JPH0649386A - Production of dispersion of high pigment concentration - Google Patents

Abstract

PURPOSE:To produce a highly pigment-concentrated dispersion for an offset printing ink improved in flow and the critical temperature of flow. CONSTITUTION:10-40wt.%, based on the resin component, pigment composition comprising 100 pts.wt. organic pigment and 1-15 pts.wt. organic color derivative of the formula: P-[X-R]n (wherein P is a residue of an at least one organic color selected from among an azo dye, a phthalocyanine dye, a quinacridone dye, an anthraquinone dye, a dioxane dye, and a thioindigo dye, X is a bivalent bonding group, R is a 6-21 C saturated or unsaturated aliphatic hydrocarbon group, and n is an integer of 1-4) is added to a rosin-modified phenolic resin and dispersed therein at 40-120 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a dispersion having a high pigment concentration, which is excellent in fluidity of a dispersion, particularly fluidity when heated in a dispersion process.

[0002]

2. Description of the Related Art Generally, in order to achieve a vivid color tone and high tinting strength in various coatings or ink compositions, it is necessary to miniaturize the pigment dispersion vehicle. In this dispersion step, dispersion with a high pigment concentration is generally performed in order to improve production efficiency, and then various vehicles and solvents are mixed to prepare a printing ink or paint.

Generally, the fluidity of a dispersion having a high pigment concentration is temperature-dependent, and the fluidity improves as the temperature rises, so dispersion at high temperature is advantageous from the viewpoint of production efficiency. However, a dispersion having a high pigment concentration has a critical temperature, and when it exceeds a certain temperature, the dispersion loses fluidity, and even if it is heated, the fluidity does not increase, and on the contrary, a phenomenon occurs. This critical temperature is around 50 to 90 ° C., which is the same as the dispersion temperature during the dispersion process. Therefore, the dispersion of high pigment concentration above the critical temperature is not only a poor dispersion but also the removal from the disperser,
Transport becomes difficult, and a dispersion having a high pigment concentration cannot be obtained, which hinders improvement in production efficiency. This phenomenon remarkably appears in a dispersion of offset ink having a high pigment concentration. Further, if the pigment dispersion prepared as a product also has poor fluidity, it may cause deterioration in gloss and poor printability.

In order to solve the various problems described above, Japanese Patent Publication No. 58-28303, Japanese Patent Publication No. 59-40172,
JP-A-58-167654, JP-A-59-168070, JP-B-63-2
No. 0869, Japanese Examined Patent Publication No. 58-28303, Japanese Examined Patent Publication No. 1-34268 and Japanese Examined Patent Publication No. 1-34269 have been improved with compounds in which an acidic group or a basic group is introduced into a pigment skeleton. Has little effect because the organic solvent content is low. Further, JP-A-63-363 describes a method of mixing a compound obtained by introducing a substituent of a polymer resin into a side chain, but the effect of improving fluidity in a high pigment concentration dispersion is insufficient. In addition, there is no effect of increasing the critical temperature.

[0005]

DISCLOSURE OF THE INVENTION The present invention has improved the above-mentioned various drawbacks, and produced a high pigment concentration dispersion for offset printing inks having an improved fluidity of a high pigment concentration dispersion and an increased critical temperature of fluidity. It provides a method.

[0006]

The present invention provides an organic pigment 10
A pigment composition comprising 0 part by weight and 1 to 15 parts by weight of an organic dye derivative represented by the following general formula (1) is blended in an amount of 10 to 40% by weight with respect to a rosin-modified phenol resin.
The present invention relates to a method for producing a high pigment concentration dispersion for printing ink, which comprises dispersing at 0 to 120 ° C. Formula (1) P- [X-R] n (In the formula, P is at least one organic dye residue selected from azo type, phthalocyanine type, quinacridone type, anthraquinone type, dioxazine type and thioindigo type, and X is divalent. R is a saturated or unsaturated aliphatic hydrocarbon group having 6 to 21 carbon atoms, and n is an integer of 1 to 4, respectively.)

The organic pigment represented by the present invention and the dye derivative P represented by the formula (1) are azo type (soluble azo pigment, insoluble azo pigment), phthalocyanine type (unsubstituted or halogen substituted). ), Quinacridone-based (unsubstituted, halogen-substituted, alkyl-substituted, quinacridonequinone solid solution), anthraquinone-based (anthrapyrimidine-based,
Ansanthuron type, flavanthrone type, pyranthrone type, perylene type, indanthrene type), dioxazine type and thioindigo type.

