JP3485770B2 - Colorant - Google Patents

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, pigments generally have poor dispersibility in a medium as they are, and therefore, when blended in paints, inks or resins, the pigments are dispersed in a pigment dispersion resin (dispersant). Used as a color concentrate or a colorant, but when the dispersibility of the pigment in such a resin dispersant is poor, the pigment agglomerates. For inks, paints, resin molded products, etc. prepared using a colorant containing pigment particles, the resulting coating film may have various effects such as a decrease in gloss, a decrease in sharpness, an opacity, a decrease in coloring power and a color separation. However, such a colorant cannot sufficiently exhibit the performance of the pigment when it is made into an ink or a paint, or when the resin is colored.

[0003]

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

[0004]

The above object can be achieved by the present invention described below. That is, the present invention, the Re organic pigment and its
A colorant for paint comprising a dispersant for dispersing in a paint medium, wherein the dispersant is a copolymer containing at least a vinyl chloride unit, a vinyl alcohol unit and an amine-modified vinyl unit as monomer components. It is a colorant for paints, which is a resin.

It has been found according to the invention that certain copolymers are excellent as pigment dispersants. The dispersant has excellent compatibility with the material to be colored. Therefore, the colored article with the coloring agent of the present invention has gloss, sharpness, transparency, coloring power,
Excellent in color separation prevention, especially no pigment aggregation is observed,
It has a very excellent transparency, which is equivalent to coloring with a dye.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following 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 or the like. The copolymerization monomer composition of the dispersant contains 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. The monomer composition so that the average degree of polymerization of
It is preferable to prepare the dispersant resin by setting saponification conditions and amine modification conditions.

Regarding the introduction of vinyl alcohol units into the dispersant, lower fatty acid vinyl such as vinyl acetate and vinyl propionate is copolymerized, and the resulting copolymer is KOH, NaOH, sodium alcoholate, etc. in a suitable solvent. It is carried out by the method of saponification with an alkali or an acid such as hydrochloric acid or sulfuric acid as a catalyst and purification 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 rate (mol%) so that the above range is maintained. . Incidentally, the vinyl acetate unit, the vinyl propionate unit, etc. as the unsaponifiable portion may be present in a slight amount in the range of 0.5 to 10% by weight of the dispersant, or the acrylic acid or methacrylic acid unit may be present. The alkyl ester of acid, the ester of maleic acid or methacrylic acid, vinylidene chloride, various vinyl ether units and the like may be polymerized in a slight amount.

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

The amine compounds used for amine modification include primary, secondary or tertiary amines such as aliphatic amines, alicyclic amines and aromatic amines, specifically ethylamine and propyl. 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,
2,4-lutidine, quinoline, morpholine and the like can be mentioned.

In the above dispersant, when the amount of vinyl chloride unit is less than 60% by weight, the dispersibility of the pigment is lowered, while when it is more than 95% by weight, the compatibility with the adhesive agent composed of polyurethane resin is lowered and the dispersant is used. It is disadvantageous. or,
Even if the amount of vinyl alcohol unit is more than 16% by weight,
Even if it is less than 2% by weight, the dispersibility of the pigment is lowered, and the compatibility with vehicle resins such as paints and printing inks is lowered. Further, if the amine-modified vinyl unit is more than 5% by weight or less than 0.05% by weight, the dispersibility of the pigment is lowered, the compatibility with various vehicles is lowered, and the transparency of the colored product is reduced. descend.

Further, in the copolymer composed of such unit components, when the average degree of polymerization is lower than 200, the dispersibility of the pigment is lowered, and conversely, when the average degree of polymerization is higher than 800, the viscosity is high. Therefore, the kneadability with the pigment is remarkably deteriorated and the handling becomes difficult. Therefore, the average degree of polymerization is preferably in the range of 200 to 800. A copolymer having a component ratio and an average degree of polymerization within the above range is excellent in the 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 transparent, transparent colorant is obtained.

The pigment used in the present invention is a pigment which has been conventionally used in various types, and any known pigment can be used. Specifically, phthalocyanine type, azo type, condensed azo type, azo lake type, anthraquinone type, perylene
Perinone series, indigo / thioindigo series, isoindolinone series, azomethineazo series, dioxazine series, quinacridone series, aniline black series, triphenylmethane series,
Organic pigments such as carbon black, titanium oxide, iron oxide, iron hydroxide, chromium oxide, spinel type firing system,
Examples thereof include chromic acid type, chrome vermillion type, dark blue type, aluminum powder type, bronze powder type and the like. These pigments may be in any form, and these pigments may be 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 or a three roll mill. At this time, the dispersant is used in the range 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 a powdery pigment (with an appropriate amount of an organic solvent as necessary), for example, by mixing and kneading meat in a three-roll mill, It is possible to obtain a colorant having excellent transparency with very few aggregated particles of the pigment. The colorant obtained may be in the form of powder, chips, paste containing an organic solvent, or liquid in which an organic solvent is a medium, and the shape thereof is not particularly limited and may be selected depending on the coloring application. Further, the colorant may include various additives such as an organic solvent, a film-forming resin that does not exist in a large amount, a flame retardant, an antioxidant, an ultraviolet absorber, a plasticizer, and a surfactant, depending on the target coloring material. It can be added.

