JPH01217077A - Pigment composition, dispersion method and coating compound - Google Patents

Abstract

PURPOSE:To obtain a pigment composition useful as offset ink, gravure ink, coating compound, etc., having excellent non-aggregation and fluidity, containing diketopyrrolopyrrole pigment and a specific quinacridone derivative in a specific ratio. CONSTITUTION:The aimed composition containing (A) 100 pts.wt. diketopyrrolopyrrole pigment {preferably a compound shown by formula I [X is 0 or S; A and B are alkyl, aryl, etc.; R1 and R2 are H, (substituted) alkyl, aryl, etc.]} and (B) 0.3-30 pts.wt. quinacridone derivative shown by formula II {R11 and R12 are group shown by formula III, IV, etc.; Q is quinacridone-based dyestuff residue; Y1 is -SO2-, etc.; Y2 is direct bond, -NR'-E-SO2- [R' is H, alkyl, etc.; E is (substituted) alkylene, etc.], etc.; R3, R6-R9 and R15-R18 are H, (substituted) alkyl or aryl; Y3 and Z3 are direct bond, -O-, etc.; R4, R5, R13 and R14 are hetero ring; Y4 is direct bond, -NR'-, etc.; R10 and R19 are alkyl, etc.; Y5 is connecting group; Z1 is -NR'-, etc.; Z2 is direct bond, etc.; Z4 is -NR'-, etc.; p, q and r are 0-2}.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the invention] (Industrial field of application) The present invention relates to a method for dispersing a diketopyrrolobylol pigment composition having excellent usability, particularly non-aggregation properties and fluidity, and a coating material. .

(Prior Art) Practically useful pigments that exhibit clear color tone and high coloring power in various coating or ink compositions generally consist of fine particles. However, fine particles of pigments make it difficult to obtain stable dispersions when dispersed in non-aqueous vehicles such as offset inks, gravure inks and paints, which has a significant impact on manufacturing operations and the value of the resulting products. It is known to cause various problems.

For example, dispersions containing pigments consisting of fine particles often exhibit high viscosities that make it difficult to remove the product from the disperser.

Not only is transportation difficult, but in worse cases, gelation may occur during storage, making it difficult to use. Furthermore, when different types of pigments are mixed and used, color separation due to agglomeration or decrease in sedimentation may result in color unevenness or a significant decrease in coloring power in the spread product. Furthermore, the gloss of the paint film surface of the color exhibit decreases.

Condition defects such as poor leveling may occur.

Further, although not directly related to pigment dispersion, some organic pigments experience a phenomenon that involves a change in the crystalline state of the pigment.

In other words, in non-aqueous vehicles such as offset inks, gravure inks, and paints, pigment crystal particles, which are energetically unstable, change their size and shape and shift to a stable state, resulting in a significant change in hue in the color spread1. Product value may be impaired due to decreased tinting strength, generation of coarse particles, etc.

In order to solve the various problems mentioned above, many proposals have been made so far, centering on copper phthalocyanine and quinacridone pigments.

The content can be broadly divided into the following two categories based on technical methods.

Act 1 is USP 3370971 and USP 29655
As seen in Publication No. 11, the surface of pigment particles is coated with a colorless compound such as silicon oxide, aluminum oxide, and tertiary butylbenzoic acid.

The second method is Japanese Patent Publication No. 41-2466 and USP 28
As typified by Japanese Patent No. 55403, this is a method in which a compound obtained by using an organic pigment as a parent skeleton and introducing substituents such as a sulfone group, a sulfonamide group, an aminomethyl group, or a phthalimidomethyl group into the side chain is mixed.

Compared to the first method, the second method has a significantly greater effect on pigment disaggregation, crystal stability, etc. in a non-aqueous vehicle, and is also very advantageous judging from the ease of manufacturing the pigment composition. It's a method.

Currently, very few compounds are known that are effective against diphtopyrrolopyrrole pigments.

For diketopyrrolopyrrole pigments, JP-A-62-2
A composition disclosed in Japanese Patent No. 95966 is known. Is 9 dispersion aid effective or not in the pigment field?

Although it will not be known until further experimentation is carried out, the combined use of phthalimidomethyl derivatives of quinacridone is not necessarily effective.

