JPH09137075A - Pigment dispersant and pigment composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the above dispersion capable of providing a dispersion of a pigment having clarity, high coloring power, excellent in flow characteristics and preservation stability, useful as an ink, etc., comprising a coloring matter of a specific formula containing an amine component residue as an active ingredient. SOLUTION: This pigment dispersion comprises a coloring matter containing an amine component residue of formula I R2 is a group of formula II [R4 and R5 are each H, a (substituted) <=40C (un) saturated alkyl, etc.; D is CH2 , etc.; (n) and (p) are each 0-5]; R3 is H, an alkyl, an alkoxy or a halogen; (j) is 0-2; (k) is 1-2; (m) is 0-3} (preferably 4-dimethylaminocyclohexylamino group, 4-diethylaminocyclohexylamino group, etc.,) an active ingredient. Preferably the residue in the coloring matter has a bonding group and is bonded to an organic coloring matter residue such as a phthalocyanine-based coloring matter residue. For example, chlorosulfonated copper phthalocyanine is reacted with 1-amino-4-N,N'-dimethylamino-cyclohexane under an alkali condition and precipitated with an acid to preferably give the objective dispersant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigment dispersant for providing a pigment dispersion excellent in dispersibility, rheological properties, non-cohesiveness, and long-term stability of these properties.

[0002]

2. Description of the Related Art Generally, when a paint, ink or other coating composition containing a pigment dispersion is required to have a clear color tone, gloss, high tinting strength or transparency, it is used to obtain these properties. It is necessary to use a pigment having a small primary or secondary particle size. However, when these pigments are dispersed in a non-aqueous vehicle, it is difficult to obtain a stable dispersion, and the following problems occur very frequently.

For example, when the above-mentioned pigment is dispersed, the viscosity of the dispersion often shows a very high viscosity, and it is difficult to take it out from the dispersing machine, or the pigment concentration in the dispersion is increased. It was difficult to improve productivity. Further, the fluidity of this dispersion exhibits a strong non-Newtonian property, and the viscosity immediately after production largely changes during storage, and further often gels. The dispersion has a strong cohesive property, and when a single pigment is dispersed, moreover, when the pigment is compounded and dispersed, agglomeration easily occurs during storage, and problems such as sedimentation and color separation often occur. .

In order to solve these problems, many proposals have been made centering on phthalocyanine pigments. For example, Japanese Patent Publication No. 41-2466 and Japanese Patent Publication No. 50-40
No. 19, sulfonic acid derivatives of pigments, Japanese Patent Publication No. 38-2713 and Japanese Patent Publication No. 39-16787, aminomethyl derivatives of pigments, and other organic dyes such as sulfamoyl derivatives and phthalimidomethyl derivatives. A method has been proposed in which various pigment derivatives used as a base are used in combination when a desired pigment is dispersed. However, even though these methods are effective in improving the non-aggregation property, they are not sufficiently satisfactory in other flow characteristics, transparency, dispersion stability, etc., and development of a method for solving the above-mentioned problems Is strongly desired.

[0005]

When the pigment is dispersed,
There is a strong demand for development of a pigment dispersant for providing a pigment dispersion which is vivid, has high coloring power and is excellent in dispersibility, flowability, non-aggregation property and storage stability.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that the following organic dye derivatives are useful as a pigment dispersant satisfying the above. After finding out, the present invention has been completed. That is,
The present invention includes (1) the following partial structural formula (i)

[0007]

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(In the formula, R ₂ is the following partial structural formula (ii)

[0009]

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(Where R_Four, R_FiveEach independently
Saturation of hydrogen or optionally substituted C10 or less
Alternatively, it represents an unsaturated alkyl group. Or R_Four, R_Five
May be substituted with nitrogen, oxygen or sulfur atoms at
Form a heterocycle, or R _Four, Or R_FiveAdjoin with
It may have a cyclic structure with a methylene group. D is -CH_Two
-, -NR₆-(Where R₆Is hydrogen or has 10 carbon atoms
The following optionally substituted alkyl group or aryl
Represents a group) or -O-, and n and p are respectively
It represents an integer of 0 to 5. ) Is a group represented by R_ThreeIs hydrogen
Represents atoms, alkyl groups, alkoxyl groups, halogen atoms
, J is an integer of 0 to 2, k is an integer of 1 to 2, and m is 0.
Represents an integer of 3 respectively. ) Amine component residue represented by
A pigment dispersant containing a dye having a group A as an active ingredient, (2)
Amine component residue A is 4-dimethylaminocyclohexyl
Amino group, 4-diethylaminocyclohexylamino
Group, 3,5-bisdimethylaminocyclohexylamino
Group or 3,5-bisdiethylaminocyclohexylami
(1) pigment dispersant and (3) dye
The min component residue A is bonded to the organic dye residue via the linking group.
(1) or (2) pigment dispersant, (4) linking group
-Y₁− (Where Y₁Is -NR₁− (Where R₁Is
Hydrogen or an optionally substituted alkyl having 10 or less carbon atoms
A alkyl group or an aryl group), -SO_Two-, -C
H_TwoNHCOCH_Two-, -CO-, -CH_TwoRepresents-)
Or the following partial structural formula (iii)

[0011]

