JP2006291194A - Pigment dispersant, pigment composition using the same, and pigment dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment dispersant which improves the flow characteristics of inks, coatings and the like, and is effective for preparing products having low thixotropy and excellent characteristics such as excellent colorability, transparency and temporal viscosity stability, to provide a pigment composition, and to provide a pigment dispersion. <P>SOLUTION: This pigment dispersant in which a quinophthalone skeleton is bound to a triazine skeleton through an arylene group or a heteroaromatic group, and a basic functional group is bound to a triazine ring through a bonding group. The pigment composition containing the pigment dispersant, and the pigment dispersion. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a pigment dispersant used for dispersing pigment particles, a pigment composition containing the pigment dispersant, and a pigment dispersion.

In general, many pigments having high coloring power and clear color tone have fine primary particles, but these pigments are usually aggregates of primary particles. In order to draw out the characteristics of the pigment itself, it is necessary to disperse from the aggregated state to a finer state. In general, the finer the pigment particles, the more difficult it is to disperse in a uniform state.
Many dispersions having a poor dispersion state have a high viscosity and are difficult to handle such as dispersion and transfer. In addition, in some cases, the dispersion is gelled and becomes unusable. When different types of pigments are mixed and used, phenomena such as color separation or sedimentation due to aggregation of pigments may cause color unevenness of the color-extended product and significant reduction in coloring power. In addition, poor dispersion may cause problems such as a decrease in coating film gloss and poor leveling.

Some organic pigments may cause a change in the crystal state of the pigment in the dispersion medium. That is, this is a phenomenon in which pigment particles that are unstable in energy change their size and shape in a non-aqueous vehicle and shift to a more stable crystalline state. In such a case, usually, the product value is remarkably lowered by causing problems such as a significant decrease in coloring power, a change in hue, and generation of coarse particles.
In order to solve the above problems, it is known that it is effective to use various derivatives having a pigment skeleton or a structure close thereto. Various structures have been disclosed so far, such as pigment derivatives in which functional groups such as acidic groups, basic groups, and phthalimidomethyl groups are introduced into the pigment skeleton, and pigment derivatives in which the pigment skeleton is bonded to a part of the resin. Have been used for a long time in applications such as dispersants, particle growth inhibitors and crystal transition inhibitors.

  Among these, pigment dispersants having a quinophthalone skeleton are disclosed in Patent Documents 1 to 5, and all are used in colored curable compositions such as resist inks for color filters. All of these have an effect of improving the dispersion state, but the dispersion particle diameter is finer, and the properties are not sufficient for preparing a pigment dispersion having good fluidity and storage stability with time.

JP 2003-167112 A JP 2002-179799 A JP 2002-121418 A JP 2002-121457 A JP 2001-335711 A

  It is an object of the present invention to provide a pigment dispersant effective for dispersing pigments in various applications such as inks and paints, and a pigment composition containing the same. Furthermore, it aims at providing the pigment dispersion which is excellent in characteristics, such as coloring power and transparency, low viscosity, and favorable storage stability.

（式中、Ｑは置換基を有していてもよいキノフタロン残基を表し、
Ｘ₁は、−ＮＲ’ＳＯ₂−、−ＳＯ₂ＮＲ’−、−ＣＯＮＲ’−、−ＣＨ₂ＮＲ’ＣＯＣＨ₂ＮＲ’−、または−ＮＲ’ＣＯ−から選ばれる基を表し、
Ｘ₂は、置換基を有していてもよく炭素数が２０以下のアリーレン基または置換基を有していてもよく炭素数が２０以下の複素芳香環から選ばれる基を表し（これらの基は、−ＮＲ’−、−Ｏ−、−ＳＯ₂−または−ＣＯ−から選ばれる２価の連結基で相互に結合されていてもよい。）、
Ｘ₃は、−ＮＲ’−または−Ｏ−を表し、
（ただし、Ｒ’は、水素原子、置換基を有していてもよく炭素数が２０以下のアルキル基、置換基を有していてもよく炭素数が２０以下のアルケニル基または置換基を有していてもよく炭素数が２０以下のアリール基を表す。）
ＡおよびＢは、それぞれ独立に、下記一般式２もしくは３で表される基、−Ｏ−（ＣＨ₂）_n−Ｒ₈、−ＯＲ₉、−ＮＲ₁₀Ｒ₁₁、−Ｃｌ、−Ｆまたは−Ｘ₃−Ｘ₂−Ｘ₁−Ｑから選ばれる基を表し（Ｒ₈は置換されていてもよい含窒素複素環残基を表し、Ｒ₉、Ｒ₁₀、Ｒ₁₁は、それぞれ独立に、水素原子、置換基を有していてもよく炭素数が２０以下のアルキル基、置換基を有していてもよく炭素数が２０以下のアルケニル基または置換基を有していてもよく炭素数が２０以下のアリール基を表し、ｎは０〜２０の整数を表す。）、ＡおよびＢのいずれか一方は、下記一般式２もしくは３で表される基、−Ｏ−（ＣＨ₂）_n−Ｒ₈、−ＯＲ₉、または−ＮＲ₁₀Ｒ₁₁であり、
ｔは１〜３の整数を表す。）

（式中、Ｙ₁は−ＮＲ’−または−Ｏ−を表し、
Ｙ₂は、置換基を有していてもよく炭素数が２０以下のアルキレン基、置換基を有していてもよく炭素数が２０以下のアルケニレン基または置換基を有していてもよく炭素数が２０以下のアリーレン基から選ばれる基を表し（これらの基は、−ＮＲ’−、−Ｏ−、−ＳＯ₂−または−ＣＯ−から選ばれる２価の連結基で相互に結合されていてもよい。ただし、Ｒ’は、一般式１で定義されたものを表す。）、
Ｒ₁およびＲ₂は、それぞれ独立に、置換基を有していてもよく炭素数が２０以下のアルキル基または置換基を有していてもよく炭素数が２０以下のアルケニル基を表す（Ｒ₁とＲ₂が一体となって、更なる窒素原子、酸素原子または硫黄原子を含み置換されていてもよい複素環構造を形成してもよい。）。）

（式中、Ｚ₁は、トリアジン環と窒素原子を結ぶ単結合、−ＮＲ’−、−ＮＲ’−Ｇ−ＣＯ−、−ＮＲ’−Ｇ−ＣＯＮＲ’’−、−ＮＲ’−Ｇ−ＳＯ₂−、−ＮＲ’−Ｇ−ＳＯ₂ＮＲ’’−、−Ｏ−Ｇ−ＣＯ−、−Ｏ−Ｇ−ＣＯＮＲ’−、−Ｏ−Ｇ−ＳＯ₂−、または−Ｏ−Ｇ−ＳＯ₂ＮＲ’−を表し（Ｇは、置換基を有していてもよく炭素数が２０以下のアルキレン基、置換基を有していてもよく炭素数が２０以下のアルケニレン基または置換基を有していてもよく炭素数が２０以下のアリーレン基を表し、Ｒ’およびＲ’’は、それぞれ独立に、水素原子、置換基を有していてもよく炭素数が２０以下のアルキル基、置換基を有していてもよく炭素数が２０以下のアルケニル基または置換基を有していてもよく炭素数が２０以下のアリール基を表す。）、
Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆は、それぞれ独立に、水素原子、置換基を有していてもよく炭素数が２０以下のアルキル基、置換基を有していてもよく炭素数が２０以下のアルケニル基または置換基を有していてもよく炭素数が２０以下のアリール基を表し、
Ｒ₇は、置換基を有していてもよく炭素数が２０以下のアルキル基または置換基を有していてもよく炭素数が２０以下のアルケニル基を表す。）。 The present invention provides the following pigment dispersant, pigment composition, and pigment dispersion.
(1) A pigment dispersant represented by the following general formula 1.

