JPH0819347B2 - Pigment composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a pigment composition having excellent suitability for use, particularly non-aggregation property, non-crystallinity and fluidity.

(Prior Art) In general, practically useful pigments that exhibit a vivid color tone and high coloring power in various coating or ink compositions consist of fine particles. However, it is difficult to obtain a stable dispersion of fine pigment particles when dispersed in non-aqueous vehicles such as mofsetto inks, gravure inks and pigments, which has a significant impact on the manufacturing process and the value of the resulting products. It is known to cause various problems that cause

For example, dispersions containing pigments consisting of fine particles often have high viscosities, which not only makes it difficult to remove and transport the product from the disperser, but in the worse case, it causes gelation during storage and is used. It can be difficult. Further, when different kinds of pigments are mixed and used, color separation due to agglomeration or phenomena such as sedimentation may cause unevenness in color and a marked decrease in coercive force in the developed product. Furthermore, the coating surface of the color-developed product may have poor gloss, poor leveling, and other defective states.

Moreover, although not directly related to the dispersion of the pigment, some organic pigments have a phenomenon accompanied by a change in the crystalline state of the pigment.

That is, in non-aqueous vehicles such as offset inks, gravure inks, and paints, the crystal particles of energetically unstable pigments change their size and form and shift to a stable state. The commercial value may be impaired due to a decrease in coloring power, generation of coarse particles, and the like.

In order to solve the above-mentioned various problems, many proposals have been made up to now mainly on copper phthalocyanine and quinacridone pigments.

The contents can be roughly classified into the following two when classified according to the technical method.

The first method is to coat the surface of the pigment particles with a colorless compound such as silicon oxide, aluminum oxide and tertiary butyl benzoic acid as seen in USP 337091 and USP 2965511.

In the second method, as represented by JP-B-41-2466 and US Pat. No. 2,855,403, a substituent such as a sulfone group, a sulfonamide group, an aminomethyl group or a phthalimidomethyl group is introduced into a side chain using an organic pigment as a parent skeleton. This is a method of mixing the compounds obtained by the above.

The second method has a remarkably large effect on the non-aggregation property and crystal stability of the pigment in the non-aqueous vehicle as compared with the first method, and is extremely advantageous even when judged from the ease of producing the pigment composition. Is the way.

(Problems to be Solved by the Invention) The present invention provides a pigment dispersion for obtaining a stable dispersion excellent in non-aggregation, non-crystallinity, and fluidity when manufacturing offset inks, gravure inks, paints, and the like. An agent and a pigment composition are provided.

(Means for Solving the Problems) The present invention provides a pigment composition comprising a pigment and a pigment dispersant represented by the formula (I) (provided that when the pigment is a diketopyrrolopyrrole pigment, Q in the formula (I) is quinacridone. Except when it is a system dye).

It represents -OR ₅ or -X ₂ -X ₁ -Q.

Q: Dianthraquinonyl dye, Phthalocyanine dye,
Represents an organic dye residue selected from quinacridone dye, dioxazine dye, anthrapyrimidine dye, anthanthrone dye, indanthrone dye, flavanthrone dye, perinone dye, perylene dye or thioindigo dye .

X ₁ : represents an alkylene group having 10 or less carbon atoms and optionally having a side chain.

X _2: linked by X ₁ and the nitrogen atom represents a linking group which binds with a different nitrogen atom and a triazine ring, a nitrogen atom bonded to the X _1.

Y, Z: -NR'- or -O- is represented. However, R'represents a hydrogen atom, an optionally substituted saturated or unsaturated alkyl group or aryl group having 20 or less carbon atoms.

R ₁ , R ₂ , R ₃ , and R ₄ are each independently an optionally substituted saturated or unsaturated alkyl group, or R ₁ and R ₂ , or R ₃ and R ₄ are nitrogen, oxygen, or sulfur. Represents an optionally substituted heterocycle containing atoms.

R _{5 represents a} hydrogen atom or an optionally substituted saturated or unsaturated alkyl group or aryl group having 20 or less carbon atoms.

m, n: each independently represents a number of 1 to 20.

p: represents a number that is not zero and is 4 or less.

In the formula (I), X ₁ represents an alkylene group having 10 or less carbon atoms which may be substituted, and a methylene group is most preferable in production.

