JP2010262003A - Ink composition for color filter, colored cured film, and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition capable of satisfactorily exhibiting optical characteristics of a Pigment Green 58 and having excellent ejection properties and shelf stability of ink in an inkjet method. <P>SOLUTION: In the ink composition including an unsaturated compound (A) of general formula, a tetra or more functional multifunctional compound (B), 0 to 150 wt.% bifunctional or more multifunctional epoxy compound (C) compounded in the total of the components (A) and (B) and a pigment dispersion liquid (D) formed by dispersing pigment in a dispersant, the ratio (A)/(B) by weight of the component (A) to the component (B) is 0/100 to 90/10, the ratio (pigment/resin) of an amount of the pigment and an amount of resin in a solid component excluding all solvent components in the ink composition is 20 to 60 wt.%, the dispersant in the component (D) is an acrylic dispersant and the ratio (dispersant/pigment) of an amount of the dispersant to the amount of the pigment is 35 to 120 wt.%. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an ink composition for a color filter, a colored cured film, and a color filter. More specifically, the present invention relates to an ink composition suitable for an ink jet method, and has high optical properties especially for a green component among red, green, and blue. (High Y value (brightness) and contrast), and an ink composition excellent in storage stability, a colored cured film obtained thereby, and a color filter provided with this colored cured film About.

  Color filters used in various color liquid crystal display devices are prepared by adding red (R), green (G), and blue (B) coloring components to the photosensitive resin in addition to the photopolymerization initiator and various additives. After applying the color resist on a predetermined substrate and drying, it is a mainstream to form a pixel pattern by a photolithography method through a series of steps. However, with the recent enlargement of mother glass, the production of color filters by the ink jet method has been put into practical use instead of the conventional color filter production method by the photolithography method.

  Various improvements have also been made to the colorant that forms each color pattern of the color filter, and the development of new pigments proceeds. Among them, one of the pigments that has recently been put into practical use is Pigment Green 58 (C.I. Pigment Green 58: manufactured by DIC Corporation) using brominated chlorinated zinc phthalocyanine as a coloring material. This is the same chromaticity as the conventional chlorinated copper phthalocyanine pigment (CIPigment Green 7) and chlorinated brominated copper phthalocyanine (CIPigment Green 36) used to form a green coloring pattern. In addition, it is said that the same brightness can be expressed with a smaller amount of light than the conventional product (see Non-Patent Document 1). However, when this Pigment Green 58 is applied to an ink composition, it is difficult to disperse and is inferior in storage stability, and even if the dispersal is completed, the Y value that is an index of brightness and the contrast value that affects the screen display ability May deteriorate over time.

DIC Technical Review No.14 / 2008, P42-43

  Therefore, the present inventors have newly developed C.I. I. As a result of intensive investigations to solve problems in applying CI Pigment Green 58 (hereinafter, abbreviated as “PG-58”) to an ink composition, a dispersant having a specific molecular skeleton structure is used. The present inventors have found that various problems can be solved by dispersing the pigment and forming an ink composition with the ratio of the pigment and the dispersant within a predetermined range, thereby completing the present invention.

  Therefore, an object of the present invention is to provide an ink composition that can sufficiently develop the optical properties of the newly developed Pigment Green 58 and that is excellent in ink ejection properties and storage stability in the inkjet method. Objective.

〔式中、Ｒ₁、Ｒ₂、Ｒ₃、及びＲ₄は独立に水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を示し、Ｒ₅は水素原子又はメチル基を示す。また、Ａは-CO-、-SO₂-、-C(CF₃)₂-、-Si(CH₃)₂-、-CH₂-、-C(CH₃)₂-、-O-、9,9-フルオレニル基又は直結合を示し、Ｘは４価のカルボン酸残基を示し、Ｙ₁及びＹ₂は独立に水素原子又は-OC-Z-(COOH)_m（Zはカルボン酸残基を示し、ｍは１〜３の数を示す）であり、ｎは１〜２００の数を示す。〕 That is, the present invention is an ink composition used for producing a color filter by an inkjet method, and an unsaturated compound (A) represented by the following general formula (1) in a solvent (H), having 4 or more functional groups. The polyfunctional compound (B), a bifunctional or higher polyfunctional epoxy compound (C) blended in an amount of 0 to 150% by weight based on the total of the components (A) and (B), and a pigment are dispersed in the dispersant The ratio (A) / (B) of the weight of the component (A) and the component (B) is 0/100 to 90/10, and the pigment dispersion (D) is used. The ratio of pigment amount to resin amount (pigment / resin) in the solid component excluding the solvent component is 20 to 60% by weight, and the dispersant in component (D) is an acrylic dispersant, The ratio of the amount of dispersant to the amount of pigment (dispersant / pigment) is 35 to 120% by weight. Ri, besides, the pigment is C. I. This is an ink composition for a color filter, which is CI Pigment Green 58.

[Wherein R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ represents a hydrogen atom or a methyl group. A is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9 , 9-fluorenyl group or a direct bond, X represents a tetravalent carboxylic acid residue, Y ₁ and Y ₂ independently represent a hydrogen atom or —OC—Z— (COOH) _m (Z is a carboxylic acid residue) M represents a number of 1 to 3), and n represents a number of 1 to 200. ]

  In addition, the present invention is a colored cured film for a color filter obtained by applying the ink composition by an inkjet method, drying and curing.

  Furthermore, this invention is a color filter provided with said colored cured film for color filters.

