JPH09122470A - Pigment dispersant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film for improving fluidity of ink or the like, preventing the cohesion of a pigment and providing clear and excellent gloss by using a compound of specified structure or its metallic salt or ammonium, or else amine salt as a pigment dispersant. SOLUTION: As a pigment dispersant, a compound represented by a general formula I (In the formula, (n) represents an organic coloring matter residue except azo-coloring matter residue, A represents ethylene or phenylene, or else napthylene, and a substituent can be contained therein. B represents hydroxyl or a group represented by -NH-A-SO3 H, and (n) represents an integer of 1-2.) or metallic salt or its ammonium, or else amine salt is used. Excellent dispersion effect is demonstrated for all of organic pigments by the above- mentioned pigment 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 which provides a pigment dispersion excellent in non-aggregating property.

[0002]

2. Description of the Related Art Generally, a pigment deteriorates in fluidity due to agglomeration generated when dispersed in a paint or an ink vehicle.
Color separation when mixed with other pigments or decrease in gloss on the coated surface,
It often causes various undesirable phenomena.

As a method for improving such a defect of the pigment, surface treatment of the pigment with a surfactant, metallic soap, various resins and the like, and use of various derivatives of organic pigments have been proposed.

For example, USP 3,296,001 is a method of treating phthalocyanine blue with a calcium salt of rosin, and USP 3,582,380 is a method of treating lysole rubin with a metal salt of dialkylsulfosuccinic acid, U.
The use of quinacridone pigment derivatives in SP 3,275,637 and the use of diarylide / disazopyrazolone pigment derivatives in JP-A-3-9957 are reported.
However, as a matter of fact, the effect of giving non-cohesiveness in paints and inks has not yet been sufficiently satisfied.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a pigment dispersant which gives a remarkable improvement effect on the aggregation of organic pigments in a non-aqueous vehicle.

[0006]

As a result of intensive studies, the inventors of the present invention have succeeded in developing a pigment dispersant which is extremely useful in practical use and which solves the above problems. I) A pigment dispersant which is a compound represented by [Chemical Formula 1], a metal salt thereof, or an ammonium or amine salt thereof.

Embedded image [In the formula, U may be an organic dye residue other than an azo dye residue, and A may be an ethylene group, a phenylene group, or a naphthylene group, which may contain a substituent. B represents a group represented by a hydroxyl group or a -NH-A-SO ₃ H. n is 1-2
Indicates an integer. ]

Examples of organic dyes other than azo dyes represented by U include phthalocyanine dyes (Examples 1 to 1).
4, 19, 31, 32), quinacridone dyes (Examples 15, 21, 24, 26), dioxazine dyes (Examples 23, 34), anthraquinone dyes (Example 16,
20, 27, 29, 33), anthrapyrimidine dye, indanthrone dye (Example 18), anthanthrone dye (Example 28), flavanthrone dye, bilanthrone dye, perinone dye, perylene dye. Examples thereof include pigments or dyes such as pigments (Examples 17, 22, 25) and isoindoline pigments (Examples 30, 35).

Typical aliphatic or aromatic amines in which A is an ethylene group, a phenylene group, or a naphthylene group and have one sulfone group are taurine, sulfanilic acid, methanilic acid, orthanilic acid, naphthoic acid, tobiasic acid, 2-aminophenol-4-sulfonic acid, 2-
Methoxyaniline-5-sulfonic acid, 4-chloroaniline-3-sulfonic acid, 2-nitroaniline-4-sulfonic acid, 4B acid (p-toluidine-m-sulfonic acid), 2
B acid (o-chloro-p-toluidine-m-sulfonic acid), C acid (3-amino-6-chlorotoluene-4-sulfonic acid), CB acid (3-amino-6-chlorobenzoic acid-4-) Sulfonic acid), gamma acid (2-amino-8-naphthol-6-sulfonic acid) and the like.