X of the dye derivative represented by the formula (1) of the present invention is a divalent linking group, and is --CH ₂ NH-- or --SO ₂ NH.
_{-, - CH 2 NHCO -,} - CH 2 NHCOCH 2 NH
-, -CONH- and the like are preferable.

R of the organic dye derivative represented by the formula (1) of the present invention is a saturated or unsaturated aliphatic hydrocarbon group having 6 to 21 carbon atoms, such as hexyl group, heptyl group, octyl group,
Nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group (stearyl group), nonadecyl group, eicosyl group, heneicosyl group, dodecynyl group, octadecynyl group (oleyl Group),
It is at least one selected from an octadecidienyl group (linole group), an octadecitrienyl group (linolene group), and the like, and a saturated or unsaturated aliphatic hydrocarbon group having 8 to 18 carbon atoms is preferable.

The method for producing the organic dye derivative represented by the formula (1) of the present invention can be applied to an organic dye such as --CH ₂ C by a conventional method.
_{l, -SO 2 Cl, -CH 2} NHCOCH 2 Cl, -C
After introducing a substituent such as OCl, it is general to react with a primary amine having a saturated or unsaturated aliphatic hydrocarbon group having 6 to 21 carbon atoms. Industrially advantageous is a method of reacting a coupler component or a diazo component with an aliphatic hydrocarbon group, followed by coupling.

The addition amount of the organic dye derivative is 10
1 to 15 parts by weight is preferable with respect to 0 parts by weight. If it is less than 1 part by weight, the effect of improving the fluidity is small,
Even if it is used in excess of parts by weight, the effect of the amount used cannot be obtained and the coloring power also decreases, which is not preferable.

As a method for preparing the pigment composition, the desired effect can be obtained by simply mixing the pigment powder and the powder of the organic dye derivative of the present invention. However, kneader, roll mill, attritor, super mill, various types Mechanically mixing with a pulverizer or the like, or adding a solution containing the organic dye derivative of the present invention to a suspension system of water or an organic solvent for the pigment to deposit the organic dye derivative on the surface of the pigment, an organic solvent, or sulfuric acid. Even better results can be obtained by performing a close mixing method such as co-dissolving the pigment and the organic dye derivative in a solvent having a strong dissolving power such as and coprecipitating with a poor solvent such as water. In the case of an azo type, a raw material in which a substituent of an organic dye derivative is introduced into a coupler component or a diazo component in advance and an unsubstituted raw material are mixed and coupled, and a mixture of a direct organic dye derivative and a pigment is directly mixed. A good result can be obtained by the method of adjusting.

The rosin-modified phenol resin of the present invention comprises phenols such as phenol, p-tertiarybutylphenol, p-octylphenol, p-nonylphenol, cresol and bisphenol A, and aldehydes such as formaldehyde, paraformaldehyde and acetaldehyde. , A phenol resin such as a resol type phenol resin obtained by condensation in the presence of a basic catalyst or a novolak type phenol resin obtained by condensation in the presence of an acidic catalyst, wood rosin, gum rosin, tall oil rosin, polymerized rosin, It is a resin obtained by reacting with a rosin such as a leveled rosin. In addition, a polyhydric alcohol such as glycerin, pentaerythritol, ethylene glycol, propylene glycol, and rosin are partially esterified in advance, and then a resin reacted with a phenol resin, and a phenol resin and a polyhydric alcohol are further reacted. Resins that have been reacted and then reacted with rosins can also be used. Further, in the present invention, as the rosin, a modified rosin obtained by modifying a part of the rosin with an unsaturated carboxylic acid such as phthalic anhydride, maleic anhydride or trimellitic acid can be used.

Vehicles for offset printing inks include 20 to 50% by weight of a rosin-modified phenolic resin or a drying oil-modified resin thereof, 0 to 30% by weight of a vegetable oil such as linseed oil, tung oil or soybean oil, and n-paraffin. 10 to 60% by weight of a solvent such as isoparaffin, aromatech, naphthene and α-olefin. In the present invention, an offset printing ink is prepared by dispersing a pigment composition in a rosin-modified phenolic resin with a high pigment concentration and then mixing various vehicles and a solvent.

