JP2000302993A - Colorant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colorant comprising a zinc phthalocyanine compound showing a stronger greening effect than a conventional β-type copper phthalocyanine pigment. SOLUTION: This colorant comprises a zinc phthalocyanine compound having the maximum absorption wavelength of 650-700 nm and the absorbance at the maximum absorption wavelength of >=0.2 in an absorption spectrum measured under the following conditions: throwing 3 mg zinc phthalocyanine compound and 10 mL THF into a 20 mL vial (screw tube bottle) and dispersing the mixture for 10 min with an ultrasonic cleansing machine to obtain a homogeneous dispersion; filtering the dispersion through a sample-predisposing filter having a diameter of 14 mm and a pore size of 0.2 μm and; diluting the filtrate to a 1/50 concentration level with THF and measuring the absorption spectrum of the diluted filtrate with a spectrophotometer (UV-1600PC, Shimadzu Corporation). The colorant is suitable as a colorant for a cyan toner and an ink-jet ink for high image quality color printing and copying.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a colorant. Specifically, the present invention relates to a method in which the maximum absorption wavelength is 650.
It relates to a colorant comprising a zinc phthalocyanine compound in the range of -700 nm.

[0002] The present invention further relates to a colorant of blue having high fastness, for example, coloring of fibers, paint for automobiles, paint for construction materials, coloring of printing materials, ink for writing implements, coloring of glass flakes, coloring of spectacle lenses. Excellent effect when used as a coloring agent. The present invention exerts a very excellent effect particularly when used for a colorant and a cyan-based colorant for an inkjet ink.

[0003]

2. Description of the Related Art Copper phthalocyanine pigments are widely used in various fields in the field of the color material industry because of their excellent fastness, vivid color tone, and high coloring power. Among the copper phthalocyanine pigments, blue pigments have various crystal systems, but those of industrial importance are α, β, and ε types. These are all in the blue range, but have different hues depending on the crystal system. Α-type is reddish, β-type is greenish, and ε-type is reddest. Among them, the β-type pigment has the largest production amount. β-type pigments are often used for colorants that require a cyan hue due to their greenish blue color.

[0004] In a full-color printing machine or copier, all colors are produced by mixing four colorants of cyan, magenta, yellow and black.
Therefore, in order to achieve vivid color development, the color balance between colorants is important. In recent years, there has been an increasing demand for higher precision image quality in color printing and color copying, and when considering the balance between magenta, yellow, and black, the ideal cyan color tone is even more green than before. It is changing to a strong blue color. Therefore, there has been a problem that the tint of the conventional β-type copper phthalocyanine pigment has become incompatible.

As means for solving such a problem, Japanese Patent Application Laid-Open No. 5-19536 discloses a colorant comprising a mixture of a β-type copper phthalocyanine pigment and a polychloro copper phthalocyanine pigment. JP-A-6-266161 discloses a colorant comprising a copper phthalocyanine pigment having a specific substituent.
Discloses a colorant comprising a copper phthalocyanine pigment having a particle size of 0.3 μm or less.
No. 60 discloses a colorant comprising a copper phthalocyanine pigment having an α-type crystal content of 7% or less.

[0006] However, none of these can sufficiently solve the above-mentioned problems.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a colorant containing a zinc phthalocyanine compound having a greener color than conventional β-type copper phthalocyanine pigments.

Another object of the present invention is to provide a colorant for a cyan toner or an ink-jet ink suitable for high-quality color printing or copying.

[0009]

That is, the above objects of the present invention are achieved by the following (1).