(Problems to be Solved by the Invention) The present invention is aimed at obtaining a stable dispersion with excellent non-aggregation properties and fluidity when producing offset inks, gravure inks, paints, etc. made of diketopyrrolopyrrole pigments. The present invention provides a pigment composition and a method for dispersing the pigment.

[Structure of the invention]

(Means for Solving the Problems) The present invention provides 0.0 parts by weight of a quinacridone derivative represented by the following formula (I) per 100 parts by weight of a diketopyrrolopyrrole pigment.
This invention relates to a method for dispersing pigment composition 1 and a paint using 3 to 30 parts by weight.

The diketopyrrolopyrrole pigment may be a compound represented by formula (II) or a mixture of two or more compounds having different structures represented by formula (II).

These compounds are described in U.S. Pat. No. 4,415,685.

European Patent Application Publication No. 133,156 or Japanese Patent Application Publication (A) No. 61-120861.61
-183363.62-149759 etc.

In formula (II), X represents a sulfur atom, and A and B may be the same or different from each other and are alkyl, aralkyl, cycloalkyl, aryl, or a carbocyclic or heterocyclic aromatic residue. represents a group, +R1 and R2 are hydrogen atoms, unsubstituted or substituted alkyl residues, alkenyl, alkynyl;

It represents an aralkyl, cycloalkyl, carbamoyl, alkylcarbamoyl, arylcarbamoyl, alkoxycarbonyl, aryl, alkanoyl or aroyl group.

When A and B represent an alkyl group in formula (II), this alkyl group may or may not be 9-branched, or may be cyclic, and may be saturated. It may be well or phthalocyanine saturated. Preferably 1 to 18 pieces.

More preferably, 1 to 12 pieces, particularly preferably.

Preferably, it has 1 to 6 carbon atoms. Specific examples include methyl, ethyl, isopropyl, nibutyl, tertiary butyl, tertiary amyl, cyclohexyl, octyl, decyl, dodecyl or stearyl.

When A and B in formula (II) represent an aralkyl group, it preferably contains 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and is branched. The unbranched or unbranched alkyl or alkenyl group preferably contains a monocyclic to tricyclic ring, more preferably a monocyclic or tricyclic ring residue. Examples include benzyl and phenylethyl.

In formula (II), when A and B represent carbocyclic aromatic residues, monocyclic to tetracyclic, especially monocyclic or bicyclic residues, i.e. phenyl, diphene (in the formula T, ,
T, , T3 have different positions and are each independently hydrogen, halogen, carbamoyl, and cyano.

Trifluoromethyl + alkylcarbamoyl of CZ to CI3 + alkyl of CI to C+Z alkoxy + alkoxy of CI to C4 + C1 to C1! Alkyl mercapto 02-C13
alkoxycarbonyl, Cz~C+s alkanoylamino, C8~C+Z monoalkylamino, C2~CZ
a dialkylamino, unsubstituted or halogen + CI ~
Substituted by C1□ alkyl or Cl-CI2 alkoxy. phenoxy, phenylmercapto,
represents phenoxycarbonyl, phenylcarbamoyl or benzoylamino;
~C4 alkyl, cyano, C, xc4 alkoxy,
Unsubstituted or substituted by chlorine or methyl.

Phenoxy, carbamoyl, 02-C2 alkyl carbamoyl.

) or represents phenylcarbamoyl, unsubstituted or substituted by chlorine, methyl or methoxy.

(In the formula, T represents methyl, isobutyl, chlorine, bromine, methoxy, phenoxy or cyano, and T represents methyl,
chlorine or cyano, and T represents methyl or chlorine); more specifically, A is phenyl, 4-chlorophenyl or 4-biphenyl residue, and B is phenyl, 3- or 4-chlorophenyl, 4-methylphenyl.

4-isobutylphenyl, 4-diphenyl or 3-
Examples include cyanophenyl residues.

In formula (II), when A and B represent heterocyclic aromatic residues, monocyclic to tricyclic residues are preferred.

These may be purely heterocyclic or may contain one heterocycle and one or more fused benzene rings, specifically one e.g.

Pyridyl, pyrimidyl, pyrazinyl, triazinyl.

