JP2013071951A - Compound having azo pigment skeleton, pigment dispersant including the compound, pigment composition, pigment dispersion, ink and resist composition for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment dispersant for improving the pigment dispersibility of an azo pigment with respect to a water-insoluble solvent.SOLUTION: The compound used as a pigment dispersant includes a unit represented by formula (1), (wherein R1 is an alkyl group or a phenyl group, R2-R6 are a hydrogen atom, an ester group, an amide group, or the like, and L1-L2 are a divalent linking group) bonded with a specific polymer resin unit.

Description

  The present invention relates to a novel compound in which an azo dye skeleton unit is bonded to a polymer resin unit, a pigment dispersant containing the compound, a pigment composition, and a pigment dispersion. Further, the present invention relates to an ink and a color filter resist composition using the pigment dispersion as a colorant.

  If the pigment is refined to improve the spectral properties such as pigment coloring power and transparency, crystal growth or transition is likely to occur due to thermal history or contact with the solvent in the dispersion process or subsequent manufacturing process. This causes problems such as a reduction in coloring power and transparency.

  In order to improve the dispersibility of these pigments, various pigment compositions and pigment dispersants constituting the same have been proposed. For example, an example using an acid known as Solsperse (registered trademark) or a comb polymer dispersant having a basic site is disclosed (see Patent Document 1). Furthermore, in the inkjet recording method, an example of using a polymer dispersant in which a chromophore having a molecular weight smaller than 95% of the molecular weight of the azo pigment is bonded to a side chain or a terminal of a water-soluble polymer is used as a dispersant for the azo pigment. It is disclosed (see Patent Document 2).

  On the other hand, in R (red), G (green), and B (blue) color filters using organic pigments, two or more types of pigments are used after being color-tuned in order to obtain required color characteristics. In particular, in the case of a green color filter, an example in which an azo yellow pigment is used for toning is described in a copper phthalocyanine green pigment as a main pigment (see Patent Document 3).

International Publication No. 99-42532 Pamphlet US Pat. No. 7,582,152 Japanese Patent Laid-Open No. 11-14825

  However, since the pigment dispersant described in Patent Document 1 has insufficient affinity for azo pigments, the pigment dispersibility is not sufficient. Further, for the pigment dispersant described in Patent Document 2, a water-soluble polymer is used, and the dispersibility of the pigment dispersant with a water-insoluble solvent as a dispersion medium is not sufficient.

  In addition, when an azo pigment is used for a color filter resist, the dispersibility of the pigment is poor and stable dispersion is difficult, which causes a problem of deteriorating the color characteristics of the color filter.

  Accordingly, an object of the present invention is to provide a pigment dispersant that improves pigment dispersibility in a water-insoluble solvent by having high affinity for azo pigments, particularly high affinity for acetoacetanilide pigments. Furthermore, an object of this invention is to provide the pigment composition which has the favorable dispersibility with respect to a water-insoluble solvent. Another object of the present invention is to provide a pigment dispersion that is well dispersed in a water-insoluble solvent. Another object of the present invention is to provide an ink and a resist composition for a color filter that have a good pigment dispersion state and excellent color characteristics by using the pigment dispersion.

  The above object is solved by the present invention described below. That is, the present invention relates to a polymer having a partial structural formula represented by the following general formula (2) and / or a partial structural formula represented by the following general formula (3) (also referred to as “polymer resin unit”). A unit represented by the following general formula (1) (also referred to as “azo dye skeleton unit”) is bonded. Further, the unit of the general formula (1) has a high affinity for the azo pigment, and the partial structural formulas of the general formulas (2) and (3) have a high affinity for the water-insoluble solvent.

［式（１）中、Ｒ₁は炭素数１乃至６のアルキル基、フェニル基を表し、Ｒ₂乃至Ｒ₆は水素原子、ＣＯＯＲ₁₁基、ＣＯＮＲ₁₂Ｒ₁₃基を表す。Ｒ₇乃至Ｒ₁₀は水素原子、ハロゲン原子を表す。Ｒ₁₁乃至Ｒ₁₃は水素原子、炭素原子数１乃至３のアルキル基を表す。Ｌ₁乃至Ｌ₂は二価の連結基を表す。］

[In Formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms and a phenyl group, and R _{2 to} R ₆ represent a hydrogen atom, a COOR ₁₁ group, and a CONR ₁₂ R ₁₃ group. R _{7 to} R ₁₀ represent a hydrogen atom or a halogen atom. R _{11 to} R _{13 each} represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. L _{1 to} L ₂ represent a divalent linking group. ]

［式（２）中、Ｒ₁₄は水素原子、アルキル基を表す。］

[In the formula (2), R ₁₄ represents a hydrogen atom or an alkyl group. ]

［式（３）中、Ｒ₁₅は水素原子、アルキル基を表し、Ｒ₁₆は水素原子、アルキル基、アラルキル基を表す。］

[In the formula (3), R ₁₅ represents a hydrogen atom or an alkyl group, and R ₁₆ represents a hydrogen atom, an alkyl group or an aralkyl group. ]

  The present invention also provides a pigment dispersant, a pigment composition, and a pigment dispersion containing at least the compound having the above-described configuration. The present invention also provides an ink and a color filter resist composition using the pigment dispersion as a colorant.

  The present invention provides a novel compound in which an azo dye skeleton unit and a polymer resin unit are bonded. This compound according to the present invention has a high affinity for non-water-soluble solvents, particularly non-polar solvents, and high affinity for azo pigments, particularly acetoacetanilide pigments. When used as a pigment dispersant, Good dispersibility, especially C.I. I. A pigment composition is provided that provides improved dispersibility of Pigment Yellow 155. Moreover, the pigment dispersion excellent in the dispersibility to a water-insoluble solvent is provided by using this pigment composition as a pigment dispersant. Furthermore, an ink and a color filter resist composition having good pigment dispersibility and excellent color characteristics are provided by having the pigment composition.

In CDCl ₃ the compound having an azo dye skeleton unit according to the present invention (19) is a diagram showing the ¹ H NMR spectrum at room temperature, at 400 MHz. In CDCl ₃ the compound having an azo dye skeleton unit according to the present invention (20) is a diagram showing the ¹ H NMR spectrum at room temperature, at 400 MHz.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments.

  First, the structure of the compound having an azo dye skeleton unit of the present invention will be described. The compound having an azo dye skeleton unit of the present invention is a polymer having a partial structural formula represented by the following general formula (2) and / or a partial structural formula represented by the following general formula (3) (“polymer resin”). A unit represented by the following general formula (1) (also referred to as “azo dye skeleton unit”) is bonded to the “unit”. Further, the unit of the general formula (1) has a high affinity for the azo pigment, and the partial structural formulas of the general formulas (2) and (3) have a high affinity for the water-insoluble solvent.

［式（１）中、Ｒ₁は炭素数１乃至６のアルキル基、フェニル基を表し、Ｒ₂乃至Ｒ₆は水素原子、ＣＯＯＲ₁₁基、ＣＯＮＲ₁₂Ｒ₁₃基を表す。Ｒ₇乃至Ｒ₁₀は水素原子、ハロゲン原子を表す。Ｒ₁₁乃至Ｒ₁₃は水素原子、炭素原子数１乃至３のアルキル基を表す。Ｌ₁乃至Ｌ₂は二価の連結基を表す。］

[In Formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms and a phenyl group, and R _{2 to} R ₆ represent a hydrogen atom, a COOR ₁₁ group, and a CONR ₁₂ R ₁₃ group. R _{7 to} R ₁₀ represent a hydrogen atom or a halogen atom. R _{11 to} R _{13 each} represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. L _{1 to} L ₂ represent a divalent linking group. ]

［式（２）中、Ｒ₁₄は水素原子、アルキル基を表す。］

[In the formula (2), R ₁₄ represents a hydrogen atom or an alkyl group. ]

［式（３）中、Ｒ₁₅は水素原子、アルキル基を表し、Ｒ₁₆は水素原子、アルキル基、アラルキル基を表す。］

[In the formula (3), R ₁₅ represents a hydrogen atom or an alkyl group, and R ₁₆ represents a hydrogen atom, an alkyl group or an aralkyl group. ]

  First, the azo dye skeleton unit represented by the above formula (1) provided in the present invention will be described in detail.

The alkyl group for R ₁ in the above formula (1) is not particularly limited as long as it has 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and n-butyl. And linear, branched or cyclic alkyl groups such as a group, n-pentyl group, n-hexyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and cyclohexyl group.

The substituent of R _{1 in} the above formula (1) may be further substituted with a substituent as long as the affinity for the pigment is not significantly inhibited. In this case, examples of the substituent that may be substituted include a halogen atom, a nitro group, an amino group, a hydroxyl group, a cyano group, and a trifluoromethyl group.

R ₁ in the above formula (1) can be arbitrarily selected from the substituents listed above, but is preferably a methyl group from the viewpoint of affinity for the pigment.

R _{2 to} R ₆ in the formula (1) can be selected from a hydrogen atom, a COOR ₁₁ group, and a CONR ₁₂ R ₁₃ group so that at least one is a COOR ₁₁ group or a CONR ₁₂ R ₁₃ group. From the viewpoint of the affinity, it is preferable that R ₂ and R ₅ are COOR ₁₁ groups, and R ₃ , R ₄ and R ₆ are hydrogen atoms.

Examples of the alkyl group in R _{11 to} R ₁₃ in the above formula (1) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

R _{11 to} R ₁₃ in the above formula (1) can be arbitrarily selected from the substituents listed above and a hydrogen atom, but from the viewpoint of affinity for the pigment, R ₁₁ and R ₁₂ are methyl groups, The case where R ₁₃ is a methyl group or a hydrogen atom is preferred.

Examples of the halogen atom in R _{7 to} R ₁₀ in the above formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R _{7 to} R ₁₀ in the above formula (1) can be arbitrarily selected from the substituents listed above and a hydrogen atom, but are preferably hydrogen atoms from the viewpoint of affinity for the pigment.

The formula (1) substitution position of R ₇ to R _10, acyl acetamide group and L ₁ in the acyl acetamide group and position o- position of L _1, m-position, exemplified when substituted with p- position It is done. Regarding the affinity for the pigment due to the difference in these substitution positions, the case where the acylacetamide group and L ₁ are substituted at the p-position is most preferred, which is preferable.

L ₁ in the above formula (1) represents —O—, —CO—, —NR ₁₇ — (R ₁₇ represents a hydrogen atom or an alkyl group), —R ₁₈ — (R ₁₈ represents an alkylene group). And a divalent linking group selected from the group consisting of combinations thereof.

Specific examples of L _{1 in} the above formula (1) include —O—, —O—CO—, —O—CO—NR ₁₇ —, —O—R ₁₈ —, —O—R ₁₈ —O—CO. —, —O—R ₁₈ —O—CO—NR ₁₇ —, —CO—, —CO—O—, —CO—NR ₁₇ —, —CO—O—R ₁₈ —, —CO—O—R ₁₈ —. O—, —NR ₁₇ —CO—, —NR ₁₇ —CO—NR ₁₇ —, —R ₁₈ —O—CO—, —R ₁₈ —O—CO—NR ₁₇ — (R ₁₇ represents a hydrogen atom, an alkyl group, And R ₁₈ represents an alkylene group).

Examples of the alkyl group in R ₁₇ of L _{1 in} the above formula (1) include a methyl group, an ethyl group, and a propyl group.

Examples of the alkylene group in R ₁₈ of L _{1 in} the above formula (1) include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.

L ₁ in the above formula (1) can be arbitrarily selected from the linking groups listed above, but —NH—CO—, —O—CO—, —O—C ₂ H ₄ —O from the viewpoint of ease of production. The case of -CO- is preferred.

L ₂ in the above formula (1) represents a divalent linking group, and binds the azo dye skeleton unit and the polymer resin unit via L ₂ .

L ₂ in the above formula (1) is not particularly limited as long as it is a divalent linking group, but is preferably a carboxylic acid ester group or a carboxylic acid amide group from the viewpoint of ease of production.

In the above formula (1), the substitution positions of L ₁ and L ₂ are in terms of affinity for the pigment, and the position of L ₁ is 2,5-position, 3,5-position relative to L ₂ Is preferred.

