JPH04275373A - Disazo pigment and printing ink composition - Google Patents

Abstract

PURPOSE:To obtain the subject pigment having yellow color, excellent in transparency and fluidity and useful for offset ink, etc., by using a tetrazotized dichlorobenzidine as the diazo component and a mixture of specific compounds at specific ratio as mixed coupler component. CONSTITUTION:The objective pigment can be produced by using a diazo component consisting of tetrazotized 3,3'-dichlorobenzidine and a mixed coupler component consisting of 97.9-60mol% of acetoaceto-o-toluidide, 2-40mol% of acetoaceto- m-xylydide and 0.1-10mol% of an acetoacetoanilide compound of formula (X is -COOH, -S03H, etc.; Y is H, OH, CH3 or Cl). A printing ink composition is produced from the pigment and a printing ink vehicle.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is directed to disazo pigments, which, when used in offset inks in particular, can produce inks with transparency and density sufficient to enable production of offset yellow inks in the process, and with good fluidity. Concerning pigments and printing ink compositions.

0002

BACKGROUND OF THE INVENTION Conventionally, process offset inks have been obtained by flashing a wet cake to form ink, and by dispersing the dried wet cake using a three-roll mill, a sand mill, or a shot mill. However, the former method suffers from large variations in quality due to opacity and loss of density due to the heat during flushing.The latter method, which is less affected by this, has been reconsidered in recent years, but inks made from dry wet cake pigments are It was significantly inferior in terms of transparency, fluidity, and concentration compared to those from Wet cake pigments are obtained by coupling a tetrazotized product of 3,3'-dichlorobenzidine with acetoacetanilide, but the quality deteriorates due to significant crystal growth due to heat during drying. On the other hand, as a known technique of two-component coupling, Japanese Patent Publication No. 55-106
In Publication No. 30, there is an example of a mixed coupling of two coupling components, namely acetoacetanilide and one having a polar group in its phenyl group, but the dry product of this pigment also has poor transparency, fluidity, density, and clarity. was significantly inferior in this respect. Japanese Patent Publication No. 1-110578 also describes acetoacetanilide, acetoacetoorthoanisidide, acetoacetoorthotoluidide, acetoacetoorthochloroanilide, acetoacetomethaxylidide, and acetoaceto-2,5-dimethoxy-4-chloro-anilide. An example is described of a pigment derived by coupling a mixture of two or more selected from the above, but the dry product of this pigment was also significantly inferior to the wet cake as mentioned above.

0003

[Problems to be Solved by the Invention] The present invention provides a disazo pigment and a disazo pigment that, when used in an offset ink, can provide an ink with transparency and density sufficient to enable production of an offset yellow ink in the process, and with good fluidity. A printing ink composition is provided.

0004

[Means for Solving the Problems] The present invention uses a tetrazotized product of 3,3'-dichlorobenzidine as a diazo component, and contains 97.9 to 60 mol% of acetoacetoorthotoluidide and 2 to 40 mol% of acetoacetomethaxylidide. Mol% and acetoacetanilide compound represented by the following general formula (1) 0
．． It relates to a disazo pigment comprising 1 to 10 mol % as a mixed coupler component.

[Chemical formula 2] [wherein, X is -COOH, -SO3 H, -S
O3 M, -NR1 R2, -CONR1 R2,
-SO2 NR1 R2 , -CONH(CH2)n
NR1 R2 , -SO2 NH(CH2)n N
R1 R2 (However, R1 and R2 are each a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or -C2H
4 represents an OH group, n represents an integer of 1 to 3, and M represents a metal ion. ), Y represents H, OH, CH3, Cl. ]
The invention also relates to a printing ink composition characterized in that it consists of the disazo pigment described above and a printing ink vehicle.