Examples include furanyl, pyrrolyl, thiophenyl, quinolyl, coumarinyl, benzofuranyl, benzimidazolyl, and benzoxacylyl. Whether it is a carbocyclic aromatic or a heteroaromatic residue, 1 indicates the usual water-insolubilizing substituents, for example as described in European Patent Application No. 94911'. There is also.

In addition, 9 quinacridone derivatives related to the present invention are as follows:
), 2), and these include JP-A-56-118462.56-167762.58-
145762.59-96175゜61-246261
Some of them are publicly known from publications such as publications.

/ ＼ R1fu R18) -11嬶-O-(CH,)n-Rzo, -0Rzr
, -NR2□Rzx, C1,F or -
Ys-Y+ represents Q, however * R11+ R
I2 are each independent.

or −〇　　(CHz)n　Rz.

It is.

Q: Represents a quinacridone dye residue.

YI: Sow +, Chz NHCOC
H! +, -co-, or an alkylene group which may have a side chain having 10 or less carbon atoms.

Y2: Direct bond or -NR'-E-3゜2
- or -NR"-E-Co-, however.

E represents an optionally substituted saturated or unsaturated alkylene group or arylene group, and R' represents a hydrogen atom or an optionally substituted saturated or unsaturated alkyl group or aryl group.

In addition, E or R', R" shown below is the above-mentioned E.
Or it represents the same content as R'.

Rs + Ra + Rt * Rs + R9+ R
li Rli1 R+'rtR11Rzt+ RB, R
zs: Each independently represents a hydrogen atom or an optionally substituted saturated or unsaturated alkyl group or aryl group.

Yz, Zs: each independently bonds directly or represents 10- or -NR'-.

Ra+Rs*R+s+Rli: each independently an optionally substituted saturated or unsaturated alkyl group.

Aryl group or R=, Rs or R13+ Rli
represents an optionally substituted heterocycle containing a nitrogen, oxygen or sulfur atom.

Y4: Direct bond or -NR"-, -NR'
-E-3o□-, -NR"-E-3o□NR"-9-N
R"-E-Co- or -NR'-E-CONR"-.

R8°, R19: Each independently represents an optionally substituted saturated or unsaturated alkyl group or aryl group.

Ys: Bonds with YI through a nitrogen atom and forms a triazine ring.

It represents a linking group that is bonded to a nitrogen atom or oxygen atom that is different from the nitrogen atom that is bonded to YI.

Z, Knee NR”- or -〇-.

Z2: Direct bond or -E-3O, -NR"
- or -E-Co-NR'-.

Z4: Direct bond or -NR'-, -NR'
-E-Co-, -NR"-E-CONR"-, -NR'
E Sow, NR” E 5OzN
R-, -0-E-Co-, -0-E-CONR'-.

-0-E-3o, -, -0-E-3Ox C0NR'-
, -0-E-3o□- or 10-E-3ONR'-.

R2°: represents an optionally substituted heterocycle containing a nitrogen atom.

j, l, m, n: Each independently represents a number from 0 to 20. However, Il+m is never zero for j+.

p, q, r: Each independently represents a number from 0 to 4.

However, p+q+r is never zero.

The compound represented by Formula 2 (I) may have substituents with different structures represented by the same general formula in one molecule.

In formula (I), E in Yz, Ya, Zz, Z- represents an optionally substituted saturated or unsaturated alkylene group or arylene group, preferably an optionally substituted phenylene group, Examples include a naphthylene group or a saturated alkylene group which may have a side chain having 10 or less carbon atoms.

The amine component or alcohol component used to form is, for example, dimethylaminomethyl, dimethylaminoethyl, dimethylaminopropyl, dimethylaminoamyl, dimethylaminobutyl, diethylaminoethyl, diethylaminopropyl, diethylaminohexyl,
Diethylaminoethoxypropyl, diethylaminobutyl, diethylaminopentyl, dipropylaminobutyl, dibutylaminopropyl, dibutylaminoethyl, dibutylaminobutyl, diisobutylaminopentyl, N
, N-methyl-laurylaminopropyl, N,N-monoethylhexylaminoethyl, distearylaminoethyl.

dioleylaminoethyl, distearylaminobutylamine or alcohol, or N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine,
N-Aminopropylpiperidine.

