TW202244072A - Polymeric dispersant, pigment dispersion composition, and photosensitive colored composition - Google Patents

Abstract

Provided are a polymeric dispersant having satisfactory pigment-dispersing properties and storage stability and a pigment dispersion composition obtained using the polymeric dispersant. A photosensitive colored composition obtained using the pigment dispersion composition has satisfactory developability and gives cured objects having excellent solvent resistance. Also provided are a color filter including the cured object of the photosensitive colored composition and an image display element including the color filter. This polymeric dispersant has a quaternary ammonium cation group (g-1) having one or more groups selected from the group consisting of an ethylenically unsaturated group and groups each having a carbon-carbon triple bond.

Description

Polymer dispersant, pigment dispersion composition and photosensitive coloring composition

The present invention relates to a polymer dispersant, a pigment dispersion composition, a photosensitive coloring composition using the pigment dispersion composition, a color filter and an image display element using the photosensitive coloring composition.

At present, based on the viewpoint of saving resources and energy, photosensitive resin compositions curable by active energy rays such as ultraviolet rays and electron beams have been widely used in various coatings, printing, paints, adhesives and other fields. Photosensitive resin compositions are used in the field of electronic materials such as printed wiring boards, and are used in solder resists, resists for color filters, etc. A color filter is generally composed of a transparent substrate such as a glass substrate, red, green and blue pixels formed on the transparent substrate, a black matrix formed on the pixel boundary, and a protective film formed on the pixel and the black matrix. A color filter having such a structure is usually manufactured by sequentially forming a black matrix or a colored pattern of pixels and a pattern of a protective film on a transparent substrate. Various methods have been proposed as methods for forming various patterns. Among them, a photolithography method is proposed that uses a photosensitive resin composition dispersed with pigments/dye as a resist, and repeats coating, exposure, development and baking. The color filter produced by this method can obtain a colored pattern with excellent durability and few defects such as pinholes. Therefore, become the current mainstream.

Generally, the photosensitive resin composition used in the photolithography method contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a pigment/dye (also called a colorant) and a solvent. In the method of making a color filter using the photosensitive resin composition, since the black matrix, red, green, and blue patterns are repeatedly formed, the cured product of the photosensitive resin composition is required to be able to withstand high baking Temperature resistance and resistance to various solvents exposed in the manufacturing process.

In recent years, displays such as liquid crystal and organic EL have been required to have higher image quality and finer resolution, and color filters have also been required to design designs that can achieve higher brightness and expand the range of color reproduction. In order to achieve high brightness and expand the range of color reproduction, although there are examples of using only dyes as colorants, compared with pigments, dyes have poor heat resistance and solvent resistance, and due to the limited use ratio and types, in most cases Next, the color material contains pigments. When using pigments to form color filters, uniform miniaturization of pigments is essential. By miniaturizing the pigment, the light passing through the color filter can be reduced from being scattered by the pigment particles, and the contribution to the transmittance is high, thereby achieving high brightness. However, finer pigment particles tend to aggregate, and there is a problem that the dispersibility of the pigment and the storage stability of the pigment dispersion composition tend to decrease. As a method of improving the dispersibility of the micronized pigment in the pigment dispersion composition, it is effective to use the pigment and the dispersant in combination.

In addition, in order to expand the range of color reproduction, efforts are also made to formulate high-concentration colorants. As the concentration of the colorant increases, the concentration of the dispersant and the concentration of other components are relatively reduced, so it is required that even with a smaller amount of the dispersant, the pigment dispersibility and the storage stability and heat resistance of the pigment dispersion composition can still be exhibited. Various resist properties such as resistance, solvent resistance, and pattern adhesion.

A general dispersant has both a site for adsorption on a pigment and a site with high affinity for solvents and other resin compositions. The part that is adsorbed on the pigment is changed according to the state of the surface of the pigment and the optimum structure. For example, a dispersant having a basic adsorption site is used for a pigment having an acidic surface, and in many cases, an amine group is used for the basic adsorption site as in Patent Document 1. In addition, in recent years, as in Patent Documents 1 to 3, dispersants that introduce a photosensitive ethylenically unsaturated group into a dispersant to impart a hardening function have also been developed. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese National Publication No. 2008-542523 [Patent Document 2] International Publication No. 2006/075754 [Patent Document 3] International Publication No. 2013/175978

[Problem to be solved by the invention]

However, when using the dispersants disclosed in Patent Documents 1 to 3, although a hardened product with good solvent resistance can be obtained, the pigment dispersibility is insufficient, and it may be difficult to use alone, or the storage stability of the pigment dispersion composition also needs improve. In addition, since the dispersibility of the finely divided pigment is insufficient, the pigment particles are aggregated, and when used as a material of a color filter, there are problems such as a decrease in brightness, and improvement is required.

The present invention was made to solve the above-mentioned problems, and an object of the present invention is to provide a polymer dispersant having excellent pigment dispersibility and storage stability, and a pigment dispersion composition using the polymer dispersant. Furthermore, it is an object to provide a photosensitive coloring composition capable of obtaining a cured product having good developability and excellent solvent resistance, a color filter having the cured product, and an image display device having the same. [Means to solve the problem]

The present invention includes the following aspects. [1] A polymer dispersant characterized by having a quaternary ammonium cation group (g-1) containing at least one selected from the group consisting of ethylenically unsaturated groups and groups having carbon-carbon triple bonds. [2] The polymer dispersant as in [1], wherein the quaternary ammonium cation group (g-1) contained in the polymer dispersant has a group selected from (meth)acryloxy, vinyl and propynyl More than one of the group formed. [3] The polymer dispersant as in [1] or [2], wherein the quaternary ammonium cation group (g-1) contained in the aforementioned polymer dispersant has a group selected from the following formula (1), the following formula ( 2) and one or more of the groups represented by the following formula (3): -(CH ₂ ) _m -OX-(CO)-CR ¹ =CH ₂ (1) -(CH ₂ ) _m - X-CR ¹ =CH ₂ (2) -(CH ₂ ) _m -XC≡CH (3) (In formulas (1)~(3), m is an integer from 1 to 20, and X is a single bond or carbon number 1 A divalent linking group of ~20, R ¹ represents a hydrogen atom or a methyl group). [4] The polymer dispersant according to any one of claims 1 to 3, wherein the quaternary ammonium cation group (g-1) contained in the aforementioned polymer dispersant has a formula (4) selected from the following One or more of the groups represented by the formula (5), the following formula (6) and the following formula (7): -(CH ₂ ) _m -O-(CO)-(NH)-(CH ₂ ) _n -O-(CO)-CR ¹ =CH ₂ (4) -(CH ₂ ) _m -O-(CO)-CR ¹ =CH ₂ (5) -(CH ₂ ) _m -CR ¹ =CH ₂ (6) -(CH ₂ ) _m -C≡CH (7) (In the formulas (4) to (7), m and n are independently an integer of 1 to 20, and R ¹ represents a hydrogen atom or a methyl group). [5] The polymer dispersant according to any one of [1] to [3], wherein the polymer dispersant is a reactant of a polymer compound (a-0) and a functional group-containing halogen compound (b) ( a-1) A reactant with compound (c), the aforementioned polymer compound (a-0) has a tertiary amino group (g-0), and the aforementioned compound (c) has a group reactive with the aforementioned functional group and ethylene The aforementioned halogenated compound (b) containing a functional group is a halogenated alkanol with 1 to 20 carbons or a halogenated fatty acid with 1 to 20 carbons, and the aforementioned compound (c) is selected from the group containing isocyanate (methyl ) acrylates, (meth)acrylates containing epoxy groups, and (meth)acrylates containing halogenated alkyl groups. [6] The polymer dispersant according to any one of [1] to [3], wherein the polymer dispersant is a reactant of the polymer compound (a-0) and the unsaturated group-containing halogen compound (d) , the aforementioned polymer compound (a-0) has a tertiary amino group (g-0), and the unsaturated group contained in the aforementioned unsaturated group-containing halogen compound (d) is selected from ethylenically unsaturated groups and carbon-carbon More than one of the group formed by the base of the triple bond. [7] The polymer dispersant as in [6], wherein the halogen compound (d) containing an unsaturated group is selected from (meth)acrylic acid esters and alkyl halides containing 1 to 20 carbons and 1 to 20 carbons. More than one of the group of vinyl compounds with alkyl halides of ~20. [8] The polymer dispersant according to any one of [5] to [7], wherein the aforementioned polymer compound (a-0) is selected from the group consisting of Block polymers of monomers and other monomers with ethylenically unsaturated groups and monomers with tertiary amino groups (g-0) and ethylenically unsaturated groups and quaternary ammonium with no unsaturated groups One or more of the block polymers of cationic and ethylenically unsaturated monomers and other ethylenically unsaturated monomers. [9] A pigment dispersion composition containing a polymer dispersant (A), a pigment (B), and a solvent (C-1), characterized in that the aforementioned polymer dispersant (A) is such as [1] to [ 8] The polymer dispersant according to any one of the above. [10] The pigment dispersion composition according to [9], wherein the aforementioned pigment (B) contains a pigment having a halogenated phthalocyanine skeleton. [11] The pigment dispersion composition according to any one of [9] to [10], further comprising a binder resin (D-1). [12] The pigment dispersion composition as in [11], wherein 10 to 80 parts by mass of the aforementioned polymer dispersant (A) is contained with respect to 100 parts by mass of the aforementioned pigment (B), and 10 to 80 parts by mass of the aforementioned binder agent resin (D-1). [13] A photosensitive coloring composition characterized by comprising: the pigment dispersion composition of [9] or [10], a binder resin (D-2), a reactive diluent (E), and a photopolymerizer Starter (F). [14] The photosensitive coloring composition according to [13], wherein 10 to 80 parts by mass of the aforementioned polymer dispersant (A) is contained with respect to 100 parts by mass of the aforementioned pigment (B), and 50 to 280 parts by mass of the aforementioned The binder resin (D-2) contains 40-200 parts by mass of the aforementioned reactive diluent (E), and contains 0.1-10 parts by mass of the aforementioned photopolymerization initiator (F). [15] A photosensitive coloring composition characterized by comprising: the pigment dispersion composition of [11] or [12], a binder resin (D-2), a reactive diluent (E), and a photopolymerizer Starter (F). [16] The photosensitive coloring composition according to [15], wherein 10 to 80 parts by mass of the aforementioned polymer dispersant (A) is contained with respect to 100 parts by mass of the aforementioned pigment (B), and a total of 50 to 280 parts by mass of The aforementioned binder resins (D-1) and (D-2) contain 40-200 parts by mass of the aforementioned reactive diluent (E), and 0.1-10 parts by mass of the aforementioned photopolymerization initiator (F). [17] A cured resin film obtained by curing the photosensitive coloring composition according to any one of [13] to [16]. [18] A color filter having a cured product of the photosensitive coloring composition according to any one of [13] to [16]. [19] An image display device comprising the color filter of [18]. [Invention effect]

According to the present invention, a polymer dispersant having excellent pigment dispersibility and storage stability, and a pigment dispersion composition using the polymer dispersant can be provided. Also, by using the pigment dispersion composition in a photosensitive coloring composition, a cured product having good developability and excellent solvent resistance can be obtained. Furthermore, the color filter which has the hardened|cured material of this photosensitive coloring composition, and the image display element equipped with it can be provided.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments. Also, in the present specification, "(meth)acryloxy" means one or more selected from methacryloxy and acryloxy. The same applies to "(meth)acrylic acid".