In the present invention, the pigment C.I. I. A pigment dispersion (D) in which CI Pigment Green 58 is dispersed with a dispersant is added to the ink composition. Here, the dispersing agent is an additive that adsorbs or adheres to the surface of the pigment and inhibits aggregation of the pigments, and the basic structure of a general dispersing agent is that the adsorbing part that adsorbs to the pigment surface and the pigments. And a solid repulsion part for preventing aggregation. Usually, the adsorbing part has a structure having a charge opposite to that of the pigment surface. For example, when the pigment surface has been subjected to an acid treatment, the adsorbing part has Na ⁺ , amine or imino structure. Often doing. On the other hand, the steric repulsion part is also referred to as a molecular skeleton, and is connected by a long chain hydrocarbon chain, acrylic, ester, ether, etc., and the dispersant is an acrylic, ester, It is named separately such as ether type. In addition, since the dispersant has a charge on one side and a hydrocarbon structure on the other side, the dispersant is a kind of surfactant. In the ink composition, the surface of the pigment is added. Although the adsorbing dispersant can be stabilized with the solid repulsion part protruding to the solvent side, the adsorption of the dispersing agent on the pigment surface is not permanent, and the dissociation and adsorption are repeated with a certain probability, and the equilibrium state It is thought that it keeps.

  By the way, pigments tend to be miniaturized for the purpose of preventing a decrease in contrast ratio due to light scattering. In particular, pigments used as colorants for color filters have a primary particle size of about 100 nm or less. It is general. And in order to coat the pigment having such a particle size, the amount of the dispersant used is theoretically about 30% by weight with respect to the weight of the pigment. Thus, it is difficult to ensure sufficient stability with this amount of dispersant. This is understood because aggregation of the pigments occurred before the dispersing agent deviating from the pigment surface re-adsorbed. Therefore, in the case of an amount of the dispersant that can sufficiently cover the surface area of the pigment, in reality, stable dispersion cannot be realized, and an excessive amount of dispersant is added to cause adsorption and separation between the pigment and the dispersant. It is necessary to move the equilibrium reaction to at least the adsorption side. However, when the amount of the dispersant used is increased, the curing component for forming the colored cured film of the color filter and the pigment content for expressing the optical function are relatively reduced in the ink composition. In particular, the dispersant may not only directly contribute to the developability and curability when obtaining a colored cured film, but may also be a factor that inhibits it.

  Therefore, the present inventors have used C.I. I. A trial and error study was conducted on the dispersion stability of CI Pigment Green 58 and the incompatible properties required for the ink composition to obtain a colored cured film. As a result, an acrylic dispersant was used and a pigment for the dispersant was used. Surprisingly, in the dispersion stability, curability and developability of the ink composition, the ratio (dispersant / pigment) with respect to the ink composition is 35 to 120% by weight, preferably 40 to 100% by weight. It has been found that a colored cured film having satisfactory results and excellent optical characteristics can be obtained, and in particular, the temporal stability of the optical characteristics can be secured.

  When the ratio of the dispersant to the pigment (dispersant / pigment) is less than 35% by weight, the viscosity increases when the pigment dispersion (D) is stored at room temperature, and at least a treatment such as refrigerated storage is performed. Necessary. In particular, when preparing an ink composition, in order to achieve stability over a wide range against various variations in the composition required as required, such as viscosity adjustment, color characteristic adjustment, and drying characteristic adjustment of the ink composition The ratio of the dispersant to the pigment is required to be at least 35% by weight. Incidentally, if the proportion of the dispersant is less than 25% by weight, the viscosity cannot be kept stable even in refrigerated storage. On the other hand, if the proportion of the dispersant exceeds 120% by weight, the ratio of the resin or monomer necessary for imparting the function, such as the film forming function when the ink composition is cured, is relatively reduced, and the film physical properties are improved. However, sufficient reliability cannot be demonstrated. It is possible to realize a composition capable of exhibiting sufficient reliability in a wide range for imparting various functions required for ink compositions, such as film forming functions and electrical reliability functions due to a decrease in the degree of cure, and fluctuations in properties. % Or less.

  In addition, by using a dispersant other than an acrylic-based dispersant so as to have the above-mentioned ratio with respect to the pigment, it is possible to ensure dispersion stability and obtain a pigment dispersion having appropriate viscosity characteristics. However, in the case of a dispersant other than an acrylic type, a change with time particularly becomes a problem with respect to optical characteristics. A characteristic change is a decrease in the Y value (luminance) and contrast value. In the early case, after preparing the pigment dispersion, it is about a few days, and clearly after a month at the latest, the Y value and the contrast value Decline is confirmed. Such changes are not observed when an acrylic dispersant is used. As the acrylic dispersant, any dispersant having an adsorption part and a steric repulsion part may be used as long as at least the molecular skeleton of the steric repulsion part has an acrylic structure. By obtaining a pigment dispersion (D) by dispersing the pigment at a ratio, an appropriate viscosity stability is exhibited, and an optical composition exhibiting optically specific stability over time is obtained, thereby obtaining an ink composition capable of coexisting these. be able to. Specific examples of acrylic dispersants include, for example, BYK Chemie's Disperbyk-112, 116, 2000, 2001, 2009, 2020, 2025, 2050 and 2070, Enomoto Kasei Co., Ltd. The company's florene DOPA-15B, DOPA-15BHFS, DOPA-17HF, DOPA-22, DOPA-33 and DOPA-44 can be exemplified.

