JPH11100542A - Colorant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colorant not undergoing the agglomeration of the constituent pigment and giving a colored article excellent in gloss, clarity, tinting strength and color separation resistance by including a dispersant being a copolymer resin essentially consisting of vinyl chloride units, vinyl alcohol units and amine-modified vinyl units and a pigment. SOLUTION: This colorant comprises a dispersant being a copolymer resin consisting essentially of desirably 60-95 wt.% vinyl chloride units, desirably 2-16 wt.% vinyl alcohol units and desirably 0.05-5 wt.% amine-modified vinyl units and desirably having an average degree of polymerization of 200-800 (e.g. a resin obtained by feeding a vinyl chloride/vinyl acetate copolymer together with methanol, toluene, NaOH and morpholine being an amine compound into a reactor and simultaneously effecting the saponification of the copolymer and the introduction of amine-modified vinyl units) and a pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a pigment colorant,
More specifically, various paints such as paints for woodworking and paints for building materials,
Surface treatment agents such as artificial leather and synthetic leather, gravure ink,
In addition to ink fields such as offset inks, thermoplastic resins, thermosetting resins, various resin fields such as adhesives, etc., since the light transmittance of the formed coating film is good,
The present invention relates to a pigment colorant useful in many fields such as a color filter field.

[0002]

2. Description of the Related Art Conventionally, pigments, as they are, generally have poor dispersibility in a medium, and therefore, when incorporated into paints, inks, resins, or the like, pigments are dispersed in a pigment dispersing resin (dispersant). (For example, a color concentrate or a coloring agent). However, when the dispersibility of the pigment in such a resin dispersant is poor, the pigment is aggregated and thus aggregated. For inks, paints or resin molded products prepared using a coloring agent containing pigment particles, various properties such as a decrease in gloss, a decrease in clarity, an opacity, a decrease in coloring power, a color separation, etc. However, such a colorant cannot sufficiently exhibit the performance of a pigment when formed into an ink or a paint or when a resin is colored.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to reduce the gloss, sharpness, and opacity of a coating film or a colored resin when the coating film is formed from ink or paint or when the resin is colored. It is an object of the present invention to provide a pigment colorant capable of stably dispersing a pigment by eliminating various problems such as reduction in coloring power, coloring power, and color separation.

[0004]

The above objects are achieved by the present invention described below. That is, the present invention provides a colorant comprising a pigment and a dispersant thereof, wherein the dispersant is a copolymer resin containing at least a vinyl chloride unit, a vinyl alcohol unit, and an amine-modified vinyl unit as a monomer component. Characteristic coloring agent.

According to the present invention, it has been found that a specific copolymer is excellent as a dispersant for a pigment. The dispersant has excellent compatibility with the coloring material. Therefore, a colored article with the coloring agent of the present invention has gloss, sharpness, transparency, coloring power,
Excellent color separation prevention, especially no aggregation of pigment is seen,
It has a very excellent transparency equivalent to coloring with a dye.

[0006]

Next, the present invention will be described in more detail with reference to preferred embodiments. The dispersant used in the present invention is produced by a general suspension polymerization method, emulsion polymerization method, solution polymerization method, bulk polymerization method and the like. The comonomer composition of the dispersant is 60 to 95% by weight of vinyl chloride units, 2 to 16% by weight of vinyl alcohol units, and 0.05 to 5% by weight of amine-modified vinyl units. Monomer composition so that the average degree of polymerization of 200 to 800,
It is preferable to prepare a dispersant resin by setting saponification conditions and amine modification conditions.

For the introduction of a vinyl alcohol unit into a dispersant, a lower fatty acid vinyl such as vinyl acetate or vinyl propionate is copolymerized, and the obtained copolymer is dissolved in an appropriate solvent in KOH, NaOH, sodium alcoholate or the like. This is carried out by a method of saponification using an alkali or an acid such as hydrochloric acid or sulfuric acid as a catalyst and purifying it by a conventional method. Since the introduction of the vinyl alcohol unit is preferably in the range of 2 to 16% by weight, it is necessary to adjust the copolymerization amount of the lower fatty acid vinyl unit and the saponification ratio (mol%) so as to maintain the above range. . The vinyl acetate unit, vinyl propionate unit, etc. as the saponified portion may be present in a slight amount in the range of, for example, 0.5 to 10% by weight of the dispersant, or may be acrylic acid or methacrylic acid. Alkyl acid esters, maleic acid or methacrylic acid esters, vinylidene chloride, various vinyl ether units, and the like may be polymerized in a small amount.

On the other hand, the introduction of the amine-modified vinyl unit can be carried out simultaneously with the saponification reaction. That is, various amine compounds described below are added to the saponification reaction system,
By heating and stirring until a desired degree of saponification is obtained for a certain period of time, a vinyl alcohol unit is obtained, and at the same time, an amine is introduced into a side chain of the copolymer by a reaction between a chlorine atom of a vinyl chloride unit and an amine compound. . In the amine modification, it is preferable that the amount of the amine compound used is such that the amine-modified vinyl unit in the copolymer is in the range of 0.05 to 5% by weight.