＜Polymer Dispersant (A)＞ The polymer dispersant (A) has a quaternary ammonium cation group (g-1) containing one or more selected from an ethylenically unsaturated group and a group having a carbon-carbon triple bond. In this specification, the so-called quaternary ammonium cation group refers to a group with 4 carbon atoms bonded to a nitrogen atom, and does not include an amide bond or a urea bond. Since the following pigment dispersion composition contains a polymer dispersant (A), the pigment dispersibility is good, and when the photosensitive coloring composition is photohardened, the polymer dispersant (A) has an ethylenically unsaturated group and The bases of the carbon-carbon triple bonds are also polymerized and incorporated into the cured product. Therefore, a cured film having various properties such as heat resistance, solvent resistance, and pattern adhesion can be obtained. In addition, since the polymer dispersant (A) has a quaternary ammonium cation group, it has high hydrophilicity and improves developability as a photosensitive coloring composition. In addition, the polymer dispersant (A) has an ethylenically unsaturated group and a group having a carbon-carbon triple bond to polymerize and incorporate into the hardened product, so that the effect of preventing dispersant and colorant bleeding can also be expected.

The polymer dispersant (A) contains a polymer main chain and a quaternary ammonium cationic group (g-1). The quaternary ammonium cation group (g-1) has at least one selected from ethylenically unsaturated groups and groups having a carbon-carbon triple bond. That is, the quaternary ammonium cation composed of the aforementioned quaternary ammonium cation group (g-1) has 4 substituents bonded to nitrogen, including the substituent containing the polymer main chain and 3 substituents other than base. Among the three substituents, at least one of a substituent having an ethylenically unsaturated group and a substituent including a carbon-carbon triple bond is included. From the viewpoint of ease of synthesis, it is preferably a substituent that does not contain a polymer main chain and only one of the three substituents has an ethylenically unsaturated group or a carbon-carbon triple bond.

The aforementioned ethylenically unsaturated group is not particularly limited, but it is preferably an ethylenically unsaturated group possessed by (meth)acryloxy and vinyl groups from the viewpoint of good curability when used as a photosensitive composition. That is, the quaternary ammonium cation group (g-1) contained in the polymer dispersant (A) preferably has at least one of a (meth)acryloxy group and a vinyl group.

The aforementioned substituent having a carbon-carbon triple bond is not particularly limited, and is preferably a propynyl group from the viewpoint of good hardenability when made into a photosensitive composition. That is, the quaternary ammonium cation group (g-1) contained in the polymer dispersant (A) preferably has a propynyl group.

Based on the viewpoint of having affinity with the pigment (B) described later, the aforementioned ethylenically unsaturated group and the aforementioned group having a carbon-carbon triple bond preferably have a compound selected from the group consisting of the following formula (1), the following formula (2) and the following An ethylenically unsaturated group or a group having a carbon-carbon triple bond as one of the groups represented by the above formula (3). That is to say, the quaternary ammonium cation group (g-1) contained in the aforementioned polymer dispersant (A) preferably has the following formula (1), the following formula (2) and the following formula (3) Indicates more than one of the groups of bases.

-(CH ₂ ) _m -OX-(CO)-CR ¹ =CH ₂ (1) -(CH ₂ ) _m -X-CR ¹ =CH ₂ (2) -(CH ₂ ) _m -XC≡CH (3 ) (In formulas (1) to (3), m is an integer of 1 to 20, X is a single bond or a divalent linking group with ¹ to 20 carbons, and R represents a hydrogen atom or a methyl group). In the formulas (1)~(3), m is 1~20, preferably 1~10, more preferably 1~6. The divalent linking group represented by X has 1-20 carbon atoms, preferably 1-10 carbon atoms, more preferably 1-6 carbon atoms. The divalent linking group represented by X may include an ether bond, an ester bond, an amide bond, and the like. Specific examples include alkylene oxides such as methylene and ethylene, (poly)alkylene oxides such as methylene oxide, ethylene oxide, and bisethylene oxide.

Based on the viewpoint of the ease of synthesis of the polymer dispersant (A) and the ease of obtaining raw materials or not greatly impairing the affinity with the pigment (B), the above-mentioned ethylenically unsaturated group and the above-mentioned group having a carbon-carbon triple bond More preferably, it is ethylenic unsaturation possessed by one selected from the group consisting of groups represented by the following formula (4), the following formula (5), the following formula (6) and the following formula (7). group or a group having a carbon-carbon triple bond. That is to say, the quaternary ammonium cation group (g-1) contained in the aforementioned polymer dispersant (A) preferably has the following formula (4), the following formula (5), the following formula (6) and one or more of the groups represented by the following formula (7).

-(CH ₂ ) _m -O-(CO)-(NH)-(CH ₂ ) _n -O-(CO)-CR ¹ =CH ₂ (4) -(CH ₂ ) _m -O-(CO)- CR ¹ =CH ₂ (5) -(CH ₂ ) _m -CR ¹ =CH ₂ (6) -(CH ₂ ) _m -C≡CH (7) (In formulas (4)~(7), m and n are independently an integer of ¹ to 20, and R represents a hydrogen atom or a methyl group). In formulas (4)~(7), the definitions and preferred ranges of m and R1 are the same as those shown in formulas ( ¹ )~(3). n is 1-19, preferably 1-9, more preferably 1-5.

Among the four nitrogen-bonded substituents of the quaternary ammonium cation composed of the aforementioned quaternary ammonium cation group (g-1), except for the substituent comprising the polymer main chain and the substituent having an ethylenically unsaturated group The remaining substituents other than the group are not particularly limited, but are preferably an alkyl group having 1 to 10 carbons, an alkoxyalkyl group having 1 to 10 carbons, more preferably an alkyl group having 1 to 4 carbons. Specific examples include methyl, ethyl and the like.

The quaternary ammonium cationic group (g-1) of the polymer dispersant (A) of one embodiment of the present invention (hereinafter referred to as the polymer dispersant (A) of this embodiment) has an ethylenically unsaturated group When, for example, the quaternary ammonium cation group (g-1) can be introduced into the polymer dispersant (A) by the following method. That is, the structure of the quaternary ammonium cation group (g-1) of this embodiment is obtained through the following two-stage reaction. The first stage reaction: to the tertiary amine group (g-0) of the polymer compound (a-0) (hereinafter also referred to as "polymer compound (a-0)") having a tertiary amine group (g-0) ) Adding a functional group-containing halogen compound (b) makes the tertiary amino group (g-0) undergo a quaternization reaction. The second stage reaction: to the functional group derived from the halogen compound (b) containing the functional group, add the compound (c) having a reactive group with the functional group and an ethylenically unsaturated group (hereinafter also referred to as "compound (c)") response.

Also, as another introduction method of the quaternary ammonium cation group (g-1), it is possible to use the tertiary amine group (g- 0) A method of introducing an ethylenically unsaturated group and a group having a carbon-carbon triple bond by adding an unsaturated group-containing halogen compound (d). In this case, the quaternization of the tertiary amino group (g-0) and the introduction of ethylenically unsaturated groups and groups with carbon-carbon triple bonds can be carried out by a one-stage reaction. Compared with the above two-stage reaction, it is possible Tendency to shorten reaction time. In addition, the steric barrier around the quaternary ammonium cation of the quaternary ammonium cation group (g-1) becomes smaller, and the pigment dispersibility and storage stability of the pigment dispersion composition and the photosensitive coloring composition can be improved.

As an example of the polymer compound (a-0) of this embodiment, the polymer compound which homopolymerized or copolymerized the monomer which has a tertiary amino group and an ethylenically unsaturated group is mentioned. As such a polymer compound, for example, poly tertiary amines such as polymers of vinyl tertiary amines or polymers of allyl tertiary amines; or vinyl tertiary amines or allyl tertiary amines and other Polytertiary amines obtained by copolymerization of monomers with ethylenically unsaturated groups; polymers obtained by ring-opening polymerization of 1-substituted aziridines or 2-oxazolines; ethylenediamine or hexamethylene Polyalkylene amines formed by polycondensation of polyfunctional amine compounds such as diamines and alkanes such as halides. The aforementioned polymer compound (a-0) may contain, in addition to the tertiary amine group (g-0), a primary amine group, a secondary amine group, and an unsaturated group within a range that does not impair the effect. 4th grade ammonium cationic group, amide, imide, urea, urethane, etc. A functional group-containing halogen compound (b) and a compound (c) having a group reactive with the functional group and an ethylenically unsaturated group can also be added to these. As described above, since the amine structure contributes greatly to the dispersibility of the pigment, it is preferable that amide, imide, urea, and urethane bonds are not substantially contained. Examples of the monomer having other ethylenically unsaturated groups include (meth)acrylate esters having an alkyl group, aryl group, aralkyl group, cycloalkyl group, (poly)oxyalkylene group structure, and the like. Among them, the polymer compound (a-0) preferably uses a monomer having a tertiary amino group (g-0) and an ethylenically unsaturated group, and a quaternary ammonium cationic group containing an unsaturated group and Monomers with ethylenically unsaturated groups and block polymers with other monomers with ethylenically unsaturated groups.

The amine content of the above-mentioned polymer compound (a-0) (the total amount of primary amine, secondary amine, and tertiary amine when it contains primary or secondary amine groups) can be determined by measuring the amine value (according to JIS K7237 and other standard measurement values), and the amount can be quantitatively determined. The amine content of the polymer compound (a-0) in this embodiment is not particularly limited, but is preferably 10 mgKOH/g-300 mgKOH/g, more preferably 20 mgKOH/g-200 mgKOH/g. When the amine value is 10mgKOH/g or more, the functional group-containing halogen compound (b) can be added in a mild environment to provide a polymer dispersant with improved heat resistance, solvent resistance, and pattern adhesion for colored patterns. (A), and improve the affinity with the pigment (B) described later to obtain sufficient pigment dispersibility and storage stability of the pigment dispersion composition. On the other hand, when the amine value is less than 200 mgKOH/g, yellowing of colored patterns caused by amines can be suppressed.

Moreover, the molecular weight (weight average molecular weight in terms of polystyrene) of the polymer compound (a-0) of this embodiment is not specifically limited, Preferably it is 1000-40000, More preferably, it is 3000-30000. In addition, the molecular weight distribution (the value obtained by dividing the weight average molecular weight in terms of polystyrene by the number average molecular weight) of the polymer compound (a-0) is preferably 1.0 to 3.0, more preferably within the range of 1.0 to 2.0. When the molecular weight and molecular weight distribution of the polymer compound (a-0) are within the above range, the viscosity of the pigment dispersion composition can be controlled within an appropriate range, sufficient pigment dispersibility and storage stability of the pigment dispersion composition can be obtained, and at the same time Can ensure excellent heat resistance, solvent resistance, pattern adhesion, developability, etc.

The polymer compound (a-0) may use a commercial item, or may prepare by itself. When commercially available products are used, examples of suitable polymer compounds include DISPERBYK series manufactured by BYK CHEMIE, SOLSPHERE series manufactured by LUBRIZOL, EFKA-PX series manufactured by BASF, and the like. These high molecular compounds may be used individually or in combination of 2 or more types as needed.