(In the formula, Q represents an optionally substituted quinophthalone residue,
X _{1 is, -NR'SO 2 -, - SO 2} NR '-, - CONR' -, - CH 2 NR'COCH 2 NR'-, or represents a group selected from -NR'CO-,
X ₂ represents a group selected from an arylene group having 20 or less carbon atoms which may have a substituent or a heteroaromatic ring which may have a substituent and which has 20 or less carbon atoms (these groups May be bonded to each other by a divalent linking group selected from —NR′—, —O—, —SO ₂ —, and —CO—).
X ₃ represents —NR′— or —O—,
(However, R ′ may have a hydrogen atom, an optionally substituted alkyl group having 20 or less carbon atoms, an optionally substituted alkenyl group having 20 or less carbon atoms, or a substituted group. And represents an aryl group having 20 or less carbon atoms.)
A and B are each independently a group represented by the following general formula 2 or 3, —O— (CH ₂ ) _n —R ₈ , —OR ₉ , —NR ₁₀ R ₁₁ , —Cl, —F or — Represents a group selected from X ₃ -X ₂ -X ₁ -Q (R ₈ represents an optionally substituted nitrogen-containing heterocyclic residue; R ₉ , R ₁₀ and R ₁₁ are each independently hydrogen; It may have an atom, a substituent, may have an alkyl group having 20 or less carbon atoms, may have a substituent, may have an alkenyl group having 20 or less carbon atoms, or may have a substituent. . represents up to 20 aryl group, n represents an integer of 0 to 20), it is either one of a and B, a group represented by the following general formula 2 or _{3, -O- (CH 2) n} - R ₈ , —OR ₉ , or —NR ₁₀ R ₁₁ ,
t represents an integer of 1 to 3. )

Wherein Y ₁ represents —NR′— or —O—,
Y ₂ may have a substituent, may have an alkylene group having 20 or less carbon atoms, may have a substituent, may have an alkenylene group having 20 or less carbon atoms, or may have a substituent. Represents a group selected from an arylene group having a number of 20 or less (these groups are bonded to each other by a divalent linking group selected from —NR′—, —O—, —SO ₂ — or —CO—). Provided that R ′ represents the one defined by the general formula 1.),
R ₁ and R ₂ each independently have a substituent, may have an alkyl group having 20 or less carbon atoms, or may have a substituent, and represents an alkenyl group having 20 or less carbon atoms (R ₁ and R ₂ may be combined to form an optionally substituted heterocyclic structure containing a further nitrogen atom, oxygen atom or sulfur atom. )

(In the formula, Z ₁ represents a single bond connecting a triazine ring and a nitrogen atom, —NR′—, —NR′—G—CO—, —NR′—G—CONR ″ —, —NR′—G—SO _{2 -, - NR'-G-} SO 2 NR '' -, - O-G-CO -, - O-G-CONR '-, - O-G-SO 2 - or -O-G-SO _2, NR′- (G represents an alkylene group having 20 or less carbon atoms which may have a substituent, an alkenylene group having 20 or less carbon atoms which may have a substituent, or a substituent. And may represent an arylene group having 20 or less carbon atoms, and R ′ and R ″ each independently have a hydrogen atom or a substituent, and may have an alkyl group or substituent having 20 or less carbon atoms. And may represent an alkenyl group having 20 or less carbon atoms or a substituent, and an aryl group having 20 or less carbon atoms).
R ₃ , R ₄ , R ₅ , and R ₆ each independently have a hydrogen atom, a substituent, or an alkyl group having 20 or less carbon atoms, a substituent, or a carbon number. An alkenyl group having 20 or less or a substituent which may have an aryl group having 20 or less carbon atoms,
R ₇ may have a substituent, may have an alkyl group having 20 or less carbon atoms, or may have a substituent, and represents an alkenyl group having 20 or less carbon atoms. ).

(2) A pigment composition containing the pigment and the pigment dispersant described in (1).
(3) The pigment composition according to (2), which contains a yellow pigment as a pigment.
(4) The yellow pigment is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 185, C.I. I. The pigment composition according to (3), which is at least one pigment selected from CI Pigment Yellow 13.
(5) The pigment composition according to any one of (2) to (4), which contains a green pigment as a pigment.
(6) The green pigment is C.I. I. Pigment green 7 or C.I. I. The pigment composition according to (5), which is CI Pigment Green 36.

(7) The pigment composition according to any one of (2) to (4), which contains a red pigment or an orange pigment as a pigment.
(8) Red pigment or orange pigment is C.I. I. Pigment red 254, pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 177, C.I. I. Pigment red 207, C.I. I. Pigment red 48: 1, C.I. I. Pigment orange 71, C.I. I. The pigment composition according to (7), which is at least one pigment selected from CI Pigment Orange 73.
(9) A pigment dispersion obtained by dispersing the pigment composition according to any one of (2) to (8) in a non-aqueous medium.

  The pigment dispersant of the present invention has a high effect for dispersing various pigments in a fine and low viscosity compared to conventional pigment dispersants. By using this, the transparency and coloring power are high, and storage is possible. It becomes possible to prepare a dispersion having good stability. Moreover, by using the pigment composition or pigment dispersion containing the pigment dispersant of the present invention, products such as paints and inks can be easily prepared with high quality.

  The pigment dispersant of the present invention is a compound in which a quinophthalone skeleton and a triazine skeleton are bonded via an arylene group or a heteroaromatic ring, and a basic functional group is bonded to triazine via a linking group. By using this, various pigments are dispersed in a non-aqueous medium, whereby a pigment dispersion having good characteristics can be prepared. Although the pigment dispersant having a similar structure is disclosed in Patent Document 4 and Patent Document 5 described above, it is difficult to synthesize the pigment dispersant of the present invention by these conventional techniques.

一般式４において、ＤおよびＥはそれぞれ独立に、水素原子、ハロゲン原子、炭素数１〜２０のアルキル基、ＤおよびＥが結合したベンゼン環とともに形成し、置換基を有してもよい芳香環または複素環、ヒドロキシル基、炭素数１〜３のアルコキシル基、カルボキシル基あるいはその塩あるいは炭素数１〜２０のエステルあるいは炭素数１〜２０のアミド、スルホン基あるいはその塩、スルファモイル基、−ＮＲ’Ｒ’’−、ニトロ基から選ばれるいずれかの基を表す（式中、Ｒ’及びＲ’’は、それぞれ独立に、水素原子、置換基を有していてもよく炭素数が２０以下のアルキル基、置換基を有していてもよく炭素数が２０以下のアルケニル基または置換基を有していてもよく炭素数が２０以下のアリール基を表す。）。また、ｐは４以下の整数を、ｑは４−ｐで算出される整数を表す。これらのうち、Ｅが水素原子または塩素原子や臭素原子などのハロゲン原子であり、ｐが４である場合が特に好ましい。 In the general formula 1, Q represents a quinophthalone residue which may have a substituent represented by the following general formula 4.

In General Formula 4, D and E each independently form a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a benzene ring to which D and E are bonded, and an aromatic ring that may have a substituent. Or a heterocyclic ring, a hydroxyl group, an alkoxyl group having 1 to 3 carbon atoms, a carboxyl group or a salt thereof, an ester having 1 to 20 carbon atoms, an amide having 1 to 20 carbon atoms, a sulfone group or a salt thereof, a sulfamoyl group, -NR ' R ″ — represents any group selected from a nitro group (wherein R ′ and R ″ each independently have a hydrogen atom or a substituent and have 20 or less carbon atoms) An alkyl group, a substituent which may have an alkenyl group having a carbon number of 20 or less, or an aryl group which has a carbon number of 20 or less. P represents an integer of 4 or less, and q represents an integer calculated by 4-p. Among these, it is particularly preferable that E is a hydrogen atom or a halogen atom such as a chlorine atom or a bromine atom, and p is 4.

（式中、Ｄ、Ｅ、ｐ、ｑは、それぞれ一般式４で定義されたものを表す。） The quinophthalone compound used to form the quinophthalone residue represented by the general formula 4 includes various quinaldines and various phthalic anhydrides represented by the following general formula 5 or various phthalic acids represented by the following general formula 6. It can be synthesized by dehydration condensation in benzoic acid or various high-boiling solvents.