N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-aminomethylpiperidine, or N-hydroxymethylpiperidine, N-hydroxyethylpiperidine,
N-hydroxyethylpiperidine, N-hydronachiethylpipecoline, N-hydroxypropylpipecoline, N-
These include hydrnaxymethylpyrrolidine, N-hydranoxybutylpyrrolidine, N-hydroxyethylmorpholine, N-hydroxybutylmorpholine, and the like.

Formula -〇　(CHz)n　Rz.

The amine component or alcohol component used to form the
Methylpiperazine, 1-amino-4-cyclopentylpiperazine, 1-cyclopentylpiperazine, N-methyl-3-piperidinemethanol.

N-methyl-3-hydroxypiperidine, N-ethyl-
These include 3-hydroxypiperidine, N-methyl-4-piperiditul, N-methyl-2-hydroxyethylpyrrolidine, and the like.

In addition, Y represents a linking group that is bonded to Y through a nitrogen atom and bonded to the triazine ring through a nitrogen atom or oxygen atom that is different from the nitrogen atom that is bonded to Yl, and is a component used to form Y5. is, for example, hydrazine, 1,2-
Dimethylhydrazine, ethylenediamine, l,2-diaminopropane, 1,3-diaminopropane, N-methylethylenediamine, 1-butylhydrazine, 1,4-diaminobutane, 1゜2-diamino-2-methylpropane, 1.2 -diethylhydrazine, N,N'-dimethylethylenediamine, N-ethylethylenediamine, N-methyl-1,3-propanediamine, 1,5-diaminopenkune, 2,2-dimethyl-1,3-propanediamine, N -isopropylethylenediamine, N,N''-diethylethylenediamine, 1,6-hexanediamine, 1
．． 7-Diaminohebutane, N,N”-diethyl 1,3-
Propanediamine, N'-isopropyl-2-methyl-
1,2-propanediamine, l.

8-diaminooctane, N,N'-dimethyl 1. 6-
Hexanediamine, 1,9-diaminononane, 1°IO
-diaminodecane, hydroxylamine, N-isopropylhydroxylamine, N-(t-butyl)hydroxylamine, ethanolamine, l-amino-2-propatol, 2-amino-1-propatol, 3-amino-1- propatool, 2-(methylamino)ethanol, 2-amino-1-butanol, 4-amino-1-butanol, 2-amino-2-methyl-1-butanol, 2
-amino-1-hentanol, 5-amino-1-pentanol.

2-(propylamino)ethanol, 2-amino-1-
Hexanol, 6-amino-1-hexanol.

2-(t-butylamino)ethanol, 2-amino-3
-Methyl-1-pentanol, 2-amino-4-methyl-1-pentanol, 1,2-phenylenediamine, l
, 3-phenylenediamine, 1,4-phenylenediamine, 2-aminophenol, 3-aminophenol, 4
-aminophenol, 2,5-diaminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, bis-(3-aminopropyl)-ether, 1,2-
Bis-(3-aminopropoxy)-ethane, 1,3-bis-(3-aminopropoxy)-2,2-dimethylpropane.

lauryl aminopropylamine, methylimino-bis-
Propylamine, 3-piperidine methanol.

2-aminomethylpiperidine, 2-piperidineethanol, 4-aminomethylpiperidine, 1,3-di(4-
piperidyl)-propane, 3-hydrnaxypyrrolidine,
Homopiperazine, N-aminopropylpiperazine, 2-
Methylpiperazine, 2,6-dimethylpiperazine, 2,
5-dimethylpiperazine, piperazine, etc.

To produce the compound represented by formula (I), first synthesize an amine component to be introduced as a substituent, and then react this with a quinacridone compound into which a substituent capable of reacting with the amine component has been introduced, or There is a method in which a quinacridone compound into which a substituent that can react with an amine component is introduced is subjected to several reactions to finally form a substituent for the amine component on the quinacridone skeleton. Sodium hydroxide, sodium carbonate, potassium hydroxide as agents.

Basic compounds such as potassium carbonate, triethylamine, pyridine, and p-dimethylaminopyridine may also be used in combination. In addition, water, methanol, ethanol, propyl alcohol, and isopropyl alcohol are used as solvents for these reactions.

