JPH09202861A - Pigment composition for coloration - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition comprising a pigment and a specific primary long chain alkyl carboxylic acid in a specific ratio, excellent in pigment dispersibility, coatability, gloss, hue clarity and colorability, and useful for coloring inks, coating materials developing agents such as toners, etc. SOLUTION: This pigment composition comprises (A) 0.01-90wt.% of a pigment, (B) 1-80wt.% of a compound of the formula [R is H, CH3 ; (n) is 20-50], and, if necessary, (C) 1-90wt.% of a thermoplastic resin or wax having a Vicat softening temperature of <=300 deg.C on the basis of JIS K-7206. The composition is obtained e.g. by mixing the dry powder or aqueous wet cake of the component A, the component B and water, if necessary, the component C, a surfactant and other additives by the use of a Henschel mixer, etc., charging the mixture into a flasher, etc., and subsequently heating and kneading the charged mixture to remove residual water.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a coloring pigment composition useful as a coloring material for printing inks, paints, thermoplastic resins and the like.

[0002]

2. Description of the Related Art Conventionally, a dispersant or a flushing agent for dispersing a pigment in a paint vehicle or a printing ink varnish or for flushing an aqueous wet cake into an oil vehicle or an oil varnish in the production of paints or printing inks. As, for example, rosin soap, rosin-modified resin,
Plasticizers, surfactants and phospholipids such as lecithin have been used. However, when the above-mentioned dispersant or flushing agent is used in paints or printing inks, the water resistance of the coating film, the heat resistance, weather resistance, etc. may be reduced, bleeding, etc. may cause a decrease in physical properties, lecithin, etc. When natural phospholipids are used, there are problems such as deterioration and spoilage due to oxidation and rancidity, and the present situation is that sufficient effects have not been obtained.

Further, the coloring material of the thermoplastic resin is a powdery dry color in which a pigment and a dispersant are mixed, a liquid color or a paste color in which a pigment is dispersed in a liquid dispersant at room temperature, and a solid at room temperature. There is a pellet-shaped, flake-shaped or bead-shaped master batch in which a pigment is dispersed in a resin of, for example, as a dispersant, stearic acid, zinc stearate, magnesium stearate, aluminum stearate, calcium stearate, ethylene. One or more kinds of bisamide, polyethylene wax, polypropylene wax, and derivatives thereof, for example, waxes and resins made of acid-modified or hydroxyl-modified compounds have been generally used.

However, for example, when these dispersants are used as a coloring material for a thermoplastic resin, a high degree of pigment dispersion such as high-speed spinning of the colored thermoplastic resin with a diameter of a few tenths of a micron or a film formation is obtained. When the above is required, yarn breakage at the time of spinning due to poor pigment dispersion, clogging of the filter of the melt spinning machine, and defective molding of the film may occur. In order to solve these problems, efforts have been made to improve the processing method of the coloring material of the thermoplastic resin and to improve the pigment dispersibility by a powerful kneader, but all of them exhibit sufficient pigment dispersibility. Was not.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a coloring pigment composition which is improved in the above various drawbacks and is excellent in hue, tinting strength and dispersibility.

[0006]

That is, the present invention is characterized by containing 0.01 to 90% by weight of a pigment (a) and 1 to 80% by weight of a compound (b) represented by the general formula (I). The present invention provides a coloring pigment composition. (However, n is an integer of 20 or more and 50 or less, and R is H or CH _3. ) Further, the present invention provides JIS K-7.
The above-mentioned pigment composition for coloring is characterized by containing 1 to 90% by weight of a thermoplastic resin or wax (c) having a Vicat softening temperature of 300 ° C. or lower defined by 206.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the pigment (a) may be either an organic pigment or an inorganic pigment, and includes an extender pigment and a metal pigment. Examples of organic pigments include natural dye pigments such as mudder lake, logwood lake, and cochineal lake, nitroso pigments such as naphthol green B and naphthol green Y, nitro pigments such as naphthol S and resole fast yellow 2G, and permanent red 4R. , Insoluble azo pigments such as Brilliant Fast Scarlet, Hansa Yellow, Benzidine Yellow,
Insoluble azo pigments such as resole red, lake red C, lake red D, soluble azo pigments such as brilliant carmine 6B, permanent red F5R, pigment scarlet 3B, bordeaux 10B, phthalocyanine blue, phthalocyanine green, sky blue and the like. Basic dye pigments such as phthalocyanine pigments, rhodamine lake, malachite green lake, methyl violet lake, acid dye pigments such as peacock blue lake, eosin lake, quinoline yellow lake, indanthrene blue, thioindigo maroon, etc. Dye pigments, mordant pigments such as alizarin lake, quinacridone red, quinacridone violet, perylene red, perylene scarlet, isoindolinone yellow, dioxazine violet Aniline black, organic fluorescent pigments.