Examples of the acetoacetanilide compound represented by the general formula (1) include the following compounds. Acetoacetoorthocarboxyanilide, Acetoacetomethacarboxyanilide, Acetoacetoparacarboxyanilide, Acetoaceto-2-carboxy-3-chloroanilide, Acetoaceto-2-carboxy-4-chloroanilide, Acetoaceto-2-carboxy-5-chloroanilide , Acetoaceto-2-carboxy-6-chloroanilide, Acetoaceto-2-carboxy-3-methylanilide, Acetoaceto-2-carboxy-4-methylanilide, Acetoaceto-2-carboxy-5-methylanilide, Acetoaceto-2-carboxy -6-methylanilide, acetoaceto-2-carboxy-3-hydroxyanilide, acetoaceto-2-carboxy-4-hydroxyanilide, acetoaceto-2-carboxy-5-hydroxyanilide, acetoaceto-3-carboxy-2
-chloroanilide, acetoaceto-3-carboxy-4
-chloroanilide, acetoaceto-3-carboxy-5
-chloroanilide, acetoaceto-3-carboxy-6
-chloroanilide, acetoaceto-3-carboxy-2
-methylanilide, acetoaceto-3-carboxy-4
-methylanilide, acetoaceto-3-carboxy-5
-Methylanilide, acetoaceto-3-carboxy-6
-Methylanilide, acetoaceto-3-carboxy-2
-Hydroxyanilide, acetoaceto-3-carboxy-4-hydroxyanilide, acetoaceto-3-carboxy-5-hydroxyanilide, acetoaceto-3-carboxy-6-hydroxyanilide, acetoaceto-4
-carboxy-2-chloroanilide, acetoacetate-4
-carboxy-3-chloroanilide, acetoacetate-4
-carboxy-2-methylanilide, acetoacetate-4
-carboxy-3-methylanilide, acetoacetate-4
-carboxy-2-hydroxyanilide, acetoaceto-4-carboxy-3-hydroxyanilide, acetoacetoorthosulfonylanilide, acetoacetomethasulfonylanilide, acetoaceto parasulfonylanilide, acetoaceto-2-sulfonyl-3-chloroanilide, acetoaceto-2 -sulfonyl-4-
Chloranilide, acetoaceto-2-sulfonyl-5
-chloroanilide, acetoaceto-2-sulfonyl-
6-chloroanilide, acetoaceto-2-sulfonyl-3-methylanilide, acetoaceto-2-sulfonyl-4-methylanilide, acetoaceto-2-sulfonyl-5-methylanilide, acetoaceto-2-sulfonyl-6-methylanilide, acetoacetate -2-sulfonyl-3-hydroxyanilide, acetoacetate-2
-sulfonyl-4-hydroxyanilide, acetoaceto-2-sulfonyl-5-hydroxyanilide, acetoaceto-3-sulfonyl-2-chloroanilide, acetoaceto-3-sulfonyl-4-chloroanilide,
Acetoaceto-3-sulfonyl-5-chloroanilide, Acetoaceto-3-sulfonyl-6-chloroanilide, Acetoaceto-3-sulfonyl-2-methylanilide, Acetoaceto-3-sulfonyl-4-methylanilide, Acetoaceto-3-sulfonyl- 5-methylanilide, acetoaceto-3-sulfonyl-6-methylanilide, acetoaceto-3-sulfonyl-2-hydroxyanilide, acetoaceto-3-sulfonyl-
4-hydroxyanilide, acetoaceto-3-sulfonyl-5-hydroxyanilide, acetoaceto-3-sulfonyl-6-hydroxyanilide, acetoaceto-
4-Sulfonyl-chloroanilide, acetoacetate-4
-Sulfonyl-3-chloroanilide, acetoacetate-
4-sulfonyl-2-methylanilide, acetoaceto-4-sulfonyl-3-methylanilide, acetoaceto-4-sulfonyl-2-hydroxyanilide, acetoaceto-4-sulfonyl-3-hydroxyanilide, 2-acetoacetylbenzenesulfonic acid Sodium salt, potassium salt, calcium salt, barium salt, strontium salt, manganese salt, zinc salt, magnesium salt, aluminum salt, sodium salt, potassium salt, calcium salt, barium salt, strontium salt of 3-acetoacetylbenzenesulfonic acid, Manganese salt, zinc salt, magnesium salt, aluminum salt, sodium salt, potassium salt, calcium salt, barium salt, strontium salt, manganese salt, zinc salt, magnesium salt, aluminum salt, 4-acetoacetylbenzenesulfonic acid. Acetyl-2-chlorobenzenesulfonic acid sodium salt, 4-acetoacetyl-3-chlorobenzenesulfonic acid sodium salt, 4-acetoacetyl-2-methylbenzenesulfonic acid sodium salt, 4-acetoacetyl-3-methylbenzenesulfone Sodium salt of acid, sodium salt of 4-acetoacetyl-2-hydroxybenzenesulfonic acid, 4-acetoacetyl-3-