(1) A coloring agent containing a zinc phthalocyanine compound having a maximum absorption wavelength in the range of 650 to 700 nm and an absorbance at the maximum absorption wavelength of 0.2 or more in an absorption spectrum measured under the following conditions: : A zinc phthalocyanine compound (3 mg) and tetrahydrofuran (in the present specification,
10 ml of the mixture (abbreviated simply as THF) is added, and the mixture is dispersed with an ultrasonic cleaner for 10 minutes to obtain a uniform dispersion. The dispersion is filtered through a sample pretreatment filter having a diameter of 14 mm and a pore size of 0.2 μm. The absorption spectrum of the diluted solution obtained by diluting this filtrate 50-fold with THF was measured using a spectrophotometer (UV
-1600PC; manufactured by Shimadzu Corporation).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The coloring agent according to the present invention is characterized by comprising a zinc phthalocyanine compound having a maximum absorption wavelength of 650 to 700 nm and being soluble in an organic solvent in a certain amount or more. . In particular, THF solvent 1
3 mg in 0 ml, and dispersed by an ultrasonic cleaner for 10 minutes to obtain a uniform dispersion. The dispersion is filtered through a filter for sample pretreatment having a diameter of 14 mm and a pore diameter of 0.2 μm, and the filtrate is filtered with THF. A zinc phthalocyanine compound having an absorbance at a maximum absorption wavelength of 0.2 or more as measured by using a spectrophotometer (UV-1600PC; manufactured by Shimadzu Corporation) to measure the absorption spectrum of a diluted solution diluted 50 times. It can be said that those characterized by the following are more preferable.

The maximum absorption wavelength of the zinc phthalocyanine compound contained in the coloring agent is 650 to 700 nm. When the maximum absorption wavelength is out of the range of 650 to 700 nm, the color when used as a colorant or the like is deviated from the cyan type, so that the colorant containing the phthalocyanine compound has high color purity characteristics. Is not preferred. On the other hand, the maximum absorption wavelength in THF solvent is 65
When it is in the range of 0 to 700 nm, it can be said that it is particularly preferable because the color when used as a colorant or the like conforms to cyan.

The zinc phthalocyanine compound contained in the coloring agent is put in an amount of 3 mg in 10 ml of a THF solvent and dispersed by an ultrasonic cleaner for 10 minutes to obtain a uniform dispersion. The dispersion is 14 mm in diameter and 0.1 μm in pore size. The solution was filtered through a 2 μm sample pretreatment filter, and the filtrate was washed with THF for 5 hours.
Diluent having a solubility of at least 0.2 as measured by using a spectrophotometer (UV-1600PC; manufactured by Shimadzu Corporation) to measure the absorption spectrum of the diluted solution diluted to 0 times. Is preferred. Β-type copper phthalocyanine pigment, which has been the mainstream of cyan colorants,
3 mg in 10 ml of THF solvent, and 1
Dispersion was carried out for 0 minute to obtain a uniform dispersion, and this dispersion was filtered through a filter for sample pretreatment having a diameter of 14 mm and a pore diameter of 0.2 μm. The filtrate obtained by diluting the filtrate 50 times with THF was completely colored. The absorbance at the maximum absorption wavelength of the diluted solution measured using a spectrophotometer (UV-1600PC; manufactured by Shimadzu Corporation) was 0. Since the β-type copper phthalocyanine pigment has no compatibility with the resin at all, the coloring power is increased by finely dispersing as much as possible. On the other hand, the zinc phthalocyanine compound contained in the coloring agent of the present invention dissolves in a certain amount or more in a THF solvent and is compatible with a resin. There is an effect that a desired coloring power can be exhibited even if the pigment is not sufficiently finely dispersed, or an equivalent coloring power can be exhibited with a smaller amount of addition than conventional pigments.

A filter for sample pretreatment necessary for preparing a dispersant necessary for preparing a filtrate for measuring absorbance having a maximum absorption wavelength has a diameter of 14 mm and a pore diameter of 0.2 μm.
Any condition that satisfies the conditions (standards) of
Commercially available products such as chromatodisc (manufactured by GL Sciences Inc.) can be used.

The coloring agent of the present invention contains a zinc phthalocyanine compound having a bluish range but having a strong greenish tint. Preferably, the spectral reflectance at 460 nm is measured when the spectral reflectance is measured under the following conditions. The ratio (A / B) of the ratio (A) to the spectral reflectance at 545 nm (B) is preferably 1.0 to 2.5.

