JPH04139261A - Pigment composition and pigment dispersion - Google Patents

Abstract

PURPOSE:To obtain a figment composition capable of producing a pigment dispersion excellent in fluidity, excellent in gloss and coloring power and useful for a paint and an ink by blending a poly-halogenated copper phthalocyanine with a specified amount of poly-halogenated heterometal phthalocyanines in which the central metal is a specified metal such as Mg. CONSTITUTION:With 100 pts.wt. poly-halogenated copper phthalocyanine, 0.3-30 pts.wt., preferably 3-10 pts.wt. one or more poly-halogenated heterometal phthalocyanines (preferably containing 3-4 valent metal, e.g. Fe, V, Ti, Si or Sn as central metal) in which the central metal is one metal atom selected from Mg, Si, Ti, V, Mn, Fe, Co, Ni, Zn, Ge and Sn are blended, thus obtaining the objective pigment composition.

Description

[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention provides a pigment dispersion that is suitable for use with highly halogenated copper phthalocyanine, which is widely used as a green pigment, and has particularly excellent fluidity. The present invention relates to a pigment composition and a pigment dispersion thereof.

(Prior Art) Conventionally, highly halogenated copper phthalocyanine has been widely used in coloring materials because of its beautiful color tone and excellent resistance to various types, but it also has unsatisfactory properties depending on the application.

That is, the particle size of highly halogenated copper phthalocyanine is generally very small, and one of the major drawbacks caused by this is agglomeration. This tendency is markedly observed in non-aqueous dispersion systems such as paints and graphia inks, or as a result of pigment aggregation, they exhibit large structural viscosity in fluidity, causing practical problems such as gelation.

Several methods have been proposed to improve large structural viscosity. For example, USP 3,891,455
This method involves mixing a blue copper phthalocyanine derivative with highly halogenated copper phthalocyanine, as disclosed in Japanese Patent Application Laid-Open No. 52-132031. These methods either improve the fluidity of the pigment dispersion or have the disadvantage that it becomes monochromatic or bluish. Furthermore, in order to improve the defect of bluish hue and exhibit excellent gloss and high fluidity, derivatives of halogenated copper phthalocyanine were used as disclosed in Japanese Patent Application Laid-open No. 168070/1982 and Japanese Patent Publication No. 4143/1983. The drawback of a single color or bluish tinge when mixed with highly halogenated copper phthalocyanine has not been satisfactorily solved.

(Problems to be Solved by the Invention) The present inventors have improved the disadvantage of the color shifting to a bluish tinge by adding a dispersant, and have developed a practically excellent high-halogen The objective is to obtain a copperphthalonanine pigment.

[Structure of the invention]

(Means for Solving the Problems) That is, the present invention provides that the central metals Mg, Si, TiV, Mn, F
At least one highly halogenated dissimilar metal phthalocyanine selected from e, Co, Ni, Zn, Ge, and Sn 0.3
~30 parts by weight of the pigment composition.

The structures of the highly halogenated heterometallic phthalocyanine in the present invention are represented by formulas (I) to (I[[).

M, PcXn (I) R+ -M2 PcXn (II) R2R3
M3 P cXn (I[) (Tax2M1~M
3 represents a di- to tetravalent central metal.

PcXn is a halogenated phthalocyanine residue (X represents a chlorine atom or a bromine atom, and n represents an integer of 8 to 16.

), and R+, R2, and R3 are -CI.

OH, -3○3H, -3O3C6H3(R,)R6(R
4, R5 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a nitro group, a sulfone group, a halogen atom, and R2R3
In some cases, it represents one oxygen atom. ) represents.

M1 to M3 are Mg as a divalent to tetravalent central metal.

Si, Ti, V, Mn, Fe, Co, Ni, Zn.

Ge, Sn, especially Fe, V, Ti, Si,
Highly halogenated phthalocyanine having a trivalent or tetravalent metal such as Sn as the central metal is preferred.

R1-R3 in formulas (I[) and (I[) are usually -CI immediately after synthesizing the highly halogenated phthalocyanine.
This will change depending on post-processing. When added, either structure or a mixture thereof may be used.