Sodium salt of hydroxybenzenesulfonic acid, acetoacetoorthoaminoanilide, acetoacetomethaminoanilide, acetoacetoparaminoanilide, acetoacetoortho-N-methylaminoanilide, acetoacetoortho-N-ethylaminoanilide, acetoacetoortho-N -butylaminoanilide, acetoacetoortho-N,N-stearylaminoanilide, acetoacetoortho-N,N-dimethylaminoanilide, acetoacetoortho-N,N-diethylaminoanilide, acetoacetoortho-N,N-dibutylaminoanilide, Acetoacetoorthoaminoanilide, acetoacetomethaminoanilide, acetoacetoparaaminoanilide, acetoacetopara-N-methylaminoanilide, acetoacetopara-N
-ethylaminoanilide, acetoacetopara-N-butylaminoanilide, acetoacetopara-N-stearylaminoanilide, acetoacetopara-N,N-dimethylaminoanilide, acetoacetopara-N,N-diethylaminoanilide, acetoacetopara-N,N-diethylaminoanilide para-N,N-dibutylaminoanilide, acetoaceto-2-chloro-4-N,
N-dimethylaminoanilide, acetoaceto-2-chloro-4-N,N-diethylaminoanilide, acetoaceto-2-chloro-4-N,N-dibutylaminoanilide, acetoaceto-2-methyl-4-N,N-dimethyl Aminoanilide, acetoaceto-2-methyl-4-N,N
-diethylaminoanilide, acetoaceto-2-methyl-4-N,N-dibutylaminoanilide, acetoaceto-2-hydroxy-4-N,N-dimethylaminoanilide, acetoaceto-2-hydroxy-4-N,N-diethylaminoanilide , acetoaceto-2-hydroxy-
4-N,N-dibutylaminoanilide, 2-acetoacetylbenzamide, 3-acetoacetylbenzamide,
4-acetoacetylbenzamide, 3-acetoacetyl-2-chlorobenzamide, 3-acetoacetyl-4-
Chlorobenzamide, 3-acetoacetyl-5-chlorobenzamide, 3-acetoacetyl-6-chlorobenzamide, 3-acetoacetyl-2-methylbenzamide, 3-acetoacetyl-4-methylbenzamide, 3-
Acetoacetyl-4-methylbenzamide, 3-acetoacetyl-5-methylbenzamide, 3-acetoacetyl-6-methylbenzamide, 3-acetoacetyl-2
-Hydroxybenzamide, 3-acetoacetyl-2-
Hydroxybenzamide, 3-acetoacetyl-4-hydroxybenzamide, 3-acetoacetyl-5-hydroxybenzamide, 3-acetoacetyl-6-hydroxybenzamide, 4-acetoacetyl-N,N-dimethylbenzamide, 4-acetoacetyl- N,N-diethylbenzamide, 4-acetoacetyl-N,N-dibutylbenzamide, 2-acetoacetylbenzenesulfonylamide, 3-acetoacetylbenzenesulfonylamide, 4-acetoacetylbenzenesulfonylamide, 4-acetoacetylbenzenesulfonyl dimethyl amide, 4-acetoacetylbenzenesulfonyldiethylamide, 4-acetoacetylbenzenesulfonyldibutylamide, acetoaceto-p-dimethylaminopropylaminosulfonylanilide, acetoaceto-
p-diethylaminopropylaminosulfonylanilide, acetoaceto-p-dibutylaminopropylaminosulfonylanilide, acetoaceto-p-stearylaminopropylaminosulfonylanilide, acetoaceto-p-dimethylaminoethylaminosulfonylanilide, acetoaceto-p-diethylaminoethylaminosulfonylanilide , acetoaceto-p-dibutylaminoethylaminosulfonylanilide, acetoaceto-p-stearylaminoethylaminosulfonylanilide, acetoaceto-p-dimethylaminopropylaminocarboanilide, acetoaceto-p-diethylaminopropylaminocarboanilide, acetoaceto-p-
dibutylaminopropylaminocarboanilide, acetoaceto-p-stearylaminopropylaminocarboanilide, acetoaceto-p-dimethylaminoethylaminocarboanilide, acetoaceto-p-diethylaminoethylaminocarboanilide, acetoaceto-p-dibutylaminoethylaminocarboanilide, acetoaceto-p-stearylaminoethylaminocarboanilide,
4-acetoacetylbenzenesulfonyl diethylolamide, 4-acetoacetyl-N,N-diethylolbenzamide.

