JPH07292305A - Offset ink composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition good in flow characteristics in producing the printing ink and stability thereof with time by adding an additive comprising a drying inhibitor, a pigment and a quaternary ammonium salt of a specific color acid to a vehicle for the offset ink. CONSTITUTION:This offset ink composition excellent in flowability in producing the printing ink and stability thereof with time is obtained by adding an additive comprising a drying inhibitor (e.g. dibutylhydroxytoluene), a pigment (e.g. a phthalocyanine-based pigment) and a quaternary ammonium salt of a color acid expressed by the formula (P is an organic coloring matter residue such as an azo-, a phthalocyanine-, a quinacridone-, an anthraquinone- or a dioxazine- based one; X is sulfonic acid or carboxylic acid; R<1> is an 8-20C alkyl; R2 to R4 each is a 1-20C alkyl) in an amount of 0.1-20wt.% based on the pigment to a vehicle for the offset ink.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an offset ink composition, and more particularly to an offset ink composition having excellent fluidity during ink production and printing ink stability over time.

[0002]

2. Description of the Related Art Generally, pigments are often dispersed in high concentrations during the production of printing inks, and an increase in viscosity is a major drawback when handling the base ink or when pumping. Conventionally, in order to eliminate such drawbacks, a method of adding an amine-based activator to an organic pigment (Japanese Patent Publication No. 48-1821 and Japanese Patent Publication No. 57-37623), pigments and primary and secondary grades. A method of adding a salt-forming salt with an amine during the production of a pigment or an ink (Japanese Patent Publication No. 39-28
884, JP-A-60-124657, and JP-B-45-11026) improve the fluidity to deal with the problem.

However, offset inks often contain a drying inhibitor due to problems such as prevention of skinning of the ink during storage of the ink on the printing press and drying suitability of the ink. In the case of an offset ink system containing the same, the effects of the treatment with the above-mentioned amine-based activator and the treatment with the salt-forming salt of the pigment and the primary and secondary amines are reduced to half. Offset ink applies a thin film of ink to the surface of the printing plate and transfers the applied ink to the printing material,
The printing ink is fixed by being dried by absorption of the solvent, evaporation of the solvent, oxidative polymerization of the varnish and the like. Therefore, the printing ink is preferably dried immediately after transfer, but conversely, it is desired that the printing ink does not dry during storage and printing of the printing ink. Further, the printing operation may be interrupted, and if the printing ink dries, a work to remove the dried ink is required at the start of the next printing, which is not economically preferable. Therefore, a printing ink that does not dry during storage of printing ink and that dries quickly on the printing material after printing is ideal. In order to satisfy these demands, it is general that a dryer that is effective on the material to be printed and a drying inhibitor that is effective during storage and printing are used together in the printing ink. The drying inhibitor suppresses the oxidative polymerization of the varnish, and controls the printing ink by contact with air or by acting on the peroxide or polymerization initiation radicals generated in the printing ink by heat. Generally, phenolic polymerization inhibitors such as hydroquinone are used, but various polymerization inhibitors are used according to the performance of the ink. It is known that treatment with an amine-based activator and salt formation between a pigment and an amine are effective in the stability and fluidity of a printing ink over time. However, these additives are also offset inks in which a drying inhibitor is present. The system has a drawback that its effect is significantly reduced.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides an offset ink composition which, when used in an offset ink containing a drying inhibitor, is excellent in fluidity during the production of the ink and in the stability of the printing ink over time. It is a thing.

[0005]

The present invention has found the use of additives for the production and storage of printing inks for the above problems. That is, the present invention provides a vehicle for an offset ink, a drying inhibitor, a pigment, and a pigment acid represented by the following general formula (1).
The present invention relates to an offset ink composition containing an additive composed of a high grade ammonium salt forming salt. General formula (1) (P-X) ^- [N (R ₁ , R ₂ , R ₃ ,
R ₄ )] ⁺ (wherein P is an organic dye residue selected from azo, phthalocyanine, quinacridone, anthraquinone, and dioxazine, X is a sulfonic acid group or a carboxylic acid group, and R ₁ is a carbon atom having 8 carbon atoms. ~ 20 alkyl groups, R ₂ R ₃ R ₄
Represents an alkyl group having 1 to 20 carbon atoms. )

The pigment used in the present invention is a known pigment, and corresponds to an organic pigment used for offset ink such as azo type, phthalocyanine type, quinacridone type, anthraquinone type and dioxazine type. For example, a copper phthalocyanine-based pigment (CI Pigment Blue 1
5, 15: 1, 15: 2, 15: 3, 15: 4, 15:
6, C.I. I. Pigment Green 7, 3
6), monoazo pigment (C.I. Pigment Re
d 3, 4, 5, 23, 48: 1, 48: 2, 48:
3, 48: 4, 49: 1, 49: 2, 53: 1, 57:
1), a disazo pigment (C.I. Pigment Ye)
low 12, 13, 14, 17, 83), anthraquinone pigment (CI Pigment Red 17)
7), quinacridone pigment (CI Pigment)
Red 122, C.I. I. PigmentViolet
19), dioxazine-based pigments (CI Pigmen)
t Violet 23) and the like.

