepared, and the same evaluations as in Example 1 were carried out. The results are shown in Table 1 below.

(Comparative Example 1)

Except that the polymer 1 (pigment dispersant) was changed to the copolymer D-1 (= 85/15 [weight ratio], weight average molecular weight: 15000) of methyl methacrylate and methacrylic acid in Example 1 A red pigment dispersion composition (R11) was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was carried out. The results are shown in Table 1 below.

(Comparative Example 2)

The polymer 1 (pigment dispersant) was obtained in the same manner as in Example 1, except that the polymer 1 (methacrylic acid) and the end methacryloylated polymethyl methacrylate copolymer D-2 (= 15/85 [weight ratio], weight average molecular weight: A red pigment-dispersed composition (R12) was prepared in the same manner as in Example 1 except that the composition was changed, and the same evaluation as in Example 1 was carried out. The results are shown in Table 1 below.

(Comparative Example 3)

The polymer 1 (pigment dispersant) was changed to styrene-terminated methacryloylated polymethyl methacrylate copolymer D-3 (= 15/85 [weight ratio], weight average molecular weight: weight average molecular weight 30000) in Example 1 A red pigment dispersion composition (R13) was prepared in the same manner as in Example 1, except that the pigment dispersion composition (R13) was used. The results are shown in Table 1 below.

(Comparative Example 4)

The polymer 1 (pigment dispersant) was obtained in the same manner as in Example 1 except that the following monomer 5 and polymethyl methacrylate having a methacryloyl group at the terminal (AA-6: manufactured by Toagosei Chemical Industry Co., Ltd.) A red pigment-dispersed composition (R14) was prepared in the same manner as in Example 1 except that the weight average molecular weight was changed to 4 (= 10/90 [weight ratio], weight average molecular weight: 25000) The results are shown in Table 1 below.

(Comparative Example 5)

Polymer 1 (pigment dispersant) was obtained in the same manner as in Example 1 except that the following monomer 6, methacrylic acid, and polymethyl methacrylate having a methacryloyl group at the terminal (AA-6: manufactured by Toagosei Chemical Industry Co., Ltd.) (R15) was prepared in the same manner as in Example 1, except that the copolymer D-5 (= 10/10/80 [weight ratio], weight average molecular weight: . The results are shown in Table 1 below.

(Comparative Example 6)

Polymer 1 (pigment dispersant) was prepared in the same manner as in Example 1 except that the following monomer 7, methacrylic acid, and polymethyl methacrylate having a methacryloyl group at the terminal (AA-6: manufactured by Toagosei Chemical Industry Co., Ltd.) (R16) was prepared in the same manner as in Example 1, except that the copolymer D-6 (= 10/10/80 [weight ratio], weight average molecular weight: . The results are shown in Table 1 below.

(Example 11)

A green pigment dispersion composition was obtained in the same manner as in Example 1 except that the red pigment dispersion composition was changed to a pigment dispersion composition obtained by using a mixed solution containing the green pigment of the following composition (2) (G1) was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2 below.

[Composition (2)]

ㆍ C.I.Pigment Green 36 ... 60 parts

ㆍ C.I.Pigment Yellow 150 ... 40 copies

ㆍ 30% solution of polymer 1 (pigment dispersant) ... 150 parts

ㆍ 2-Acetoxy-1-methoxypropane ... 750 parts

(Examples 12 to 20)

Green pigment dispersion compositions (G2 to G10) were prepared in the same manner as in Example 11 except that the pigment dispersant (Polymer 1) used in Example 4 was changed to Polymer 2 to Polymer 10 (pigment dispersant) Evaluation was carried out in the same manner as in 11. The results are shown in Table 2 below.

(Comparative Examples 7 to 12)

The procedure of Example 11 was repeated except that the polymer 1 (pigment dispersant) was changed to any one of (D-1) to (D-6) G16) was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2 below.

(Example 21)

The procedure of Example 11 was repeated except that the red pigment dispersion composition was changed to a blue pigment dispersion composition (B1) obtained by using a mixed solution containing a blue pigment of the following composition (3) A blue pigment dispersion composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 3 below.