  A preferred combination of substituents in the azo dye skeleton unit represented by the above formula (1) is a combination of the units represented by the above formula (1) represented by units of the following formulas (4) and (5). The case is preferable in terms of affinity for the pigment.

［式（４）中、Ｌ₁乃至Ｌ₂は二価の連結基を表す。］

[In Formula (4), L < ₁ > thru | or L < ₂ > represent a bivalent coupling group. ]

［式（５）中、Ｌ₁乃至Ｌ₂は二価の連結基を表す。］

[In Formula (5), L < ₁ > thru | or L < ₂ > represent a bivalent coupling group. ]

  Next, the polymer resin unit having either or both of the monomer units represented by the above formula (2) or (3) of the present invention will be described.

Examples of the alkyl group for R ₁₄ in the general formula (2) include a methyl group and an ethyl group. R ₁₄ can be arbitrarily selected from the above alkyl group and a hydrogen atom, but is preferably a hydrogen atom or a methyl group from the viewpoint of ease of production.

Examples of the alkyl group represented by R ₁₅ in the general formula (3) include a methyl group and an ethyl group. R ₁₅ can be arbitrarily selected from the above alkyl group and a hydrogen atom, but is preferably a hydrogen atom or a methyl group from the viewpoint of ease of production.

Examples of the alkyl group represented by R ₁₆ in the general formula (3) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, n -Octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-behenyl group, isopropyl group, isobutyl group, Examples thereof include linear, branched or cyclic alkyl groups such as isodecyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, cyclopentyl group and cyclohexyl group.

Examples of the aralkyl group for R ₁₆ in the general formula (3) include a benzyl group and a phenethyl group.

R ₁₆ in the general formula (3) can be arbitrarily selected from the substituents listed above, but in a non-aqueous solvent, the case where R ₁₆ has 4 or more carbon atoms has an affinity for the dispersion medium. This is preferable.

  The polymer resin unit of the present invention can control the affinity with the dispersion medium by changing the ratio of the monomer unit represented by the above formula (2) or (3).

  When the dispersion medium is a nonpolar solvent such as styrene, it is preferable to increase the proportion of the monomer unit represented by the above formula (2) from the viewpoint of affinity with the dispersion medium. In the case of a solvent having a certain degree of polarity such as an acid ester, it is preferable from the viewpoint of affinity with the dispersion medium to increase the proportion of the monomer unit represented by the above formula (3).

  The molecular weight of the polymer resin unit of the present invention is preferably such that the number average molecular weight is 500 or more in terms of improving the dispersibility of the pigment. A higher molecular weight is more effective in improving the dispersibility of the pigment, but an excessively high molecular weight is not preferable because the affinity for a water-insoluble solvent deteriorates. Accordingly, the number average molecular weight of the polymer resin unit is preferably up to 200000. In addition, considering the ease of production, the number average molecular weight of the polymer resin unit is more preferably in the range of 2,000 to 50,000.

  In addition, as disclosed in JP-A-2003-53001, a polyoxyalkylenecarbonyl-based dispersant is known in which a dispersibility is improved by introducing an aliphatic chain branched to the terminal. In the polymer resin unit of the present invention, if a telechelic polymer resin unit is synthesized by a method such as ATRP (Atom Transfer Radial Polymerization) described later, an aliphatic chain branched at the end can be introduced. Dispersibility may be improved.

  The position of the azo skeleton unit in the compound having the azo skeleton unit of the present invention may be randomly scattered, but it is more dispersible if it is unevenly distributed by forming one or more blocks at one end. The effect to improve is high.

  The greater the number of azo skeleton units in the compound having an azo skeleton unit of the present invention, the higher the affinity for the pigment. However, if the number is too large, the affinity for the water-insoluble solvent deteriorates. Accordingly, the number of azo skeleton units is preferably in the range of 1 to 10 and more preferably in the range of 1 to 5 with respect to the number of monomers 100 forming the polymer resin unit.

  The bisazo skeleton unit represented by the above formula (1) has tautomers represented by the following formulas (7) and (8) as shown in the following figure. The body is also within the scope of the present invention.

［式（７）及び（８）中のＲ₁乃至Ｒ₁₀、Ｌ₁、Ｌ₂は式（１）におけるＲ₁乃至Ｒ₁₀、Ｌ₁、Ｌ₂と各々同義である。］

[R ₁ to R _10, L _1, L ₂ in Formula (7) and (8) are each synonymous with R ₁ through R _10, L _1, L ₂ in Formula (1). ]

  The azo skeleton unit represented by the above formula (1) according to the present invention can be synthesized according to a known method. An example of a synthesis scheme up to the azo compound intermediate (13) is shown below.

［式（９）乃至（１３）中のＲ₁乃至Ｒ₁₀は、上記式（１）と同意義を表す。式（１０）中のＸ₁は脱離基を表す。式（９）及び（１３）中のＸ₂は、反応して上記式（１）における連結基Ｌ₁を形成する置換基を表す。］

[R _{1 to} R _{10 in} Formulas (9) to (13) have the same meaning as in Formula (1) above. X ₁ in the formula (10) represents a leaving group. X ₂ in the formulas (9) and (13) represents a substituent that reacts to form the linking group L ₁ in the above formula (1). ]

  In the scheme exemplified above, Step 1 of amidating an aniline derivative represented by Formula (9) and an acetoacetate analog represented by Formula (10) to synthesize an intermediate (11) that is an acetoacetanilide analog 1 The intermediate (11) and the aniline derivative (12) are diazo-coupled to synthesize the azo compound (13), thereby synthesizing the azo compound intermediate (13).

First, step 1 will be described. In Step 1, a known method can be used [eg, Datta E. Ponde, et al., “The Journal of Organic Chemistry” (USA), American Chemical Society, 1998, Vol. 63, No. 4, pages 1058-1063]. In addition, when R ₁ in formula (11) is a methyl group, it can be synthesized by a method using diketene instead of the raw material (10) [for example, Kiran Kumar Solinguram Sai, two others, “The Journal of Organic Chemistry "(USA), American Chemical Society, 2007, Vol. 72, No. 25, pages 9761-9964].

  The aniline derivative (9) and the acetoacetic acid analog (10) are each commercially available and can be easily obtained. Further, it can be easily synthesized by a known method.

  Although this step can be performed without a solvent, it is preferably performed in the presence of a solvent in order to prevent rapid progress of the reaction. The solvent is not particularly limited as long as it does not inhibit the reaction. For example, alcohols such as methanol, ethanol and propanol, esters such as methyl acetate, ethyl acetate and propyl acetate, diethyl ether and tetrahydrofuran , Ethers such as dioxane, hydrocarbons such as benzene, toluene, xylene, hexane and heptane, halogen-containing hydrocarbons such as dichloromethane, dichloroethane and chloroform, N, N-dimethylformamide, N, N-dimethylimidazolidinone Amides such as acetonitrile, nitriles such as acetonitrile and propionitrile, acids such as formic acid, acetic acid and propionic acid, water and the like. In addition, two or more of the above solvents can be used as a mixture, and the mixing ratio at the time of mixing and use can be arbitrarily determined according to the solubility of the substrate. Although the usage-amount of the said solvent can be defined arbitrarily, the range of 1.0 thru | or 20 mass times is preferable with respect to the compound represented by the said Formula (9) at the point of reaction rate.

  This step is usually performed in a temperature range of 0 ° C. to 250 ° C. and is usually completed within 24 hours.

  Next, step 2 will be described. In step 2, a known method can be used. Specifically, the method shown below is mentioned, for example. First, the corresponding diazonium salt is synthesized by reacting the aniline derivative (12) with a diazotizing agent such as sodium nitrite or nitrosylsulfuric acid in a methanol solvent in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid. Further, this diazonium salt is coupled with intermediate (11) to synthesize azo compound (13).

  The said aniline derivative (12) is marketed variously and can be obtained easily. Further, it can be easily synthesized by a known method.

  Although this step can be performed without a solvent, it is preferably performed in the presence of a solvent in order to prevent rapid progress of the reaction. The solvent is not particularly limited as long as it does not inhibit the reaction. For example, alcohols such as methanol, ethanol and propanol, esters such as methyl acetate, ethyl acetate and propyl acetate, diethyl ether and tetrahydrofuran , Ethers such as dioxane, hydrocarbons such as benzene, toluene, xylene, hexane and heptane, halogen-containing hydrocarbons such as dichloromethane, dichloroethane and chloroform, N, N-dimethylformamide, N, N-dimethylimidazolidinone Amides such as acetonitrile, nitriles such as acetonitrile and propionitrile, acids such as formic acid, acetic acid and propionic acid, water and the like. In addition, two or more of the above solvents can be used as a mixture, and the mixing ratio at the time of mixing and use can be arbitrarily determined according to the solubility of the substrate. Although the usage-amount of the said solvent can be defined arbitrarily, the range of 1.0 thru | or 20 mass times is preferable with respect to the compound represented by the said Formula (12) at the point of reaction rate.

  This step is usually performed in a temperature range of −50 ° C. to 100 ° C. and is usually completed within 24 hours.

  Examples of the method for synthesizing the compound having the azo skeleton unit represented by the above formula (1) from the obtained bisazo compound intermediate (13) include the methods shown in the following (i) to (ii). .

  First, the method (i) will be described in detail with a scheme shown below.

［式（１３）乃至（１５）中のＲ₁乃至Ｒ₁₀は、上記式（１）と同意義を表す。式（１３）及び（１４）中のＸ_2、Ｘ₃は、反応して上記式（１）における連結基Ｌ₁を形成する置換基を表す。式（１４）及び（１５）中のＸ₄は反応して上記式（１）における連結基Ｌ₂を形成する置換基を表す。Ｐ₁は、少なくとも上記式（２）もしくは（３）で表される単量体単位のいずれか、もしくは両方を有する高分子樹脂ユニットを表す。］

[R _{1 to} R _{10 in} Formulas (13) to (15) are as defined above in Formula (1). X _{2 and} X ₃ in the formulas (13) and (14) represent a substituent that reacts to form the linking group L ₁ in the formula (1). X ₄ in the formulas (14) and (15) represents a substituent which reacts to form the linking group L ₂ in the above formula (1). P ₁ represents a polymer resin unit having at least _one of the monomer units represented by the above formula (2) or (3) or both. ]

First, step 3 will be described. In step 3, a known method can be used. Specifically, for example, by using an azo compound (13) in which X ₂ is a substituent having an amino group and a raw material in which X ₃ in formula (14) is a substituent having a carboxyl group, the linking group L An azo skeleton unit represented by the above formula (1) in which ₁ has a —NH—CO— bond can be synthesized. Further, by using the azo compound (13) in which X ₂ is a substituent having a hydroxyl group and a raw material in which X ₃ in the formula (14) is a substituent having a carboxyl group, the linking group L ₁ is —O—. An azo skeleton unit represented by the above formula (1) having a CO-bond can be synthesized. Further, by using the azo compound (13) in which X ₂ is a substituent having a carboxyl group and a raw material in which X ₃ in the formula (14) is a substituent having a hydroxyl group, the linking group L ₁ is —CO—. An azo skeleton unit represented by the above formula (1) having an O-bond can be synthesized. Further, by using the azo compound (13) in which X ₂ is a substituent having a carboxyl group and a raw material in which X ₃ in the formula (14) is a substituent having an amino group, the linking group L ₁ is —CO—. An azo skeleton unit represented by the above formula (1) having an NH-bond can be synthesized. Further, the azo compound (13) in which X ₂ is a substituent having —O—C ₂ H ₄ —OH and a raw material in which X ₃ in the formula (14) is a substituent having a carboxyl group are linked. The azo skeleton unit represented by the above formula (1) in which the group L ₁ has a —O—C ₂ H ₄ —O—CO— bond can be synthesized. Specifically, a method using a dehydrating condensing agent such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (for example, Melvin S. Newman, et al., “The Journal of Organic Chemistry”). ", (USA), American Chemical Society, 1961, Vol. 26, No. 7, p. 2525-2528), the Schotten-Baumann method (e.g. Norman O. V. Sontag," Chemical Reviews ", (USA)). , American Chemical Society, 1953, Vol. 52, No. 2, p. 237-416).