1. Dispersion liquid preparation conditions: 0.05 g of a zinc phthalocyanine compound, 0.95 g of a polyester resin (Vylon 200; manufactured by Toyobo Co., Ltd.), 4.0 g of THF, and 4.0 g of glass beads having a diameter of 1 mm were put in a 9 ml screw tube bottle, and a paint shaker was added. And disperse for 5 hours.

2. Thin film preparation conditions: The dispersion prepared in 1 was coated with a coating film having a spectral reflectance at 460 nm of 8
The film thickness is adjusted so as to be 0%, and the film is applied with a bar coater.

3. Spectral reflectance measurement conditions: The coating film prepared in 2 is measured by the method described in JIS Z8722.

When the above measurement is carried out using a β-type copper phthalocyanine pigment, the ratio of the spectral reflectance at 460 nm to the spectral reflectance at 545 nm is 3 or more, and as a result, the intensity of greenness is insufficient. It has become. On the other hand, if the ratio of the spectral reflectance at 460 nm to the spectral reflectance at 545 nm is smaller than 1.0, the greenish tint becomes too strong, which is not preferable.

Specific examples of the polyester resin necessary for preparing a dispersant necessary for preparing a thin film for measuring a spectral reflectance include, for example, polyethylene terephthalate, polybutylene terephthalate, polycyclohexane terephthalate and the like. And preferably polyethylene terephthalate.

The coloring agent of the present invention preferably comprises a zinc phthalocyanine compound produced in a benzonitrile solvent. The production in a benzonitrile solvent is preferable because the purity is high, and as a result, a zinc phthalocyanine compound having high solubility in a solvent or a resin is obtained. As a method for producing a zinc phthalocyanine compound in a benzonitrile solvent, a known general method can be used. That is, there are a Weyler method produced by reacting urea and a metal salt in the presence of a condensed acid using phthalic anhydride or phthalic anhydride as a raw material, a phthalonitrile method produced by reacting phthalonitrile with a metal salt, and the like. In addition, it can also be produced using phthalic acid, phthalic diamide, 1,3-diiminoisoindoline and derivatives thereof as raw materials. Of these, the phthalonitrile method using phthalonitrile as a raw material is preferred. When the phthalonitrile method is used, the metal compound and phthalonitrile are preferably reacted in a benzonitrile solvent at a reaction temperature of 30 to 300 ° C, preferably 80 to 200 ° C.

Examples of the zinc phthalocyanine compound contained in the coloring agent according to the present invention include zinc phthalocyanine (all 16 substitutable carbon atoms on the phthalocyanine skeleton are hydrogen atoms and the central metal is zinc), hexadecafluorozinc Phthalocyanine (All of the 16 substitutable carbon atoms on the phthalocyanine skeleton are fluorine atoms,
The central metal is zinc), and the following general formula (1)

[0023]

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(Wherein, R represents a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group which may have a substituent). Can be mentioned. In the present invention, these may be used alone, or two or more of them may be used in combination.

The coloring agent of the present invention is not particularly limited as long as it is used for coloring metals, wood, concrete, plastic, glass, leather, fibers, clothes, and the like.
For example, colorants for plastics include pellets,
There are flakes, masterbatch colors in plate form, dry colors in granular form, liquid paste colors, and the like. In the case of a colorant for plastics, the constituent components of the colorant include the phthalocyanine compound, other dyes, pigments, metal salts of fatty acids, esters, amides, plastics, monomers, and the like.