Examples of the inorganic pigments include natural products such as clay, barite, mica and ocher, chromate salts such as yellow lead, zinc yellow and barium yellow, ferrocyanide compounds such as dark blue, silver vermilion, etc.
Cadmium yellow, zinc sulfide, antimony white, sulfides such as cadmium red, sulfates such as barium sulfate, lead sulfate, strontium sulfate, zinc oxide, titanium white, Benkara, iron black, oxides such as chromium oxide, aluminum hydroxide Such as hydroxide, calcium silicate, silicate such as Gunjou,
Examples thereof include carbonates such as calcium carbonate and magnesium carbonate, carbon black, pine smoke, bone black, carbon such as graphite, aluminum powder, bronze powder, metal powder such as zinc dust, arsenate and phosphate. When the content of the pigment (a) in the coloring pigment composition is less than 0.01% by weight, the coloring power is weak, and when it exceeds 90% by weight, the coloring pigment composition tends to be brittle and difficult to handle.

In the present invention, the compound (b) represented by the general formula (I) is a long-chain alkyl primary carboxylic acid having a methylene chain number n of 20 or more. Methylene chain number n is 20
When the amount is less than the range, preferable dispersibility cannot be obtained and bleeding may occur when a high degree of pigment dispersion is required as in a commonly used dispersant such as stearic acid. Those having a methylene chain number of more than 50 are difficult to synthesize at present and are not realistic. As the compound (b) represented by the general formula (I), commercially available products include “Unicid” manufactured by Petrolite. When the content of the compound (b) in the coloring pigment composition is less than 1% by weight, the effect on the dispersibility and the coloring power is weak, and when it exceeds 80% by weight, the resin to be colored tends to aggregate and causes a flow mark. It is easy to become.

A thermoplastic resin or wax (c) having a Vicat softening temperature of 300 ° C. or lower defined in JIS K-7206 increases compatibility with a resin to be colored,
And / or to enhance mechanical properties such as tensile strength and flexural strength, and / or to impart flexibility to the pigment composition for coloring. When the softening temperature of the thermoplastic resin or the wax (c) exceeds 300 ° C., the viscosity of the coloring pigment composition is too high, and therefore, when used for coloring a printing ink or a paint, coloring failure occurs, or the thermoplastic resin When used for coloring, the color unevenness or flow mark may occur. Further, when it is used for coloring printing ink, paint, thermoplastic resin, etc., it may adversely affect bleeding, weather resistance or heat resistance.

The thermoplastic resin or wax (c) is not particularly limited as long as it is compatible with the resin to be colored, and includes those modified with a functional group or crosslinked. The thermoplastic resin or wax (c) is preferably contained in the coloring pigment composition in an amount of 1 to 90% by weight.
If less than 1% by weight, the effect is poor even if compounded, 90% by weight
If it exceeds, the other components will be relatively small and the composition will not be balanced.

In the production of the coloring pigment composition of the present invention, a dry powder pigment may be used, or an aqueous wet cake of pigment (also called wet cake or filter cake) may be used. For example, when a dry powder pigment is used, the two components of the powder pigment (a) and the compound (b) are mixed with a Henschel mixer or the like by adding a surfactant and other additives in advance, if necessary. , A roll mill, an extruder, or by kneading and dispersing, or by adding three components of powder pigment (a), compound (b), and water in advance, if necessary, a surfactant and other additives, and using a Henschel mixer or Mix with a disper, etc., flasher, kneader, extruder, roll mill, ball mill, steel mill,
A sand mill, an attritor, a high-speed mixer, a homomixer, etc. are charged, heated and kneaded, and then the remaining water is evaporated and dried under normal pressure or reduced pressure to be removed, whereby the coloring pigment composition of the present invention is obtained. can get. The latter method is applicable not only to dry powder pigments but also to aqueous wet cakes. The thermoplastic resin or wax (c) may be added / mixed / dispersed after mixing / dispersing (a) (b), or may be mixed / dispersed simultaneously with (a) (b).

The coloring pigment composition of the present invention can be used for coloring almost all polyolefin resins, and contains a reinforcing material such as an inorganic filler or glass fiber or organic fiber for the purpose of improving physical properties. May be. For example, it is possible to achieve uniform coloring without color unevenness without adversely affecting mechanical properties such as strength and heat resistance, which could not be achieved by conventional coloring using a masterbatch.