Further, the linking group L ₁ is —NH— by using an azo compound (13) in which X ₂ is a substituent having an amino group and a raw material in which X ₃ in the formula (14) is a substituent having an isocyanate group. An azo skeleton unit represented by the above formula (1) having a CO—NH— bond can be synthesized. Further, the linking group L ₁ is —O— by using an azo compound (13) in which X ₂ is a substituent having a hydroxyl group and a raw material in which X ₃ in the formula (14) is a substituent having an isocyanate group. An azo skeleton unit represented by the above formula (1) having a CO—NH— bond can be synthesized. Specific examples of the method using these isocyanate groups include a method using an amine catalyst such as triethylamine.

  Although this step can be performed without a solvent, it is preferably performed in the presence of a solvent in order to prevent rapid progress of the reaction. The solvent is not particularly limited as long as it does not inhibit the reaction. For example, ethers such as diethyl ether, tetrahydrofuran and dioxane, hydrocarbons such as benzene, toluene, xylene, hexane and heptane, dichloromethane Halogen-containing hydrocarbons such as dichloroethane and chloroform, amides such as N, N-dimethylformamide and N, N-dimethylimidazolidinone, and nitriles such as acetonitrile and propionitrile. Moreover, the said solvent can be used in mixture of 2 or more types according to the solubility of a board | substrate, The mixing ratio in the case of mixing use can be defined arbitrarily. Although the usage-amount of the said solvent can be defined arbitrarily, the range of 1.0 thru | or 20 mass times is preferable with respect to the compound represented with the said General formula (13) at the point of reaction rate.

  This step is usually performed in a temperature range of 0 ° C. to 250 ° C. and is usually completed within 24 hours.

Next, a method for synthesizing the polymer resin unit P ₁ used in step 4 will be described. In the synthesis of the polymer resin unit P ₁ , a known polymerization method can be used [for example, Krzysztof Matyjazewski, et al., “Chemical Reviews” (USA), American Chemical Society, 2001, 101, 2921-90. ].

  Specific examples include radical polymerization, cationic polymerization, and anionic polymerization. From the viewpoint of ease of production, radical polymerization is preferably used.

  The radical polymerization can be performed by using a radical polymerization initiator, irradiation with radiation, laser light, or the like, combined use of a photopolymerization initiator and light, heating, or the like.

  The radical polymerization initiator is not particularly limited as long as it can generate radicals and initiate a polymerization reaction, and is selected from compounds that generate radicals by the action of heat, light, radiation, redox reaction, and the like. For example, an azo compound, an organic peroxide, an inorganic peroxide, an organometallic compound, a photopolymerization initiator, and the like can be given. More specifically, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethyl) Valeronitrile), azo polymerization initiators such as 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxyisopropyl carbonate, tert-to Organic peroxide polymerization initiators such as xylperoxybenzoate and tert-butylperoxybenzoate, inorganic peroxide polymerization initiators such as potassium persulfate and ammonium persulfate, hydrogen peroxide-ferrous iron, peroxide Examples thereof include redox initiators such as benzoyl-dimethylaniline and cerium (IV) salt-alcohol. Examples of the photopolymerization initiator include benzophenone series, benzoin series, acetophenone series, and thioxanthone series. These radical polymerization initiators may be used in combination of two or more.

  The amount of the polymerization initiator used here is in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the monomer, and the amount is adjusted so that a copolymer having a target molecular weight distribution can be obtained. It is preferable to do this.

The polymer resin unit represented by P ₁ can be produced by any method such as solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, etc., and is particularly limited. However, solution polymerization in a solvent capable of dissolving each component used in production is preferred. Specifically, for example, alcohols such as methanol, ethanol and 2-propanol, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and diethyl ether, ethylene glycol monoalkyl ethers, or acetates thereof, propylene glycol Polar organic solvents such as monoalkyl ethers or their acetates and diethylene glycol monoalkyl ethers, and nonpolar solvents such as toluene and xylene may be used alone or in admixture. Among these, it is more preferable to use a solvent having a boiling point of 100 to 180 ° C. alone or in combination.

  The preferred range of the polymerization temperature varies depending on the type of radical polymerization reaction. Specifically, polymerization is generally performed in a temperature range of −30 to 200 ° C., and a more preferable temperature range is 40 to 180 ° C.

The polymer resin unit represented by P ₁ can control the molecular weight distribution and the molecular structure using a known method. Specifically, for example, a method using an addition-cleavage type chain transfer agent (see Japanese Patent No. 4254292 and Japanese Patent No. 0372617), an NMP method using amine oxide radical dissociation and bonding [for example, Craig J . Hawker, et al., “Chemical Reviews” (USA), American Chemical Society, 2001, Vol. 101, pages 3661-3688], an ATRP method in which a halogen compound is used as a polymerization initiator and polymerization is performed using a heavy metal and a ligand. [For example, Masami Kamigaito, two others, “Chemical Reviews” (USA), American Chemical Society, 2001, Vol. 101, pages 3687-3746], dithiocarboxylic acid ester, xanthate compound, etc. are used as polymerization initiators. RAFT method (for example, Japanese translations of PCT publication No. 2000-515181), MADIX method (for example, WO99 / 05099 pamphlet), DT method [for example, Atsushi G oto, et al., “Journal of The American. Chemical. Society” (USA), American Chemical Society, 2003, Vol. 125, pages 8720-8721], etc. are used to control molecular weight distribution and molecular structure. The polymer resin unit can be manufactured.

Next, step 4 will be described. In step 4, a known method can be used. Specifically, for example, by using a polymer resin unit P ₁ having a carboxyl group and a raw material in which X ₄ in the formula (14) is a substituent having an amino group, the linking group L ₂ is bonded to a carboxylic acid amide bond. It is possible to synthesize a compound having an azo dye skeleton unit represented by the above formula (1). Further, by using a polymer resin unit P ₁ having a carboxyl group and a raw material in which X ₄ in the formula (14) is a substituent having a hydroxyl group, the linking group L ₂ has the above-described formula ( A compound having an azo dye skeleton unit represented by 1) can be synthesized. Specifically, a compound having an azo dye skeleton unit can be synthesized using the same method as in Step 3 above.

  Next, the method (ii) will be described in detail with the scheme shown below.

［式（１３）中のＲ₁乃至Ｒ₁₀は、上記式（１）と同意義を表す。式（１３）乃至（１８）中のＸ_2、Ｘ₃は、反応して上記式（１）における連結基Ｌ₁を形成する置換基を表す。式（１４）及び（１６）中のＸ₄、Ｘ₅は反応して上記式（１）における連結基Ｌ₂を形成する置換基を表す。式（１６）及び式（１７）中のＡは、塩素原子、臭素原子、ヨウ素原子を有する置換基、もしくは重合性基を有する置換基を表す。Ｐ₁は、少なくとも上記式（２）もしくは（３）で表される単量体単位のいずれか、もしくは両方を有する高分子樹脂ユニットを表す。ｎは整数を表す。］

[R _{1 to} R _{10 in} Formula (13) represent the same meaning as in Formula (1) above. X _{2 and} X ₃ in the formulas (13) to (18) represent a substituent that reacts to form the linking group L ₁ in the formula (1). X ₄ and X _{5 in the} formulas (14) and (16) represent a substituent that reacts to form the linking group L ₂ in the formula (1). A in Formula (16) and Formula (17) represents a substituent having a chlorine atom, a bromine atom or an iodine atom, or a substituent having a polymerizable group. P ₁ represents a polymer resin unit having at least _one of the monomer units represented by the above formula (2) or (3) or both. n represents an integer. ]

In the scheme exemplified above, Step 6 in which the raw material (14) and the raw material (16) are esterified or amidated to synthesize the intermediate (17), A in the intermediate (17) is used as an initiator, or Step 7 for polymerizing intermediate polymer resin unit (18) having either or both of the monomer units represented by formula (2) or (3) as a monomer, X _{2 in} formula (13) And X ₃ in the formula (18) react to form a linking group L ₂ to synthesize a compound having an azo dye skeleton unit.

  First, step 6 will be described. In step 6, intermediate (17) can be synthesized using the same method as in step 4 of method (i) above.

Specifically, for example, by using a compound (14) in which X ₄ is a substituent having an amino group and X ₅ is a carboxylic acid derivative (16), an intermediate in which the linking group L ₂ has a carboxylic acid amide bond. (17) can be synthesized. Further, by using the compound (14) in which X ₄ is a substituent having a hydroxyl group and X ₅ is a carboxylic acid derivative (16), an intermediate (17) in which the linking group L ₂ has a carboxylic acid ester bond is obtained. Can be synthesized. Further, by using the compound (14) in which X ₄ is a substituent having a carboxyl group or an acid derivative group thereof and X ₅ is an alcohol derivative (16), an intermediate in which the linking group L ₂ has a carboxylic acid ester bond. (17) can be synthesized.

  Examples of the carboxylic acid derivative (16) include chloroacetic acid, α-chloropropionic acid, α-chlorobutyric acid, α-chloroisobutyric acid, α-chlorovaleric acid, α-chloroisovaleric acid, α-chlorocaproic acid, α- Chlorophenylacetic acid, α-chlorodiphenylacetic acid, α-chloro-α-phenylpropionic acid, α-chloro-β-phenylpropionic acid, bromoacetic acid, α-bromopropionic acid, α-bromobutyric acid, α-bromoisobutyric acid, α- Bromovaleric acid, α-bromoisovaleric acid, α-bromocaproic acid, α-bromophenylacetic acid, α-bromodiphenylacetic acid, α-bromo-α-phenylpropionic acid, α-bromo-β-phenylpropionic acid, iodoacetic acid , Α-iodopropionic acid, α-iodobutyric acid, α-iodoisobutyric acid, α-iodovaleric acid, α-iodoisovaleric acid, α-iodo Proic acid, α-iodophenylacetic acid, α-iododiphenylacetic acid, α-iodo-α-phenylpropionic acid, α-iodo-β-phenylpropionic acid, β-chlorobutyric acid, β-bromoisobutyric acid, iododimethylmethylbenzoic acid And halogen atom-containing compounds such as 1-chloroethylbenzoic acid, and polymerizable group-containing compounds such as acrylic acid, methacrylic acid, vinylbenzoic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. In the present invention, acid halides and acid anhydrides of these carboxylic acid derivatives can be used in the same manner.

  Examples of the alcohol derivative (16) include 1-chloroethanol, 1-bromoethanol, 1-iodoethanol, 1-chloropropanol, 2-bromopropanol, 2-chloro-2-propanol, 2-bromo-2- Examples include halogen atom-containing compounds such as methylpropanol, 2-phenyl-1-bromoethanol and 2-phenyl-2-iodoethanol, and polymerizable group-containing compounds such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. .

Next, step 7 will be described. In step 7, the polymer resin unit represented by the formula (18) can be synthesized using the same method as the synthesis of the polymer resin unit P _{1 in} the method (i).

  Next, step 8 will be described. In step 8, a known method can be used. Specifically, a compound having an azo dye skeleton unit can be synthesized using the same method as in step 3 of the above method (i).

  The compounds represented by the above formulas (1), (11), (13), (15), (17), and (18) obtained in each step use ordinary organic compound isolation and purification methods. be able to. Examples of isolation and purification methods include recrystallization methods and reprecipitation methods using organic solvents, column chromatography using silica gel, and the like. By purifying these methods alone or in combination of two or more, it can be obtained with high purity.

  The compounds represented by the above formulas (11), (13), (15), and (17) obtained in the above steps are analyzed by nuclear magnetic resonance spectroscopy [ECA-400, manufactured by JEOL Ltd.], ESI. -Identification and quantification were performed by TOF MS (LC / MSD TOF, manufactured by Agilent Technologies) and HPLC analysis [LC-20A, manufactured by Shimadzu Corporation].

  The compounds represented by the above formulas (1) and (18) obtained in the above steps are high-speed GPC [HLC8220GPC, manufactured by Tosoh Corporation], nuclear magnetic resonance spectroscopy [ECA-400, JEOL Ltd. The product was identified and quantified by acid value measurement [automatic titration measuring device COM-2500, manufactured by Hiranuma Sangyo Co., Ltd.] based on JIS K-0070.

  Next, the pigment dispersant and pigment composition of the present invention will be described. The compound having an azo dye skeleton unit represented by the above formula (1) of the present invention has a high affinity with an azo pigment, particularly an acetoacetanilide pigment, and also has a high affinity with a water-insoluble solvent. The pigment dispersant can be used alone or in combination of two or more.