In the method for producing a pigment dispersion according to the present invention, the pigment composition is added to the rosin-modified phenol resin in an amount of 10 to 4
Formulated in a high concentration of 0% by weight, preferably 15-35% by weight, at a temperature of 40-120 ° C, preferably 60-100 ° C.
Disperse with. Even if the dispersion temperature is lower than 40 ° C. or higher than 120 ° C., the fluidity of the high pigment concentration dispersion is lowered, which is not preferable. By using a dissolver, a high speed mixer, a homomixer, a sand mill, a roll mill, an attritor, a kneader or the like as a disperser, the pigment can be well dispersed. In the dispersion method, the powdery pigment composition is used for dispersion, but the drying step may be omitted and the pastey pigment composition may be directly dispersed by flushing using a flasher or the like.

The mechanism of action of the pigment composition of the present invention is as follows:
Since the organic dye residue of the organic dye derivative is adsorbed to the pigment and the saturated or unsaturated aliphatic hydrocarbon group is oriented in the surface layer, the affinity with the resin component contained in the vehicle for offset printing ink is increased, It is estimated that the fluidity of the high pigment concentration dispersion is improved. In addition, since the aliphatic hydrocarbon group is bonded via the organic dye residue, it has an action of preventing a decrease in the resin adsorption of the pigment caused by the transfer of the aliphatic hydrocarbon group into the vehicle by heat, and particularly, It is estimated that the fluidity in the heated state during the dispersion process is improved.

[0017]

EXAMPLES The present invention will be described below with reference to examples. In the examples, “part” means “part by weight” and “%” means “% by weight”. Production Example 1 35% hydrochloric acid (38 parts) and 3,3′-dichlorobenzidine hydrochloride (41 parts) were added to water (500 parts) to dissolve them, and ice (460 parts) was added and the mixture was cooled to 0 ° C. . Water (70
Part), sodium nitrite (19.5 parts) is dissolved, and this aqueous solution is added to obtain a diazo component. On the other hand, N-hexyl-4- (acetoacetylamino) benzenesulfoamide (86 parts) was dissolved in methanol (1000 parts),
Sodium acetate (60 parts) dissolved in water (300 parts)
Is added to form a coupler component. Then, the previously prepared diazo component was added over 1 hour, and the
Stir for 0 minutes to complete the coupling reaction. Water (1
(000 parts), followed by filtration, washing with water and drying to obtain 118 parts of the organic dye derivative [A].

Production Example 2 Sodium hydroxide (4 parts) and 2-amino-5-methylbenzenesulfonic acid (18.5 parts) were added to water (400 parts) and dissolved, and 35% hydrochloric acid (25 parts), Add 35% calcium chloride (58 parts) and ice (200 parts) and cool to 0 ° C. Sodium nitrite (7 parts) is dissolved in water (25 parts), and this aqueous solution is added to obtain a diazo component. On the other hand, 3-hydroxy-N-octyl-2-naphthamide (30 parts) was dissolved in ethanol (700 parts), and water (3 parts) was added.
An aqueous solution of sodium hydroxide (10 parts) dissolved in (00 parts) is added to obtain a coupler component. Then, the diazo component prepared above is added over 30 minutes, and the addition of 30
Stir for minutes. Water (1000 parts) was added and the mixture was heated to 70 ° C., filtered, washed with water and dried to give an organic dye derivative [B] 45
I got a copy.

Production Example 3 Tri (chloromethyl) copper phthalocyanine (72 parts), dodecylamine (55 parts) and pyridine (24 parts) were added to dioxane (500 parts), and the mixture was stirred at 90 ° C. for 3 hours. After adding water (1000 parts), filtration, washing with water and drying were carried out to obtain 114 parts of the organic dye derivative [C].

Production Example 4 100% sulfuric acid (500 parts) was added to copper phthalocyanine [C.
I. Pigment Blue 15: 3] (58 copies)
And N- (hydroxymethyl) stearamide (63 parts)
And stirred at 100 ° C. for 2 hours. The mixture was cooled to room temperature, poured into a mixture of water (1000 parts) and ice (1000 parts), filtered, washed with water, further washed with methanol (1000 parts) and dried to obtain 85 parts of an organic dye derivative [D]. .