(In the formula, D, E, p, and q each represent those defined by General Formula 4.)

  For example, benzoic acid and various phthalic anhydrides are heated and melted at a temperature of 130 ° C. or higher, and then quinaldine is added. In this reaction, quinaldine and various phthalic anhydrides are usually used in a molar ratio of 1: 1 to 1: 5. Quinardine and benzoic acid are usually used in a molar ratio of 1: 2 to 1:20, but can be increased or decreased as necessary depending on the stirring state of the system. After the raw material is melted, it is heated to 150 to 180 ° C. and stirred for 3 to 8 hours. At that time, the reaction mixture can be subjected to component analysis by a method such as high performance liquid chromatography to determine the end point of the reaction. After completion of the reaction, the reaction mixture is cooled to 130-150 ° C. and optionally diluted with water, followed by addition of an aqueous alkaline solution, for example 5-20% by weight aqueous sodium hydroxide or aqueous potassium hydroxide. By this operation, benzoic acid becomes a water-soluble alkali metal salt and can be separated from the produced quinophthalone compound by filtration. Thereafter, the quinophthalone compound used for forming the quinophthalone residue represented by the general formula 4 can be obtained by washing with water and drying.

  Further, as a post-treatment method other than the method using the aqueous alkali solution, purification methods using various solvents are effective. For example, the reaction mixture is diluted with a solvent such as methanol, ethanol, propanol, isopropanol, ethylene glycol, ethylene glycol monobutyl ether, toluene, xylene, or a mixture thereof. Since benzoic acid dissolves in these solvents, if the product is insoluble, it can be separated by filtration.

（式中、Ｘ₁、Ｘ₂、Ｘ₃、Ａ、Ｂ、ｔは、それぞれ一般式１で定義されたものを表す。） The above dehydration condensation reaction may be carried out after synthesizing a compound represented by the following general formula 7 by the method described below in addition to the above method. The reaction conditions and post-treatment methods at that time are the same as in the case of reacting various quinaldines with various phthalic anhydrides or various phthalic acids.

(In the formula, X ₁ , X ₂ , X ₃ , A, B, and t each represent those defined by General Formula 1.)

（式中、Ｘ₃’は１級または２級のアミノ基またはヒドロキシル基を表し、Ｑ、Ｘ₁、Ｘ₂、ｔは、それぞれ一般式１で定義されたものを表す。） The compound represented by the general formula 1 or 7 is synthesized by first synthesizing an intermediate having the structure represented by the following general formula 8 or 9, and then reacting with cyanuric chloride and A and B introduction sources. Can do.

(In the formula, X ₃ ′ represents a primary or secondary amino group or hydroxyl group, and Q, X ₁ , X ₂ , and t each represent those defined in Formula 1.)

The method for synthesizing the intermediate represented by the general formula 8 or 9 is particularly limited as long as the method can finally synthesize the intermediate represented by the general formula 8 or 9 There are no, but some of them are illustrated below.
The first example is a method in which various primary or secondary diamines or various hydroxylamines are allowed to act after the quinophthalone compound or quinaldine is chlorosulfonated.

  The chlorosulfonation reaction can be performed according to a known method. For example, a quinophthalone compound or quinaldine is dissolved in chlorosulfonic acid and heated and stirred at 40 to 140 ° C. for 1 to 8 hours. After cooling to 40-50 ° C., thionyl chloride is added and stirred for an additional 1-8 hours. At that time, the reaction can be followed by determining the end point by measuring the absorption spectrum of the sulfuric acid solution. After completion of the reaction, the reaction mixture is poured into a large amount of ice water, filtered and washed with ice water to obtain a chlorosulfonated quinophthalone compound or quinaldine.

  The obtained quinophthalone compound or chlorosulfonate of quinaldine is slurried in water. Next, various diamines or various hydroxylamines are added and stirred at 5 to 80 ° C. for 1 to 5 hours. At that time, the reaction mixture can be subjected to component analysis by a method such as high performance liquid chromatography to determine the end point of the reaction. After completion of the reaction, the reaction mixture can be filtered, washed with water, and dried to obtain an intermediate represented by general formula 8 or general formula 9. In this reaction, when various diamines or various hydroxylamines have low solubility in water, a solvent that does not inhibit the reaction, such as acetone, may be used. Further, since hydrogen chloride is generated as the reaction proceeds, various inorganic bases, tertiary amines, and the like may be added as necessary.

The various diamines used in this reaction are not particularly limited as long as they are compounds that can form a structure of -X ₁ -X ₂ -X ₃ '. For example, 1,2-phenylene diamine, 1,3-phenylene diamine 1,4-phenylenediamine, 2,5-diaminobenzenesulfonic acid, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,4-diaminopyrimidine, 4,5-diaminopyrimidine, 2,3-diamino Examples include pyridine, 2,5-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,6-diaminopurine, 3,5-diamino-1,2,4-triazole, and acetoguanamine. . The amount of these diamines is not particularly limited as long as it is an equimolar amount or more of the quinophthalone compound or quinaldine chlorosulfonated product, but the amount used is about 1 to 5 times the molar amount of the quinophthalone compound or quinaldine chlorosulfonated product. It is preferable to do.

  In the first example, an intermediate having a structure represented by the general formula 8 or 9 may be synthesized by using p-aminoacetanilide or the like instead of various diamines or various hydroxylamines. In that case, the quinophthalone compound or the chlorosulfonated quinaldine and p-aminoacetanilide are reacted in the same manner as when various diamines are used, and then the acetamido group is hydrolyzed, thereby being represented by the general formula 8 or 9. Structural intermediates can be synthesized.

The second example is a method in which various diamines or various hydroxylamines are allowed to act on a quinophthalone compound or quinaldine after introducing a linking group by a method such as chloroacetamidomethylation.
The chloroacetamidomethylation reaction can be performed according to a known method. For example, a quinophthalone compound or quinaldine is dissolved in sulfuric acid and then α-chloroacetamide and paraformaldehyde are added. The mixture is stirred at 20-120 ° C. for 2-10 hours to effect chloroacetamidomethylation. At that time, the reaction can be traced by a method such as high performance liquid chromatography, and the end point of the reaction can be determined by the consumption of the quinophthalone compound or quinaldine. After completion of the reaction, the reaction mixture is cooled, poured into a large amount of ice water, filtered, and washed with ice water to obtain a chloroacetamide methylated product of quinophthalone compound or quinaldine.

The obtained quinophthalone compound or chloroacetamide methylated product of quinaldine is slurried in water, and various diamines or various hydroxylamines are added. Then, it stirs at 5-80 degreeC for 1 to 5 hours. At that time, the reaction mixture can be subjected to component analysis by a method such as high performance liquid chromatography to determine the end point of the reaction. After completion of the reaction, the reaction mixture can be filtered, washed with water, and dried to obtain an intermediate represented by general formula 8 or general formula 9. The various diamine or various hydroxylamine used in this reaction, the compound is not particularly limited as long as it is a compound capable of forming a structure of -X ₁ -X ₂ -X ₃ ', for example illustrated in the first embodiment Is mentioned. The amount of various diamines or various hydroxylamines is not particularly limited as long as it is an equimolar amount or more of the quinophthalone compound or quinaludine chloroacetamide methylated product, but is 1 to 5 times the quinophthalone compound or quinaldine chloroacetamide methylated product. It is preferable to use a molar amount. In this reaction, when various diamines or various hydroxylamines have low solubility in water, a solvent that does not inhibit the reaction, such as acetone, may be used. Since hydrogen chloride is generated as the reaction proceeds, various inorganic bases, tertiary amines, and the like may be added as necessary. Similarly to the case of the first example, an intermediate having a structure represented by the general formula 8 or 9 may be synthesized using p-aminoacetanilide or the like instead of various diamines or various hydroxylamines.

The third example is a method of synthesizing a compound represented by the following general formula 10 from trimellitic anhydride and quinaldine, then chlorinating a carboxyl group, and reacting the obtained acid chloride with various diamines or various hydroxylamines. It is. The compound represented by the following general formula 10 can be synthesized in the same manner as the quinophthalone compound used to form the quinophthalone residue represented by the general formula 4.