  The pigment composition of the present invention is used in paints, inks, resin molded articles and the like, and contains at least one compound having a azo dye skeleton unit represented by the above formula (1) according to the present invention as a pigment dispersant. It is characterized by that.

  Examples of the pigment that can be used in the present invention include monoazo pigments, bisazo pigments, and polyazo pigments. Among them, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 175, C.I. I. An acetoacetanilide pigment typified by Pigment Yellow 180 has a stronger affinity with the pigment dispersant of the present invention. In particular, C.I represented by the following formula (6): I. Pigment Yellow 155 is more preferable because the dispersion effect of the polyester having the bisazo dye skeleton unit of the present invention is high. The above pigments may be used alone or in combination of two or more.

  In addition, as a pigment which can be used for this invention, even if it is a pigment other than the above yellow pigments, if it is a pigment with affinity with the pigment dispersant of this invention, it can be used conveniently and is not limited.

  For example, C.I. I. Pigment Orange 1, C.I. I. Pigment Orange 5, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 15, C.I. I. Pigment Orange 16, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 36, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 62, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 67, C.I. I. Pigment Orange 72, C.I. I. Pigment Orange 74, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 4, C.I. I. Pigment Red 5, C.I. I. Pigment Red 12, C.I. I. Pigment Red 16, C.I. I. Pigment Red 17, C.I. I. Pigment Red 23, C.I. I. Pigment Red 31, C.I. I. Pigment Red 32, C.I. I. Pigment Red 41, C.I. I. Pigment Red 17, C.I. I. Pigment Red 48, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 53: 1, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 112, C.I. I. Pigment Red 144, C.I. I. Pigment Red 146, C.I. I. Pigment Red 166, C.I. I. Pigment Red 170, C.I. I. Pigment Red 176, C.I. I. Pigment Red 185, C.I. I. Pigment Red 187, C.I. I. Pigment Red 208, C.I. I. Pigment Red 210, C.I. I. Pigment Red 220, C.I. I. Pigment Red 221, C.I. I. Pigment Red 238, C.I. I. Pigment Red 242, C.I. I. Pigment Red 245, C.I. I. Pigment Red 253, C.I. I. Pigment Red 258, C.I. I. Pigment Red 266, C.I. I. Pigment Red 269, C.I. I. Pigment Violet 13, C.I. I. Pigment Violet 25, C.I. I. Pigment Violet 32, C.I. I. Pigment Violet 50, C.I. I. Pigment Blue 25, C.I. I. Pigment Blue 26, C.I. I. Pigment Brown 23, C.I. I. Pigment Brown 25, C.I. I. And azo pigments such as Pigment Brown 41.

  These may be crude pigments, or may be prepared pigment compositions as long as they do not significantly inhibit the effect of the pigment dispersant of the present invention.

  The mass composition ratio of the pigment to the pigment dispersant in the pigment composition of the present invention is preferably in the range of 100: 1 to 100: 100. More preferably, it is a range of 100: 5 to 100: 50 in terms of pigment dispersibility.

  The pigment composition of the present invention can be produced by a wet method or a dry method. Considering that the compound having an azo dye skeleton unit of the present invention has high affinity with a water-insoluble solvent, wet-type production capable of easily producing a uniform pigment composition is preferred. Specifically, for example, it is obtained as follows. The pigment dispersant and, if necessary, the resin are dissolved in the dispersion medium, and the pigment powder is gradually added while stirring to fully adjust the dispersion medium. Furthermore, the pigment can be stably finely dispersed into uniform fine particles by applying mechanical shearing force with a disperser such as a kneader, roll mill, ball mill, paint shaker, dissolver, attritor, sand mill, or high speed mill.

  The dispersion medium that can be used in the pigment composition of the present invention is determined according to the intended use of the pigment composition, and is not particularly limited, but is a compound having an azo dye skeleton unit of the above formula (1) of the present invention. In order to obtain a high pigment dispersion effect, the dispersion medium is preferably a water-insoluble solvent. Here, the water-insoluble solvent refers to a solvent that does not dissolve in water or a solvent that dissolves in water at 25 ° C. in an amount of 30% by mass or less based on the mass of water. Specific examples of the water-insoluble solvent include esters such as methyl acetate, ethyl acetate, propyl acetate, hexane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, petroleum ether, cyclohexane, benzene, Isopar E, Isopar G, Isopar H, Isopar L, Isopar M, Isopar V, Shellsol A100, Shellsol A150 manufactured by Shell Chemicals Japan Co., Ltd., etc. Hydrocarbons, halogen-containing hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, trichloroethylene, tetrabromoethane, methyl ethyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, cyclohexanone, etc. Ketones, ethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, diethylene glycol monobutyl ether acetate, glycol ether esters such as propylene glycol monomethyl ether acetate.

  The dispersion medium that can be used in the pigment composition of the present invention may be a polymerizable monomer. Specifically, styrene, α-methylstyrene, α-ethylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4- Dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinyl bromide, vinyl iodide, vinyl acetate, vinyl propionate, vinyl benzoate, methyl methacrylate , Ethyl methacrylate, propyl methacrylate, butyl methacrylate, Methacrylic acid-n-octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, behenyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methyl acrylate, ethyl acrylate, acrylic Acid-n-butyl, isobutyl acrylate, propyl acrylate, acrylate-n-octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, behenyl acrylate, 2-chloroethyl acrylate, phenyl acrylate , Vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, vinyl naphthalene, acrylonitrile Methacrylonitrile, it can be mentioned acrylamide.

  The resin that can be used in the pigment composition of the present invention is determined according to the intended use of the pigment composition and is not particularly limited. Specifically, for example, polystyrene resin, styrene copolymer, polyacrylic acid resin, polymethacrylic acid resin, polyacrylic acid ester resin, polymethacrylic acid ester resin, acrylic acid ester copolymer, methacrylic acid ester copolymer , Polyester resin, polyvinyl ether resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Other examples include polyurethane resins and polypeptide resins. Two or more of these dispersion media can be mixed and used. The pigment composition produced by the method of the present invention can be isolated by a known method such as filtration, decantation or centrifugation. The solvent can also be removed by washing.

  The pigment composition of the present invention may further contain an auxiliary agent during production. Specifically, for example, surface active agents, pigments and non-pigment dispersants, fillers, standardizers, resins, waxes, antifoaming agents, antistatic agents, dustproofing agents, extenders, dark colorants ( shading colorants), preservatives, drying inhibitors, rheology control additives, wetting agents, antioxidants, UV absorbers, light stabilizers, or combinations thereof. Further, the pigment dispersant of the present invention may be added in advance during the production of the crude pigment.

  Next, the pigment dispersion of the present invention will be described. The pigment dispersion of the present invention comprises the above pigment composition and a water-insoluble solvent. The pigment composition may be dispersed in a water-insoluble solvent, or each component of the pigment composition may be dispersed in a water-insoluble solvent. Specifically, for example, it is obtained as follows. If necessary, the pigment dispersant and the resin are dissolved in the water-insoluble solvent, and the pigment or the pigment composition powder is gradually added while stirring, so that the water-insoluble solvent is sufficiently blended. Further, by applying mechanical shearing force with a dispersing machine such as a ball mill, paint shaker, dissolver, attritor, sand mill, or high speed mill, the pigment can be stably finely dispersed into uniform fine particles.

  The water-insoluble solvent that can be used in the pigment dispersion of the present invention is determined according to the intended use of the pigment dispersion and is not particularly limited. Here, the water-insoluble solvent refers to a solvent that does not dissolve in water or a solvent that dissolves in water at 25 ° C. in an amount of 30% by mass or less based on the mass of water. Specifically, for example, esters such as methyl acetate, ethyl acetate, propyl acetate, hexane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, petroleum ether, cyclohexane, benzene, toluene, xylene, mineral Isopar E, Isopar G, Isopar H, Isopar L, Isopar L, Isopar M, Isopar V, manufactured by Spirit, ExxonMobil, Inc., hydrocarbons such as Shellsol A100 and Shellsol A150 manufactured by Shell Chemicals Japan, chloroform , Halogen-containing hydrocarbons such as carbon tetrachloride, dichloroethane, trichloroethylene and tetrabromoethane, ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone and cyclohexanone, ethylene Recall monobutyl ether acetate, 3-methoxybutyl acetate, diethylene glycol monobutyl ether acetate, glycol ether esters such as propylene glycol monomethyl ether acetate.

  The water-insoluble solvent that can be used in the pigment dispersion of the present invention may be a polymerizable monomer. Specifically, styrene, α-methylstyrene, α-ethylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4- Dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, Styrene monomers such as pn-decyl styrene and pn-dodecyl styrene, olefin monomers such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinyl bromide, vinyl iodide, etc. Vinyl esters such as vinyl halides, vinyl acetate, vinyl propionate, vinyl benzoate, etc. , Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, -n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, behenyl methacrylate, phenyl methacrylate, dimethyl methacrylate Methacrylate monomers such as aminoethyl, diethylaminoethyl methacrylate, methacrylonitrile, methyl acrylate, ethyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid propyl, acrylic acid-n-octyl, acrylic Acrylates such as dodecyl acid, 2-ethylhexyl acrylate, stearyl acrylate, behenyl acrylate, 2-chloroethyl acrylate, acrylonitrile, acrylamide, phenyl acrylate, etc. DOO monomers, vinyl methyl ether, vinyl ethyl ether, vinyl ethers such as vinyl isobutyl ether, vinyl methyl ketone, vinyl hexyl ketone, may be mentioned vinyl ketone compounds such as methyl isopropenyl ketone. These can be used alone or in combination of two or more according to the intended use.

  The water-insoluble solvent used in the pigment dispersion of the present invention may contain an organic solvent that can be mixed with the water-insoluble solvent, if necessary, for improving pigment dispersibility. Examples of the organic solvent that can be used include alcohols such as methanol, ethanol, propanol, and phenol, or phenols, ketones such as acetone, ethers such as diethyl ether, dipropyl ether, tetrahydrofuran, and dioxane, and ethylene glycol monoethyl ether. And glycol ethers such as diethylene glycol monoethyl ether, aliphatic carboxylic acids such as acetic acid, 2-ethylhexanoic acid and acetic anhydride, or acid anhydrides thereof. These solvents can be used alone or in combination of two or more.

  The resin that can be used in the pigment dispersion of the present invention is determined according to the intended use of the pigment composition and is not particularly limited. Specifically, for example, polystyrene resin, styrene copolymer, polyacrylic acid resin, polymethacrylic acid resin, polyacrylic acid ester resin, polymethacrylic acid ester resin, acrylic acid ester copolymer, methacrylic acid ester copolymer , Polyester resin, polyvinyl ether resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Other examples include polyurethane resins and polypeptide resins. Two or more of these resins can be mixed and used.

  Next, the ink of the present invention will be described.

  The pigment dispersion of the present invention is suitable as a colorant for ink. By using the pigment dispersion of the present invention, an ink having good dispersibility of the pigment is provided.

  The ink of the present invention may contain an organic solvent that can be mixed with the water-insoluble solvent used in the pigment dispersion, if necessary, in order to adjust the surface tension and viscosity. Examples of the organic solvent that can be used include alcohols such as methanol, ethanol, propanol, and phenol, or phenols, ketones such as acetone, ethers such as diethyl ether, dipropyl ether, tetrahydrofuran, and dioxane, and ethylene glycol monoethyl ether. And glycol ethers such as diethylene glycol monoethyl ether, aliphatic carboxylic acids such as acetic acid, 2-ethylhexanoic acid and acetic anhydride, or acid anhydrides thereof. These solvents can be used alone or in combination of two or more.

  As the colorant for the ink used in the present invention, the pigment dispersion shown in the present invention is necessarily used. However, as long as the dispersibility of the pigment dispersion of the present invention is not hindered, the above-mentioned pigment dispersion and other colorants are used. An agent can be used in combination.