Preparation Example 5 100% sulfuric acid (500 parts) was added to copper phthalocyanine [C.
I. Pigment Blue 15: 3] (58
Part), paraformaldehyde (9 parts) and chloroacetamide (28 parts) are added, and the mixture is stirred at 100 ° C. for 2 hours. After cooling to room temperature, water (1000 parts) and ice (100 parts)
0 part) mixture, filtered and washed with water. The obtained water paste and stearylamine (81 parts) are added to dioxane (500 parts), and the mixture is stirred at 95 ° C for 3 hours. The mixture was cooled to 50 ° C., a 5% hydrochloric acid aqueous solution (1000 parts) was added, and the mixture was filtered, washed with water and dried to obtain 90 parts of an organic dye derivative [E].

Production Example 6 Chlorosulfonic acid (500 parts) was mixed with copper phthalocyanine [C. I. Pigment Blue 15: 3] (58
Part) and stirred at 100 ° C. for 2 hours. Cool to room temperature, pour into a mixture of water (1000 parts) and ice (1000 parts), filter and wash with water. Add the resulting water paste and stearylamine (54 parts) to methanol (500 parts),
Stir at 65 ° C. for 3 hours. The mixture was cooled to room temperature, a 5% hydrochloric acid aqueous solution (1000 parts) was added, and the mixture was filtered, washed with water, and dried to obtain 91 parts of an organic dye derivative [F].

Production Example 7 An organic dye derivative [N] was obtained by replacing stearylamine in Production Example 5 with ethylamine and performing the same reaction.

[0024]

[Table 1]

Example 1 Insoluble azo (CI Pigment Yellow)
12) Mix 100 parts with 5 parts of the organic dye derivative [A],
A pigment composition was obtained. A vehicle for offset ink consisting of 10 parts of a pigment composition, 60 parts of a rosin-modified phenolic resin gel varnish and No. 1 solvent (ink solvent manufactured by Nippon Oil Co., Ltd.) was used at 10 μm while keeping a sand mill at 80 ° C.
The base ink for offset ink was prepared by dispersing until it became m or less. As rosin modified phenolic resin,
To 50 parts of Tamanol 361 (manufactured by Arakawa Chemical Co., Ltd.), 20 parts of linseed oil was added, and No. 5 solvent (manufactured by Nippon Oil Co., Ltd.) was added and heated and melted at 200 ° C. to be used. Subsequently, 2 parts of aluminum octylate was added to 98 parts of this varnish to form a gel varnish. The obtained base ink for offset ink showed excellent fluidity at 80 ° C.

Comparative Example 1 Azo Yellow (C.I. Pigment Yellow)
12) Flowability at 80 ° C. of the base ink for offset ink prepared by adjusting 15 parts by the same operation as in Example 1 was poor.

Example 2 Water (22000 parts), 35% hydrochloric acid (730 parts) and 3,
3'-Dichlorobenzidine hydrochloride (1047 parts) is added and dissolved, ice (16000 parts) is added and the mixture is cooled to 0 ° C. Sodium nitrite (577 parts) in water (1800 parts)
Part) and dissolve this solution to obtain the diazo component. On the other hand, to a solution prepared by adding acetoacetylanilide (1330 parts) and sodium hydroxide (660 parts) to water (15500 parts) and dissolving 90% acetic acid (1180 parts) in water (7700 parts) was added 20 parts. After 30 minutes of addition at 0 ° C., a solution of N-hexyl-4- (acetoacetylamino) benzenesulfoamide (86 parts) in methanol (1000 parts) is further added to form a coupler component. Next, 2 parts of the diazo component prepared previously are added.
Add at 0 ° C. over 1 hour and stir for an additional 30 minutes to complete the coupling reaction. After adding water (28,000 parts), it was filtered, washed with water and dried to obtain 2430 parts of an insoluble azo pigment composition containing the organic dye derivative [A].
15 parts of the pigment composition and 35 parts of the rosin-modified phenolic resin vehicle used in Example 1 were dispersed while maintaining the sand mill at 80 ° C. to 10 μm or less to prepare a base ink for offset ink. The obtained base ink for offset ink showed excellent fluidity at 80 ° C.

Example 3 Soluble Azo (CI Pigment Red 57: 1)
5 parts of the organic dye derivative [B] was mixed with 100 parts to obtain a pigment composition. 15 parts of the pigment composition and 35 parts of the rosin-modified phenolic resin vehicle used in Example 1 were dispersed until the temperature became 10 μm or less while maintaining the sand mill at 80 ° C.,
The base ink for offset ink was adjusted. The obtained base ink for offset ink showed excellent fluidity at 80 ° C.