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(Here, Y ₁ is the same as above, Y ₂ is a diamine-based bond chain, B ′ is —OH, —Cl or a bond chain,
i represents 0 or 1, respectively. However, Y ₁ is -NR _1-
In the case of, i is 0, and when Y ₁ is other than -NR _1-, i is 1. ) (Where the linking group is a group represented by the partial structural formula (iii), the amine component residue A is bonded to the triazine ring by one or two) The pigment dispersion of (3) Agent, (5) Y ₂ is the following formula

[0013]

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A pigment dispersant (4) which is a group represented by:
(6) The organic dye residue is a phthalocyanine dye residue, a dianthraquinonyl dye residue, an anthraquinone dye residue, a quinacridone dye residue, a diketopyrrolopyrrole dye residue, a dioxazine dye residue. , Anthrapyrimidine dye residue, anthanthrone dye residue, indanthrone dye residue, flavanthrone dye residue, pyranthrone dye residue, perinone dye residue, perylene dye residue (these 1 to 12 carboxyl groups, sulfone groups or halogen atoms may be bonded to the dye residue)
(1) to (5), the pigment dispersant according to any one of (1) to (5), and (7) an amine component residue A bonded to an organic dye residue.
The pigment dispersant according to any one of (1) to (6), wherein the number of 1 is 8, and (8) a dye having an amine component residue A is represented by the following formula (1):

[0015]

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(In the formula, Q represents an organic dye residue, X ₁ represents a carboxyl group, a sulfone group or a halogen atom, and X ₂
Is a substituent shown below, g represents an integer of 0 to 12, and h represents an integer of 1 to 4. ) Is a compound represented by (1)
Pigment dispersant, X ₂ is —Y ₁ —A (wherein Y ₁ is —NR ₁ — (wherein R ₁ is hydrogen or an optionally substituted alkyl group having 10 or less carbon atoms, or aryl). represents a _{group), - SO 2 -, -} CH 2 NHC
Represents OCH ₂ —, —CO—, —CH ₂ —, A is the following partial structural formula (i)

[0017]

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(In the formula, R ₂ is the following partial structural formula (ii)

[0019]

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(Here, R ₄ and R ₅ each independently represent hydrogen or an optionally substituted saturated or unsaturated alkyl group having 10 or less carbon atoms. Or R ₄ and R _5
May form an optionally substituted heterocycle containing a nitrogen, oxygen or sulfur atom, or may have a cyclic structure with an adjacent methylene group at R ₄ or R ₅ . D is -CH ₂
-, -NR _6- (wherein R ₆ is hydrogen or has 10 carbon atoms)
Represents an optionally substituted alkyl group or aryl group) or —O—, and n and p each represent an integer of 0 to 5), R ₃ represents a hydrogen atom, Represents an alkyl group, an alkoxyl group, or a halogen atom, j is an integer of 0 to 2, k is an integer of 1 to 2, and m is 0.
To 3) or the following partial structural formula (i
v)

[0021]

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(In the formula, Y ₁ and A are the same as above, and Y _1
2 represents a diamine-based bond chain, B represents an amine component residue A, -OH, or -Cl, and i represents 0 or 1. However, when Y ₁ is -NR _1- , i is 0, and Y ₁
I is 1 when is other than -NR _1- . And (9) an organic dye residue derived from copper phthalocyanine, wherein Y ₁ is —SO ₂ —, —CH.
_{2 -, - CH 2 NHCOCH 2} - a (4), (5)
Alternatively, the pigment dispersant according to any one of (8). (10)
A dye having an amine component residue A is represented by the following formula (2)

[0023]

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(1) or (8) which is a dye represented by
Pigment dispersant of (11) organic dye residue is represented by the following formula

[0025]

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Derived from a compound represented by the formula: wherein Y ₁ is --SO _2- , --CH _2- , --CH ₂ NHC.
The pigment dispersant according to any one of (4), (5) or (8), which is OCH ₂ —, and (12) the organic dye residue is represented by the following formula:

[0027]

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## STR6 ## wherein R ₇ is --H or --CH ₃ , and is derived from Y
₁ is _{-SO 2 -, - CH 2 -} , - CH 2 NHCOCH 2
The pigment dispersant according to any one of (4), (5) or (8), wherein (13) the organic dye residue is

[0029]

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(Wherein R ₈ is --H, --Cl) and Y ₁ is-
_{SO 2 -, - CH 2 -} , - CO -, - CH 2 NHCOC
H ₂ - is a (4), (5) or a pigment dispersing agent according to any one of (8), (14) an organic pigment residue is represented by the following formula

[0031]

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Derived from a compound represented by the following formula, wherein Y ₁ is --SO _2- , --CH _2- , --CH ₂ NHC.
The pigment dispersant according to any one of (4), (5) or (8), which is OCH ₂ —, and (15) the organic dye residue is represented by the following formula:

[0033]

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Derived from a compound represented by the formula: wherein Y ₁ is --SO _2- , --CH _2- , --CH ₂ NHC.
The pigment dispersant according to any one of (4), (5) or (8), which is OCH ₂ —, and (16) the organic dye residue is represented by the following formula:

[0035]

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Derived from a compound represented by the following formula, wherein Y ₁ is --SO _2- , --CH _2- , --CH ₂ NHC.
OCH ₂ - is (4), (5) or a pigment dispersing agent according to any one of (8), (17) an organic pigment residue is represented by the following formula

[0037]