The additive used in the present invention can be prepared by the following method. For pigments having an acidic group (sulfonic acid, carboxylic acid group, etc.), a quaternary ammonium salt can be added to these dyes to form a salt of the pigment and the quaternary ammonium salt. . Further, for a pigment having no acidic group, a salt and a quaternary ammonium salt can be prepared by introducing a required amount of the acidic group into the dye and then adding a quaternary ammonium salt. .

Explaining the additive of the present invention, as a method for adding a salt-forming product of a pigment and a quaternary ammonium salt (hereinafter referred to as an additive), it may be added during the pigment synthesis.
The pigments may be mixed after completion. The desired effect can be obtained by simply mixing the pigment powder and the additive, but mechanically mixing with a kneader, roll mill, attritor, super mill, various pulverizers, etc., or using pigment water or an organic solvent. Even better results can be obtained by performing an intimate mixing method such as adding the additive of the present invention to the suspension system.

It is also possible to produce additives in the system during pigment synthesis to obtain an organic pigment composition. When the dye has an acidic group like a monoazo pigment, an additive is produced during pigment synthesis by adding a quaternary ammonium salt before or after coupling to obtain an organic pigment composition. be able to. For pigments that do not have acidic groups, the required amount of acidic groups is introduced into the dye or raw material of the dye, and this is added during pigment synthesis.
An organic pigment composition can be obtained by forming an additive in the pigment by adding the primary ammonium salt.

In the quaternary ammonium salt used in preparing the additive of the present invention, one or more of the substituents has 8 carbon atoms.
To 20 alkyl groups, preferably 10 to 1 carbon atoms
Eight alkyl groups are particularly effective. R ₂ R ₃ R ₄
Represents an alkyl group having 1 to 20 carbon atoms. For example, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryltrimethylammonium chloride, dilauryldimethylammonium chloride, octyltrimethylammonium chloride, dioctyldimethylammonium chloride, decyltrimethylammonium chloride, didecyldimethylammonium chloride and the like can be mentioned. .

When the additive of the present invention is used, the addition amount is preferably 1 to 15 parts by weight with respect to 100 parts by weight of the organic pigment. If the amount is less than 1 part by weight, the effect is small.
Even if the amount is more than the amount by weight, the effect of the amount used cannot be obtained.

The additive used in the present invention is effective in an offset ink system containing a drying inhibitor, and as a vehicle for the offset ink, for example, a rosin-modified phenol resin, petroleum resin, alkyd resin, or 20 to 50 parts by weight of these dry oil-modified resins, 0 to 30 parts by weight of vegetable oils such as flaxseed oil, tung oil and soybean oil, 10 to 60 parts by weight of solvents such as normal paraffin, aromatic, naphthene and α-olefin, and dried. It comprises 0.1 to 10 parts by weight of inhibitor. The vehicle for offset ink is mixed with the organic pigment of the present invention, and other known additives such as an ink solvent, a drier, a leveling improver and a thickener are appropriately mixed to obtain a printing ink composition. As the drying inhibitor used in the offset ink, generally, a phenolic antioxidant such as hydroquinone is often used, but various polymerization inhibitors can be used depending on the performance of the ink. For example, hydroquinone, P-methoxyphenol, tert-butylhydroquinone, methylhydroquinone, 2,6-
Di-tert-butyl-4-methylphenol, mono (α-methylbenzyl) phenol, di (α-methylbenzyl) phenol, tri (α-methylbenzyl) phenol, 2,2′-methylenebis (4-methyl-6) -T
ert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol),
4,4'-butylidene bis (6-tert-butyl-3
-Methylphenol), 4,4'-thiobis (6-te
rt-butyl-3-methylphenol), 1,1-bis (4-hydroxyphenyl) -cyclohexane, 2,5
-Di-tert-butylhydroquinone, 2,5-di-
Examples include tert-amyl hydroquinone and the like.

