JP3872356B2 - Manufacturing method of printing ink - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention is a streamlined printing ink that directly produces printing inks using pre-pigments without going through the form of pigments, which overcomes the disadvantages of conventional methods and allows for the production of improved quality printing inks. It relates to the manufacturing method.
[0002]
[Prior art]
In general, copper phthalocyanine pigments are, for example, urea method (Wiler method) in which phthalic acid or its derivative, urea or its derivative is heated in an organic solvent in the presence of a copper compound and a catalyst, or phthalodinitrile is present in the presence of a copper compound. It is synthesized by a method such as a nitrile method in which a reaction is performed under heating in an organic solvent. 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 it is as a pigment.
[0003]
For this reason, conventionally, when producing printing ink, primary copper particles are finely adjusted (less than 1 μm) by a method of pigmentation represented by dry grinding method and wet grinding method to prepare crude copper phthalocyanine as a pigment. Appropriate properties are used, and the printing ink composition is made of pigmented copper phthalocyanine (copper phthalocyanine pigment) such as a roll mill such as a three-roll mill, a kneader dispersing machine such as a kneader, or a dispersing machine such as a ball mill or a bead mill. Is uniformly dispersed in a printing ink resin or resin solution.
[0004]
Since this process of pigmentation requires a great deal of labor, as a streamlined method for producing printing ink, without using pigments, it is crushed as crude copper phthalocyanine, for example, with a dry attritor (dry pulverization). A method for producing a printing ink simultaneously with pigmentation in a printing ink production process using a pre-prepared (Pre) pigment (pigment precursor) prepared in a fine manner has been proposed (Japanese Patent Publication No. 55-6670, (Kaihei 2-294365, JP-A-9-272833, etc.).
[0005]
In particular, the methods described in JP-A-2-294365 and JP-A-9-272833 in which dry pulverization is carried out in the presence of a resin for printing ink alleviates the aggregation of the pre-pigment and reduces the pre-pigment to the pigment. in that the efficiency of the conversion and inked a method for producing a very good printing inks.
For example, in the method described in JP-A-9-272833, crude copper phthalocyanine is dry-pulverized together with 20 to 80% by weight of a resin for printing ink as a pre-pigment, and this is used as a solvent for printing ink or printing. This is a method for producing printing ink simultaneously with pigmentation of a pre-pigment by heating to 80 to 170 ° C. in an ink varnish.
[0006]
However, in the method using the printing ink resin as described above, a relatively large amount of resin is required to obtain a sufficient effect. However, the use of a large amount of resin has problems for safe operation such as adhesion of the ground material to the inside of the pulverizer due to heat generated during dry pulverization and risk of ignition of the ground material due to heat storage. In addition, the resin may cause structural destruction such as oxidation and breakage (open) cracks due to impact and heat generation during dry pulverization, and the deteriorated resin has not only the hue side of the ink but also viscoelasticity and emulsification characteristics. It may have a significant effect on printability.
[0007]
[Problems to be solved by the invention]
The object of the present invention is to reduce the aggregation of the pre-pigment in a streamlined method of producing a printing ink directly using a copper phthalocyanine pre-pigment without going through the form of the pigment, and to add a large amount of resin in the conventional method. It is an object of the present invention to provide a method for producing an excellent quality printing ink at a low cost without causing various adverse effects on the printing ink and on the production process as generated by using the ink.
[0008]
[Means for Solving the Problems]
When preparing pre-pigments by dry pulverization, the present inventors greatly reduce the amount of printing ink resin used during dry pulverization by using crude copper phthalocyanine surface-treated with a rosin compound in advance. In addition, the inventors have found that the same effect as that obtained by using a large amount of resin can be obtained, and based on this finding, the present invention has been completed.
[0009]
That is, the present invention provides a printing ink containing at least copper phthalocyanine and a printing ink resin using a copper phthalocyanine pre-pigment directly without going through the form of a pigment. A pre-pigment composition prepared by dry pulverizing crude copper phthalocyanine surface-treated with a rosin compound , wherein the pre-pigment composition comprises the above surface-treated crude copper phthalocyanine as an extender pigment and / or A method for producing a printing ink, comprising using a dry pulverized resin together with a printing ink resin .
