KR20110018645A - Composition of pigment dispersed liquid, colored resin composition, color filter and display device having the same - Google Patents

Abstract

PURPOSE: A pigment dispersion composition is provided to ensure low viscosity in granulation and high concentration process, excellent storage stability, and good contrast. CONSTITUTION: A pigment dispersion composition comprises pigment, dispersants, dispersion resins and solvents. The dispersants are acrylate-based dispersant containing butyl methacrylate or N,N-dimethylaminoethylmethacrylate. The dispersion resin is a copolymer obtained by copolymerizing (a) a compound of chemical formula 1, (b) a compound with an unsaturated bond capable of copolymerization with (a) and (c) compounds, and (c) a compound with an unsaturated bond and a carboxyl group.

Description

Pigment dispersion composition, colored resin composition, color filter and an image display device having the same {COMPOSITION OF PIGMENT DISPERSED LIQUID, COLORED RESIN COMPOSITION, COLOR FILTER AND DISPLAY DEVICE HAVING THE SAME}

The present invention relates to a pigment dispersion composition, a colored resin composition, a color filter, and an image display device having the same.

Color filters are widely used in imaging devices, liquid crystal displays (LCDs), and the like, and their application ranges are rapidly expanding. Color filters used in liquid crystal displays, imaging devices, and the like are generally uniformly formed by spin or slit coating a colored photosensitive resin composition containing a pigment dispersion composition corresponding to each color of red, green, and blue on a substrate on which a black matrix pattern is formed. After application, the coating film formed by heating and drying (hereinafter sometimes referred to as "prebaking") is exposed and developed, and further heat-curing (hereinafter sometimes referred to as "post-firing") as necessary. Is produced by repeating each of the colors to form pixels of each color. In addition, even in a process that does not require a developing step such as an inkjet method and a printing method other than the coating method, a color filter is manufactured through a colored resin composition using the pigment dispersion composition as a coloring material.

The color filter using the above-mentioned colored resin composition requires physical properties such as high brightness and high contrast, and recently, pixels with high color reproducibility are required. Thereby, the content of the pigment and carbon black of the coloring material used for the said coloring resin composition is increasing. However, when the content of the coloring material in the colored resin composition is increased, the pigment must be atomized in order to exhibit excellent optical properties, and in particular, storage stability, such as high viscosity in the preparation of a high concentration pigment dispersion composition, or gelation of the pigment dispersion composition during storage. This becomes poor, and therefore, there is a problem that optical characteristics such as brightness and contrast are also lowered.

An object of the present invention is to provide a finely pigmented high concentration pigment dispersion composition having a low viscosity, excellent storage stability and excellent optical properties such as brightness and contrast.

Further, another object of the present invention is to provide a colored resin composition comprising the aforementioned pigment dispersion composition as the coloring material.

Further, another object of the present invention is to provide a high quality color filter excellent in brightness, contrast and color reproducibility produced using the colored resin composition.

Further, another object of the present invention is to provide an image display device provided with the color filter.

The present invention for achieving the above object comprises a pigment (A), a dispersant (C), a dispersion resin (D) and a solvent (E), the dispersant (C) is BMA (butyl methacrylate) Or an acrylate-based dispersant comprising DMAEMA (N, N-dimethylaminoethyl methacrylate), wherein the dispersion resin (D) is a copolymer obtained by copolymerizing the following compounds (D1), (D2) and (D3). Provided are pigment dispersion compositions characterized by:

(D1): a compound represented by the following formula (1)

<Formula 1>

(In Formula 1, R ₁ is hydrogen or methyl group, R ₂ is a substituted or unsubstituted divalent C ₁ ~ C ₆ alkyl or alkenyl group, A is a substituted or unsubstituted benzene group, cyclohexyl group, Alkyl group or alkenyl group of C ₁ to C ₆ , wherein substituents of R ₂ and A are independently fluorine, chlorine, bromine, iodine, C ₁ to C ₆ alkyl group, C ₁ to C ₃ perhalogenated alkyl group, hydroxy group, A C ₁ to C ₆ ketone group, a C ₁ to C ₆ ester group, a N, N- (C ₁ -C ₃ ) alkyl substituted amide group or a combination comprising one or more of these substituents.)

(D2): a compound having an unsaturated bond copolymerizable with (D1) and (D3)

(D3): A compound having a carboxyl group and an unsaturated bond.

(D1) may be at least one selected from compounds represented by the following formula (2).

<Formula 2>

(In Formula 2, R ₁ is hydrogen or methyl group, R ₂ is a substituted or unsubstituted divalent C ₁ ~ C ₆ alkyl or alkenyl group, wherein the substituent of R ₂ is fluorine, chlorine, bromine, iodine , C ₁ to C ₆ alkyl group, C ₁ to C ₃ perhalogenated alkyl group, hydroxy group, C ₁ to C ₆ ketone group, C ₁ to C ₆ ester group, N, N- (C ₁ -C ₃ ) Alkyl substituted amide groups or combinations comprising one or more of these substituents.)

The dispersion resin (D) may be an unsaturated group-containing resin obtained by further reacting a compound obtained by copolymerizing the above (D1), (D2) and (D3) with a compound (D4) having an unsaturated bond and an epoxy group in one molecule. have.

It is preferable that said (D2) is an aromatic vinyl compound, an unsaturated carboxylic ester compound containing the substituent which has an aromatic ring, or N-substituted maleimide.

The dispersion resin (D) has a ratio of 2 to 50 mol% of the structural unit derived from (D1) with respect to the total number of moles of the constituents derived from each of (D1), (D2) and (D3). It is preferable that the structural unit derived from and (D2) is 2 to 50 mol%, and the structural unit derived from (D3) is 2 to 70 mol%.

It is preferable that the ratio of the component derived from said (D4) is 5-80 mol% with respect to the number-of-moles of the component derived from (D3) in the said binder resin (D).

The pigment dispersion composition may further comprise a dispersing aid (B).

The amount of the dispersion aid (B) may be 0 to 20 parts by mass based on 100 parts by mass of the solid content of the pigment (A).

Moreover, the usage-amount of the said dispersing agent (C) may be 5-60 mass parts with respect to 100 mass parts of solid content of a pigment (A).

In addition, the usage-amount of the said dispersion resin (D) may be 5-60 mass parts with respect to 100 mass parts of solid content of pigment (A).