In addition to the polyolefin resin, the coloring pigment composition of the present invention contains polystyrene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-EPDM-styrene (AES). ) Resin, acrylic resin, polyamide, polycarbonate, polyacetal, polyurethane, alkyd resin, vinyl resin, polyester, amino resin, polyether, polyarylate, epoxy resin, polysulfone, polyimide, phenol resin, etc.

Further, the pigment composition for coloring of the present invention can be used for coloring paints, printing inks, lubricants, hot melt resins, thermal inks, adhesives and the like.
The coloring pigment composition of the present invention is extremely effective in improving the dispersibility and coloring power of the pigment, but these improvements are due to the affinity for the pigment due to the carboxyl group in the composition, and It is speculated that the compound (b) is adsorbed on the surface of the pigment due to the formation of a polar bond with the pigment, which serves as a protective layer and contributes to the prevention of dispersion and aggregation of the pigment.

[0016]

The present invention will be specifically described below with reference to examples.
In the examples, “part” means “part by weight” and “%” means “% by weight”.
The softening temperature is measured according to JIS K-7206. The compound (b) used in the examples is shown in Table 1.

[Table 1]

(Example 1) Phthalocyanine blue "Rionol Bull-FG7330" (manufactured by Toyo Ink Manufacturing Co., Ltd.) 40 parts Compound 1 10 parts Polypropylene "Mitsui Noblen JH-G" (manufactured by Mitsui Toatsu Kagaku, softening temperature: 163 ° C.) 50 parts The above three components were kneaded with a kneader, and the screw diameter was 65 m.
m was extruded into pellets to obtain a masterbatch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow.

Polypropylene "Mitsui Noblen JH-
After mixing 2 parts of the obtained masterbatch with 100 parts of "G", a vertical test spinning machine (spinning tester manufactured by Fuji Filter Co., Ltd.) was used to perform spinning at 230 ° C. under the hopper, at a kneading portion, and at a die portion of 230 ° C. It was stretched 3 times to obtain a polypropylene fiber of 5 denier. Good dispersibility was exhibited without any problem in spinnability, clogging and stretching. Next, in order to compare the clogging property of the undispersed pigment, 23.3 parts of the obtained masterbatch was used as polypropylene "Mitsui Noblen JH-".
G ”was mixed with 100 parts, and 3 kg of the mixture was extruded by a single-screw extruder with a screw diameter of 30 mm equipped with a 500-mesh wire net at the tip, the pressure rise value at the tip was measured, and clogging of undispersed pigment was observed. Was evaluated respectively. Table 2 shows the results
Shown in

Further, in order to compare the dispersion coloring properties of pigments, 2 parts of the obtained masterbatch was used as 5 parts of titanium oxide masterbatch "TET12534W-T" (manufactured by Toyo Ink Mfg. Co.) and polypropylene "Mitsui Hypol J800".
(Mitsui Petrochemical Co., Ltd., softening temperature: 166 ° C.) 100
The compounded material was kneaded with a two-roll mill and molded into a 2 mm thick plate by a cooling press. Next, color difference meter KUR
The reflectance at a wavelength of 640 nm was measured using ABO Color-7E (manufactured by KURABO), and the Kubelka-Munk function value (k / s value) at the reflectance was determined and used as the coloring intensity. Table 2 shows the results. Furthermore, softening temperature: 140 ° C polyethylene "Hi-Zex 2100
100 parts of "J" (manufactured by Mitsui Petrochemical Industry Co., Ltd.) was mixed with 3 parts of the obtained masterbatch, and the back pressure was 0K using an injection molding machine.
Plates were molded at g / cm ² . Table 3 shows the results of evaluation of the mechanical properties of the obtained molded product, surface color unevenness and pigment dispersibility, and the masterbatch productivity.

Example 2 Instead of Compound 1, Compound 4 was used.
A masterbatch was obtained in the same manner as in Example 1 except that was used. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. When the obtained masterbatch was used to carry out spinning in the same manner as in Example 1, the spinnability, the clogging property, and the drawability exhibited good dispersibility without any problems. Further, various evaluations were made in the same manner as in Example 1. The results are shown in Tables 2 and 3.

(Example 3) Titanium oxide "Ty Pure R-101" (manufactured by EI DuPont) 20 parts Rouge "Toda Color 180ED" (manufactured by Toda Kogyo Co., Ltd.) 60 parts Compound 2 20 parts 3 parts of the above 3 components The mixture was kneaded with the present roll mill and pelletized with an extruder having a screw diameter of 65 mm to obtain a masterbatch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Also, to 100 parts of a polyethylene composition containing 20% talc,
3 parts of the obtained masterbatch were mixed, a plate was molded with an injection molding machine at a back pressure of 0 Kg / cm ² , and various evaluations were performed in the same manner as in Example 1. The results are shown in Table 3.