Also, the formula The amine or alcohol component used to form the is, for example, 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-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-hexylaminoethyl,
Amine or alcohol of N, N-distearylaminoethyl, N, N-dioleylaminoethyl, N, N-distearylaminobutyl, or N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-amino Ethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-aminomethylpiperidine, or N-hydroxymethylpiperidine, N-hydroxyethyl Examples thereof include piperidine, N-hydroxypropyl piperidine, N-hydroxyethyl pipericon, N-hydroxypropyl pipecoline, N-hydroxymethyl pyrrolidine, N-hydroxybutyl pyrrolidine, N-hydroxyethyl morpholine, N-hydroxybutyl morpholine.

In addition, X ₂ is bonded to X ₁ at a nitrogen atom, and forms a triazine ring,
A component which represents a linking group bonded at a nitrogen atom different from the nitrogen atom bonded to X ₁ and is used to form X ₂ is, for example, hydrazine, 1,2-dimethylhydrazine, ethylenediamine, 1,2-diamino. Propane, 1,3-diaminopropane, N-methylethylenediamine, t-butylhydrazine,
1,4-diaminobutane, 1,2-diamino-2-methylpropane, 1,2-diethylhydrazine, N, N'-dimethylethylenediamine, N-ethylethylenediamine, N-methyl-
1,3-propanediamine, 1,5-diaminopentane, 2,2-
Dimethyl-1,3-propanediamine, N-isopropylethylenediamine, N, N'-diethylethylenediamine, 1,6
- hexanediamine, 1,7-diamino-heptane, N, N'-diethyl-1,3-propanediamine, N ¹ - isopropyl -
2-methyl-1,2-propanediamine, 1,8-diaminooctane, N, N'-dimethyl-1,6-hexanediamine, 1,9
-Diaminonanone, 1,10-diaminodecane, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,5-diaminobenzenesulfonic acid, bis-
(3-Aminopropyl) -ether, 1,2-bis- (3-
Aminopropoxy) -ethane, 1,3-bis- (3-aminopropoxy) -2,2-dimethylpropane, laurylaminopropylamine, methylimino-bis-propylamine, 2-aminomethylpiperidine, 4-aminomethylpiperidine, 1,3-di- (4-piperidyl) -propane, homopiperazine, N-aminopropylpiperazine, 2-methylpiperazine, 2,6-dimethylpiperazine, 2,5-dimethylpiperazine, piperazine and the like. Several synthetic routes are conceivable for producing the pigment dispersant according to the present invention, and the three methods shown as 1), 2) and 3) below are typical. The outline of the production method will be described by taking the pigment dispersant represented by the formula (II) as an example.

(CuPc represents a copper phthalocyanine residue) 1) Chloromethylation of phthalocyanine by a conventional method to produce a compound represented by the formula (III).

Formula (III) CuPc—CH ₂ Cl Next, the compound of formula (III) is reacted with 1,3-diaminopropane to produce the compound of formula (IV).

By reacting cyanuric chloride with a compound of formula _{(IV) CuPc-CH 2 NH} (CH 2) 3 NH 2 Formula (IV) producing a compound of formula (V).

The compound represented by the formula (V) is reacted with N, N-dimethylaminoethylamine to produce the pigment dispersant represented by the formula (II).

2) Cyanuric chloride is reacted with N, N-dimethylaminoethylamine to produce a compound represented by the formula (VI).

Next, the compound represented by the formula (VI) is reacted with 1,3-diaminopropane to produce the compound represented by the formula (VII).

Formula (VII) The compound represented by formula (VII) is reacted with the compound represented by formula (III) to produce a pigment dispersant represented by formula (II).

3) A compound represented by formula (IV) is reacted with a compound represented by formula (VI) to produce a pigment dispersant represented by formula (II).

When producing the pigment dispersant according to the present invention, a basic compound such as sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, triethylamine, pyridine, or P-dimethylaminopyridine is used as an acid binder during the reaction. You may use it. The solvent used in the reaction is water or methanol, ethanol, propyl alcohol, isopropyl alcohol, acetiton,
Dioxane, N, N-dimethylformamide, N-methyl-2
-General organic solvents such as pyrrolidinone, dimethylsulfoxide, cyclohexane, toluene and xylene are mentioned. The pigment dispersant obtained in the present invention exhibits an excellent dispersing effect on almost all pigments that are generally commercially available.
For example, azo pigments such as soluble and insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, perylene / perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments. , Anthrapyrimidine pigments, Ansanthuron pigments, Indanthrone pigments, Flavanthrone pigments, Pyranthrone pigments, Vat dye pigments,
It can be used for organic pigments such as basic dye-based pigments and inorganic pigments such as carbon black, titanium oxide, yellow lead, cadmium yellow, cadmium red, rouge, iron black, zinc white, navy blue, and ultramarine.