  In the present invention, the pigment dispersion (D) may contain an organic pigment or an inorganic pigment other than PG-58 (hereinafter collectively referred to as “other pigments”). When a pigment other than 58 is included, the blending amount of the other pigment is preferably 70% by weight or less in the total pigment. Among other pigments, organic pigments include, for example, azo lake, insoluble azo (PY-150), phthalocyanine (PG-7, PG-36 & PB-15.6) cyanine, quinophthalone (PY138), quinacdrine , Dioxazine (PV-23), isoindolinone (PY-139), berylone, anthraquinone (PR-177), pyrrolopyrrole (PR-254), perylene, etc. 1 type (s) or 2 or more types can also be used together. Examples of inorganic pigments include miloli blue, iron oxide, cobalt-based, manganese-based, ultramarine blue, bitumen, cobalt blue, cerulean blue, pyridian, emerald green, cobalt green, and the like. It can also be used together. These other pigments are preferably dispersed to an average particle diameter of 0.4 μm or less, which is the lower limit of the wavelength of visible light, in order to color while maintaining the transparency of the coating film. It is more preferable that the average particle diameter range is from 0.01 to 0.25 μm. In particular, the yellow pigment, which is a complementary color component to PG-58, is blended in the pigment at a ratio of 70% by weight or less to adjust the hue to match the currently required Green color of the color filter. Can do.

  In the present invention, the ratio of the pigment amount to the resin amount (pigment / resin) in the solid component excluding all solvent components in the ink composition is 20 to 60% by weight, preferably 40 to 55% by weight. Like that. If the ratio of the pigment to the resin amount is less than 20% by weight, desired color characteristics cannot be obtained. Conversely, if the ratio exceeds 60% by weight, the pigment tends to aggregate, causing head clogging during ink ejection. The amount of resin in the solid component is the total excluding the dispersant in each component including the component (A), the component (B), the component (C), and the pigment and the dispersant in the component (D). It is.

  The ink composition in the present invention preferably contains the unsaturated compound (A) represented by the general formula (1) described above as a constituent component of the resin. This component (A) is a polybasic acid with respect to the compound having a hydroxy group obtained by reacting (meth) acrylic acid with an epoxy compound having two glycidyl ether groups derived from bisphenols. One or more each of dicarboxylic acid or its acid anhydride (hereinafter also referred to as “dicarboxylic acid”) and tetracarboxylic acid or its acid dianhydride (hereinafter also referred to as “tetracarboxylic acid”) It is an epoxy (meth) acrylate acid adduct obtained by reacting. By containing the unsaturated compound (A) represented by the general formula (1) as a constituent component of the resin, it is advantageous in terms of heat resistance and high temperature of the glass transition point. About the weight average molecular weight (Mw) of (A) component, Preferably it is the range of 2000-20000. In the present specification, (meth) acrylic acid means acrylic acid, methacrylic acid or both.

The component (A) is preferably derived from an epoxy compound represented by the following general formula (2). Although this epoxy compound is derived from bisphenols, oligomer units are mixed when bisphenols are converted to glycidyl ether. If the average value of l in the general formula (2) is in the range of 0 to 10, There is no problem in the performance as an ink composition.

In the general formula (2), R ₁ , R ₂ , R ₃ , R ₄ and A each have the same meaning as in the general formula (1), but R ₁ , R ₂ , R ₃ and R ₄ Is preferably a hydrogen atom, and A is preferably a 9,9-fluorenyl group. l is an integer of 0 to 10, preferably 0 or an integer of 0 to 2. Here, the 9,9-fluorenyl group refers to a group represented by the following general formula (3).

  In the present invention, the reaction between the epoxy compound and (meth) acrylic acid in obtaining the component (A) is performed using about 2 moles of (meth) acrylic acid with respect to 1 mole of the epoxy compound. Good. The reaction product obtained by this reaction is an epoxy (meth) acrylate compound represented by the following general formula (5). Then, the hydroxy group in the epoxy (meth) acrylate compound molecule is reacted with a) dicarboxylic acid and b) tetracarboxylic acid to obtain an acid adduct of epoxy (meth) acrylate.

  a) As the dicarboxylic acid, a chain hydrocarbon dicarboxylic acid or an acid anhydride thereof, an alicyclic dicarboxylic acid or an acid anhydride thereof, an aromatic dicarboxylic acid or an acid anhydride thereof, or the like can be used. Among these, as the chain hydrocarbon dicarboxylic acid or its acid anhydride, for example, succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citralmalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, Examples thereof include compounds such as oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, and further dicarboxylic acids into which an arbitrary substituent is introduced or acid anhydrides thereof. Examples of the alicyclic dicarboxylic acid or its acid anhydride include compounds such as hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, and further, an arbitrary substituent is introduced. Dicarboxylic acids or acid anhydrides thereof may also be used. Furthermore, examples of the aromatic dicarboxylic acid or acid anhydride thereof include compounds such as phthalic acid and isophthalic acid, and further dicarboxylic acids into which an arbitrary substituent is introduced or acid anhydrides thereof may be used. .

  In addition, as b) tetracarboxylic acids, chain hydrocarbon tetracarboxylic acid or its acid dianhydride, alicyclic tetracarboxylic acid or its acid dianhydride, aromatic polyvalent carboxylic acid or its acid dianhydride, etc. Can be used. Among these, examples of the chain hydrocarbon tetracarboxylic acid or its acid anhydride include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and the like, and tetracarboxylic acids into which a substituent is further introduced. Or its acid anhydride may be sufficient. Examples of the alicyclic tetracarboxylic acid or its acid anhydride include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid norbornanetetracarboxylic acid, and the like. May be a tetracarboxylic acid having a substituent introduced therein or an acid anhydride thereof. Furthermore, examples of the aromatic polyvalent carboxylic acid or acid anhydride thereof include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid or acid anhydride thereof, and further substitution. It may be a tetracarboxylic acid having an introduced group or an acid anhydride thereof.