The proportion of the mixed coupler component used in the present invention is 97.9 to 60 mol% of acetoacetoorthotoluidide.
, 2 to 40 mol % of acetoacetomethaxylidide and 0.1 to 10 mol %, preferably 1 to 5 mol % of an acetoacetanilide compound represented by the following general formula (1). The ratio of acetoacetoorthotoluidide and acetoacetomethaxylide used is for adjusting the hue of the process yellow ink. Furthermore, if the amount of the acetoacetanilide compound represented by the general formula (1) exceeds the above-mentioned value, it is not preferable because it causes opacity and poor dispersion.

[0007] In the present invention, the coupling reaction between the tetrazotized product of 3,3'-dichlorobenzidine and the mixed coupler is not particularly limited, but it is carried out in a conventional manner under acetic acid acidity. The conditions at this time are PH6 to PH3, temperature 10°C to 30°C, and time 30 to 60 minutes. Next, this pigment slurry is adjusted to the alkaline side (PH9 to PH14), and an alkali salt solution of rosin is added. The amount of rosin added is 1 to 50% by weight based on the pigment. Next, this slurry is heated at a temperature of 80° C. for about 30 minutes. Next, the pH was adjusted to the acid side (PH is PH4 to PH6) to precipitate rosin on the pigment surface, and after keeping it warm for 30 minutes, it was filtered, washed with water, dried,
Perform pulverization.

The disazo pigment composition of the present invention is used as a processing offset ink. The offset ink composition consists of 3 to 35% by weight of the disazo pigment of the present invention, 97 to 45% by weight of an offset ink vehicle, and 0 to 20% by weight of other adjuvants and extender pigments, and the offset ink vehicle is rosin-modified phenol. 20 to 50% by weight of resins such as resins, petroleum resins, alkyd resins, or drying oil-modified resins, 0 to 30% by weight of vegetable oils such as linseed oil, tung oil, soybean oil, n-paraffins, isoparaffins, aromatics, naphthenes. , 10 to 60% by weight of a solvent such as α-olefin.

[0009]

[Effects of the Invention] In general, the transparency and density of offset inks can be improved by making pigment particles finer. However, in the two-component mixed coupling of acetoacetanilide and a polar group-containing coupler component, the pigment particles undergo crystal growth due to the heat of the drying process. This is because acetoacetanilide has extremely low heat resistance. However, in the present invention, the pigment particles are made finer, and at the same time, the crystal growth of the pigment particles due to the heat of the drying process is suppressed, and furthermore, the wetting of the printing varnish is improved, and the transparency, density, and fluidity are improved.

0010

[Examples] The present invention will be specifically explained below with reference to Examples. In the examples, all "parts" indicate parts by weight.

Example 1 25.3 parts of 3,3'-dichlorobenzidine and 16.5 parts of 35% hydrochloric acid are added to 400 parts of water. After cooling this solution to 0°C, 57 parts of 20% sodium nitrite solution was added and stirred for 1 hour. A small amount of sulfamic acid is added to eliminate excess sodium nitrite, resulting in a tetrazo solution of 3,3'-dichlorobenzidine. On the other hand, acetoacetoorthotruidide 2
6.7 parts and 12.3 parts of acetoacetomethaxylidide and 3
-Add and dissolve 1.4 parts of acetoacetyl-4-methylbenzamide and 20 parts of caustic soda. 1 in this solution
Add 360 parts of 0% acetic acid little by little to form a suspension, and add the above tetrazo solution over about 30 minutes. During this time, the temperature of the reaction solution is maintained at about 15°C. After adjusting the pH of the obtained disazo pigment slurry from 10 to 11 with caustic soda, 70 parts of a 10% alkali salt solution of rosin was added. This slurry was heated to 80° C., stirred for 30 minutes, then adjusted to pH 4 to 6 by adding hydrochloric acid, filtered, and washed with water. The resulting pigment presscake was dried at 80° C. and ground.