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in more detail with reference to embodiments of the invention.
The present invention uses a crude copper phthalocyanine that has been surface-treated in advance with a rosin compound in a method for directly producing a printing ink using a pre-precursor (pigment precursor) of copper phthalocyanine that has not undergone a pigmentation step. it is either not used at all for a printing ink resin during dry grinding, it is characterized by the use pre pigment composition made adjustment in very small amount.
[0011]
In general, copper phthalocyanine after completion of the synthesis reaction is obtained by removing the solvent from the reaction slurry under reduced pressure, then removing the reaction impurities by a method such as acid treatment, alkali treatment, washing with warm water, washing with water, filtering and drying, Prepared as crude copper phthalocyanine.
The crude copper phthalocyanine previously surface-treated with the rosin compound used in the present invention is rosin in any step of the copper phthalocyanine synthesis stage, the reaction slurry after the reaction is completed, or the above-mentioned crude copper phthalocyanine preparation stage. Manufactured by mixing and treating system compounds.
[0012]
As a method for treating the rosin compound, a conventionally known treatment method such as adding the rosin compound as an alkaline aqueous solution or a solution dissolved in an organic solvent to a reaction system or a reaction slurry after completion of the reaction can be used. In the above process, the process in the reaction slurry after completion of the reaction and the process in the process of distilling off the solvent are desirable because there are few restrictions on the processing amount and the processing method.
[0013]
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, rosin-modified alkyd resin, rosin. Examples thereof include various rosin-modified resins such as a modified maleic acid resin, a rosin-modified phenol resin, a rosin-modified fumaric acid resin, a rosin-modified polyamide resin, and a rosin-modified polyester resin. These can be used alone or in combination of two or more. The treatment amount of these rosin compounds is preferably in the range of 1 to 50% by weight based on the crude copper phthalocyanine.
[0014]
Among the above rosin compounds, those having a low melting point are originally mixed with crude copper phthalocyanine and dry pulverized to prepare a pre-pigment composition. Prone to sticking and ignition. However, rosin-based compound, so when it is used in a form that treating the surface of the crude copper phthalocyanine, and at the same time the risk as described above is significantly improved, to uniformly treat the surface of the crude copper phthalocyanine Thus, even when used in a relatively small amount, the aggregation of particles at the preparation stage of the crude copper phthalocyanine composition is alleviated, and the aggregation of particles at the preparation of the pre-pigment composition is effectively alleviated. For this reason, even if it does not use the resin for printing ink again at the time of dry-type grinding | pulverization, the effect similar to having used a lot of resin is acquired by use of a small quantity, and it becomes possible to provide the improved printing ink.
[0015]
In the present invention, dry pulverization can be performed in the presence of extender pigments. Examples of the extender pigment, rather good any one as long as it little affects the hue and transparency of the pigment refractive index less, for example, calcium carbonate or zinc oxide (zinc white), barium sulfate and barite powder, clay, Examples include talc, alumina white, white carbon (fine silica), and mixtures thereof. A preferred extender pigment is calcium carbonate.
[0016]
In the present invention, dry pulverization can also be performed with a printing ink resin that does not interfere with safe driving. The resin for a printing ink to be used, but it may also in general any resin as long as it is used in printing inks. For example, a phenol resin and a modified product thereof, a maleic resin and a modified product thereof, an alkyd resin and a modified product thereof, a petroleum resin, a modified rosin and the like, and a mixture thereof, preferably a rosin modified phenol resin, It is also included in the rosin compound used in the present invention. The extender pigment and / or printing ink resin is preferably used in an amount of 1 to 50% by weight based on the crude copper phthalocyanine.
[0017]
In the dry pulverization of the present invention, in addition to the dry attritor, those using a pulverizing medium such as beads such as a ball mill or a vibration mill, a kneader such as a twin screw extruder or a kneader, a pulverizer such as a jet mill, A strong stirrer such as a Henschel mixer or a type that does not use grinding media can be used, but a type that uses grinding media is preferred in terms of grinding efficiency.
[0018]
In general, dry pulverization in the presence of a resin requires attention to the fixation and ignition of the pulverized material inside the pulverizer due to heat generated during pulverization. Usually, pulverization is performed in the temperature range of 80 to 150 ° C. under cooling. The method of the present invention is also advantageous for sticking and ignition problems, and the pulverization can be performed at a higher temperature. On the other hand, it may be performed at a lower temperature, and the temperature during pulverization is not particularly limited.
[0019]
In general, crude copper phthalocyanine contains about several percent by weight of reaction impurities, but the reaction impurities hinder the conversion of pre-pigments into pigments, which may cause yellowing of printing inks and suitability for printing inks. Also has a significant impact. In the present invention, it is preferable to use high-purity crude copper phthalocyanine having a purity measured by a sulfuric acid method of 97% or more.
[0020]
As the reaction impurities, impurities contained in the crystal of copper phthalocyanine that cannot be removed by ordinary washing are particularly problematic. However, according to the sulfuric acid method, all reaction impurities contained in the crystal can be measured. Purity measurement by the sulfuric acid method follows the following procedure.
(Purity measurement method by sulfuric acid method)
Crude copper phthalocyanine (5.0 g) is dissolved in 50 ml of 98 wt% sulfuric acid by heating (90-100 ° C., 40 minutes), and 150 ml of 15 wt% sulfuric acid is added to this solution for recrystallization. After allowing to cool, peptize in 25 ml of water, add 10 ml of 28 wt% ammonia water and heat (90-100 ° C., 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
[0021]
The crude copper phthalocyanine used in the present invention is preferably copper phthalocyanine synthesized by performing the urea method (Weiler method) under pressure (preferably 0.1 to 0.7 MPa). Copper phthalocyanine synthesized under pressure has an advantage that the amount of reaction impurities incorporated into the copper phthalocyanine crystal is less than copper phthalocyanine synthesized under normal pressure and can be prepared with high purity.
[0022]
When preparing the pre-pigment composition by dry pulverization, if necessary, dry pulverization may be performed by adding a pigment treatment agent or dispersant such as a conventionally known pigment derivative or polymer dispersant, or a surfactant or rosin. Can do. In addition, it is conventionally known that a petroleum-based solvent or an organic solvent generally used for printing ink can be blended as necessary, and that pulverization can be performed in a nitrogen gas atmosphere for the purpose of preventing deterioration of the resin. It is the same as the method.
[0023]
【Example】
Next, the present invention will be described more specifically with reference to pigment production examples, examples and comparative examples. In the text, parts or percentages are based on weight.
[0024]
Pigment production example 1
To a 5 L container, 1000 parts of phthalic anhydride, 2000 parts of urea, 10 parts of ammonium molybdate, 180 parts of cuprous chloride and 2000 parts of Hysol P (manufactured by Nippon Petrochemical Co., Ltd.) were added and reacted at 200 ° C. for 4 hours. .
After completion of the reaction, the solvent was distilled off under reduced pressure, the reaction product was put into 20000 parts of 2% dilute sulfuric acid aqueous solution, stirred at 80 ° C. for 2 hours, filtered, washed with hot water, and washed with water (until the filtrate became neutral). Thus, an aqueous paste of crude copper phthalocyanine was obtained. Next, this aqueous paste was dried at 90 ° C. to obtain 900 parts of crude copper phthalocyanine having a purity measured by a sulfuric acid method of 96.0%.
[0025]
Pigment production example 2
890 parts of crude copper phthalocyanine having a purity of 98.0% as measured by the sulfuric acid method was obtained in the same manner as in Pigment Production Example 1 except that the heating reaction was performed at 200 ° C. for 4 hours under a pressure of 0.3 MPa.