Comparative Example 2 Soluble Azo (CI Pigment Red 57: 1)
The base ink for offset ink prepared by adjusting 15 parts by the same operation as in Example 1 had poor fluidity at 80 ° C.

Example 4 Copper Phthalocyanine Blue (CI Pigment B
lue 15: 3) 100 parts of organic dye derivative [C] 5
The parts were mixed to obtain a pigment composition. 15 parts of the pigment composition and 35 parts of a rosin-modified phenolic resin vehicle are dispersed while keeping the sand mill at 80 ° C. to 10 μm or less,
The base ink for offset ink was adjusted. The obtained base ink for offset ink showed excellent fluidity at 80 ° C.

Comparative Example 3 Copper Phthalocyanine Blue (CI Pigment B
flu 15: 3) 15 parts of the base ink for offset ink prepared by the same operation as in Example 1 had poor fluidity at 80 ° C.

Comparative Example 4 A pigment composition was obtained by the same procedure except that the organic dye derivative of Example 4 was changed to [N]. The base ink for offset ink prepared by adjusting each pigment composition in the same manner as in Example 1 had poor fluidity at 80 ° C.

Examples 5 to 7 The pigment composition conductors of Example 4 were respectively subjected to [D], [E],
A similar operation was carried out except that [F] was used to obtain a pigment composition. The base inks for offset inks prepared by adjusting each pigment composition in the same manner as in Example 1 all showed excellent fluidity at 80 ° C.

Examples 8 to 11 15 parts of the pigment composition of Example 4 and 35 parts of a rosin-modified phenolic resin vehicle were placed in a sand mill at 40 ° C. and 6 parts, respectively.
While maintaining at 0 ° C, 100 ° C and 120 ° C, dispersion was performed until the particle size became 10 µm or less, and a base ink for offset ink was prepared. The obtained base inks for offset ink all showed excellent fluidity at each dispersion temperature.

Comparative Examples 5-8 15 parts of the pigment composition of Comparative Example 3 and 35 parts of a rosin modified phenolic resin vehicle were placed in a sand mill at 40 ° C. and 6 parts, respectively.
While maintaining at 0 ° C, 100 ° C and 120 ° C, dispersion was performed until the particle size became 10 µm or less, and a base ink for offset ink was prepared. Each of the obtained base inks for offset inks was inferior in fluidity at each dispersion temperature. showed that.

Table 2 shows the fluidity of the pigment composition and the base ink for offset ink according to the present invention. For the evaluation of fluidity, a glass plate rheometer of JIS K5702 was used to measure the length of ink 1 cc flowing at 80 ° C. for 10 minutes. The larger the number, the better the fluidity.

From the results of Example 4 and Examples 8 to 11, the fluidity at 100 ° C. was the most excellent, and the fluidity was lowered when dispersed at a temperature lower than 100 ° C. or higher than 100 ° C. It exhibits excellent fluidity at the dispersion temperature. On the other hand, in Comparative Example 3 and Comparative Examples 5 to 8, the critical temperature is 60 ° C., and it is shown that the fluidity deteriorates when dispersed at a temperature higher than 60 ° C.

[0038]

[Table 2]

[0039]

INDUSTRIAL APPLICABILITY The present invention eliminates the disadvantage that the fluidity is remarkably lowered especially at high temperature when a pigment having a high concentration is mixed and dispersed in a rosin-modified phenol resin, and the organic dye of the general formula (1) is eliminated. By adding the derivative, the fluidity of the pigment dispersion can be lowered and the critical temperature of the flow can be increased, so that the high-concentration pigment dispersion can be economically produced.

Claims (1)

[Claims] 1. A pigment composition comprising 100 parts by weight of an organic pigment and 1 to 15 parts by weight of an organic dye derivative represented by the following general formula (1) is blended in an amount of 10 to 40% by weight based on a rosin-modified phenol resin. And then dispersing at 40 to 120 ° C. for producing a high pigment concentration dispersion for printing ink. Formula (1) P- [X-R] n (In the formula, P is at least one organic dye residue selected from azo type, phthalocyanine type, quinacridone type, anthraquinone type, dioxazine type and thioindigo type, and X is divalent. R is a saturated or unsaturated aliphatic hydrocarbon group having 6 to 21 carbon atoms, and n is an integer of 1 to 4, respectively.)