  Chlorination of the carboxyl group can be performed according to a known method. For example, the compound represented by the general formula 10 is added to chlorosulfonic acid and stirred at 10 to 30 ° C. for 1 to 3 hours, and then thionyl chloride is added and stirred at 40 to 50 ° C. for 2 to 5 hours. The reaction mixture is poured into a large amount of ice water, filtered and washed with ice water to obtain a water cake of carboxylic acid chloride.

The obtained carboxylic acid chloride is slurried in water and various diamines or various hydroxylamines are added. Then, it stirs at 10-80 degreeC for 1 to 5 hours. At that time, the reaction mixture can be subjected to component analysis by a method such as high performance liquid chromatography to determine the end point of the reaction. After completion of the reaction, the reaction mixture is filtered, washed with water, and dried to obtain an intermediate represented by the general formula 8. The various diamine or various hydroxylamine used in this reaction, the compound is not particularly limited as long as it is a compound capable of forming a structure of -X ₁ -X ₂ -X ₃ ', for example illustrated in the first embodiment Is mentioned. The amount of various diamines or various hydroxylamines used is not particularly limited as long as it is an amount of equimolar or more with respect to the carboxylic acid chloride, but it is preferable to use an amount of about 1 to 5 times mol with respect to the carboxylic acid chloride. In this reaction, when various diamines or various hydroxylamines have low solubility in water, a solvent that does not inhibit the reaction, such as acetone, may be used. Since hydrogen chloride is generated as the reaction proceeds, various inorganic bases, tertiary amines, and the like may be added as necessary. Moreover, you may synthesize | combine the intermediate body of the structure represented by General formula 8 using p-aminoacetanilide etc. instead of various diamine or various hydroxylamine similarly to the case of a 1st example.

A fourth example is a method in which various aminoquinaldines and various acid chlorides having an acetamide group are reacted, and then acetamide is hydrolyzed and converted to an amino group.
The reaction of various aminoquinaldines and various acid chlorides having an acetamide group can be performed according to a known method. For example, various aminoquinaldines and 4-acetamidobenzenesulfonyl chloride are stirred at 10 to 50 ° C. for 1 to 5 hours in the presence of various inorganic bases or tertiary amines in various solvents. The solvent used in that case will not be specifically limited if it does not inhibit reaction. The kind of the various inorganic bases or tertiary amines to be used is not particularly limited as long as it is an amount that can neutralize the hydrogen chloride that is generated. The reaction mixture can be subjected to component analysis by a method such as high performance liquid chromatography to determine the end point of the reaction. The compound represented by the following general formula 11 produced by the above reaction may be purified by filtration, washing with water, and drying, but can also be used in the subsequent reaction without performing such an operation.

  After adding water to the solution containing the compound represented by the general formula 11 produced above, hydrochloric acid is further added until the pH becomes 1 or less, and the mixture is heated to reflux temperature. When a low-boiling solvent other than water is used when synthesizing the compound represented by the general formula 11, the solvent is distilled off until the reflux temperature reaches 100 ° C. The acetamide group is converted to an amino group by stirring the reaction solution at 100 ° C. for 1 to 5 hours. At that time, the reaction mixture can be subjected to component analysis by a method such as high performance liquid chromatography to determine the end point of the reaction. After completion of the reaction, the reaction solution is cooled to room temperature and neutralized, and the product is filtered and washed with water to obtain an intermediate represented by the general formula 9.

The fifth example is a method in which various aminoquinaldines and various acid chlorides having a nitro group are reacted and then the nitro group is reduced and converted to an amino group.
The reaction of various aminoquinaldines and various acid chlorides having a nitro group can be performed according to a known method. For example, various aminoquinaldines and 4-nitrobenzoyl chloride are reacted in the same manner as in the case of synthesizing the compound of the above general formula 11, and the resulting product is filtered and washed to obtain a compound represented by the following general formula 12 Can be obtained.

  The compound represented by the general formula 12 produced above is slurried in water, and sodium sulfide nonahydrate is added. The amount of sodium sulfide nonahydrate added is not particularly limited as long as it is more than the amount capable of reducing the nitro group. The slurry is stirred at 50-80 ° C. to reduce nitro groups to amino groups. At that time, the reaction mixture can be subjected to component analysis by a method such as high performance liquid chromatography to determine the end point of the reaction. After completion of the reaction, the product is sufficiently washed to remove impurities derived from sodium sulfide, whereby an intermediate represented by the general formula 9 can be obtained.

（式中、Ｑは、一般式１で定義されたものを表す。） The reduction of the nitro group may be carried out after synthesizing the quinophthalone compound represented by the following general formula 13 from the compound represented by the general formula 12 and various phthalic anhydrides. In that case, the compound represented by the following general formula 13 can be synthesized in the same manner as the quinophthalone compound used to form the quinophthalone residue represented by the general formula 4.

(In the formula, Q represents one defined by the general formula 1.)

The intermediate represented by the general formula 8 can be obtained by reducing the nitro group of the compound represented by the general formula 13 synthesized above. The synthesis conditions in that case are the same as those in the case of synthesizing the compound represented by the general formula 9 from the compound represented by the general formula 12.
Reaction which manufactures the compound represented by General formula 1 or General formula 7 using the intermediate body represented by General formula 8 or General formula 9 manufactured by the above method can be performed in accordance with a well-known method. .

（式中、Ｑ、Ｘ₁、Ｘ₂、Ｘ₃は、それぞれ一般式１で定義されたものを表す。） For example, the intermediate represented by the general formula 8 or 9 and cyanuric chloride in various solvents are stirred at 5 to 15 ° C. for 1 to 5 hours in the presence of various inorganic bases or tertiary amines. 14 or a compound represented by the general formula 15 is synthesized. Although the solvent used in that case will not be specifically limited if it does not inhibit reaction, Lower ketones, such as acetone, are especially preferable. Moreover, the usage-amount of cyanuric chloride will not be specifically limited if it is the quantity more than an intermediate body represented with General formula 8 or General formula 9, and this mole. The kind of the various inorganic bases or tertiary amines to be used is not particularly limited, and the amount used is not particularly limited as long as it is an amount that can neutralize the generated hydrogen chloride. The reaction mixture can be subjected to component analysis by a method such as high performance liquid chromatography to determine the end point of the reaction. After completion of the reaction, the product is filtered and washed to obtain a compound represented by the following general formula 14 or general formula 15.

(In the formula, Q, X ₁ , X ₂ , and X ₃ are each defined by General Formula 1.)

  The compound represented by the general formula 14 or the general formula 15 produced above and various amine components or various alcohol components are stirred in various solvents at a temperature of 40 to 100 ° C. for 1 to 8 hours. A compound represented by 7 is synthesized. Although the solvent used in that case will not be specifically limited if reaction is not inhibited, Solvents with high solubility, such as 1, 4- dioxane, are especially preferable. Since hydrogen chloride is generated as the reaction proceeds, various inorganic bases or tertiary amines may be added as necessary. In that case, the kind of various inorganic bases or tertiary amines to be used is not particularly limited, and the amount used is not particularly limited as long as it is an amount capable of neutralizing the generated hydrogen chloride. The reaction mixture can be subjected to component analysis by a method such as high performance liquid chromatography to determine the end point of the reaction. When a solvent other than water is used in this reaction, the product is insolubilized by pouring the reaction mixture into a large amount of water or adding water to the reaction mixture and then distilling off the solvent. After completion of the reaction, the product can be separated and washed by filtration or decantation to obtain a compound represented by general formula 1 or general formula 7.