In order to achieve another object of the present invention, the present invention provides a colored resin composition comprising a coloring material, wherein the coloring material is a pigment dispersion composition according to the present invention.

In order to achieve another object of the present invention, the present invention provides a color filter comprising a colored layer formed using a colored resin composition, wherein the colored resin composition is a colored resin composition according to the present invention. To provide.

In order to achieve still another object of the present invention, the present invention provides an image display device comprising the above-described color filter.

The present invention provides a pigment dispersion composition having low viscosity, excellent storage stability, and excellent contrast, even when the pigment is atomized and concentrated. Accordingly, the pigment dispersion composition may be usefully used as a coloring material of the colored resin composition, and when the pixel is formed, a color filter having excellent brightness, contrast, and color reproducibility may be obtained, and an image display apparatus including the same.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The pigment dispersion composition according to the present invention comprises a pigment (A), a dispersing aid (B), a dispersant (C), a dispersion resin (D) and a solvent (E).

Pigment (A)

The pigment may be used an organic pigment or an inorganic pigment generally used in the art.

The pigment may be used a variety of pigments used in printing inks, inkjet inks, and the like, specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindolin Pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinoneyl pigments, anthrapyrimidine pigments, ananthronerone pigments, indanthrone pigments, pravantron pigments, pyrantrones (pyranthrone) pigments, diketopyrrolopyrrole pigments and the like.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Specifically, oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black Or a composite metal oxide.

In particular, the organic pigments and inorganic pigments include compounds that are specifically classified as pigments in the color index (Published by The society of Dyers and Colourists), and more specifically, the color index (CI) number of Although a pigment is mentioned, It is not necessarily limited to these.

C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38

C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64, and 76

C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58

C.I Pigment Brown 28

C.I pigment black 1 and 7, etc.

The said pigments (A) can be used individually or in combination of 2 or more types, respectively.

The content of the pigment (A) is in the range of 30 to 90% by mass, preferably 50 to 75% by mass, based on the mass fraction of the total solids in the pigment dispersion composition. If the content of the pigment (A) is in the range of 30 to 90% by mass based on the above criteria, it is preferable because it contains a pigment of high concentration but has a low viscosity and excellent storage stability.

Dispersion aid (B)

The dispersing aid (B), which can be selectively added as needed, serves to disperse the pigment into fine particles to prevent reagglomeration, and to form a color filter having high contrast and excellent transparency.

The said dispersing aid (B) is a compound which generally uses an organic pigment as a mother skeleton and introduce | transduced an acidic group, a basic group, or an aromatic group into a side chain as a substituent. In this case, the organic pigments used may specifically include a quinacridone pigment, a phthalocyanine pigment, an azo pigment, a quinophthalone pigment, an isoindolin-based pigment, an isoindolinone pigment, a quinoline pigment, a diketopyrrolopyrrole pigment, and a benzoimide. Dazolone pigments; and the like. The organic pigments also include light yellow aromatic polycyclic compounds such as naphthalenes, anthraquinones, triazines, and quinolines, which are not generally referred to as pigments.

As the dispersion aid (B), those described in Japanese Patent Application Laid-Open No. 11-49974, Japanese Patent Application Laid-Open No. 2006-265528, Korean Patent Publication No. 2006-0093659 and the like can be used. Commercially available dispersing preparations (B) include SOLSPERSE-5000, SOLSPERSE-12000, SOLSPERSE-22000, BYK-SYNERGIST 2100, BYK-SYNERGIST 2100, BYK-SINERGIST 2105, BASF EFKA-6745, EFKA-6750, etc. of Lubrizol. Can be.

In addition, the dispersing aid (B) may be those specifically described in Korean Patent Publication No. 2006-0111415, and may specifically exemplify a compound represented by the following Chemical Formulas 3 to 9, but is not limited to these examples. Do not.

Said dispersion aid (B) can be used individually or in combination of 2 types or more, respectively.

<Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

<Formula 7>

<Formula 8>

<Formula 9>

The usage-amount of the said dispersing aid (B) is 0-20 mass parts normally with respect to 100 mass parts of solid content of a pigment (A), More preferably, it is the range of 1-5 mass parts. When the content of the dispersing aid (B) exceeds 20 parts by mass based on the above standards, the color inherent in the pigment is changed, and there is a problem of discoloration due to hard baking during the color filter manufacturing process.

Dispersant (C)

The dispersant (C) is added to maintain the stability and deagglomeration of the pigment.

The dispersant (C) according to the present invention contains an acrylate dispersant (hereinafter referred to as an acrylic dispersant (C1)) containing BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate).

In this case, it is preferable to apply the acrylic dispersant (C1) prepared by the living control method as shown in Korean Patent Laid-Open Publication No. 2004-0014311, as a commercial product of the acrylate-based dispersant prepared through the living control method DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150.

The illustrated acrylic dispersant (C1) may be used alone or in combination of two or more thereof.

The dispersing agent (C) which concerns on this invention can use together the pigment dispersing agent of another resin type with the acrylic dispersing agent (C1) manufactured by the said living control method.

The other resin type pigment dispersants include (partially) known pigment dispersants of known resin types, in particular polycarboxylic acid esters, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids represented by polyurethanes, polyacrylates. Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or free ) Oily dispersants such as amides or salts thereof formed by the reaction of a polyester having a carboxyl group with a poly (lower alkyleneimine); Water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide and phosphate esters.

As a commercial item of the said resin type dispersing agent, As a cationic resin dispersing agent, For example, brand names of BYK (BIC) company: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK- 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF brand name: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Kawaken Fine Chemical's trade names: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; Trade names of Ajinomoto Co., Ltd .: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; The brand names of Kyoeisha Chemical Co., Ltd .: FLORENE DOPA-17HF, Floren DOPA-15BHF, Floren DOPA-33, Floren DOPA-44, etc. are mentioned.

The usage-amount of the said dispersing agent (C) is 5-60 mass parts normally with respect to 100 mass parts of solid content of the pigment (A) used, More preferably, it is the range of 15-50 mass parts. When the content of the dispersing agent (C) exceeds 60 parts by mass based on the above criteria, the viscosity may be increased. When the content of the dispersant (C) is less than 5 parts by mass, it may be difficult to atomize the pigment, or may cause problems such as gelation after dispersion.

Dispersion Resin (D)

The dispersion resin (D) acts as a dispersion medium of the pigment (A), it is possible to produce a pigment dispersion composition more excellent by mixing the dispersion resin (D) than the use of the dispersant (C) alone.

