JP2002161220A - Pigment composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an a type copper phthalocyanine pigment composition having higher heat resistance than that of the conventional α type copper phthalocyanine pigment composition. SOLUTION: This pigment composition is characterized in that in a copper phthalocyanine pigment composition comprising an α type copper phthalocyanine pigment (A) and a tetrahalogenated copper phthalocyanine (B), a copper phthalocyanine containing a halogen substituent group localized in one phenylene group is used as the tetrahalogenated copper phthalocyanine (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an α-type copper phthalocyanine (organic solvent unstable type) pigment composition.

[0002]

2. Description of the Related Art As a copper phthalocyanine pigment exhibiting a reddish blue color, an α-type copper phthalocyanine pigment is known, and is used for various coloring applications such as aqueous flexographic ink, resin coloring, paint and printing.

However, α-type copper phthalocyanine has relatively low heat resistance in its crystal structure, and when used as a coloring agent such as a thermoplastic resin which requires a relatively high processing temperature, the α-type copper phthalocyanine generates heat due to heat during processing and molding. Crystal transition occurs to thermodynamically stable β-type copper phthalocyanine (organic solvent stable type), discolors to greenish blue, and causes crystal growth at the same time as the crystal transition, resulting in a marked decrease in coloring power. There was a problem.

In order to prevent such discoloration and reduction in coloring power and to maintain the original hue and coloring power of α-type copper phthalocyanine, JP-B-54-44296 discloses that the corresponding phthalocyanine skeleton contains phthalimidomethyl. A method of adding a group-introduced copper phthalocyanine derivative is described.

[0005]

However, with the above copper phthalocyanine derivatives, the α-type copper phthalocyanine pigment still has insufficient heat resistance retention ability.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above-mentioned situation, and found that a hydrogen atom of one phenylene group forming a phthalocyanine skeleton was substituted for a copper phthalocyanine derivative conventionally used. By using a tetrahalogenated copper phthalocyanine in which one is substituted with a halogen atom, that is, a halogen atom is localized, the heat resistance of the α-type copper phthalocyanine pigment can be improved while maintaining a reddish blue hue. And completed the present invention.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The present invention provides a pigment composition comprising a mixture of an α-type copper phthalocyanine pigment (A) and a tetrahalogenated copper phthalocyanine (B), wherein the halogen atom is localized as the tetrahalogenated copper phthalocyanine (B). By using the localized compound, the conventional Japanese Patent Publication No. 54-442 can be used.
It is intended to provide an α-type copper phthalocyanine pigment composition having better heat resistance than a mixture of a copper phthalocyanine derivative proposed in JP-A-96-96 and the like.

As the α-type copper phthalocyanine pigment (A) used in the present invention, any known and commonly used ones can be used. Specifically, a crude copper phthalocyanine produced by a conventionally known Wyler method or a phthalodinitrile method is used, and a crude copper phthalocyanine produced by performing a pigmentation by a conventionally known acid pasting method or an acid slurry method is used. can do. Alternatively, fine particle α-type copper phthalocyanine produced by the phthalodinitrile method can be used directly.

The α-type copper phthalocyanine pigment (A)
In the X-ray diffraction method, 2θ (CuKα / Ni) is 6.
8 °, 7.4 °, 9.9 °, 15.6 °, 16.2 °,
There are diffraction peaks at 24.0 °, 25.0 °, 26.7 °, and 27.6 °, with the characteristic that the intensity is strong at 6.8 ° and low at 9.9 °.

Next, the tetrahalogenated copper phthalocyanine (B), which characterizes the present invention, will be explained. It is a compound having the chemical structure represented by 1. Where Equation 1
Wherein X is a chlorine atom, a bromine atom or an iodine atom which may be the same or different.

Equation 1

[0012]

Embedded image

It is important in the present invention that the halogen substituent is localized in one phenylene group in the present invention. For example, the following formula 2 having the same number of substituents but different positions of the substituents. In the case of a conventionally known compound having the chemical structure represented by, the excellent heat resistance as in the present invention cannot be obtained. In addition, X in Formula 2 has the same meaning as the definition in Formula 1.

Equation 2

[0015]

Embedded image

As the halogen atom used in the tetrahalogenated copper phthalocyanine (B) used in the present invention, any halogen atom can be used, and these can be used alone or in combination of two or more. Of these, chlorine or bromine is generally used industrially.

The copper tetrahalide phthalocyanine (B) used in the present invention is produced, for example, by reacting 1 mol of a tetrahalogenated phthalodinitrile with 3 mol of an unsubstituted phthalodinitrile with 1 mol of a copper compound. can do. Alternatively, they can be similarly produced using tetrahalogenated phthalic acids and unsubstituted phthalic acids instead of the above-mentioned tetrahalogenated phthalodinitrile and unsubstituted phthalodinitrile. The reaction temperature is not particularly limited, but is generally 383 to 40.
It can be selected from 3K (Kelvin temperature).