Examples of the metal of the metal salt of the compound represented by the general formula (I) include Mn, Sr, Ba, Ca and Al. Examples of the amine of the amine salt include dehydroabiethylamine, stearylamine and the like.

To prepare the pigment dispersant of the present invention,
Organic dyes with amino groups are needed. To do this, add an organic dye and hydroxylamine sulfate in a mixed solvent of concentrated sulfuric acid and isopropyl alcohol, use ammonium molybdate as a catalyst, heat to generate an amino radical, and directly introduce an amino group into the organic dye by a radical reaction. The method of doing is advantageous. Moreover, the organic dye having an amino group can be produced by various other methods.

When the organic dye having an amino group is prepared in advance by the above method, the pigment dispersant of the present invention is generally prepared by the following two methods 1) and 2). Here, the pigment dispersant (a) [Chemical Formula 2] is used as an example to outline the preparation method.

Embedded image (However, CuPC represents a copper phthalocyanine residue.)

1) First, a compound (II) represented by [Chemical Formula 3] is obtained by reacting monoaminocopper phthalocyanine with cyanuric chloride.

Embedded image

Next, the compound (II) is reacted with one sulfanilic acid, and the remaining one Cl is hydrolyzed to obtain the pigment dispersant (a).

2) First, cyanuric chloride and sulfanilic acid 1
When the individual compounds are reacted, the compound (III) represented by [Chemical Formula 4]
Is obtained.

Embedded image

Next, monoamino copper phthalocyanine and (II
After reacting I), the remaining one Cl is hydrolyzed to obtain the pigment dispersant (a). Further, various preparation methods other than those shown in 1) and 2) are possible.

[0016]

The pigment dispersant of the present invention exerts an excellent dispersing effect on all commercially available organic pigments. Among them, the most effective effect is obtained when used for organic pigments having the same or similar structure. It is preferable to add 0.5 to 30 parts by weight of the pigment dispersant of the present invention to 100 parts by weight of the organic pigment. 0.
If the amount is less than 5 parts by weight, the intended effect cannot be obtained, and if the amount is more than 30 parts by weight, the desired effect cannot be obtained.

The method of using the pigment dispersant of the present invention includes:
The pigment dispersant and the pigment are usually powder-mixed and used, but they may be added to the non-aqueous vehicle together with the pigment. It is also possible to mix and use the pigment in advance when preparing the pigment itself. The pigment dispersant of the present invention is not limited to non-aqueous vehicles such as paints and inks, but can be used for coloring plastics.

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

Production Example 1 Preparation of monoamino copper phthalocyanine 200 g of concentrated sulfuric acid (98%) and isopropyl alcohol 1
11.6 g of copper phthalocyanine in 5.4 g of mixed solvent,
After adding 13.4 g of hydroxylamine sulfate and 0.3 g of ammonium molybdate and reacting at 60 ° C. for 5 hours, this solution was discharged into 1 l of ice water, filtered, washed with water and taken out to remove one amino group. 10.4 g of introduced monoamino copper phthalocyanine is obtained.

Then, 10 parts of monoamino copper phthalocyanine is added to 100 parts of water and dispersed, 3.1 parts of cyanuric chloride in an amount that reacts with one amino group is added, and the mixture is reacted at 20 ° C. for 1 hour. Next, 2.9 parts of sulfanilic acid was added and reacted at 90 ° C. for 1 hour to hydrolyze the remaining 1 Cl to obtain 14.5 parts of the pigment dispersant (a) having the structure of [Chemical formula 2]. can get.

Embedded image

Production Example 2 To 100 parts of water, 10 parts of monoaminocopper phthalocyanine was added and dispersed, 3.1 parts of cyanuric chloride in an amount capable of reacting with one amino group was added, and the mixture was reacted at 20 ° C. for 1 hour. Then 5.
8 parts of sulfanilic acid is added and reacted at 90 ° C. for 1 hour to obtain 17.1 parts of a pigment dispersant (b) having a structure of [Chemical formula 5].