The dispersion resin (D) according to the present invention may be a copolymer obtained by copolymerizing the following (D1), (D2) and (D3) compounds:

(D1): a compound represented by the following formula (1)

<Formula 1>

(In Formula 1, R ₁ is hydrogen or methyl group, R ₂ is a substituted or unsubstituted divalent C ₁ ~ C ₆ alkyl or alkenyl group, A is a substituted or unsubstituted benzene group, cyclohexyl group, Alkyl group or alkenyl group of C ₁ to C ₆ , wherein substituents of R ₂ and A are independently fluorine, chlorine, bromine, iodine, C ₁ to C ₆ alkyl group, C ₁ to C ₃ perhalogenated alkyl group, hydroxy group, A C ₁ to C ₆ ketone group, a C ₁ to C ₆ ester group, a N, N- (C ₁ -C ₃ ) alkyl substituted amide group or a combination comprising one or more of these substituents.)

(D2): a compound having an unsaturated bond copolymerizable with (D1) and (D3)

(D3): A compound having a carboxyl group and an unsaturated bond.

The dispersion resin (D) may be polymerized together by adding other monomers in addition to the above monomers. That is, it is included in this invention also when monomers other than said (D1)-(D3) are contained and copolymerized further.

(D1) may be at least one selected from compounds represented by the following formula (2).

<Formula 2>

(In Formula 2, R ₁ is hydrogen or methyl group, R ₂ is a substituted or unsubstituted divalent C ₁ ~ C ₆ alkyl or alkenyl group, wherein the substituent of R ₂ is fluorine, chlorine, bromine, iodine, C ₁ ~ C ₆ alkyl group, C ₁ ~ C ₃ perhalogenated alkyl group, hydroxy group, C ₁ ~ C ₆ ketone group, C ₁ ~ C ₆ ester group, N, N- (C ₁ -C ₃ ) alkyl Substituted amide groups or combinations comprising one or more of these substituents.)

Specific examples of the compound (D2) having an unsaturated bond copolymerizable with (D1) and (D3) include an aromatic vinyl compound, an N-substituted maleimide compound, an unsubstituted or substituted alkyl ester of an unsaturated carboxylic acid, and an alicyclic substituent. And unsaturated carboxylic acid ester compounds containing a unsaturated carboxylic acid ester compound containing a substituent having an aromatic ring, a carboxylic acid vinyl ester system, an oxetane group, and the like. Among the above compounds, aromatic vinyl compounds and N-substituted maleimide compounds are more preferable. These can be used individually or in combination of 2 types or more, respectively.

Specifically as said aromatic vinyl compound, vinyltoluene, styrene, (alpha) -methylstyrene, (alpha)-chlorostyrene, divinylbenzene, etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively. In particular, the pigment dispersion composition containing the binder resin prepared using vinyltoluene in the aromatic vinyl compound as (D2) can obtain an effect of excellent physical properties such as viscosity, storage stability and contrast.

Moreover, as said N-substituted maleimide type compound, the compound specifically represented by following formula (10) can be illustrated.

<Formula 10>

In Formula 10, R ₃ is a C ₁ ~ C ₂₀ aliphatic or aromatic hydrocarbon containing or without a hetero atom.

Specific examples of the R ₃ include a phenyl group, benzyl group, naphthyl group, cyclohexyl group, methyl group, ethyl group, propyl group, and the like, and particularly preferably benzyl group and cyclohexyl group. These can be used individually or in combination of 2 types or more, respectively.

Moreover, as an unsubstituted or substituted alkyl ester compound type of the said unsaturated carboxylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acryl specifically, Elate, amino ethyl (meth) acrylate, etc. are mentioned. These can be used individually or in combination of 2 types or more, respectively.

Moreover, as an unsaturated carboxylic ester compound type containing the said alicyclic substituent, specifically cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acryl Latex, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) Acrylate, mendidienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, pineneyl ( Meth) acrylate, etc. are mentioned. These can be used individually or in combination of 2 types or more, respectively.

Moreover, as an unsaturated carboxylic ester compound containing the substituent which has the said aromatic ring, specifically, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy-2-methylethyl (meth) acrylate, Phenoxyethoxyethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, 2-phenylphenoxyethyl (meth) acrylate, 4-phenylphenoxyethyl (meth) acrylate , 3- (2-phenylphenyl) -2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylate, and the like. These can be used individually or in combination of 2 types or more, respectively.

Moreover, as said carboxylic acid vinyl ester type compound, vinyl acetate, a vinyl propionate, etc. are mentioned specifically ,. These can be used individually or in combination of 2 types or more, respectively.

Specific examples of the unsaturated oxetanyl compound containing the oxetane group include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, and 3- (meth). Chryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyl Oxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl ) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (methacryloyloxyethyl) jade Cetane, 3- (methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-triple Loromethyloxetane, 3- (methacryloyloxyethyl) -2-pentafluoroethyl oxetane, 3- (methacryloyloxyethyl) -2-phenyloxetane, 2, 2 -Difluoro-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxyethyl ) -2,2,4,4-tetrafluorooxetane, etc. are mentioned. These can be used individually or in combination of 2 types or more, respectively.

The compound (D3) having the carboxyl group and the unsaturated bond is not limited as long as it is a carboxylic acid compound having a polymerizable unsaturated double bond, and can be used alone or in combination of two or more. As said (D3), Monocarboxylic acids, such as acrylic acid, methacrylic acid, a crotonic acid, are mentioned as a specific example; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids; and mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals such as ω-carboxypolycaprolactone mono (meth) acrylate. Of the compounds exemplified above, acrylic acid and methacrylic acid may be preferably used because of their excellent copolymerization reactivity.

The copolymer obtained by copolymerizing (D1) to (D3) used in the present invention, that is, the ratio of the constituents derived from each of (D1) to (D3) in the binder resin (D) constitutes the above copolymer. It is preferable to exist in the following ranges by mole fraction with respect to the total mole number of components.