The amount of the tetrahalogenated copper phthalocyanine (B) used in the present invention is 3 to 25 parts by weight, particularly preferably 8 to 18 parts by weight, per 100 parts by weight of the α-type copper phthalocyanine pigment (A). Department. If the amount is small, sufficient heat resistance cannot be obtained, and if the amount is too large, the clear hue inherent in the α-type copper phthalocyanine is dull, which is not preferable.

Any method can be used to mix the α-type copper phthalocyanine pigment (A) and the tetrahalogenated copper phthalocyanine (B) to obtain the composition of the present invention.
The tetrahalogenated copper phthalocyanine (B) may be mixed with the dry powder of the type copper phthalocyanine pigment (A) in a dry powder state, or may be mixed in a wet cake or slurry state.

Further, the tetrahalogenated copper phthalocyanine (B) may be produced in the presence of the α-type copper phthalocyanine pigment (A), or the α-type copper phthalocyanine pigment (A) and the tetrahalogenated copper phthalocyanine ( B) may be generated simultaneously. The reaction temperature can be selected, for example, from the above range.

The copper phthalocyanine pigment is finer as the value of the BET specific surface area measured by nitrogen adsorption is larger, exhibits higher coloring power, and is preferred as a coloring agent. The BET specific surface area of the pigment composition of the present invention measured by preferable nitrogen adsorption is 70 to 130 m ² / g. When this is used as a known and conventional coloring agent, it is equivalent to the α-type copper phthalocyanine pigment (A). Alternatively, it shows higher coloring power. The BET specific surface area in the present invention is determined by the method defined in Annex 2 of Japanese Industrial Standard JIS Z 8830-1990, and more specifically, the sample deaeration temperature is 120 ° C, the deaeration time is 20 minutes, Sampling amount 0.2
g can be measured by the one-point method at a relative nitrogen pressure of 0.29.

The pigment composition of the present invention can be used for any of various known and commonly used applications. For example, by uniformly dispersing the medium to be colored, the medium can be colored. If necessary, a mixture (masterbatch) with a resin containing the pigment composition in a concentrated state may be prepared in advance and diluted with a medium to be colored for use. As the resin for the masterbatch, a resin having excellent compatibility with the medium to be colored is selected.

When the form of the masterbatch is included, the pigment composition of the present invention is used in an amount of 0.01 to 200 parts by weight, preferably 0.02 to 150 parts by weight, per 100 parts by weight of the resin.
Use parts by weight together. Ultimately, the pigment composition of the present invention is used in an amount of 0.0
Generally, the amount is 1 to 40 parts by weight, preferably 0.02 to 15 parts by weight.

Examples of the medium to be colored include, for example, polyolefins such as polyethylene and polypropylene, polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate, and various thermoplastics for molding used in injection molding of polystyrene, polycarbonate, polyphenylene sulfide and the like. Resins.

The method of dispersion in the medium to be colored is generally carried out by previously mixing the α-type copper phthalocyanine pigment (A) and the copper tetrahalide phthalocyanine (B) to form the pigment composition of the present invention. However, instead of preparing a pigment composition in advance, the above (A) and (B) can be added to a medium to be colored and simultaneously dispersed. In dispersing, it is preferable to apply heat as necessary to bring the resin into a molten state.

The pigment composition of the present invention thus obtained is obtained by mixing a copper phthalocyanine derivative conventionally proposed in JP-B-54-44296 with an α-type copper phthalocyanine pigment (A). Applications that receive a strong thermal history compared to when used as a composition, particularly preferably 5
When used as a colorant such as polyolefin or polycarbonate requiring a molding temperature of 03 to 593K,
Maintaining a reddish blue hue and high tinting strength without lowering the tinting strength due to crystal growth caused by heat during processing and forming a green hue due to crystal transition to β-type copper phthalocyanine. Can be.

[0027]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples. In the following, “%” means “% by weight” unless otherwise specified.

Example 1 A 500-ml glass reactor equipped with a stirrer, a thermometer, and a cooling tube was charged with 220 g of ethylene glycol saturated with ammonia, 39.2 g (0.3 mol) of phthalodinitrile, Phthalodinitrile 27.6 g (0.1 mol), cuprous chloride 10.1
g (0.1 mol) was charged and reacted at 393 K for 3 hours with stirring.

After the completion of the reaction, the mixture was cooled to 323 K, and the product was filtered off.
And washed. Then, the mixture was peptized in the order of 1000 g of 1% hydrochloric acid and 1000 g of 1% caustic soda, and each was washed at 363 K for 1 hour. After sufficiently washing the obtained wet cake with water, it was dried at 363 K to obtain 67.7 g of a blue product. FD mass spectrometer (manufactured by HITACHI; M2000)
As a result of analysis in A), it was found to contain 85% of the tetrachlorocopper phthalocyanine represented by the above formula 1, wherein X is a chlorine atom.

11.9 g of a pulverized product of a reaction product containing tetrachlorocopper phthalocyanine represented by the formula 1 as a main component
Commercially available α-type copper phthalocyanine pigment (“FASTOGEN BLUE GP-” manufactured by Dainippon Ink and Chemicals, Inc.)
100 ") to obtain a pigment composition. This pigment composition contains 9% of tetrachlorocopper phthalocyanine represented by the formula 1.

