JP3159049B2 - Method for producing pigment composition, pigment composition and use thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a greenish β-type copper phthalocyanine pigment by pulverizing crude copper phthalocyanine in a dry manner and then treating it in an organic solvent, or treating it in a varnish or solvent for printing ink. The present invention relates to a method for producing a printing ink containing a β-type copper phthalocyanine pigment.

[0002]

2. Description of the Related Art Generally, copper phthalocyanine after synthesis is called crude copper phthalocyanine, and cannot be used as it is as a pigment for printing ink because it is a giant β-type crystal particle of about 10 to 200 μm. This crude copper phthalocyanine can be used as a printing ink in a size (0.02-0.
Reduction to about 1 μm) is called pigmentation. There are various methods for pigmentation.

[0003] The most common one is a method called a solvent salt milling method. This method is a method in which a crude copper phthalocyanine is ground with a grinding agent such as salt and an organic solvent that promotes crystal transition to β-form. The β-type copper phthalocyanine pigment prepared by this method has an aspect ratio (ratio of the minor axis to the major axis of the primary particles) of 1 to 3, and is suitable for printing inks such as clear green and high coloring power, and is widely used. However, several times the amount of the grinding agent is required for the pigment, and the process of recovering the grinding agent and the organic solvent requires much time and labor.

[0004] On the other hand, a method is also known in which crude copper phthalocyanine is pulverized by a dry method and then treated with an organic solvent or the like. This method has a simplified process as compared with the above-mentioned solvent salt milling method. Is the way.

[0005] A method is also known in which crude copper phthalocyanine is pulverized by a dry method and then directly treated in a varnish for printing ink or a solvent for printing ink to directly produce printing ink. This is a very effective means for supplying a copper phthalocyanine pigment ink. However, since the milled material obtained by dry-milling the crude copper phthalocyanine is a strong aggregate, the dispersion of the milled material,
Transformation of α-form crystal to β-form is very difficult.

[0006] In order to solve such a problem, British Patent No. 1224627 discloses a method of adding 1 to 8 times the amount of resin when dry-milling crude copper phthalocyanine.
JP-A-2-294365 discloses a method in which a resin such as rosin-modified phenol is added in an amount of 0.5 to 10% by weight when a crude copper phthalocyanine is dry-ground. These methods can be said to be very effective in terms of preventing aggregation of the copper phthalocyanine particles by the effect of the added resin and using the same resin as the added resin later.

[0007]

A method of solvent-treating a milled product of dry-ground crude copper phthalocyanine, or a method of producing a printing ink directly by treating it in a varnish for printing ink or a solvent for printing ink. The method of dry grinding together with a resin is a very effective means, but does not solve the problem that the primary particles of the pigment become acicular, and the problems of reddish hue and fluidity remain.

In order to suppress the particle growth, a method of adding a pigment derivative or a growth inhibitor is also known.
These additives are often not preferred as components of the final printing ink. Therefore, in the present invention, without using such additives affecting printability, β-type copper phthalocyanine pigment having a small aspect ratio and a green hue,
And a printing ink containing the same.

[0009]

SUMMARY OF THE INVENTION The present invention is, relative to crude copper phthalocyanine, resin 1 to 200 wt%, and the solvent was added 0.5 to 20% by weight relative to the resin, from 70 to 9
The present invention relates to a method for producing a pigment composition, which is characterized by performing dry pulverization at 0 ° C. Furthermore, the present invention relates to the above-mentioned production method in which a resin containing a solvent is added. Furthermore, the present invention relates to the above production method, wherein the solvent is a solvent for printing ink. Furthermore, the present invention relates to the above production method, wherein the resin is a rosin-modified phenol resin. Furthermore, the present invention relates to a pigment composition obtained by the above production method. Furthermore, the present invention relates to a method for producing a printing ink obtained by adding the above pigment composition to a solvent or a varnish for a printing ink and treating it.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The dry pulverization of the present invention is to pulverize crude copper phthalocyanine using a pulverizer incorporating a pulverization medium such as beads without substantially interposing a liquid substance.
The pulverization is performed using a pulverizing force or a destructive force due to collision between the pulverizing media. As the dry pulverizer, a known method such as a dry attritor, a ball mill, and a vibration mill can be used. Alternatively, dry pulverization may be performed by flowing nitrogen gas or the like as necessary to make the inside of the dry pulverizer into a deoxygenated atmosphere.

