JP3170697B2 - Pigment dispersant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigment dispersant which provides a pigment dispersion having excellent non-aggregation properties.

[0002]

2. Description of the Related Art In general, pigments are deteriorated in fluidity, color separation when mixed with other pigments, or reduced in gloss of a coated surface due to agglomeration caused when dispersed in a paint or ink vehicle. And various other undesirable phenomena often occur.

As methods for improving such pigment defects, surface treatment methods of pigments with surfactants, metallic soaps, various resins, etc., and utilization of various derivatives of organic pigments have been proposed.

For example, US Pat. No. 3,296,001 discloses a method of treating phthalocyanine blue with a rosin calcium salt, US Pat. No. 3,582,380 describes a method of treating lysole rubin with a metal salt of dialkyl sulfosuccinic acid, US Pat.
In P4,391,648, phthalocyanine green is treated with aromatic polyester, and USP 3,27
No. 5,637, a derivative of a quinacridone pigment, USP 3,
532 and 520 report the use of derivatives of disazo yellow, and JP-A-3-9957 reports the use of derivatives of diarylide / disazopyrazolone pigments.

[0005] However, it is a fact that an insoluble azo pigment and a soluble azo pigment have not yet been sufficiently satisfactory in the effect of imparting non-aggregation properties in inks and paints.

[0006]

SUMMARY OF THE INVENTION The present invention provides an insoluble azo pigment and a pigment dispersant which has a remarkable effect of improving the cohesion of the soluble azo pigment in a non-aqueous vehicle.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have succeeded in developing a pigment dispersant which is practically extremely useful for solving the above-mentioned problems. A pigment dispersant which is a compound represented by the formula [I] (formula 1) or a metal salt thereof or an ammonium or amine salt thereof.

Wherein Q represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a hydroxyl group. W represents any of the groups represented by Chemical Formula 2, and m represents an integer of 0 or 1.

## STR2 ## K represents a coupler component residue for an azo pigment.
A and B each represent a hydroxyl group, a lower alkoxy group or a group represented by the following formula, Y represents NH or an oxygen atom, and n represents 1
Represents an integer of from 6 to

Wherein R ¹ and R ² are each independently a substituted or unsubstituted alkyl group or a heterocyclic ring formed by R ¹ and R ² , which contains nitrogen, oxygen, or sulfur and contains a substituent. Is also good. However, A and B are each independent, and at least one is a group represented by (Chemical Formula 4).

[Formula 4]

When Y is --NH-- or --O--, typical amine and alcohol components include, for example, amines or alcohols of dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl, diethylaminopropyl and dibutylaminopropyl. It is.

Alternatively, N-aminoethylpiperidine, N
-Aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, N-aminopropyl-4-
Pipecoline, N-aminopropylmorpholine, or N
-Hydroxyethyl piperidine, N-hydroxyethyl pipecoline, N-hydroxyethyl morpholine and the like.

The metal salt of the compound represented by the general formula [I] is obtained when the coupler component K for an azo pigment is, for example, β-oxynaphthoic acid, and the metal is Mn or Sr. , Ba and the like. Examples of the amine salts include stearylamine salts.

In order to prepare the pigment dispersant of the present invention, the following two methods 1) and 2) are representative. The outline of the preparation method is described below using the pigment dispersant (a) (Formula 6) as an example.

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1) First, one amino group of 3,3'-dichlorobenzidine is reacted with cyanuric chloride to obtain a compound (III) represented by the following chemical formula (7).

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Next, the compound (III) is reacted with N, N-dimethylaminopropylamine to obtain a compound (IV) (base) represented by the following formula (8).

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Next, the compound (IV) is diazotized by a conventional method and coupled with acetoaceto-2,5-dimethoxy-4-chloroanilide to obtain a pigment dispersant (a).

2) First, reacting cyanuric chloride with N, N-dimethylaminopropylamine to obtain a compound (V) represented by the following chemical formula (9).

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Reaction of compound (V) with 3,3'-dichlorobenzidine gives compound (IV). Next, the compound (IV) is diazotized by a conventional method and coupled with acetoaceto-2,5-dimethoxy-4-chloroanilide to obtain a pigment dispersant (a). Various preparation methods other than those described in 1) and 2) are also possible.

[0017]

The pigment dispersant of the present invention exerts an excellent dispersing effect on all commercially available azo pigments. Among them, the effect is most effective when used for an azo pigment having a coupling component having the same or similar structure.

It is preferable to add 0.5 to 40 parts by weight of the pigment dispersant of the present invention to 100 parts by weight of the azo pigment.
If the amount is less than 0.5 parts by weight, the intended effect cannot be obtained,
Further, even if it is used in an amount of more than 40 parts by weight, the effect cannot be obtained.

