JPS6056757B2 - Coloring composition for polyurethane resin paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a coloring composition that can be blended into a clear polyurethane resin paint and dissolved and dispersed to form a glossy coating without uneven coloring as a colored paint.

There are two methods for coloring polyurethane resin solutions: one is to directly turn a mixture of pigment, urethane resin, and solvent into a paint using a ball mill, sand mill, attritor, etc., as is the case with general paints, and the other is to create a coloring composition in which the pigment is easily dispersed. There is a method of adding color to a polyurethane resin solution. The present invention relates to a coloring method using the latter method.

Polyurethane resin paints generally include one-component polyurethane paints and two-component polyurethane paints, which can be colored by the method described above. As for the method of adding and dispersing a coloring composition to the above-mentioned clear polyurethane resin solution, the base pigment is almost never directly added due to the problem of pigment dispersibility, and in order to facilitate pigment dispersion, usually, Pigments that have been subjected to easy dispersion processing are used. Therefore, as a coloring composition in which such a pigment is subjected to easy dispersion processing, 1) a paste-like composition in which the pigment is molded with polyol or plasticity; 2) a pigment is reacted with tolylene diisocyanate in a solvent and dispersed using a ball mill or a sand mill. 3) A non-powder colorant made by blending a polystyrene resin, a pigment, a polyalkylene or a wax, and a low-volatility organic liquid (Japanese Patent Publication No. 5201/1983).

A powder pigment composition obtained by mixing an emulsion of a styrene-alkyl methacrylate copolymer and an aqueous pigment dispersion, further adding an aqueous inorganic metal salt solution, filtering the precipitate, washing with water, and drying. (Japanese Patent Publication No. 45-18578) ω Examples include powder-free colorants prepared by crushing vinyl chloride-vinyl acetate copolymer and pigment in a ridge.

In the case of paste colorants, in the case of two-component polyurethane resin paints, one-component polyurethane resin paints allow the polyol component of the paste component to react with a curing agent solution consisting of an isocyanate compound and a solvent. In this case, polyol or plasticity remains in the coating film, causing bleeding onto the coating film and deterioration of the coating film.

In the case of the liquid coloring agent (2), there are disadvantages such as phenomena such as pigment precipitation and color separation easily occurring during storage, and changes in pigment concentration due to solvent volatilization.

Powdered colorants like those in (3) and (4) are convenient for automatic measurement and easy to handle, but colorants made from Styrene 7 resin generally have poor compatibility with polyurethane resins and are not compatible with solvents. does not melt easily. (5) The uncolored powder obtained by grinding vinyl chloride-vinyl acetate copolymer and pigment is generally compatible with urethane resins, but it has poor solubility in solvents, and vinyl chloride decomposes under heating. As a result, stabilizers are required to avoid adverse effects such as hydrolysis on urethane resins.

Therefore, in order to be compatible with the urethane resin solution and to be stably interposed in the solvent, the present inventors have developed a colored composition kneaded with a pigment, urethane resin, and polyester polyol.
It has been found that it dissolves quickly in a urethane resin solution and has good dispersibility.

In particular, it has been discovered that in this case, the polyester polyol increases the solubility in the urethane resin solution and has a remarkable effect on improving dispersibility. In addition, among polyester polyols, we have found that the use of solid polyester polyols (Mp3O to 70'C) reduces bleeding onto the coating film and further improves solubility.
The inventors have discovered that a blend of vinyl chloride-vinyl acetate copolymer can provide both coating film suitability and bleed prevention effect, and have thus arrived at the present invention. That is, the present invention provides a coloring composition comprising 10 to 9 parts by weight of a thermoplastic polyurethane resin, 10 to 9 parts by weight of a pigment, 1 to 5 parts by weight of a polyester polyol, and 0 to 2 parts by weight of a vinyl chloride-vinyl acetate copolymer. It is a thing.

Pigments used in the present invention include known pigments such as azo pigments, copper phthalocyanine pigments, titanium oxide, iron oxide pigments, quinacridone pigments, anthraquinone pigments, isoindolinone pigments, thioindigo pigments, and carbon black. can be mentioned.

The thermoplastic urethane resins used in the present invention include adipate-based and polycaprolactone-based polyester urethane resins, and polyoxytetramethylene glycol-based polyether urethane resins.