By dry milling, β-type copper phthalocyanine becomes α
Crystal transition to the form. That is, the ratio of the α-type crystal is increased by increasing the pulverization efficiency or lengthening the pulverization time. On the other hand, when the α-type copper phthalocyanine particles undergo β transition with an organic solvent or the like, a part of the particles are in a dissolved state, so that the particles grow in crystal, and a desirable shape cannot be obtained.

Therefore, in the present invention, the ratio of the α-type in the α / β mixed crystal type copper phthalocyanine obtained by the dry pulverization is reduced by the presence of the resin and the solvent at the time of the dry pulverization. The aspect ratio of the crushed particles is reduced.

In the present invention, the solvent and the resin to be added during the dry pulverization of the crude copper phthalocyanine include:
The resin and the organic solvent may be separately added, or the organic solvent may be previously contained in the resin.

The type of the solvent may be any organic solvent capable of converting α-form crystals to β-form.
Aromatic compounds such as toluene, xylene, chlorobenzene and nitrobenzene, aliphatic hydrocarbon compounds such as mineral spirits, kerosene and ligroin, isopropanol, butanol, isobutanol, ethyl cellosolve,
One or a mixture of two or more of alcohol compounds such as butyl cellosolve and cyclohexanol, ester compounds such as ethyl acetate, butyl acetate and butyl cellosolve acetate, and ketone compounds such as acetone and methyl ethyl ketone can be used.

When the final product is printing ink, it is preferable to use a solvent for printing ink since there is no need for a step of removing the solvent. Solvents for printing inks, such as high-boiling-point petroleum solvents, aliphatic hydrocarbon solvents, and higher alcohol solvents, which are solvents that do not contain aromatics alone or in combination of two or more as long as they are suitable for printing inks Can be used arbitrarily.

As the type of the resin added together with the solvent,
Rosin-modified phenolic resins, rosin-modified maleic resins, petroleum resins, alkyd resins, and other resins applicable to printing inks can be used singly or in combination of two or more, but rosin-modified phenol resins are preferred. .

In the present invention, the amount of the resin is generally 1 to 200% by weight based on the crude copper phthalocyanine, and the amount of the solvent is 0.5 to 20% by weight based on the resin. It is necessary to determine the addition amount of the resin and the solvent while taking into account the dry grinding temperature. That is, since the softening point of the resin used is lowered by containing the solvent, the risk of adhesion and fixation of the resin inside the dry pulverizer increases when the temperature is high and the processing amount is large. The pulverization time can be arbitrarily set depending on the apparatus or the desired pulverized particle size.

When a β-type copper phthalocyanine pigment is produced by subjecting the obtained milled product to a solvent treatment, the solvent treatment is usually carried out using an organic solvent alone or a mixed system of an organic solvent and water. In the case of a mixed system, a solvent having a high affinity for water is generally used as a mixed system, and a solvent having no affinity for water is generally used as an emulsion using a surfactant. As the organic solvent, a solvent added together with the resin described above can be used.

The aspect ratio of the primary pigment particles produced in this manner is in the range of 1 to 3 which is almost the same as that of the primary pigment particles obtained by the solvent salt milling method, and the hue is green. In addition, when the pigment obtained by this method was compared with a pigment obtained by a conventional solvent salt milling method, it was confirmed that the pigment had the same quality in terms of gloss, fluidity, and the like. .

When the obtained milled material is mixed with a varnish for printing ink or a solvent for printing ink to directly produce a printing ink containing a β-type copper phthalocyanine pigment, the solvent for printing ink or the solvent in the varnish is as follows. As long as the solvent is suitable for printing inks, such as a high-boiling-point petroleum solvent, an aliphatic hydrocarbon solvent, a higher alcohol solvent, etc., a solvent containing no aromatic solvent can be used alone or in combination of two or more.