  Examples of the colorant that can be used in combination include various compounds such as condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and compounds represented by allylamide compounds. Specifically, examples of the yellow pigment include C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 62, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 97, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 111, C.I. I. Pigment Yellow 120, C.I. I. Pigment Yellow 127, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 168, C.I. I. Pigment Yellow 174, C.I. I. Pigment Yellow 176, C.I. I. Pigment Yellow 181, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 191, C.I. I. Pigment Yellow 194, C.I. I. Pigment Yellow 213, C.I. I. Pigment Yellow 214, C.I. I. Bat Yellow 1, 3, 20, Mineral Fast Yellow, Navel Yellow, Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NCG, C.I. I. Solvent Yellow 9, C.I. I. Solvent Yellow 17, C.I. I. Solvent Yellow 24, C.I. I. Solvent Yellow 31, C.I. I. Solvent Yellow 35, C.I. I. Solvent Yellow 58, C.I. I. Solvent Yellow 93, C.I. I. Solvent Yellow 100, C.I. I. Solvent Yellow 102, C.I. I. Solvent Yellow 103, C.I. I. Solvent Yellow 105, C.I. I. Solvent Yellow 112, C.I. I. Solvent Yellow 162, C.I. I. Solvent Yellow 163 or the like can be used.

  Examples of red pigments include C.I. I. Pigment Red 9, C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 146, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 216, C.I. I. Pigment Red 224, C.I. I. Pigment Red 226, C.I. I. Pigment Red 242, C.I. I. Examples of green pigments such as CI Pigment Red 254 include C.I. I. Pigment Green 7, C.I. I. Examples of blue pigments such as CI Pigment Green 36 and poly (12 to 16) bromophthalocyanine green include C.I. I. Pigment Blue -15: 3, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 60 and the like, purple pigments include C.I. I. Pigment Violet 19, C.I. I. Pigment Violet 23 or the like can be used.

  Furthermore, in the case of using ink, in addition to the above components, as necessary, a plasticizer, a surfactant, a viscosity modifier, an antifoaming agent, an ultraviolet absorber, a rust inhibitor, an antioxidant, and a reduction inhibitor. Further, various additives such as an evaporation accelerator and a chelating agent may be contained.

  In addition, since the ink of the present invention has good dispersibility and color tone of the pigment, it can be used as a color filter ink by using a color filter resist composition described later.

  Next, the color filter resist composition of the present invention will be described.

  The pigment dispersion of the present invention is suitable as a colorant for a color filter resist composition containing at least a binder resin and a colorant. By using the pigment dispersion of the present invention, it is possible to provide a color filter resist composition that maintains good dispersibility of the pigment and is excellent in color characteristics.

  In a color filter in which two or more kinds of pixels having different spectral characteristics are arranged adjacent to each other on a substrate, the pigment dispersion of the present invention is applied to at least one of the plurality of pixels (for example, red, green, and blue). By using the body, highly transparent and high color purity pixels can be obtained. In particular, the color filter resist composition has excellent color characteristics when used as a colorant for toning green and red pixels. Is provided.

  Binder resins that can be used in the color filter resist composition of the present invention include known non-reactive random copolymers, block copolymers, graft copolymers, copolymers having reactive groups, and reactivity. Examples thereof include a medium molecular weight oligomer having a group, a monomer having a reactive group, or a polymer containing a crosslinking agent. The reactive group is determined by the curing method of the colored ink, but is a known methylol group, isocyanate group, epoxy group, oxetane group, vinyl group, acryloyl group, methacryloyl group, hydroxyl group, carboxyl group, amino group, imino group and Examples thereof include reactive derivatives thereof.

  Examples of the monomer constituting the heat-drying type or heat-crosslinking type polymer include alkyl esters, cycloalkyl esters, and alkyl cycloalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as acrylic acid and methacrylic acid. , Aromatic vinyl monomers such as ethylene, propylene, butylene, isobutylene, butadiene, isoprene, styrene, α-methylstyrene, vinylnaphthalene, and the like, and the macromonomer having a hydrophobic molecular chain as described above And a macromonomer in which an α, β-ethylenically unsaturated group is bonded to a single or copolymer chain of a monomer having a hydrophobic group.

  The reactive monomer constituting the heat-drying type or heat-crosslinking type polymer includes acrylic acid having a carboxyl group, methacrylic acid, maleic acid, 2-hydroxyalkyl acrylate having a hydroxyl group, 2-hydroxyalkyl methacrylate, Glycidyl acrylate having an epoxy group, glycidyl methacrylate, N-methylol acrylamide having a methylol group, N-methylol methacrylamide, N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, N-methylol melamine, N-methylol benzoguanamine, silane group Γ-methacryloxypropyltrimethoxysilane having an isocyanate group, isocyanate ethyl acrylate having an isocyanate group, isocyanate ethyl methacrylate, 2- (p- Seo propenylphenyl) propyl (-2) isocyanate. As the macromonomer having a molecular chain having a group that reacts with a crosslinking agent, the above-mentioned reactive monomer (co) polymer chain or reactive monomer and the above-mentioned hydrophobic monomer are co-polymerized. And a macromonomer having an α, β-ethylenically unsaturated group bonded to the polymer chain.

  Examples of crosslinking agents include trimethylolpropane polyglycidyl ether having an epoxy group, pentaerythritol polyglycidyl ether, methoxymethylolated melamine having a methylol group, butoxymethylol melamine, methoxymethylol benzoguanamine, and poly (hexamethylenecarbodiimide) diisocyanate having a carbodiimide group. Is a urethane reaction product of bismonomethoxypolyethylene glycol and polyoxyethylene sorbite monolaurate, polybranched polycarbodiimide, trimethylolpropane-tris having an isocyanate group (tolylene diisocyanate adduct), trimethylolpropane-tris ( Hexamethylene diisocyanate adduct) phenolic phenolic mask isocyanate It is below.

  The binder resin in the ultraviolet radical curable type, the photo cationic polymerization type, the electron beam curable type, and the thermal polymerization type ink is a known monomer having an unsaturated double bond or a polymerizable cyclic ether group having addition polymerization or addition crosslinkability. Bodies, oligomers and polymers are used.

  Examples of the above addition polymerizable oligomer and polyfunctional monomer include urethane acrylates such as (polytetramethylene glycol-hexamethylene diisocyanate polyurethane) -bisacrylate, bisphenol A epoxy resin-bisacrylate, and phenol novolac epoxy resin. -Epoxy acrylates such as polyacrylate, poly (hexylene isophthalate) -bisacrylate, (trimethylolpropane-adipic acid-based polyester) -polyacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, tricyclodecanedi Methanol diacrylate, diacrylate of bisphenol A-ethylene oxide adduct, trimethylolpropane triacrylate, pentaerythritol Triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like.

  Examples of the alicyclic diepoxy compound include 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate and limonene dioxide, and examples of the oxatene compound include oxaten alcohol, dioxetane, and phenyl. Examples include oxetane, xylylene oxetane, and 2-ethylhexyl oxetane. Examples of the vinyl ether compound include triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, and the like.

  When the resist composition for a color filter of the present invention is an ultraviolet radical curable type, a photocationic polymerization type, an electron beam curable type, or a thermal polymerization type, it is configured to contain an initiator. The initiator that can be used in the color filter resist composition of the present invention is not particularly limited. Examples of the photopolymerization initiator include 1-hydroxycyclohexyl-phenyl ketone, 2,2-dimethoxy- 1,2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1 -Propan-1-one, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, bisacylphosphine oxide, benzoin Tyl ether, benzoin isobutyl ether, benzoin isopropyl ether, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2- (3-dimethylamino-2-hydroxypropoxy) -3,4-dimethyl-9H-thioxanthone-9-one meso Chloride, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyl-diphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl), ethyl p-dimethylaminobenzoate Ester, p-dimethylaminobenzoic acid isoamyl ester, 1,3,5-triacroylhexahydro-s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (Trichloromethyl) -s-tria , 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, methyl benzoylformate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Examples of polymerization initiators include triarylsulfonium salts and aryliodonium salts, sensitizers include 1-chloro-4-propoxythioxanthone, and thermal polymerization initiators include azobisisobutyronitrile and azobiscyanoisovaleric acid. , Dimethyl 2,2′-azobisisobutyrate and the like.

  In order to dissolve or disperse the binder resin, polymerization initiator, colorant and the like satisfactorily, the color filter resist composition of the present invention contains an organic solvent that can be mixed with the water-insoluble solvent used in the pigment dispersion as necessary. It can also be contained. Examples of the organic solvent that can be used include alcohols such as methanol, ethanol, propanol, and phenol, or phenols, ketones such as acetone, ethers such as diethyl ether, dipropyl ether, tetrahydrofuran, and dioxane, and ethylene glycol monoethyl ether. And glycol ethers such as diethylene glycol monoethyl ether, aliphatic carboxylic acids such as acetic acid, 2-ethylhexanoic acid and acetic anhydride, or acid anhydrides thereof. These solvents can be used alone or in combination of two or more.

  Further, when the color filter resist composition of the present invention is applied to a glass substrate, a colored film glass is formed by adding a silane coupling agent having a reactive organic functional group to the composition. Adhesion to the substrate is improved, and excellent coating performance can be brought about. As these compounds, known silane coupling agents are used. Examples of reactive organic functional groups include silane coupling agents having an epoxy group, thiol group, hydroxyl group, amino group, ureido group, vinyl group, acryloyl group, and the like. Specifically, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- ( Aminoethyl) -γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane and the like.

  As described above, since the color filter resist composition of the present invention is configured to contain the pigment dispersion of the present invention as a colorant, the color filter that maintains good pigment dispersibility and has excellent color characteristics. A resist composition can be provided.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example and a comparative example, this invention is not limited to the following Example, unless the summary is exceeded. In the following description, “parts” and “%” are based on mass unless otherwise specified.

  The measurement method used in this example is shown below.

(1) Molecular weight measurement The molecular weight of the compound having the polymer resin unit and the azo dye skeleton unit used in the present invention is calculated in terms of polystyrene by size exclusion chromatography (SEC). Measurement of molecular weight by SEC was performed as follows.

The sample was added to the eluent below so that the sample concentration was 1.0% by mass, and the solution that was allowed to stand at room temperature for 24 hours was filtered through a solvent-resistant membrane filter with a pore diameter of 0.2 μm as the sample solution. The measurement was performed under the following conditions.
Device: High-speed GPC device "HLC-8220GPC" [manufactured by Tosoh Corporation]
Column: Double eluent of LF-804: THF
Flow rate: 1.0 ml / min
Oven temperature: 40 ° C
Sample injection volume: 0.25 ml

  In calculating the molecular weight of the sample, standard polystyrene resin [TSO Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, manufactured by Tosoh Corporation] F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500] were used.

(2) Acid value measurement The acid value of the compound having a polymer resin unit and an azo dye skeleton unit in the present invention is determined by the following method.

Basic operation is based on JIS K-0070.
1) Weigh accurately 0.5 to 2.0 g of sample. The mass at this time is defined as W (g).
2) Put the sample in a 50 ml beaker, and add 25 ml of a tetrahydrofuran / ethanol (2/1) mixture to dissolve.
3) Titration is performed using a 0.1 mol / l ethanol solution of KOH and a potentiometric titration measuring device [for example, an automatic titration measuring device “COM-2500” manufactured by Hiranuma Sangyo Co., Ltd. can be used. ].
4) The amount of KOH solution used at this time is S (ml). At the same time, a blank is measured, and the amount of KOH used at this time is defined as B (ml).
5) Calculate the acid value according to the following formula. f is a factor of the KOH solution.

(3) Composition analysis The structure of the polymer resin unit and the compound having an azo dye skeleton unit in the present invention was determined using the following apparatus.
¹ H NMR
ECA-400 manufactured by JEOL Ltd. (solvent heavy chloroform)

[Example 1]
The polymer resin unit represented by P ₁ was obtained by the following method.

<Synthesis example of polymer resin unit (1)>
A polymer resin unit (1) having an isophthalic acid moiety at the terminal and containing a monomer unit in which R ₁₄ in the above formula (2) is a hydrogen atom was produced according to the following method.

  In a four-necked flask, 10.0 parts of dimethyl 5-aminoisophthalate (69) and 5.00 parts of triethylamine were dissolved in 100.0 parts of chloroform and cooled to 10 ° C. or lower with ice. To this solution, 10.9 parts of 2-bromoisobutyric acid bromide (70) was added and stirred at room temperature for 12 hours. After completion of the reaction, the organic phase was washed with water, the solution was concentrated, methanol was added, and purification by recrystallization gave 9,58 parts of compound (71) (yield 57.1%).