The amine compound used for the amine modification includes primary, secondary and tertiary amines such as aliphatic amines, alicyclic amines and aromatic amines. Amine, butylamine,
Cyclohexylamine, ethanolamine, naphthylamine, aniline, o-toluidine, diethylamine, dioctylamine, diisobutylamine, diethanolamine, N-methylaniline, trimethylamine, triethylamine, triisobutylamine, tridecylamine, N-methyldiphenylamine, hexamethylenetetramine, Triethanolamine, tributylamine, pyridine, α-picoline, β-picoline, γ-picoline,
Examples include 2,4-lutidine, quinoline, morpholine and the like.

In the above dispersant, if the amount of the vinyl chloride unit is less than 60% by weight, the dispersibility of the pigment is reduced. On the other hand, if it is more than 95% by weight, the compatibility with the adhesive composed of the polyurethane resin is reduced, and It is disadvantageous. or,
Even if the amount of vinyl alcohol units is more than 16% by weight,
If the amount is less than 2% by weight, the dispersibility of the pigment is reduced, and the compatibility with a vehicle resin such as a paint or a printing ink is reduced. Also, if the amount of the amine-modified vinyl unit is more than 5% by weight or less than 0.05% by weight, the dispersibility of the pigment is reduced, the compatibility with various vehicles is reduced, and the transparency of the coloring matter is reduced. descend.

When the average degree of polymerization is lower than 200, the dispersibility of the pigment in the copolymer composed of each unit component is reduced, and when the average degree of polymerization is higher than 800, the viscosity increases. Therefore, the average degree of polymerization is preferably in the range of 200 to 800, since the kneadability with the pigment becomes extremely poor and handling becomes difficult. A copolymer having a component ratio and an average degree of polymerization within the above ranges is excellent in dispersibility of the pigment, and the pigment is finely dispersed by mixing the dispersant with the pigment and the solvent and performing an appropriate dispersing step. A dispersed transparent colorant is obtained.

The pigment used in the present invention is a pigment conventionally used in various types, and any known pigment can be used. Specifically, phthalocyanine, azo, condensed azo, azo lake, anthraquinone, perylene
Perinone type, indigo / thioindigo type, isoindolinone type, azomethine azo type, dioxazine type, quinacridone type, aniline black type, triphenylmethane type,
Organic pigments such as carbon black, titanium oxide, iron oxide, iron hydroxide, chromium oxide, spinel firing,
Chromic acid type, chromium vermillion type, navy blue type, aluminum powder type, bronze powder type and the like can be mentioned. These pigments may be in any form, and these pigments may have been subjected to various dispersion treatments by various known methods.

[0013]

The colorant of the present invention can be obtained by kneading the dispersant and the pigment with a kneading machine such as a sand grind mill, a ball mill, an attritor mill, a three-roll mill or the like. At this time, the dispersant is used in an amount of about 10 to 500 parts by weight per 100 parts by weight of the pigment. When kneading the dispersant and the pigment, for example, by mixing the dispersant (with an appropriate amount of an organic solvent if necessary) to the powdered pigment, for example, by mixing and kneading with a three-roll mill, It is possible to obtain a colorant having excellent transparency with very few aggregated particles of the pigment. The obtained colorant may be in the form of a powder, a chip, a paste containing an organic solvent, or a liquid in which an organic solvent is used as a medium. In addition, the coloring agent may include various additives, for example, an organic solvent, a film-forming resin that is not a large amount, a flame retardant, an antioxidant, an ultraviolet absorber, a plasticizer, and a surfactant, depending on the target coloring material. Can be added.

The colorants of the present invention obtained as described above include, for example, various paints such as paints for woodworking and building materials, surface treatment agents such as artificial leather and synthetic leather, and inks such as gravure ink and offset ink. Fields, thermoplastic resins, thermosetting resins, various resin fields such as adhesives, as well as other, because the light transmittance of the formed coating film is good,
It is useful in many fields such as the field of color filters.

[0016]

EXAMPLES The present invention will be described more specifically below with reference to synthetic examples of resins used as dispersants, coloring agents prepared using the same, and examples using the coloring agents.
Unless otherwise specified, parts and percentages in the text are based on weight. Synthesis Example 1 Deionized water 200 in an autoclave equipped with a stirrer
Parts, vinyl chloride 72 parts, vinyl acetate 28 parts, trichloroethylene 3 parts, di (2-ethylhexyl) peroxydicarbonate 3 parts and partially saponified polyvinyl alcohol 1
The polymerization reaction was carried out by continuously charging the mixture at 60 ° C. for 8 hours while stirring. Decrease the internal pressure of the autoclave, cool it,
After sufficiently washing with deionized water and filtration and drying, 80 parts of a copolymer having a vinyl chloride unit of 75.3%, a vinyl acetate unit of 24.7% and an average degree of polymerization of 380 was obtained.