Various amine components or various alcohol components used in this reaction are particularly limited as long as they form a structure represented by general formula 2, general formula 3 or —O— (CH ₂ ) _n —R ₈ after completion of the reaction. Not.
Examples of the amine component or alcohol component used for forming the structure represented by the general formula 2 include N, N-dimethylaminomethyl, N, N-dimethylaminoethyl, N, N-dimethylaminopropyl, N , N-dimethylaminoamyl, N, N-dimethylaminobutyl, N, N-diethylaminoethyl, N, N-diethylaminopropyl, N, N-diethylaminohexyl, N, N-diethylaminoethoxypropyl, N, N-diethylaminobutyl N, N-diethylaminopentyl, N, N-dipropylaminobutyl, N, N-dibutylaminopropyl, N, N-dibutylaminoethyl, N, N-dibutylaminobutyl, N, N-diisobutylaminopentyl, N , N-methyl-laurylaminopropyl, N, N-ethyl-hexyl Minoethyl, N, N-distearylaminoethyl, N, N-dioleylaminoethyl, N, N-distearylaminobutyl amine or alcohol, or N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N -Aminoethylpiperidine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-aminomethylpiperidine, or N-hydroxymethylpiperidine, N- Hydroxyethylpiperidine, N-hydroxypropylpiperidine, N-hydroxyethylpipecoline, N-hydroxypropylpipecoline, N-hydroxymethylpyrrolidine, N-hydroxybutylpyrrolidine, N-hydroxyethylmorpholine, N- Mud carboxybutyl morpholine and the like. The amount of these various amine components or various alcohol components used is not particularly limited as long as it is an equimolar amount or more of the compound represented by General Formula 14 or General Formula 15, but is represented by General Formula 14 or General Formula 15. The amount is preferably twice or more moles of the compound.

Examples of the amine component or alcohol component used to form the structure of the general formula 3 or —O— (CH ₂ ) _n —R ₈ include N-methylpiperazine, N-ethylpiperazine, and N-butyl. Piperazine, 1-amino-4-methylpiperazine, 1-amino-4-cyclopentylpiperazine, 1-cyclopentylpiperazine, N-methyl-3-piperidinemethanol, N-methyl-3-hydroxypiperidine, N-ethyl-3-hydroxy Examples include piperidine, N-methyl-4-piperidinol, N-methyl-2-hydroxyethylpyrrolidine and the like. The amount of these various amine components or various alcohol components used is not particularly limited as long as it is an equimolar amount or more of the compound represented by General Formula 14 or General Formula 15, but is represented by General Formula 14 or General Formula 15. The amount is preferably twice or more moles of the compound.

  When the compound represented by the general formula 7 is synthesized by the above method, various phthalic anhydrides are synthesized according to the synthesis method of the quinophthalone compound used to form the quinophthalone residue represented by the general formula 4 after that. By reacting, the compound represented by the general formula 1 can be synthesized.

Specific examples of the pigment dispersant represented by the general formula 1 are shown below, but the present invention is not limited to the following examples.

The pigment composition of the present invention contains a pigment and a pigment dispersant represented by the general formula 1 (the pigment dispersant of the present invention).
As pigments, commercially available azo, ansanthrone, anthrapyrimidine, anthraquinone, isoindolinone, isoindoline, indanthrone, quinacridone, quinophthalone, dioxazine, diketo Organic pigments such as pyrrolopyrrole, thioindigo dyes, pyranthrone dyes, phthalocyanine dyes, flavanthrone dyes, perinone dyes, perylene dyes, benzimidazolone dyes, or carbon black, titanium oxide, yellow lead, cadmium yellow, Inorganic pigments such as cadmium red, petal, iron black, zinc white, bitumen and ultramarine can be used. Two or more of these pigments may be used in combination. Of these pigments, organic pigments are preferably used.

  The pigment composition of the present invention preferably contains a yellow pigment. The yellow pigment to be used is not particularly limited. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,193,194,199,198,213,214 and the like. Among them, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 185, C.I. I. At least one pigment selected from CI Pigment Yellow 13 is preferred; I. Pigment Yellow 138 is particularly preferable. These may be used alone or in combination of two or more.

  The pigment composition of the present invention preferably contains a green pigment. The green pigment to be used is not particularly limited. I. Pigment green 7, 10, 36, 37, and the like. Among them, C.I. I. Pigment green 7 or C.I. I. Pigment Green 36 is preferable. These may be used alone or in combination of two or more. Further, these green pigments and the yellow pigment described above may be used in combination to adjust the hue.

  The pigment composition of the present invention preferably contains a red pigment or an orange pigment. The red pigment or orange pigment to be used is not particularly limited. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 146, 177, 178, 184, 185, 187, 200, 202, 207, 208, 210, 246, 254, 255, 264, 270, 272, C.I. I. Pigment orange 71, 73, and the like. Among them, C.I. I. Pigment red 254, 255, 264, 177, 207, 48: 1, C.I. I. At least one pigment selected from CI pigment oranges 71 and 73 is preferable. These may be used alone or in combination of two or more. Moreover, these red pigments or orange pigments and the above yellow pigments may be used in combination to adjust the hue.

As the pigment used in the pigment composition of the present invention, the above-mentioned commercially available pigments may be used as they are, but if necessary, they are refined to a desired particle size by a method such as solvent salt milling or dry milling. You may use after.
For example, when an organic pigment is refined by solvent salt milling, a mixture composed of at least three components of an organic pigment, a water-soluble inorganic salt, and a water-soluble solvent is made into a clay-like mixture and strongly kneaded with a kneader or the like. The kneaded mixture is put into water and stirred with various stirrers to form a slurry. By filtering this, the water-soluble inorganic salt and the water-soluble solvent are removed. The above-mentioned slurrying, filtration, and water washing are repeated to obtain a refined organic pigment.

  As the water-soluble inorganic salt, sodium chloride, potassium chloride and the like can be used. These inorganic salts are used in an amount of 1 times by weight or more, preferably 20 times by weight or less of the organic pigment. When the amount of the inorganic salt is less than 1 times by weight, it is difficult to sufficiently miniaturize the pigment. On the other hand, when the amount is more than 20 times by weight, a great amount of labor is required to remove the water-soluble inorganic salt and the water-soluble solvent after kneading, and at the same time, the amount of the pigment that can be processed at one time is reduced. It is not preferable in terms.

  In the above-described method for refining the pigment, heat is often generated with kneading, and therefore, from the viewpoint of safety, it is preferable to use a water-soluble solvent having a boiling point of about 120 to 250 ° C. Examples include 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol. Monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Examples include low molecular weight polypropylene glycol.

In the above-described method for refining a pigment, a single pigment may be used, or two or more kinds of pigments may be mixed and used. Further, the pigment dispersant represented by the general formula 1 may be mixed with the pigment and used. In that case, finer particles can be obtained as compared with the case of making the particles finer with only the pigment, and at the same time, the pigment dispersant can be uniformly treated in the pigment, so that a higher quality pigment composition can be prepared. Therefore, it is preferable.
In the pigment composition of the present invention, the addition amount of the pigment dispersant represented by the general formula 1 is preferably 0.5 to 30 parts by weight with respect to 100 parts by weight of the pigment. When the amount of the pigment dispersant represented by the general formula 1 is less than 0.5 parts by weight, the pigment dispersion effect is small and not preferable. Moreover, even if it uses more than 30 weight part, the dispersion | distribution effect according to addition amount cannot be expected, and also a viscosity characteristic, a coating-film physical property, etc. fall depending on the case.

  As a method for preparing the pigment composition of the present invention, a sufficient dispersion effect can be obtained simply by mixing the pigment powder and the powder of the pigment dispersant represented by the general formula 1, but a dissolver, a high speed mixer, a homomixer, A method of mechanically mixing using a kneader, a roll mill, an attritor, a sand mill, various pulverizers, or a solution in which a pigment dispersant represented by the general formula 1 is dissolved in a suspension of pigment in water or an organic solvent. A method of adding and dispersing a pigment dispersant on the surface of the pigment, a method of dissolving an organic pigment and a pigment dispersant in a solvent having strong dissolving power such as sulfuric acid, and then co-precipitating by injecting into a poor solvent such as water Thus, a higher dispersion effect can be obtained.