  In a four-neck flask, 0.60 part of compound (71), 58.2 parts of styrene (72), N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine 0.60 part, copper bromide ( I) 0.24 parts and 5.00 parts of N, N-dimethylformamide were added and dissolved by stirring, and nitrogen bubbling was performed for 1 hour. Then, it heated up at 110 degreeC and stirred for 1 hour. After completion of the reaction, the reaction mixture was diluted with chloroform and the organic phase was washed with water. Then, the solution was concentrated, reprecipitated with methanol, and the deposited precipitate was separated by filtration to obtain Compound (73). 160.0 parts of dioxane was added to 20.0 parts of the obtained compound (73), dissolved by stirring, 6.00 parts of concentrated hydrochloric acid was added, and the mixture was refluxed at 120 ° C. for 7 hours. After completion of the reaction, the solution was concentrated, reprecipitated with methanol, and the precipitated precipitate was filtered to obtain a polymer resin unit (1). The obtained polymer resin unit (1) was subjected to physical property confirmation using the above apparatus. The analysis results are shown below.

[Result of analysis of polymer resin unit (1)]
[1] Results of molecular weight measurement (GPC):
Weight average molecular weight (Mw) = 10508, Number average molecular weight (Mn) = 9610
[2] Results of acid value measurement:
5.05mg KOH / g
[3] Results of ¹ H NMR (400 MHz, CDCl ₃ , room temperature):
δ [ppm] = 8.52 (s, 1H), 8.14 (d, 2H), 8.07 (t, 1H), 7.37-6.27 (m, 462H), 2.45-0 .77 (m, 277H)

<Synthesis example of polymer resin unit (2)>
A polymer resin unit (2) having a carboxylic acid moiety at the end and containing a monomer unit in which R ₁₄ in the above formula (2) is a hydrogen atom was produced according to the following method.

  In a four-necked flask, 0.30 part of ethyl 2-bromoisobutyrate (74), 60.0 parts of styrene (72), 5.00 parts of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, bromide 0.24 parts of copper (I) and 5.0 parts of N, N-dimethylformamide were added and dissolved by stirring, and nitrogen bubbling was performed for 1 hour. Then, it heated up at 110 degreeC and stirred for 2 hours. After completion of the reaction, the reaction mixture was diluted with chloroform and the organic phase was washed with water. Then, the solution was concentrated, reprecipitated with methanol, and the deposited precipitate was separated by filtration to obtain a compound (75). To 20.0 parts of the obtained compound (75), 160.0 parts of dioxane was added and dissolved by stirring, 6.00 parts of concentrated hydrochloric acid was added, and the mixture was refluxed at 120 ° C. for 7 hours. After completion of the reaction, the solution was concentrated, reprecipitated with methanol, and the precipitated precipitate was filtered to obtain a polymer resin unit (2). The obtained polymer resin unit (2) was subjected to physical property confirmation by the above apparatus. The analysis results are shown below.

[Result of analysis of polymer resin unit (2)]
[1] Results of molecular weight measurement (GPC):
Weight average molecular weight (Mw) = 37367, number average molecular weight (Mn) = 29626
[2] Results of acid value measurement:
3.05mgKOH / g
[3] Results of ¹ H NMR (400 MHz, CDCl ₃ , room temperature):
[delta] [ppm] = 7.37-6.27 (m, 1430H), 2.45-0.77 (m, 858H)

<Synthesis example of polymer resin unit (3)>
A monomer unit having a carboxylic acid moiety at the end, wherein R ₁₄ in the above formula (2) is represented by a hydrogen atom, and R ₁₅ in the above formula (3) is represented by a hydrogen atom and R ₁₆ is represented by a hydrogen atom. A polymer resin unit (3) containing monomer units was produced according to the following method.

  In a four-necked flask, 1.85 parts of methyl 2-bromopropionate (76), 35.2 parts of t-butyl acrylate (77), N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine 80 parts, 1.54 parts of copper (I) bromide and 250 parts of N, N-dimethylformamide were added and dissolved by stirring, and nitrogen bubbling was performed for 1 hour. Then, it heated up at 70 degreeC and stirred for 20 minutes. After completion of the reaction, the reaction mixture was diluted with chloroform and the organic phase was washed with water. The solution was then concentrated and dried with a vacuum pump to obtain a tert-butyl acrylate polymer.

  In a four-necked flask, 4.00 parts of tert-butyl acrylate polymer, 42.0 parts of styrene (72), 0.63 parts of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, copper bromide ( I) 0.26 part and 10.0 part of N, N-dimethylformamide were added and dissolved by stirring, and nitrogen bubbling was performed for 1 hour. Then, it heated up at 110 degreeC and stirred for 1 hour. After completion of the reaction, the reaction mixture was diluted with chloroform and the organic phase was washed with water. Then, the solution was concentrated, reprecipitated with methanol, and the deposited precipitate was separated by filtration to obtain Compound (78). To 20.0 parts of the obtained compound (78), 160.0 parts of dioxane was added and dissolved by stirring, 6.00 parts of concentrated hydrochloric acid was added, and the mixture was refluxed at 120 ° C. for 7 hours. After completion of the reaction, the solution was concentrated, reprecipitated with methanol, and the deposited precipitate was filtered off to obtain a polymer resin unit (3). The obtained polymer resin unit (3) was subjected to physical property confirmation by the above apparatus. The analysis results are shown below.

[Analysis results of polymer resin unit (3)]
[1] Results of molecular weight measurement (GPC):
Weight average molecular weight (Mw) = 16802, number average molecular weight (Mn) = 10230
[2] Results of acid value measurement:
40.2mgKOH / g
[3] Results of ¹ H NMR (400 MHz, CDCl ₃ , room temperature):
δ [ppm] = 7.37-6.27 (m, 713H), 2.45-0.77 (m, 428H)

<Synthesis example of polymer resin unit (4)>
A polymer resin unit (4) having a carboxylic acid moiety at the terminal and containing a monomer unit in which R ₁₄ in the above formula (2) is a hydrogen atom was produced according to the following method.

  100 parts of propylene glycol monomethyl ether was heated while being purged with nitrogen, and refluxed at a liquid temperature of 120 ° C. or higher. To this solution, 100 parts of styrene (72), 1.2 parts of β-mercaptopropionic acid (79) and tert-butyl peroxybenzoate [Organic peroxide polymerization initiator Perbutyl Z (registered trademark) (manufactured by NOF Corporation) A mixture of 1.0 part was added dropwise over 3 hours, and after completion of the addition, the solution was stirred for 3 hours. Distilling at atmospheric pressure while raising the liquid temperature to 170 ° C, and after the liquid temperature reached 170 ° C, the solvent was distilled off at 1 hPa under reduced pressure for 1 hour to obtain a polymer solid. The solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was separated by filtration to obtain a polymer resin unit (4). The obtained polymer resin unit (4) was subjected to physical property confirmation using the above apparatus. The analysis results are shown below.

[Result of analysis of polymer resin unit (4)]
[1] Results of molecular weight measurement (GPC):
Weight average molecular weight (Mw) = 25303, number average molecular weight (Mn) = 10450
[2] Results of acid value measurement:
5.0mgKOH / g
[3] Results of ¹ H NMR (400 MHz, CDCl ₃ , room temperature):
[delta] [ppm] = 7.37-6.27 (m, 500H), 2.45-0.77 (m, 300H)

<Synthesis example of polymer resin unit (5)>
A monomer unit in which R ₁₄ in the above formula (2) is a hydrogen atom and a monomer unit in which R ₁₅ in the above formula (3) is a hydrogen atom, R ₁₆ is a hydrogen atom and an n-butyl group A resin (5) containing units was produced according to the following method.

  100 parts of propylene glycol monomethyl ether was heated while being purged with nitrogen, and refluxed at a liquid temperature of 120 ° C. or higher. To this solution, 152 parts of styrene (72), 38 parts of n-butyl acrylate (80), 10 parts of acrylic acid (81), and tert-butyl peroxybenzoate [organic peroxide polymerization initiator perbutyl Z (trademark registration) ) (Manufactured by NOF Corporation)] A mixture of 1.0 part was added dropwise over 3 hours, and after completion of the addition, the solution was stirred for 3 hours. Distilling at atmospheric pressure while raising the liquid temperature to 170 ° C, and after the liquid temperature reached 170 ° C, the solvent was distilled off at 1 hPa under reduced pressure for 1 hour to obtain a polymer solid. The solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was separated by filtration to obtain a polymer resin unit (5). The obtained polymer resin unit (5) was subjected to physical property confirmation by the above apparatus. The analysis results are shown below.

[Result of analysis of polymer resin unit (5)]
[1] Results of molecular weight measurement (GPC):
Weight average molecular weight (Mw) = 36820, Number average molecular weight (Mn) = 19530
[2] Results of acid value measurement:
36.0 mgKOH / g
[3] Results of ¹ H NMR (400 MHz, CDCl ₃ , room temperature):
[delta] [ppm] = 7.37-6.27 (m, 695H), 3.98 (br, 35H) 2.45-0.77 (m, 417H)

  Resins (6) to (26) listed in Table 1 below were obtained by a method according to the above resins (1) to (5). The results are shown below.

［表１中、Ｘ、は下記式（２）を表し、Ｙは下記式（３）を表し、Ｚは上記式（３）のＲ₁₆が水素原子である場合を表す。「Ｂｎ」は無置換のベンジル基を表す。重合形態が「ランダム」とは下記（Ｘ）、（Ｙ）、（Ｚ）で表さられる単量体単位の配列が無秩序な共重合体であることを表し、「ブロック」とは下記（Ｘ）、（Ｙ）、（Ｚ）で表さられる単量体単位の配列がブロックを形成しているブロック共重合体であることを表す。「＊＊＊」は高分子樹脂ユニットとの連結部位を表す。］

[In Table 1, X represents the following formula (2), Y represents the following formula (3), and Z represents the case where R _{16 in the} above formula (3) is a hydrogen atom. “Bn” represents an unsubstituted benzyl group. The polymerization form “random” means that the arrangement of the monomer units represented by the following (X), (Y), (Z) is a disordered copolymer, and “block” means the following (X ), (Y), and (Z) represent that the arrangement of the monomer units is a block copolymer forming a block. “***” represents a connecting portion with the polymer resin unit. ]

［式（２）中、Ｒ₁₄は水素原子、アルキル基を表す。］

[In the formula (2), R ₁₄ represents a hydrogen atom or an alkyl group. ]

［式（３）中、Ｒ₁₅は水素原子、アルキル基を表し、Ｒ₁₆は水素原子、アルキル基、アラルキル基を表す。］

[In the formula (3), R ₁₅ represents a hydrogen atom or an alkyl group, and R ₁₆ represents a hydrogen atom, an alkyl group or an aralkyl group. ]

［式（Ｚ）中、Ｒ₁₉は水素原子、アルキル基を表す。］

[In the formula (Z), R ₁₉ represents a hydrogen atom or an alkyl group. ]

[Example 2]
A compound having an azo dye skeleton unit represented by the above formula (1) was obtained by the following method.

<Synthesis Example of Azo Dye Intermediate (87)>
An azo dye intermediate (87) represented by the following structure was produced according to the following scheme.

  To 30 parts of chloroform, 3.11 parts of p-nitroaniline (82) was added, and the mixture was ice-cooled to 10 ° C. or less, and 1.89 parts of diketene (83) was added. Then, it stirred at 65 degreeC for 2 hours. After completion of the reaction, the mixture was extracted with chloroform and concentrated to obtain 4.80 parts of compound (84) (yield 96.0%).

  40.0 parts of methanol and 5.29 parts of concentrated hydrochloric acid were added to 4.25 parts of dimethyl 2-aminoterephthalate (85), and the mixture was ice-cooled to 10 ° C or lower. To this solution, 2.10 parts of sodium nitrite dissolved in 6.00 parts of water was added and reacted at the same temperature for 1 hour. Next, 0.990 parts of sulfamic acid was added and the mixture was further stirred for 20 minutes (diazonium salt solution). 4.51 parts of the compound (84) was added to 70.0 parts of methanol, and the mixture was cooled to 10 ° C. or less with ice, and the diazonium salt solution was added. Thereafter, a solution obtained by dissolving 5.83 parts of sodium acetate in 7.00 parts of water was added and reacted at 10 ° C. or lower for 2 hours. After completion of the reaction, 300 parts of water was added and stirred for 30 minutes, and then the solid was filtered off and purified by recrystallization from N, N-dimethylformamide to obtain 8.65 parts of compound (86) ( Yield 96.1%).