Further, 216 parts of methanol, 24 parts of toluene
Along with 8 parts of sodium hydroxide and 4 parts of morpholine
After charging into a reactor and reacting at 40 ° C. for 6 hours, it is sufficiently washed with methanol and deionized water, and filtered and dried. The obtained polymer was further dissolved in 400 parts of methyl ethyl ketone, 1500 parts of methanol was added dropwise while stirring to reprecipitate, and 64 parts of a copolymer powder was obtained by filtration and drying. It has a vinyl chloride unit of 85.8%, a vinyl alcohol unit of 11.5%, a vinyl acetate unit of 2.2%, a morpholine (amine) -modified vinyl unit of 0.5%, and an average degree of polymerization of 320.
Was a copolymer of The resin dispersants shown in Table 1 were synthesized in the same manner.

Table 1

Synthesis Example 6 Methyl methacrylate 5.0 parts Butyl methacrylate 46.5 parts Styrene 38.5 parts N, N′-dimethylaminoethyl methacrylate 5.0 parts N, N, N-dimethyl-benzylammoniumethyl 1. Methacrylate 5.0 parts Toluene 500 parts Azobisisobutyronitrile 2. Part The above components were mixed and dissolved, and this solution was polymerized at 85 to 90 ° C. for 5 hours to obtain a viscous polymerization solution. The toluene was distilled off from the polymerization solution to obtain a paste dispersant having a solid content of about 30%.

"Preparation of Colorant" Colorant 1 Disazo yellow pigment (Seika Fast Yellow 2720 manufactured by Dainichi Seika Kogyo Co., Ltd.) 6 per 100 parts of the dispersant of Synthesis Example 1
0 parts and 240 parts of cyclohexanone were mixed, premixed with a dissolver, and then dispersed with a three-roll mill to obtain a colorant. In the same manner as described below, colorants shown in Table 2 below were obtained (the numbers in the table are parts).

Table 2

Synthetic Example 1 of Resin To 150 parts of 1,4-adipate having an average molecular weight of 2,000 and 4.4 parts of 1,3-butanediol, 34.3 parts of isophorone diisocyanate was added, and the mixture was heated at 100 ° C. for 4 hours. After reacting for hours, N, N-dimethylformamide was added to 470.
9 parts, and add isophorone diamine 1 with a dropping funnel.
3.1 parts are gradually dropped, solid content 30%, viscosity 200P
a. s polyurethane resin (PU-1) (molecular weight of about 10
000).

Synthesis Example 2 150 parts of 1,4-adipate having an average molecular weight of 1,500,
18.5 parts of 1,4-butanediol, 287.0 parts of N, N-dimethylformamide and 28
To the mixture of 7.0 parts, 77.5 parts of diphenylmethane-4,4-diisocyanate was added, and the mixture was reacted at 80 ° C. for 5 hours to obtain a solid content of 30% and a viscosity of 500 dPa.s. Thus, a polyurethane resin (PU-2) having a molecular weight of about 150,000 was obtained.

25 parts of the coloring agent 1, 100 parts of a polyurethane resin (PU-1) and 50 parts of a solvent (N, N-dimethylformamide) were sufficiently stirred with a disper to obtain a yellow paint (No. 1). In the same manner, a paint having the composition shown in Table 3 below was obtained.

Table 3

Each coating material obtained in the above Examples and Comparative Examples was applied on a polypropylene film with a clearance of 50 μm and dried to obtain each coated material. The results for these coatings are shown in Table 4 below.

Table 4 In addition, No. 7 to 11 and 15 to 17 are comparative examples.

The evaluation method in Table 4 is as follows. 1. 1. Tinting power, gloss, transparency and sharpness ；; extremely good ；; good △; somewhat good ×; 2. Color separation (comparison between paint immediately after stirring and paint left for 15 hours) ○: No color separation ×: Color separation Haze

[0029]

According to the present invention as described above, it has been found that a specific copolymer is excellent as a pigment dispersant. The dispersant has excellent compatibility with the coloring material. Therefore, the colored article with the coloring agent of the present invention is excellent in gloss, sharpness, transparency, coloring power, and color separation prevention property, and in particular, shows no aggregation of pigment at all, and is extremely excellent in transparency equivalent to coloring with a dye. Give a feeling.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Isao Kondo

Claims (2)

[Claims] 1. A colorant comprising a pigment and a dispersant thereof, wherein the dispersant is a copolymer resin containing at least a vinyl chloride unit, a vinyl alcohol unit and an amine-modified vinyl unit as monomer components. Colorant. 2. A dispersant comprising at least 60 to 95% by weight of a vinyl chloride unit, 2 to 16% by weight of a vinyl alcohol unit and 0.05 to 5% by weight of an amine-modified vinyl unit.
And the average degree of polymerization of the dispersant is from 200 to 800.
The coloring agent according to claim 1, which is: