JP2003231829A - Method for producing printing ink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a printing ink reducing aggregation of pre-pigment and having excellent quality at a low cost without having various bad influences on such production process to occur by using resins in conventional methods in large amounts and on printing ink in the rationalized method for directly producing printing ink by using a pre-pigment of copper phthalocyanine without passing a form of pigment through. <P>SOLUTION: In the method for directly producing the printing ink containing at least copper phthalocyanine and a resin for printing ink by using a pre- pigment of copper phthalocyanine without passing a form of pigment through, a pre-pigment composition prepared by pulverizing, in a dried state, a crude copper phthalocyanine previously surface-treated with a rosin compound is used as the pre-pigment of copper phthalocyanine. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

The present invention overcomes the drawbacks of the prior art processes and enables the production of printing inks of improved quality,
The present invention relates to a streamlined method for producing a printing ink which directly produces a printing ink by using a pre-pigment without going through a pigment form.

[0002]

2. Description of the Related Art Generally, copper phthalocyanine pigments include, for example, a urea method (Wyler method) in which phthalic acid or its derivative, urea or its derivative are heated and reacted in an organic solvent in the presence of a copper compound and a catalyst, and phthalodinitrile. It is synthesized by a method such as a nitrile method in which is reacted by heating in an organic solvent in the presence of a copper compound. The synthesized copper phthalocyanine is called crude copper phthalocyanine, and since the primary particles are very coarse (10 to 100 μm), it cannot be used as a pigment as it is.

For this reason, conventionally, in the production of printing ink, the primary particles are finely adjusted (1 μm or less) by a method of pigmenting a crude copper phthalocyanine represented by a dry grinding method or a wet grinding method. It is used as a pigment that has aptitude as a pigment. Printing ink compositions include pigmented copper phthalocyanine (copper phthalocyanine pigment) in roll mills such as triple rolls, kneading and dispersing machines such as kneaders, ball mills and bead mills. It is manufactured by uniformly dispersing it in a resin for a printing ink or a resin solution using the disperser.

Since this pigmentation process requires a great deal of labor, a rationalized method for producing printing ink is as follows.
In a process for producing a printing ink, a pre-pre pigment (pigment precursor) finely prepared by pulverizing (dry pulverizing) crude copper phthalocyanine with a dry attritor without using a pigment is used. A method for producing a printing ink at the same time as pigmentation has been proposed (Japanese Patent Publication No. 55-667).
No. 0, JP-A-2-294365, JP-A 9-
No. 272833).

Particularly, dry pulverization is carried out in the presence of a resin for printing inks, as disclosed in JP-A-2-294365 and JP-A-9-2.
The method described in Japanese Patent No. 72833 is a very excellent method for producing a printing ink, in that the aggregation of the pre-pigment is alleviated, and the conversion of the pre-pigment into a pigment and the conversion to an ink are made efficient. For example, in the method described in JP-A-9-272833, crude copper phthalocyanine is used in an amount of 20-80
Dry pulverized with a resin for printing ink in weight% is used as a pre-pigment, and this is heated in a solvent for printing ink or a varnish for printing ink to 80 to 170 ° C. It is a manufacturing method.

However, the method using the resin for printing ink as described above requires a relatively large amount of resin in order to obtain a sufficient effect. However, the use of a large amount of resin poses a problem for safe operation, such as the adherence of the abraded material inside the pulverizer due to the heat generated during dry pulverization and the risk of ignition of the abraded material due to heat storage. In addition, the resin may cause structural destruction such as oxidation or breakage (opening) due to impact or heat generation during dry pulverization, and the deteriorated resin not only affects the hue surface of the ink, but also the viscoelasticity and emulsification characteristics. It is considered that the printability is also seriously affected.

[0007]

The object of the present invention is to reduce the agglomeration of pre-pigments in a streamlined process for producing direct printing inks using copper phthalocyanine pre-pigments without going through the pigment form. Further, it is to provide a method for producing a printing ink of excellent quality at a low cost without various adverse effects on the production process and the printing ink, which are caused by using a large amount of resin in the conventional method. .

[0008]

Means for Solving the Problems The inventors of the present invention use a crude copper phthalocyanine which has been surface-treated with a rosin compound in advance when preparing a pre-pigment by dry pulverization. It was found that the amount of use resin for use can be significantly reduced, and the same effect as that obtained by using a large amount of resin can be obtained, and the present invention was completed based on this finding.