Similarly, resins for printing ink varnishes for producing printing inks include resins suitable for printing inks such as rosin-modified phenolic resin, rosin-modified maleic acid resin, petroleum resin, and alkyd resin; A drying oil or polymerization drying oil suitable for a printing ink such as linseed oil can be used singly or in combination of two or more kinds together with other additives for a printing ink.

The aspect ratio of the primary pigment particles in the printing ink thus manufactured is in the range of 1 to 3 which is almost the same as that of the primary pigment particles obtained by the solvent salt milling method, and the hue is greenish. In addition, when the pigment obtained by this method is compared with a printing ink produced from a pigment of a conventional solvent salt milling method, it has the same quality in terms of gloss, fluidity, and the like. It was confirmed that.

【Example】

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples. In the examples, a β-type copper phthalocyanine pigment obtained by pigmenting crude copper phthalocyanine by solvent salt milling (5 times the amount of sodium chloride) is used as a standard pigment. The device was used.

[0024]

Example 1 70 parts by weight of crude copper phthalocyanine and 30 parts by weight of rosin-modified phenol resin were added to a dry attritor.
No. 5 Solvent (manufactured by Nippon Oil Co., Ltd.)
Grinding was performed at 0 ° C. for 1 hour. Next, the obtained milled material 24
The mixture was mixed with 36 parts by weight of a varnish for printing ink and 7 parts by weight of No. 7 solvent, stirred gently at 90 ° C. for 2 hours, and then kneaded once with three rolls at 60 ° C. 0.5 μm or less. Next, after adding 22 parts by weight of varnish and 11 parts by weight of No. 7 solvent to the obtained base ink and adjusting it to the final ink, and comparing with the standard ink containing the same pigment, the ink of the present example showed coloring power,
It had the same quality as the standard ink in terms of gloss and hue. The content of the α-type crystal was 1% or less.

[0025]

Example 2 70 parts by weight of crude copper phthalocyanine and 63 parts by weight of rosin-modified phenol resin were added to a dry attritor.
7 parts by weight of F Solvent 7 (manufactured by Nippon Oil Co., Ltd.) was added and pulverized at 70 ° C for 1 hour. Next, the obtained ground material 3
2 parts by weight were added to 22 parts by weight of a varnish for printing ink and 13 parts by weight of AF Solvent No. 7 and gently stirred at 90 ° C. for 2 hours, and then kneaded once with three rolls at 60 ° C. to obtain pigment particles. Was dispersed to 7.5μ or less. Next, 22 parts by weight of varnish and 11 parts by weight of AF Solvent No. 7 were added to the obtained base ink to adjust the final ink, and the ink was compared with a standard ink containing the same pigment. It had the same quality as the standard ink in terms of gloss, hue, etc. The content of the α-type crystal was 1% or less.

[0026]

Example 3 100 parts by weight of the same rosin-modified phenol resin as used in Example 2 was heated to the softening point, and AF
Solvent 7 was added by 10 parts by weight and completely dissolved. 70 parts by weight of crude copper phthalocyanine in a dry attritor,
70 parts by weight of a rosin-modified phenol resin in which a solvent was dissolved was added and pulverized at 70 ° C. for 1 hour. Next, 32 parts by weight of the obtained crushed material was added to 22 parts by weight of a varnish for printing ink,
F Solvent No. 7 (13 parts by weight) was added, and the mixture was gently stirred at 90 ° C. for 2 hours and then kneaded once with three rolls at 60 ° C., whereby the pigment particles were dispersed to 7.5 μm or less. next,
After adding 22 parts by weight of varnish and 11 parts by weight of AF Solvent No. 7 to the obtained base ink and adjusting it to the final ink, when compared with a standard ink containing the same pigment, the ink of this example showed coloring power, gloss, It had the same quality as the standard ink in terms of hue and the like. The content of the α-type crystal was 1% or less.