When preparing the polymer compound (a-0) by yourself, for example, using a known block polymer production method, use a monomer with a tertiary amino group (g-0) and an ethylenically unsaturated group, and optionally contain A method of block polymerization of quaternary ammonium cationic monomers with unsaturated groups and ethylenically unsaturated monomers with other monomers with ethylenically unsaturated groups. Specific examples of monomers having a tertiary amino group (g-0) and an ethylenically unsaturated group include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, Dimethylaminobutyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, diethylaminobutyl (meth)acrylate, (meth)acrylate base) pentamethylpiperidinyl acrylate, tetramethylpiperidinyl (meth)acrylate, N,N-dimethyl(meth)acrylamide, N,N-diethyl(methyl) Acrylamide, N-isopropyl (meth)acrylamide, dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, diacetone (methyl) (meth)acrylamides such as acrylamide or acrylmorpholine. These monomers may be used alone or in combination of two or more. As a specific example of the monomer containing the quaternary ammonium cation group which does not have an unsaturated group, and the ethylenically unsaturated group, the organic halogen compound salt of the monomer which has a tertiary amino group is mentioned. The organic halogen compound salt is not particularly limited, but from the viewpoint of ease of acquisition, specific examples include methyl chloride, ethyl chloride, propyl chloride, butyl chloride, benzyl chloride, chlorinated ethanol, methyl bromide , ethyl bromide, propyl bromide, butyl bromide, benzyl bromide, ethanol bromide, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, benzyl iodide, ethanol iodide, etc. Also, the introduction of the quaternary ammonium cationic group may not use the above-mentioned monomers, but after block polymerization of monomers with tertiary amine groups and other monomers with ethylenically unsaturated groups, at any temperature, catalyst An organic halogen compound salt is added to the tertiary amine in the presence, and a part or all of the tertiary amine is substituted with a quaternary ammonium cation group and introduced. On the other hand, as other monomers having ethylenically unsaturated groups that can improve affinity with other pigment dispersion compositions, for example, monomers having alkyl, aryl, aralkyl, cycloalkyl, alkanedi (Meth)acrylates such as alcohol groups are not particularly limited as long as the affinity with other pigment dispersion compositions is not impaired. As specific examples, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, ( Isobutyl methacrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylate Base) lauryl acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate (Meth)acrylates such as phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate or ethoxypolyethylene glycol (meth)acrylate , Styrene such as styrene or α-methylstyrene, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether or isobutyl vinyl ether, etc. Vinyl ethers, fatty acid vinyl esters such as vinyl acetate or vinyl propionate, etc. These monomers may be used alone or in combination of two or more.

The functional group-containing halogen compound (b) is not particularly limited as long as it is a monohalogen compound having a functional group. The number of functional groups that the functional group-containing halogen compound (b) has is not particularly limited. From the viewpoint of reaction control when the polymer compound (a-0) is synthesized by adding a functional group-containing halogen compound (b) or further compound (c) to synthesize a polymer dispersant (A), the functional group-containing halogen compound (b) The number of functional groups it has is preferably one. The type of functional group is not particularly limited, but is preferably a hydroxyl group or a carboxyl group from the viewpoint of the ease of synthesis of the polymer dispersant (A). Examples include halogenated alkanols with 1 to 20 carbon atoms or halogenated fatty acids with 1 to 20 carbon atoms. More specifically, 2-bromoethanol, 4-bromo-1-butanol, 8-bromooctyl alcohol, 2-chloroethanol, bromoacetic acid, bromobutyric acid, bromodecanoic acid, chloroacetic acid and the like are exemplified. Among them, bromoacetic acid and halogenated alkanols are preferred, and halogenated alkanols are more preferred, from the viewpoint of the ease of acquisition and the ease of synthesis of the polymer dispersant (A). Examples of the halogenated alkanol include brominated alkanols such as ethylene bromohydrin and 4-bromo-1-butanol.

As will be described later, the addition rate of the compound (c), that is, the total amount of the added compound (c) relative to the total amount of functional groups derived from the functional group-containing halogen compound (b) (the functional group before the addition of the compound (c) Under the premise that the proportion (mole %) of the total amount of the group) is substantially 100 mol%, the addition rate of the halogen compound (b) containing the functional group, that is, the ratio of the ethylenically unsaturated group to the polymer compound (a- 0) The introduction ratio (mole %) of the total amount of amine groups possessed is preferably at least 1 mol%, more preferably at least 5 mol%, and still more preferably at least 10 mol%. If the addition ratio of the functional group-containing halogen compound (b) is 5 mol% or more, a sufficient amount of ethylenically unsaturated groups can be introduced as the polymer dispersant (A), and resin curing with excellent solvent resistance can be obtained. membrane. As the addition ratio of the functional group-containing halogen compound (b) increases, the amount of ethylenically unsaturated groups introduced into the polymer dispersant (A) can be increased, and the solvent resistance of the cured resin film tends to be improved. Also, as the addition rate of the halogen compound (b) containing the functional group increases, the polarity as the polymer dispersant (A) increases due to the increase in the proportion of the quaternary ammonium cationic group (g-1), so it has the potential to be used as a photosensitive The tendency to improve the developability of permanent coloring compositions. On the other hand, the addition ratio of the functional group-containing halogen compound (b) may also be 100 mole %, but from the viewpoint of improving the pigment dispersibility or storage stability of the pigment dispersion composition or photosensitive coloring composition, the addition rate of the halogen compound (b) containing The addition rate of the halogen compound (b) of the functional group is preferably at most 50 mol%, more preferably at most 30 mol%.

Also, as will be described later, the addition rate of the compound (c), that is, the total amount of the added compound (c) relative to the total amount of functional groups derived from the functional group-containing halogen compound (b) (before the addition of the compound (c) On the premise that the ratio (mole %) of the total amount of functional groups) is substantially 100 mol%, the polymer compound (a-0) only contains tertiary amino groups as amino groups (meaning substantially no 1st and 2nd grade amine groups), the addition rate of the halogen compound (b) containing functional groups, that is, the total amount of 4th grade ammonium cationic groups (g-1) relative to the polymer compound (a-0) The ratio (mole %) of the total amount of amine groups is preferably at least 1 mol%, more preferably at least 5 mol%, and more preferably at least 10 mol%. If the addition ratio of the functional group-containing halogen compound (b) is 5 mol% or more, a sufficient amount of quaternary ammonium cation groups (g- 1) A cured resin film with excellent solvent resistance can be obtained. As the addition ratio of the functional group-containing halogen compound (b) increases, the amount of ethylenically unsaturated groups introduced into the polymer dispersant (A) can be increased, and the solvent resistance of the cured resin film tends to be improved. Also, as the addition rate of the halogen compound (b) containing the functional group increases, the polarity as the polymer dispersant (A) increases due to the increase in the proportion of the quaternary ammonium cationic group (g-1), so it has the potential to be used as a photosensitive The tendency to improve the developability of permanent coloring compositions. On the other hand, the addition ratio of the functional group-containing halogen compound (b) may also be 100 mole %, but from the viewpoint of improving the pigment dispersibility or storage stability of the pigment dispersion composition or photosensitive coloring composition, the addition rate of the halogen compound (b) containing The addition rate of the halogen compound (b) of the functional group is preferably at most 50 mol%, more preferably at most 30 mol%.

The polymer dispersant (A) of this embodiment can freely adjust the introduction amount of the ethylenically unsaturated group, or the tertiary amino group (g-0) and the quaternary amino group (g-0) and the quaternary The proportion of ammonium cationic groups (g-1). Therefore, based on the above findings, the solvent resistance of the cured resin film, the developability of the photosensitive coloring composition, and the balance of various performances of the pigment dispersion composition and the photosensitive coloring composition in terms of pigment dispersibility and developability can be considered. To determine the ratio of the tertiary amine group (g-0) to the quaternary ammonium cationic group (g-1) contained in the polymer dispersant (A). For example, when using a pigment with a halogenated phthalocyanine skeleton as the pigment (B) described later, if the content of the tertiary amino group (g-0) of the polymer dispersant (A) increases, the affinity for the pigment will increase and the pigment dispersion will be improved. In terms of properties, if the content of the quaternary ammonium cationic group (g-1) in the polymer dispersant (A) increases, the affinity for the pigment will decrease and the pigment dispersibility will also decrease. Therefore, when using a pigment with a halogenated phthalocyanine skeleton, it is preferable to contain about 50-92 mole % of tertiary amino groups (g-0) relative to the total amount of amino groups in the polymer dispersant (A), and more preferably Preferably, it contains about 70~90 mole% of tertiary amino groups (g-0).

The compound (c) is not particularly limited as long as it is a compound having a functional group reactive with the functional group of the functional group-containing halogen compound (b) and an ethylenically unsaturated bond. Examples include ethylenically unsaturated monomers having high electron-withdrawing substituents such as isocyanate groups, epoxy groups, oxetanyl groups, acyl halide groups, and carboxylic anhydrides, or halogens, acids, sulfonate esters, etc. The ethylenically unsaturated monomer that leaves the group. Among them, from the viewpoint of ease of acquisition and reactivity, ethylenically unsaturated monomers having isocyanate groups, epoxy groups, and acyl chloride groups are preferred, and more preferred are (meth)acrylates containing isocyanate groups, Epoxy (meth)acrylates, halogenated alkyl-containing (meth)acrylates, isocyanate-containing vinyl compounds, epoxy-containing vinyl compounds and halogenated alkyl-containing vinyl compounds. Specifically, 2-isocyanatoethyl (meth)acrylate, 2-(2-(meth)acryloxyethyloxy)ethyl isocyanate, glycidyl (meth)acrylate, ( Chloromethyl meth)acrylate, 2-chloroethyl (meth)acrylate, 2-bromoethyl (meth)acrylate, allyl isocyanate, allyl oxirane, allyl chloroformate Wait.

Addition rate of compound (c), that is, the total amount of added compound (c) relative to the total amount of functional groups derived from the halogen compound (b) containing functional groups (the total amount of functional groups before compound (c) is added) The proportion (mole %) of is preferably substantially 100 mole%. That is, it is preferable that the functional group derived from the functional group-containing halogen compound (b) does not substantially remain. Here, "substantially no functional group derived from the functional group-containing halogen compound (b)" means that the unreacted functional group derived from the functional group-containing halogen compound (b) is 0.1 mol% or less, preferably 0.01 mol% or less.

The unsaturated group-containing halogen compound (d) is not particularly limited as long as it is one or more halogen compounds selected from ethylenically unsaturated groups and groups having a carbon-carbon triple bond. For example, halogenated alkenyl compounds with 1 to 20 carbons and alkyne halides with 1 to 20 carbons are examples, and the linking group with 1 to 20 carbons may also contain ether bonds, ester bonds, amide bonds, etc. Specific examples include allyl bromide, allyl chloride, 4-bromo-1-butene, 4-chloro-1-butene, 5-bromo-1-pentene, 5-chloro-1-pentene, 6 -Bromo-1-hexene, 6-chloro-1-hexene, propargyl bromide, propargyl chloride, 4-bromo-1-butyne, 4-chloro-1-butyne, 5-bromo-1 -pentyne, 5-chloro-1-pentyne, 6-bromo-1-hexyne, 6-chloro-1-hexyne, bromomethyl (meth)acrylate, chloromethyl (meth)acrylate, ( Bromoethyl methacrylate, chloroethyl (meth)acrylate, bromopropyl (meth)acrylate, chloropropyl (meth)acrylate, bromobutyl (meth)acrylate, chlorine (meth)acrylate Butyl ester etc. Among them, based on the viewpoint of ease of acquisition or reactivity, and not hindering the affinity with the pigment (B) described later, (meth)acrylates containing alkyl halides with 1 to 20 carbons, and (meth)acrylates with 1 to 20 carbons are preferred. The vinyl compound and propyne halide compound of halogenated alkyl in 20 are preferably allyl bromide, propargyl bromide, bromomethyl (meth)acrylate, and bromoethyl (meth)acrylate.

The addition rate of the ethylenically unsaturated group-containing halogen compound (d), that is, the introduction ratio (mole %) of the ethylenically unsaturated group to the total amount of amine groups contained in the polymer compound (a-0), is based on For the same reason as the aforementioned functional group-containing halogen compound (b) (and the added state of compound (c)), the minimum addition rate is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably It is more than 10 mol%. Moreover, the maximum addition rate may be 100 mol%, preferably less than 60 mol%, more preferably less than 40 mol%.

The amine value of the polymer dispersant (A) in this embodiment is preferably 0 mgKOH/g-300 mgKOH/g, more preferably 10 mgKOH/g-250 mg KOH/g, and more preferably 20 mgKOH/g-200 mgKOH/g.