The pigment dispersion of the present invention is obtained by dispersing the pigment composition of the present invention in a non-aqueous medium.
The pigment dispersion of the present invention can be prepared by dispersing a mixture of a pigment, the pigment dispersant of the present invention, an organic solvent, and a resin (varnish) with various dispersers. Moreover, you may add and disperse | distribute various additives, a resin type dispersing agent, etc. other than said raw material as needed. When preparing the pigment dispersion, the pigment and the pigment dispersant may be added as a pigment composition obtained by mixing in advance, or may be added separately and then dispersed. Further, the order of addition of each raw material and the addition method are not particularly limited.

  Examples of the resin used to prepare the pigment dispersion of the present invention include petroleum resin, casein, shellac, rosin modified maleic resin, rosin modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, Chloride rubber, oxide rubber, hydrochloric acid rubber, phenol resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, vinyl chloride, vinyl chloride-vinyl acetate copolymer, acrylic resin, methacrylic resin, Examples include polyurethane resins, silicone resins, fluororesins, drying oils, synthetic drying oils, styrene-modified maleic acid resins, polyamide resins, polyimide resins, benzoguanamine resins, melamine resins, urea resins, chlorinated polypropylene, butyral resins, and vinylidene chloride resins. .

Moreover, you may use photosensitive resin as resin. Examples of photosensitive resins include (meth) acrylic compounds having reactive substituents such as isocyanate groups, aldehyde groups, and epoxy groups on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups. Or a resin in which a photocrosslinkable group such as (meth) acryloyl group or styryl group is introduced into the polymer, or a styrene-maleic anhydride copolymer or α-olefin-maleic anhydride copolymer And a linear polymer containing an acid anhydride such as hydroxyalkyl (meth) acrylate and the like obtained by half-esterification with a (meth) acrylic compound having a hydroxyl group.
The resin can be used in an amount of 10 to 200 parts by weight with respect to 100 parts by weight of the pigment.

The organic solvent used for preparing the pigment dispersion of the present invention is not particularly limited, and any solvent generally used as a solvent can be used. For example, cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, toluene, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether, toluene, methyl ethyl ketone, methyl isobutyl ketone , Ethyl acetate, butyl acetate, n-hexane, methanol, ethanol, isopropyl alcohol, butanol, dioxane, dimethylformamide, Solvesso 100 (manufactured by Exxon Chemical Co., Ltd.), Swazol 1000 (manufactured by Cosmo Matsuyama Oil Co., Ltd.), petroleum solvent, etc. These can be used alone or in combination. Can.
The organic solvent can be used in an amount of 20 to 2000 parts by weight with respect to 100 parts by weight of the pigment.

The disperser used for preparing the pigment dispersion of the present invention is not particularly limited. For example, a horizontal sand mill, a vertical sand mill, an annular bead mill, an attritor, a microfluidizer, a high speed mixer, a homomixer, a ball mill, and a roll mill. , Stone mill, ultrasonic disperser, paint conditioner, etc., and any disperser or mixer usually used for preparing various dispersions can be used.
Further, before dispersion with various dispersers, pre-dispersion using a kneader mixer such as a kneader or a three-roll mill, or solid dispersion using a two-roll mill or the like may be performed. In addition, after being dispersed with various dispersers, post-processing for storing for several hours to one week in a heated state at 30 to 80 ° C., and post-processing using an ultrasonic disperser or a collision type beadless disperser Is effective for imparting dispersion stability to the pigment dispersion.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this.
Production Example 1 <Synthesis of Quinophthalone Derivative A>
In a stirring vessel, 540 g of benzoic acid was added and heated to 130 ° C. to melt. To the molten benzoic acid, 34 g of quinaldine and 204 g of tetrachlorophthalic anhydride were added. The reaction vessel was heated to 160 ° C. and stirred for 10 hours. Thereafter, the mixture was cooled to 130 ° C., and 950 g of a 25% aqueous sodium hydroxide solution was added. The resulting suspension was poured into 10 L of water, heated to 80 ° C. and stirred for 1 hour. The suspension was subjected to suction filtration, washed with water until the filtrate became neutral, and then dried to obtain 89 g (91%) of a quinophthalone derivative represented by the following general formula 16.

Production Example 2 <Synthesis of Quinophthalone Derivative B>
The operation was performed in the same manner as in Production Example 1 except that 139 g of trimellitic anhydride was used instead of 204 g of tetrachlorophthalic anhydride and the heating time at 160 ° C. was changed to 24 hours. 65 g (86%) of quinophthalone derivative B was obtained.

Production Example 3 <Synthesis of Pigment Dispersant A>
To 1000 g of chlorosulfonic acid, 100 g of the quinophthalone derivative A represented by the general formula 16 was gradually added at 10 to 20 ° C. with stirring. After completion of the addition, the mixture was stirred at 40 to 50 ° C. for 1 hour, and then 180 g of thionyl chloride was added and stirred at the same temperature for 3 hours. The reaction mixture was cooled to room temperature and gradually poured into 10 L of ice water while maintaining a temperature of 10 ° C. or lower. The resulting precipitate was filtered and washed with ice water to obtain a chlorosulfonated product (hydrous cake) of quinophthalone derivative A. This was slurried in 3 L of ice water, 32 g of 1,3-phenylenediamine was added, and the mixture was stirred at 5 ° C. for 3 hours and then at 50 ° C. for 1 hour. After completion of the stirring, filtration, washing with water and drying were performed to obtain 102 g (70%) of an intermediate A represented by the following general formula 18.

Acetone 400 g was cooled to 5 ° C., and cyanuric chloride 44 g was added. Subsequently, 96 g of intermediate A represented by the general formula 18 was gradually added while maintaining 5 ° C. Then, 90 g of 10% -sodium carbonate aqueous solution was added and stirred at 5 ° C. for 3 hours. The resulting precipitate was filtered and washed with water, and then slurried again in 400 g of acetone. This was filtered and washed with acetone to obtain an intermediate B (acetone-containing cake) represented by the following general formula 19.

The obtained intermediate B (acetone-containing cake) represented by the general formula 19 was gradually added to a mixed solution of 320 g of 1,4-dioxane and 103 g of N-aminoethylpiperidine at a temperature of 60 ° C. or lower. Then, it stirred at 90 degreeC for 5 hours. The reaction mixture was cooled to room temperature and poured into 5 L of water. The resulting precipitate was filtered, washed with water, and dried to obtain 116 g (78%) of pigment dispersant A represented by the following general formula 20.

Production Example 4 <Synthesis of Pigment Dispersant B>
100 g of 98% sulfuric acid was added with 100 g of quinophthalone derivative A represented by general formula 16, and dissolved by stirring. Subsequently, 93 g of α-chloroacetamide and 39 g of paraformaldehyde were added at 30 ° C. or lower, and the mixture was stirred at 25 ° C. for 2 hours. Thereafter, the mixture was heated to 60 ° C., stirred for 4 hours, cooled to room temperature, and poured into 10 L of ice water. The resulting precipitate was filtered and washed with ice to obtain an intermediate C (hydrated cake) represented by the following general formula 21.

Intermediate C (hydrous cake) represented by general formula 21 was slurried in 3 L of acetone, 32 g of 1,4-phenylenediamine was added, and the mixture was stirred at 10 ° C. for 2 hours and then at 50 ° C. for 2 hours. After the stirring, filtration, acetone washing, and drying were performed to obtain an intermediate D110g (75%) represented by the following general formula 22.

Acetone 400 g was cooled to 5 ° C., and cyanuric chloride 44 g was added. Subsequently, the intermediate D97g represented by the general formula 22 was gradually added at a temperature of 15 ° C. or lower. Thereafter, 16.3 g of triethylamine was added, and the mixture was stirred at 15 ° C. for 3 hours. The resulting precipitate was filtered and washed with water, and then slurried again in 400 g of acetone. This was filtered and washed with acetone to obtain an intermediate E (acetone-containing cake) represented by the following general formula 23.

The obtained intermediate E (acetone-containing cake) represented by the general formula 23 was gradually added to a mixed solution of 320 g of 1,4-dioxane and 81 g of N-methylpiperazine at a temperature of 60 ° C. or lower. Then, it stirred at 90 degreeC for 7 hours. The reaction mixture was cooled to room temperature and poured into 5 L of water. The resulting precipitate was filtered, washed with water, and dried to obtain 118 g (84%) of pigment dispersant B represented by the following general formula 24.