Example 2 4-acetoacetylbenzamide 1 was used in place of 3-acetoacetyl-4-methylbenzamide used in Example 1.
．． The same procedure as in Example 1 was carried out except that 3 parts were used.

Example 3 The same procedure as in Example 1 was carried out except that 1.7 parts of sodium 4-acetoacetylbenzenesulfonate was used in place of 3-acetoacetyl-4-methylbenzamide used in Example 1.

Example 4 The same procedure as in Example 1 was carried out except that 2.0 parts of acetoaceto-p-dimethylaminopropylaminosulfonylanilide was used in place of 3-acetoacetyl-4-methylbenzamide used in Example 1. Ta.

Example 5 The same procedure as in Example 1 was carried out except that 2.0 parts of acetoaceto-p-diethylaminopropylaminocarboanilide was used in place of 3-acetoacetyl-4-methylbenzamide used in Example 1. .

Example 6 The same procedure as in Example 1 was carried out except that 1.9 parts of acetoaceto-p-dimethylaminopropylaminocarboanilide was used in place of 3-acetoacetyl-4-methylbenzamide used in Example 1. Ta.

Example 7 The same procedure as in Example 1 was carried out except that 2.0 parts of 4-acetoacetylbenzenesulfonyl diethylolamide was used in place of 3-acetoacetyl-4-methylbenzamide used in Example 1. .

Example 8 The same procedure as in Example 1 was carried out except that 1.3 parts of acetoacetoorthocarboxyanilide was used in place of 3-acetoacetyl-4-methylbenzamide used in Example 1.

Example 9 Acetoacetyl-4-hydroxy-4 was used in place of 3-acetoacetyl-4-methylbenzamide used in Example 1.
- Example 1 except that 1.4 parts of carboxyanilide was used
I did the same thing.

Example 10 Acetoacetyl-4-carboxy-4 was used in place of 3-acetoacetyl-4-methylbenzamide used in Example 1.
- Example 1 except that 1.4 parts of hydroxyanilide was used
I did the same thing.

Example 11 Example 1 except that 1.9 parts of 4-acetoacetyl-N,N-diethylolbenzamide was used in place of 3-acetoacetyl-4-methylbenzamide used in Example 1.
I did the same thing.

Ten parts of the dry disazo pigment obtained in each example were mixed with 90 parts of an offset ink varnish containing a rosin-modified phenol resin as a binder and dispersed using a three-roll mill to prepare an offset ink. The performance of this offset ink is summarized in Table 1 in comparison with an offset ink (standard ink) prepared using a disazo pigment synthesized without adding general formula (1). In Table 1, L* indicates the transparency of the ink, and the smaller the value, the greater the transparency.The density is the Causar value (reflectance density), and the greater the value, the greater the density.The fluidity is the spread. It is expressed as a 60 second value (mm) using a meter, and the higher the value, the greater the fluidity.

[0022]

[Table 1]

Claims (2)

[Claims] Claim 1: A tetrazotized product of 3,3'-dichlorobenzidine is used as a diazo component, 97.9 to 60 mol% of acetoacetoorthotoluidide, 2 to 40 mol% of acetoacetomethaxylidide and the following general formula (1 ) A disazo pigment comprising 0.1 to 10 mol % of an acetoacetanilide compound represented by the following formula as a mixed coupler component. [Chemical formula 1] [wherein, X is -COOH, -SO3 H, -S
O3 M, -NR1 R2, -CONR1 R2,
-SO2 NR1 R2 , -CONH(CH2)n
NR1 R2 , -SO2 NH(CH2)n N
R1 R2 (However, R1 and R2 are each a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or -C2H
4 represents an OH group, n represents an integer of 1 to 3, and M represents a metal ion. ), Y represents H, OH, CH3, Cl. ] 2. A printing ink composition comprising a disazo pigment according to claim 1 and a printing ink vehicle.