Common organic solvents include acetone, dioxane, N,N-dimethylformamide, N-methyl-2-pyrrolidinone, dimethyl sulfoxide, cyclohexane, toluene, xylene, and the like.

Further, as the quinacridone derivative, at least one selected from a quinacridone dye, a methylolated product of melamine, benzoguanamine or urea, and an alkoxymethylated product thereof, and at least one selected from an optionally substituted phthalimide and N-oxymethylphthalimide. Examples include a compound formed by reacting with a species, a compound having a carboxyl group produced by hydrolyzing the compound, or a compound whose carboxyl group forms a salt with a metal.

These compounds may have, for example, formulas (I[), (IV)
These compounds have, for example, the formula ([[), (IV
), the triazine ring or urea bond is bonded with the quinacridone parent skeleton in between.

Q: represents the same content as Q shown in formula (II).

RZ4+ R-! S: hydrogen atom, halogen atom, alkyl group.

Represents an alkoxy group, nitro group, sulfone group or carboxyl group.

s, t: represents a number from O to 4.

The methylolated product of melamine or its alkoxymethylated product used in the present invention may be either a di-substituted product to a hexa-substituted product, and industrially, raw materials containing mono-substituted products to hexa-substituted products and polymers thereof are used. Often. Similarly, in the case of penzoguanamine, a methylolated product of urea, or an alkoxymethylated product thereof, an excellent pigment dispersion effect can be obtained regardless of the number of substituents.

In the compound obtained in the present invention, the methylol group or alkoxymethyl group does not necessarily need to completely react with phthalimide or N-oxymethylphthalimide, and even if some methylol group or alkodimethyl group remains unreacted. Shows extremely excellent dispersion effect.

Furthermore, it is possible to use melamine, benzoguanamine or urea, paraformaldehyde and alcohol as raw materials instead of using methylolated or alkoxymethylated products of melamine, benzoguanamine or urea as raw materials.

In addition, the compound obtained in the present invention contains a compound such as formula (Vl), for example, by a crosslinking reaction of the raw material quinacridone dye with a methylolated product or an alkoxymethylated product of melamine, benzoguanamine, or urea. It was found that even in this case, an extremely excellent dispersion effect was exhibited.

Formula (V) C’H2 Q: represents the same content as Q shown in formula (II).

RZ4.3: Represents the same content as R24°S shown in formula (I[[) or (IV).

When N-methylol phthalimide was used as a raw material, some phthalimide groups were also directly introduced into the quinacridone parent skeleton. For example, a compound of formula (VI) is produced, which also shows an extremely excellent dispersion effect.

Q: represents the same content as Q shown in formula (II).

Rxa, Rzs, S, t: Represents the same content as Rta, R□, S, t shown in formula (III) or (IV).

Furthermore, compounds obtained by hydrolyzing phthalimide groups, such as those represented by formula (■), and their metal salts such as sodium, calcium, barium, aluminum, and strontium also exhibited extremely excellent dispersion effects.

Q: represents the same content as Q shown in formula (II).

Rzi, Rzt, S, t: Rta1 RZ? shown in formula (III) or (IV)? , S, represents the same content as t.

Acids such as sulfuric acid and polyphosphoric acid can be used as reaction solvents for producing the compounds of the present invention.

When producing the compound of the present invention, the amount of methylolated products of melamine, benzoguanamine, or urea and their alkoxymethylated products is 0.00% per mole of quinacridone dye.
A compound with the best dispersion performance can be obtained when 2 to 6 moles of optionally substituted phthalimide and 0.2 to 10 moles of N-oxymethylphthalimide are used as raw materials, but if the charging molar ratio is outside this range, Although the amount of impurities increases even when manufactured using the above method, in practical use, a sufficient dispersion effect can be obtained by increasing the amount added.

The amount of the quinacridone derivative obtained in the present invention in the pigment is preferably 0.3 to 30 parts by weight per 100 parts by weight of the pigment. If it is less than 0.3 parts by weight, the effect of the pigment dispersant obtained in the present invention cannot be obtained, and even if it is used in an amount greater than 30 parts by weight, the effect of the amount used cannot be obtained.

Examples of methods for using the quinacridone derivatives according to the present invention include the following methods.