[Composition (3)]

C.I.Pigment Blue 15: 6 ... 85 parts

ㆍ C.I.Pigment Violet 23 ... Part 15

ㆍ 30% solution of polymer 1 (pigment dispersant) ... 150 parts

ㆍ 2-Acetoxy-1-methoxypropane ... 750 parts

(Examples 22 to 30)

Blue pigment dispersion compositions (B2 to B10) were prepared in the same manner as in Example 21 except that Polymer 1 (pigment dispersant) was changed to Polymer 2 to Polymer 10 (pigment dispersant) in Example 21 , And the same evaluation as in Example 21 was carried out. The results are shown in Table 3 below.

(Comparative Examples 13 to 18)

Blue pigment dispersion compositions (B11 to B16) were prepared in the same manner as in Example 21 except that Polymer 1 (pigment dispersant) was changed to any one of the following D-1 to D-6 in Example 21, And the same evaluation as in Example 1 was carried out. The results are shown in Table 3 below.

As clearly shown in Tables 1 to 3, the pigment dispersion compositions of the Examples using the polymers 1 to 10 as specific pigment dispersants according to the present invention all have low viscosity of the composition, excellent dispersibility of the pigment and excellent dispersion stability , It can be seen that a high contrast can be obtained in the coating film obtained by this pigment dispersion composition. It is presumed that the reason why the coating of the pigment dispersion composition of the present invention achieves a high contrast is that the pigment particles are dispersed in a finely-divided state.

On the other hand, the pigment dispersion composition of the comparative example using a known pigment dispersant outside the range of the present invention has a comparatively high viscosity so that the dispersibility of the pigment is lower than that of the present invention and the dispersion stability is inferior, and the film obtained using the pigment dispersion composition Sufficient contrast was not obtained. Particularly, when the polymers D-4 and D-5 were used, the pigment dispersion compositions of Comparative Example 16 and Comparative Example 17 showed good dispersibility, but a remarkable increase in viscosity was observed over time, and the dispersion stability was insufficient.

(Example 31)

&Lt; Preparation of photocurable composition >

(4) were further added to the pigment dispersion composition (R1) containing the red pigment obtained in Example 1, and the mixture was stirred and mixed to obtain a photocurable composition (color resist solution) of Example 31 of the present invention Lt; / RTI &gt;

[Composition (4)]

ㆍ Dipentaerythritol hexaacrylate ... 80 parts

(Photopolymerizable compound)

Synthesis of 4- [o-bromo-p-N, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine 30 copies

(Photopolymerization initiator)

2-acetoxy-1-methoxypropane solution (solid content: 40%) of benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 10,000) 200 parts

(Alkali-soluble resin)

ㆍ 2-Acetoxy-1-methoxypropane (Solvent) ... 490 part

&Lt; Evaluation of alkali developability and applicability of photocurable composition >

(3) Alkali developing property

The obtained photo-curable composition (color resist solution) was coated on a glass substrate (1737, manufactured by Corning) having a size of 100 mm x 100 mm so as to have a coating film thickness of 2.0 탆 after drying and dried in an oven at 90 캜 for 60 seconds, .

Thereafter, the coating film was immersed in a 1% aqueous solution of an alkali developing solution CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.), and pure water was sprayed in a shower shape to wash the developing solution. Then, the immersion time required until the film completely disappeared was measured as the developing time, and evaluated by the following criteria. The results are shown in Table 4. Here, a short development time indicates that the developer has excellent alkali developability.

○: Development time is less than 40 seconds

△: Development time is 40 to 60 seconds

X: Development time exceeds 60 seconds

(4) Coating property

The obtained photo-curable composition (color resist solution) was applied to a slit coating apparatus equipped with a slit head having a slit gap of 50 m and an effective coating width of 540 mm so that the gap between the slit and the substrate was 2.0 mu m after drying And a photo-curable composition (color resist solution) obtained at a coating speed of 170 mm / sec was coated on a glass substrate having a width of 550 mm, a length of 650 mm and a thickness of 0.7 mm to obtain a coated surface having a length of 640 mm.