  To 58 parts of N, N-dimethylformamide, 8.58 parts of the compound (86) and 0.40 part of palladium-activated carbon (palladium 5%) were added, and the reaction was carried out in a hydrogen gas atmosphere (reaction pressure 0.1 to 0.4 MPa). ) And stirred at 40 ° C. for 3 hours. After completion of the reaction, the solution was filtered and concentrated to obtain 7.00 parts of compound (87) (yield 87.5%).

<Synthesis Example of Compound (19) Having Azo Dye Skeleton Unit>
A compound (19) having an azo dye skeleton unit was produced from the azo dye intermediate (87) according to the following scheme.

  10.0 parts of the polymer resin unit (1) synthesized in Example 1 was dissolved in 100 parts of chloroform and cooled to 10 ° C. or lower with ice. To this solution, 0.78 part of oxalyl chloride and 0.10 part of N, N-dimethylformamide were added and stirred at room temperature for 12 hours. To the resulting reaction mixture, a mixture of 3.30 parts of the azo dye intermediate (87) and 1.0 g of triethylamine was added dropwise over 1 hour at 0 ° C. or lower. After completion of dropping, the solution was heated to 60 ° C. and stirred for 3 hours. After completion of the reaction, the reaction mixture was neutralized with acetic acid, poured into 250 mL of water, extracted with chloroform, and the organic phase was washed twice with 250 mL of water. After drying the organic phase with anhydrous sodium sulfate, the precipitate was filtered off, the filtrate was concentrated, and purified by reprecipitation with methanol to obtain 9.5 parts of compound (19) having an azo dye skeleton unit (yield) 95.0%).

  It was confirmed using the above-described devices that the obtained product had a structure represented by the above formula. The analysis results are shown below.

[Analytical result of compound (19) having azo dye skeleton unit]
[1] Results of molecular weight measurement (GPC):
Weight average molecular weight (Mw) = 17240, number average molecular weight (Mn) = 10680
[2] Results of acid value measurement:
0.34mgKOH / g
[3] Results of ¹ H NMR (400 MHz, CDCl ₃ , room temperature) (see FIG. 1):
δ [ppm] = 15.67 (s, 2H), 11.44 (s, 2H), 8.64 (s, 2H), 8.38 (s, 1H), 8.16 (d, 2H), 8.04 (t, 1H) 7.80 (d, 2H), 7, 77 (s, 2H), 7, 71 (br, 2H), 7.37-6.27 (m, 497H), 4. 08 (s, 6H), 3.98 (s, 6H), 2.95 (s, 2H), 2.88 (s, 2H), 2.70 (s, 6H), 2.61 (s, 2H) ) 2.45-0.77 (m, 298H)

<Synthesis Example of Compound (20) Having Azo Dye Skeleton Unit>
A compound (20) having an azo dye skeleton unit was produced from the azo dye intermediate (87) according to the following scheme.

  1.00 parts of 5-nitroisophthalic acid (88) was dissolved in a mixture of 10.0 parts of chloroform and 0.10 parts of N, N-dimethylformamide, and ice-cooled to 10 ° C or lower. To this solution, 3.60 parts of oxalyl chloride was added and stirred at room temperature for 12 hours. A mixture of 4.00 parts of the azo dye intermediate (87), 1.00 parts of triethylamine, and 40.0 parts of N-methylpyrrolidone was added dropwise to the obtained reaction mixture over 1 hour. After completion of dropping, the solution was heated to 60 ° C. and stirred for 3 hours. After completion of the reaction, the reaction mixture was neutralized with acetic acid, filtered, and dispersed and washed twice in water to obtain 4.32 parts of an azo dye intermediate (89) (yield 93.1%).

  Next, 4.00 parts of the azo dye intermediate (89) and 0.30 parts of palladium-activated carbon (palladium 5%) were added to 150.0 parts of N, N-dimethylformamide, and the reaction was performed under a hydrogen gas atmosphere (reaction). The mixture was stirred at 70 ° C. for 12 hours under a pressure of 0.1 to 0.4 MPa. After completion of the reaction, the solution was filtered and concentrated to obtain 3.35 parts of Compound (90) (yield 86.3%).

  Next, 1.00 parts of the azo dye intermediate (90) was added to 200.0 parts of dehydrated tetrahydrofuran and dissolved. After dissolution, 10.0 parts of the polymer resin unit (2) obtained in Example 1 dissolved in dehydrated tetrahydrofuran 40.0 parts at 50 ° C. was added, and 1-ethyl-3- (3-dimethylaminopropyl) was added. 1.15 parts of carbodiimide hydrochloride (EDC.HCl) was added and stirred at 50 ° C. for 5 hours. After completion of the reaction, the mixture was poured into 250 mL of water and extracted with chloroform, and then the organic layer was washed twice with 250 mL of water. After drying the organic layer with anhydrous sodium sulfate, the precipitate is filtered off, the solvent of the filtrate is distilled off, purified by column chromatography, and then purified by reprecipitation with methanol (20) 9.5 parts were obtained (yield 95.0%).

  It was confirmed using the above-described devices that the obtained product had a structure represented by the above formula. The analysis results are shown below.

[Analytical result of compound (20) having azo dye skeleton unit]
[1] Results of molecular weight measurement (GPC):
Weight average molecular weight (Mw) = 26395, Number average molecular weight (Mn) = 2420
[2] Results of acid value measurement:
0.82mgKOH / g
[3] Results of ¹ H NMR (400 MHz, CDCl ₃ , room temperature) (see FIG. 2):
δ [ppm] = 15.67 (s, 2H), 11.44 (s, 2H), 8.64 (s, 2H), 8.38 (s, 1H), 8.16 (d, 2H), 8.04 (t, 1H) 7.80 (d, 2H), 7, 77 (s, 2H), 7, 71 (br, 2H), 7.37-6.27 (m, 1140H), 4. 08 (s, 6H), 3.98 (s, 6H), 2.95 (s, 2H), 2.88 (s, 2H), 2.70 (s, 6H), 2.61 (s, 2H) ) 2.45-0.77 (m, 684H)

  The same operations as in the production examples of the compounds (19) and (20) having the azo skeleton unit were performed to produce compounds (21) to (68) having an azo skeleton unit represented by the above formula (1). Table 2 below shows compounds having an azo skeleton unit of the present invention.

［表２中、Ｘ、は下記式（２）を表し、Ｙは下記式（３）を表し、Ｚは上記式（３）のＲ₁₆が水素原子である場合を表す。Ｗは下記（Ｗ−１）、（Ｗ−２）及び（Ｗ−３）を表し、Ｖは下記（Ｖ−１）、（Ｖ−２）を表す。「Ｐｈ」は無置換のフェニル基を表し、「Ｂｎ」は無置換のベンジル基を表し、（ｎ）、（ｉ）はそれぞれアルキル基が直鎖状、分岐状であることを表し、「＊」はＷとの連結部位を表し、「＊＊」はＶとの連結部位を表し、「＊＊＊」は高分子樹脂ユニットとの連結部位を表す。］

[In Table 2, X represents the following formula (2), Y represents the following formula (3), and Z represents the case where R _{16 in the} above formula (3) is a hydrogen atom. W represents the following (W-1), (W-2) and (W-3), and V represents the following (V-1) and (V-2). “Ph” represents an unsubstituted phenyl group, “Bn” represents an unsubstituted benzyl group, (n) and (i) represent that the alkyl group is linear or branched, and “*” "Represents a connecting site to W," ** "represents a connecting site to V, and" *** "represents a connecting site to the polymer resin unit. ]

［式（２）中、Ｒ₁₄は水素原子、アルキル基を表す。］

[In the formula (2), R ₁₄ represents a hydrogen atom or an alkyl group. ]

［式（３）中、Ｒ₁₅は水素原子、アルキル基を表し、Ｒ₁₆は水素原子、アルキル基、アラルキル基を表す。］

[In the formula (3), R ₁₅ represents a hydrogen atom or an alkyl group, and R ₁₆ represents a hydrogen atom, an alkyl group or an aralkyl group. ]

［式（Ｚ）中、Ｒ₁₉は水素原子、アルキル基を表す。］

[In the formula (Z), R ₁₉ represents a hydrogen atom or an alkyl group. ]

［式（Ｗ−１）中、Ｒ₁乃至Ｒ₁₀は、式（１）におけるＲ₁乃至Ｒ₁₀と各々同義である。］

[In Formula (W-1), R _{1 to} R ₁₀ are respectively synonymous with R _{1 to} R ₁₀ in Formula (1). ]

［式（Ｗ−２）中、Ｒ₁乃至Ｒ₁₀は、式（１）におけるＲ₁乃至Ｒ₁₀と各々同義である。］

Wherein (W-2), R ₁ to R ₁₀ are each synonymous with R ₁ through R ₁₀ in the formula (1). ]

［式（Ｗ−３）中、Ｒ₁乃至Ｒ₁₀は、式（１）におけるＲ₁乃至Ｒ₁₀と各々同義である。］

[In Formula (W-3), R _{1 to} R ₁₀ are respectively synonymous with R _{1 to} R ₁₀ in Formula (1). ]

［式（Ｖ−１）中、Ｗは上記（Ｗ−１）、（Ｗ−２）及び（Ｗ−３）を表し、Ｌ₂は式（１）におけるＬ₂と同義である。］

Wherein (V-1), W is the (W-1), represents a (W-2) and (W-3), L ₂ has the same meaning as L ₂ in Formula (1). ]

［式（Ｖ−２）中、Ｗは上記（Ｗ−１）、（Ｗ−２）及び（Ｗ−３）を表し、Ｌ₂は式（１）におけるＬ₂と同義である。］

Wherein (V-2), W is the (W-1), represents a (W-2) and (W-3), L ₂ has the same meaning as L ₂ in Formula (1). ]

[Comparative Example 1]
As a comparative example of the azo dye skeleton unit represented by the above formula (1), a comparative azo dye skeleton unit represented by the following formulas (91) and (92) was produced according to the above production method, The compounds for comparison (91) and (92) were obtained by amidating the group and the carboxyl group of the resin (4).

[Example 3]
The pigment dispersion of the present invention was prepared by the following method.

<Preparation Example 1 of Pigment Dispersion>
18.0 parts of the pigment represented by the above formula (6) as the azo pigment, 3.6 parts of the compound (19) having the azo dye skeleton unit as the pigment dispersant, 180 parts of styrene as the water-insoluble solvent, glass beads ( 130 parts of (φ1 mm) were mixed, dispersed with an attritor (manufactured by Nihon Coke Kogyo Co., Ltd.) for 3 hours, and filtered through a mesh to obtain a pigment dispersion (DIS1).

<Preparation Example 2 of Pigment Dispersion>
The same procedures as in Preparation Example 1 of the pigment dispersion except that the compound (19) having an azo dye skeleton unit was changed to (20) to (68), respectively, and the pigment dispersions (DIS2) to (DIS50) were respectively performed. )

<Pigment Dispersion Preparation Example 3>
A pigment dispersion (DIS51) and (DIS52) were obtained in the same manner as in Preparation Example 1 of the pigment dispersion except that styrene was changed to toluene or butyl acrylate.

<Preparation Example 4 of Pigment Dispersion>
In Preparation Example 1 of the pigment dispersion, the same operation was performed except that the pigment represented by the above formula (6) was changed to the pigment represented by the following formulas (93) and (94). The bodies (DIS53) and (DIS54) were obtained.

[Comparative Example 2]
A pigment dispersion serving as a reference value for evaluation and a pigment dispersion for comparison were prepared by the following method.

<Preparation Example 1 for Reference Pigment Dispersion>
A pigment dispersion for reference (DIS55) was obtained in the same manner as in Preparation Example 1 for the pigment dispersion of Example 3 except that the compound (19) having an azo dye skeleton unit was not added.