Embedded image

Production Example 3 Preparation of Monoaminotrichlorocopper Phthalocyanine In the same manner as in Production Example 1, monoaminotrichlorocopper phthalocyanine having one amino group introduced was prepared using trichlorocopper phthalocyanine instead of copper phthalocyanine.

Next, monoaminotrichlorocopper phthalocyanine is dispersed in 100 parts of water, 2.7 parts of cyanuric chloride which reacts with one amino group is added, and the mixture is reacted at 30 ° C. for 1 hour. Then add 2.5 parts of sulfanilic acid and add 2 at 80 ° C.
After reacting for a time, the remaining Cl is hydrolyzed to obtain 13.9 parts of a pigment dispersant (c) having a structure of [Chemical Formula 6].

[Chemical 6]

Production Example 4 After reacting with sulfanilic acid in Production Example 2, 30% Na was added.
After adjusting the pH to about 10 with an OH aqueous solution, a CaCl ₂ aqueous solution is added to obtain 17.8 parts of a pigment dispersant (d) having a structure of [Chemical Formula 7] laked with Ca.

Embedded image

Production Example 5 After reacting with sulfanilic acid in Production Example 1, an aqueous solution of stearylamine in acetic acid was added, and pH was brought to about 30% with NaOH.
Adjustment to 10 yields 19.1 parts of a pigment dispersant (e) having the structure of [Chemical formula 8] as a stearylamine salt.

Embedded image

Production Example 6 10 parts of monoaminohexachlorocopper phthalocyanine having one amino group are dispersed in 100 parts of water, 2.3 parts of cyanuric chloride which reacts with the amino groups are added, and the mixture is added at 20 ° C. for 1 hour. React. Then add 2.2 parts of methanylic acid and add 9
The reaction is carried out at 0 ° C. for 1 hour to hydrolyze the remaining Cl.
Then, after adjusting the pH to 10 with a 30% NaOH aqueous solution, 14.2 parts of a pigment dispersant (f) having a structure of [Chemical Formula 9] is obtained by adding a BaCl ₂ aqueous solution and making a lake with Ba.

Embedded image

Production Example 7 5.3 parts of sulfanilic acid and 1.8 parts of sodium carbonate were added to 100 parts of water to completely dissolve sulfanilic acid. After adding 5.6 parts of cyanuric chloride to this product and reacting at 20 ° C. for 1 hour, 10 parts of monoaminoquinacridone were added to 90
After reacting for 2 hours at ℃, the remaining Cl was hydrolyzed.
0] was obtained to obtain 18.2 parts of a pigment dispersant (g).

Embedded image

Production Example 8 Pigment having the structure of [Chemical Formula 11] was repeated except that 10 parts of diaminoindanthrene was used in place of taurine and monoaminoquinacridone in place of sulfanilic acid in Production Example 7. 19.9 parts of dispersant (h) was obtained.

Embedded image

Production Example 9 PigmentRed 1 having 2-aminophenol-4-sulfonic acid in place of sulfanilic acid and one amino group in place of monoaminoquinacridone in Production Example 7.
Pigment dispersant (i) 16.2 having the structure of [Chemical Formula 12] was repeated by repeating the same procedure except that 10 parts of 77 was used.
Got a part.

Embedded image

Production Example 10 A completely similar procedure was repeated except that 10 parts of Pigment Violet 23 having one amino group was used instead of naphthoic acid and monoaminoquinacridone in place of sulfanilic acid in Production Example 7. 15.3 parts of a pigment dispersant (j) having a structure of] was obtained.