After the application, the pressure was reduced to 0.5 Torr by a reduced pressure dryer, pre-baked on a hot plate at 90 캜 for 60 seconds, and then the coated surface was observed with a microscope and the applicability was evaluated according to the following criteria.

○: The presence of irregularities, foreign matter, and eyeholes in the form of spots or stripes was not confirmed

X: existence of non-uniformity of coating, stain, and eyehole in spot shape or stripe shape was confirmed

&Lt; Preparation of color filter using photocurable composition >

The obtained photo-curable composition (color resist solution) was coated on a 100 mm x 100 mm glass substrate (1737, manufactured by Corning) in such a manner that the x value, which is an index of color density, was 0.650 and dried in an oven at 90 캜 for 60 seconds Prebake). After that, the coated film was coated with a 1% aqueous solution of an alkali developing solution CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.) at a dose of 200 mJ / cm 2 (roughness 20 mW / cm 2) And stopped. After stopping, pure water was sprayed in a shower shape to wash the developer. Then, the coated film on which the exposure and development were performed as described above was heat-treated in an oven at 220 캜 for 1 hour (post-baking) to form a coloring pattern (colored resin film) for the color filter on the glass substrate, Color filter).

&Lt; Evaluation of color filter &

The prepared color filter substrate was evaluated for heat resistance (color stability against heat) of Y value, contrast, and coloring pattern as follows. The results are shown in Table 4 below.

(5) Y value

The prepared color filter substrate was measured for Y value using an object color measurement system MCPD-2000 manufactured by Ohtsuka Electronics, Osaka, Japan. The larger the Y value is, the higher the transmittance is. The measurement results of the x value and the y value in the chromaticity diagrams performed together are also shown in Table 4 below.

(6) Contrast

The polarizing plate was placed on the colored resin film of the colored filter substrate to sandwich the colored resin film and the luminance when the polarizing plate was orthogonal to the luminance at the time of parallel measurement was measured using BM-5 of TOPCON CORPORATION product, The values obtained by dividing by the luminance at the time of orthogonality (= luminance at the time of parallel / luminance at the time of orthogonality) are used as an index for evaluating the contrast. The larger the value, the higher the contrast.

(7) Heat resistance (Stability of color filter filter against heat)

The obtained color filter substrate was heated using a hot plate LWB-03 (manufactured by Litho Tech Japan Co., Ltd.) at 230 ° C for 30 minutes. The color density (E * ab) before and after heating by the L * a * b * indicator was measured using the object color measurement system MCPD-2000 from Ohtsuka Electronics, Osaka, Japan to calculate the color difference ΔE * ab, In accordance with the evaluation criteria of &quot; The smaller ΔE * ab, the smaller the color change such as fading and the better the color stability against heat, that is, the heat resistance of the color filter.

?:? E * ab is less than 2.0

Δ: ΔE * ab is 2.0 or more and less than 3.0

×: ΔE * ab is 3 or more

(Examples 32 to 40)

The procedure of Example 31 was repeated except that the pigment dispersion composition (R1) obtained in Example 1 was changed to the pigment dispersion compositions (R2) to (R10) obtained in Examples 2 to 10, The composition (color resist solution) was prepared and evaluated in the same manner as in Example 31. The results are shown in Table 4 below.

(Comparative Examples 19 to 24)

Except that the pigment dispersion composition (R1) obtained in Example 1 was changed to the pigment dispersion compositions (R11) to (R16) obtained in Comparative Examples 1 to 6, The composition (color resist solution) was prepared and evaluated in the same manner as in Example 31. The results are shown in Table 4 below.

(Example 41)

The components shown in the following composition (5) were further added to the pigment dispersion composition (G1) obtained in Example 11 and stirred and mixed to prepare a photocurable composition (color resist solution) of the present invention containing a green pigment.