  About said a) dicarboxylic acid and b) tetracarboxylic acid, 1 or more types can be used, respectively, About the usage-amount of a) dicarboxylic acid and b) tetracarboxylic acid, the molar ratio of a / b is 0. It should be in the range of 1 to 10, preferably 0.2 to 1.0. As for this use ratio, an appropriate ratio can be selected in consideration of the optimum molecular weight, curability, light transmittance, heat resistance, solvent resistance and the like of the component (B).

  In addition, a known method can be employed for the reaction of the epoxy (meth) acrylate compound with a) dicarboxylic acid and b) tetracarboxylic acid in obtaining the component (A), but preferably epoxy (meth). It is preferable to carry out the reaction quantitatively so that the acid component is 3/4 mol per 1 mol of hydroxy group in the acrylate compound molecule. The reaction temperature is 90 to 130 ° C, preferably 95 to 125 ° C.

An example of a method for producing the component (A) is as follows when 9,9-bis (4-hydroxyphenyl) fluorene is used as a starting material. First, 9,9-bis (4-hydroxyphenyl) fluorene and epichlorohydrin are reacted to synthesize a bisphenolfluorene type epoxy compound represented by the following general formula (4). By reacting with (meth) acrylic acid represented by CH ₂ ═CR ₅ —COOH, a bisphenolfluorene type epoxy acrylate resin represented by the following general formula (5) is synthesized. Next, the bisphenol fluorene type epoxy acrylate resin and the acid component are reacted under heating in a propylene glycol monomethyl solvent to obtain a fluorene type alkali-soluble resin represented by the formula (1) as the component (A). Can do. Here, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ in the general formulas (4) and (5) are the same as those in the general formula (1), and A represents a 9,9-fluorenyl group.

  In the present invention, the polyfunctional compound (B) having a functionality of 4 or more is included in the ink composition, and preferably a polyfunctional reactive monomer or oligomer having a functionality of 4 or more, particularly an acrylate compound. Or a melamine compound. Having a polyfunctional structure having four or more functional groups develops a crosslinked structure after final curing, which is advantageous in terms of electrical reliability. Specific examples of the polyfunctional acrylate compound having 4 or more functional groups include methylol propane such as ditrimethylolpropane tetra (meth) acrylate, tetrafunctional or higher acrylate, pentaerythritol tetra (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, skeletons such as pentaerythritol and dipentaerythritol, tetra- or higher functional acrylates, pentaacrylate esters, etc. Acrylates and the like. These may be used alone or in combination of two or more. Furthermore, these acrylates may be monomers or oligomers. Here, the tetrafunctional or higher polyfunctional compound (B) is a substance having four or more functional groups that are considered to contribute to the polymerization reaction in one molecular chain, and among these, the monomer or oligomer (B) The component is preferably a compound having an acrylic structure as a functional group and a compound having a melamine structure. Moreover, even if it is except the structure illustrated above, what is necessary is just 4 functional or more, and it is not influenced by the main frame | skeleton of an acrylate or a melamine. In addition, the unsaturated compound as the component (A) and a part of the bifunctional or higher functional epoxy compound as the component (C) are converted into a tetrafunctional or higher functional compound as the condition of the component (B). However, in the present invention, polyfunctional compounds having four or more functional groups are classified as the component (A) or the component (B). (C) It considers excluding from the object of a component.

  In addition, for polyfunctional melamines having 4 or more functionalities, for example, in the case of amino resins, monomethoxymethylated melamine resins, dimethoxymethylated melamine resins, trimethoxymethylated melamine resins, tetramethoxymethylated melamine resins, pentamethoxymethylated Melamine resin, hexamethoxymethylated melamine resin, butylated melamine resin, monomethylol melamine resin, dimethylol melamine resin, trimethylol melamine resin, tetramethylol melamine resin, pentamethylol melamine resin, hexamethylol melamine resin, imino group-containing methoxymethyl Illustrative examples include melamine resin, benzoguanamine resin, butylated benzoguanamine resin, glycoluril resin, butylated urea resin, and methylated methylol urea resin. These may be used alone or in combination of two or more.

  Further, when an acrylic component is used in the component (B), a photopolymerization initiator may be added. For example, acetophenones such as acetophenone and p-tert-butylacetophenone, benzophenone, 2-chlorobenzophenone, p, benzophenones such as p'-bis (dimethylamino) benzophenone, benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether and benzoin butyl ether, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane- Α-aminoalkylphenones such as 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenyl-phos Bisacylphosphine oxides such as fine oxides, glycines such as N-phenylglycine, 2,4-trichloromethyl - (piperonyl) -6-triazine, 2,4-trichloromethyl - (4'-methoxy styryl) triazines, such as 6-triazine. These may be used alone or in combination of two or more. The photopolymerization initiator can also be used in combination with known photopolymerization accelerators (sensitizers) such as p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester. About the usage-amount of a photoinitiator component, it is preferable that it is 0.1-20 weight part with respect to 100 weight part of total amounts of the acryl component amount in (B) component, and (A) component.

  In the present invention, the weight ratio (A) / (B) of the component (A) to the component (B) is 0/100 to 90/10, preferably 10/90 to 30/70. Is good. If (A) / (B) exceeds the range of 90/10, the viscosity stability of the ink composition may be lowered.