Embedded image

Production Example 11 The same procedure as in Production Example 7 was repeated except that 10 parts of Pigment Red 149 having one amino group was used instead of monoaminoquinacridone.
14.4 parts of a pigment dispersant (k) having the structure of

Embedded image

Production Example 12 The same procedure as in Production Example 7 was repeated except that 10 parts of Pigment Red 168 having one amino group was used instead of monoaminoquinacridone.
15.6 parts of a pigment dispersant (l) having the structure of

Embedded image

Production Example 13 Pigment Yellow 139 having one amino group instead of monoaminoquinacridone in Production Example 7.
The same procedure was repeated except that 10 parts were used to obtain 17.5 parts of pigment dispersant (m) having the structure of [Chemical Formula 16].

Embedded image

It was confirmed by elemental analysis that the pigment dispersants (a) to (m) in the production examples had the desired structures. Elemental analysis is C, H, N, S, Cl, Cu,
For Ca and Ba, C, H and N are automatic analysis methods,
S and Cl were measured by the column chromatography method of the flask combustion method. Cu, Ca, and Ba were measured by an emission analysis method.

Next, the composition of the pigment dispersant (a) (C ₄₁ H
Table 1 shows the results of elemental analysis of ₂₃ N ₁₃ O ₄ S ₁ Cu ₁ ). The analytical value about oxygen shows a theoretical value.

[Table 1] From the analysis results in Table 1, values of C, H, N, S, and Cu were almost close to the theoretical values, and it was confirmed that the compound having the target structure was obtained.

Pigment dispersants (b) other than (a)
Similarly for (m), C, H, N, S, Cl, Cu,
Elemental analysis of Ca and Ba was carried out, and it was confirmed that compounds each having a substantially intended structure were obtained.

The effects will be described with reference to examples and comparative examples. Parts and percentages in the examples are shown by weight. The chemical structure of each pigment dispersant indicated by the alphabet corresponds to that shown in the production example.

[0038]

[Examples and Comparative Examples]

Example 1 C.I. I. Pigment Blue 15 9.0 parts Pigment dispersant (a) 1.0 part One-pack type urethane varnish 45.0 parts (resin solid content 30%, weight average molecular weight about 50,000) Thinner 45.0 parts (toluene / IPA / MEK = 40/20/40) 100 parts of alumina beads (3 mm in diameter) were put and dispersed for 60 minutes with a paint conditioner.

The obtained urethane ink for gravure was separated from the alumina beads, and the viscosity and the gloss after the color development were measured. The results showed excellent properties as shown in Table 2.

The viscosity and gloss were measured according to the following methods. Viscosity: 25 ° C using a B type viscometer, 30 rpm and 60 r
It was measured in pm. Gloss: A bar coater (winding thickness: 0.15 mm) was used to develop the color on the polypropylene film, and then the developed surface after drying was measured for 60 ° / 60 ° reflectance with a gloss meter.

Comparative Example 1 In Example 1, P was added without adding the pigment dispersant (a).
ink containing 10 parts of IGMENT BLUE 15 was prepared. The results were inferior to those of Example 1 as shown in Table 2.

Examples 2 to 6 Example 1 was repeated as in Example 1 except that 1.0 parts of the pigment dispersants (b) to (f) were used instead of the pigment dispersant (a). I made an ink. Table 2 shows the results.

Comparative Examples 2 to 10 Pigment Green 36 and Pigment instead of Pigment Blue 15 in Comparative Example 1
Green7, Pigment Red 122, P
igment Blue 60, Pigment Re
d 177, Pigment Violet 23, P
igment Red 149, Pigment Re
d 168 and Pigment Yellow 139 were each set to 10 parts to prepare an ink containing no pigment dispersant. Table 2 shows the results.

Examples 7 to 30 Pigment Green 36 and Pigment in place of Pigment Blue 15 in Example 1
Green7, Pigment Red 122, Pi
gment Blue 60, Pigment Red
177, Pigment Violet 23, Pi
gment Red 149, Pigment Red
Each of 168 and Pigment Yellow 139 was used in an amount of 9.0 parts, and various types of pigment dispersants to be used 1.0 times were prepared in various combinations (a) to (m). Table 2 shows the results.