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(Wherein R ₉ represents a methyl group, a 3,5-dimethylphenyl group, a 4-methoxyphenyl group or a 4- (phenylazo) phenyl group). , Y ₁ is —SO ₂ —, —CH
_{2 -, - CH 2 NHCOCH 2} - a (4), (5)
Or the pigment dispersant according to any one of (8), (18)
The organic dye residue has the following formula

[0039]

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Derived from a compound represented by the following formula, wherein Y ₁ is --SO _2- , --CH _2- , --CH ₂ NHC.
The pigment dispersant according to any one of (4), (5) or (8), which is OCH ₂ —, and (19) the organic dye residue is represented by the following formula:

[0041]

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(Wherein R ₁₀ represents -Cl or -Br and q is 0 to 4), and Y ₁ is -SO ₂ -,-. CH ₂ −, −
CH ₂ NHCOCH ₂ − is the pigment dispersant according to any one of (4), (5) or (8), and (20) the organic dye residue is represented by the following formula:

[0043]

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(Wherein R ₁₁ represents --Cl or --Br) and is derived from a compound represented by the following formula:
Y ₁ is —SO ₂ —, —CH ₂ —, —CH ₂ NHCOCH
₂ is a pigment dispersant according to any one of (4), (5) or (8), and (21) an organic dye residue is represented by the following formula:

[0045]

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Derived from a compound represented by the following formula, wherein Y ₁ is --SO _2- , --CH _2- , --CH ₂ NHC.
OCH ₂ - is (4), (5) or a pigment dispersing agent according to any one of (8), (22) a pigment, resin and (1) to the pigment dispersion according to any one of (21) And (23) a pigment composition according to (22) which is a liquid.

The pigment dispersant of the present invention has the above partial structural formula.
A dye having an amine component residue A represented by (i), particularly an organic pigment dye is used as an active ingredient. R in the above partial structural formula (i)
₂ is, for example, a group represented by the partial structural formula (ii),
R ₃ is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group or the like (C ₁
To C ₆ ) alkyl group, methoxy group, ethoxy group, n-
Propoxy group, isopropoxy group, n-butoxy group, s
ec-butoxy group, t-butoxy group, pentoxy group, hexoxy group and other (C ₁ -C ₆ ) alkoxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms and other halogen atoms, and j is 0 to 2 is an integer, k is an integer of 1 to 2, and m is an integer of 0 to 3.

In the above partial structural formula (ii), R ₄ , R ₅
Are each independently a hydrogen atom or an optionally substituted saturated or unsaturated alkyl group having 10 or less carbon atoms,
Alternatively, R ₄ and R ₅ may form an optionally substituted heterocycle containing a nitrogen, oxygen or sulfur atom, or R ₄ or R ₅ may have a cyclic structure with an adjacent methylene group. Specific examples are as follows. 1. Examples of hydrogen or an optionally substituted saturated or unsaturated alkyl group having 10 or less carbon atoms include a methyl group, an ethyl group, a propyl group, an allyl group, and the like. 2. Examples of the case where R ₄ and R ₅ form an optionally substituted heterocycle containing a nitrogen, oxygen or sulfur atom include

[0049]

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And the like. 3. Examples of the case where R ₄ or R ₅ has a cyclic structure with the adjacent methylene group are:

[0051]

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And the like. D is -CH ₂ -, - NR
_6- (wherein R ₆ represents hydrogen or an optionally substituted alkyl group or aryl group having 10 or less carbon atoms)
Alternatively, it is —O—, and n and p are each an integer of 0 to 5. Examples of the optionally substituted alkyl group having 10 or less carbon atoms in R ₆ include a methyl group, an ethyl group, a propyl group, an alkoxyethyl group, an alkoxypropyl group, and the like. Examples of the aryl group which may be present include a phenyl group, a methylphenyl group, an ethylphenyl group, and a chlorophenyl group. Next, an example of the amine component residue A is specifically shown below.

[0053]

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[0054]

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[0055]

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[0056]

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Examples of the dye used in the present invention include those in which the amine component residue A is bonded to an organic dye residue, particularly to an organic pigment dye residue, preferably 1 to 8, more preferably 1 to 4. To be Examples of organic pigment dye residues include phthalocyanine dye residues, dianthraquinonyl dye residues, anthraquinone dye residues, quinacridone dye residues, diketopyrrolopyrrole dye residues, and dioxazine dye residues. Group, anthrapyrimidine dye residue, anthanthrone dye residue, indanthrone dye residue, flavanthrone dye residue, pyranthrone dye residue, perinone dye residue, perylene dye residue, etc. Can be mentioned. 1 to 12 carboxyl groups, sulfone groups or halogen atoms may be bonded to these dye residues.

The amine component residue A may be directly bonded to an organic dye residue, particularly an organic pigment dye residue, but it is bonded to an organic dye residue, especially an organic pigment dye residue, via a linking group. Is preferable. As the linking group, for example, -Y _1-
(Y ₁ is —NR ₁ — (wherein R ₁ represents hydrogen or an optionally substituted alkyl group having 10 or less carbon atoms, or an aryl group), —SO ₂ —, —CH ₂ NHCOCH.
_{2 -, - CO -, -} CH 2 - groups represented by the representative) or the partial structural formula (iii) and the like.

R ₁ in —NR ₁ — of Y ₁ is hydrogen or an optionally substituted alkyl group having 10 or less carbon atoms,
Or an aryl group. Examples of the alkyl group having 10 or less carbon atoms which may be substituted include a methyl group, an ethyl group, a propyl group, an alkoxyethyl group, an alkoxypropyl group and the like, which may be substituted having 10 or less carbon atoms. Examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group and the like.