  Moreover, in this invention, the polyfunctional epoxy compound (C) more than bifunctional is included, and the compounding quantity of this (C) component is 0 to 150 weight% with respect to the sum total of (A) + (B) component, Preferably Is 5 to 100% by weight. If it exceeds 150% by weight, the storage stability may decrease, for example, the viscosity may increase due to long-term storage. Here, the polyfunctional epoxy compound (C) is composed of an epoxy compound having two or more epoxy groups in one molecule. For example, a novolak type epoxy resin such as a phenol novolak type epoxy or a cresol novolak type epoxy, or a bisphenol A type epoxy. Typical examples include bis-type epoxy resins such as bisphenol F-type epoxy, biphenyl-type epoxy resins, and alicyclic epoxy resins. In the ink composition of the present invention, such a component (C) is blended to increase the degree of crosslinking and contribute to the improvement of reliability and the like.

  Furthermore, in this invention, if it is a range which does not inhibit the other performance of the ink composition for color filters, a viscosity modifier (E) can also be added from the objective of adjusting the appropriateness | suitability of application | coating by the inkjet method. The viscosity modifier (E) includes those that lower the viscosity and those that increase the viscosity. Generally, the solvent is also included as a viscosity lowering agent, but in the present invention, a normal solvent is a viscosity. It is regarded as a solvent, not a regulator, and a reactive diluent having a low molecular functional group is used as a viscosity modifier. On the other hand, those that increase the viscosity include silica-based airgel in which silica particles are dispersed, amide-based wax, and bentonite-based thickener, and these are added as necessary to adjust the viscosity. .

  Furthermore, the ink composition for a color filter of the present invention may contain, for example, a surfactant for improving wettability and a coupling agent for improving adhesion (collectively ( F) component)). Of these, the surfactant is desirably contained in the ink composition in the range of 0.01 to 0.2% by weight.

  The ink composition of the present invention is formed by dissolving or dispersing at least the above-described components (A) to (D) (if necessary, further (E) or (F) component) in a solvent (H). Examples of the solvent (H) include ketones such as methyl ethyl ketone, cyclohexanone and methylcyclohexanone, cellosolves such as methyl cellosolve, ethyl cellosolve and cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol n-propyl ether, Propylene glycol monoalkyl ethers such as propylene glycol n-butyl ether, propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol n-butyl ether acetate , Diethylene glycol dimethyl ether, Diethylene glycol dialkyl ethers such as ethylene glycol diethyl ether and diethylene glycol dibutyl ether, lactate esters such as methyl lactate and ethyl lactate, acetate esters such as n-butyl acetate, γ-butyrolactone, N-methylpyrrolidone, dimethyl sulfoxide, etc. The organic solvent can be illustrated.

  In this invention, you may make it a solvent (H) consist of 2 or more types of mixed solvents, and the boiling point of any solvent is good to be the range of 120-350 degreeC. Moreover, about the usage-amount of a solvent (H), although it can adjust suitably according to the composition of an ink composition, the usage-amount of the solvent (H) with respect to a total of 100 weight part of (A)-(F) component, for example. The amount is generally 50 to 1000 parts by weight.

  The composition of the present invention is an ink composition suitable for producing a color filter by an ink-jet method, and a known method can be adopted for conditions for applying the ink composition or obtaining a cured film. . As an example, after applying an ink composition to a predetermined region such as a glass substrate by an ink jet method, for example, a drying treatment is performed at 50 to 130 ° C. for 1 to 10 minutes, and then at 200 to 260 ° C., 0.5%. Predetermined pixels can be formed by performing thermosetting for ˜2 hours. At this time, similarly to a general ink jet method, an ink composition is ejected onto a substrate having a predetermined black matrix pattern, and a colored cured film for a color filter is formed through steps such as drying and curing. Obtainable.

  The ink-jet ink composition of the present invention is an ink composition adapted to PG-58, which is a newly developed green pigment, and is a PG-58 pigment that is optically characteristic at room temperature while maintaining ink-jet characteristics. By building a technique that can stabilize the viscosity, it is possible to maintain and secure a stable viscosity.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these. In addition, unless otherwise indicated in an Example, a part represents a weight part and% represents weight%.

[Example of formulation of Green dispersion A]
As shown in Table 1, 105 g of PG-58 (trade name manufactured by DIC: FASTOGEN Green A110 (registered trademark)) as a pigment and PY-150 (trade name manufactured by LANXESS: “YELLOW PIGMENT E4GN”) as a pigment are also used. 45 g, 300 g of BCA (butyl carbitol acetate) as a solvent, and 122.4 g of an acrylic dispersant A (trade name: DISPERBYK-2025 (registered trademark) manufactured by Big Chemie Japan) as a dispersant are prepared. The sample was collected in a stainless steel container and kneaded with a three roll coated with a ceramic coating until fluidity appeared. After 170 g of BCA was further added to and mixed with the kneaded material obtained, the mixture was dispersed with a horizontal sand mill until the average particle size of the pigment became 100 nm or less. After completion of the dispersion, the dispersion was diluted with 329.2 g of BCA to obtain a test dispersion A having a solid content of 21.8%.