(Example 4) Phthalocyanine green "Rionol Green Y-102" (manufactured by Toyo Ink Manufacturing Co., Ltd.) 1 part Compound 3 5 parts Polyethylene "Mirason 68" (manufactured by Mitsui Petrochemical Co., Ltd., softening temperature: 84 ° C.) 94 parts The above three components were kneaded with a three-roll mill and pelletized with an extruder having a screw diameter of 65 mm to obtain a masterbatch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. In addition, 100 parts of polyethylene "Mirason 11P" (manufactured by Mitsui Petrochemical Industry Co., Ltd.) was mixed with 5 parts of the obtained masterbatch, and a plate was molded with an injection molding machine at a back pressure of 0 kg / cm ² , and Various evaluations were made in the same manner as in 1. The results are shown in Table 3.

Example 5 Condensed Azo Yellow “Chromophtal Yellow GR” (manufactured by Ciba Geigy) 35 parts Compound 4 60 parts Polypropylene “Mitsui Hypol J900P” (manufactured by Mitsui Chemicals, softening temperature: 165 ° C.) 5 parts above The three components were kneaded with a three-roll mill and pelletized with an extruder having a screw diameter of 65 mm to obtain a masterbatch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. In addition, 100 parts of polypropylene "Mitsui High Pole J800" (manufactured by Mitsui Petrochemical Industry Co., Ltd.) was mixed with 3 parts of the obtained masterbatch, and a plate was molded with an injection molding machine at a back pressure of 0 Kg / cm ² to carry out. Various evaluations were made in the same manner as in Example 1. The results are shown in Table 3.

(Example 6) Phthalocyanine green "Lionol green 2Y-301" (manufactured by Toyo Ink Mfg. Co.) 0.01 part Compound 5 5.99 parts Polyethylene "Petrosene 356" (manufactured by Tosoh Corp., softening temperature: 74.degree. C.) ) 94 parts The above three components were kneaded with a three-roll mill and pelletized with an extruder having a screw diameter of 65 mm to obtain a masterbatch. At this time, a master batch could be obtained smoothly without breaking strands or pulsating flow. Further, 10 parts of the obtained masterbatch was mixed with 100 parts of polypropylene resin "Mitsui High Pol J740" (manufactured by Mitsui Petrochemical Industry Co., Ltd.), and a back pressure of 0 Kg / cm was obtained with an injection molding machine.
^The plate was molded in ² and various evaluations were performed in the same manner as in Example 1. The results are shown in Table 3.

Comparative Example 1 A masterbatch was obtained in the same manner as in Example 1 except that stearic acid was used instead of compound 1. At this time, a masterbatch could be obtained smoothly without causing strand breakage or pulsating flow, but when the obtained masterbatch was spun in the same manner as in Example 1, yarn breakage due to clogging occurred. Occurred. Also, a plate was molded in the same manner as in Example 1 and various evaluations were performed. The results are shown in Tables 2 and 3.

(Comparative Example 2) A masterbatch was obtained in the same manner as in Example 3 except that triacontane was used instead of the compound 2. At this time, it was possible to obtain a masterbatch smoothly without causing strand breaks or pulsating flow,
When the obtained masterbatch was used for spinning in the same manner as in Example 1, yarn breakage due to clogging occurred. Also,
A plate was molded in the same manner as in Example 1 and various evaluations were performed. The results are shown in Table 3.

(Comparative Example 3) A masterbatch was obtained in the same manner as in Example 4 except that ethylene-acrylic acid copolymer wax "AC-580" (manufactured by Allied Chemical Co.) was used in place of Compound 3. . At this time, a masterbatch could be satisfactorily obtained without causing strand breakage or pulsating flow, and the obtained masterbatch was used in Example 1.
When spinning was performed in the same manner as above, yarn breakage due to clogging occurred. Also, a plate was molded in the same manner as in Example 1 and various evaluations were performed. The results are shown in Table 3.

Comparative Example 4 A masterbatch was obtained in the same manner as in Example 5 except that pentacontane was used instead of compound 4. At this time, it was possible to obtain a masterbatch smoothly without causing strand breaks or pulsating flow,
When the obtained masterbatch was used for spinning in the same manner as in Example 1, yarn breakage due to clogging occurred. Also, a plate was molded in the same manner as in Example 1 and various evaluations were performed. The results are shown in Table 3.

Comparative Example 5 A masterbatch was obtained in the same manner as in Example 6 except that dotecanoic acid was used instead of compound 5. At this time, a masterbatch could be obtained smoothly without causing strand breakage or pulsating flow, but when the obtained masterbatch was spun in the same manner as in Example 1, yarn breakage due to clogging occurred. Occurred. Also,
A plate was molded in the same manner as in Example 1 and various evaluations were performed. The results are shown in Table 3.