The diamine-based binding chain in Y ₂ of the partial structural formula (iii) is derived from, for example, a diamine compound shown below. Specific examples thereof include hydrazine, monomethylhydrazine, 1,2-dimethylhydrazine, monoethylhydrazine, 1,2-diethylhydrazine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane and N-methylethylenediamine. , 1,4
-Diaminobutane, 1,2-diamino-2-methylpropane, N, N'-dimethylethylenediamine, N, N '
-Diethylethylenediamine, 1,6-hexanediamine, N, N'-diethyl-1,3-propanediamine,
1,4-phenylenediamine, 1,3-phenylenediamine, 1,4-xylylenediamine, 1,3-xylylenediamine, 2-aminomethylpiperidine, 4-aminomethylpiperidine, 2-aminopiperidine, 4-amino Piperidine, 1,3-di- (4-piperidinyl) -propane, homopiperazine, piperazine, 1-aminopiperazine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,3-di (aminomethyl) cyclohexane Etc. Preferred diamine compounds for Y ₂ include, for example, hydrazine, ethylenediamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 1,4-diaminocyclohexane, 1,3.
-Diaminocyclohexane, 1,3-di (aminomethyl) cyclohexane, piperazine and the like. B is -OH, -Cl or a binding chain. When B is a binding chain,
The amine component residue A binds to the binding chain. Therefore, B
When A is -OH or -Cl, one amine component residue A is bonded to the triazine ring, and when B is a bonding chain, two amine component residues A are bonded to the triazine ring. become.

Examples of the dye used in the present invention include the dye represented by the above formula (1). Equation (1) above
In the above, the organic dye residue represented by Q may be an organic dye capable of introducing a linking group used when linking side chain portions. Specifically, phthalocyanine dyes, dianthraquinonyl dyes, anthraquinone dyes, quinacridone dyes, diketopyrrolopyrrole dyes, dioxazine dyes, anthrapyrimidine dyes, ansanthrone dyes, indanthrone dyes Examples of the dye include, but are not limited to, dyes, flavanthrone dyes, pyranthrone dyes, perinone dyes, and perylene dyes.

In the above formula (1), X ₁ is a carboxyl group, a sulfone group or a halogen atom. The carboxyl group and the sulfone group are used when connecting a side chain portion to an organic dye described later, a -CO-Cl group and a -SO group.
_{The 2-} Cl group is generated by being hydrolyzed by water in the reaction system in the course of the reaction after connecting with the side chain portion, but depending on the conditions of the post reaction, it is possible to prevent this hydrolysis, It is also possible to synthesize an organic dye having neither a carboxyl group nor a sulfone group. Halogen is introduced for the purpose of improving the color tone when dispersed together with a pigment, and specific examples thereof include halogenation of a derivative having phthalocyanine as a dye base. As the halogen, chlorine and bromine are used from the viewpoint of economy and the like, and the introduction method is a known method. Such a carboxyl group,
Whether or not the sulfo group and the halogen are introduced and the amount to be introduced are determined based on the characteristics of the dispersion, and are not always necessary components.

In the above formula (1), X ₂ is -Y ₁ -A.
Alternatively, it is a group represented by the partial structural formula (iv). Here, Y ₁ , Y ₂ , A and B of X ₂ are the same as above.

The dye used in the present invention includes, for example, (1) a method of introducing a linking group into a dye matrix in advance and reacting a prepared side chain component, and (2) a dye matrix starting material containing a side chain component. Examples of the method include a method of introducing the compound and synthesizing a dye matrix using this as a raw material, but any method may be used as long as the desired derivative is finally obtained, and the method is not limited to these methods. Specific examples of the method for synthesizing each linking group and the method for introducing a side chain include, but are not limited to, the following methods. 1. When Y ₁ is —NR ₁ — When the dye base or the dye raw material has an active halogen, the halogen is introduced by a deoxidation reaction with a side chain having an amine component at the terminal, or an amino is added to the dye base or the dye raw material. When there is a group, a method of reacting this amino group with cyanuric chloride and then reacting with a terminal side chain represented by A described later can be mentioned. 2. In the case where Y ₁ is —SO ₂ —, there may be mentioned a method in which the dye base or the dye raw material is treated with chlorosulfonic acid, and the chlorosulfonated dye base or the dye raw material is isolated and then reacted with a side chain component.

3. When Y ₁ is —CH ₂ NHCOCH ₂ — When N-methylolchloroacetic acid amide is dehydrated and condensed on the dye base or dye raw material under dehydration conditions such as concentrated sulfuric acid solvent, the side chain component is reacted with the chlorine at this end. There is a method of doing it. When Y ₁ is —CO— When the dye base or the dye raw material has a carboxylic acid, the carboxylic acid is acid-halogenated by a known method and introduced by a deoxidation reaction with a side chain having a component reacting with the carboxylic acid. There is a method. 5. In the case where Y ₁ is —CH ₂ —, formalin and hydrochloric acid, chlorosulfonic acid or the like are allowed to act on the dye matrix or dye raw material under dehydrating conditions, or a chloromethylating agent such as chloromethyl methyl ether is allowed to act. .

