JPH03223364A - Copper phthalocyanine pigment composition and pigment dispersion composition made therefrom - Google Patents

Abstract

PURPOSE:To make the waste water treatment in the pigment production unnecessary by dry pulverizing a crude copper phthalocyanine without using pulverizing aid and compounding the resulting copper phthalocyanine with a specific phthalocyanine deriv. CONSTITUTION:A crude copper phthalocyanine, obtd. by reacting (a deriv. of) phthalic anhydride, urea, and a copper source in an org. solvent at 120-270 deg.C for 2-15hr, is dry-pulverized at 20-130 deg.C without using a pulverizing aid to give copper phthalocyanine, which is compounded with a phthalocyanine deriv. of formula I or II (wherein X is H, Al, Fe, Co, Ni, Cu, or Zn; Pc is a phthalocyanine residue; R1 to R4 are each H or 1-20C alkyl excepting the case when all of them are H; Y is H, halogen, NO2, NH2, or SO3H; Z is H, Ca, Ba, Sr, or Al; (n) is 1-4; and (l) is a valence of Z) in an amt. of 1-20wt.% of the copper phthalocyanine.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a copper phthalocyanine pigment composition and a pigment dispersion composition using the same. More specifically, it relates to a composition characterized in that crude copper phthalocyanine is dry-milled together with a phthalocyanine derivative without the addition of a milling aid, or that the crude copper phthalocyanine is dry-milled without the addition of a milling aid and then a phthalocyanine derivative is mixed therein. It is.

(Prior art) Fine copper phthalocyanine pigments are used in large quantities in the color material industry because they have beautiful color tone, high coloring power, and good functions such as weather resistance and heat resistance. Widely used.

Usually crude copper phthalocyanine is prepared from phthalic anhydride or its derivatives, urea and a copper source, or phthalodinitrile or its derivatives and a copper source.

It is produced by reacting ammonium molybdate or titanium tetrachloride in the presence or absence of a catalyst with alkylbenzene, trichlorohensen, or nitrohensen in an organic solvent under normal pressure or increased pressure. But because.

The synthesized phthalocyanine molecules undergo crystal growth one after another in the synthesis solvent, and can only be obtained in the form of coarsely acicular crystals with a major axis of lθ ~ 200 μm, which is useful for coloring inks, paints, plastics, etc. As a pigment its value is very low or non-existent.

Therefore, crude copper phthalocyanine is a particle with high color utility value, that is, 0. It is necessary to refine the particles to about 1 to 0.5 μm (hereinafter, this operation will be referred to as pigmentation).

Two methods are used to obtain finely divided α-type pigments: the acid pasting method, which involves dissolving the pigment in a large amount of concentrated sulfuric acid, and the acid slurry method, which creates sulfate with a large amount of sulfuric acid at an insufficient concentration to dissolve the pigment. However, it has the disadvantage that a large amount of sulfuric acid must be used, which is not desirable from the standpoint of wastewater treatment.

Further, as a method for producing a finely divided β-type copper phthalocyanine pigment, crude steel phthalocyanine is dry-pulverized with a grinding aid such as anhydrous sodium ferronaninide or anhydrous barium chloride at a high temperature of 100 to 150°C for a long time. In the so-called tri-salt milling method, crude copper phthalocyanine is charged into a double-arm dispersion mixer together with a grinding aid such as a water-soluble inorganic salt such as sodium chloride, and an organic liquid such as an alcohol, polyol, or amine, and wet-milled. In the so-called salt milling method, crude copper phthalocyanine is dry-milled in the absence of milling aids and organic liquids, and then treated with an organic solvent or the like. The so-called tri-milling method requires a multi-step process and a large amount of energy.

Furthermore, when the α-type and β-type copper phthalocyanine pigments obtained by the above method are used in applications such as inks and paints, there is a problem in that a large amount of energy is required to disperse the aggregated particles in a vehicle. As a method to solve these problems, Japanese Patent Publication No. 55-6670 discloses that crude copper phthalocyanine is dry-pulverized and directly used as an ink.
It has been shown that pigment pastes can be obtained by suspension in solvents or resin solutions used in paints without prior conversion to pigment form. Furthermore, in order to effectively utilize the above technology, JP-A-60-195161 discloses a copper phthalocyanine pigment composition obtained by dry-pulverizing crude copper phthalocyanine together with a phthalimidomethyl phthalocyanine derivative. The products were not sufficient in terms of suitability for use, such as dispersibility, color strength, sharpness, gloss, and stability over time, and improvements were desired.