 [Composition (5)]

ㆍ Dipentaerythritol hexaacrylate ... 50 parts

  (Photopolymerizable compound)

Synthesis of 4- [o-bromo-p-N, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine 20 copies

  (Photopolymerization initiator)

2-acetoxy-1-methoxypropane solution (solid content: 40%) of benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 10,000) 50 parts

 (Alkali-soluble resin)

ㆍ 2-Acetoxy-1-methoxypropane (Solvent) ... 180 parts

&Lt; Photo-curing composition and production and evaluation of color filter using the same [

The obtained photo-curable composition (color resist solution) was coated on a glass substrate (1737, manufactured by Corning) having a size of 100 mm x 100 mm so as to have an y value of 0.600 which is an index of color density and dried in an oven at 90 캜 for 60 seconds Bake). After that, the coated film was coated with a 1% aqueous solution of alkali developing solution CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.) for 60 seconds, and then exposed to light of 200 mJ / And stopped. After stopping, pure water was sprayed in a shower shape to wash the developer. Then, the coated film on which the exposure and development were performed as described above was heat-treated in an oven at 220 캜 for 1 hour (post-baking) to form a coloring pattern (colored resin film) for the color filter on the glass substrate, Color filter).

Evaluation of the alkali developability and coatability of the obtained photo-curable composition (color resist solution) was carried out in the same manner as in Example 31. [

The Y value, contrast, and heat resistance of the produced color filter substrate were evaluated in the same manner as in Example 31. [ These results are shown in Table 5 below.

(Examples 42 to 50)

(Color resist) was obtained in the same manner as in Example 41 except that the pigment dispersion composition obtained in Example 11 was changed to the pigment dispersion compositions (G2) to (G10) obtained in Examples 11 to 20, Solution) was prepared. The evaluation was carried out in the same manner as in Example 31. The results are shown in Table 5 below.

(Comparative Examples 25 to 30)

The same procedures as in Example 41 were carried out except that the pigment dispersion composition (G1) obtained in Example 11 was changed to the pigment dispersion compositions (G11 to G16) obtained in Comparative Examples 7 to 12, Was prepared and evaluated in the same manner as in Example 31. The results are shown in Table 5 below.

(Example 51)

The components shown in the following composition (6) were further added to the pigment dispersion composition (B1) obtained in Example 21 and stirred and mixed to prepare the photocurable composition (color resist solution) of the present invention containing a blue pigment.

[Composition (6)]

ㆍ Dipentaerythritol hexaacrylate ... 150 parts

  (Photopolymerizable compound)

Synthesis of 4- [o-bromo-p-N, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine 60 parts

  (Photopolymerization initiator)

2-acetoxy-1-methoxypropane solution (solid content: 40%) of benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 10,000) 400 parts

  (Alkali-soluble resin)

ㆍ 2-Acetoxy-1-methoxypropane (Solvent) ... 1440 part

&Lt; Preparation and evaluation of photo-curing composition and color filter using the same [

The prepared photo-curable composition (color resist solution) was coated on a 100 mm x 100 mm glass substrate (1737, manufactured by Corning) in such a manner that the y value as an index of color density became 0.090 and dried in an oven at 90 캜 for 60 seconds Prebake). After that, the coated film was coated with a 1% aqueous solution of alkali developing solution CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.) for 60 seconds, and then exposed to light of 200 mJ / And stopped. After stopping, pure water was sprayed on the shower to wash the developer. Then, the coated film on which the exposure and development were performed as described above was heat-treated (post baking) in an oven at 220 ° C for 1 hour to form a coloring pattern (colored resin film) for the color filter on the glass substrate, (Color filter).

Evaluation of the alkali developing solution and coatability of the obtained photo-curable composition (color resist solution) was carried out in the same manner as in Example 31. [

The Y value and the contrast of the fabricated color filter substrate were measured and the heat resistance was evaluated in the same manner as in Example 31. [ These results are shown in Table 6 below.

(Examples 52 to 60)

The same procedures as in Example 51 were carried out except that the pigment dispersion composition (B1) obtained in Example 21 was changed to the pigment dispersion compositions (B2) to (B10) obtained in Examples 22 to 30, (Color resist solution) was prepared and evaluated in the same manner as in Example 31. The results are shown in Table 6 below.

(Comparative Examples 31 to 36)

The same procedures as in Example 51 were carried out except that the pigment dispersion composition (B1) obtained in Example 21 was changed to the pigment dispersion compositions (B11) to (B16) obtained in Comparative Examples 13 to 18, (Color resist solution) was prepared and evaluated in the same manner as in Example 31. The results are shown in Table 6 below.