The diamine-based bonding chain represented by Y ₂ is Y ₁
Is a group other than —NR ₁ — for bonding the triazine skeleton to the dye-side linking group represented by Y ₁ . Therefore, when Y ₁ is -NR _1- , Y ₂ is unnecessary. This is because cyanuric chloride is usually used when a triazine skeleton is introduced. Therefore, when a reactive group such as an amino group capable of reacting with the active chlorine is present in the dye mother nucleus or the dye raw material, the reactive group is Y. _This is because it becomes ₁ (-NR _1- ), and cyanuric chloride can be directly bonded to Y ₁ . Next, this introduction method will be described in detail. 1: When the dye mother nucleus or dye raw material has an amino group, first, this amino group is reacted with cyanuric chloride by a deoxidation reaction, and then an amine component represented by A described later is further reacted, There is a method in which cyanuric chloride is reacted with 2 equivalents of an amine in advance, and then the remaining 1 equivalent of active chlorine is linked with a dye mother nucleus or an amino group of a dye material by a deoxidation reaction. 2: When the dye or the dye raw material does not have an amino group, the diamine compound described below is introduced into the dye mother nucleus or the dye raw material by the above-mentioned coupling method, and then cyanuric chloride and the amine component represented by A are deoxidized. React by reaction,
A method of previously reacting cyanuric chloride with 1 equivalent of a diamine compound and 2 equivalents of an amine component represented by A, and introducing the other functional group of the bifunctional connecting component into the dye mother nucleus or the dye raw material by the above-mentioned connecting method. Is mentioned.

The amine component residue represented by A is mainly obtained by nuclear hydrogenation of aromatic amines. There are various production methods, and one example thereof is as follows. A) A method in which the amino group of mononitroanilines is alkylated by a known method and then the desired product is obtained by hydrogenation reaction. B) Monoacetyl A method of alkylating non-acetylated amines of phenylenediamines, removing the acetyl groups by hydrolysis, and then obtaining the desired product by hydrogenation reaction, c) alkylating the amino groups of monocyanoanilines and then hydrogenating A method for obtaining a target product by a reaction, d) a method for obtaining a target product by a hydrogenation reaction after alkylating an amino group of a mononitroalkylaminobenzene, e) a halogen of a mononitrohalogenobenzene and an arbitrary amine compound There is a method of obtaining an intended product by a hydrogenation reaction after condensing an amino group by a deoxidation reaction, but the method is not limited thereto.

B is usually reacted with the amine component described in A. However, during the reaction, active chlorine on the triazine ring may be hydrolyzed to -OH, or -Cl may remain unreacted. However, it is possible to prevent these phenomena depending on the synthesis conditions, and the -OH and -Cl groups are not essential. Further, in the dispersant having the partial structural formula (iv), most of B is the above-mentioned amine component, and some of them are —OH groups or —C.
It may be a mixture of l. Further, the amine component of A and the amine component of B may have the same structure or different structures.

When the above-mentioned pigment dispersant described above is used, the pigment to be dispersed is not particularly limited, but it is preferable to use it for a pigment of the same color, and further, the organic dye residue and the mother nucleus are common. It is more preferable to use it for dispersing the pigment. The amount used is preferably 0.5 to 3 with respect to an organic pigment or an inorganic pigment such as carbon black.
It is 0% by weight, more preferably about 1 to 20% by weight.

The pigment composition of the present invention comprises a pigment, a resin and the above pigment dispersant. Examples of the resin include resins used in inks and paints such as ordinary gravure ink such as rosin, polyamide resin, vinyl chloride resin, nitrocellulose, aminoalkyd resin, acrylic resin, aminoacrylic resin and urethane resin. The amount of the resin used is preferably 5% by weight or more, and more preferably about 50 to 200% by weight, based on the pigment.

In order to produce the pigment composition of the present invention, for example, the respective dry powders or press cakes are mechanically mixed with various pulverizers such as a ball mill, a kneader, a bead mill and an attritor (semi) solid. To obtain a pigment composition in the form of powder or powder, or by adding a resin, a pigment and a pigment dispersant to a solvent, and dispersing using a disperser such as a dissolver, a homomixer, a kneader, a roll mill, a sand mill and an attritor. It is sufficient to obtain a liquid pigment composition. Examples of the solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl cellosolve acetate, methyl cellosolve acetate, propylene glycol monomethyl ether acetate, and other organic solvents used in inks and paints. Incidentally, the pigment and the pigment dispersant may be added separately,
Further, both may be simply mixed or the one produced by the following method may be added. Examples of the method include, for example, a method in which a pigment and a pigment dispersant are dissolved in a solvent having a strong solubility such as sulfuric acid and then coprecipitated with a poor solvent such as water, or after the pigment is suspended in water or an organic solvent. , A method of adding a dissolved pigment derivative and depositing it on the surface to coat the pigment dispersant on the surface of the pigment. Further, the pigment and the pigment dispersant may be added after the resin is dissolved in the above organic solvent to prepare a non-aqueous vehicle. In this case, the above organic solvent may be further added, if necessary, depending on the viscosity of the non-aqueous vehicle.

When such a pigment dispersant of the present invention is used, a non-aqueous vehicle such as rosin varnish, polyamide resin varnish, vinyl chloride resin varnish varnish vehicle for gravure ink, nitrocellulose lacquer, acrylic lacquer, aminoalkyd resin. In paint vehicles, amino acrylic resin paint vehicles, urethane resin paint vehicles, etc., the viscosity of the dispersion is lower than when the pigment is used alone, the structural viscosity is reduced, color separation is prevented, sedimentation is prevented by aggregation, and dispersion is performed. A remarkable effect can be obtained in terms of stability.