Structural unit derived from (D1): 2-50 mol%,

Structural unit derived from (D2): 2-50 mol%,

Structural units derived from (D3): 2 to 70 mol%

The method for producing a copolymer obtained by copolymerizing the above (D1) to (D3) is not particularly limited as long as it is obtained by copolymerizing (D1) to (D3), and various known polymerization methods can be used. The solution polymerization method is more preferable among the polymerization methods of. The polymerization temperature and the polymerization time vary depending on the type and ratio of the monomer to be introduced, the target binder resin molecular weight and the acid value, but are preferably polymerized at 60 ° C to 130 ° C for 1 to 10 hours. And a part or whole quantity of a polymerization initiator may be put in a flask at the said process, and a part or whole quantity of (D1), (D2), and (D3) may be put in a flask.

In addition, when using a solvent in the said process, the solvent used at the time of a normal radical polymerization reaction can be used, Specifically, tetrahydrofuran, dioxane, ethylene glycol dimethyl ethyl, diethylene glycol dimethylethyl, acetone, Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ethyl acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene Glycol monomethyl ether, toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide and the like. These solvents can be used alone or in combination of two or more thereof.

Moreover, as a polymerization initiator used for said process, the polymerization initiator normally used can be added, It does not restrict | limit in particular. Specifically, diisopropyl benzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxy isopropyl carbonate, t-amyl peroxy-2-ethylhexanoate, t-butyl Organic peroxides such as peroxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitoryl), dimethyl2,2'-azobis (2-methylpropionate), etc. And nitrogen compounds. These can be used individually or in combination of 2 or more types.

Moreover, in order to control molecular weight and molecular weight distribution, mercapto type chain transfer agents, such as n-dodecyl mercapto, mercapto acetic acid, and mercapto acetate, alpha -methylstyrene dimer, etc. can also be used as a chain transfer agent. The amount of the α-methylstyrene dimer or mercapto compound used is 0.005 to 5% by mass fraction based on the total amount of (D1), (D2) and (D3). In addition, the said polymerization conditions can also adjust an input method and reaction temperature suitably in consideration of the amount of heat generation by a manufacturing facility, superposition | polymerization, etc ..

The dispersion resin (D) according to the present invention is an unsaturated-containing resin obtained by further reacting a compound obtained by copolymerizing (D1), (D2) and (D3) with a compound (D4) having an unsaturated bond and an epoxy group in one molecule. Can be. Reactivity can be provided to a dispersion resin by adding (D4) to the said copolymer.

As a specific example of the compound (D4) which has an unsaturated bond and an epoxy group in the said 1 molecule, glycidyl (meth) acrylate, 3, 4- epoxycyclohexyl (meth) acrylate, 3, 4- epoxycyclohexylmethyl (meth) Acrylate, methylglycidyl (meth) acrylate, and the like. Among these, glycidyl (meth) acrylate is used more preferably. These can be used individually or in combination of 2 types or more, respectively.

It is preferable that the ratio of the structural unit derived from (D4) in the said dispersion resin (D) is 5-80 mol% with respect to the mole number of the structural component derived from (D3) in the said binder resin (D), and it is 10-70 Mole% is more preferable. When the composition ratio of the above (D4) is within the above range on the basis of the above standard, sufficient reactivity is imparted, which is preferable because it is excellent in reliability.

The said dispersion resin (D) can be manufactured by making the copolymer and (D4) obtained by copolymerizing said (D1), (D2), and (D3) react, for example by the following method.

5 to 80 mole% (D4) in molar fraction of the copolymer obtained by substituting the atmosphere in the flask with nitrogen for air and copolymerizing the above (D1) to (D3) and the structural unit derived from (D3) in the copolymer. As the reaction catalyst of the carboxyl group and the epoxy group, for example, trisdimethylaminomethylphenol is 0.01 to 5% by mass fraction with respect to the total amount of (D1) to (D4) and as a polymerization inhibitor, for example hydroquinone (D1). The copolymer and (D4) described above can be reacted by adding 0.001 to 5% in a mass fraction to the total amount of) to (D4) in a flask and reacting at 60 to 130 ° C for 1 to 10 hours. In addition, similarly to the polymerization conditions, the charging method and the reaction temperature may be appropriately adjusted in consideration of the amount of heat generated by the production equipment, the polymerization and the like.

The usage-amount of the said dispersion resin (D) is 5-60 mass parts normally with respect to 100 mass parts of solid content of the pigment (A) used, More preferably, it is the range of 10-50 mass parts. When the content of the dispersion resin (D) exceeds 60 parts by mass based on the above criteria, the viscosity may be increased by the dispersion resin, and less than 5 parts by mass, the amount of the dispersion resin is insufficient to obtain an atomized pigment dispersion composition.

The dispersion resin (D) has an acid value in the range of 20 to 200 (KOHmg / g). When the acid value is in the above range, it is preferable because the colored resin composition including the pigment dispersion composition according to the present invention can improve the film remaining ratio in manufacturing the color filter using exposure. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration using an aqueous potassium hydroxide solution.

In addition, the dispersion resin (D) of the present invention is not particularly limited, but the weight average molecular weight in terms of polystyrene thereof is preferably in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of the dispersion resin (D) is in the range of 3,000 to 100,000, pigment dispersion is easy, the viscosity is low, and the storage stability is preferable, because it is preferable.

Moreover, it is preferable that it is 1.5-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the dispersion resin (D) of this invention, it is more preferable that it is 1.8-4.0. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of 1.5 to 6.0 is preferred because of easy dispersion of the pigment, low viscosity and excellent storage stability.

Solvent (E)

The solvent (E) is not particularly limited and various organic solvents used in the art can be used.

Specific examples of the solvent (E) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether and diethylene glycol di. Diethylene glycol dialkyl ethers such as ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, and ethyl cellosolve acetate, and propylene glycol monomethyl Alkylene glycol alkyl ether acetates such as ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; In methyl Ketones such as ketones, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, ethyl 3-ethoxypropionate, 3 Ester, such as methyl methoxy propionate, and cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

In view of applicability and drying property, the solvent (E) may preferably use an organic solvent having a boiling point of 100 to 200 ° C in the solvent, and more preferably alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy. Ester, such as ethyl propionate and 3-methoxy methyl propionate, can be used, More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate, 3- Methyl methoxy propionate etc. can be used.

The solvent (E) mentioned above can be used individually or in mixture of 2 or more types, respectively.

Content of the said solvent (E) is 60-90 mass% normally with a mass fraction with respect to the pigment dispersion composition whole quantity containing it, Preferably it is 70-85 mass%. If the content of the solvent (E) is in the range of 60 to 90% by mass based on the above criteria, it is applied by a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, or the like. Since coating property becomes favorable at the time of carrying out, it is preferable.