That is, the constituents of the colorant of the present invention include:
What is necessary is just to contain the above-mentioned phthalocyanine compound, and in addition, it may have various dyes, pigments and other additives according to the usage form and the like. Therefore, the present invention also includes a coloring agent composed of only the phthalocyanine compound. On the other hand, when it also has a constituent component other than the phthalocyanine compound, the amount of the zinc phthalocyanine compound used as an essential component is uniquely different from the optimum range because the optimal range greatly differs depending on the use form and application. Although not specified, it is preferably 5 to 80% by weight based on the whole colorant. When the use amount of the phthalocyanine compound is less than 5% by weight, the coloring power to the object to be colored is insufficient and the excellent properties of the phthalocyanine compound cannot be effectively exhibited, which is not preferable. On the other hand, 80% by weight
If the number exceeds 3, there is a disadvantage that coloring of the object to be colored is difficult to be uniform, which is not preferable.

[0027]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

EXAMPLE 1 3 m of zinc phthalocyanine was placed in a 20 ml screw vial.
g, 10 ml of THF was added, and the mixture was dispersed with an ultrasonic cleaner for 10 minutes to obtain a uniform dispersion. This dispersion is 14 m in diameter
m, and filtered through a sample pretreatment filter (Chromatodisc: GL Sciences Inc.) having a pore size of 0.2 μm. The absorption spectrum of the diluted solution obtained by diluting the filtrate 50 times with THF was measured with a spectrophotometer (UV-1600P).
C; manufactured by Shimadzu Corporation). The results are shown in Table 1 below.

Example 2 An absorption spectrum was measured in the same manner as in Example 1 except that hexadecafluorozinc phthalocyanine was used instead of zinc phthalocyanine. The results are shown in Table 1 below.

Comparative Example 1 In Example 1, instead of zinc phthalocyanine, β
The absorption spectrum was measured in the same manner as in Example 1 except that the copper phthalocyanine type pigment (CIPB15: 3) was used.
The results are shown in Table 1 below.

[0031]

[Table 1]

[0032]

The colorant comprising the zinc phthalocyanine compound of the present invention has a blue hue that is more green than conventional β-type copper phthalocyanine pigments. Therefore, when considering the balance between magenta, yellow, and black, which are important for vivid color development in full-color printers and color copiers, the ideal blue color of cyan is greenish blue. As a colorant for cyan toner and inkjet ink, it can be widely used for color printing and copying with higher precision and higher image quality.

The coloring agent containing the zinc phthalocyanine compound of the present invention is soluble in an organic solvent or resin in a certain amount or more compared to the conventional β-type copper phthalocyanine pigment which is not compatible with an organic solvent or resin. I do. Therefore, the β-type copper phthalocyanine pigment is finely dispersed in an organic solvent or a resin as much as possible to increase the coloring power. On the contrary,
The zinc phthalocyanine compound contained in the coloring agent of the present invention dissolves in a predetermined amount or more in a THF solvent, and is also compatible with a resin. Therefore, when used for coloring a resin, it is sufficiently finely dispersed. There is an effect that a desired coloring power can be exhibited even without such a pigment, and an equivalent coloring power can be exhibited with a smaller amount of addition than conventional pigments.

Continued on the front page (72) Inventor Yoshinobu Asako 1-25-12 Kannondai, Tsukuba-shi, Ibaraki Japan Co., Ltd. Nippon Shokubai F-term (reference) 4J038 EA011 JB27 KA08 4J039 BC60 BE01

Claims (1)

[Claims] 1. A colorant comprising a zinc phthalocyanine compound having a maximum absorption wavelength in the range of 650 to 700 nm and an absorbance at the maximum absorption wavelength of 0.2 or more in an absorption spectrum measured under the following conditions: A zinc phthalocyanine compound (3 mg) and THF (10 ml) are placed in a 20 ml screw vial, and dispersed by an ultrasonic cleaner for 10 minutes to obtain a uniform dispersion. The dispersion is filtered through a sample pretreatment filter having a diameter of 14 mm and a pore size of 0.2 μm. The absorption spectrum of the diluted solution obtained by diluting this filtrate 50 times with THF was measured by a spectrophotometer (UV-
1600PC; manufactured by Shimadzu Corporation).