[0045]

[Table 2] As shown in Table 2, the pigment dispersant (a) according to the present invention
The effect was observed in all cases where (m) was added, but among them, the most excellent effect was observed when a pigment dispersant prepared from pigments having the same structure was blended. Further, even if these inks were allowed to stand for 1 week and then measured with the same viscometer, almost no increase in viscosity was observed.

Example 31 10 parts of an acrylic copolymer consisting of 50% by weight of n-butyl methacrylate, 30% by weight of butyl methacrylate, and 20% by weight of methacrylate, 74.9 parts of cyclohexanone and 14.3 parts of Pigment Blue 15;
0.8 part of the pigment dispersant (a) was placed in a container and sufficiently dispersed by a ball mill to prepare a blue composition for a color filter. The results of measuring the fluidity and the gloss of the spread product of this composition are shown in Table 3.

Comparative Example 11 A blue composition was prepared in the same manner as in Example 31 except that the pigment dispersant (a) was not added and Pigment Blue 15 was 15.1 parts. The results of measuring the fluidity and the gloss of the spread product of this composition are shown in Table 3. (The viscosity and gloss were measured in the same manner as in the urethane ink for gravure.)

Examples 32 to 35 Pigment Blue 15 in Example 31 14.
Piment Green 36, Pi instead of 3 parts
gment Red 177, PigmentViol
et 23, Pigment Yellow 139
14.3 parts were used, and instead of 0.8 parts of the pigment dispersant (a), 0.8 parts of the pigment dispersants (c), (i), (j), and (m) were respectively used, and a green color for a color filter. , Red, purple, yellow compositions were made. The results of measuring the fluidity and gloss of the spread product of these compositions are shown in Table 3.

Comparative Examples 12 to 15 Pigment dispersants (c), (i) in Examples 32 to 35,
Pigment G without adding (j) and (m)
reen 36, Pigment Red 177, P
igment Violet 23, Pigment
Green with 139 each of Yellow 139,
Red, purple and yellow compositions were made. The results of measuring the fluidity and gloss of the spread product of these compositions are shown in Table 3.

[0050]

[Table 3] As shown in Table 3, also in the resin varnish for the color filter, the one containing the pigment dispersant according to the present invention showed excellent results in fluidity and gloss.

Further, the pigment to which the pigment dispersant according to the present invention is added is a nitrocellulose lacquer, a baked melamine alkyd paint, a constantly dried alkyd paint, a urethane resin paint, an acrylic lacquer, an aminoacrylic resin baked paint, a polyamide / nitrified cotton ink, Offset inks such as various rosin-modified resins, lime rosin inks, and vinyl chloride resin inks also showed good dispersibility without causing aggregation.

[0052]

INDUSTRIAL APPLICABILITY The pigment dispersant of the present invention exerts a remarkable improving effect on non-aqueous vehicles such as inks and paints in almost all organic pigments, and only improves the fluidity of inks and paints. In addition, it is possible to obtain a coating having a clear and excellent luster by preventing pigment aggregation. Furthermore, the pigment dispersant of the present invention is extremely useful practically because of its ease of preparation.

Claims (2)

[Claims] 1. A pigment dispersant which is a compound represented by the following general formula (I) [Chemical formula 1] or a metal salt thereof or an ammonium or amine salt thereof. Embedded image [In the formula, U may be an organic dye residue other than an azo dye residue, and A may be an ethylene group, a phenylene group, or a naphthylene group, which may contain a substituent. B represents a group represented by a hydroxyl group or a -NH-A-SO ₃ H. n is 1-2
Indicates an integer. ] 2. An organic dye residue U is a phthalocyanine dye residue, a quinacridone dye residue, a dioxazine dye residue, an anthraquinone dye residue, an anthrapyrimidine dye residue, an indanthrone dye residue. A group, an anthanthrone dye residue, a flavanthrone dye residue, a bilanthrone dye residue, a perinone dye residue, a perylene dye residue, or an isoindoline dye residue. Pigment dispersant.