Additive (F)

In the pigment dispersion composition of the present invention, additives (F) such as fillers, other high molecular compounds, curing agents, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, leveling agents, and the like, as necessary, are not changed within the scope of the present invention. It is also possible to add.

Specific examples of the filler include glass, silica, alumina and the like.

Specific examples of the other polymer compound include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Can be.

The curing agent is used to increase core hardening and mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, and the like. Examples of the epoxy compound include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, noblock type epoxy resins, other aromatic epoxy resins, and alicyclic epoxy resins. , Glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins, aliphatic, cycloaliphatic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, isoprene ( Co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like. As said oxetane compound, carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, cyclohexane dicarboxylic acid bis oxetane, etc. are mentioned, for example.

The said hardening | curing agent can use together the hardening auxiliary compound which can make ring-opening-polymerize the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with a hardening | curing agent. As said hardening auxiliary compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example. As said carboxylic anhydride, what is marketed as an epoxy resin hardener can be used. As said epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) ( New Nippon Ewha Co., Ltd.) etc. are mentioned. The said hardening | curing agents can be used individually or in mixture of 2 or more types, respectively.

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercapto propyl Trimethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. are mentioned. These adhesion promoters can be used individually or in combination of 2 or more types, respectively.

Specific examples of the antioxidant include hindered phenols such as 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like.

Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

As the leveling agent, fluorine-based or silicon-based may be used. Specifically, in the case of fluorine-based, FIC-475 of DIC Corp. and BYK-333 of BYK-Chemi Corp. may be used.

Process for preparing pigment dispersion composition

The pigment dispersion composition of this invention can be manufactured by the following method, for example. A pigment (A), a dispersing aid (B), a dispersing agent (C), a dispersing resin (D), and a solvent (E) are added to knead and disperse. Dispersion is mainly using vertical or horizontal sand grinders, pin mills, slit mills, ultrasonic dispersers, etc., and fine dispersion with beads formed of glass or zirconia having a particle diameter of 0.01 to 1 mm. Treatment gives a pigment dispersion. Before the bead dispersion, a two-roll mill, a three-roll mill, a ball mill, a trom mill, a disperser, a kneader, a kneader, a homogenizer, a blender, a single axis or a biaxial A kneading dispersion process can also be performed using an extruder etc., giving a strong shearing force.

Colored resin composition and preparation method

The colored resin composition according to the present invention comprises the pigment dispersion composition according to the present invention as a coloring material. At this time, the coloring resin composition can apply a well-known composition except having used the pigment dispersion composition as a coloring material.

Hereinafter, an example of a colored photosensitive resin composition including the pigment dispersion composition according to the present invention as a coloring material will be described, but the present invention is not limited thereto.

The coloring photosensitive resin composition which concerns on the Example of this invention is a coloring material (G-1) which is a pigment dispersion composition, a photopolymerizable compound (G-2), a photoinitiator (G-3), binder resin (G-4), and a solvent. (G-5).

The photopolymerizable compound (G-2) is a compound which can be polymerized by the action of light and a photopolymerization initiator, and a monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, or the like can be used. Moreover, the said photoinitiator (G-3) can use 1 or more types chosen from the group which consists of a triazine type compound, an acetophenone type compound, a biimidazole type compound, and an oxime compound. The binder resin (G-4) may be a resin generally used in the art that is soluble in an alkaline developer. The solvent (G-5) disperses or dissolves the above-mentioned components, and does not react with the above-mentioned components, and those having good volatility may be used. The colored photosensitive resin composition may further include various additives (G-6) generally used in the art within a range capable of improving reliability and coating properties.

As described above, by mixing the components (G-1) to (G-6) in a conventional stirrer, it is possible to produce a colored photosensitive resin composition.

Color filter

The present invention provides a color filter comprising a colored layer formed by using the colored resin composition, in the following, when the colored resin composition is a colored photosensitive resin composition, an example of a color filter using the same and a manufacturing method thereof will be described in detail. Shall be.

A method for manufacturing a color filter comprising a colored layer formed using the colored photosensitive resin composition according to the present invention comprises the steps of applying a colored photosensitive resin composition on a substrate, selectively exposing a portion of the colored photosensitive resin composition And removing the exposed or non-exposed areas of the colored photosensitive resin composition.

First, the composition of the present invention is applied onto a substrate (not limited, usually glass or silicon wafer) or a layer containing solids of the colored photosensitive resin composition formed first and preliminarily dried to remove volatile components such as solvents and to form a smooth coating film. Get The thickness of the coating film at this time is about 1-3 micrometers normally.

In the above description, the substrate may be a substrate of the color filter itself, or may be a portion where the color filter is positioned in a display device. The substrate may be a glass plate, a silicon wafer and a plate of a plastic substrate such as polyethersulfone (PES), polycarbonate (PC), or the like. That is, the substrate may be a substrate made of silicon (Si), silicon oxide (SiO _x ), a glass plate, or a polymer substrate of a plastic substrate.

In addition, the coating may be applied to the upper surface of the substrate by a coating method such as spin, slit after spin, slit, roll, spray, inkjet method.

In order to obtain the desired pattern to the coating film obtained in this way, an ultraviolet-ray is irradiated to a specific area | region through a mask. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that a parallel light beam may be irradiated uniformly to the whole exposure part, and a mask and a board | substrate will be correctly aligned. As the ultraviolet rays for the exposure, g-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm) and the like can be used.

In this case, the photomask includes a light blocking layer for shielding light rays and a light transmitting portion for transmitting light in a predetermined pattern. The irradiation amount of light rays may be appropriately selected depending on the colored photosensitive resin composition used, and the present invention is not limited thereto.

When curing is finished, the coating film is contacted with an aqueous alkali solution to dissolve and develop the non-exposed areas. By doing in this way, the colored layer of a desired pattern can be formed on a board | substrate. After image development, after drying at 150-230 degreeC for about 10 to 60 minutes can be performed as needed.

The developing solution used for image development after the said patterned exposure is the aqueous solution containing an alkaline compound and surfactant normally.

The alkaline compound may be either an inorganic or organic alkaline compound.

Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate And potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.

In addition, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoiso Propylamine, diisopropylamine, ethanolamine and the like.

The inorganic and organic alkaline compounds exemplified above may be used alone or in combination of two or more thereof.