That is, the present invention provides a printing ink containing at least copper phthalocyanine and a resin for printing ink,
In a method of directly producing using a copper phthalocyanine pre-pigment without going through the form of a pigment, as a copper phthalocyanine pre-pigment, was prepared by dry-milling a crude copper phthalocyanine surface-treated with a rosin compound. A method for producing a printing ink, which comprises using a prepigment composition.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the embodiments of the present invention will be described.
The present invention will be described in more detail. The present invention uses a crude copper phthalocyanine that has been surface-treated with a rosin-based compound in a method for directly producing a printing ink using a copper phthalocyanine pre-pigment (pigment precursor) that has not been subjected to a pigmentation step. This is characterized in that no resin for printing ink is used at the time of dry pulverization or a prepigment composition prepared by using a very small amount is used.

Generally, the copper phthalocyanine after the completion of the synthesis reaction is prepared by removing the solvent from the reaction slurry under reduced pressure, removing the reaction impurities by acid treatment, alkali treatment, and further washing with warm water, washing with water, filtration and the like. Dried and prepared as crude copper phthalocyanine. The crude copper phthalocyanine surface-treated with a rosin-based compound in advance used in the present invention is
It is produced by a method of mixing and treating a rosin compound in a step of synthesizing copper phthalocyanine or in a reaction slurry after completion of the reaction, or in any step of the step of preparing crude copper phthalocyanine described above.

As the method for treating the rosin compound, a conventionally known treatment method such as adding the rosin compound as an aqueous alkali solution or as a solution dissolved in an organic solvent to a reaction system or a reaction slurry after the reaction can be used. However, the treatment in the reaction slurry after the completion of the reaction and the treatment in the step of distilling off the solvent in the above steps are preferable because there are few restrictions on the treatment amount and the treatment method.

Examples of the rosin compound used in the present invention include wood rosin, gum rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin and metal salts thereof, or rosin-modified acrylic resin and rosin-modified alkyd. Examples include various rosin-modified resins such as resins, rosin-modified maleic acid resins, rosin-modified phenolic resins, rosin-modified fumaric acid resins, rosin-modified polyamide resins and rosin-modified polyester resins. These are 1
One kind or a mixture of two or more kinds can be used. The treatment amount of these rosin compounds is preferably in the range of 1 to 50% by weight with respect to the crude copper phthalocyanine.

The above-mentioned rosin compounds, of which the type having a low melting point is originally a small amount, when mixed with crude copper phthalocyanine and dry-ground to prepare a pre-pigment composition, It tends to cause sticking of the ground material and ignition. However, when the rosin-based compound is used in a form in which the surface of the crude copper phthalocyanine is treated with the rosin-based compound, the risk as described above is significantly improved, and at the same time, the surface of the crude copper phthalocyanine is uniformly treated. As a result, even if a relatively small amount is used, the aggregation of particles at the stage of preparing the crude copper phthalocyanine composition is mitigated, and the aggregation of particles at the time of preparing the pre-pigment composition is effectively mitigated. Therefore, even if the resin for printing ink is not used again or a small amount is used at the time of dry pulverization, the same effect as when a large amount of resin is used can be obtained, and an improved printing ink can be provided.

In the present invention, dry grinding can be carried out in the presence of an extender pigment. The extender pigment may be any one as long as it has a small refractive index and little influence on the hue or transparency of the pigment, for example, calcium carbonate, zinc oxide (zinc white), barium sulfate and barite powder, clay, talc,
Alumina white, white carbon (fine silica),
And mixtures thereof. A preferred extender pigment is calcium carbonate.

Further, in the present invention, dry pulverization can be carried out with a resin for printing ink which does not hinder safe operation. The resin used for printing ink may be any resin as long as it is generally used for printing ink. Examples thereof include phenol resins and modified products thereof, maleic acid resins and modified products thereof, alkyd resins and modified products thereof, petroleum resins, modified rosins and the like, and mixtures thereof, but preferably rosin modified phenol resins, which are It is also included in the rosin compound used in the present invention. The extender pigment and / or the resin for printing ink is preferably used in the range of 1 to 50% by weight based on the crude copper phthalocyanine.

In the dry pulverization of the present invention, in addition to the dry attritor, pulverization media such as beads such as ball mills and vibration mills, kneaders such as twin-screw extruders and kneaders, and jet mills are used. A crusher, a strong stirrer such as a Henschel mixer, or a type that does not use crushing media can be used, but a type that uses crushing media is preferable in terms of crushing efficiency.