[0013]

EXAMPLES The present invention will be specifically described with reference to the following examples. In the examples, “part” means “part by weight” and “%” means “% by weight”.

Production Example 1 18.5 parts of 2-amino-5-methylbenzenesulfonic acid are completely dissolved by stirring with 400 parts of water and 4 parts of sodium hydroxide at room temperature for 30 minutes. 35% hydrochloric acid 25
After adding 1 part, 20 parts of ice is added and cooled to 0 ° C to 3 ° C. Add 7 parts of sodium nitrite dissolved in 25 parts of water and add
What was continuously stirred for 30 minutes at a temperature of not higher than 0 ° C. is used as a diazo component. On the other hand, 19 parts of β-oxynaphthoic acid was added to 1000 parts of water.
And 10 parts of sodium hydroxide are dissolved at 15 ° C., and this is used as a coupler component. The above-mentioned diazo component is added dropwise to this coupler component over 30 minutes, and the stirring is continued for another 1 hour to complete the coupling reaction. To the obtained dye slurry, 118 parts of distearyldimethylammonium chloride is added, and stirred for 2 hours to form a salt-forming product composed of the dye and distearyldimethylammonium chloride. After heating at 60 ° C., filtration and washing with water were carried out to obtain 138 parts of additive (A) in terms of solid content.

Comparative Production Example 1 Additive (B) was obtained in the same manner as in Production Example 1 except that 118 parts of distearyldimethylammonium chloride was replaced with 54 parts of stearylamine. Comparative Production Example 2 The same operation was carried out by replacing 118 parts of distearyldimethylammonium chloride of Production Example 1 with 90 parts of distearylamine to obtain an additive (C). Comparative Production Example 3 118 parts of distearyldimethylammonium chloride of Production Example 1 was replaced with 50 parts of dibutyldimethylammonium chloride.
By replacing the parts, the same operation was performed to obtain an additive (D). Production Example 2 118 parts of distearyldimethylammonium chloride of Production Example 1 was replaced with dioctyldimethylammonium chloride 7
The same operation was carried out in place of 0 part to obtain an additive (E).

Production Example 3 To 400 parts of water were added 25.3 parts of 3,3'-dichlorobenzidine and 16.5 parts of 35% hydrochloric acid. After cooling this solution to 0 ° C., 57 parts of 20% sodium nitrite solution is added and stirred for 1 hour. A small amount of sulfamic acid is added to eliminate excess sodium nitrite to obtain a tetrazo solution of 3,3'-dichlorobenzidine. On the other hand, 53 parts of acetoacetanilide-4-sulfonic acid is added to 20 parts of caustic soda and 700 parts of water and dissolved. To this solution, 360 parts of 10% acetic acid was added little by little to form a suspension, and the above tetrazo solution was added thereto over about 30 minutes. During this time, the temperature of the reaction solution is maintained at about 15 ° C. to complete the coupling reaction. To the obtained yellowish yellow slurry, 53 parts of lauryltrimethylammonium chloride is added and stirred for 2 hours to form a salt-forming product composed of yellowish sulfonic acid and lauryltrimethylammonium chloride. After heating to 60 ° C, it is filtered, washed with water and converted to solid content to 8
8 parts of additive (F) are obtained.

Comparative Production Example 4 Lauryltrimethylammonium chloride 5 of Production Example 3
The same operation was performed by replacing 3 parts with 37 parts of laurylamine to obtain an additive (G). Comparative Production Example 5 Lauryltrimethylammonium chloride 5 of Production Example 3
The same operation was performed by changing 3 parts to 62 parts of dilaurylamine to obtain an additive (H). Production Example 4 Lauryltrimethylammonium chloride 5 of Production Example 3
3 parts was replaced with 80 parts of dilauryl dimethyl ammonium chloride and the same operation was performed to obtain an additive (I).

Production Example 5 The coupling reaction is completed using the tetrazo solution used in Production Example 3 and 32 parts of acetoacetanilide and 6 parts of acetoacetanilide-4-sulfonic acid as coupling components. 6 parts of lauryltrimethylammonium chloride is added to the obtained yellowish yellow slurry to form a salt-forming product composed of sulfonic acid and lauryltrimethylammonium chloride which are present as a part of yellowish yellow. After heating at 60 ° C., the mixture was filtered and washed with water to obtain a pigment composition (J).