[Example of formulation of Green dispersion B]
75 g of PG-58 as a pigment, 75 g of PY-150 as a pigment, 300 g of 1,3-BGDA (1,3-butylene glycol diacetate) as a solvent, and 122.4 g of acrylic dispersant A as a dispersant Each was prepared and kneaded until fluidity was obtained in the same manner as in the case of obtaining the test dispersion A. After 170 g of 1,3-BGDA was further added and mixed into the kneaded material obtained, it was dispersed with a horizontal sand mill until the average particle size of the pigment became 100 nm or less. After completion of the dispersion, the mixture was diluted with 329.2 g of 1,3-BGDA to obtain a test dispersion B having a solid content of 21.8%. Note that PG-58, PY-150, and acrylic dispersant A were all the same as those used in obtaining test dispersion A (the same applies to the following formulation examples unless otherwise noted). Is).

[Prescription example of Green dispersion C]
105 g of PG-58 as a pigment, 45 g of PY-150 as a pigment, 300 g of 1,3-BGDA as a solvent, and acrylic dispersant B as a dispersant (trade name: Floren DOPA-17HF manufactured by Kyoeisha Chemical Co., Ltd.) 285.7 g of each was prepared and kneaded until fluidity was obtained in the same manner as in obtaining the test dispersion A. Further, 170 g of 1,3-BGDA was added to the kneaded mixture and mixed, and then dispersed in a horizontal sand mill until the average particle size of the pigment became 100 nm or less. After completion of the dispersion, 1,3-BGDA was diluted with 165.9 g to obtain a test dispersion C having a solid content of 21.8%.

[Prescription example of Green dispersion D]
Prepare 75 g of PG-58 as a pigment, 75 g of PY-150 as a pigment, 300 g of BCA as a solvent, and 285.7 g of acrylic dispersant B as a dispersant. It knead | mixed until fluidity came out. After 170 g of BCA was further added to and mixed with the kneaded material obtained, the mixture was dispersed with a horizontal sand mill until the average particle size of the pigment became 100 nm or less. After the dispersion was completed, BCA was diluted with 165.9 g to obtain a test dispersion D having a solid content of 21.8%.

[Prescription example of Green dispersion E]
105 g of PG-36 (BASF AG) trade name as pigment, 45 g of PY-150 as pigment, 300 g of BCA as solvent, and acrylic dispersant A as dispersant 122.4 g of each was prepared and kneaded until fluidity was obtained in the same manner as when obtaining the test dispersion A. After 170 g of BCA was further added to and mixed with the kneaded material obtained, the mixture was dispersed with a horizontal sand mill until the average particle size of the pigment became 100 nm or less. After the dispersion was completed, BCA was diluted with 329.2 g to obtain a test dispersion E having a solid content of 21.8%.

[Prescription example of Green dispersion F]
Prepare 75 g of PG-36 as a pigment, 75 g of PY-150 as a pigment, 300 g of 1,3-BGDA as a solvent, and 122.4 g of an acrylic dispersant A as a dispersant. It kneaded until fluidity came out like the time of obtaining. Further, 170 g of 1,3-BGDA was added to the kneaded mixture and mixed, and then dispersed in a horizontal sand mill until the average particle size of the pigment became 100 nm or less. After completion of the dispersion, the mixture was diluted with 329.2 g of 1,3-BGDA to obtain a test dispersion F having a solid content of 21.8%.

[Prescription example of Green dispersion G]
105 g of PG-58 as a pigment, 45 g of PY-150 as a pigment, 300 g of 1,3-BGDA as a solvent, and an ester-based dispersant C as a dispersant (trade name: BYK-220S manufactured by Big Chemie Japan) Trademarks)) were prepared and kneaded until fluidity was obtained in the same manner as in the case of obtaining the test dispersion A. Further, 170 g of 1,3-BGDA was added to the kneaded mixture and mixed, and then dispersed in a horizontal sand mill until the average particle size of the pigment became 100 nm or less. After completion of the dispersion, 1,3-BGDA was diluted with 365.9 g to obtain a test dispersion G having a solid content of 21.8%.

[Prescription example of Green dispersion H]
Prepare 75 g of PG-58 as a pigment, 75 g of PY-150 as a pigment, 300 g of BCA as a solvent, and 85.7 g of an ester dispersant C as a dispersant. And kneaded until fluidity was obtained. After 170 g of BCA was further added to and mixed with the kneaded material obtained, the mixture was dispersed with a horizontal sand mill until the average particle size of the pigment became 100 nm or less. After the dispersion was completed, BCA was diluted with 365.9 g to obtain a test dispersion H having a solid content of 21.8%.

[Example 1]
The rotor was placed in a beaker (1000 ml) and placed on a magnetic stirrer. 133.6 g of BCA was weighed as a solvent, and 15.6 g of YX4000HK (manufactured by Japan Epoxy Resin Co., Ltd.) which is a biphenyl type epoxy resin was added as component (C) while stirring. After confirming these dissolutions, 13.40 g of component (B) SR-444 (pentaerythritol triacrylate (PETA), manufactured by Sartomer Japan, Inc.) and methoxymethylated melamine (Cymel 370, manufactured by Nippon Cytec Industries, Inc.) ) 15.6 g was added and stirred. Next, 818.7 g of the above-mentioned Green dispersion A previously dispersed and prepared as component (D) was added and further stirred. Furthermore, after adding 2.5 g of a silane coupling agent and 0.3 g of a surfactant as additives, the mixture was further stirred for 30 minutes, filtered under pressure with a 1 μm filter, and as shown in Table 2, A test ink composition was obtained.

[Example 2]
Test according to Example 2 in the same manner as in Example 1 except that 818.7 g of Green Dispersion B prepared above was added as component (D) and 133.6 g of 1,3-BGDA was used as the solvent. An ink composition was obtained.