In this specification, the "generalized amine value" is defined as the amine value when the quaternary ammonium cation group is also regarded as an amine group. On the other hand, the value measured in accordance with the above-mentioned JIS K7237 and other specifications is the actual measured value of the amine value of the above-mentioned polymer dispersant (A). In this specification, in order to distinguish it from the "generalized amine value", it is sometimes called It is the "narrow sense amine value". The broad-sense amine value (V ¹ ) of the polymer dispersant (A) in this embodiment is based on the narrow-sense amine value (V ⁰ ), using the amine value (V ^a ) of the polymer compound (a-0) and the 4-level The value calculated from the ratio (B) (mole %) of the total amount of ammonium cation groups (g-1) to the total amount of amine groups that the polymer compound (a-0) has.

V ¹ =[V ⁰ +V ^a ×B]×[Mw ^a /Mw ¹ ] (4) (where: V ¹ : generalized amine value of polymer dispersant (A) V ⁰ : polymer dispersant (A ) narrow sense amine value V ^a : the amine value of the polymer compound (a-0) B: the total amount of quaternary ammonium cationic groups (g-1) relative to the total amount of amine groups possessed by the polymer compound (a-0) Ratio (mole %) Mw ¹ : weight average molecular weight of polymer dispersant (A) Mw ^a : weight average molecular weight of polymer compound (a-0)

When the polymer compound (a-0) only contains tertiary amino groups as amino groups, and the addition rate of the compound (c), that is, the total amount of the added compound (c) is relative to the halogen compound derived from the functional group ( When the proportion (mole %) of the total amount of functional groups (the total amount of functional groups before compound (c) is added) in b) is substantially 100 mol%, the total amount of quaternary ammonium cation groups (g-1) The ratio (mole %) (B) to the total amount of amine groups that the polymer compound (a-0) has is the same value as the addition ratio of the functional group-containing halogen compound (b).

The unsaturated group value of the polymer dispersant (A) in this embodiment is preferably 50-1000 μmol/g, more preferably 100-800 μmol/g, and even more preferably 200-600 μmol/g. When the unsaturated group value is 50 μmol/g or more, the heat resistance, solvent resistance, and adhesion of the cured resin film are good. The unsaturated group value of the polymer dispersant (A) can be determined by the addition of the functional group-containing halogen compound (b) and compound (c) to the polymer compound (a-0) or the unsaturated group-containing halogen compound ( d) Controlling the addition amount of the polymer compound (a-0).

The unsaturated group value of the polymer dispersant (A) is a calculated value based on the amount of raw materials used and the reaction rate at the time of synthesis being 100%.

The weight average molecular weight of the polymer dispersant (A) of this embodiment is preferably 1,000-50,000, more preferably 1,000-35,000. In addition, the molecular weight distribution of the polymer dispersant (A) (the value obtained by dividing the weight average molecular weight in terms of polystyrene by the number average molecular weight) is preferably in the range of 1.0 to 3.5, more preferably in the range of 1.0 to 2.5. When the molecular weight and molecular weight distribution of the polymer dispersant (A) are within the above range, the viscosity of the pigment dispersion composition can be controlled in an appropriate range, sufficient pigment dispersibility and storage stability of the pigment dispersion composition can be obtained, and at the same time, Ensure excellent heat resistance, solvent resistance, graphic adhesion, developability, etc.

The polymer dispersant (A) of this embodiment is a quaternary ammonium salt. The quaternary ammonium cation group as a cationic group has a polymer main chain and a quaternary ammonium cation group (g-1) having an ethylenically unsaturated group. About the said ethylenically unsaturated group, it is the same as the said ethylenically unsaturated group. The counter ion which forms a salt with the cation of this embodiment is not specifically limited. Examples thereof include halide ions such as chlorine, bromine, and iodine; hydroxyl ions; nitrate ions, nitrite ions; sulfate ions, and the like. Among them, halide ions are preferred, and bromide ions are more preferred. The quaternary ammonium cation group and the main chain of the polymer can be directly bonded or bonded via an organic group (such as a divalent hydrocarbon group that can have heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms). The above-mentioned ethylenically unsaturated group possessed by the quaternary ammonium cation group is included in the 4 substituents bonded to the nitrogen of the quaternary ammonium cation, any of the 3 substituents other than the substituents of the polymer main chain. more than one.

The polymer dispersant (A) of this embodiment preferably has a quaternary ammonium cation group represented by general formula (8). The polymer dispersant (A) may have a quaternary ammonium cation group represented by general formula (8) in the polymer main chain.

(其中，R ²~R ³分別獨立表示碳數1~3之烷基，Y表示具有乙烯性不飽和鍵之取代基)。

(wherein, R ² to R ³ independently represent an alkyl group having 1 to 3 carbon atoms, and Y represents a substituent having an ethylenically unsaturated bond).

In the general formula (8), Y preferably has a substituent having a (meth)acryloxy group, a vinyl group or a propargyl group.

In the general formula (8), Y is more preferably a group represented by the following formulas (1) to (3) from the viewpoint of the affinity with the pigment (B) described later.

-(CH ₂ ) _m -OX-(CO)-CR ¹ =CH ₂ (1) -(CH ₂ ) _m -X-CR ¹ =CH ₂ (2) -(CH ₂ ) _m -XC≡CH (3 ) (In formulas (1) to (3), m is an integer of 1 to 20, X is a single bond or a divalent linking group with ¹ to 20 carbons, and R represents a hydrogen atom or a methyl group). In the formulas (1)~(3), m is 1~20, preferably 1~10, more preferably 1~6. The divalent linking group represented by X has 1-20 carbon atoms, preferably 1-10 carbon atoms, more preferably 1-6 carbon atoms. The divalent linking group represented by X may also include an ether bond, an ester bond, an amide bond, and the like.

Also, in the general formula, Y is more preferably represented by the following formula (4)~ (7) The base of representation.

-(CH ₂ ) _m -O-(CO)-(NH)-(CH ₂ ) _n -O-(CO)-CR ¹ =CH ₂ (4) -(CH ₂ ) _m -O-(CO)- CR ¹ =CH ₂ (5) -(CH ₂ ) _m -CR ¹ =CH ₂ (6) -(CH ₂ ) _m -C≡CH (7) (In formulas (4)~(7), m and n are independently an integer of ¹ to 20, and R represents a hydrogen atom or a methyl group). In formulas (4)~(7), the definitions and preferred ranges of m and R1 are the same as those shown in formulas ( ¹ )~(3). n is 1-19, preferably 1-9, more preferably 1-5.

＜Manufacturing method of polymer dispersant (A)＞ The polymer dispersant (A) can be produced by adding a functional group-containing halogen compound (b) to the tertiary amine group (g-0) of the polymer compound (a-0), and then adding the compound (c). As a method of adding a functional group-containing halogen compound (b) to the tertiary amine group (g-0) of the aforementioned polymer compound (a-0), it is preferable to use a tertiary amine group (g-0) and a halogenated alkyl group. The Menschutkin reaction of the condensation reaction. Specifically, the polymer compound (a-0) and the halogen compound (b) containing a functional group are mixed in any proportion and reacted at room temperature to 150°C, preferably 50°C to 130°C to obtain a high The reactant (a-1) of the molecular compound (a-0) and the functional group-containing halogen compound (b) (hereinafter also referred to as "reactant (a-1)").

As a method of adding the compound (c) having a functional group derived from the functional group-containing halogen compound (b) to the reactant (a-1), a conventional addition reaction can be utilized. Specifically, the reactant (a-1) and the compound (c) can be mixed in any proportion, and after adding a catalyst or a polymerization inhibitor if necessary, the solution is heated at room temperature to 150°C, preferably at 50°C to 130°C. Reaction under the condition of ℃.

Also, the catalyst is not particularly limited as long as it increases the nucleophilicity of the functional group of the functional group-containing halogen compound (b) or improves the electrophilicity of the compound (c). Specific examples include phosphorus compounds such as triphenylphosphine, organometallic compounds such as chromium and tin, and the like. In addition, the polymerization inhibitor is added to prevent polymerization and gelation of the ethylenically unsaturated groups in the compound (c) when the compound (c) is added. The species is not particularly limited, but specific examples thereof include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, dibutylhydroxytoluene, and the like.

Furthermore, the polymer dispersant (A) can also be produced by one-stage reaction of adding an unsaturated group-containing halogen compound (d) to the tertiary amine group (g-0) of the polymer compound (a-0). The method of adding the unsaturated group-containing halogen compound (d) to the tertiary amino group (g-0) of the polymer compound (a-0) is the same as the method of adding the functional group-containing halogen compound (b). The polymer dispersant (A) is a polymer compound (a-0) having a complex structure as described above by adding a functional group-containing halogen compound (b) and a compound (c) or adding an unsaturated group-containing halogen compound (d) Alternatively, it is difficult to display the entire image as a chemical structural formula or the like.

＜Pigment dispersion composition＞ The pigment dispersion composition of this embodiment contains a polymer dispersant (A), a pigment (B) and a solvent (C-1). The said pigment dispersion composition contains binder resin (D-1) as needed.

[Polymer Dispersant (A)] The polymer dispersant (A) of this embodiment can use what was mentioned above. In addition, as the pigment dispersion composition of this embodiment, other dispersants may be used in combination within the range that does not impair the effect of the present invention. The amount of unsaturated groups contained in the entire dispersant is preferably 50-1000 μmol/g, more preferably 100-800 μmol/g, and still more preferably 200-600 μmol/g. For example, when other dispersants are used in combination, an amine group-containing polymer dispersant is preferred, a tertiary amine group-containing polymer dispersant is preferred, and the aforementioned polymer compound (a-0) is more preferably used in combination. When other dispersants are used together, the ratio of the total amount of quaternary ammonium cationic groups (g-1) contained in the polymer dispersant (A) to the total amount of amine groups contained in all dispersants is also preferably 5 moles % or more, more preferably 8-50 mol%, and more preferably 10-30 mol%. When the total ratio of the quaternary ammonium cation group (g-1) is 5 mol% or more, the heat resistance, solvent resistance, and adhesion of the cured resin film can be improved. That is, when other dispersants are used together, the introduction amount of ethylenically unsaturated groups or tertiary amine groups (g- 0) to the ratio of quaternary ammonium cationic groups (g-1). Thereby, it is possible to achieve a balanced pigment dispersion that has both the solvent resistance of the resin cured film and the developability of the photosensitive coloring composition, and the various performances of the pigment dispersant and the photosensitive coloring composition. Composition, but from the viewpoint of further improving the adjustment procedure and the solvent resistance of the cured resin film, it is preferable to use the polymer dispersant (A) alone.

The content of the polymer dispersant (A) in the pigment dispersion composition is preferably 10-80 parts by mass, more preferably 12-60 parts by mass, and more preferably 15 parts by mass relative to 100 parts by mass of the pigment (B) described later. ~40 parts by mass.

[Pigment (B)] The pigment (B) in this embodiment is not particularly limited as long as it can be uniformly dispersed with other components to form a pixel of a color filter. Pigments of various colors such as pigments of the three primary colors of red, green, and blue light, yellow, orange, and purple pigments that can be used as complementary colors, and black, brown, and other pigments used in the black matrix can be used. In addition, examples of the chemical structure of the pigment (B) include isoindolinone, isoindoline, azomethine, anthraquinone, anthrone, xanthene, diketopyrrolopyrrole, perylene , all organic pigments such as perinone, quinacridine, indigoid, dioxazine, indigo, phthalocyanine, anthocyanin, azo or carbon black or titanium black, Inorganic pigments such as titanium dioxide.