Production Example 6 58 parts of copper phthalocyanine was added to 500 parts of 5% fuming sulfuric acid, and the mixture was stirred at 100 ° C. for 2 hours. Cool to room temperature, pour into a mixture of 1000 parts of water and 1000 parts of ice, filter and wash with water. The obtained copper phthalocyanine sulfonate was added to water 1
Reslurry to 000 parts and add 42 parts of dilauryldimethylammonium chloride to form salt. 70 ° C
After heating to 90 ° C., the mixture was filtered and washed with water to obtain 90 parts of additive (K). Production Example 7 Dilauryldimethylammonium chloride 4 of Production Example 6
2 parts was replaced with 38 parts of didecyldimethylammonium chloride and the same operation was performed to obtain an additive (L).

Comparative Production Example 6 Dilauryldimethylammonium chloride 4 of Production Example 7
The same operation was carried out by replacing 2 parts of laurylamine with 19 parts to obtain an additive (M). Comparative Production Example 7 Dilauryldimethylammonium chloride 4 of Production Example 7
The same operation was performed by replacing 2 parts with 36 parts of dilaurylamine to obtain an additive (N). Comparative Production Example 8 Dilauryldimethylammonium chloride 4 of Production Example 7
The same operation was performed by replacing 2 parts with 23 parts of dibutyldimethylammonium chloride to obtain an additive (0).

Example 1 Soluble azo (CI Pigment Red 57:
1) Mix 100 parts with 5 parts of the additive (A) of Production Example 1,
A pigment composition was obtained.

The resulting pigment was made into an ink and tested. The varnish used was 50 parts of Tamanol 361 (Arakawa Chemical Co., Ltd .: rosin-modified phenolic resin), and 20 parts of linseed oil.
No. 5, No. 5 solvent (manufactured by Nippon Oil Co., Ltd .: ink solvent) was added, and the mixture was heated and dissolved at 200 ° C. to produce.
Then, 98 parts of this varnish was mixed with aluminum octylate 2
Part was added to form a gel varnish. 70 parts of the obtained gel varnish and 20 parts of the pigment composition according to the present invention, No. 5 solvent 8
Parts, and 2 parts of a drying inhibitor (dibutylhydroxytoluene: polymerization inhibitor) were mixed and mixed and kneaded with a three-roll to obtain an offset ink having a tack value of 9.0. The resulting offset ink showed excellent fluidity and stability over time.

Comparative Example 1 The fluidity of the offset ink prepared by the same procedure as in Example 1 except that the additive (A) was not added was poor. Comparative Example 2 Soluble Azo (CI Pigment Red 57:
1) 5 parts of the additive (B) of Comparative Production Example 1 was mixed with 100 parts to prepare a comparative pigment. The offset ink prepared by the same operation as in Example 1 with 20 parts of this comparative pigment was inferior in fluidity. Comparative Example 3 Soluble Azo (CI Pigment Red 57:
1) 5 parts of the additive (C) of Comparative Production Example 2 was mixed with 100 parts to prepare a comparative pigment. The offset ink prepared by the same operation as in Example 1 with 20 parts of this comparative pigment was inferior in fluidity. Comparative Example 4 Soluble Azo (CI Pigment Red 57:
1) 5 parts of the additive (D) of Comparative Production Example 3 was mixed with 100 parts to prepare a comparative pigment. The offset ink prepared by the same operation as in Example 1 with 20 parts of this comparative pigment was inferior in fluidity.

Example 2 Soluble azo (CI Pigment Red 57:
1) Mix 100 parts with 5 parts of the additive (E) of Production Example 2,
A pigment composition was obtained. An offset ink prepared by preparing 20 parts of this pigment composition in the same manner as in Example 1 showed excellent fluidity and stability over time. Example 3 Insoluble azo (CI Pigment Yellow)
12) 10 parts of the additive (F) of Production Example 3 was mixed with 100 parts to obtain a pigment composition. An offset ink prepared by preparing 20 parts of this pigment composition in the same manner as in Example 1 showed excellent fluidity and stability over time.

Comparative Example 5 The fluidity of the offset ink prepared by the same procedure as in Example 3 except that the additive (F) was not added was poor. Comparative Example 6 Insoluble azo (CI Pigment Yellow)
12) 100 parts of the additive (G) of Comparative Production Example 4 was mixed with 10 parts to prepare a comparative pigment. The offset ink prepared by the same operation as in Example 1 with 20 parts of this comparative pigment was inferior in fluidity. Comparative Example 7 Insoluble azo (CI Pigment Yellow)
12) 10 parts of the additive (H) of Comparative Production Example 5 was mixed with 100 parts to prepare a comparative pigment. The offset ink prepared by the same operation as in Example 1 with 20 parts of this comparative pigment was inferior in fluidity.