(Comparative Example 6) Condensed Azo Yellow "Chromophtal Yellow GR" (manufactured by Ciba Geigy) 35 parts Polypropylene "Mitsui Hypol J900P" (manufactured by Mitsui Chemicals, softening temperature: 165 ° C) 65 parts 65 parts of the above 2 components The mixture was kneaded with the present roll mill and pelletized with an extruder having a screw diameter of 65 mm to obtain a masterbatch. When the obtained masterbatch was used for spinning in the same manner as in Example 1, yarn breakage due to clogging occurred. In addition, polypropylene "Mitsui high pole J80
0 "(manufactured by Mitsui Petrochemical Industry Co., Ltd.) was mixed with 3 parts of the obtained masterbatch, and the back pressure was 0K using an injection molding machine.
The plate was molded at g / cm ² and various evaluations were performed. The results are shown in Table 3.

[0031]

[Table 2]

[0032]

[Table 3]

* 1 Retention rate of mechanical properties of resin colored by masterbatch with respect to mechanical properties of uncolored resin (100%). ○: 96% or more △: 90 to 96% ×: 90% or less * 2 The color unevenness on the surface of the molded product was visually evaluated. ○: No color unevenness △: Some color unevenness ×: Significant color unevenness * 3 A kneaded product containing 100 parts of the resin to be colored and 3 parts of the masterbatch was pressed under the condition of a press temperature of 170 ° C, and was pressed.
A film with a thickness of 1 mm was obtained. The size and number of coarse particles of the pigment in the obtained film were measured with a Luzex 450 image processor (manufactured by Toyo Ink Co., Ltd.). 5: 50 μm or less particle number 700 particles / cm ² or less 4: 50 μm or less particle number 700 to 1000 particles / cm ² 3: 50 μm or less particle number 1000 to 7000 particles / cm ² 2: 50 μm or less particle number 7000 to 27,000 particles / cm ² 1: 50 μm or less particles 27,000 particles / cm ² or more

(Example 7) Compound 1 50 parts Polyethylene wax "131P" (manufactured by Sanyo Kasei Co., Ltd.) 100 parts Benzidine yellow aqueous wet cake (pigment content: 37%) 300 parts "Rionol Yellow GGT" (Toyo Ink) Polyethylene "Sumikasen G808" 120 parts (manufactured by Sumitomo Chemical Co., Ltd., softening temperature: 78 ° C) The above four components were put in a kneader and heated to 150 ° C to knead. After 20 minutes, the copolymer was softened, the water was evaporated, the copolymer was adsorbed by the pigment in the pigment aqueous wet cake, and the phase was changed to gradually increase the viscosity. Further, 300 parts of the above-mentioned aqueous pigment wet cake was added and kneaded with heating, and after 1 hour, the viscosity became extremely high as the residual water evaporated, and flushing and dispersion were completed. Then, the cooling was rapidly started to room temperature, the kneading was followed by the pulverization, and when the particle diameter became several mm, the coloring pigment composition was taken out and the work was completed.

Next, 50 parts of this coloring pigment composition, 2.5 parts of diethylethanolamine, 47 parts of water and 0.5 part of a defoaming agent (silicone emulsion) were charged into a disper, and dissolved and dispersed. Furthermore, for 75 parts of this composition, polyethylene wax "Topco PW-M-10"
22.5 parts (manufactured by Toyo Petrolite Co., Ltd.) and 2.5 parts of Compound 1 were added and dispersed continuously to complete ink formation. When this printing ink was subjected to flexo or gravure printing on ace paper (made by Tojo Paper Co., Ltd.) with a diluent of water or water / isopropyl alcohol (1/1), all of them had good printability and had extremely high gloss. It was possible to obtain the printed matter of.

(Comparative Example 7) A printing ink was obtained in the same manner as in Example 7 except that rosin glycerin ester "Ester gum H" (manufactured by Arakawa Chemical Industry Co., Ltd.) was used in place of Compound 1. When printing was performed in the same manner as in Example 7, there was no problem in practical use, but the printability and printing effect were inferior to those in Example 7, and the gloss was particularly inferior.