As shown in Tables 4 to 6, all of the photocurable compositions of the examples containing the pigment dispersion composition of the present invention are excellent in developability and have a low viscosity of the composition, so that the dispersibility and dispersion stability of the pigment are good , And the coating performance was also excellent. The color filter substrate (color filter) produced by using the photo-curing composition of the examples had a high transmittance in all colors of red, green and blue in comparison with the comparative example in the light transmittance seen from the Y value , The color characteristics are good from the x value and the y value in the chromaticity diagram, and a high contrast is obtained from the contrast evaluation result. Further, it can be seen that the formed color filter is suppressed from discoloration or discoloration due to heat, and also has excellent color stability against heat. On the other hand, in the comparative example, the transmittance was also low, and sufficient contrast was not obtained. When the photo-curing compositions such as Comparative Examples 22 and 23 using the polymers D-4 and D-5 were used, the coating properties were inferior and the Y value, contrast, and heat resistance of the formed color filter could not be all satisfied. The photo-curable composition such as the polymer D-6 and Comparative Example 24 exhibited good dispersibility and dispersion stability of the pigment, but had poor heat resistance and coating properties. As a pigment dispersion composition for a color filter, .

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a pigment dispersion composition having high pigment dispersibility and dispersion stability by using a polymer which imparts excellent dispersibility and dispersion stability to the pigment, and a pigment dispersion composition having high pigment dispersibility and dispersion stability, Can provide a photo-curing composition which is cured by the curing agent, has excellent developability, is excellent in light transmittance and contrast, and can form a colored film having good heat resistance.

Further, according to the present invention, it is possible to provide a color filter having good color characteristics, excellent light transmittance and contrast, and a method of manufacturing such a color filter.

Claims (11)

A pigment dispersion composition for a color filter, which comprises a pigment in a organic solvent and a polymer having a structural unit represented by the following general formula (1) as a pigment dispersant.

[In the above general formula (1), R ¹ represents hydrogen or a methyl group, R ² represents an alkylene group, and Z represents a nitrogen-containing heterocyclic structure selected from the following general formula (2) or general formula (3) .]

X is any one selected from the group consisting of a single bond, an alkylene group, -O-, -S-, -NR-, and -C (= O) -, wherein R Represents a hydrogen atom or an alkyl group. In the general formula (2), the ring A and the ring B each independently represent an aromatic ring, and in the general formula (3), the ring C represents an aromatic ring. delete The pigment dispersion composition for a color filter according to claim 1, wherein the pigment dispersant is a graft copolymer further comprising a polymerizable oligomer having an ethylenic unsaturated bond at a terminal thereof as a copolymer unit. The pigment dispersion composition for a color filter according to claim 1, wherein the pigment dispersant is a copolymer further comprising a monomer having an acid group as a copolymerized unit. The pigment dispersion composition for a color filter according to claim 1, wherein the acid value of the pigment dispersant is 10 to 150 mgKOH / g. The pigment dispersion composition for a color filter according to claim 1, further comprising an alkali-soluble resin. The composition of claim 1, wherein the pigment is selected from the group consisting of CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Green 36, CI Pigment Red 177, CI Pigment Red 254, CI Pigment Blue 15: By weight or more based on the total weight of the pigment dispersion composition. A photocurable composition for a color filter, which comprises the pigment dispersion composition for a color filter according to claim 1, a photopolymerizable compound, and a photopolymerization initiator. The photocurable composition for a color filter according to claim 8, wherein the photopolymerization initiator comprises at least one member selected from the group consisting of a triazine compound, a ropin dimer compound, and a oxime compound. A color filter having a coloring pattern formed by using the photo-curable composition for a color filter according to claim 8 on a substrate. A photosensitive film forming process for forming a photosensitive film by applying the photo-curable composition for a color filter according to claim 8 directly or through another layer to a substrate to form a colored pattern by sequentially performing pattern exposure and development in the formed photosensitive film And a coloring pattern forming step of forming a coloring pattern on the substrate.