1. A pigment composition obtained by pre-mixing a pigment and a quinacridone derivative is added to a non-aqueous vehicle and dispersed.

2. Disperse the pigment and quinacridone derivative separately in a non-aqueous vehicle, etc. and mix the resulting dispersion. 3. Disperse the pigment and quinacridone derivative separately in a non-aqueous vehicle, etc., and mix the resulting dispersion. . In this case, the quinacridone derivative may be dispersed using only a solvent.

4. After dispersing the pigment in a nonaqueous vehicle or the like, a quinacridone derivative is added to the resulting dispersion.

There are four methods, and any of these methods can achieve the desired effect.

As for the preparation method of the pigment composition shown in item 1 above, the desired effect can be sufficiently obtained by simply mixing the B powder and the powder of the quinacridone derivative related to the present invention.

Kniter, roll, attritor, super mill.

The quinacridone derivative can be mixed mechanically using various types of grinders, or the solution containing the quinacridone derivative according to the present invention can be added to a suspension system of the pigment in water or an organic solvent, and the quinacridone derivative can be deposited on the surface of the pigment. Even better results can be obtained by performing an intimate mixing method such as co-dissolving the pigment and quinacridone derivative in a strong solvent and co-precipitating with a poor solvent such as water.

Further, as shown in 2 to 4 above. In the use of pigments and quinacridone derivatives, dispersion of the pigment or quinacridone derivative in a non-aqueous vehicle or solvent.

Good dispersion of the pigment can be achieved by using a daysilver, high speed mixer, homo mixer, Nigu, roll mill, sand mill, attritor, etc. as a dispersing machine for these mixing.

According to the invention, therefore, a lime rosin varnish.

Gravure inks such as polyamide resin varnish or vinyl chloride resin varnish, nitrocellulose lacquer.

Air drying or baking of amino alkyd resin is a paint, acrylic lacquer, baking amino acrylic resin is a paint.

In non-aqueous vehicles such as urethane resin paints.

Compared to when pigments are used alone, the dispersion exhibits good fluidity such as lower viscosity and structural viscosity, and at the same time, there are no problems such as color separation or crystal changes, and the gloss of printed matter or coatings is good. You can get beautiful products.

In particular, the quinacridone derivatives related to the present invention are:

It has an extremely excellent dispersion effect not only in oil-modified amino alkyd resin paints but also in oil-free alkyd resin paints.

The use of quinacridone derivatives according to the present invention is not limited to non-aqueous vehicles, but also other printing inks, paints,
Even when it comes to coloring plastics.

A colored product with excellent dispersion effect and strong tinting power can be obtained.

The outline of the method for synthesizing two quinacridone derivatives according to the present invention will be shown below as production examples. In addition, the following “part” and “%”
” means “parts by weight” or “% by weight”, and the numbers of the quinacridone derivatives correspond to the abbreviations shown in Table-1.

[Production Example 1] 50 parts of mono(chlorosulfonated) quinacridone and 50 parts of water
After dispersing in 0 parts, diethylaminopropylamine 10
0 parts was added, stirred at 60''C for 2 hours, filtered, washed with water until neutral, and dried to obtain quinacridone derivative (I) 6.
I got 0 copies.

[Production Example 2] 50 parts of mono(chloromethylated) quinacridone and 500 parts of water
After dispersing in 2-(ethylamino)ethanol 12
Then, 100 parts of a methanol solution containing 25 parts of cyanuric chloride was added and stirred at 10°C for 1 hour.

Add 80 parts of N-methyl-4-piperiditul to 80°
The mixture was stirred at C for 2 hours. The product was filtered, washed with water until neutral, and then dried to obtain 90 parts of quinacridone derivative (25).

[Production Example 3] After dispersing 50 parts of di(chloroacetamidomethylated)quinacridone in 500 parts of water, 6 parts of diethylaminopropylamine and 4 parts of 1-amino-2-propanol were added and stirred at 20°C for 12 hours. 0 next.

After adding 100 parts of a methanol solution in which 9 parts of cyanuric chloride was dissolved and stirring at 100C for 1 hour, N-methyl-2
-Add 30 parts of hydroxyethylpyrrolidine and 70°C
The mixture was stirred for 2 hours. The product was filtered, washed with water until neutral, and then dried to obtain 69 parts of quinacridone derivative (30).