[0026]
Pigment production example 3
100 parts of the crude copper phthalocyanine obtained in Pigment Production Example 1 was added to a dry attritor and ground for 30 minutes. The content of the β-type crystal form of this crude copper phthalocyanine ground product was 43%. Next, 400 parts of isobutyl alcohol and 600 parts of water were added to 100 parts of the obtained ground product, 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, heated at 80 ° C. for 1 hour, filtered, washed with water, dried and pulverized to obtain a powdered copper phthalocyanine pigment (CIPigment Blue 15: 3) Got.
[0027]
Comparative Example 1
18 parts of the β-type copper phthalocyanine pigment obtained in Pigment Production Example 3 is mixed with 67 parts of a printing ink varnish (rosin-modified phenolic resin varnish, non-volatile content 70%), and the mixture is kneaded 3 times with 3 rolls. An ink was obtained. To this base ink, 19 parts of varnish for printing ink, 6 parts of No. 7 solvent (petroleum solvent manufactured by Nippon Oil Co., Ltd.) and 10 parts of compound (ink adjustment 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 to obtain a light-colored ink (coloring power determination).
The blue ink and the light color ink were used as comparative inks according to a conventional method.
[0028]
Example 1
In Pigment Production Example 2, an aqueous paste of crude copper phthalocyanine after sulfuric acid treatment was peptized in 20000 parts of water, 45 parts of hydrogenated rosin was added as an alkaline aqueous solution, and the mixture was stirred at 50 ° C. for 30 minutes. Next, hydrochloric acid was added to adjust the pH to 4.0, and the mixture was stirred at 50 ° C. for 1 hour. Then, the slurry was filtered, washed with water and dried (90 ° C.) to prepare crude copper phthalocyanine having a surface treated with hydrogenated rosin 5%. did.
[0029]
50 parts of the above surface-treated crude copper phthalocyanine and 9.5 parts of calcium carbonate were added to a dry attritor and pulverized for 1 hour. Next, 8.5 parts of a resin for printing ink (rosin-modified phenolic resin) was added and further pulverized for 10 minutes. The β-type crystal content of the obtained pre-pigment composition was 48%.
Next, 50 parts of the obtained pre-pigment composition, 119 parts of varnish for printing ink (rosin-modified phenolic resin: 70% non-volatile content) and 3 parts of No. 7 solvent were stirred at 110 to 120 ° C. for 2 hours in a jacketed dissolver. The mixture was kneaded twice with three rolls to obtain a base ink.
[0030]
To this base ink, 29 parts of printing ink varnish, 14 parts of No. 7 solvent, and 19 parts of compound were added to prepare 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 to obtain a light color ink. The obtained blue ink and light color ink have the same hue and coloring power 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.
[0031]
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, and then the reaction solvent was reduced in pressure. Except for distilling off, a crude copper phthalocyanine having a surface treated with 20% rosin-modified phenol resin was prepared in the same manner as in Example 1.
[0032]
60 parts of the above surface-treated crude copper phthalocyanine and 10 parts of calcium carbonate were added to a dry attritor 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 varnish for printing ink (rosin-modified phenolic resin: 70% non-volatile content) and 3 parts of No. 7 solvent were stirred at 110 to 120 ° C. for 2 hours in a jacketed dissolver. The mixture was kneaded twice with three rolls to obtain a base ink.
[0033]
In addition to this base ink, 29 parts of printing ink varnish, 14 parts of No. 7 solvent, and 20 parts of compound were added to prepare a blue printing ink.
The following were obtained in the same manner as in Example 1 to obtain the blue ink and the light color ink of the present invention and compared with the respective inks prepared by the conventional method of Comparative Example 1, but with the same hue and coloring power. It also showed good performance with regard to ink suitability such as emulsification characteristics.
[0034]
Example 3
To a dry attritor, add 60 parts of crude copper phthalocyanine and 5 parts of calcium carbonate obtained by surface-treating 20% of the rosin-modified phenolic resin prepared in Example 2 (weight average molecular weight: 123,000, acid value: 20). Milled for hours. Next, this ground product was transferred to a Henschel mixer, and 5 parts of a resin for printing ink (rosin-modified phenol resin) was added and mixed for 30 minutes.