<Preparation Example 2 for Reference Pigment Dispersion>
In Preparation Example 3 of the pigment dispersion of Example 3 above, the same operations were performed except that the compound (19) having an azo dye skeleton unit was not added, and the pigment dispersions for reference (DIS56) and (DIS57) Got.

<Preparation Example 3 of Reference Pigment Dispersion>
In Preparation Example 4 of the pigment dispersion of Example 3 above, the same operations were performed except that the compound (19) having an azo dye skeleton unit was not added, and the pigment dispersions for reference (DIS58) and (DIS59) Got.

<Preparation Example 1 for Comparative Pigment Dispersion>
The compound (19) having an azo dye skeleton unit in Preparation Example 1 of the pigment dispersion of Example 3 was used as the polymer dispersant Solsperse 24000SC (registered trademark) [manufactured by Lubrizol Co., Ltd.] described in Patent Document 1, and the comparative compound. Except for changing to (91) and (92), the same operation was performed to obtain comparative pigment dispersions (DIS60) to (DIS62), respectively.

[Example 4]
A pigment dispersion using a compound having an azo dye skeleton unit of the present invention and a comparative pigment dispersion were evaluated by the following methods.

<Evaluation of pigment dispersibility>
The pigment dispersibility of the compound having an azo dye skeleton unit of the present invention was evaluated by conducting a gloss test of the coating film of the pigment dispersion. That is, scoop out the pigment dispersion with a dropper and place it on the straight line on the top of Super Art Paper [SA Kanto 180kg 80 × 160, Oji Paper Co., Ltd.], and apply evenly onto the art paper using a wire bar (# 10). The gloss (reflection angle: 60 °) after drying was measured with a gloss meter Gloss Meter VG2000 [manufactured by Nippon Denshoku Industries Co., Ltd.]. As the pigment is more finely dispersed, the smoothness of the coating film is improved and the gloss is improved. Therefore, the gloss of the coating film of the pigment dispersions (DIS55) to (DIS59) not added with the pigment dispersant is used as a standard. As the values, the gloss improvement rates of the coating films of the pigment dispersions (DIS1) to (DIS54) were evaluated as follows.
A: Gloss improvement rate is 20% or more B: Gloss improvement rate is 10% or more and less than 20% C: Gloss improvement rate is 1% or more and less than 10% D: Gloss improvement rate is less than 1% or gloss reduction

  If the gloss improvement rate was 10% or more, it was judged that the pigment dispersibility was good.

  Table 3 shows the evaluation results of the pigment dispersion of the present invention.

[Comparative Example 3]
Reference pigment dispersions (DIS55) to (DIS59) and comparative pigment dispersions (DIS60) to (DIS62) were evaluated in the same manner as in Example 4. The evaluation results are shown in Table 3.

  Table 3 confirms that the compound having an azo dye skeleton unit of the present invention is useful as an azo pigment dispersant because the compound having an azo dye skeleton unit of the present invention gives an azo pigment dispersion having good dispersibility. It was done.

[Example 5]
The ink of the present invention was prepared by the following method.

<Ink Preparation Example 1>
The following composition and 90.00 parts of glass beads (φ1 mm) were mixed, dispersed with an attritor (manufactured by Nihon Coke Industries Co., Ltd.) for 3 hours, and filtered through a mesh to obtain an ink (INK1).
・ C. I. Pigment Green 36 6.00 parts-Pigment represented by formula (6) 4.00 parts-Compound having azo dye skeleton unit (19) 2.00 parts-Diethylene glycol monobutyl ether acetate 70.00 parts

<Ink Preparation Example 2>
In the ink preparation example 1, the compound (19) having an azo dye skeleton unit is converted into (21), (22), (36), (40), (50), (51), (52), (54). , (58) and (60) were the same except that the inks (INK2) to (INK11) were obtained.

<Ink Preparation Example 3>
In the ink preparation example 1, the same operation was performed except that the pigment represented by the above formula (6) was changed to the pigment represented by the above formulas (93) and (94). And (INK13) were obtained.

[Comparative Example 4]
Ink serving as a reference value for evaluation and comparative ink were prepared by the following methods.

<Preparation Example 1 of Reference Ink>
The same operation as in Preparation Example 1 of the ink of Example 5 except that the compound (19) having an azo dye skeleton unit was not added, to obtain a reference ink (INK14).

<Preparation Example 2 of Reference Ink>
Ink Preparation Example 3 of Example 5 was carried out in the same manner as above except that the compound (19) having an azo dye skeleton unit was not added to obtain reference inks (INK15) and (INK16).

<Comparative ink preparation example 1>
The compound part (19) having an azo dye skeleton unit in Preparation Example 1 of the ink of Example 5 was replaced with the polymer dispersant Solsperse 24000SC (registered trademark) [manufactured by Lubrizol Co., Ltd.] described in Patent Document 1 and the comparative compound ( 91) and (92), except that the same operation was performed to obtain comparative inks (INK17) to (INK19), respectively.

[Example 6]
The resist composition for a color filter of the present invention was prepared by the following method.

<Preparation Example 1 of Color Filter Resist Composition>
To the ink (INK1) obtained in Example 5, a solution of the following components was slowly added and stirred at room temperature for 3 hours. This was filtered through a 1.5 μm filter to obtain a color filter resist composition (REG1).
・ Methylated benzoguanamine resin [manufactured by Sanwa Chemical Co., Ltd.] (binder resin) 15.0 parts ・ Diethylene glycol monobutyl ether acetate 40.00 parts

<Preparation Example 2 of resist composition for color filter>
The same operation was performed except that the ink (INK1) was changed to the inks (INK2) to (INK11) in Preparation Example 1 of the facial color filter resist composition, and the color filter resist compositions (REG2) to (REG11) was obtained.

<Preparation Example 3 of resist composition for color filter>
The same operation was performed except that the ink (INK1) was changed to the inks (INK12) and (INK13) in Preparation Example 1 of the color filter resist composition, and the color filter resist composition (REG12) and ( REG13) was obtained.

[Comparative Example 5]
A color filter resist composition that serves as a reference value for evaluation and a comparative color filter resist composition were prepared by the following methods.

<Preparation Example 1 of Resist Composition for Color Filter for Reference>
A color filter resist composition (REG14) was prepared in the same manner as in Preparation Example 1 of the color filter resist composition of Example 6 except that the ink (INK1) was changed to the ink (INK14). Obtained.

<Preparation Example 2 of Resist Composition for Color Filter for Reference>
The same procedure as in Preparation Example 1 of color filter resist composition of Example 6 except that the ink (INK1) was changed to the inks (INK15) and (INK16), respectively, and the color filter resist composition for reference color filter respectively. Products (REG15) and (REG16) were obtained.

<Preparation Example 1 for Comparative Color Filter Resist>
The same operation was performed except that the ink (INK1) was changed to the inks (INK17) to (INK19) in Preparation Example 1 of the color filter resist of Example 6 above, and each of the color filter resists (REG17) for comparison was used. ) To (REG19) were obtained.

[Example 7]
The color filter resist composition using the compound having an azo dye skeleton unit of the present invention and a comparative color filter resist were evaluated by the following methods.

<Color characteristic evaluation>
The color characteristics of the color filter resist composition using the compound having an azo dye skeleton unit of the present invention were evaluated by discharging the resist composition onto a glass substrate with an ink jet type coating experimental apparatus and performing a brightness test. That is, the color filter resist composition described in Example 6 was loaded into a cartridge, discharged onto a glass substrate on which pixels were formed with a black matrix, and dried at 180 ° C. for 2 hours. The thickness of the green filter was adjusted so that y = 0.6, and the color characteristics (x, y, Y) were measured with a microspectrophotometer. As the pigment is more finely dispersed, the lightness Y in the green chromaticity is improved. Therefore, the green filters of the color filter resist compositions (REG14) to (REG16) to which no polyester having a bisazo dye skeleton is added. The improvement rate of the lightness Y of the green filters of the color filter resist compositions (REG1) to (REG13) was evaluated as follows using the lightness Y of the color filter as a reference value.
A: Lightness improvement rate is 20% or more B: Lightness improvement rate is 10% or more and less than 20% C: Lightness improvement rate is 1% or more and less than 10% D: Lightness improvement rate is less than 1% or a reference decrease

  If the brightness improvement rate was 10% or more, it was judged that the product had good color characteristics.

  Table 4 shows the evaluation results of the color filter resist composition of the present invention.

[Comparative Example 6]
The reference color filter resist compositions (REG14) to (REG16) and the comparative color filter resist compositions (REG17) to (REG19) were evaluated in the same manner as in Example 7. The evaluation results are shown in Table 4.

  From Table 4, since the color filter resist composition of the present invention has a good pigment dispersion state and excellent color characteristics, the pigment dispersion of the present invention is useful as a colorant for the ink and color filter resist composition. It was confirmed that there was.

  The compound having an azo dye skeleton represented by at least the formula (1) of the present invention is particularly preferably used as a dispersant for dispersing an azo pigment in a water-insoluble solvent. Further, the compound having an azo dye skeleton unit represented by the formula (1) of the present invention is not only used as a pigment dispersant, but also an oil-based paint, a thermal transfer recording sheet, a colorant for oil-based ink for writing, light It can also be used as a dye for recording media.

Claims (16)

A unit represented by the following general formula (1) is bonded to a polymer having a partial structural formula represented by the following general formula (2) and / or a partial structural formula represented by the following general formula (3). The compound characterized by the above-mentioned.

[In Formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms and a phenyl group, and R _{2 to} R ₆ represent a hydrogen atom, a COOR ₁₁ group, and a CONR ₁₂ R ₁₃ group. R _{7 to} R ₁₀ represent a hydrogen atom or a halogen atom. R _{11 to} R _{13 each} represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. L _{1 to} L ₂ represent a divalent linking group. ]

[In the formula (2), R ₁₄ represents a hydrogen atom or an alkyl group. ]

[In the formula (3), R ₁₅ represents a hydrogen atom or an alkyl group, and R ₁₆ represents a hydrogen atom, an alkyl group or an aralkyl group. ] The compound according to claim ₁ , wherein R ₁ in formula (1) is a methyl group. The compound according to claim 1 or 2, wherein R ₂ and R ₅ in the formula (1) are COOR ₁₁ (R ₁₁ is as defined above), and R ₃ , R ₄ and R ₆ are hydrogen atoms. . The compound according to any one of claims 1 to 3, wherein R ₁₁ and R ₁₂ in the formula (1) are a methyl group, and R ₁₃ is a hydrogen atom or a methyl group. L ₁ in Formula (1) is —O—, —CO—, —NR ₁₇ — (R ₁₇ represents a hydrogen atom or an alkyl group), —R ₁₈ — (R ₁₈ represents an alkylene group.) The compound according to any one of claims 1 to 4, wherein the compound is a divalent linking group selected from the group consisting of a combination thereof. L ₁ in Formula (1) is, -NH-CO -, - O -CO -, - that O-R ₁₈ -O-CO- is (R ₁₈ represents the same meanings as claim 5.) 6. A compound according to any one of claims 1 to 5, characterized in that The L ₂ in the formula (1) and the carboxyl group in the polymer according to claim 1 are bonded via a carboxylic acid amide bond or a carboxylic acid ester bond. 7. The compound according to any one of items 1 to 6. A compound according to any one of claims 1 to 7 R ₇ to R ₁₀ in the formula (1) is characterized in that it is a hydrogen atom. The compound represented by any one of claims 1 to 8, wherein the unit represented by the formula (1) is represented by the following general formula (4) to general formula (5).

[In Formula (4), L < ₁ > thru | or L < ₂ > represent a bivalent coupling group. ]

[In Formula (5), L < ₁ > thru | or L < ₂ > represent a bivalent coupling group. ]   A pigment dispersant comprising at least the compound according to any one of claims 1 to 9.   A pigment composition comprising at least the compound according to any one of claims 1 to 10 and an azo pigment.   The pigment composition according to claim 11, wherein the azo pigment is an acetoacetanilide pigment. The pigment composition according to claim 12, wherein the azo pigment is an azo pigment represented by the following formula (6).

  A pigment dispersion comprising the pigment composition according to any one of claims 11 to 13 and a water-insoluble solvent.   An ink comprising at least one pigment dispersion according to claim 14.   A color filter resist composition comprising at least one pigment dispersion according to claim 14.

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