Production Example 5 <Synthesis of Pigment Dispersant C>
100 g of quinophthalone derivative B represented by the general formula 17 was added to 500 g of chlorosulfonic acid and stirred at 20 ° C. for 3 hours. Subsequently, 42 g of thionyl chloride was added and stirred at 50 ° C. for 2 hours. The reaction mixture was cooled to room temperature, poured into 5 L of ice water, filtered and washed with water to obtain a carboxylic acid chloride of quinophthalone derivative B (hydrous cake). It was slurried in 1500 g of acetone, 93 g of 1,5-diaminonaphthalene was added, and the mixture was stirred at 40 ° C. for 4 hours. Subsequently, 42 g of sodium carbonate was added, stirred at 80 ° C. for 1 hour, filtered, washed with water and dried to obtain 111 g (77%) of an intermediate F represented by the following general formula 25.

400 g of acetone was cooled to 5 ° C. or lower, and 44 g of cyanuric chloride was added. Subsequently, the intermediate F73g represented by General formula 25 was gradually added at the temperature of 15 degrees C or less. Thereafter, 16.3 g of triethylamine was added and stirred at 10 ° C. for 3 hours. The resulting precipitate was filtered and washed with water, and then slurried again in 400 g of acetone. This was filtered and washed with acetone to obtain an intermediate G (acetone-containing cake) represented by the following general formula 26.

The obtained intermediate G (acetone-containing cake) represented by the general formula 26 was gradually added to a mixed solution of 320 g of 1,4-dioxane and 125 g of N-aminopropyl-2-pipecoline at a temperature of 60 ° C. or lower. did. Then, it stirred at 95 degreeC for 5 hours. The reaction mixture was cooled to room temperature and poured into 5 L of water. The resulting precipitate was filtered, washed with water, and dried to obtain 111 g (82%) of a pigment dispersant C represented by the following general formula 27.

Production Example 6 <Synthesis of Pigment Dispersant D>
84 g of 8-aminoquinaldine was dissolved by stirring in 1100 g of methanol, and then 57 g of sodium carbonate and 112 g of 4-acetamidobenzenesulfonyl chloride were added. The mixture was stirred at 25 ° C. to 35 ° C. for 4 hours. After stirring, 600 g of water and 152 g of 35% -hydrochloric acid were added and heated to the reflux temperature, and methanol was distilled off until the reflux temperature reached 100 ° C. After distilling off, 400 g of water was added, and the mixture was cooled to 60 ° C. or lower. Then, the pH was adjusted to 12.0 with a 25% -aqueous sodium hydroxide solution, and the mixture was stirred at 50 ° C. for 1 hour. After leaving to room temperature, the pH was adjusted to 4.0 with acetic acid and stirred at room temperature for 1 hour. Filtration, washing with water and drying yielded 116 g (77%) of intermediate H represented by the following general formula 28.

In 400 g of acetone cooled to 5 ° C., 45 g of cyanuric chloride was added and dissolved. Into this, a solution prepared by dissolving 50 g of intermediate H represented by the general formula 28 in 120 g of N-methyl-2-pyrrolidone was added dropwise while maintaining 5 ° C. Subsequently, 85 g of 10% -sodium carbonate aqueous solution was added dropwise while keeping the temperature at 5 ° C., and the product was filtered and washed with water. The obtained water cake was slurried again in 400 g of acetone, filtered and washed with acetone to obtain an intermediate I (acetone-containing cake) represented by the following general formula 29.

The obtained intermediate I (acetone-containing cake) represented by the general formula 29 was gradually added to a mixed solution of 320 g of 1,4-dioxane and 105 g of diethylaminopropylamine at a temperature of 60 ° C. or lower. Then, it stirred at 50-60 degreeC for 1.5 hours, and 90 degreeC for 3.5 hours. 200 g of water was added to the reaction mixture and heated to reflux temperature to distill off 1,4-dioxane. Cool to room temperature and adjust the pH to 4.0 with acetic acid to dissolve the product. The reaction mixture was poured into 1 L of water and the pH was adjusted to 11 with sodium hydroxide. The supernatant was removed by decantation and washed until neutral. It vacuum-dried at 50 degreeC and obtained intermediate body J96g (92%) represented by the following general formula 30

270 g of benzoic acid was melted at 160 ° C., and intermediate J78 g represented by the general formula 30 was added and dissolved therein. Next, 103 g of tetrachlorophthalic anhydride was added and stirred at 160 ° C. for 4 hours. After stirring, 1000 g of methanol was gradually added. The reaction mixture was poured into 7500 g of water, adjusted to pH 11 with an aqueous sodium hydroxide solution, and stirred at 80 ° C. for 1 hour. The resulting precipitate was filtered, washed with water and dried to obtain 98 g (89%) of a pigment dispersant D represented by the following general formula 31.

Production Example 7 <Synthesis of Pigment Dispersant E>
To 500 g of acetone, 79.1 g of 8-aminoquinaldine and 60.7 g of triethylamine were added and dissolved uniformly. Subsequently, a solution in which 111 g of 4-nitrobenzoyl chloride was dissolved in 340 g of acetone was dropped. After completion of the dropwise addition, the mixture was stirred at 25 to 35 ° C. for 1 hour and then at reflux temperature for 3 hours. After stirring, 2000 g of water and 125 g of 25% -aqueous sodium hydroxide solution were added and stirred at reflux temperature for 1 hour. The reaction mixture was poured into a beaker containing 6700 g of water and then stirred at room temperature for 1 hour. The product was filtered, washed with water and dried to obtain 150 g (98%) of an intermediate K represented by the following general formula 32.

680 g of benzoic acid was added to the stirring vessel and heated to 160 ° C. to melt. In the molten benzoic acid, 93.3 g of an intermediate K represented by the general formula 32 and 260 g of tetrachlorophthalic anhydride were added and stirred at 160 ° C. for 10 hours. Thereafter, the mixture was cooled to 130 ° C., and 750 g of methanol was gradually added. 470 g of sodium hydroxide was dissolved in 17000 g of water, and the above reaction mixture was poured into it. The resulting suspension was heated to 80 ° C. and stirred for 1 hour. This was subjected to suction filtration, washed with water until the filtrate became neutral, and then dried to obtain 104 g (60%) of an intermediate L represented by the following general formula 33.

47.0 g of the intermediate L represented by the general formula 33 was mixed with 1000 g of water to obtain a slurry. To this was added 196 g of sodium sulfide nonahydrate, stirred at 70 ° C. for 24 hours, and then filtered to separate the product. The product separated by filtration was added to 3000 ml of 1N-hydrochloric acid to form a slurry, stirred at room temperature for 1 hour, filtered and washed with water. Subsequently, it was added to 2000 ml of 1N-sodium hydroxide aqueous solution to form a slurry, stirred at room temperature for 1 hour, filtered and washed with water. Slurry with water, filtration, and water washing were repeated until the filtrate became neutral, followed by drying to obtain 40 g (90%) of intermediate M represented by the following general formula 34.

Acetone 400 g was cooled to 5 ° C., and cyanuric chloride 44 g was added. Next, 87 g of the intermediate M represented by the general formula 34 was gradually added while maintaining 5 ° C. Then, 90 g of 10% -sodium carbonate aqueous solution was added and stirred at 5 ° C. for 3 hours. The product was filtered and washed with water, and then slurried again in 400 g of acetone. This was filtered and washed with acetone to obtain an intermediate N (acetone-containing cake) represented by the following general formula 35.

The obtained intermediate N (acetone-containing cake) represented by the general formula 35 was gradually added to a mixed solution of 320 g of 1,4-dioxane and 105 g of diethylaminopropylamine at a temperature of 60 ° C. or lower. Then, it stirred at 50-60 degreeC for 2 hours, and 90 degreeC for 4 hours. The reaction mixture was cooled to room temperature and poured into 5 L of water. The resulting precipitate was filtered, washed with water, and dried to obtain 105 g (75%) of a pigment dispersant E represented by the following general formula 36.