(Problems to be Solved by the Invention) The object of the present invention is to obtain a copper phthalocyanine pigment composition that does not require wastewater treatment when turning into a pigment.

Another object of the present invention is to obtain a copper phthalocyanine pigment composition that does not require a large amount of energy when turning into a pigment.

Furthermore, the present invention has 1 dispersibility, 9 tinting strength, and 1 sharpness in non-aqueous vehicles such as paints and printing inks.

The purpose of this invention is to obtain a copper phthalocyanine pigment dispersion composition that has excellent gloss and stability over time.

[Structure of the invention]

(Means for Solving the Problems) The present invention comprises copper phthalocyanine obtained by dry-pulverizing crude copper phthalocyanine without the addition of a grinding aid, and 1 to 20% by weight of the following formula (I) or (
A copper phthalocyanine pigment composition comprising a phthalocyanine derivative represented by II).

and a pigment dispersion composition obtained by dispersing this in a non-aqueous vehicle.

The production method for crude copper phthalocyanine is not particularly limited, or phthalic anhydride or its derivatives, urea and a copper source, or phthalodinitrile or its derivatives and a copper source are mixed in an organic solvent in the presence or absence of a catalyst. Inside 120-270°C1 preferably 170-2
It is produced by reacting at 30°C for 2 to 15 hours, preferably 3 to 7 hours, under normal pressure or increased pressure. Note that low chlorination copper phthalocyanine may be used as the crude steel phthalocyanine.

The phthalocyanine derivatives according to the present invention are represented by the following general formula.

(In the formula, X is H, A1. Fe, Co, Ni, Cu
.

Zn and Pc are phthalocyanine residues + R+ to R4 are each independently a hydrogen atom and an alkyl group having 1 to 20 carbon atoms (except in the case where all of them are hydrogen atoms).

Y is hydrogen atom, halogen atom, -No2゜-N
l2. -3O, H, Z are H, Ca, Ba.

Sr, Aβ, and n are integers of 1 to 4, and 1 represents the valence of Z.

) The amount of the phthalocyanine derivative added is preferably 1 to 20% by weight, and if it is less than 1% by weight, the pigment dispersion will have poor coloring power, clarity, gloss, and stability over time;
Adding more than 6 is not economical. A more preferable addition amount is 2 to 15% by weight. More preferably 3 to 12% by weight
It is.

In addition, the effect of the crystal growth inhibitor by blending the phthalocyanine derivative becomes apparent when the pigment dispersion is produced using the obtained pigment composition, so the timing of addition to the crude steel phthalocyanine is limited even before dry grinding. Even after dry grinding, the pigment quality remains unchanged and the timing of addition is not particularly limited.

For dry pulverization in the process, for example, a ball mill, vibration mill, attritor, or other pulverizer can be used. The grinding temperature can be freely set within the range of 20 to +30°C. The pigment composition obtained by dry grinding is a mixture of α-type copper phthalocyanine and β-type copper phthalocyanine, and the content of α-type copper phthalocyanine is 10 to +0096.
Preferably 20-9oo6. More preferably 30-8
It is 096.

The pigment dispersion composition of the present invention can be obtained by blending the copper phthalocyanine pigment composition of the present invention into a printing ink vehicle such as an offset ink or a gravure ink, or a coating vehicle. As the vehicle, it is particularly preferable to use a non-aqueous vehicle containing an aromatic organic solvent such as toluene or xylene.

As a paint, copper phthalocyanine pigment composition 0°1-1
5% by weight. Paint vehicle 99.9-55 Weight 96. It consists of other adjuvants and extender pigments of 0 to 30% by weight. Vehicles for paint include resin mixtures such as acrylic resins, alkyd resins, epoxy resins, polyurethanes, polyesters, melamine resins, etc. 80-20% by weight, and solvents such as hydrocarbons, alcohols, ketones, ether alcohols, ethers, esters, etc. 60-10% by weight. It consists of 96.

In gravure ink, 1 copper phthalocyanine pigment composition of the present invention 3 to 20 weight 96. Vehicle 97 for gravure ink
~60 weight 96. It consists of 0 to 20% by weight of other adjuvants and extender pigments. The vehicle for gravure ink is
Lime rosin, rosin ester, maleic acid resin, polyamide resin, vinyl resin, nitrocellulose, ethylene-vinyl acetate copolymer resin, urethane resin, polyester resin.

Resin mixture such as alkyd resin 10-50% by weight 96° Solvent such as hydrocarbon, alcohol, ketone, ether alcohol, ether, ester etc. 30-80% by weight? It consists of 6.