The preferable density | concentration of the alkaline compound in the said alkaline developing solution is the range of 0.01-10 mass%, More preferably, it is 0.03-5 mass%.

Surfactant in alkaline developing solution can use all of a nonionic surfactant, anionic surfactant, or a cationic surfactant.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, and poly Oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts.

These surfactant can be used individually or in combination of 2 or more types, respectively.

The density | concentration of surfactant in alkaline developing solution is 0.01-10 mass% normally, Preferably it is 0.05-8 mass%, More preferably, it is 0.1-5 mass%.

.

The color filter is usually a black matrix and three primary color pixels of red, green and blue arranged on a substrate, but by performing the above operation using the colored photosensitive resin composition of the present invention containing a coloring material corresponding to a certain color. The black matrix and the three primary color pixels are disposed on a substrate by obtaining the black matrix or the pixel of the color and performing the same operation using the colored photosensitive resin composition of the present invention containing the coloring material corresponding to the desired color for other colors. can do. Of course, the photosensitive resin composition of this invention can also be apply | coated only to one color, two colors, or three colors of a black matrix and three primary colors.

In addition, although the black matrix which is a light shielding layer can also use the coloring (colored black) photosensitive resin of this invention, since it is formed by the chromium layer etc., for example, the coloring photosensitive resin composition of this invention for formation of a black matrix. There is no need to use.

The color filter manufactured using the coloring photosensitive resin composition of this invention has little in-plane film thickness difference, For example, it can make in-plane film thickness difference 0.15 micrometer or less and further 0.05 micrometer or less with the film thickness of 1-3 micrometers. . Therefore, the color filter obtained in this way is excellent in smoothness, and it can manufacture a liquid crystal display device of excellent quality by high yield by assembling this to a color liquid crystal display device.

Image display

The present invention also includes an image display device having the above-described color filter in its right.

The liquid crystal display of the present invention includes a configuration known in the art, except that the above-described color filter is provided. That is, all of the liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention.

For example, the image display device is a transmissive type having a thin film transistor (TFT element), a counter electrode substrate having a pixel electrode and an alignment layer facing each other at predetermined intervals, and injecting a liquid crystal material into the gap portion to form a liquid crystal layer. And a liquid crystal display device. There is also a reflective liquid crystal display device in which a reflective layer is provided between the substrate of the color filter and the colored layer.

As another example, a liquid crystal display device including a TFT (Thin Film Transistor) substrate joined on a transparent electrode of a color filter, and a backlight fixed at a position where the TFT substrate overlaps the color filter. The TFT substrate includes an outer frame made of a light-proof resin surrounding a peripheral surface of a color filter, a liquid crystal layer made of a nematic liquid crystal imposed in the outer frame, and a plurality of pixel electrodes provided for each region of the liquid crystal layer. , A transparent glass substrate on which the pixel electrode is formed, and a polarizing plate formed on the exposed surface of the transparent glass substrate.

The polarizing plate has a polarizing direction that traverses vertically and is made of an organic material such as polyvinyl alcohol. A plurality of pixel electrodes are connected with a plurality of thin film transistors each formed on a glass substrate of a TFT substrate. If a predetermined potential difference is applied to a specific pixel electrode, a predetermined voltage is applied between the specific pixel electrode and the transparent electrode. Therefore, the electric field formed according to the voltage changes the orientation of the region corresponding to the specific pixel electrode of the liquid crystal layer.

Hereinafter, the present invention will be described in more detail with reference to Examples, but embodiments of the present invention disclosed below are exemplified to the last, and the scope of the present invention is not limited to these embodiments. The scope of the invention is indicated in the appended claims, and moreover, contains all modifications within the meaning and range equivalent to the claims. In addition, "%" and "part" which show content in a following example and a comparative example are a mass reference | standard unless there is particular notice.

Synthesis Example 1 Synthesis of Dispersion Resin D-A

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, while 52 parts (0.25 mole) of 2-phenylthioethyl acrylate and 44 parts (0.25 mole) of benzyl methacrylate were used as the monomer dropping lot. ), 12.9 parts (0.15 mole) of methacrylic acid, 41.3 parts (0.35 mole) of vinyltoluene, 4 parts of t-butylperoxy-2-ethylhexanoate, and 40 parts of propylene glycol monomethyl ether acetate (PGMEA), followed by stirring It prepared by mixing and prepared 6 parts of n-dodecanethiol and 24 parts of PGMEA as a chain transfer agent dripping tank, and stirred and mixed. Thereafter, 395 parts of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen from air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C to proceed for 8 hours to obtain a dispersion resin D-A having a solid acid value of 70 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 23,000, and molecular weight distribution (Mw / Mn) was 2.4.

At this time, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin was measured using an HLC-8120GPC (manufactured by Tosoh Corporation) apparatus, and the column was used by serially connecting TSK-GELG4000HXL and TSK-GELG2000HXL. The column temperature was 40 ° C, the mobile phase solvent was tetrahydrofuran, the flow rate was 1.0 ml / min, the injection amount was 50 µl, and the detector RI was used. The measurement sample concentration was 0.6 mass% (solvent = tetrahydrofuran), a calibration standard. The material used was TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation).

Synthesis Example 2 Synthesis of Dispersion Resin D-B

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, while 52 g (0.25 mole) of 2-phenylthioethylacrylate and 26.4 g (0.15 mole) of benzyl methacrylate were used as the monomer dropping lot. , 21.5 g (0.25 mol) of methacrylic acid, 41.3 g (0.35 mol) of vinyltoluene, 4 parts of t-butylperoxy-2-ethylhexanoate, 40 parts of propylene glycol monomethyl ether acetate (PGMEA), and then stirred and mixed. It prepared, and, as a chain transfer agent dropping tank, 6 parts of n-dodecanethiol and 24 parts of PGMEA were put, and the thing which stirred and mixed was prepared. Thereafter, 395 parts of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen from air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was performed for 2 hours while maintaining 90 DEG C, and after 1 hour, the temperature was raised to 110 DEG C and held for 5 hours. Bubbling was initiated. Subsequently, 21.3 g (0.15 mol) of glycidyl methacrylate, 0.4 part of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 part of triethylamine were added to the flask, The reaction was continued for time to obtain a dispersion resin DB having a solid acid value of 75 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 19,000, and molecular weight distribution (Mw / Mn) was 2.4.