(Preparation of acrylic resin solution)
700 g of cyclohexanone was added to a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, and heated to 80 ° C. After substituting the inside of the reaction vessel with nitrogen, 133 g of n-butyl methacrylate, 46 g of 2-hydroxyethyl methacrylate, 43 g of methacrylic acid, 74 g of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 2 A mixture of 4.0 g of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000.
After cooling to room temperature, about 2 g of the resin solution was heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. Cyclohexanone was added so that the nonvolatile content of the resin solution was 20% to obtain an acrylic resin solution.

(Preparation of yellow-treated pigment)
Quinophthalone yellow pigment C.I. I. Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BSF Corporation) 300 g, a mixture of 300 g of sodium chloride and 150 g of diethylene glycol was used in a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), 120 The mixture was kneaded at 2 ° C. for 2 hours. Next, this kneaded material was put into 5 liters of warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry. Filtration and washing with water were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C. to obtain 290 g of a yellow-treated pigment.

(Preparation of green processing pigment)
Phthalocyanine green pigment C.I. I. A mixture of 300 g of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.), 300 g of sodium chloride, and 150 g of diethylene glycol was kneaded at 120 ° C. for 2 hours using a 1 gallon kneader (manufactured by Inoue Seisakusho). . Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 290 g of a green-treated pigment was obtained.

(Examples 1-14 and Comparative Examples 1-9)
Various pigments, pigment dispersants A to E obtained in Production Examples 3 to 7, the acrylic resin solution, and cyclohexanone as a solvent were weighed in a 140 ml screw cap bottle in the blending amounts shown in the table. 150 g of zirconia beads having a diameter of 1.25 mm were added and dispersed for 15 hours with a paint conditioner to obtain a pigment dispersion.

(Evaluation of each pigment dispersion)
The viscosity and thixo index value (TI value) of each pigment dispersion were measured with a B-type viscometer. Further, the gloss of a coating film applied to a PET film with a wet thickness of 12 μm and dried at 150 ° C. for 2 minutes was measured. After the pigment dispersion was stored at 40 ° C. for 1 week, the rate of increase in viscosity was measured, and the results were ◎ (almost no thickening), ○ (slightly thickening was observed, but usable range), △ (thickening was Cannot be used), x (noticeable due to significant thickening). These results are summarized in Table 1. As shown in Table 1, those using the pigment dispersant of the present invention had a low viscosity, a small thixotropic property, and an excellent fluidity. Moreover, the viscosity stability with time was also good.

  By using the pigment dispersant, pigment composition, and pigment dispersion of the present invention, it not only has excellent non-aggregation property, non-crystallinity, gloss and transparency of the coating film, but also has low viscosity and low thixotropic properties. In addition, products such as inks and paints having good viscosity stability over time can be easily obtained. The pigment dispersant, pigment composition, and pigment dispersion of the present invention are gravure inks, various general paints for automobiles, woods, metals, etc., backcoat paints for magnetic tapes, radiation cure inks, inks for inkjet printers Suitable for applications such as color filter inks.

Claims (9)

A pigment dispersant represented by the following general formula 1.

(In the formula, Q represents an optionally substituted quinophthalone residue,
X _{1 is, -NR'SO 2 -, - SO 2} NR '-, - CONR' -, - CH 2 NR'COCH 2 NR'-, or represents a group selected from -NR'CO-,
X ₂ represents a group selected from an arylene group having 20 or less carbon atoms which may have a substituent or a heteroaromatic ring which may have a substituent and which has 20 or less carbon atoms (these groups May be bonded to each other by a divalent linking group selected from —NR′—, —O—, —SO ₂ —, and —CO—).
X ₃ represents —NR′— or —O—,
(However, R ′ may have a hydrogen atom, an optionally substituted alkyl group having 20 or less carbon atoms, an optionally substituted alkenyl group having 20 or less carbon atoms, or a substituted group. And represents an aryl group having 20 or less carbon atoms.)
A and B are each independently a group represented by the following general formula 2 or 3, —O— (CH ₂ ) _n —R ₈ , —OR ₉ , —NR ₁₀ R ₁₁ , —Cl, —F or — Represents a group selected from X ₃ -X ₂ -X ₁ -Q (R ₈ represents an optionally substituted nitrogen-containing heterocyclic residue; R ₉ , R ₁₀ and R ₁₁ are each independently hydrogen; It may have an atom, a substituent, may have an alkyl group having 20 or less carbon atoms, may have a substituent, may have an alkenyl group having 20 or less carbon atoms, or may have a substituent. . represents up to 20 aryl group, n represents an integer of 0 to 20), it is either one of a and B, a group represented by the following general formula 2 or _{3, -O- (CH 2) n} - R ₈ , —OR ₉ , or —NR ₁₀ R ₁₁ ,
t represents an integer of 1 to 3. )

Wherein Y ₁ represents —NR′— or —O—,
Y ₂ may have a substituent, may have an alkylene group having 20 or less carbon atoms, may have a substituent, may have an alkenylene group having 20 or less carbon atoms, or may have a substituent. Represents a group selected from an arylene group having a number of 20 or less (these groups are bonded to each other by a divalent linking group selected from —NR′—, —O—, —SO ₂ — or —CO—). Provided that R ′ represents the one defined by the general formula 1.),
R ₁ and R ₂ each independently have a substituent, may have an alkyl group having 20 or less carbon atoms, or may have a substituent, and represents an alkenyl group having 20 or less carbon atoms (R ₁ and R ₂ may be combined to form an optionally substituted heterocyclic structure containing a further nitrogen atom, oxygen atom or sulfur atom. )

(In the formula, Z ₁ is a single bond connecting a triazine ring and a nitrogen atom, —NR′—, —NR′—G—CO—, —NR′—G—CONR ″ —, —NR′—G—SO _{2 -, - NR'-G-} SO 2 NR '' -, - O-G-CO -, - O-G-CONR '-, - O-G-SO 2 - or -O-G-SO _2, NR′- (G represents an alkylene group having 20 or less carbon atoms which may have a substituent, an alkenylene group having 20 or less carbon atoms which may have a substituent, or a substituent. And may represent an arylene group having 20 or less carbon atoms, and R ′ and R ″ each independently have a hydrogen atom or a substituent, and may have an alkyl group or substituent having 20 or less carbon atoms. And may represent an alkenyl group having 20 or less carbon atoms or a substituent, and an aryl group having 20 or less carbon atoms).
R ₃ , R ₄ , R ₅ , and R ₆ each independently have a hydrogen atom, a substituent, or an alkyl group having 20 or less carbon atoms, a substituent, or a carbon number. An alkenyl group having 20 or less or a substituent which may have an aryl group having 20 or less carbon atoms,
R ₇ may have a substituent, may have an alkyl group having 20 or less carbon atoms, or may have a substituent, and represents an alkenyl group having 20 or less carbon atoms. ).   A pigment composition comprising a pigment and the pigment dispersant according to claim 1.   The pigment composition according to claim 2, comprising a yellow pigment as the pigment.   The yellow pigment is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 185, C.I. I. The pigment composition according to claim 3, which is at least one pigment selected from CI Pigment Yellow 13.   The pigment composition according to any one of claims 2 to 4, comprising a green pigment as a pigment.   The green pigment is C.I. I. Pigment green 7 or C.I. I. The pigment composition according to claim 5, which is CI Pigment Green 36.   The pigment composition in any one of Claims 2-4 containing a red pigment or an orange pigment as a pigment.   Red or orange pigments are C.I. I. Pigment red 254, pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 177, C.I. I. Pigment red 207, C.I. I. Pigment red 48: 1, C.I. I. Pigment orange 71, C.I. I. The pigment composition according to claim 7, which is at least one pigment selected from CI Pigment Orange 73. The pigment dispersion formed by disperse | distributing the pigment composition in any one of Claims 2-8 to a non-aqueous medium.