The method of using the pigment dispersant of the present invention includes:
Usually, a pigment dispersant and a pigment are used in the form of a powder blend, but they may be added to a non-aqueous vehicle together with the pigment. Also, it can be used by blending it in advance when preparing the pigment itself.

For example, benzidine disazo yellow
Compound (IV) as part of the base during pigment synthesis
After the compound (base) is used in combination and tetrazotized (the combined base is diazotized), the coupling reaction is carried out in the usual manner, and the compound can be directly compounded in a synthetic system without compounding powder. The desired effect can be obtained by any of the above methods.

The pigment dispersant of the present invention is not limited to non-aqueous vehicles such as paints and inks, but can also be used for coloring plastics.

Hereinafter, an outline of a method for synthesizing the pigment dispersant of the present invention will be described as a production example. In the examples, "parts" indicates parts by weight.

Production Example 1 To 100 parts of water, 10 parts of 3,3'-dichlorobenzidine was added and dispersed, and 7.3 parts of cyanuric chloride was added thereto in an amount to react with one amino group. Let react. Next, 8.1 parts of N, N-dimethylaminopropylamine is added and reacted at 80 ° C. for 1 hour to obtain 18.5 parts of an amine having the structure of the following formula.

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The above-mentioned base (17.6 parts) is diazotized in a conventional manner, and subjected to a coupling reaction with acetoaceto-2,5-dimethoxy-4-chloroanilide (9.2 parts), whereby the structure of the formula (11) is obtained. Pigment dispersant (a) 2 having
8.0 parts were obtained.

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Production Example 2 The same procedure as in Production Example 1 was carried out until the diazotization was carried out. -Phenyl-3-methyl-5-pyrazolone, 1- (p-tolyl)-
Pigment dispersants (b) to (g) having the structures of Chemical Formulas 12 to 17 were obtained by repeating the procedure of Production Example 1 except for using 3-methyl-5-pyrazolone, respectively. .

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Production Example 3 10 parts of o-dianisidine was added to 100 parts of water and dispersed.
7.6 parts of cyanuric chloride which reacts with one amino group is added and reacted at 30 ° C. for 1 hour. Next, 10.7 parts of N, N-diethylaminopropylamine were added,
For 1 hour, and the amine 2 having the structure of
Obtain 1.8 parts.

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The base (19.2 parts) is diazotized in a conventional manner, and is subjected to a coupling reaction with 5.9 parts of acetoacetanilide. Parts were obtained.

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Production Example 4 The amine of Production Example 3 was used, and diazotization was carried out in exactly the same manner as described above, and 1- (p-tolyl) -3- was used as a coupler.
By repeating the same procedure using methyl-5-pyrazolone and 1-phenyl-3-carbethoxy-5-pyrazolone, the pigment dispersants (i) having the structures of (Chemical Formula 20) and (Chemical Formula 21), j) was obtained.

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Production Example 5 10 parts of 4,4'-methylene-bis- (2-chloroaniline) was added to 100 parts of water for dispersion, and 6.9 parts of cyanuric chloride was added thereto in an amount to react with one amino group. And react at 20 ° C for 2 hours. Next, 8.2 parts of N, N-dimethylaminopropylamine was added and reacted at 90 ° C. for 1 hour.
20.4 parts of an amine having the structure of 2) are obtained.

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The base (18.1 parts) is diazotized according to a conventional method, and is subjected to a coupling reaction with 11.9 g of naphthol AS-ITR to thereby give 26.5 parts of a pigment dispersant (k) having the structure of (Formula 23). was gotten.

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Production Example 6 The amine of Production Example 5 was used, and the procedure was the same until diazotization. The naphthol AS-PH, β-
Pigment dispersants (1) and (m) having the structures of (Formula 24) and (Formula 25) were obtained by repeating the same procedure using naphthol.

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Production Example 7 4,4'-Diaminophenyl ether 10 in 100 parts of water
9.2 parts of cyanuric chloride in an amount that reacts with one amino group and then reacts at 30 ° C. for 1 hour. Next, 15.9 parts of N, N-dibutylaminoethyl alcohol was added and reacted at 90 ° C. for 2 hours to obtain 29.0 parts of an amine having the structure of (Formula 26).

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The pigment dispersant (n) having the structure of (Chemical Formula 27) was obtained by diazotizing 19.6 parts of the above-mentioned base according to a conventional method and subjecting it to a coupling reaction with 11.8 parts of naphthol AS-ITR. One part was obtained.

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Production Example 8 In Production Example 7, instead of 4,4'-diaminophenyl ether, 4,4'-diaminodiphenylsulfone, 1,4-
Bis (4-aminophenoxy) benzene, 3,3'-
The same procedure was repeated except that dimethyl-4,4'-diaminophenylmethane was used.
9), a pigment dispersant (o) having the structure of
(P) and (q) were obtained.