[0073]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, “parts” means “parts by weight”. Example 1 Copper phthalocyanine 5 chlorsulfonated by a known method
0 part was suspended in 500 parts of water, and 1-amino-4-N,
N'-dimethylamino-cyclohexane 30.7 parts to 0
The temperature was gradually raised to 60 ° C while maintaining the pH at 10 while being added at -5 ° C and a sodium hydroxide aqueous solution was appropriately added, and the mixture was reacted at the same temperature for 2 hours, followed by acid precipitation, and filtering the precipitate,
After washing with water and drying, the pigment dispersant (1) 4 represented by the following formula
1.6 parts are obtained.

[0074]

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Example 2 50 parts of chlorosulfonated copper phthalocyanine was added to 50 parts of water.
Suspended in 0 parts and 12.4 parts of ethylenediamine at 0 to 5 ° C.
, While adding the sodium hydroxide aqueous solution appropriately, p
While maintaining H10, the temperature was gradually raised to 60 ° C. and the reaction was carried out at the same temperature for 2 hours. Then, the mixture was cooled to 0 to 5 ° C., 38.0 parts of cyanuric chloride were added, and the pH was maintained at 5 to 1 while maintaining pH 10.
React at 0 ° C. for 2 hours. Furthermore 1-amino-3,5-
70.5 parts of N, N′-dimethylaminocyclohexane was added, the mixture was reacted at 40 ° C. for 3 hours, the precipitate was filtered, washed with water and dried to obtain 45 parts of a pigment dispersant (2) represented by the following formula. .

[0076]

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Example 3 4.4'-Diamino-1,1'-biantraquinonyl 4
4.4 parts were added to 300 parts of N-methylpyrrolidone, 36.8 parts of cyanuric chloride and 10.6 parts of sodium carbonate were added, and the mixture was reacted at 70 ° C. for 3 hours, and then 1-aminomethyl-N, N ′. -Add 64 parts of diethylaminocyclohexane and react at 70 ° C for 3 hours, add 300 parts of water into the reaction system and adjust the liquidity to pH 7, then filter, wash and dry to disperse the pigment represented by the following formula. 105 parts of agent (3) was obtained.

[0078]

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Embodiment 4

[0080]

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10 parts of the above compound was added to 1-amino-3,5
-N, N'-dimethylaminomethylcyclohexane 10
In addition to 0 parts, the mixture was reacted at 95 ° C for 1 hour. The reaction solution is poured into a mixed solution of water and methanol, and the precipitate is filtered, washed,
After drying, 16.5 parts of a pigment dispersant (4) represented by the following formula was obtained.

[0082]

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Example 5

[0084]

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10 parts of the above compound was suspended in 100 parts of water, 2.6 parts of ethylenediamine was added, and the mixture was stirred at 95 ° C. for 1 hour. Next, 7.5 parts of cyanuric chloride was added to adjust the pH to 9
React at 2 ℃ for 2 hours while maintaining -10, and then 1
-Amino-4-N, N'-dimethylaminopropylaminocyclohexane (16 parts) was added, the mixture was reacted at 70 ° C for 4 hours while maintaining pH 10, the precipitate was filtered, washed and dried to obtain a pigment dispersant represented by the following formula. (5) 29.2 parts were obtained.

[0086]

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A pigment dispersant having the structural formula shown below was produced in the same manner as in the above examples. The abbreviations on the upper left of the structural formulas correspond to the numbers in the examples.

[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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In order to evaluate the dispersibility of the pigment dispersant produced as described above, dispersion was carried out by the following method, and evaluation was performed. The above mixture was placed in a container, zirconia beads were added, and the mixture was dispersed by a paint shaker to prepare a coating material (liquid pigment composition of the present invention).

The paint prepared by the above method was compared with the paint prepared by the same method without adding a pigment dispersant according to the following evaluation method. (Evaluation method 1) The viscosity of the obtained coating material was measured with a B-type viscometer (measurement temperature 25 ° C), and the evaluation was performed by relative comparison with a coating material to which a pigment dispersant was not added. It was good. ◯: Very good Δ: Good ×: Equivalent to the one without addition (Evaluation method 2) The obtained coating was applied to a glass substrate with a bar coater, and the transparency was visually observed to evaluate the pigment dispersant. Relative evaluation was carried out with unadded paint. ○: Very good transparency △: Good transparency ×: Equivalent to non-added one

The dispersion and evaluation results are shown in Table 1 below. The abbreviations for the dispersant section correspond to the abbreviations for the examples.