In this case, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured under the same conditions as in Synthesis Example 1.

Synthesis Example 3 Synthesis of Dispersed D-C

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, and as a monomer dropping lot, 88 parts (0.5 moles) of benzyl methacrylate, 12.9 parts (0.15 moles) of methacrylic acid, vinyl 41.3 parts of toluene (0.35 mol), 4 parts of t-butylperoxy-2-ethylhexanoate, 40 parts of propylene glycol monomethyl ether acetate (PGMEA) were added, stirred and mixed, and prepared as a chain transfer agent dropping tank. -6 parts of dodecanethiol and 24 parts of PGMEA were added and stirred and prepared. Thereafter, 395 parts of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen from air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C to proceed for 8 hours to obtain a dispersion resin D-C having a solid acid value of 70 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 21,000, and molecular weight distribution (Mw / Mn) was 2.2.

In this case, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured under the same conditions as in Synthesis Example 1.

Synthesis Example 4 Synthesis of Dispersed D-D

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, and as the monomer dropping lot, 70.4 g (0.4 mol) of benzyl methacrylate, 21.5 g (0.25 mol) of methacrylic acid, vinyl 41.3 g (0.35 mol) of toluene, 4 parts of t-butylperoxy-2-ethylhexanoate, and 40 parts of propylene glycol monomethyl ether acetate (PGMEA) were prepared after stirring and mixing, n- as a chain transfer agent dripping tank. 6 parts of dodecanethiol and 24 parts of PGMEA were added and stirred and prepared. Thereafter, 395 parts of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was performed for 2 hours while maintaining 90 DEG C, and after 1 hour, the temperature was raised to 110 DEG C and held for 5 hours. Bubbling was initiated. Subsequently, 21.3 g (0.15 mol) of glycidyl methacrylate, 0.4 part of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 part of triethylamine were added to the flask, The reaction was continued for time to obtain a dispersion resin DD having a solid acid value of 75 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 16,300, and molecular weight distribution (Mw / Mn) was 2.2.

In this case, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured under the same conditions as in Synthesis Example 1.

&Lt; Example 1 >

Among the components shown in Table 1 below, 20 parts of a pigment (A), a dispersing aid (B), a dispersing agent (C), a dispersing resin (D), a solvent (E1) and a solvent (E2) are mixed into a container, followed by a high speed stirrer ( After stirring for 2 hours at 5m / s linear speed through a 0.5Hp high speed mixer manufactured by Shinwon Industrial Machinery, 40 parts of the solvent (E2) were further mixed, and then a transverse bead mill (manufactured by Dyno, ECM-Lab) ), 0.3 mm zirconia beads were used to disperse for 3 hours at a rate of linear velocity of 8 m / s and a flow rate of 2 kg / min, and after dispersion was completed, 12.7 parts of the remaining amount of solvent (E2) were added to the pigment dispersion composition R1. Was prepared.

The average particle size and viscosity of the pigment dispersion composition thus obtained were measured, and the results are shown in Table 3 below. At this time, the average particle size was measured by a particle size analyzer (Otsuka Electronics Korea Co., ELS 8000), the viscosity was measured by a Brookfield viscometer (Brookfield Viscometer DV-I +, manufactured by Brookfield) at 25 ℃.

Thereafter, a glass substrate of 2 square inches (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. Using the pigment dispersion composition R1 according to the present invention on this glass substrate, a colored resin composition (G1 to G6) having a composition as shown in Table 2 was prepared, and then the film thickness was 2.0 μm using the thus obtained colored resin composition. Spin coating was followed by drying for 20 minutes at 150 ° C. in a clean oven. As for the obtained colored board | substrate, Contrast was measured using the Contrast measuring machine (Chibo Saka Corporation make, CT-1). The measurement results are shown in Table 3 below.

Pigment (A) C.I. Pigment Red 254 (BK-CF; manufactured by BASF Corporation) Part 15 Dispersion aid (B) Solsperse 22000 (manufactured by Lubrizol) 0.3 part Dispersant (C) Disperbyk-2000 (manufactured by BYK-chemi) Part 4.5 Dispersion Resin (D) Dispersion D-A Part 4.5 Solvent (E1) n-butyl alcohol Part Three Solvent (E2) Propylene Glycol Monomethyl Ether Acetate Part 72.7

Coloring material (G1) Pigment Dispersion Composition R1 Part 33.5 Monomer (G2) Dipentaerythritol hexaacrylate
(KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) Part 23 Initiator (G3) Ethanone-1- [9-ethyl-6- (2-methyl-
4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime)
(Irgacure OXE02; manufactured by Ciba) Part 10 Binder Resin (G4) Methacrylic acid / N-phenylmaleimide / styrene / benzyl methacrylate / glycerol monomethacrylate copolymer as alkali-soluble resin (copolymerization mass ratio = 15/25/15/35/10, Mw = 13,500) Part 20 Additive (G5) Fluorine Leveling Agent F-475 (manufactured by DIC Corporation) 0.05 parts Solvent (G6) Propylene Glycol Monomethyl Ether Acetate Part 13.45

<Example 2>

Pigment (A) of Example 1 was prepared by C.I. The same operation as in Example 1 was carried out except that Pigment Blue 15: 6 (EP-193; manufactured by DIC Corporation) was changed to Solsperse 5000 (manufactured by Lubrizol). The evaluation results are shown in Table 3 below.

<Example 3>

Pigment (A) of Example 1 was prepared by C.I. The same operation as in Example 1 was carried out except that Pigment Green 58 (A-110; manufactured by DIC Corporation) was changed to Dispersion Aid (B) to Solsperse 5000 (manufactured by Lubrizol). The evaluation results are shown in Table 3 below.

<Example 4>

Operation similar to Example 1 was performed except having changed the dispersion resin D of Example 1 from dispersion resin D-A (synthesis example 1) to dispersion resin D-B (synthesis example 2). The evaluation results are shown in Table 3 below.

Example 5

The same operation as in Example 1 was carried out except that the dispersion resin (D) of Example 1 was reduced from 4.5 parts to 2 parts and the propylene glycol monomethyl ether acetate was increased from 72.7 parts to 75.2 parts. The evaluation results are shown in Table 3 below.

<Example 6>

The same operation as in Example 1 was carried out except that the dispersion resin (D) of Example 1 was increased from 4.5 parts to 7 parts and the propylene glycol monomethyl ether acetate was reduced from 72.7 parts to 70.2 parts. The evaluation results are shown in Table 3 below.