(Example 8) Compound 2 60 parts Aqueous wet cake of phthalocyanine blue (pigment content: 46%) "Lionol blue FG7334P" (manufactured by Toyo Ink Mfg. Co.) 650 parts Ethylene / vinyl acetate copolymer "Smitate HE10" (Sumitomo Chemical Co., Ltd., softening temperature: 40 ° C.) 80 parts 25% ammonia water 280 parts Isopropyl alcohol 50 parts The above 5 components are put into a ball mill and dispersed and kneaded for 20 hours to give an aqueous dispersion of a pigment composition for coloring. It was created. The obtained pigmented aqueous pigment composition dispersion was in a good dispersed state without aggregation or sedimentation of the pigment. Next, 100 parts of this coloring pigment composition aqueous dispersion and 2.5 parts of diethylethanolamine.
Parts and 0.5 parts of a defoaming agent (silicone emulsion) were placed in a disper, and mixed and dispersed. Furthermore, for 75 parts of this composition, polyethylene wax "Topco PW-M
-10 "22.5 parts and 2.5 parts of compound 2 were added and dispersed continuously to complete the formation of an ink. When printing was performed in the same manner as in Example 7, there was no practical problem.

(Comparative Example 8) A printing ink was obtained in the same manner as in Example 8 except that hydrogenated rosin "Stevelite" (manufactured by Rika Hercules Co., Ltd.) was used in place of Compound 2. When printing was performed in the same manner as in Example 7, there was no practical problem.

Regarding Examples 7 and 8 and Comparative Examples 7 and 8,
Detailed results are shown in Table 4.

[Table 4]

Judgment ○: Good Δ: Slightly bad ×: Bad Plate fog: The surface of the cylinder cannot be scratched with a doctor, so that the surface is dirty and ink is transferred to a non-character portion. Plate jam: The intaglio is clogged. Roll clogging: The plate of the rubber roll is clogged. Entanglement: Ink bleeds or spot-like stains adhere inside or between prints. Rolled eyes: White lines with a small amount of ink, called streaks or stripes. Swimming: The density is not uniform and the density is uneven in the form of spots or liquid. Gloss: Measured at a reflection angle of 60 degrees using a digital photometer "GM-26D" (manufactured by Murakami Color Co., Ltd.).

(Example 9) Compound 3 40 parts Titanium oxide "Taipec CR-50" (manufactured by Ishihara Sangyo Co., Ltd.) 100 parts Ultramarine "Gunjou # 2000" (manufactured by Daiichi Kasei Co., Ltd.) 1 part Quinacridone red "Sinkashared" YRT759D "(manufactured by Ciba Geigy) 1 part Acrylic resin (softening temperature: 100 ° C.) 33 parts Butyl cellosolve 80 parts The above 6 components are stirred with a disper for 1 hour, then kneaded and dispersed with a sand mill for 1 hour to obtain a pigment content of 40%. A pigment paste (coloring pigment composition) was prepared. The composition of the acrylic resin is, by weight ratio, methyl methacrylate / ethyl acrylate / styrene / methacrylic acid = 20/40/3.
It is 2/8. To 100 parts of this pigment paste, 7 parts of the above acrylic resin, 3 parts of amino resin "Cymel 303" (manufactured by Mitsui Cyanamid Co., Ltd.) and 133 parts of butyl cellosolve were added and mixed well to obtain an acrylic baking paint having a pigment content of 0.16%. It was The obtained paint was applied to a tin plate with a spray coater and baked in an oven at 200 ° C for 10 minutes. The paintability was good.

Comparative Example 9 A pigment paste was obtained in the same manner as in Example 9 except that the acrylic resin used in Example 9 was used instead of the copolymer obtained from Compound 3. Using the obtained pigment paste, a baking paint was prepared and applied in the same manner as in Example 9. At this time, the surface smoothness was slightly inferior to that of Example 9.

(Example 10) Compound 4 40 parts Carbon black "MB-45" (manufactured by Mitsubishi Chemical Corporation) 60 parts Polybutylene terephthalate "Novadul 5010R3" 6 parts (manufactured by Mitsubishi Engineering Plastics, softening temperature: 210 ° C) Dimethyl Formamide 14 parts 2,6-ditert-butyl-p-cresol 1 part The above 5 components are charged in a kneader and heated and kneaded. When the contents become viscous, start cooling and knead for 1 hour. Next, 25 parts of water is added to precipitate a kneaded material, and the material is milled in a kneader while applying pressure. Take this out, 7
A pigment paste (pigment composition for coloring) was obtained by drying for 12 hours in a hot air dryer at 0 ° C. 80 parts of xylene was added to 20 parts of the obtained coloring pigment composition and mixed well to obtain a pigment paste. It was easily dissolved and dispersed. To 20 parts of this pigment paste, 6 parts of xylene and 92 parts of the amino resin used in Example 9 were added and mixed well to obtain a black baking coating having excellent dispersibility. When the obtained coating material was applied in the same manner as in Example 9 and baked at 280 ° C., the coatability was good.