The method for synthesizing the highly halogenated heterometallic phthalocyanine in the present invention includes a method in which the heterometallic phthalocyanine is synthesized by a known method and then further halogenated, or a method using a cyclization condensation reaction. Examples of methods for synthesizing different metal phthalocyanines include Mo5er, F, H,, and T.
homas A, L,, The Phthalocya
Nies, CRC Press Inc., 1983. Examples of the halogenation method include a method using a eutectic salt of aluminum chloride and common salt as a solvent, as described in JP-A No. 52-155625, and a method as described in USP No. 2,662,085. There is a method using lorosulfonic acid as a solvent, or a method using titanium tetrachloride as a solvent as described in JP-A-1-279975.

The highly halogenated dissimilar metal phthalocyanine and the highly halogenated copper phthalocyanine thus produced can be mixed in the form of dry powder, press cake or slurry, or both can be mixed with concentrated sulfuric acid or a solvent. 1. There is also a method of kneading using mechanical energy, which is carried out simultaneously with the usual pigment formation. Examples of the method of mixing using mechanical energy include adding diethylene glycol and salt or Glauber's salt, and kneading and mixing the mixture using a kneader.

In addition, a highly halogenated copper phthalocyanine and a highly halogenated dissimilar metal phthalocyanine are prepared separately.

It may also be added during production of paints, printing inks, etc.

Regarding the amount of highly halogenated dissimilar metal phthalocyanine added, if it is less than 0.3 parts by weight of highly halogenated dissimilar metal phthalocyanine per 100 parts by weight of highly halogenated copper phthalocyanine, it will not show any practical effect, but if it is mixed in excess of 30 parts by weight. Since this results in a decrease in resistance, it is necessary to add 0.3 to 30 parts by weight, preferably 3 to IO parts by weight.

Highly halogenated copper phthalocyanine pigments used in the blend include highly chlorinated steel phthalocyanine, highly brominated copper phthalocyanine, highly chlorinated brominated copper phthalocyanine, and mixtures thereof. As a method for producing these highly halogenated phthalocyanine pigments.

Method using talolsulfonic acid as a solvent (USP 2.
662゜085), a patent featuring titanium tetrachloride (JP-A-1-279975), a one-plane phase method (JP-A-54-16535), a cyclization condensation method (JP-A-54-16535),
1-46323). Further, the effect is also recognized in pigments produced by a method using a eutectic salt of aluminum chloride and common salt as a solvent (such as US Pat. No. 2.247.752).

The pigment dispersion of the present invention includes paints, printing inks, and the like.

The paint consists of 0.1 to 15% by weight of the pigment composition of the present invention, 99.9 to 55% by weight of a paint vehicle, and 0 to 30% by weight of other adjuvants and extender pigments. Resin, epoxy resin.

Chlorinated rubber, vinyl chloride, synthetic resin emulsion, silicone resin, water-soluble resin, polyurethane, polyester,
Melamine resin, urea resin or mixture thereof 80~
20 weight 06, hydrocarbons, alcohol.

Ketones, ether alcohols, ethers, esters.

It consists of water and a solvent of 60-10% by weight.

In gravure ink, 1 pigment composition of the present invention 3 to 20 weight 96. Vehicle for gravure ink 97-60 Weight 96.
Consists of other adjuvants and extender pigments 0 to 20 weight 045,
The vehicle for graphia ink is gum rosin.

Wood rosin, tall oil rosin, lime rosin, rosin ester, maleic acid resin, polyamide resin.

Vinyl resin, nitrocellulose, cellulose acetate.

Ethyl cellulose, ethylene-vinyl acetate copolymer resin,
Resin mixture of urethane resin, polyester resin, alkyd resin, gilt night, dammar, shellac etc. 10~
50 weight 06. Hydrocarbons, alcohols.

Ketones, ether alcohols, ethers, esters.

It consists of water and a solvent of 30 to 80% by weight.

The offset ink consists of 3 to 35% by weight of the pigment of the present invention, a vehicle for offset ink of 97 to 45% by weight, and 0 to 20% by weight of other auxiliaries and extender pigments, and the vehicle for the offset ink is rosin-modified phenolic resin, petroleum resin, , alkyd resins, or these drying oil-modified resins 20-50% by weight 96 Vegetable oils such as linseed oil, tung oil, soybean oil 0-30% by weight 06+n'' Rough-in, isoparaffin, aromatic, naphthene, alpha-olefin It consists of a solvent of 10 to 60% by weight.