The blending of the pigment dispersant obtained in the present invention with the pigment is as follows:
0.1 to 30 parts by weight is preferable for 100 parts by weight of the pigment. If the amount is less than 0.1 part by weight, the effect of the pigment dispersant obtained in the present invention cannot be obtained, and if the amount is more than 30 parts by weight, the effect of the amount used cannot be obtained.

The method of using the pigment dispersant according to the present invention includes, for example, the following method.

1. A pigment composition obtained by previously mixing a pigment and a pigment dispersant is added to a non-aqueous vehicle or the like and dispersed.

2. The pigment and the pigment dispersant are separately added and dispersed in a non-aqueous vehicle or the like.

3. Separately disperse the pigment and pigment dispersant in a non-aqueous vehicle or the like in advance and mix the resulting dispersion.

 In this case, the pigment dispersant may be dispersed only with the solvent.

4. After dispersing the pigment in a non-aqueous vehicle or the like, a pigment dispersant is added to the resulting dispersion.

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

Regarding the method for preparing the pigment composition shown in the above item 1, the desired effect can be sufficiently obtained by simply mixing the pigment powder and the powder of the pigment dispersant according to the present invention.
Mechanically mixing with an attritor, super mill, various pulverizers, etc., or adding a solution containing the pigment dispersant according to the present invention to a suspension of pigment with water or an organic solvent, and depositing the pigment dispersant on the pigment surface Alternatively, better results can be obtained by performing a close mixing method such as co-dissolving the organic pigment and the pigment dispersant in a solvent having a strong dissolving power such as sulfuric acid and co-precipitating with a poor solvent such as water. it can.

In the use of a pigment and a pigment dispersant as described in 2 to 4 above, dispersers and high-speed mixers are used as dispersing machines for dispersing a pigment or a pigment dispersant in a non-aqueous vehicle or a solvent, mixing these, and the like. By using a homomixer, a kneader, a roll mill, a sand mill, an attritor, etc., the pigment can be dispersed well.

Therefore, according to the present invention, gravure inks such as lime rosin varnish, polyamide resin varnish or vinyl chloride resin varnish, nitrocellulose lacquer, normal dry or baked paint of amino alkyd resin, acrylic lacquer, amino acryl resin baked paint, urethane resin In non-aqueous vehicles such as paints, it shows good fluidity such as a decrease in dispersion viscosity and a decrease in structural viscosity as compared with the case where pigments are used alone, and prints without problems such as color separation and crystal change. Alternatively, it is possible to obtain a beautiful product having good gloss of the coating film.

In particular, the pigment dispersant according to the present invention has an extremely excellent dispersing effect not only in oil-modified amino alkyd resin coatings but also in oil-free alkyd resin coatings.

Further, the use of the pigment dispersant according to the present invention is not limited to the non-aqueous vehicle, and other printing inks, paints,
Furthermore, even in the coloring of plastics, it is possible to obtain a colored product having an excellent dispersing effect and a strong coloring power.

Hereinafter, production examples of the pigment dispersant according to the present invention will be described. In the following, "parts" means "parts by weight", and the numbers of the pigment dispersants in the production examples correspond to the abbreviations of the pigment dispersants shown in Table 1.

[Production Example 1] Chloromethylated phthalocyanine (50 parts) was dispersed in water (700 parts), ethylenediamine (5 parts) was added, and the mixture was stirred at 20 ° C for 2 hours. Next, 15 parts of cyanuric chloride was added and stirred at the same temperature for 3 hours. After the completion of stirring, 33 parts of N, N-dibutylaminopropiaminine was added, the temperature was raised to 60 ° C., and the mixture was further stirred for 2 hours. The precipitate is filtered, washed with water and dried to give a pigment dispersant (1).
I got 90 copies.