[Production Example 4] 13 parts of melamine in 300 parts of 98% sulfuric acid at 10-20°C
Then, 18 parts of paraformaldehyde was added to 20 parts of paraformaldehyde.
Add below 'C, heat and stir at 70-80°C for 4 hours. Next, the mixture is cooled to 20-30°C, and 16 parts of quinacridone is added thereto, followed by stirring at the same temperature for 2 hours.

Next, 50 parts of phthalimide was added and stirred at 50-60°C for 3 hours. The reaction solution was poured into 5000 parts of ice water, filtered, washed with water, and dried to obtain a quinacridone derivative (3+
-3:Oa- Note that quinacridone derivative 43 is a comparative example.

In order to evaluate the dispersion effect of the quinacridone derivative obtained in the present invention, 5% of the quinacridone derivative was added to the diketopyrrolobylol pigment represented by 2NX) to prepare a paint with the following formulation. .

In addition.

Formulation (I) Pigment 9.5 parts Quinacridone derivative 0.5 parts Alkyd resin varnish (non-volatile content 60%) 26.4 parts Melamine resin varnish (non-volatile content 50%) 13.6 parts Thinner 20 parts (xylene/n) -butanol = 8/2) Mixed varnish added after dispersion 48.3 parts (alkyd/melamine-7
/3 (solid content)) Formulation (2) Pigment 9.5 parts Quinacridone derivative 0.5 parts Alkyd resin varnish (non-volatile content 60%) 26.4 parts Melamine resin varnish (non-volatile content 50%) 13.6 parts Mixed varnish to be added after the number of Swasol 20 parts 48.3 parts (alkyd/melamine = 7/3 (solid content)) Place the above mixture in a container, add a steel ball, disperse with a paint shaker, and apply to the paint. It was created. These paints were compared with a paint to which no quinacridone derivative was added (a paint in which no quinacridone derivative was added in the above formulation and the pigment was 10 parts) according to the evaluation method described below. Table 2 shows an example of the results. Note that the numbers of the quinacridone derivatives in Table 2 correspond to the abbreviations shown in Table 1.

Evaluation method (I) The viscosity of the obtained coating material was measured using a B-type viscometer (at a measurement temperature of 25° C.) and determined based on its TI value (6 rPm/60 rpm).

0: 1.0 to 1.5 Δ: 1.5 to 2.0
The paint was adjusted with thinner to give a spraying time of 3 seconds, was sprayed onto a tinplate plate using an air spray gun, and then baked, and the overall sharpness of the coated surface was evaluated by visual inspection and by measuring the 20° gloss with a gloss meter.

○: Excellent Δ: Good ×: Poor Mixture Added quinacridone derivative Evaluation (I)
Evaluation (2) 4o Δ 6 Δ 0 12 Δ 017
Q Q19
Q Δ20
Q Q23
△ Δ25
△ 031
Q Q35 Q
○37 Δ
038 Q ○4
3 × ×2)
Not added × ×11
△ Δ13
Q ○26 Δ
Δ28 △ 02
9 0 Q34
Δ 039
0 Δ42 Δ
043xx When the viscosity of these paints was measured using the same viscosity needle after being left for one week, almost no increase in viscosity was observed.

Also.

I made a light color paint of 1/10 strength with white paint adjusted with titanium white, adjusted the viscosity to 23 seconds with Ford Cup 4, and observed the state of agglomeration in a test tube, but even after a month, the color separated. No precipitation was observed.

Furthermore, III to which one quinacridone derivative according to the present invention was added showed good dispersibility without causing aggregation even in nitrocellulose lacquer, acrylic resin paint, and gravure ink.

Note that similar results were obtained with diketopyrrolobyrrole pigments other than Formula 2 (IX).