Furthermore, the polyol used is a polyester polyol, which is a component of the urethane resin.

Particularly preferred in this case is a solid polyol with a melting point of about 30 to 70°C. Adding polyester polyol improves the dispersibility of the pigment and makes it easier to dissolve in solvents.
By using a polyester polyol of 0 to 7 CfC), it is characterized in that it can have the effect of preventing bleeding to the coating surface.

Furthermore, a vinyl chloride-vinyl acetate copolymer is added to the above formulation to prevent bleeding of the polyester polyol and to impart coating suitability. When producing the coloring composition of the present invention, first, a pigment, a polyester polyol, and a vinyl chloride-vinyl acetate copolymer are blended with a thermoplastic polyurethane resin, and the mixture is heated at a temperature of 95 to 50°C using a mixer such as a Henshil mixer or a kneader. The resulting product is further kneaded using a mixing machine such as a mixing roll at 40 to 150°C. After cooling, the resulting product is cut with a pelletizer, etc., and the pellet-shaped coloring composition is You can get things. By blending the thus obtained coloring composition into a clear polyurethane resin solution and stirring, a uniformly colored polyurethane resin paint can be obtained in a short time.

Furthermore, this coloring composition has the characteristic that it is easily dissolved in a solvent and can maintain a stable state for a long time without sedimentation.

Also, when made into a paint film, it can create a much glossier surface compared to the colored paint film of general paints.

Incidentally, it is perfectly acceptable to use paint additives such as ultraviolet absorbers, surfactants, and stabilizers in combination with the above-mentioned coloring composition.

Next, the present invention will be specifically explained with reference to Examples.

Example 1 Copper phthalocyanine blue (product of Dainichiseika Kagyo Co., Ltd.), 19 parts by weight of thermoplastic polyester urethane resin (product name: Rezamin P9l45, product of Dainichiseika Kogyo Co., Ltd.), polyester polyol (product name: Adecan You Ace) F9-30 Asahi Denka Kogyo product) 14 parts by weight, vinyl chloride-vinyl acetate copolymer (trade name: Zeon 400x)
150P1 Nippon Zeon Co., Ltd. product) 9 parts by weight and dibutyltin dilaurate (Stabilizer KS2Ol Kyodo Yakuhin Co. product) 0.2 parts by weight were mixed into a seconder and heated at a temperature of 100 to 1.
The three powders were mixed and kneaded at 10°C, and this kneaded product was further heated to a temperature of 6°C.
The two powders are kneaded using a mixing roll at 0 to 70°C to obtain a kneaded product. This kneaded material is cooled and then cut with a pelletizer to obtain a pellet-shaped coloring composition. This is designated as sample 1. It has very good solubility and dispersibility, which are listed in Table 1. Example 2 Carbon black (#45B1 product from Mitsubishi Chemical Industries, Ltd.) 4 parts, thermoplastic polyester urethane resin (Rezamin P9l4 product from Dainichiseika Industries Ltd.) 30 parts
Parts by weight, 2 parts by weight of polyester polyol (Adekanyu Ace F9-30, product of Asahi Denka Kogyo Co., Ltd.), Vinyl chloride-vinyl acetate copolymer (trade name: Zeon 400 x 150P)
1 Nippon Zeon Co. product) 1 weighing part, dibutyltin dilaurate (Stabilizer KS2Ol Kyodo Yakuhin Co. product) 0.
2 parts by weight were blended into a kneader, mixed and kneaded at a temperature of 95 to 105°C, and then the kneader was heated to a temperature of 60 to 70'C.
The mixture is kneaded for 20 minutes using a mixing roll to obtain a kneaded product.

After cooling, this kneaded material is cut with a pelletizer to obtain a pellet-like colored composition. This is designated as sample 2. This colored composition has excellent suitability for coating films and also has excellent stability as a coating material. Example 3 63 parts by weight of Permanent Yellow GG (Hoechst product), 24 parts by weight of thermoplastic urethane resin (Lethermin P9l45, product of Dainichiseika Kogyo Co., Ltd.), 5 parts by weight of polyester polyol (ADEKA UACE F9-30, product of Asahi Denka Kogyo Co., Ltd.) Parts by weight, vinyl chloride-vinyl acetate (Zeon 400 x 150P
1 Nippon Zeon Co. product) 8 parts by weight, dibutyltin dilaurate (Stabilizer KS2O. Kyodo Yakuhin Co. product) 0.
Blend 1 part by weight in a seconder at a temperature of 95 to 10C),
3 powders are mixed and kneaded, and this mixture is further kneaded into 2 powders using a mixing roll at 60 to 70°C to obtain a kneaded product.