Among them, the pigment (B) of this embodiment preferably includes a green pigment having a halogenated phthalocyanine skeleton represented by the following formula (1).

In formula (1), M represents a divalent or tetravalent metal atom. From the viewpoint of color reproducibility, zinc or copper is preferable, and zinc is particularly preferable. X represents any one of a hydrogen atom, a chlorine atom, or a bromine atom, and includes at least one of a chlorine atom or a bromine atom. According to brightness or color reproducibility, change the additional ratio of chlorine atoms and bromine atoms. The more chlorine atoms and the fewer bromine atoms, the higher the brightness will be. Conversely, the more bromine atoms and the fewer chlorine atoms, the better the color reproducibility will be. The chlorine atom is preferably from 1 to 10, more preferably from 1.5 to 8. The number of bromine atoms is preferably from 5 to 15, more preferably from 7 to 14.

By using a green pigment with a halogenated phthalocyanine skeleton and the above-mentioned polymer dispersant (A), sufficient pigment dispersibility and storage stability of the pigment dispersion composition can be obtained, and a color filter with high brightness and a wide color reproduction range can be provided. Light flakes can also impart heat resistance, solvent resistance, and pattern adhesion to colored patterns.

As a halogenated phthalocyanine pigment, you may use a commercial item, and you may prepare it yourself. Examples of commercially available products include C.I. Pigment Green 7, 36, 58, and 59, among which C.I. Pigment Green 58 and 59 are preferably used because of high brightness and high color reproducibility. When preparing by yourself, use known manufacturing methods. For example, the phthalocyanine skeleton is formed under the catalyst of ammonium monomolybdate, etc., using phthalic acid or phthalonitrile, etc., in which a part or all of the hydrogen atoms of the aromatic ring are replaced by halogen atoms, etc. method, and the method of halogenating phthalocyanine with chlorine or bromine. The crude pigments obtained by these methods are dried and ground in a ball mill or a vibrating mill, and processed by known solvent salt milling methods to obtain desired green pigments.

About the pigment (B) of this embodiment, the green pigment which has a halogenated phthalocyanine frame|skeleton may be used individually, and may be used in combination of 2 or more types. Also, other pigments are not suitable for green pigments having a halogenated phthalocyanine skeleton. Specific examples of other pigments include C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125 , 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, Orange pigments of 55, 59, 61, 64, 65, 71, 73, etc.; C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215 , 216, 224, 242, 254, 255, 264, 265, etc. red pigments; C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60, etc. blue pigments; C.I. Pigment Violet 1, 19, Purple pigments such as 23, 29, 32, 36, 38, etc.; brown pigments such as C.I. Pigment Brown 23, 25, etc.; C.I. Pigment Black 1, 7, carbon black, titanium black, iron oxide and other black pigments. These pigments may be used alone or in combination of two or more depending on the intended pixel color.

In addition, the pigment (B) of this embodiment may use not only a pigment but also a dye together. When dyes are used, compared with pigments, higher brightness, wider color reproduction range, and better developability can be expected. On the other hand, when a pigment is used, it has excellent heat resistance and less color change after forming a colored pattern than a dye. Dyes and pigments can also be used depending on the required performance and pixel color of the purpose.

As the dye, it is preferable to use acid dyes having acidic groups such as carboxyl groups, acid dyes and Salts of nitrogen compounds, sulfonamides of acid dyes, etc. As specific examples of these dyes, acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid magenta; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50 , 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52 ,57,69,73,80,87,88,91,92,94,97,103,111,114,129,133,134,138,143,145,150,151,158,176,183,198 , 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; Acid Violet 6B, 7, 9, 17, 19; Acid Yellow 1, 3, 9, 11, 17, 23, 25, 29 , 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and their derivatives, etc. Among them, acid dyes of xanthene, anthraquinone series, or phthalocyanine series are preferred. These dyes may be used alone or in combination of two or more. When using a dye, it is preferably 20 to 80 parts by mass relative to 100 parts by mass of the pigment (B).

＜Solvent (C-1)＞ The solvent (C-1) is not particularly limited as long as it does not react with each component contained in the pigment dispersion composition or the photosensitive coloring composition of this embodiment and can dissolve or disperse these solvents. As the solvent (C-1), the same solvent as that used in the production of the polymer dispersant (A) can be used, and the solvent contained after the reaction may be used as it is or may be further added. Moreover, when other components are added, it can coexist with it. Specific examples of the solvent (C-1) include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol Monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Ethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate, etc. These may be used alone or in combination of two or more. And, among these, glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, which are preferably used in the manufacture of color filters, are preferable.

＜Binder resin (D-1)＞ The binder resin (D-1) is not particularly limited, preferably (meth)acrylic resins, epoxy (meth)acrylic resins, vinyl ester resins and other resins commonly used in negative resists, preferably Resin containing ethylenically unsaturated double bonds such as vinyl and (meth)acryl groups and substituents that contribute to alkali solubility of carboxylic acid, phosphoric acid, sulfonic acid, etc. By using these resins, a photosensitive coloring composition having excellent pattern adhesion and developability can be provided. Moreover, the said polymer dispersing agent (A) does not correspond to a binder resin.

Among these resins, a (meth)acrylic resin having a (meth)acryl group and a carboxyl group is preferably used from the viewpoint of being easy to provide a resin having a wide range of characteristics. A commercially available resin may be used, or it may be prepared by itself. When self-prepared, use the known free radical polymerization method to polymerize the base polymer with more than one polymerizable monomer in the technical field, and add (meth)acryl and/or carboxylic acid to the base polymer , can synthesize binder resin (D-1). As a method of adding a (meth)acryl group, for example, after polymerizing the base polymer using a polymerizable monomer having a reactive group such as a hydroxyl group, an amino group, a carboxyl group, an epoxy group, or an isocyanate group, adding a polymerization inhibitor After the catalyst is added, a (meth)acryl-containing monomer having a functional group that can be bonded to the reactive groups is added, and the method is reacted at 50-150°C. Moreover, as a method of adding a carboxyl group, for example, the following methods are exemplified. A method of reacting a basic polymer having a hydroxyl group with a polybasic acid anhydride such as succinic anhydride to generate a carboxyl group. A method of reacting a base polymer having a carboxyl group with a (meth)acryl group-containing monomer having an epoxy group, and then reacting a polybasic acid anhydride such as succinic anhydride to generate a carboxyl group. A method of reacting a base polymer having an epoxy group with a (meth)acryl group-containing monomer having a carboxyl group, and then reacting a polybasic acid anhydride such as succinic anhydride to generate a carboxyl group. Alternatively, a method in which carboxyl groups remain in the base polymer. In order to properly control the molecular weight during synthesis and to properly adjust the viscosity after synthesis, the solvent contained in the pigment dispersion composition (C-1) may also be added.

The physical properties of the binder resin (D-1) are not particularly limited, but based on the ease of manufacture of the photosensitive coloring composition and the compatibility with other compositions, the preferred weight average molecular weight: 1000~50000, solid content Acid value: 10~200mgKOH/mg, unsaturated group equivalent: 100~3000g/mol, viscosity: within the range of 0.1~1000dPa‧s.

When the pigment dispersion composition of this embodiment contains a binder resin (D-1), it is preferably 10 to 80 parts by mass, more preferably 12 to 50 parts by mass, and still more preferably 100 parts by mass of the pigment (B). 15 to 40 parts by mass.

＜Manufacturing method of pigment dispersion composition＞ The pigment dispersion composition of this embodiment is a specific amount of polymer dispersant (A), pigment (B), solvent (C-1) and binder resin (D-1) as an optional component. The processing step finely disperses the pigment (B). In this dispersion treatment step, devices such as a paint shaker, bead mill, ball mill, roller mill, stone mill, jet mill, homogenizer, planetary mixer, and self-rotating mixer are often used. In addition, in the dispersion treatment step, when beads having a diameter of 0.01 to 10 mm are used, the uniform micronization of the pigment (B) can be effectively performed. There is no limitation on the material of the beads, but glass beads or zirconia beads are preferably used in consideration of hardness and pollution to the pigment dispersion composition. Regarding the appropriate time, temperature, bead diameter, and usage amount of the dispersion treatment, since the appropriate conditions vary with the composition of the pigment dispersion composition and the size of the device, it is only necessary to adjust it appropriately. Finally, for the purpose of removing fine dust and coarse particles and aggregates of the pigment (B) in the pigment dispersion composition, it is preferable to filter the pigment dispersion composition with a glass filter or the like.

＜Photosensitive coloring composition＞ The photosensitive coloring composition of this embodiment contains the above-mentioned pigment dispersion composition, binder resin (D-2), reactive diluent (E) and photopolymerization initiator (F). The photosensitive coloring composition of this embodiment may contain a solvent (C-2). In the photosensitive coloring composition of this embodiment, it is preferable that the total binder resin (D) of the aforementioned binder resin (D-1) and (D-2) contains 50 to 280 parts by mass of the pigment (B) relative to 100 parts by mass Parts by mass, the reactive diluent (E) contains 40 to 200 parts by mass, and the photopolymerization initiator (F) contains 0.1 to 10 parts by mass. The solvent (C-2) may be the same as the solvent (C-1) contained in the pigment dispersion composition, or a different one may be added.

＜Binder resin (D-2)＞ The binder resin (D-2) may be the same as or different from the binder resin (D-1) contained in the above-mentioned pigment dispersion composition. In addition, the binder resin (D-1) may be used as (D-2) without newly adding it as the binder resin (D-2). The total content of the binder resin (D-1) and (D-2) is preferably 50-280 parts by mass, more preferably 75-230 parts by mass, relative to 100 parts by mass of the pigment (B). parts by mass, and more preferably 100 to 200 parts by mass.

＜Reactive diluent (E)＞ The reactive diluent (E) is not particularly limited as long as it is a low-molecular compound containing an ethylenically unsaturated double bond such as a vinyl group or a (meth)acryloxy group. Specific examples of the reactive diluent (E) include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate , diallyl phenyl phosphate and other aromatic vinyl monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; methyl (meth)acrylate, ethyl (meth)acrylate Ester, Propyl (meth)acrylate, Butyl (meth)acrylate, β-Hydroxyethyl (meth)acrylate, Hydroxypropyl (meth)acrylate, Ethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, Propylene glycol di(meth)acrylate, Ethylene glycol di(meth)acrylate, Trimethylolpropane di(meth)acrylate, Trimethylolpropane Tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acrylate of tri(hydroxyethyl)isocyanurate, etc. base) acrylic monomer; triallyl cyanurate, etc. These may be used alone or in combination of two or more. Among these, compounds having a plurality of (meth)acryloxy groups are preferable, and trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa( Compounds having three or more (meth)acryloyloxy groups such as meth)acrylate and tri(meth)acrylate of tri(hydroxyethyl)isocyanurate.

The content of the reactive diluent (E) is preferably 40-200 parts by mass, more preferably 60-180 parts by mass, and still more preferably 80-160 parts by mass, relative to 100 parts by mass of the pigment (B).

＜Photopolymerization initiator (F)＞ The photopolymerization initiator (F) is preferably a photoradical generator, and its specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, etc., and their alkyl ethers ; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-tert-butyldioxy-1-methylethyl Base) acetophenones such as acetophenone; 2-methylanthraquinone, 2-amylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, etc. Dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone and other thioxanthones; acetophenone dimethyl ketal, benzyl dimethyl ketal, etc. Ketals; benzophenone, 4-(1-tert-butyldioxy-1-methylethyl)benzophenone, 3,3',4,4'-tetra(tert-butyl Benzophenones such as dioxycarbonyl)benzophenone; 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one; 2-Benzene -2-dimethylamino-1-(4-morpholinophenyl)butanone-1; acyl phosphine oxides; and xanthones, etc. These may be used alone or in combination of two or more.