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Production Example 9 The amine of Production Example 5 was used, and β-oxynaphthoic acid was used as a coupler in exactly the same manner until diazotization. The coupling reaction was added to MnSO ₄ at 45 ° C.
An aqueous solution was added, and the mixture was laked with Mn to obtain a pigment dispersant (r) having the structure of (Formula 31).

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Production Example 10 In Production Example 9, Sr (NO ₃ ) ₂ and B were used instead of MnSO _4.
The same procedure was repeated, except that an aqueous solution of aCl ₂ and stearylamine acetate was used, and laked and stearylamine salts were formed with Sr and Ba (Formula 32), (Formula 3)
3) a pigment dispersant (s) having the structure of
(T) and (u) were obtained. Further, a pigment dispersant (v) having a structure of not being laked by a metal (formula 35) was also obtained.

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It was confirmed by elemental analysis that the pigment dispersants (a) to (v) in the production examples had the desired structure. Elemental analysis was performed for C, H, N, and Cl, C, H, and N were performed by an automatic analysis method, and Cl was performed by a column chromatography method of a flask combustion method.

Next, the pigment dispersant (a) and the composition formula (C ₃₇ ,
The results of elemental analysis of H ₄₆ , N ₁₁ , O ₄ , and NCl ₃ are shown below. * For O, the theoretical value was entered.

From the results of this analysis, values close to theoretical values were obtained for all of C, H, N, and Cl, and it was confirmed that a compound having the desired structure was obtained. Elemental analyzes of C, H, N, and Cl were similarly performed on the pigment dispersants (b) to (v) other than (a), and it was confirmed that compounds having almost the desired structures were obtained. .

Next, the effects of the present invention will be described with reference to Examples and Comparative Examples. Parts and percentages in Examples are shown on a weight basis. The chemical structure of each pigment dispersant represented by an alphabet corresponds to that shown in Production Examples.

In the table, the pigment dispersant indicated by [] indicates a pigment dispersant produced by a coupler having the same structure as the pigment used.

[0042]

[Examples and Comparative Examples]

Example 1 A C.I. I. Pigment Yellow 83 9.5 parts Pigment dispersant (a) 0.5 part Alkyd resin varnish (nonvolatile content 60%) 26.4 parts Melamine resin varnish (nonvolatile content 50%) 13.6 parts Thinner (xylene / n) -Butanol = 8/2) 20 parts Alumina beads (diameter 3 mm) 100 parts are added and dispersed by a paint conditioner for 60 minutes. Then, 31.9 parts of alkyd resin-based varnish (non-volatile content: 60%) 16.4 parts of melamine resin-based varnish (non-volatile content: 50%) [Alkyd resin / melamine resin = 7/3 (solid content)] are added and dispersed for 10 minutes. . The obtained paint was separated from the alumina beads, and the viscosity and gloss after coating were measured. The results showed excellent properties as shown in Table 1.

Comparative Example 1 In Example 1, no pigment dispersant (a) was added.
Pigment Yellow 83 in 10 parts was prepared. The results were inferior to Example 1 as shown in Table 1.

Examples 2 to 4 Example 1 was repeated except that 0.5 parts of the pigment dispersants (b), (c) and (e) were used instead of the pigment dispersant (a) in Example 1. Each coating was made. Table 1 shows the results.

Comparative Examples 2 to 20 In Comparative Example 1, instead of Pigment Yellow 83, Pigment Yellow 12, 14, 13,
17, Pigment Orange 13, 34, P
iigment Yellow 97, 81, 74, 1,
Pigment Orange 16, Pigment
Red 37, 38, 5, 170, 3, 48-4, 4
8-3 and 48-1 were each 10 parts, and a coating material without adding a pigment dispersant was prepared. Table 1 shows the results.

Examples 5 to 48 In Example 1, pigments of Comparative Examples 2 to 20 were used in place of Pigment Yellow 83, and a pigment dispersant was prepared by variously combining paints (a) to (v) in the production examples. Created. Table 1 shows the results.

The viscosities in the table were measured with a Brookfield viscometer. Gloss was measured with a gloss meter at 60 ° / 60 ° reflectance. For color separation resistance, use a melamine alkyd varnish with a base paint of titanium oxide prepared in advance, cut so that the ratio of pigment to titanium oxide becomes 1/10, make a light-colored paint, and place it in a test tube. The state of aggregation was observed. The judgment was made with the following ◎, △, Δ, ×. ：: Completely uniform. ：: Slight white streaks are observed. Δ: White stripe pattern. X: White is completely separated.