[0027]

Example 4 100 parts by weight of the same rosin-modified phenol resin as used in Example 2 was heated to the softening point, and AF
Solvent No. 7 was completely dissolved by adding 20 parts by weight. 70 parts by weight of crude copper phthalocyanine in a dry attritor,
7 parts by weight of a rosin-modified phenol resin in which a solvent was dissolved was added and pulverized at 90 ° C. for 1 hour. Next, 22 parts by weight of the obtained milled material was added to 100 parts by weight of water and 60 parts by weight of isobutanol.
After gently stirring in an azeotropic state for 1 hour in addition to parts by weight,
Isobutanol was distilled off. Next, 35% by weight hydrochloric acid 8
A part by weight was added for acid purification, followed by filtration and drying. The content of α-type crystals in the pigment thus obtained was 1% or less.
When this pigment was compared with the standard pigment, the pigment of this example had the same hue as the standard pigment.

[0028]

Comparative Example 1 70 parts by weight of crude copper phthalocyanine was added to a dry attritor and pulverized at 80 ° C. for 1 hour. next,
16 parts by weight of the obtained milled material was applied to a varnish 48 for printing ink.
After adding 3 parts by weight of No. 7 solvent and gently stirring at 90 ° C. for 2 hours, the mixture was kneaded three times with three rolls at 60 ° C., and the largest pigment particle was 10.0 μm. Next, after adding 22 parts by weight of varnish and 11 parts by weight of No. 7 solvent to the obtained base ink to adjust it to a final ink, and comparing it with a standard ink containing the same pigment, the α-type in the ink of this example was obtained. Although the crystal content was 1% or less, the hue was reddish.

[0029]

Comparative Example 2 70 parts by weight of crude copper phthalocyanine and 35 parts by weight of a rosin-modified phenol resin were added to a dry attritor, and pulverized at 80 ° C. for 1 hour. Next, 24 parts by weight of the obtained milled material were added to 32 parts by weight of a varnish for printing ink and 11 parts by weight of No. 7 solvent, and the mixture was gently stirred at 90 ° C. for 2 hours and then once with three rolls at 60 ° C. When I cut the meat,
The pigment particles were dispersed below 7.5μ. Next, 22 parts by weight of varnish and No. 7 solvent 11 were added to the obtained base ink.
After adjusting the final ink by adding parts by weight, when compared with a standard ink containing the same pigment, the content of α-type crystals in the ink of this example was 1% or less, but the hue was reddish. Met.

[0030]

Comparative Example 3 70 parts by weight of crude copper phthalocyanine and 7 parts by weight of a rosin-modified phenol resin were added to a dry attritor, and pulverized at 90 ° C. for 1 hour. Next, 22 parts by weight of the obtained milled material was added to 100 parts by weight of water and 60 parts by weight of isobutanol, and the mixture was gently stirred in an azeotropic state for 1 hour, and then isobutanol was distilled off. Next, 8 parts by weight of 35% by weight hydrochloric acid was added for acid purification, followed by filtration and drying. Although the content of the α-type crystal in the pigment thus obtained was 1% or less, the hue was reddish.

[0031]

According to the present invention, it is possible to provide a β-type copper phthalocyanine pigment having the same quality as that of the pigment of the solvent salt milling method generally used at present and having a lower cost. It is. Further, according to the present invention, a greenish β-type copper phthalocyanine pigment or greenish β
The present invention can provide a printing ink containing a type copper phthalocyanine pigment.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C09B 67/20 C09B 67/04 C09B 67/08 C09B 67/12 C09D 11/10

Claims (6)

(57) [Claims] 1. A resin is added to crude copper phthalocyanine with one resin.
To 200% by weight, and 0.5 to 2
A method for producing a pigment composition, comprising adding 0% by weight and dry-pulverizing at 70 to 90 ° C. 2. The method according to claim 1, wherein a resin containing a solvent is added. 3. The solvent according to claim 1, wherein the solvent is a solvent for printing ink.
Or the production method according to 2. 4. The production method according to claim 1, wherein the resin is a rosin-modified phenol resin. 5. A pigment composition obtained by the production method according to claim 1. 6. A method for producing a printing ink, comprising adding the pigment composition according to claim 5 to a solvent or a varnish for a printing ink and treating it.