The content of the photopolymerization initiator (F) is preferably 0.1 to 10 parts by mass, more preferably 1 to 9 parts by mass, and more preferably 2 to 8 parts by mass relative to 100 parts by mass of the pigment (B).

In the photosensitive coloring composition of this embodiment, in addition to the above-mentioned components, conventional additives, fillers, etc. for photoacid generators, photobase generators, coupling agents, leveling agents, etc., which impart specific characteristics can also be formulated. The compounding quantity of these components is not specifically limited, As long as it is the range which does not inhibit the effect of this invention, it will not specifically limit.

<Manufacturing method of photosensitive coloring composition> The photosensitive coloring composition of this embodiment can be prepared by mixing the above-mentioned components using a conventional mixing device. For example, after adjusting the pigment dispersion composition first, it is produced by sequentially mixing binder resin (D-2), reactive diluent (E), photopolymerization initiator (F) and the like. And, if necessary, a solvent (C-2) may be added in addition to the solvent (C-1) contained in the pigment dispersion composition. In this case, the solvent (C) contained in the photosensitive coloring composition includes a solvent (C-1) and a solvent (C-2). Moreover, the solvent (C-2) may use the same thing as the solvent (C-1), and may differ.

The photosensitive coloring composition obtained above has sufficient pigment dispersibility and storage stability of the pigment dispersion composition, can achieve high brightness, can suppress the bleeding of dispersants or colorants, and can exhibit excellent heat resistance, Various resist properties such as solvent resistance, pattern adhesion, and developability can form colored patterns with excellent reliability. That is, by using the said photosensitive coloring composition, the color filter excellent in reliability can be provided.

＜Color Filter＞ Next, a color filter having a colored pattern formed of a hardened photosensitive coloring composition of the present invention will be described. The color filter of the present invention has a colored pattern formed using the above-mentioned photosensitive coloring composition. A color filter is generally composed of a substrate, RGB pixels formed thereon, a black matrix formed at the boundary of each pixel, and a protective film formed on the pixels and the black matrix. In this structure, except that the pixel and the black matrix (colored pattern) are formed using the above-mentioned photosensitive coloring composition, other structures can be adopted by known ones.

Next, an embodiment of a method of manufacturing a color filter will be described. Firstly, a colored pattern is formed on the substrate. Specifically, a black matrix and RGB pixels are sequentially formed on the substrate. The material of the substrate is not particularly limited, and glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamideimide substrates, polyimide substrates, aluminum substrates, and printed wiring substrates can be used appropriately , array substrate, etc.

Colored patterns can be formed by photolithography. Specifically, after coating the above-mentioned photosensitive coloring composition on a substrate to form a coating film, the coating film is exposed through a photomask of a specific pattern, and the exposed portion is photohardened. Then, after developing the unexposed part with an aqueous alkali solution, a specific colored pattern can be formed by baking.

The coating method of the photosensitive coloring composition is not particularly limited, and screen printing, roll coating, curtain coating, spray coating, spin coating, and the like can be used. And, after application of the photosensitive coloring composition, if necessary, the solvent (C) can be volatilized by heating using heating means such as a circulating oven, an infrared heater, or a hot plate. The heating conditions are not particularly limited, and can be appropriately set according to the type of photosensitive coloring composition used. Generally, heating at a temperature of 50°C~120°C for 30 seconds to 30 minutes is sufficient.

Next, the formed coating film is partially exposed by irradiating active energy rays such as ultraviolet rays or excimer lasers through a negative mask. The amount of energy rays to be irradiated may be appropriately selected according to the composition of the photosensitive coloring composition, and is preferably 30 to 2000 mJ/cm ² , for example. The light source used for exposure is not particularly limited, but low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, and the like can be used.

The alkaline aqueous solution used for development is not particularly limited, but aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; Aqueous solutions of amino compounds; tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β- Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β - Aqueous solutions of p-phenylenediamine-based compounds such as methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates, etc. Moreover, antifoaming agents and surfactants may be added to these aqueous solutions as needed. Moreover, after image development with the said alkaline aqueous solution, it is preferable to wash with water and dry.

Moreover, the baking conditions are not particularly limited, and heat treatment may be performed according to the type of the photosensitive coloring composition used. Generally, it can be heated at 130~250℃ for 10~60 minutes.

The above-mentioned coating, exposure, development and baking are repeated sequentially by using the photosensitive coloring composition for black matrix and the photosensitive coloring composition for red, green, and blue pixels to form desired coloring patterns. Then, a protective film is formed on the color pattern (RGB pixels and black matrix), but the protective film is not particularly limited, and it can be formed by a known method.

The color filter produced in this way has excellent pigment dispersibility due to the uniform miniaturization of the pigment, and achieves high brightness. It has excellent heat resistance, solvent resistance, and adhesion, and can be expected to suppress dispersants and colorants. of exudation.

<Pixel Display Device> The image display device of this embodiment is an image display device provided with the aforementioned color filter, and specific examples thereof include solid-state imaging devices such as liquid crystal display devices, organic EL display devices, CCD devices, and CMOS devices. The image display device of this embodiment may be manufactured by a usual method except for using the above-mentioned color filter. For example, when manufacturing a liquid crystal display element, the above-mentioned color filter is formed on a substrate, and then electrodes, spacers, and the like are sequentially formed. Then, form electrodes etc. on another substrate, bond the two together, inject a certain amount of liquid crystal and seal it. [Example]

The present invention will be described in detail below with reference to examples, but the present invention is not limited by these examples. In this embodiment, unless otherwise stated, all parts and percentages are based on mass.

＜Measuring method of weight average molecular weight＞ The weight average molecular weight described below means the weight average molecular weight in terms of standard polystyrene measured under the following conditions using gel permeation chromatography (GPC). String: Shodex (registered trademark) LF-804+LF-804 (manufactured by Showa Denko Co., Ltd.) Column temperature: 40°C Sample: 0.2% tetrahydrofuran solution of the object to be measured Developing solvent: tetrahydrofuran Detector: Differential refractometer (Shodex RI-71S) (manufactured by Showa Denko Co., Ltd.) Flow rate: 1mL/min

＜Amine value of polymer dispersant (A)＞ The amine value (amine value in the narrow sense) of the polymer dispersant (A) was measured based on the aforementioned method (JIS K7237). And, the generalized amine value including the quaternary ammonium cation group was calculated using the calculation method described in this specification. Moreover, the amine value of a polymer compound (a-0) uses the calculated value calculated based on the raw material usage-amount. Each result is shown in Table 1 and Table 2.

<Unsaturated group value of polymer dispersant (A)> The number of moles of ethylenically unsaturated groups per mass of polymer dispersant (A) is based on the actual polymer compound (a-0), halogen compound (b) containing functional groups, ethylenically unsaturated monomer ( c) The calculated value calculated from the usage amount of the unsaturated group-containing halogen compound (d).

The production example of the polymer dispersant (A) is shown below.

<Example A1> In the flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas introduction tube, put 133g propylene glycol monomethyl ether acetate as a solvent, 80.5g isobornyl methacrylate and 13.2g as a catalyst Tetramethylethylenediamine, the inside of the flask was replaced with nitrogen and stirred at 50°C for 1 hour. Then, 9.3 g of ethyl bromoisobutyrate and 5.6 g of cuprous chloride were added as a catalyst, and the temperature of the flask was raised to 110° C., followed by polymerization reaction for 4 hours. After the reaction, sample the solution and measure the non-volatile matter. After confirming that the polymerization conversion rate from the non-volatile matter conversion rate is 98% or more, add 61 g of propylene glycol monomethyl ether acetate and 19.5 g of methyl ether as a monomer having a tertiary amino group. Dimethylaminoethyl acrylate was further reacted at 110° C. for 2 hours. After the reaction, the solution was sampled again to measure the non-volatile matter, and after confirming that the polymerization conversion rate in terms of non-volatile matter was 98% or more, the solution was cooled. Finally, propylene glycol monomethyl ether acetate was added as a solvent so that the solid content was 40.0%, and sample BP1 was obtained as a polymer compound (a-0) containing tertiary amine groups and not containing 1st and 2nd amine groups. . The narrow-sense amine value of sample BP1 was 70 mg KOH/g, the weight average molecular weight was 5500, and the molecular weight distribution was 1.1.

Next, in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 71.3 g of the obtained sample BP1 (28.5 g in terms of solid content excluding the solvent), as a functional group-containing halogen compound (b ) of ethylene epibromohydrin 4.4g (manufactured by TCI Corporation, with respect to the total amount of amine groups of the polymer compound (a-0) sample BP1 is 100 mole%), while replacing the inside of the flask with nitrogen, stir, and heat up from room temperature to 120°C. Stir until the peak shift of 2-bromoethanol is confirmed by NMR spectrum, then cool down to room temperature to obtain the reactant (a-1) of polymer compound (a-0) sample BP1 and functional group-containing halogen compound (b) .

Then, 5.0 g of 2-isocyanatoethyl acrylate (Showa Denko KURRANTS (trademark) AOI-VM) was added as the compound (c) to the obtained reaction product (a-1). The total amount of amine groups in BP1 is 100 mol%), 10 mg of NEOSTANN U-810 (manufactured by Nitto Chemical Co., Ltd.) as a catalyst, 120 mg of 4-methoxyphenol as a polymerization inhibitor (relative to the obtained reactant (a- The solid content of 1) is 100 parts by mass, which is 0.3 parts by mass), and the inside of the flask is replaced with dry air while stirring, and the temperature is raised from room temperature to 60°C. Stir until the peak derived from the isocyanate group of 2-isocyanatoethyl acrylate disappears as confirmed by IR spectrum, and cool the solution. Finally, propylene glycol monomethyl ether acetate was added as a solvent so that the solid content would be 40.0%, and sample PD1 as a polymer dispersant (A) was obtained. The polymer dispersant (A) has a narrow-sense amine value of 0 mgKOH/g, a broad-sense amine value of 65 mgKOH/g, a weight average molecular weight of 5900, a molecular weight distribution of 1.4, and an unsaturated group value of 937 μmol/g. The results are shown in Table 1.

<Example A2~A10> Samples PD2-PD10 were obtained as polymer dispersant (A) in the same manner as in Example A1, except that the types and usage amounts of the functional group-containing halogen compound (b) and compound (c) were changed as shown in Table 1. The narrow-sense amine value and broad-sense amine value, weight average molecular weight, molecular weight distribution, and unsaturated group value of the polymer dispersant (A) are shown in Table 1.

<Example A11> In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 71.3 g of the sample BP1 obtained in the same manner as in Example A1 (28.5 g in terms of solid content excluding the solvent) was added as an unsaturated group-containing For the halogen compound (d), 1.07 g of allyl bromide (TCI company, relative to the total amount of amine groups of the polymer compound (a-0) sample BP1 is 20 mol%) was stirred while replacing the inside of the flask with nitrogen. , from room temperature to 40°C. Stir until the peak shift of allyl bromide is confirmed by the NMR spectrum, and then cool down to room temperature to obtain the reaction product of the polymer compound (a-0) sample BP1 and the unsaturated halogen compound (d) as a polymer Sample PD11 of the dispersant (A). The narrow-sense amine value and broad-sense amine value, weight average molecular weight, molecular weight distribution, and unsaturated group value of the polymer dispersant (A) are shown in Table 1.

<Example A12, A13> Samples PD12 and PD13 were obtained as the polymer dispersant (A) in the same manner as in Example A11 except that the types of the unsaturated group-containing halogen compound (d) were shown in Table 1. The narrow-sense amine value and broad-sense amine value, weight average molecular weight, molecular weight distribution, and unsaturated group value of the polymer dispersant (A) are shown in Table 1.