Claims (1)

[Scope of Claims] 1. 100 parts by weight of a diketopyrrolopyrrole pigment and 0.3 to 0.3 parts of a quinacridone derivative represented by the following general formula [I]
A pigment composition comprising 30 parts by weight. Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R_1_1, R_1_2: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -O-(CH_2)n-R_2_0, -OR_2_1,
-NR_2_2R_2_3, -Cl, -F or -Y_
5-Y_1-Q. However, R_1_1, R_1
Each of _2 is independent, and at least one of them is ▲There is a mathematical formula, chemical formula, table, etc.▼ or ▲There is a mathematical formula, chemical formula, table, etc.▼ or -O-(CH_2)n-R_2_0. Q: Represents a quinacridone dye residue. Y_1: -SO_2-, -CH_2NHCOCH_2-
, CO- or an alkylene group which may have a side chain having 10 or less carbon atoms. Y_2: Direct bond or -NR'-E-SO_
2- or -NR'-E-CO-. However, E
represents an optionally substituted saturated or unsaturated alkylene group or arylene group, and R' represents a hydrogen atom, an optionally substituted saturated or unsaturated alkyl group or aryl group. In addition, E or R', R'' shown below is the above-mentioned E
Or it represents the same content as R'. R_3, R_6, R_7, R_8, R_, R_9, R_
1_5, R_1_7, R_1_8, R_2_1, R_2
_2, R_2_3: Each independently represents a hydrogen atom, an optionally substituted saturated or unsaturated alkyl group, or an aryl group. Y_3, Z_3: each independently bonds directly or represents -O- or -NR'-. R_4, R_5, R_1_3, R_1_4: each independently an optionally substituted saturated or unsaturated alkyl group or aryl group, or R_4, R_5 or R_1_3, R_1_4 containing a nitrogen, oxygen or sulfur atom, even if substituted Represents a good heterocycle. Y_4: Direct bond or -NR'-, -NR'
E-SO_2-, -NR'-E-SO_2NR''-, -
NR'-E-CO- or -NR'-E-CONR''-
represents. R_1_0, R_1_9: each independently,
Represents an optionally substituted saturated or unsaturated alkyl group or aryl group. Y_5: bonded to Y_1 through a nitrogen atom, with a triazine ring,
Represents a linking group that is bonded through a nitrogen atom or oxygen atom that is different from the nitrogen atom that is bonded to Y_1. Z_1: represents -NR'- or -O-. Z_2: Direct bond or -E-SO_2-NR
'- or E-CO-NR'-. Z_4: Direct bond or -NR'-, -NR'
E-CO-, -NR'E-CONR''-, -NR'E-
SO_2-, -NR'-E-SO_2NR''-, -O-
E-CO-, -O-E-CONR'-, -O-E-SO
_2-, -O-E-SO_2CONR'-, -O-E-
Represents SO_2- or -O-E-SONR'-. R_2_0: represents an optionally substituted heterocycle containing a nitrogen atom. j, k, l, m, n: Each independently represents a number from 0 to 20. However, j+k and l+m are never zero. p, q, r: Each independently represents a number from 0 to 4. However, p+q+r is never zero. 2. The pigment composition according to claim 1, wherein the diketopyrrolopyrrole pigment is a compound represented by formula (II) or a mixture of two or more compounds having different structures represented by formula (II). Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X represents an oxygen or sulfur atom, and A and B may be the same or different from each other, and may be alkyl, aralkyl, or cyclo. represents an alkyl, aryl or carbocyclic or heterocyclic aromatic residue, R_
1 and R_2 are hydrogen atoms, unsubstituted or substituted alkyl residues, alkenyl, alkynyl, aralkyl, cycloalkyl, carbamoyl, alkylcarbamoyl,
Arylcarbamoyl, alkoxycarbonyl, aryl, alkanoyl or aroyl group. 3. The quinacridone derivative is a quinacridone dye, at least one selected from methylolated products of melamine, benzoguanamine or urea, and alkoxymethylated products thereof, and at least one selected from optionally substituted phthalimide and N-oxymethylphthalimide. The pigment composition according to claim 1 or 2, which is a compound formed by reacting a species with a metal, a compound having a carboxyl group produced by hydrolyzing the compound, or a compound whose carboxyl group forms a salt with a metal. 4. A method for dispersing pigments, which comprises using 0.3 to 30 parts by weight of the quinacridone derivative according to claim 1 to 100 parts by weight of the diketopyrrolopyrrole pigment. 5. A coating material comprising 100 parts by weight of a diketopyrrolopyrrole pigment and 0.3 to 30 parts by weight of the quinacridone derivative according to claim 1.