[0108]

[Table 1] Table 1 Pigment pigment dispersant Example No. Evaluation method 1 Evaluation method 2 CIPig.Blue 15 not added × × 1 ○ ○ 2 ○ ○ 6 ○ ○ 7 ○ ○ 8 ○ ○ 9 ○ ○ 10 △ △ 11 ○ ○ CIPig.Violet 23 Not added × × 4 ○ ○ 5 ○ ○ 14 ○ ○ 15 ○ ○ 16 △ ○ 17 ○ ○ 18 ○ ○ 19 ○ ○ 20 △ △

CIPig.Red 177 not added × × 3 ○ ○ 21 ○ ○ 22 ○ ○ 23 ○ ○ 24 ○ ○ 25 ○ ○ 26 △ △ 27 ○ ○ CIPig.Green 36 not added × × 1 ○ ○ 2 ○ ○ 6 △ ○ 7 ○ ○ 8 ○ ○ 12 ○ ○ 13 ○ △ to ○

Carbon black not added × × (MA-100 manufactured by Mitsubishi Chemical Corporation) 1 ○ ○ 2 ○ ○ 6 ○ ○ 7 ○ ○ 8 ○ ○ 9 ○ ○ 10 ○ ○ 11 ○ ○ CIPig.Red 122 not added × × 28 ○ ○ 29 △ ○ 30 ○ ○ 31 △ ○ 32 ○ ○

CIPig.Red 168 not added × × 33 ○ ○ 34 △ ○ 35 ○ ○ CIPig.Red 254 not added × × 42 △ ○ 43 ○ ○ 44 ○ ○ 45 ○ △ CIPig.Yellow 108 not added × × 36 ○ △ 37 ○ ○ 38 ○ ○ CIPig.Orange 43 No addition × × 46 ○ ○ 47 ○ ○ 48 △ ○

CIPig.Red 179 not added × × 49 ○ ○ CIPig.Red 149 not added × × 50 ○ ○ CIPig.Red 123 not added × × 51 ○ ○ CIPig.Red 178 not added × × 52 ○ ○ CIPig.Blue 60 Not added × × 39 ○ ○ 40 △ ○ 41 ○ ○ CIPig.Orange 51 Not added × × 53 ○ ○ 54 △ ○ 55 ○ ○ CIPig.Yellow 24 Not added × × 56 ○ ○ 57 ○ ○ 58 ○ ○

The paint using the above-mentioned pigment dispersant of the present invention showed almost no change in viscosity measured after 1 week, and even after 1 month, phenomena such as color separation and sedimentation due to pigment aggregation were observed. And was excellent in stability. In addition, the pigment dispersant of the present invention has the same effect even in a coating material using a varnish such as nitrocellulose, alkyd resin, melamine resin, polyester resin and the like.

[0114]

EFFECT OF THE INVENTION When the pigment is dispersed using the pigment dispersant of the present invention, a pigment dispersion which is clear and has high coloring power and excellent in flowability and storage stability is obtained. Expected as a pigment dispersion for color filters.

Claims (23)