[Example 3]
The rotor was placed in a beaker (1000 ml) and placed on a magnetic stirrer. ESF-300 which is 133.6 g of 1,3-BGDA as a solvent and is a bisphenolfluorene type epoxy (A in the general formula (4) is the general formula (3)) as a component (C) while stirring. 15.6 g (manufactured by Nippon Steel Chemical Co., Ltd.) was added. After confirming their dissolution, 13.40 g of component (B) dipentaerythritol hexaacrylate (trade name: DPHA, manufactured by Nippon Kayaku Co., Ltd.) and hexamethoxymelamine (trade name: Cymel 303, manufactured by Nippon Cytec Industries, Ltd.) 15 .6 g was added and stirred. Next, 818.7 g of the above-mentioned Green dispersion C dispersed and prepared in advance as component (D) was added and further stirred. Furthermore, after adding 2.5 g of a silane coupling agent and 0.3 g of a surfactant as additives, the mixture was further stirred for 30 minutes, filtered under pressure with a 1 μm filter, and used for the test according to Example 3. An ink composition was obtained.

[Example 4]
In the same manner as in Example 1, 133.6 g of BCA as a solvent was weighed, and 15.6 g of ESF-300 was added as component (C) while stirring. After confirming these dissolutions, 13.40 g of SR-444 as component (B) and 15.6 g of Mycoat 507 (DIC) made of hexabutoxymelamine were added and stirred. Next, 818.7 g of the above-mentioned Green dispersion D dispersed and prepared in advance as component (D) was added and further stirred. Further, 2.5 g of a silane coupling agent and 0.3 g of a surfactant were added as additives, and the mixture was further stirred for 30 minutes, filtered under pressure with a 1 μm filter, and used for the test according to Example 4. An ink composition was obtained.

[Example 5]
In the same manner as in Example 1, 133.6 g of BCA as a solvent was weighed, and 15.6 g of Epicoat 152 (E-152 manufactured by Japan Epoxy Resin Co., Ltd.) which is a novolak type epoxy resin was added as component (C) while stirring. . After confirming these dissolutions, 13.40 g of component (B) SR-444 and 15.6 g of Mycoat 507 were added and stirred. Next, 818.7 g of the above-mentioned Green dispersion C dispersed and prepared in advance as component (D) was added and further stirred. Further, 2.5 g of a silane coupling agent and 0.3 g of a surfactant were added as additives, and the mixture was further stirred for 30 minutes, filtered under pressure with a 1 μm filter, and used for the test according to Example 5. An ink composition was obtained.

[Example 6]
In the same manner as in Example 1, 132.5 g of 1,3-BGDA as a solvent was weighed, and 15.6 g of YX4000HK was added as a component (C) while stirring. After confirming their dissolution, PGMEA (propylene glycol monomethyl ether acetate) solution of the fluorene type epoxy acrylate / acid anhydride polymerization adduct of component (A) (V259ME resin component manufactured by Nippon Steel Chemical Co., Ltd.) 56.5% 2.4 g) and 12.1 g of dipentaerythritol hexaacrylate (DPHA Nippon Kayaku Co., Ltd.) and 15.6 g of a partially methylol-type melamine (trade name: Cymel 370, manufactured by Nippon Cytec Industries, Ltd.) are added. And stirred. Next, 818.7 g of the above-mentioned Green dispersion A dispersed and prepared in advance as component (D) was added and further stirred. Furthermore, after adding 2.5 g of a silane coupling agent and 0.3 g of a surfactant as additives, the mixture was further stirred for 30 minutes, filtered under pressure through a 1 μm filter, and the test according to Example 6 An ink composition was obtained.

[Comparative Example 1]
In the same manner as in Example 1, 133.6 g of BCA as a solvent was weighed, and 15.6 g of YX4000HK was added as a component (C) while stirring. After confirming the dissolution, 13.40 g of component (B) SR-444 and 15.6 g of Cymel 370 were added and stirred. Next, 818.7 g of the above-mentioned Green dispersion liquid E previously dispersed and prepared as component (D) was added and further stirred. Furthermore, after adding 2.5 g of a silane coupling agent and 0.3 g of a surfactant as additives, the mixture was further stirred for 30 minutes, filtered under pressure with a 1 μm filter, and used for testing according to Comparative Example 1. An ink composition was obtained.

[Comparative Example 2]
In the same manner as in Example 1, 133.6 g of 1,3-BGDA as a solvent was weighed, and 15.6 g of YX4000HK was added as a component (C) while stirring. After confirming these dissolutions, 13.40 g of component (B) SR-444 and 15.6 g of Cymel 303 were added and stirred. Next, 818.7 g of the above-mentioned Green dispersion F dispersed and prepared in advance as component (D) was added and further stirred. Furthermore, after adding 2.5 g of a silane coupling agent and 0.3 g of a surfactant as additives, the mixture was further stirred for 30 minutes, filtered under pressure with a 1 μm filter, and used for testing according to Comparative Example 2. An ink composition was obtained.

[Comparative Example 3]
In the same manner as in Example 1, 133.6 g of BCA as a solvent was weighed, and 15.6 g of Epicoat 152 was added as a component (C) while stirring. After confirming the dissolution, 13.40 g of component (B) SR-444 and 15.6 g of Cymel 370 were added and stirred. Next, 818.7 g of the above-mentioned Green dispersion G dispersed and prepared in advance as component (D) was added and further stirred. Furthermore, after adding 2.5 g of a silane coupling agent and 0.3 g of a surfactant as additives, the mixture was further stirred for 30 minutes, filtered under pressure with a 1 μm filter, and used for testing according to Comparative Example 3. An ink composition was obtained.