The present invention will be explained below in detail with reference to Examples, but the present invention is not limited by the Examples. In the examples, 9 parts means parts by weight, and 1% means 96 parts by weight.

Example 1 Add 7 parts of the following copper phthalocyanine derivative to 93 parts of crude chlor-free steel phthalocyanine, and heat at 55°C in an attritor.
The mixture was dry-pulverized for 1 hour. The resulting dry milled mixture was
Linear diffraction showed an α-type content of 65%.

Example 2 100 parts of crude chlorine-free copper phthalocyanine was dry ground in an attriter at 55°C for 1 hour.

The resulting dry milled mixture had an α of 66% according to X-ray diffraction.
The type content was shown. 93 parts of this dry-pulverized product and 7 parts of the same copper phthalocyanine derivative as in Example 1 were mixed.

Comparative Example 1 100 parts of crude chlorine-free copper phthalonoanine was dry-pulverized with an attriter at 55°C for 1 hour.

The resulting dry milled mixture had an α of 65% according to X-ray diffraction.
The type content was shown.

Comparative Example 2 93 parts of crude chlorine-free copper phthalocyanine was added to JP-A-60
7 parts of the phthalimidomethyl copper phthalocyanine derivative described in No. 195161 was added.

Dry milling was carried out in an attriter at 55°C for 1 hour.

The resulting dry milled mixture showed an alpha content of 6596 by X-ray diffraction.

Examples 3-6 The method of Example I was repeated, varying the amount of derivative and the grinding conditions as shown in Table-1.

Example 7 Example 1 was carried out by changing the type of copper phthalocyanine derivative to the following one.

Practical Example 8 A test was carried out in Practical Example 2 except that the type of copper phthalocyanine derivative used was changed to that used in Example 7.

〔Evaluation methods〕

In order to evaluate the effects of the pigments in place of the present invention, paints and gravure inks having the following formulations were prepared.

Formulation l (oil-based paint) Pigment 7 parts Alkyd resin varnish 76 parts Melamine resin varnish 28 parts Shinju-12 part Formulation 2 (gravure ink) Pigment 10 parts Lime rosin varnish 80 parts Nonner 10 copies Evaluation was performed according to the evaluation method below.

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

(2) Hue and gloss The oil-based paint was adjusted with a Ford Cup 4 for 20 seconds, then sprayed on the tin plate with an air spray gun and baked to create a coated plate, and the gravure ink was spread on coated paper with a bar coater. After coloring, the hue was visually determined and the gloss was measured at 60 degrees using a gloss needle.

(3) Coloring power The oil-based paint was mixed with a white coating material, applied to art paper using an applicator, and baked, and the gravure ink was mixed with white ink, applied to coated paper using a bar coater, and evaluated visually.

(4) Stability over time (gravure ink) The ink aged at 50°C for 5 days and the newly created ink are mixed with white ink and spread on coated paper using a bar coater, and judged by the difference in coloring strength. did.

Table 2 summarizes the evaluation results for oil-based paints. Table 3 summarizes the evaluation results for gravure inks. The pigment according to the present invention shows better performance than the comparative example.

table 2 Oil-based paint evaluation results 1) BNI type viscometer rpm value /60 rpm value table Evaluation results of gravure ink 11BM type viscometer 6 rpm value / 60 rpm value 2) Change in coloring power over time

Claims (1)

[Scope of Claims] 1. Copper phthalocyanine obtained by dry-pulverizing crude copper phthalocyanine without adding a grinding aid, and 1 to 20% by weight of the copper phthalocyanine represented by the following general formula (I) or (II). A copper phthalocyanine pigment composition comprising a phthalocyanine derivative. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, X is H, Al, Fe, Co, Ni, Cu, Zn,
Pc is a phthalocyanine residue, R_1 to R_4 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (excluding when all are hydrogen atoms), Y is a hydrogen atom, a halogen atom, -NO_2, -NH_2, -SO_3H, Z represents H, Ca, Ba, Sr, Al, n represents an integer of 1 to 4, and l represents the valence of Z. 2. The copper phthalocyanine pigment composition according to claim 1, which is dry-milled in the presence of the phthalocyanine derivative. 3. The copper phthalocyanine pigment composition according to claim 1, wherein the phthalocyanine derivative is added after dry-pulverizing the crude copper phthalocyanine. 4. A pigment dispersion composition comprising the phthalocyanine pigment composition according to claim 1 dispersed in a non-aqueous vehicle.