〔Effect of the invention〕

The pigment composition of the present invention does not contain a blue phthalocyanine derivative to improve fluidity, but contains a green highly halogenated heterometallic phthalocyanine, so there is no drawback that the pigment composition has a bluish tinge.

Furthermore, the pigment dispersion of the present invention exhibits good fluidity due to reduced structural viscosity, and at the same time has high gloss and high tinting power, and can be widely used in various paints, printing inks, and the like.

(Example) The following is an outline of the method for producing the pigment composition of the present invention.
This will be explained by giving examples and comparative examples. In the example, "part", "r%"
and "parts by weight J, r weight 96" respectively.

[Manufacture example 1] 128 parts of phthalodinitrile 9 41 parts of ferric chloride.

1 part of ammonium molybdate is mixed in a mixer, placed in a reactor, heated to 210°C, and reacted to synthesize crude iron phthalocyanine. Next, aluminum chloride 200
Part 9 After heating 40 parts of common salt to form a eutectic salt at 120°C, 40 parts of crushed crude iron phthalocyanine was added and stirred for 30 minutes. In the chlorination reaction, the contents were heated to 160°C and chlorine gas was introduced at a rate of 8 parts per hour for 14 hours. After completion of chlorination, it was poured into a large amount of water, filtered, washed with water, dried, and crushed to obtain 53 parts of crude highly chlorinated iron phthalocyanine (
Structural formula (I[) where R is -CI).

The average amount of chlorine introduced into the obtained crude chlorinated iron phthalocyanine was 14.2.

[Production Example 2] 10 parts of crude highly chlorinated iron phthalocyanine synthesized in the same manner as in Production Example 1 was dispersed in 100 parts of 596 NaOH aqueous solution.
After stirring at °C for 1 hour, it was filtered, washed with water, dried, and ground (R1 in formula (n) is 10H).

[Production Example 3] 10 parts of crude highly chlorinated iron phthalocyanine produced in the same manner as in Production Example 1 and 2 parts of p-chlorobenzenesulfonic acid were mixed into 999%
4 was dissolved in 150 parts of sulfuric acid, stirred at 50°C for 2 hours, poured into a large amount of water, filtered, washed with water, dried, and crushed (formula (
R1 in II) is -803C6H4C1).

[Production Example 4] 300 parts of Hysol P (Nisseki), 12 parts of phthalodinitrile
8 parts of titanium tetrachloride, 48 parts of titanium tetrachloride, and 2 parts of pyridine were charged into a reactor, heated to 200°C, reacted, filtered, dried, and pulverized to obtain crude titanium phthalocyanine.

Next, 200 parts of aluminum chloride and 40 parts of common salt were heated to form a eutectic salt at 120°C, and then 40 parts of crude titanium phthalocyanine was added and stirred for 30 minutes.

In the chlorination reaction, the contents were heated to 160°C and chlorine gas was introduced at 8 parts per hour for 14 hours. After the chlorination was completed, it was poured into a large amount of water, filtered, washed with water, dried, and crushed to obtain a crude highly chlorinated titanium phthalocyanine.

[Production Example 5] A crude highly chlorinated tin phthalocyanine was obtained in the same manner except that 48 parts of titanium tetrachloride in Production Example 4 was replaced with 66 parts of stannic chloride.

[Production Example 6] A crude highly chlorinated nickel phthalocyanine was obtained in the same manner except that 41 parts of ferric chloride in Production Example 1 was replaced with 51 parts of nickel chloride.

In order to evaluate the effects of the pigment composition according to the present invention, paints and gravure inks having the following formulations were prepared.