Comparative Example 1

The same operation as in Example 1 was performed except that the dispersion resin D-A (Synthesis Example 1) was changed to dispersion resin D-C (Synthesis Example 3). The evaluation results are shown in Table 4 below.

Comparative Example 2

Operation similar to Example 1 was performed except changing the dispersing agent (C) of Example 1 to PB-821 (made by Ajinomoto Co., Ltd., polyester system). The evaluation results are shown in Table 4 below.

Comparative Example 3

The same operation as in Example 2 was performed except that the dispersion resin D-A (Synthesis Example 1) was changed to dispersion resin D-C (Synthesis Example 3). The evaluation results are shown in Table 4 below.

<Comparative Example 4>

The same operation as in Example 1 was performed except that the dispersion resin D-A (Synthesis Example 1) was changed to dispersion resin D-C (Synthesis Example 3). The evaluation results are shown in Table 4 below.

Comparative Example 5

The same operation as in Example 1 was performed except that the dispersion resin D-A (Synthesis Example 1) was changed to dispersion resin D-D (Synthesis Example 4). The evaluation results are shown in Table 4 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Average particle size (nm) * 1 63 54 57 60 65 68 Viscosity (cp) * 2 10 8 7 9 11 13 Storage stability * 3 ○ ○ ○ ○ ○ ○ Contrast * 4 15,780 11,340 19,150 16,030 15,290 14,890

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Average particle size (nm) * 1 93 137 77 89 98 Viscosity (cp) * 2 15 22 14 18 14 Storage stability * 3 △ X △ △ X Contrast * 4 12,100 8,300 9,210 14,050 11,310

* 1: The smaller the particle size is, the better for excellent optical characteristics (brightness, contrast).

* 2: The lower the viscosity, the better.

* 3: The storage stability is shown below through the viscosity change before and after storage after storing the pigment dispersion compositions of Examples and Comparative Examples in a 40 ℃ storage for 2 weeks.

○: less than 10%, △: more than 10% to less than 20%, X: more than 20%

* 4: Measured based on Bare 30,000: 1, the higher the value, the better.

When the acrylate-based dispersant and the dispersion resin of the present invention is included in Table 3, a highly concentrated pigment dispersion composition having low viscosity, excellent storage stability, and high contrast was obtained.

On the other hand, in the case of the pigment dispersion composition of the comparative example, particle size, viscosity, and storage stability contrast were inferior, and a high quality colored resin composition and color filter could not be obtained.

Claims (13)

It comprises a pigment (A), a dispersant (C), a dispersion resin (D) and a solvent (E), wherein the dispersant (C) is BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl meta An acrylate-based dispersant comprising an acrylate), wherein the dispersion resin (D) is a copolymer obtained by copolymerizing the following (D1), (D2) and (D3) compounds: (D1): a compound represented by the following formula (1); <Formula 1>

(In Formula 1, R ₁ is hydrogen or methyl group, R ₂ is a substituted or unsubstituted divalent C ₁ ~ C ₆ alkyl or alkenyl group, A is a substituted or unsubstituted benzene group, cyclohexyl group, Alkyl group or alkenyl group of C ₁ to C ₆ , wherein substituents of R ₂ and A are independently fluorine, chlorine, bromine, iodine, C ₁ to C ₆ alkyl group, C ₁ to C ₃ perhalogenated alkyl group, hydroxy group, A C ₁ to C ₆ ketone group, a C ₁ to C ₆ ester group, a N, N- (C ₁ -C ₃ ) alkyl substituted amide group or a combination comprising one or more of these substituents.) (D2): a compound having an unsaturated bond copolymerizable with (D1) and (D3); (D3): A compound having a carboxyl group and an unsaturated bond. The colored photosensitive resin composition according to claim 1, wherein (D1) is selected from at least one of compounds represented by the following general formula (2). <Formula 2>

(In Formula 2, R ₁ is hydrogen or methyl group, R ₂ is a substituted or unsubstituted divalent C ₁ ~ C ₆ alkyl or alkenyl group, wherein the substituent of R ₂ is fluorine, chlorine, bromine, iodine, C ₁ ~ C ₆ alkyl group, C ₁ ~ C ₃ perhalogenated alkyl group, hydroxy group, C ₁ ~ C ₆ ketone group, C ₁ ~ C ₆ ester group, N, N- (C ₁ -C ₃ ) alkyl Substituted amide groups or combinations comprising one or more of these substituents.) The unsaturated resin according to claim 1, wherein the dispersion resin (D) is further obtained by reacting a compound obtained by copolymerizing the above (D1), (D2) and (D3) with a compound (D4) having an unsaturated bond and an epoxy group in one molecule. A pigment dispersion composition, which is a group-containing resin. The pigment dispersion composition according to claim 1, wherein (D2) is an aromatic vinyl compound or N-substituted maleimide. The method of claim 1, wherein the dispersion resin (D) is a ratio of the component derived from each of (D1), (D2) and (D3) is a structural unit derived from (D1) with respect to the total moles of the component is 2 To 50 mol%, 2 to 50 mol% of structural units derived from (D2), and 2 to 70 mol% of structural units derived from (D3). The pigment dispersion composition according to claim 3, wherein the proportion of the constituent derived from (D4) is 5 to 80 mol% with respect to the constituent derived from (D3) in the dispersion resin (D). The pigment dispersion composition of claim 1, wherein the pigment dispersion composition further comprises a dispersing aid (B). The pigment dispersion composition according to claim 7, wherein the amount of the dispersion aid (B) is 0 to 20 parts by mass based on 100 parts by mass of the solid content of the pigment (A). The pigment dispersing composition of Claim 1 whose usage-amount of the said dispersing agent (C) is 5-60 mass parts with respect to 100 mass parts of solid content of a pigment (A). The pigment dispersion composition according to claim 1, wherein the amount of the dispersion resin (D) is 5 to 60 parts by mass based on 100 parts by mass of the solid content of the pigment (A). The colored resin composition containing a coloring material, The said coloring material is the pigment dispersion composition of any one of Claims 1-10, The coloring resin composition characterized by the above-mentioned. The color filter containing the colored layer formed using the colored resin composition, The said colored resin composition is the colored resin composition of Claim 11, The color filter characterized by the above-mentioned. An image display apparatus comprising the color filter of claim 12.