As shown in Table 1, the effect was observed in all cases where the pigment dispersant was added, and the most excellent effect was observed when the pigment was blended with the same coupler structure. In addition, these paints showed almost no increase in viscosity even after being left for one week and measured with the same viscometer.

Example 49 C.I. I. Pigment Yellow 83 9.5 parts Pigment dispersant (a) 0.5 part Acrylic resin varnish (nonvolatile content 60%) 26.4 parts Melamine resin varnish (nonvolatile content 50%) 13.6 parts Thinner (xylene / n) -Butanol = 8/2) 20 parts Alumina beads (diameter 3 mm) 100 parts are added and dispersed by a paint conditioner for 60 minutes. Next, 31.9 parts of an acrylic resin-based varnish (non-volatile content: 60%) 16.4 parts of a melamine-based varnish (non-volatile content: 50%) [acrylic resin / melamine resin = 7/3 (solid content)] are added and dispersed for 10 minutes. . The obtained paint was separated from the alumina beads, and the viscosity and gloss after coating were measured. Table 2 shows the results.

Comparative Example 21 A coating material was prepared in the same manner as in Example 49 except that the pigment dispersant (a) was not used and 10 parts of Pigment Yellow 83 were used. Table 2 shows the results. (The evaluation was performed in the same manner as in the case of the melamine alkyd resin paint.)

As shown in Table 2, the acrylic melamine resin paint containing the pigment dispersant according to the present invention also showed excellent results in fluidity, gloss and color separation resistance. When these paints were left for one week and measured with the same viscometer, almost no increase in viscosity was observed.
It should be noted that the pigment dispersant according to the present invention exhibited the same effect in pigments other than Pigment Yellow 83.

Example 50 Pigment Yellow 83 14.10 parts of an acrylic copolymer composed of 50% by weight of n-butyl methacrylate, 30% by weight of butyl methacrylate, and 20% by weight of methacrylate, and 74.9 parts of cyclohexanone.
3 parts and 0.8 part of the pigment dispersant (a) were placed in a container and sufficiently dispersed by a ball mill to prepare a yellow composition for a color filter. Table 3 shows the results of measuring the fluidity of the composition and the gloss of the drawn product.

Comparative Example 22 A yellow composition was prepared in the same manner as in Example 50 except that the pigment dispersant (a) was not added and Pigment Yellow 83 was 15.1 parts. Table 3 shows the results of measuring the fluidity of the composition and the gloss of the drawn product. (The methods for measuring the viscosity and gloss were the same as those for the melamine alkyd resin paint.)

As shown in Table 3, the resin varnish for a color filter in which the pigment dispersant of the present invention was blended also showed excellent results in fluidity and gloss.

Further, the pigment to which the pigment dispersant according to the present invention was added did not cause aggregation even in nitrocellulose lacquer, normal dry alkyd paint, gravure ink, offset ink and the like, and showed good dispersibility.

[0056]

The pigment dispersant of the present invention exerts a remarkable improvement effect on almost all azo pigments in non-aqueous vehicles such as paints and inks, and remarkably improves the fluidity of paints and inks. In addition to this, it is possible to eliminate color separation due to aggregation of the pigment and obtain a clear and excellent glossy coating film.

Further, the pigment dispersant of the present invention is extremely useful practically because of its ease of preparation.

[0058]

[Table 1]

[0059]

[0060]

[0061]

[Table 2]

[0062]

[Table 3]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-60-88185 (JP, A) JP-A-61-246261 (JP, A) JP-A-62-292860 (JP, A) (58) Field (Int. Cl. ⁷ , DB name) C09B 67/46 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A pigment dispersant which is a compound represented by the following general formula [I] or a metal salt thereof or an ammonium or amine salt thereof. Embedded image [Wherein Q is a hydrogen atom, a halogen atom, a lower alkyl group,
It represents a lower alkoxy group or a hydroxyl group. W represents any of the groups represented by Chemical Formula 2, and m represents an integer of 0 or 1. Embedded image K represents a coupler component residue for an azo pigment. A and B
Represents a hydroxyl group, a lower alkoxy group or a group represented by Chemical Formula 3, Y represents NH or an oxygen atom, and n represents an integer of 1 to 6. Embedded image R ¹ and R ² each independently represent a substituted or unsubstituted alkyl group or a heterocyclic ring represented by R ¹ and R ² ,
Alternatively, it may contain sulfur and contain a substituent. However, A and B are each independent, and at least one is a group represented by (Chemical Formula 4). [Formula 4] 2. K is an acetoacetanilide-based, pyrazolone-based, naphthol-AS-based, β-naphthol-based or β-oxynaphthoic acid-based compound represented by the formula [II] (formula 5). The pigment dispersant according to claim 1, which is a coupler component residue of the following. Embedded image