The pigment composition was treated with a micro soap automatic BE.
T specific surface area meter (Micro Data, Model42)
When the BET specific surface area was measured by nitrogen adsorption in 32II), it was 81 m ² / g. When a heat resistance test was performed according to the test examples described below, the 553K molded product had the same coloring power and hue as the continuous molded product and the stay molded product as compared with the 493K molded product.

Example 2 220 g of ethylene glycol saturated with ammonia, 51.1 g (0.391 mol) of phthalodinitrile, tetrachloromethane were placed in a 500-ml glass reactor equipped with a stirrer, a thermometer, and a condenser. 2.4 g (0.009 mol) of phthalodinitrile, cuprous chloride 1
0.1 g (0.1 mol) was charged and reacted at 393 K for 1 hour with stirring.

After the completion of the reaction, the mixture was cooled to 323 K, and the product was separated by filtration.
And washed. Then, the mixture was peptized in the order of 1000 g of 1% hydrochloric acid and 1000 g of 1% caustic soda, and each was washed at 363 K for 1 hour. After sufficiently washing the obtained wet cake with water, it was dried at 363 K to obtain a pigment composition.

Analysis by an FD mass spectrometer revealed that, in addition to the unsubstituted copper phthalocyanine pigment, 9% of tetrachlorocopper phthalocyanine represented by the formula 1 wherein X was a chlorine atom was contained. The BET specific surface area was 88 m ² / g. X
Line diffraction analyzer (Rigaku; RINT 110)
(Type 0), the intensity was strong at 6.8 °, and 9.
The strength at 9 ° was weak and the crystal form was the same as α-type copper phthalocyanine.

The pigment composition obtained was subjected to a heat resistance test in accordance with the test examples described below. As a result, the 553K molded product was found to have a higher tinting strength for both the continuous molded product and the stay molded product than the 493K molded product. Hue was equivalent.

Comparative Example 1 The procedure of Example 1 was repeated except that 10 g of phthalimidomethyl copper phthalocyanine was used instead of 11.9 g of the reaction product of formula 1 containing tetrachlorocopper phthalocyanine as the main component. Similarly, a pigment composition was obtained. This pigment composition contains 9% of phthalimidomethyl copper phthalocyanine. BET specific surface area is 82
m ² / g. A heat resistance test was performed on the obtained pigment composition in accordance with the test examples described below.
The molded product was inferior in coloring power to both the continuously molded product and the stay molded product as compared with the 493K molded product.

[Comparative Example 2] Reaction product 1 containing tetrachlorocopper phthalocyanine of the formula 1 as a main component used in Example 1
A pigment composition was obtained in the same manner as in Example 1 except that 1.9 g was replaced by 10 g of tetrachlorocopper phthalocyanine represented by the above formula 2 in which X is a chlorine atom. This pigment composition contains 9% of tetrachlorocopper phthalocyanine of the formula 2. The BET specific surface area was 80 m ² / g. A heat resistance test was performed on the obtained pigment composition in accordance with the test examples described below.
The coloring power was inferior to both the continuous molded product and the stay molded product as compared with the 3K molded product.

<Test Example> Heat Resistance Test Method A heat resistance test was carried out in a colored molding of polyethylene resin using the pigment compositions obtained in Examples and Comparative Examples by the following method. 0.3 g of pigment composition, 0.3 g of zinc stearate, 80% white pigment in dry color (white)
3.75 g and 600 g of a polyethylene resin were mixed to prepare a light-colored resin. This light-colored resin was molded at 493 K using an injection molding machine, and the eleventh shot was used as a light-colored standard plate. Next, continuous molding was performed at 553K, and the seventh shot was used as a test plate for a heat-resistant continuous test. Next, after stagnation at 553K for 10 minutes, molding was performed, and the second shot was used as a test plate for a heat stagnation test. The light-colored standard plate and the heat resistance test plate of each pigment composition were visually compared, and the heat resistance of hue and tinting strength was comparatively evaluated.

[0039]

By using the α-type copper phthalocyanine pigment composition containing tetrahalogenated copper phthalocyanine (B) in which four halogen atoms are localized according to the present invention, a conventionally proposed copper phthalocyanine derivative or the like is mixed. Thus, an α-type copper phthalocyanine pigment composition having more excellent heat resistance than that obtained is obtained.

Claims (3)

[Claims] 1. A copper phthalocyanine pigment composition containing an α-type copper phthalocyanine pigment (A) and a tetrahalogenated copper phthalocyanine (B), wherein the tetrahalogenated copper phthalocyanine (B) is represented by the following formula 1. A pigment composition characterized by using a compound to be prepared. However, in the formula 1, X is a chlorine atom, a bromine atom or an iodine atom which may be the same or different. Formula 1 2. An α-type copper phthalocyanine pigment (A) 100
The pigment composition according to claim 1, wherein the pigment composition is used such that the amount of the copper tetrahalide phthalocyanine (B) of the formula 1 is 3 to 25 parts by weight per part by weight. 3. The pigment composition according to claim 1, wherein the BET specific surface area measured by nitrogen adsorption is 70 to 130 m ² / g.