Next, 50 parts of the obtained pre-pigment composition, 118 parts of varnish rosin modified phenolic resin for printing ink: 70% non-volatile content, and 4.5 parts of No. 7 solvent were stirred at 110 to 120 ° C. for 2 hours in a jacketed dissolver. The mixture was kneaded twice with three rolls to obtain a base ink.
[0035]
To this base ink, 33 parts of printing ink varnish, 13 parts of No. 7 solvent, and 20 parts of compound were added to prepare a blue printing ink.
The following are obtained 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 with the respective inks obtained by the conventional method, the hue and coloring power are equivalent, such as viscoelasticity and emulsification characteristics. The ink suitability could withstand practical use.
[0036]
Example 4
Instead of hydrogenated rosin, 267 parts of rosin-modified phenol resin (weight average molecular weight: 123,000, acid value: 20) was added to the slurry after the heating reaction, and the mixture was stirred at 60 ° C. for 1 hour, and then the reaction solvent was reduced in pressure. Except for distilling off, crude copper phthalocyanine was prepared in the same manner as in Example 1 by subjecting 30% by weight of rosin-modified phenolic resin to surface treatment.
[0037]
65 parts of the crude copper phthalocyanine was added to a dry attritor and pulverized for 1 hour. Next, 50 parts of the obtained pre-pigment composition, 127 parts of printing ink varnish (rosin-modified phenolic resin: 70% non-volatile content) and 5 parts of No. 7 solvent were stirred at 110 to 120 ° C. for 2 hours in a jacketed dissolver. The mixture was kneaded twice with three rolls to obtain a base ink.
To this base ink, 40 parts of varnish for printing ink, 13 parts of No. 7 solvent, and 22 parts of compound were added to prepare a blue printing ink.
In the same manner as in Example 1, the blue ink and the light color ink of the present invention were obtained. The obtained blue ink and light color ink had the same hue and coloring power as compared with the respective inks prepared by the conventional method, and showed good ink suitability.
[0038]
【The invention's effect】
The present invention uses a pre-pigment composition (pigment precursor) finely prepared by pulverizing crude copper phthalocyanine with, for example, a dry attritor or the like, and directly producing printing ink without going through the form of pigment. In a streamlined manufacturing method of an ink composition, a pre-pigment composition prepared by dry pulverizing crude copper phthalocyanine previously surface-treated with a rosin compound as a pre-pigment composition , the pre-pigment composition By using a product obtained by dry pulverizing the above surface-treated crude copper phthalocyanine together with extender pigment and / or printing ink resin, the amount of printing ink resin mixed during dry pulverization can be greatly increased. There is provided a process for producing an excellent quality printing ink composition which reduces and improves the manufacturing disadvantages of conventional processes.

Claims (5)

In a method of directly producing a printing ink containing at least copper phthalocyanine and a resin for printing ink using a copper phthalocyanine pre-pigment without going through the form of a pigment, the surface is previously treated with a rosin compound as a copper phthalocyanine pre-pigment. A pre-pigment composition prepared by dry pulverizing a treated crude copper phthalocyanine , wherein the pre-pigment composition is prepared by dry- treating the surface-treated crude copper phthalocyanine together with extender pigments and / or printing ink resins. A method for producing a printing ink, comprising using a pulverized product. 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 based on the crude copper phthalocyanine. The method for producing a printing ink according to claim 1 or 2 , wherein the amount of the extender pigment and / or the resin for the printing ink is 1 to 50% by weight based on the crude copper phthalocyanine. The method for producing a printing ink according to any one of claims 1 to 3 , wherein the crude copper phthalocyanine is produced by performing the Weiler method under a pressurized condition. The method for producing a printing ink according to any one of claims 1 to 4 , wherein the crude copper phthalocyanine is a high-purity crude copper phthalocyanine having a purity measured by a sulfuric acid method of 97% or more.