Blend 1 (oil-based paint) Pigment (pigment composition) 7 parts alkyd resin varnish 76 parts melamine resin varnish 28 parts thinner
12 parts mixture 2 (water-soluble resin paint) Pigment (pigment composition) 6 parts water-soluble acrylic resin varnish 55 parts melamine resin varnish 9 parts thinner
30 parts blend 3 (gravure ink) Pigment (pigment composition) 10 parts polyamide/nitrocellulose varnish 7 parts thinner
20 parts of the above-mentioned mixture was placed in a container together with steel balls or glass beads and dispersed in a paint shaker to prepare a paint or gravure ink.

Evaluation was performed according to the evaluation method below.

(1) Fluidity evaluation method The viscosity of the obtained pigment dispersion was 6 and 6 using a B-type viscometer.
Measured at 0 rpm.

(2) Gloss evaluation method The oil-based paint was adjusted with thinner so that it lasted for 23 seconds in a 4-foil cup, and was sprayed on a tin plate with an air spray gun and then baked to create a coated plate, and the gravure ink was coated with a triacetate film using a bar coater. The 60 degree gloss was measured using a gloss meter.

[Comparative Example 1] 100 parts of a crude highly chlorinated copper phthalocyanine pigment synthesized as a chlorosulfonic acid solvent was mixed with 300 parts of common salt.

The pigment obtained by kneading and kneading with 140 parts of diethylene glycol for 6 hours was made into a paint using the formulation of Formulation 1.

The fluidity and gloss of the resulting paint are shown in Table I.

[Example 1] A pigment composition of the present invention consisting of 97 parts of the highly chlorinated steel phthalocyanine pigment obtained in Comparative Example I and 3 parts of the highly chlorinated iron phthalocyanine obtained in Production Example I was made into a paint using the formulation of Formulation 1. . As shown in Table I, the resulting paint had superior fluidity and gloss compared to Comparative Example I.

[Examples 2 to 4] Evaluations were made in the same manner as in Example 1, and all of them were superior in fluidity and gloss compared to Comparative Example 1.

[Comparative Example 2] A crude highly chlorinated brominated steel phthalocyanine pigment synthesized by the aluminum chloride method was made into a pigment in the same manner as in Comparative Example 1, and a paint was made using the formulation of Formulation 1. The fluidity and gloss of the resulting paint are shown in Table 1.

[Examples 5-6] Highly chlorinated brominated steel phthalocyanine pigment 9 obtained in Comparative Example 2
The pigment composition of the present invention, consisting of 7 parts and 3 parts of the highly chlorinated dissimilar metal phthalocyanine shown in the production example, was made into a paint according to the formulation of Formulation 1. The obtained paint was as shown in Table 1, Comparative Example 2.
It had superior fluidity and gloss compared to other materials.

[Comparative Example 3] 100 parts of a crude highly chlorinated copper phthalocyanine pigment synthesized using titanium tetrachloride as a solvent was obtained in the same manner as in Comparative Example 1, and a pigment was made into a paint using the formulation of Formulation 2. Table 1 shows the fluidity of the obtained paint.

[Examples 7 to 11] The pigment composition of the present invention, which consists of 93 parts of the highly chlorinated copper phthalocyanine pigment obtained in Comparative Example 3 and 7 parts of the highly chlorinated dissimilar metal phthalocyanine shown in Production Example, was applied to a paint using the formulation of Formulation 2. It became. As shown in Table 2, the obtained paint had superior fluidity compared to Comparative Example 3.

[Comparative example 4] The pigment of Comparative Example 1 was evaluated in the gravure ink of Formulation 3.

[Examples 12 to 15] The pigment composition of the present invention, consisting of 96 parts of the highly chlorinated copper phthalocyanine pigment obtained in Comparative Example 1 and 4 parts of the highly chlorinated dissimilar metal phthalocyanine shown in the production example, was used in the gravure ink of Formulation 3. evaluated. As shown in Table 3, the results were superior in fluidity and gloss compared to Comparative Example 4.

Claims (1)

[Claims] 1. Based on 100 parts by weight of highly halogenated copper phthalocyanine, the central metal is Mg, Si, Ti, V, Mn, Fe, Co.
A pigment composition comprising 0.3 to 30 parts by weight of at least one highly halogenated dissimilar metal phthalocyanine selected from , Ni, Zn, Ge, and Sn. 2. A pigment dispersion comprising the pigment composition according to claim 1 and a pigment dispersion resin.