Generally, in dry pulverization in the presence of a resin, attention must be paid to the adherence of the abraded material to the interior of the pulverizer and ignition due to the heat generated during the pulverization. Usually, the pulverization is carried out in the temperature range of 80 to 150 ° C. under cooling. However, the method of the present invention is also advantageous for the problems of sticking and ignition, and the milling can also be carried out at higher temperatures. On the contrary, the temperature at the time of crushing is not particularly limited, and the temperature may be lower.

Generally, the crude copper phthalocyanine contains a few percent by weight of reactive impurities, but the reactive impurities hinder the conversion of the pre-pigment into a pigment and cause yellowing of the printing ink. It also has a significant impact on the suitability of printing inks. In the present invention, it is preferable to use high-purity crude copper phthalocyanine having a purity of 97% or more as measured by the sulfuric acid method.

As the reaction impurities, impurities contained in the crystal of copper phthalocyanine which cannot be removed by ordinary washing poses a particular problem, but the sulfuric acid method can measure all the reaction impurities contained in the crystal. it can. Purity measurement by the sulfuric acid method follows the procedure below. (Purity measurement method by sulfuric acid method) Crude copper phthalocyanine 5.
Dissolve 0 g in 50 ml of 98% by weight sulfuric acid by heating (90-1
This solution is recrystallized by adding 150 ml of 15% by weight sulfuric acid. 25ml after cooling
The water is deflocculated in 10% of water, 10 ml of 28% by weight ammonia water is added, and the mixture is heated (90 to 100 ° C. for 30 minutes). After filtering and washing thoroughly with water, it is dried at 105 to 110 ° C. for 2 hours. Purity (%) = [mass after treatment (g) / mass before treatment (g)] × 100

The crude copper phthalocyanine used in the present invention is prepared by applying the urea method (Wyler method) under pressure (preferably 0.1).
It is preferable to use copper phthalocyanine synthesized by performing the synthesis at about 0.7 MPa). Copper phthalocyanine synthesized under pressure has an advantage that it can be prepared in high purity because the amount of reaction impurities incorporated into the copper phthalocyanine crystal is smaller than that of copper phthalocyanine synthesized under normal pressure.

When preparing the pre-pigment composition by dry pulverization, if necessary, a pigment treatment agent or dispersant such as a conventionally known pigment derivative or polymer dispersant, or a surfactant,
Dry crushing can be performed by adding rosin or the like. It is also conventionally known that solvents such as petroleum-based solvents and organic solvents that are generally used in printing inks can be blended as needed, and that crushing can be performed in a nitrogen gas atmosphere for the purpose of preventing deterioration of the resin. The method is similar.

[0023]

EXAMPLES Next, the present invention will be described more specifically with reference to pigment production examples, examples and comparative examples. In the sentence, part or%
It is based on weight.

Pigment Production Example 1 In a 5 L container, 1000 parts of phthalic anhydride and 2000 parts of urea
Parts, ammonium molybdate 10 parts, cuprous chloride 18
0 part and 2000 parts of Hisol P (manufactured by Nippon Petrochemical Co., Ltd.) were added, and the mixture was heated and reacted at 200 ° C. for 4 hours. After the reaction,
The solvent was distilled off under reduced pressure, and the reaction product was diluted with a 2% dilute sulfuric acid aqueous solution 20
It was put into 000 parts, stirred at 80 ° C. for 2 hours, filtered, washed with hot water and washed with water (until the filtrate became neutral) to obtain an aqueous paste of crude copper phthalocyanine. Next, this aqueous paste was dried at 90 ° C. to obtain a purity of 96.
900 parts of 0% crude copper phthalocyanine were obtained.

Pigment Production Example 2 Crude copper having a purity of 98.0% as measured by the sulfuric acid method as in Pigment Production Example 1 except that the heating reaction was carried out at 200 ° C. for 4 hours under a pressure of 0.3 MPa. 890 parts of phthalocyanine was obtained.

Pigment Production Example 3 100 parts of the crude copper phthalocyanine obtained in Pigment Production Example 1 was added to a dry attritor and pulverized for 30 minutes. The content of β type crystal form of this crude copper phthalocyanine ground product is 43%
Met. Next, 400 parts of isobutyl alcohol and 600 parts of water were added to 100 parts of the obtained ground product, and the mixture was heated to 80 ° C. and mixed with stirring for 5 hours. This mixture was added to 1000 parts of 1.0% dilute sulfuric acid aqueous solution, and heat-treated at 80 ° C. for 1 hour, then filtered, washed with water, dried and pulverized to obtain a powdered copper phthalocyanine pigment (CI Pigment Blue 15: 3). Got