This kneaded material is cooled and then cut with a pelletizer to obtain a pellet-shaped colored composition. This is designated as sample 3. This colored composition was stably dispersed in a solvent (dimethylformamide, methyl ethyl ketone) and was able to form a glossy coating without uneven color. Details are shown in Table 1.
Comparative Example 1 25 parts by weight of copper phthalocyanine blue (Cyanine Blue 4920, a product of Dainichiseika Kogyo Co., Ltd.) and 75 parts by weight of polyester polyol (Adekanyu Ace Y52-51, a product of Asahi Denka Kogyo Co., Ltd.) were blended and kneaded using three rolls. The meat is ground to obtain a pasty coloring composition.

This is designated as sample 4. This colored composition aggregates over time in a urethane resin solution containing a solvent. Note that when a coating film is formed using this colored composition, bleeding of the polyol is observed. Comparative Example 2 25 parts by weight of copper phthalocyanine blue (Cyanine Blue 4920, a product of Dainichiseika Kagyo Co., Ltd.), solid polyester polyol (
ADEKA UACE F9-30 Asahi Denka Kogyo product) 75
Parts by weight are blended and kneaded by heating with three rolls to obtain a solid coloring composition.

This is designated as sample 5. This colored composition is well dispersed in solvents and urethane resin solutions, but tends to aggregate over time. When this coloring composition is used, polyol bleed is hardly observed in the coating film. Comparative Example 3 5 parts by weight of copper phthalocyanine blue (Cyanine Blue 4920, product of Dainichiseika Industries, Ltd.), thermoplastic urethane resin, (
Rezamin P9l45, Dainichiseika Chemical Co., Ltd. product) 5 weighing parts,
The mixture was blended in a kneader, mixed and kneaded into three powders at 110 to 130'C, and then kneaded into two powders using a mixing roll at 70 to 80C to obtain a kneaded product.

After cooling, this kneaded material is cut with a pelletizer to obtain a pellet-shaped colored composition. This is designated as sample 6. This coloring composition is difficult to dissolve in solvents, and when a coating film is formed using this composition, aggregation of pigments is observed on the surface. Comparative Example 4 Carbon black (#45B1 Mitsubishi Chemical Industries product) 2
80 parts by weight of polyester polyol (ADEKANYU ACE Y52-51, manufactured by Asahi Denka Kogyo Co., Ltd.) were blended and kneaded using three rolls to obtain a colored composition in the form of pellets.

This is designated as sample 7. This colored composition has somewhat poor dispersion in a urethane resin solution containing a solvent, and when a coating film is formed, bleeding of the polyol is observed on the surface. Comparative Example 5 Carbon black (#45B1 Mitsubishi Chemical Industries product) 2
0 parts by weight and 8 parts of a solid polyester polyol (Adekanyu Ace F9-30, a product of Asahi Denka Kogyo Co., Ltd.) were blended, and heated and kneaded with three rolls to obtain a solid coloring composition. .

This is designated as sample 8. This colored composition tends to be slightly poorly dispersed in a urethane resin solution, and when a coating film is formed, polyol bleed is not observed on the surface much. Comparative Example 6 *1 5 weight parts of carbon black (#45B1 Mitsubishi Chemical Industries Co., Ltd. product) and 5 weight parts of thermoplastic urethane resin (Lezamin P9l45. Dainichiseika Industries Co., Ltd. product) were blended into a seconder, and 95
~10C) Three powders are mixed and kneaded at 0C, and this kneaded product is further kneaded into two powders using a 70-8 (generation) mixing roll to obtain a kneaded product.

Claims (1)

[Claims] 1 10 to 90 parts by weight of thermoplastic polyurethane, 1 to 20 parts by weight of vinyl chloride-vinyl acetate copolymer, 10 to 9 parts by weight of pigment
A coloring composition for a polyurethane resin coating comprising 0 parts by weight and 1 to 50 parts by weight of a polyester polyol.