Example 4 Insoluble azo (CI Pigment Yellow)
12) 100 parts of the additive (I) of Production Example 4 was mixed to obtain a pigment composition. An offset ink prepared by preparing 20 parts of this pigment composition in the same manner as in Example 1 showed excellent fluidity and stability over time. Example 5 20 parts of the pigment composition (J) obtained in Production Example 5 was used in Example 1
The offset ink prepared by the same procedure as above showed excellent fluidity and stability over time.

Example 6 Copper Phthalocyanine Blue (CI Pigment B
lue 15: 3) 100 parts of the additive of Production Example 6 (K)
10 parts were mixed to obtain a pigment composition. This pigment composition 2
The offset ink prepared by the same procedure except that 0 part of the drying inhibitor of Example 1, 2 parts of dibutylhydroxytoluene, was replaced with 2 parts of hydroquinone, and the offset ink showed excellent fluidity and stability over time. Example 7 Copper Phthalocyanine Blue (CI Pigment B
lue 15: 3) 100 parts of the additive of Production Example 7 (L)
10 parts were mixed to obtain a pigment composition. This pigment composition 2
The offset ink of which 0 part was prepared by the same operation as in Example 6 exhibited excellent fluidity and stability over time.

Comparative Example 8 The flowability of the offset ink prepared by the same procedure as in Example 6 except that the additive (K) was not added was poor. Comparative Example 9 Copper Phthalocyanine Blue (CI Pigment B
10 parts of the additive (M) of Comparative Production Example 6 was mixed with 100 parts of lou 15: 3) to give a comparative pigment. The offset ink prepared by the same operation as in Example 6 with 20 parts of this comparative pigment was inferior in fluidity. Comparative Example 10 Copper phthalocyanine blue (CI Pigment B
10 parts of the additive (N) of Comparative Production Example 7 was mixed with 100 parts of lou 15: 3) to give a comparative pigment. The offset ink prepared by the same operation as in Example 6 with 20 parts of this comparative pigment was inferior in fluidity.

Comparative Example 11 Copper Phthalocyanine Blue (CI Pigment B
10 parts of the additive (O) of Comparative Production Example 8 was mixed with 100 parts of lou 15: 3) to give a comparative pigment. The offset ink prepared by the same operation as in Example 6 with 20 parts of this comparative pigment was inferior in fluidity. Comparative Example 12 Copper Phthalocyanine Blue (CI Pigment B
20 parts of lue 15: 3) and 2 parts of dilauryldimethylammonium chloride, which is the quaternary ammonium salt used in Production Example 6, were prepared by the same procedure as in Example 6, and the flowability was inferior.

Table 1 shows a list of dyes and additives used in Examples and Comparative Examples.

[0031]

[Table 1]

[0032]

Table 2 shows the fluidity of the pigment composition and the offset ink according to the present invention. Liquidity is evaluated by J
Using a glass plate rheometer of IS K 5702, the length of ink 1 cc flowing at 25 ° C. for 10 minutes was measured. The larger the value, the better the fluidity. Regarding the stability with time, the offset ink prepared in each example was stored in a warmer at 60 ° C. for 48 hours, and the fluidity was measured and evaluated.

[0034]

[Table 2]

[0035]

Industrial Applicability According to the present invention, in a system of an offset ink containing a drying inhibitor, a salt-forming product comprising a pigment acid of a pigment for offset ink and a quaternary ammonium salt containing a long chain alkyl group is added. Thereby, an offset ink composition having excellent fluidity during ink production and printing ink stability over time can be obtained.

Claims (3)

[Claims] 1. A vehicle for an offset ink, comprising a drying inhibitor, a pigment, and a pigment acid represented by the following general formula (1):
An offset ink composition comprising an additive composed of a high-grade ammonium salt-forming salt. General formula (1) (P-X) ^- [N (R ₁ , R ₂ , R ₃ ,
R ₄ )] ⁺ (wherein P is an organic dye residue selected from azo, phthalocyanine, quinacridone, anthraquinone, and dioxazine, X is a sulfonic acid group or a carboxylic acid group, and R ₁ is a carbon atom having 8 carbon atoms. ~ 20 alkyl groups, R ₂ R ₃ R ₄
Represents an alkyl group having 1 to 20 carbon atoms. ) 2. The offset ink composition according to claim 1, wherein the additive amount of the general formula (1) is 0.1 to 20% by weight based on the pigment. 3. The offset ink composition according to claim 1, wherein the drying inhibitor is a phenolic polymerization inhibitor.