(Comparative Example 10) A pigment paste was obtained in the same manner as in Example 10 except that rosin pentaerythritol ester "Hariester P" (manufactured by Harima Kasei Co., Ltd.) was used in place of Compound 4. Using the obtained pigment paste,
A baking paint was prepared and applied in the same manner as in Example 10. At this time, aggregates were generated on the surface of the coating film.

With respect to Examples 9 and 10 and Comparative Examples 9 and 10, the gloss, sharpness of hue, colorability and dispersibility of the coating films were evaluated. Detailed results are shown in Table 5.

[Table 5]

Judgment: Good: Fair: Somewhat bad: Poor Gloss: Measured at a reflection angle of 60 degrees using a digital photometer "GM-26D" (manufactured by Murakami Color Co., Ltd.). Vividness of hue: The surface of the coating film should be smooth without any roughness due to the pigment paste, and no uneven color or stripe pattern should appear. Colorability: The degree of color development (color strength) of the coating film was visually determined. Dispersibility: Visual evaluation was made with a grind gauge.

(Example 11) Compound 5 35 parts Aqueous wet cake of phthalocyanine blue (pigment content: 35%) "Rionol Blue SM" (manufactured by Toyo Ink Mfg. Co., Ltd.) 1030 parts Ethylene / vinyl alcohol copolymer "Solarite K" 5 parts (Nippon Gosei Kagaku Kogyo Co., Ltd., softening temperature: 162 ° C.) Sodium dodecylbenzene sulfonate 5 parts Xylene 90 parts Water 600 parts The above 6 components were put in a disper and mixed to prepare a pigment aqueous paste. Next, this pigment aqueous paste was put into a flasher and stirred while heating to 150 ° C. The water evaporated, and when the content became highly viscous, it was taken out and dried with a spray dryer to obtain a pigment composition for coloring. To 17 parts of the obtained pigment composition for coloring, 79 parts of carnauba wax (mp: 83 ° C.), 17 parts of paraffin wax (mp: 55 ° C.) and 113 parts of a 15% MEK solution of compound 5 were added, and glass beads were added. A thermal ink was prepared by dispersing with an attritor for 2 hours. This thermal ink was applied onto a polyethylene terephthalate film having a thickness of 6 mm by a solvent coating method so that the coating thickness after drying would be 4 μm, and dried at 100 ° C. for 2 minutes to obtain a thermal transfer recording medium. The coatability was good.

(Comparative Example 11) A pigment composition for coloring was prepared in the same manner as in Example 11 except that polymerized rosin "Pentaline CJ" (manufactured by Rika Hercules Co., Ltd.) was used in place of the copolymer obtained from Compound 5. Got Using the resulting coloring pigment composition, the same as Example 11 except that a 15% MEK solution of compound 5 was replaced with a 15% xylene solution of polystyrene "Esbright 500SB" (Sumitomo Chemical Co., Ltd.). To prepare a heat-sensitive ink to obtain a heat-sensitive transfer recording medium. The coatability was good, but there was some odor.

(Example 12) Compound 4 20 parts PP / PE wax "APAO-UT2385" (manufactured by Ube Lexen) 50 parts Carbon black "Mitsubishi Carbon MA-100" (manufactured by Mitsubishi Chemical Co.) 20 parts Ethylene vinyl acetate Copolymer “DQDJ-7197” 10 parts (manufactured by Nippon Unicar Co., softening temperature: 38 ° C.) The above two components are mixed and heated and kneaded at 160 ° C. with a three-roll mill to obtain a mill base (coloring pigment composition). Obtained. Using the obtained mill base, a heat-sensitive ink was prepared in the same manner as in Example 11 to obtain a heat-sensitive transfer recording medium. The coatability was good.

Comparative Example 12 A pigment composition for coloring was obtained in the same manner as in Example 12 except that microcrystalline wax (mp: 75 ° C.) was used instead of the compound 4.
Using the obtained coloring pigment composition, xylene 1 of acrylonitrile / styrene copolymer "TTR-02" (manufactured by Fujikura Kasei Co., Ltd.) instead of the 15% xylene solution of Compound 5 was obtained.
A thermal ink was prepared in the same manner as in Example 11 except that a 5% solution was used to obtain a thermal transfer recording medium. The coatability was good.