<Example A14> In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas introduction tube, add 133 g of propylene glycol monomethyl ether acetate as a solvent, 60.0 g of isobornyl methacrylate and 13.2 g of a catalyst Tetramethylethylenediamine was stirred at 50° C. for 1 hour while replacing the inside of the flask with nitrogen. Subsequently, 9.3 g of ethyl bromoisobutyrate and 5.6 g of cuprous chloride were added as catalysts, and the temperature of the flask was raised to 110° C., followed by polymerization for 4 hours. After the reaction, sample the solution to measure the non-volatile matter, and after confirming that the polymerization conversion rate from the non-volatile matter conversion is 98% or more, add 61 g of propylene glycol monomethyl ether acetate and 40.0 g of methanomethanol as a monomer having a tertiary amine Dimethylaminoethyl acrylate was further reacted at 110° C. for 2 hours. After the reaction, the solution was sampled again and the non-volatile content was measured. After confirming that the polymerization conversion rate in terms of non-volatile content was 98% or higher, the solution was cooled. Finally, propylene glycol monomethyl ether acetate was added as a solvent so that the solid content was 40.0%, and sample BP2 was obtained as a polymer compound (a-0) containing tertiary amine groups but not containing 1st and 2nd amine groups. The narrow-sense amine value of sample BP2 was 70 mgKOH/g, the weight average molecular weight was 5500, and the molecular weight distribution was 1.1.

Then, in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 71.3 g of the obtained sample BP2 (28.5 g in terms of solid content excluding the solvent), as a functional group-containing halogen compound (b ) of 1.8 g of ethylene epibromohydrin (manufactured by TCI Corporation, 20 mol% of the total amount of amine groups relative to the sample BP2 of the polymer compound (a-0)), stirring while replacing the inside of the flask with nitrogen, and raising the temperature from room temperature to 120°C. Stir until the peak shift of 2-bromoethanol is confirmed by NMR spectrum, then cool down to room temperature to obtain the reactant (a-1) of the sample BP2 of the polymer compound (a-0) and the halogen compound (b) containing a functional group ).

Then, 2.1 g of 2-isocyanatoethyl acrylate (CURRANTS (trademark) AOI-VM manufactured by Showa Denko) was added as the compound (c) to the obtained reactant (a-1), with respect to the polymer compound (a-0) The total amount of amine groups in sample BP2 is 20 mol%), 10 mg of NEOSTANN U-810 (manufactured by Nitto Kasei Co., Ltd.) as a catalyst, and 103 mg of 4-methoxyphenol as a polymerization inhibitor (relative to the obtained reaction product ( 100 parts by mass of the solid content of a-1) is 0.3 parts by mass), while replacing the inside of the flask with dry air and stirring, the temperature was raised from room temperature to 60°C. After stirring until the disappearance of the peak derived from the isocyanate group of 2-isocyanatoethyl acrylate was confirmed by IR spectrum, the solution was cooled. Finally, propylene glycol monomethyl ether acetate was added as a solvent so that the solid content was 40.0%, and sample PD14 as a polymer dispersant (A) was obtained. The polymer dispersant (A) has a narrow-sense amine value of 101 mgKOH/g, a broad-sense amine value of 129 mgKOH/g, a weight average molecular weight of 5600, a molecular weight distribution of 1.2, and an unsaturated group value of 449 μmol/g. The results are shown in Table 1.

<Example A15> In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, add EFKA-PX4300 (manufactured by BASF, containing 3-stage amine groups and not containing 1-stage And secondary amine group, solid content 80%, amine value 57mgKOH/g, weight average molecular weight 25000) 43.8g (solid content conversion excluding solvent is 35.0g), vinyl bromide chloride as the halogen compound (b) containing functional group 0.9 g of alcohol (manufactured by TCI, 20 mol% to the total amount of amine groups in the polymer compound (a-0)) was stirred while replacing the inside of the flask with nitrogen, and the temperature was raised from room temperature to 120°C. Stir until the peak shift of 2-bromoethanol is confirmed by NMR spectrum, cool down to room temperature, and obtain the reactant (a-1) of the polymer compound (a-0) and the halogen compound (b) containing a functional group.

Then, 1.0 g of 2-isocyanatoethyl acrylate (CURRANTS (trademark) AOI-VM manufactured by Showa Denko) was added as the compound (c) to the obtained reactant (a-1), and the polymer compound (a-0) The total amount of amine groups is 20 mol%), 10 mg of NEOSTANN U-810 (manufactured by Nitto Kasei Co., Ltd.) as a catalyst, 117 mg of 4-methoxyphenol as a polymerization inhibitor (relative to the obtained reactant (a-1 100 parts by mass of the solid content of ) is 0.3 parts by mass), while replacing the inside of the flask with dry air and stirring, the temperature is raised from room temperature to 60°C. After stirring until the disappearance of the peak derived from the isocyanate group of 2-isocyanatoethyl acrylate was confirmed by IR spectrum, the solution was cooled. Finally, propylene glycol monomethyl ether acetate was added as a solvent so that the solid content was 40.0%, and sample PD15 as a polymer dispersant (A) was obtained. The polymer dispersant (A) has a narrow-sense amine value of 46 mgKOH/g, a broad-sense amine value of 57 mgKOH/g, a weight average molecular weight of 25500, a molecular weight distribution of 1.2, and an unsaturated group value of 200 μmol/g. The results are shown in Table 1.

＜Comparative examples A1~A5＞ In the same manner as in Example A1, except that instead of compound (c), the compounds and amounts listed in Table 2 were used, samples cPD1, cPD3-cPD5 were obtained as polymer dispersions without ethylenically unsaturated groups but with quaternary ammonium cation groups. agent. Also, instead of compound (c), except for using the compound and usage amount described in Table 2, sample cPD2 was obtained as a polymer dispersant having no ethylenically unsaturated group but a quaternary ammonium cationic group in the same manner as in Example A14. Table 2 shows the narrow-sense amine value and broad-sense amine value, weight average molecular weight, molecular weight distribution, and unsaturated group value of polymer dispersants not containing ethylenically unsaturated groups.

＜Comparative example A6＞ In addition to using POLYMENT NK-100PM (manufactured by Nippon Shokubai Co., Ltd.) as the polymer compound (a-0), the solid content is 49%, the amine value is 143 mgKOH/g, the weight average molecular weight is 20,000, and it contains 1st and 2nd amine groups, and does not contain Except for the dispersant of tertiary amino group) 71.4g (solid content conversion except solvent is 35.0g), sample cPD5 was obtained as the polymer dispersant without quaternary ammonium ion group in the same manner as in Example A1. Table 2 shows the narrow-sense amine value and general-sense amine value, weight average molecular weight, molecular weight distribution, and unsaturated group value of polymer dispersants without 4-grade ammonium cationic groups.

The compounds used in Table 1 and Table 2 are as follows. AOI-VM: 2-isocyanatoethyl acrylate GMA: glycidyl methacrylate

The production example of the binder resin (D-1) or (D-2) is shown below.

<Synthesis Example 1> Put 67.2 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and then heat up to 120° C. while stirring while replacing it with nitrogen. Next, in the monomer mixture formed by 16.2g of dicyclopentyl methacrylate, 51.8g of benzyl methacrylate and 26.5g of acrylic acid, add 8.0g of tertiary butyl peroxy as a polymerization initiator - For 2-ethylhexanoate, drop it into the aforementioned flask from the dropping funnel. After completion of the dropwise addition, stirring was carried out at 120° C. for 2 hours to carry out a copolymerization reaction. Next, after replacing the inside of the aforementioned flask with dry air, add 15.7 g of glycidyl methacrylate, 0.3 g of triphenylphosphine as a catalyst, and 0.2 g of hydroquinone monomethyl ether as a polymerization inhibitor. After reacting for 5 hours at °C, 74.8 g of propylene glycol monomethyl ether acetate was added as a solvent to adjust to a solid content of 40%, and a binder resin (D- 1) or (D-2) sample P1 (solid content acid value 135 mgKOH/g, unsaturated group equivalent 1100 g/mol, weight average molecular weight 10000).

<Synthesis Example 2> In the monomer mixture formed by 11.9g dicyclopentyl methacrylate, 42.7g benzyl methacrylate and 20.9g methacrylic acid, add 1.6g tertiary butyl peroxy- After the copolymerization reaction of 2-ethylhexanoate, 11.5 g of glycidyl methacrylate was added for reaction, and the binder resin (D-1) or (D-2) was obtained according to the same method as in Synthesis Example 1. Sample P2 (solid content acid value 104 mgKOH/g, unsaturated group equivalent 1100 g/mol, weight average molecular weight 32000).

The production example of the pigment dispersion composition is shown below.

<Example B1~B19> C.I. Pigment Green 58 ( DIC Fastogen Green A110) 7.5 g (100 parts by mass), any one of the samples PD1 to PD15 obtained in Examples A1 to A15 as the polymer dispersant (A-1), as the binder resin (D-1) To the sample P1 obtained in Synthesis Example 1 and the aforementioned sample PB1 as the polymer dispersant (A-2) as an optional component, propylene glycol monomethyl ether acetate as a solvent (C-1) was added to prepare zirconia beads The solid content excluding particles was 24%. After mixing and dispersing at room temperature for 2 hours with a paint shaker (Red Devil 5400 manufactured by Red Devil Equipment), the content was filtered with suction through a glass filter to obtain the pigment dispersion composition PC1~ PC19.

＜Comparative examples B1~B6, B9＞ C.I. Pigment Green 58 ( DIC Fastogen Green A110) 7.5 g (100 parts by mass), any of the samples cPD1 to cPD6 obtained in Comparative Examples A1 to A6 as a polymer dispersant (A-3), as a binder resin (D-1) For the sample P1 obtained in Synthesis Example 1, propylene glycol monomethyl ether acetate as a solvent (C-1) was added to prepare a solid content of 24% excluding zirconia beads, and the mixture was prepared by a paint shaker (manufactured by Red Devil Equipment) Red Devil 5400) was mixed and dispersed at room temperature for 2 hours, and the contents were suction filtered with a glass filter to obtain pigment dispersion compositions cPC1~cPC6, cPC9.

<Comparative examples B7, B8> In a SUS container (inner diameter 50 mm x height 100 mm) filled with 200 g of zirconia beads (YTZ ball manufactured by NIKKATO) with a diameter of 0.1 mm, C.I. Pigment Green 58 (Fastogen Green A110 manufactured by DIC) 7.5 g (100 parts by mass), the aforementioned sample PB1 as a polymer dispersant (A-2), and monomethyl ether acetate as a binder resin (D-1), prepared as solids except for zirconia beads 24%, mixed and dispersed at room temperature for 2 hours with a paint shaker (Red Devil 5400 manufactured by Red Devil Equipment), and filtered the contents with a glass filter to obtain pigment dispersion compositions cPC7 and cPC8.