Comparative Example 1 18 parts of β-type copper phthalocyanine pigment obtained in Pigment Production Example 3 was mixed with 67 parts of a varnish for printing ink (rosin-modified phenolic resin varnish, non-volatile content 70%), and 3 rolls were used to roll the mixture. The meat was beaten to obtain a base ink. To this base ink, 19 parts of a varnish for printing ink, 6 parts of No. 7 solvent (petroleum-based solvent manufactured by Nippon Oil Co., Ltd.), and 10 parts of compound (ink adjusting aid) were added to obtain a blue printing ink.
This blue ink was mixed with white ink so that the weight ratio of copper phthalocyanine pigment / titanium oxide was 1/10,
A light color ink (coloring strength judgment) was obtained. The blue ink and the light color ink were used as comparative inks by the conventional method.

Example 1 In the pigment preparation example 2, the aqueous paste of the crude copper phthalocyanine after the sulfuric acid treatment was peptized in 20,000 parts of water, and 45 parts of hydrogenated rosin was added as an alkaline aqueous solution to the solution.
It was stirred for 30 minutes. Next, hydrochloric acid was added to adjust the pH to 4.0, the mixture was stirred at 50 ° C. for 1 hour, and then the slurry was filtered, washed with water and dried (90 ° C.) to prepare a crude copper phthalocyanine surface-treated with 5% hydrogenated rosin. did.

To the dry type attritor, 50 parts of the above surface-treated crude copper phthalocyanine and 9.5 parts of calcium carbonate were added and pulverized for 1 hour. Next, 8.5 parts of a resin for printing ink (rosin-modified phenolic resin) was added and crushed for 10 minutes. The content of β-type crystals in the obtained pre-pigment composition was 48%. Then, the obtained pre-pigment composition 5
0 parts, 119 parts of varnish for printing ink (rosin-modified phenolic resin: 70% non-volatile content), 3 parts of No. 7 solvent were heated at 110-120 ° C. in a jacketed dissolver.
The mixture was stirred for 2 hours, and the mixture was kneaded twice with a triple roll to obtain a base ink.

In addition to this base ink, 29 parts of varnish for printing ink, 14 parts of No. 7 solvent, compound 1
A blue printing ink was prepared by adding 9 parts. This blue ink was mixed with white ink so that the weight ratio of copper phthalocyanine pigment / titanium oxide was 1/10 to obtain a light color ink. The obtained blue ink and light color ink have the same hue and tinting strength as compared with the respective inks prepared by the conventional method of Comparative Example 1, and also have good performance in ink suitability such as viscoelasticity and emulsification characteristics. showed that.

Example 2 178 parts of rosin-modified phenolic resin (weight average molecular weight: 123,000, acid value: 20) was added to the slurry after the heating reaction instead of hydrogenated rosin, and the mixture was stirred at 60 ° C. for 1 hour. After that, a crude copper phthalocyanine surface-treated with 20% rosin-modified phenolic resin was prepared in the same manner as in Example 1 except that the reaction solvent was distilled off under reduced pressure.

To a dry type attritor, 60 parts of the above surface-treated crude copper phthalocyanine and 10 parts of calcium carbonate were added and pulverized for 1 hour. The content of β-type crystals in the obtained pre-pigment composition was 49%. Next, 50 parts of the obtained pre-pigment composition, 123 parts of a varnish for printing ink (rosin-modified phenolic resin: non-volatile content 70%), and 3 parts of No. 7 solvent were placed in a jacketed dissolver at 110-1.
The mixture was stirred at 20 ° C. for 2 hours, and the mixture was kneaded twice with a three-roll to obtain a base ink.

In addition to this base ink, 29 parts of varnish for printing ink, 14 parts of No. 7 solvent, compound 2
A blue printing ink was prepared by adding 0 part. The following steps were carried out in the same manner as in Example 1 to obtain the blue ink and the light color ink of the present invention and compare them with the respective inks prepared by the conventional method of Comparative Example 1, but the hue and tinting strength were the same, and viscoelasticity and It also showed good performance in ink suitability such as emulsification characteristics.