[Comparative Example 4]
In the same manner as in Example 1, 133.6 g of 1,3-BGDA as a solvent was weighed, and 15.6 g of ESF-300 was added as component (C) while stirring. After confirming these dissolutions, 13.40 g of DPHA as component (B) and 15.6 g of Mycoat 507 were added and stirred. Next, 818.7 g of the above-mentioned Green dispersion H previously dispersed and prepared as component (D) was added and further stirred. Furthermore, after adding 2.5 g of a silane coupling agent and 0.3 g of a surfactant as additives, the mixture was further stirred for 30 minutes, filtered under pressure with a 1 μm filter, and used for testing according to Comparative Example 4. An ink composition was obtained.

[Comparative Example 5]
In the same manner as in Example 1, 117.3 g of BCA as a solvent was weighed, and 3.9 g of YX4000HK was added as a component (C) while stirring. After confirming these dissolutions, 36.6 g of V259ME as component (A) and 4.8 g of DPHA as component (B) were added and stirred. Next, 818.7 g of the above-mentioned Green dispersion H previously dispersed and prepared as component (D) was added and further stirred. Further, 2.5 g of a silane coupling agent and 0.3 g of a surfactant were added as additives, and the mixture was further stirred for 30 minutes to obtain a test ink composition according to Comparative Example 5.

  The ink compositions of Examples and Comparative Examples obtained above were evaluated by the following procedure. Table 2 shows the results. In addition, the case where all of these test results were acceptable was determined as “good” in the comprehensive evaluation.

<Viscosity stability test>
The prepared ink composition was previously measured for its viscosity at 50 rpm and 23 ° C. with an E-type viscometer. Thereafter, 100 g of the ink composition was transferred to a container that could be sealed, and after accelerated aging at 40 ° C. for one week, the viscosity was measured under the same conditions, and a viscosity increase of 1 mPa · sec or less from the initial viscosity was accepted.

  The following measurements were performed on an ink-coated glass substrate in which the ink composition was applied to the glass substrate at an arbitrary number of rotations, dried and cured, and the film thickness was changed. In contrast and Y-value measurements, the results of multiple trials were plotted on a graph to obtain an approximate curve, and then converted to a value at chromaticity y = 0.60 (hereinafter referred to as “data reduction”). Compared.

<Contrast>
The ink-coated glass substrate coated and cured with the ink composition was cut into 5 cm square, and the contrast was measured with a rotary contrast measuring device. The result was converted to a value at y = 0.60 according to the above data arrangement method (after plotting on a graph to obtain an approximate curve, it was converted to a value at chromaticity y = 0.60, and this was repeated several times. (Repeat), a difference of less than 8% was determined to be acceptable.

<Y value measurement>
The ink-coated glass substrate coated and cured with the ink composition was cut into 5 cm square, and the hue was measured with a colorimeter (manufactured by Otsuka Electronics Co., Ltd.). The chromaticity was measured by preparing glass substrates coated in the same process immediately after the ink composition was created and one month later, and comparing the values on the glass substrate after the lapse of one month and immediately after the ink composition was created. At this time, the change rate of the Y value obtained by conversion from the hue and chromaticity is converted into a value at y = 0.60 according to the above data arrangement method, and these are compared, and the difference is less than 3%. Things were accepted.

Claims (7)

An ink composition used for producing a color filter by an inkjet method,
In the solvent (H), the unsaturated compound (A) represented by the following general formula (1), the polyfunctional compound (B) having 4 or more functional groups, the sum of the components (A) and (B) A polyfunctional epoxy compound (C) of 0 to 150% by weight blended, and a pigment dispersion (D) in which a pigment is dispersed in a dispersant, the weight of (A) component and (B) component Ratio (A) / (B) of 0/100 to 90/10, and ratio of pigment amount to resin amount in solid component excluding all solvent components in ink composition (pigment / resin) 20 to 60% by weight, the dispersant in component (D) is an acrylic dispersant, and the ratio of the dispersant amount to the pigment amount (dispersant / pigment) is 35 to 120% by weight. , And the pigment is C.I. I. An ink composition for a color filter, which is CI Pigment Green 58.

[Wherein R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ represents a hydrogen atom or a methyl group. A is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9 , 9-fluorenyl group or a direct bond, X represents a tetravalent carboxylic acid residue, Y ₁ and Y ₂ independently represent a hydrogen atom or —OC—Z— (COOH) _m (Z is a carboxylic acid residue) M represents a number of 1 to 3), and n represents a number of 1 to 200. ]   C. I. The ink composition for a color filter according to claim 1, wherein a complementary color pigment for Pigment Green 58 is contained in the pigment in an amount of 70 wt% or less.   The ink composition for a color filter according to claim 1 or 2, further comprising a viscosity modifier (E) and a surfactant and / or a coupling agent (F).   The ink composition for a color filter according to claim 3, wherein the amount of the solvent (H) used relative to 100 parts by weight of the total of the components (A) to (F) is 50 to 1000 parts by weight.   The ink composition for a color filter according to any one of claims 1 to 4, wherein the solvent (H) comprises two or more mixed solvents, and the boiling point of any of the solvents is in the range of 120 to 350 ° C.   A colored cured film for a color filter obtained by applying the ink composition according to any one of claims 1 to 5 by an ink-jet method, drying and curing the composition.   7. A color filter comprising the colored cured film for a color filter according to claim 6.