＜Evaluation of pigment dispersibility＞ The viscosity of the pigment dispersion composition immediately after preparation was measured and evaluated with an E-type viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd., cone size 4.8cm, rotation speed 20rpm, measurement temperature 25°C). In addition, based on the measurement results of the viscosity, the pigment dispersibility is evaluated in five stages from 1 to 5 according to the following criteria, and 3 or more is acceptable. The evaluation results are shown in Table 3 and Table 4. "5": less than 6.0mPa‧s "4": Above 6.0mPa‧s and less than 8.0mPa‧s "3": Above 8.0mPa‧s and less than 10.0mPa‧s "2": 10.0mPa・s or more "1": No liquidity

＜Evaluation of storage stability of pigment dispersion composition＞ The prepared pigment dispersion composition was stored at room temperature for one month, and the viscosity of the pigment dispersion composition was measured and evaluated with an E-type viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd., measuring temperature 25°C). After one month of storage at room temperature, the viscosity increase rate of the pigment dispersion composition "(viscosity after storage - viscosity after adjustment) x 100/viscosity after adjustment" is compared with that immediately after preparation, and the following criteria are used to rank 1 to 5 out of 5 Make an evaluation. The evaluation results are shown in Table 3 and Table 4. "5": Less than 5% "4": More than 5% and less than 10% "3": More than 10% and less than 20% "2": More than 20% and less than 40% "1": Loss of liquidity within 14 days

The production example of the photosensitive coloring composition is shown below. <Examples C1~C19, Comparative Examples C1~C9> For the photosensitive coloring composition, the solid content (the total amount of components other than the solvent) of the pigment dispersion compositions PC1 to PC19 obtained in the aforementioned Examples B1 to B19 and the pigment dispersion compositions cPC1 to cPC9 obtained in Comparative Examples B1 to B9 is set to When 100 parts by mass, the solid content of the sample P2 obtained in Synthesis Example 2 as the binder resin (D-2) was 80 parts by mass, and 80 parts by mass of dipentaerythritol hexaacrylate as the reactive diluent (E), as 1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl-]-,-1-(O-acetyl 4 parts by mass of oxime) were mixed, and propylene glycol monomethyl ether acetate was added as a solvent (C-2), and mixed so that the solid content was 30%, and photosensitive coloring compositions X1~19 and cX1~cX9 were prepared. Also, as the compounding amount of each component relative to 100 parts by mass of the pigment (B), the binder resin (D-2) was 128 parts by mass, the reactive diluent (E) was 128 parts by mass, the photopolymerization initiator (F) It is 6.4 parts by mass.

<Preparation of green resist (1) for solvent resistance test> Put the photosensitive coloring compositions X1~19 and cX1~cX9 obtained in Examples C1~C19 and Comparative Examples C1~C9 on a 5 cm square glass substrate (alkali-free glass substrate) and then spin-coated so that the average thickness of the final cured coating film was 1.5 μm, and then heated at 100° C. for 3 minutes to evaporate the solvent. Next, fully expose the coating film (Ushio Electric Co., Ltd. USH-250BY as a lamp, exposure amount 40mJ/cm ² ), and then bake at 230°C for 30 minutes to obtain a green resist (1) that hardens the coating film .

<Preparation of green resist (2) for developing test> The photosensitive coloring compositions X1~19 and cX1~cX9 obtained in Examples C1~C19 and Comparative Examples C1~C9 were placed on a 5 cm square glass substrate (alkali-free glass substrate) and then spin-coated so that the average thickness of the final cured coating film was 1.5 μm, and then heated at 100° C. for 3 minutes to evaporate the solvent. Next, set a line-and-space or dot pattern mask on the substrate to expose the coating film (as a lamp, USH-250BY manufactured by Ushio Electric Co., Ltd., with an exposure amount of 40mJ/cm ² ) to light-harden it, and then use 0.2% by mass developed with an aqueous potassium hydroxide solution, and then baked at 230° C. for 30 minutes to obtain a green color resist (2) with a hardened coating film.

＜Solvent resistance test＞ Immerse the above green resist completely in N-methylpyrrolidone at 100°C for 3 minutes. Then, remove the green resist and let it air dry. The solvent resistance of the photosensitive coloring composition was evaluated by visually confirming the peeling state of the entire green resist. Based on the measurement results, evaluate the solvent resistance of the photosensitive coloring composition on a scale of 1 to 5 according to the following criteria, and 3 or higher is acceptable. The evaluation results are shown in Table 5. "5": The area ratio of the peeling part is less than 10% "4": 10% or more and less than 20% of the area ratio of peeled off parts "3": 20% or more and less than 50% of the peeling area in terms of area ratio "2": 50% or more and less than 80% of the peeling area in terms of area ratio "1": 80% or more of peeled parts in terms of area ratio

＜Development test＞ The developability test evaluates the developing speed. Regarding the development speed, in the development step of the above-mentioned green color resist (2), in the development process with 0.2% by mass of potassium hydroxide aqueous solution, measure the time until the end of the visible, and use 1 to 5 out of 5 based on the following criteria Evaluate at each stage, and more than 3 are qualified. The evaluation results are shown in Table 5. "5": less than 40 seconds "4": More than 40 seconds and less than 50 seconds "3": More than 50 seconds and less than 60 seconds "2": More than 60 seconds and less than 70 seconds "1": more than 70 seconds

From the results in Table 5, it can be seen that in Examples C1-C19, excellent pigment dispersibility and storage stability of the pigment dispersion composition were obtained. In Examples C1-C19, the photosensitive coloring compositions prepared using the pigment dispersion compositions obtained in Examples B1-B19 obtained excellent solvent resistance and excellent developability. In contrast, in Comparative Example B6 and Comparative Example C6, the pigment dispersibility of the pigment dispersion composition was remarkably poor, and it was difficult to use as a pigment dispersion composition. Moreover, it is also difficult to produce a photosensitive coloring composition using this pigment dispersion composition. Moreover, in Comparative Examples B1~B5 and B7~B9; Comparative Examples C1~C5 and C7~C9, the pigment dispersibility and storage stability of the pigment dispersion composition, and the developability of the colored photosensitive composition are good. On the other hand, it is confirmed that It has poor solvent resistance until the peeling of the photosensitive colored photosensitive composition.

From the above, according to the present invention, it is possible to provide a pigment dispersion composition excellent in pigment dispersibility and storage stability, a photosensitive coloring composition containing the pigment dispersion composition, and solvent resistance, It is a color filter that has excellent developability and is expected to suppress the dissolution and bleeding of dispersants or pigments. [Industrial availability]

According to the present invention, a pigment dispersion composition having excellent pigment dispersibility and storage stability can be provided. And, by using this pigment dispersion composition, it is possible to provide a photosensitive coloring composition having a cured product excellent in solvent resistance and developability. In addition, a color filter having a cured product of the photosensitive coloring composition, and an image display device including the same can also be provided.

Claims (19)

A polymer dispersant characterized by having a quaternary ammonium cation group (g-1) containing at least one selected from the group consisting of ethylenically unsaturated groups and groups having carbon-carbon triple bonds. Such as the polymer dispersant of claim 1, wherein the quaternary ammonium cation group (g-1) contained in the aforementioned polymer dispersant has a group selected from (meth)acryloxy, vinyl and propynyl. More than one of the group. Such as the polymer dispersant of claim 1 or 2, wherein the quaternary ammonium cation group (g-1) contained in the aforementioned polymer dispersant has a formula selected from the following formula (1), the following formula (2) and the following One or more of the groups represented by the formula (3), -(CH ₂ ) _m -OX-(CO)-CR ¹ =CH ₂ (1) -(CH ₂ ) _m -X-CR ¹ = CH ₂ (2) -(CH ₂ ) _m -XC≡CH (3) (In the formulas (1)~(3), m is an integer from 1 to 20, and X is a single bond or a divalent carbon number from 1 to 20 Linking group, R ¹ represents a hydrogen atom or a methyl group). Such as the polymer dispersant of claim 1 or 2, wherein the quaternary ammonium cation group (g-1) contained in the aforementioned polymer dispersant has the following formula (4), the following formula (5), the following One or more of the groups represented by the formula (6) and the following formula (7): -(CH ₂ ) _m -O-(CO)-(NH)-(CH ₂ ) _n -O-( CO)-CR ¹ =CH ₂ (4) -(CH ₂ ) _m -O-(CO)-CR ¹ =CH ₂ (5) -(CH ₂ ) _m -CR ¹ =CH ₂ (6) -(CH ₂ ) _m -C≡CH (7) (In the formulas (4)~(7), m and n are independently an integer of 1~20, and R ¹ represents a hydrogen atom or a methyl group). Such as the polymer dispersant of claim 1 or 2, wherein the aforementioned polymer dispersant is A reactant (a-1) of a polymer compound (a-0) and a functional group-containing halogen compound (b) and a reactant of a compound (c), The aforementioned polymer compound (a-0) has a tertiary amino group (g-0), The aforementioned compound (c) has a group reactive with the aforementioned functional group and an ethylenically unsaturated group, and the aforementioned halogen compound (b) containing a functional group is a halogenated alkanol with 1 to 20 carbons or a halogenated alkanol with 1 to 20 carbons fatty acid, The aforementioned compound (c) is selected from the group consisting of isocyanate group-containing (meth)acrylates, epoxy group-containing (meth)acrylates, and halogenated alkyl-containing (meth)acrylates. Such as the polymer dispersant of claim 1 or 2, wherein the aforementioned polymer dispersant is A reactant of a polymer compound (a-0) and an unsaturated group-containing halogen compound (d), The aforementioned polymer compound (a-0) has a tertiary amino group (g-0), The unsaturated groups contained in the unsaturated group-containing halogen compound (d) are one or more types selected from the group consisting of ethylenically unsaturated groups and groups having carbon-carbon triple bonds. Such as the polymer dispersant of claim 6, wherein the halogen compound (d) containing unsaturated groups is selected from (meth)acrylic acid esters of halogenated alkyl groups containing 1 to 20 carbons and One or more of the group consisting of alkyl halide vinyl compounds. As the polymer dispersant of claim 5, wherein the aforementioned polymer compound (a-0) is selected from Block polymers of monomers with tertiary amino groups (g-0) and ethylenically unsaturated groups and other monomers with ethylenically unsaturated groups and Monomers with tertiary amine groups (g-0) and ethylenically unsaturated groups, monomers with quaternary ammonium cationic groups without unsaturated groups and ethylenically unsaturated groups, and other monomers with ethylenically unsaturated groups monomeric block polymer More than one of the group formed. A pigment dispersion composition containing Polymer dispersant (A), Pigment (B), and Solvent (C-1), characterized by The aforementioned polymer dispersant (A) is the polymer dispersant according to any one of Claims 1 to 8. The pigment dispersion composition according to claim 9, wherein the aforementioned pigment (B) comprises a pigment having a halogenated phthalocyanine skeleton. The pigment dispersion composition according to any one of claims 9 to 10, further comprising a binder resin (D-1). Such as the pigment dispersion composition of claim 11, wherein relative to 100 parts by mass of the aforementioned pigment (B), Containing 10 to 80 parts by mass of the aforementioned polymer dispersant (A), Contains 10 to 80 parts by mass of the aforementioned binder resin (D-1). A photosensitive coloring composition characterized by containing: Such as the pigment dispersion composition of claim 9 or 10, Binder resin (D-2), reactive diluent (E), and Photopolymerization initiator (F). The photosensitive coloring composition according to claim 13, wherein relative to 100 parts by mass of the aforementioned pigment (B), Containing 10 to 80 parts by mass of the aforementioned polymer dispersant (A), Containing 50-280 parts by mass of the aforementioned binder resin (D-2), Containing 40 to 200 parts by mass of the aforementioned reactive diluent (E), Contains 0.1 to 10 parts by mass of the aforementioned photopolymerization initiator (F). A photosensitive coloring composition characterized by containing: Such as the pigment dispersion composition of claim 11, Binder resin (D-2), reactive diluent (E), and Photopolymerization initiator (F). The photosensitive coloring composition according to claim 15, wherein relative to 100 parts by mass of the aforementioned pigment (B), Containing 10 to 80 parts by mass of the aforementioned polymer dispersant (A), A total of 50 to 280 parts by mass of the aforementioned binder resins (D-1) and (D-2), Containing 40 to 200 parts by mass of the aforementioned reactive diluent (E), Contains 0.1 to 10 parts by mass of the aforementioned photopolymerization initiator (F). A cured resin film obtained by curing the photosensitive coloring composition according to claim 13 or 14. A color filter having a hardened photosensitive coloring composition according to claim 13 or 14. An image display element, which is provided with the color filter according to claim 18.