[Claims] 1. The following partial structural formula (i): (In the formula, R ₂ is the following partial structural formula (ii): (Here, R ₄ and R ₅ each independently represent hydrogen or an optionally substituted saturated or unsaturated alkyl group having 10 or less carbon atoms. Or R ₄ , R ₅ is a nitrogen, oxygen or sulfur atom. Or a cyclic structure with an adjacent methylene group at R ₄ or R ₅ may be formed, and D may be —CH ₂ — or —NR ₆
- (wherein R ₆ represents hydrogen or not more than 10 of the optionally substituted alkyl group or an aryl group having carbon atoms) or -O- and represents, n and p represents an integer of 0 to 5. ), R ₃ represents a hydrogen atom, an alkyl group, an alkoxyl group, or a halogen atom, and j is 0 to
2 is an integer, k is an integer of 1 to 2, and m is an integer of 0 to 3. ) A pigment dispersant containing as an active ingredient a dye having an amine component residue A represented by 2. The amine component residue A is a 4-dimethylaminocyclohexylamino group, a 4-diethylaminocyclohexylamino group, a 3,5-bisdimethylaminocyclohexylamino group or a 3,5-bisdiethylaminocyclohexylamino group. 1. The pigment dispersant according to 1. 3. The pigment dispersant according to claim 1, wherein the amine component residue A in the dye is bonded to the organic dye residue via a linking group. 4. The linking group is --Y _1- (wherein Y ₁ is --NR
_1- (wherein R ₁ represents hydrogen or an optionally substituted alkyl group having 10 or less carbon atoms, or an aryl group), -SO _2- , -CH ₂ NHCOCH _2- , -CO.
-, --CH _2- ) or the following partial structural formula (iii): (Here, Y ₁ is the same as above, Y ₂ is a diamine-based binding chain, B ′ is —OH, —Cl or a binding chain, and i is 0 or 1
Respectively. However, i is 0 when Y ₁ is -NR _1-.
And i is 1 when Y ₁ is other than -NR _1- . )
Is a group represented by (where the linking group is a partial structural formula (iii)
In the case of the group represented by, one or two amine component residues A are bonded to the triazine ring.) The pigment dispersant according to claim 3. 5. Y ₂ is represented by the following formula: The pigment dispersant according to claim 4, which is a diamine-based bond chain represented by: 6. The organic dye residue is a phthalocyanine dye residue, a dianthraquinonyl dye residue, an anthraquinone dye residue, a quinacridone dye residue, a diketopyrrolopyrrole dye residue, a dioxazine dye. Residue, anthrapyrimidine dye residue, anthanthrone dye residue, indanthrone dye residue, flavanthrone dye residue, pyranthrone dye residue, perinone dye residue, perylene dye residue ( The pigment dispersant according to any one of claims 1 to 5, which has 1 to 12 carboxyl groups, sulfone groups or halogen atoms bonded to these dye residues. 7. An amine component residue A that binds to an organic dye residue
The pigment dispersant according to any one of claims 1 to 6, wherein the number is 1 to 8. 8. A dye having an amine component residue A is represented by the following formula (1): (In the formula, Q is an organic dye residue, X ₁ is a carboxyl group,
Represents a sulfone group or a halogen atom, X ₂ represents a substituent described below, g represents an integer of 0 to 12, and h represents an integer of 1 to 4. The pigment dispersant according to claim 1, which is a compound represented by the formula (1). X ₂ is —Y ₁ —A (wherein Y ₁ is —NR ₁ — (wherein R ₁ is hydrogen or an optionally substituted alkyl group having 10 or less carbon atoms, or an aryl group), -SO ₂ -, - CH ₂ NHC
Represents OCH ₂ —, —CO—, —CH ₂ —, and A is the following partial structural formula (i): (In the formula, R ₂ is the following partial structural formula (ii): (Here, R ₄ and R ₅ each independently represent hydrogen or an optionally substituted saturated or unsaturated alkyl group having 10 or less carbon atoms. Or R ₄ , R ₅ is a nitrogen, oxygen or sulfur atom. _May form a heterocyclic ring which may be substituted, or may have a cyclic structure with a methylene group adjacent to R ₄ or R _5. D is —CH ₂ —, —NR ₆
-(Wherein R ₆ represents hydrogen or an optionally substituted alkyl group having 10 or less carbon atoms or an aryl group) or -O-, and n and p each represent an integer of 0 to 5) R ₃ represents a hydrogen atom, an alkyl group, an alkoxyl group or a halogen atom, and j represents 0 to 2
, K is an integer of 1 to 2 and m is an integer of 0 to 3, or the following partial structural formula (iv) (In the formula, Y ₁ and A are the same as the above, Y ₂ represents a diamine-based bond chain, B is an amine component residue A, or —O
Represents H or -Cl, and i represents 0 or 1, respectively.
However, Y ₁ is -NR ₁ - when i is 0, Y ₁ is -
I is 1 except NR ₁ −. ). 9. An organic dye residue derived from copper phthalocyanine, wherein Y ₁ is --SO _2- , --CH _2- ,
9. The pigment dispersant according to claim 4, which is —CH ₂ NHCOCH ₂ —. 10. A dye having an amine component residue A is represented by the following formula (2): The pigment dispersant according to claim 1 or 8, which is a dye represented by. 11. An organic dye residue is represented by the following formula: The pigment dispersion according to any one of claims 4, 5 and 8, wherein Y ₁ is -SO _2- , -CH _2- , or -CH ₂ NHCOCH _2-, which is derived from the compound represented by Agent. 12. An organic dye residue is represented by the following formula: (Wherein R ₇ is —H or —CH ₃ ) and Y ₁ is —SO.
_{2 -, - CH 2 -,} - CH 2 NHCOCH 2 - pigment dispersing agent according to any one of claims 4, 5 or 8 is. 13. An organic dye residue is represented by the following formula: (Wherein R ₈ is —H, —Cl) and Y ₁ is —SO ₂ —, —
The pigment dispersant according to claim 4, which is CH ₂ —, —CO—, or —CH ₂ NHCOCH ₂ —. 14. An organic dye residue is represented by the following formula: The pigment dispersion according to any one of claims 4, 5 and 8, wherein Y ₁ is -SO _2- , -CH _2- , or -CH ₂ NHCOCH _2-, which is derived from the compound represented by Agent. 15. An organic dye residue is represented by the following formula: The pigment dispersion according to any one of claims 4, 5 and 8, wherein Y ₁ is -SO _2- , -CH _2- , or -CH ₂ NHCOCH _2-, which is derived from the compound represented by Agent. 16. An organic dye residue is represented by the following formula: The pigment dispersion according to any one of claims 4, 5 and 8, wherein Y ₁ is -SO _2- , -CH _2- , or -CH ₂ NHCOCH _2-, which is derived from the compound represented by Agent. 17. An organic dye residue is represented by the following formula: (Here, R ₉ is a methyl group, 3,5-dimethylphenyl group, 4-methoxyphenyl group or 4- (phenylazo)
Represents a phenyl group. ), Wherein Y ₁ is —SO ₂ —, —CH ₂ —, —CH.
The pigment dispersant according to claim 4, which is ₂ NHCOCH ₂ −. 18. An organic dye residue is represented by the following formula: The pigment dispersion according to any one of claims 4, 5 and 8, wherein Y ₁ is -SO _2- , -CH _2- , or -CH ₂ NHCOCH _2-, which is derived from the compound represented by Agent. 19. An organic dye residue is represented by the following formula: (Here, R ₁₀ represents —Cl or —Br, and q is 0 to
4. ) Is derived from the compound represented by the formula ( ₁₎ , wherein Y ₁ is —SO ₂ —, —CH ₂ —, —CH ₂ NHC.
The pigment dispersant according to claim 4, which is OCH ₂ —. 20. An organic dye residue is represented by the following formula: (Wherein R ₁₁ represents —Cl or —Br), wherein Y ₁ is —SO.
_{2 -, - CH 2 -,} - CH 2 NHCOCH 2 - pigment dispersing agent according to any one of claims 4, 5 or 8 is. 21. An organic dye residue is represented by the following formula: The pigment dispersion according to any one of claims 4, 5 and 8, wherein Y ₁ is -SO _2- , -CH _2- , or -CH ₂ NHCOCH _2-, which is derived from the compound represented by Agent. 22. A pigment composition comprising a pigment, a resin, and the pigment dispersant according to any one of claims 1 to 21. 23. The pigment composition according to claim 22, which is liquid.