Regarding the thermal transfer recording media obtained in Examples 11 and 12 and Comparative Examples 11 and 12, the transfer energy sensitivity and the transferred image quality were temperature: 60 to 140 ° C., pressure: 2
Thermal gradient tester "HG-100" (manufactured by Toyo Seiki Seisaku-sho, Ltd.) under conditions of kg / cm, thermocompression bonding time: 3 seconds, printing speed: 60 characters / second, high density with 8 dot thermal head It was evaluated with a thermal printer. As for the abrasion resistance of the transfer ink surface, the abrasion resistance against rough paper having a smoothness of 5 to 10 seconds was measured by using a paperboard abrasion resistance tester (manufactured by Kumagai Riki Kogyo Co., Ltd.) at a temperature of 23 ° C. and a load of: 500gw / cm,
Friction frequency: evaluated under the condition of 100 reciprocations. As the image receiving paper, thermal transfer paper, mirror coated paper and OHP sheet were used. Detailed results are shown in Table 6.

[0052]

[Table 6]

Judgment ◯: Good Δ: Slightly bad ×: Poor Transfer image quality: Visual density evaluation of image density unevenness, uniformity, sharpness, and random bridges and voids was carried out using enlarged photographs and the like. Rubbing resistance: The rate at which the ink in the transferred image area adheres to the friction paper was visually determined. Transfer energy sensitivity: Transfer energy when the transfer image density is saturated. Transferred image density: The saturated image reflection density value of the solid print part was measured with a Macbeth reflection densitometer.

(Examples 13 to 14) Compounds 2 and 3 20 parts Carbon black "Mitsubishi carbon # 10" (manufactured by Mitsubishi Chemical Co.) 10 parts Negative charge control agent "Pontron E81" (manufactured by Orient Chemical Co.) 3 parts Polypropylene wax "Viscor 550P" 42 parts (manufactured by Sanyo Kasei Co., Ltd.) Polystyrene "Esbright 2V" 45 parts (manufactured by Showa Denko KK, softening temperature: 79 ° C) The above 5 components are mixed and heated and kneaded at 130 ° C with a two-roll mill. Thus, a mill base was obtained, which was roughly pulverized by a hammer mill, then finely pulverized by a jet mill and then classified to obtain a toner (a pigment composition for coloring) having an average particle diameter of 13 μm. The obtained toner was mixed with iron oxide powder "EFV200" (manufactured by Nippon Iron Powder Co., Ltd.) as a carrier to prepare a developer having a toner concentration of 5%.

Comparative Example 13 Instead of Compound 2, m-xylene bisstearic acid amide "Sripax ZXS" was used.
A toner was obtained in the same manner as in Example 13 except that (Nippon Kasei) was used. Example 13 using the obtained toner
A developer was prepared in the same manner as in.

The developers obtained in Examples 13 to 14 and Comparative Example 13 were put in a developing machine modified from a copying machine "NC3000" (manufactured by Copia), and 1/3 of A4 paper was black and unfixed. I created an image. Subsequently, using a heating roll type fixing tester in which the upper part is Teflon and the lower part is silicon rubber, the roll temperature was changed stepwise from 100 to 240 ° C. and passed through at a linear velocity of 800 cm / min for fixing evaluation. Fixability is as follows:
It was judged by measuring D (image density). The hot set temperature was measured by measuring the ID of the part of the roll that was in contact with the black solid part and was in contact with the blank part again.
The minimum temperature was increased by 5% or more from D. Further, using a copying machine "NC3000" (manufactured by Copia), the temperature is 30 ° C-
A continuous copying test was conducted under the condition of a humidity of 80%. The storage stability of the obtained developer is 2 at a temperature of 50 ° C. and a humidity of 80%.
It was evaluated under the condition of 4 hours. Detailed results are shown in Table 7.

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[Table 7] Judgment ○: Good △: Slightly bad ×: Bad

[0058]

The coloring pigment composition of the present invention is excellent in pigment dispersibility regardless of the high or low content of pigment, and coloring of a textile product or thermal ink, which requires a high degree of pigment dispersion,
In coloring coloring agents such as printing inks, paints, toners, etc., they have a great effect on the gloss, sharpness of hue and colorability. Further, conventionally, there are no coating defects such as spots and color unevenness due to many poor dispersions, and good coating properties are obtained, such as good coating properties, and good coating physical properties can be obtained. . In particular, it is extremely effective for coloring a thermoplastic resin as a molding material, exhibits high dispersion and high color development, and enables coloring without color unevenness.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsuyuki Ueki 2-33 Kyobashi, Chuo-ku, Tokyo Toyo Inki Manufacturing Co., Ltd.

Claims (2)

[Claims] 1. A coloring pigment composition comprising 0.01 to 90% by weight of a pigment (a) and 1 to 80% by weight of a compound (b) represented by the general formula (I). (However, n is an integer of 20 or more and 50 or less, and R is H or CH _3. ) 2. A coloring pigment according to claim 1, which contains 1 to 90% by weight of a thermoplastic resin or wax (c) having a Vicat softening temperature of 300 ° C. or lower as defined in JIS K-7206. Composition.