The colorant of the present invention obtained as described above is, for example, various paints such as paints for woodwork and paints for building materials, surface treatment agents for artificial leather, synthetic leather, 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 coating film formed is good,
It is useful in many fields such as the color filter field.

[0016]

EXAMPLES The present invention will be described in more detail with reference to synthetic examples of resins used as dispersants, colorants prepared using the same, and examples using the colorants.
In addition, unless otherwise specified, the contents or% 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
A portion is charged, and the mixture is continuously stirred and stirred at 60 ° C. for 8 hours for polymerization reaction. Cool down the internal pressure of the autoclave,
It was thoroughly washed with deionized water, filtered and dried to obtain 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.

Further, 216 parts of methanol and 24 of toluene
Parts, sodium hydroxide 8 parts, morpholine 4 parts,
After being charged in a reactor and reacted at 40 ° C. for 6 hours, it is thoroughly 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. This product 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.
It was a copolymer of. The resin dispersants listed 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-benzylammonium ethyl Methacrylate 5.0 parts Toluene 500 parts Azobisisobutyronitrile 2. Parts 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. Toluene was distilled off from the polymerization solution to obtain a paste-like dispersant having a solid content of about 30%.

"Preparation of Colorant" Colorant 1 Disazo yellow pigment (manufactured by Dainichiseika Seika Fast Yellow 2720) was added to 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 triple roll to obtain a colorant. The same procedure was followed to obtain the colorants shown in Table 2 below (numerical values in the table are the number of copies).

Table 2

Resin Synthesis Example 1 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 mixed at 100 ° C. for 4 hours. After reacting for a time, N, N-dimethylformamide was added to 470.
Add 9 parts and add isophoronediamine 1 with a dropping funnel.
3.1 parts was gradually added dropwise, solid content 30%, viscosity 200P
a. s polyurethane resin (PU-1) (molecular weight about 10
10,000) was obtained.

Resin Synthesis Example 2 150 parts of 1,4-adipate having an average molecular weight of 1,500,
1,4-Butanediol 18.5 parts, N, N-dimethylformamide 287.0 parts and methyl ethyl ketone 28
To 7.5 parts of the mixture, 77.5 parts of diphenylmethane-4,4-diisocyanate was added and reacted at 80 ° C. for 5 hours to give a solid content of 30% and a viscosity of 500 dPa.s. Polyurethane resin (PU-2) of s (molecular weight about 150,000) was obtained.

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

Table 3

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

Table 4 Incidentally, No. 7-11 and 15-17 are comparative examples.

The evaluation methods in Table 4 are as follows. 1. Coloring power, gloss, transparency and sharpness ⊙; extremely good ○; good Δ; somewhat good ×; poor 2. Color separation (comparison between paint immediately after stirring and paint left for 15 hours) ○: No color separation ×; Color separation 3. Haze

[0029]

According to the present invention as described above, it was found that the specific copolymer is excellent as a dispersant for the pigment. The dispersant has excellent compatibility with the material to be colored. Therefore, the colored article with the colorant of the present invention is excellent in gloss, vividness, transparency, coloring power, and color separation prevention property, in particular, no aggregation of pigment is observed, and it is very excellent in transparency equivalent to coloring with a dye. To feel.

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Masayuki Inabe 1-7-6 Nihonbashi Bakuro-cho, Chuo-ku, Tokyo Within Dainichi Seika Kogyo Co., Ltd. (72) Masatoshi Nakajima 1-7-chome Nihonbashi Bakuro-cho, Chuo-ku, Tokyo No. 6 In Dainichi Seika Kogyo Co., Ltd. (72) Inventor Isao Kondo 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (56) Reference JP-A 61-172213 (JP, A) ) JP-A-63-172710 (JP, A) JP-A-63-133316 (JP, A) JP-A-63-184914 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 17 / 00,127 / 06 C08F 8 / 32,214 / 06 C09C 1/34

Claims (2)

(57) [Claims] 1. A The Re organic pigment and its dispersed in a paint medium
In paint colorant comprising a because of the dispersing agent, coating material, wherein the dispersant is a copolymer resin containing vinyl chloride units and vinyl alcohol units and an amine-modified vinyl unit, at least as a monomer component use coloring agents. 2. The dispersant comprises at least 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.
And the average degree of polymerization of the dispersant is 200 to 800.
The colorant according to claim 1, which is