Example 3 A dry attritor was added to a rosin-modified phenol resin prepared in Example 2 (weight average molecular weight: 123,000, acid value: 2).
0) 20% surface-treated crude copper phthalocyanine 60
And 5 parts of calcium carbonate were added and crushed for 1 hour. Next, this ground product was transferred to a Henschel mixer, 5 parts of a resin for printing ink (rosin-modified phenolic resin) was added and mixed for 30 minutes. Then, 50 parts of the obtained pre-pigment composition,
118 parts of varnish rosin-modified phenol resin for printing ink: non-volatile content 70%) and 4.5 parts of No. 7 solvent were stirred for 2 hours at 110 to 120 ° C in a jacketed dissolver, and the mixture was kneaded twice with a three-roll. The meat was fleshed to obtain a base ink.

In addition to this base ink, 33 parts of varnish for printing ink, 13 parts of No. 7 solvent, compound 2
A blue printing ink was prepared by adding 0 part. The following steps were carried out in the same manner as in Example 1 to obtain the blue ink and the light color ink of the present invention, and as a result of comparing these inks with the respective inks by the conventional method, it was found that the hue and tinting power were equivalent, and viscoelasticity and emulsification The ink suitability was also sufficient for practical use.

Example 4 267 parts of rosin-modified phenolic resin (weight average molecular weight: 123,000, acid value: 20) was added to the slurry after the heating reaction instead of hydrogenated rosin, and the mixture was stirred at 60 ° C. for 1 hour. After that, a crude copper phthalocyanine surface-treated with 30% by weight of a rosin-modified phenolic resin was prepared in the same manner as in Example 1 except that the reaction solvent was distilled off under reduced pressure.

65 parts of the crude copper phthalocyanine was added to a dry attritor and pulverized for 1 hour. Then, 50 parts of the obtained pre-pigment composition, 127 parts of a varnish for printing ink (rosin-modified phenolic resin: non-volatile content 70%), and 5 parts of No. 7 solvent were mixed in a dissolver with a jacket for 11 times.
The mixture was stirred at 0 to 120 ° C. for 2 hours, and the mixture was kneaded twice with a triple roll to obtain a base ink. To this base ink, 40 parts of printing ink varnish, 13 parts of No. 7 solvent and 22 parts of compound were added to prepare a blue printing ink. Thereafter, the same procedure as in Example 1 was carried out to obtain a blue ink and a light color ink of the present invention. The obtained blue ink and light-colored ink had the same hue and tinting strength as compared with the respective inks produced by the conventional method, and showed good ink suitability.

[0038]

INDUSTRIAL APPLICABILITY The present invention uses a pre-pigment composition (pigment precursor) prepared by finely pulverizing crude copper phthalocyanine with, for example, a dry attritor to directly print it without passing through a pigment form. In a streamlined production method of a printing ink composition for producing an ink, as a pre-pigment composition, a pre-pigment composition prepared by dry-milling a crude copper phthalocyanine surface-treated with a rosin compound in advance is used. Thus, a method for producing a printing ink composition of excellent quality in which the amount of the printing ink resin mixed during dry pulverization is significantly reduced and the drawbacks in the production of the conventional method are improved is provided.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kazuo Anbara             1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Large             Within Nissei Chemical Co., Ltd. (72) Inventor Koji Tsuchiya             1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Large             Within Nissei Chemical Co., Ltd. (72) Inventor Hiromasa             1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Large             Within Nissei Chemical Co., Ltd. (72) Inventor Naonori Takami             1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Large             Within Nissei Chemical Co., Ltd. F-term (reference) 4J039 BC61 BE01

Claims (6)

[Claims] 1. A method for directly producing a printing ink containing at least a copper phthalocyanine and a resin for a printing ink by using a copper phthalocyanine pre-pigment without going through a pigment form, and as a copper phthalocyanine pre-pigment, A method for producing a printing ink, which comprises using a prepigment composition prepared by dry pulverizing a crude copper phthalocyanine surface-treated with a rosin compound. 2. The production of a printing ink according to claim 1, wherein the pre-pigment composition is obtained by dry-milling the surface-treated crude copper phthalocyanine together with an extender pigment and / or a resin for a printing ink. Method. 3. The method for producing a printing ink according to claim 1, wherein the treatment amount of the rosin compound is 1 to 50% by weight with respect to the crude copper phthalocyanine. 4. The amount of the extender pigment and / or the resin for printing ink used is 1 to 50 relative to the crude copper phthalocyanine.
The method for producing a printing ink according to any one of claims 1 to 3, wherein the method is the weight%. 5. The crude copper phthalocyanine is produced by carrying out the Weyler method under pressure conditions.
A method for producing the printing ink according to any one of 1. 6. The method for producing a printing ink according to claim 1, wherein the crude copper phthalocyanine is high-purity crude copper phthalocyanine having a purity of 97% or more measured by a sulfuric acid method.