[Production Example 2] Chloromethylated quinacridone (50 parts) was dispersed in water (700 parts), piperazine (11 parts) was added, and the mixture was stirred at 20 ° C for 2 hours.
Next, add 24 parts of cyanuric chloride and stir at the same temperature for 3 hours.
After completion of stirring, 22 parts of N, N-dibutylaminopropiaminine was added, the temperature was raised to 50 ° C, and the mixture was stirred for 1 hour. After cooling the reaction mixture to below 20 ° C, N, N-dibutylaminopropiaminine 14
Parts were added, the temperature was raised to 80 ° C, and the mixture was stirred for 2 hours. The precipitate was filtered, washed with water and dried to obtain 95 parts of pigment dispersant (5).

Anthraquinone dyes, dianthraquinonyl dyes, phthalocyanine dyes, quinacridone dyes, dioxazine dyes, anthrapyrimidine dyes, ansanthrone dyes, indathron dyes, flavanthron dyes, pyranthrone dyes, perinones A large number of pigment dispersants were produced in the same manner as in Production Examples 1 and 2 by using a series dye, a pyrylene series dye or a thioindigo series dye. Examples are shown in Table-1.

In order to evaluate the effect of the pigment dispersant according to the present invention,
A paint having the following composition was prepared.

Formulation (1) Pigment 9.5 parts Pigment dispersant 0.5 part Alkyd resin varnish (nonvolatile content 60%) 26.4 parts Melamine resin varnish (nonvolatile 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)) Compounding (2) Pigment 9.5 parts Pigment dispersant 0.5 part Oil-free polyester resin varnish 26.4 parts (nonvolatile content 60%) Melamine resin Varnish (nonvolatile content 50%) 13.6 parts Swazol 20 parts Mixed varnish added after dispersion 48.3 parts (alkyd / melamine = 7/3 (solid content)) Put the above mixture in a container and add a steel ball to paint It was dispersed with a shaker to make a paint. These paints were compared with a paint to which a pigment dispersant was not added (a paint in which the pigment dispersant was not added in the above formulation and the amount of the pigment was 10 parts) according to the following evaluation method. Table 2 shows examples of the results. The numbers of the pigment dispersants in Table 2 correspond to the abbreviations shown in Table 1.

Evaluation method (1) The viscosity of the obtained paint was measured by a B-type viscometer and determined (measuring temperature 25 ° C.). The evaluation was made by a relative comparison with the paint without the pigment dispersant added, and the one having a low viscosity was regarded as good.

◯: Good Δ: Fairly good ×: Poor Evaluation method (2) The obtained paint had a final paint viscosity of 23 for Ford cup 4.
It was adjusted with a thinner so that it would be in seconds, sprayed on a tin plate with an air spray gun, then baked, and visually evaluated the 20 ° gloss with a gloss meter for a comprehensive evaluation of the sharpness of the coated surface.

○: Excellent △: Good ×: Poor These paints showed almost no increase in viscosity even when measured for viscosity with the same viscometer after being left for 1 week. In addition, a 1 / 10-cut light-colored paint was prepared using a white paint adjusted with titanium white, the viscosity was adjusted to 23 seconds with a Ford cup 4, and placed in a test tube to observe the aggregation state. No separation or sedimentation was observed.

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

Claims (1)

[Claims] 1. A pigment composition comprising a pigment and a pigment dispersant represented by the formula (I) (except when the pigment is a diketopyrrolopyrrole pigment and Q in the formula (I) is a quinacridone dye. ). It represents -OR ₅ or -X ₂ -X ₁ -Q. Q: Dianthraquinonyl dye, Phthalocyanine dye,
Represents an organic pigment residue selected from quinacridone pigments, dioxazine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perinone pigments, perylene pigments and thioindigo pigments . X ₁ : represents an alkylene group having 10 or less carbon atoms and optionally having a side chain. X _2: linked by X ₁ and the nitrogen atom represents a linking group which binds with a different nitrogen atom and a triazine ring, a nitrogen atom bonded to the X _1. Y, Z: -NR'- or -O- is represented. However, R'represents a hydrogen atom, an optionally substituted saturated or unsaturated alkyl group or aryl group having 20 or less carbon atoms. R ₁ , R ₂ , R ₃ , and R ₄ are each independently an optionally substituted saturated or unsaturated alkyl group, or R ₁ and R ₂ , or R ₃ and R ₄ are nitrogen, oxygen, or sulfur. Represents an optionally substituted heterocycle containing atoms. R _{5 represents a} hydrogen atom or an optionally substituted saturated or unsaturated alkyl group or aryl group having 20 or less carbon atoms. m, n: each independently represents a number of 1 to 20. p: represents a number that is not zero and is 4 or less.