JPH06271681A - Material for forming fleck pattern and its composition - Google Patents

Abstract

PURPOSE:To provide the subject material composed of a polyurethane particle having prescribed-size flecks each colored with a dye or a pigment, excellent in abrasion resistance, moldability and visual appearance and useful as an admixture for PE, PP, etc. CONSTITUTION:The objective material is composed of a polyurethane particle having 10 to 200 mesh-size flecks colored with an azo-based dye or pigment. In addition, a composition for forming a fleck pattern can be obtained by blending this material with a dispersant such as a wax and a dye or a pigment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for forming a speckled pattern on a synthetic resin, and more specifically, it is blended with a thermoplastic resin such as polyethylene or polypropylene or a thermosetting resin such as unsaturated polyester. The present invention relates to a spot pattern molding material and a composition for obtaining a molded product having a spot pattern.

[0002]

2. Description of the Related Art As a method for forming a speckled pattern on a synthetic resin molded product, a method using colored aluminum flakes as a material for forming the speckled pattern, a method using colored glass, a method using colored fibers, and a colored mica are used. There are ways.
Of these, the method using colored aluminum flakes
For example, in general extrusion molding with rigid vinyl chloride,
There is a problem that the colored layer on the surface of the aluminum flakes peels off due to heat and shearing force, and the appearance is impaired. The method using colored glass is stable against heat and shearing force and can be used for most resins and molding methods. However, there is a problem of wear of the molding machine, and it is practically impossible to use it for a thermoplastic resin that involves melting and shearing of the resin during molding.

In the method using colored fibers, for example, in this method disclosed in JP-A-49-17831, discoloration of fibers due to heat is unavoidable, and at 230 ° C.
Was the upper limit of the molding temperature. The method using colored mica is
Although disclosed in Japanese Patent Application Laid-Open No. 2-245037, it is difficult to use this method in an actual molded product due to the color of colored mica and insufficient coloring. Since conventional pattern molding materials cannot be colored freely and have problems such as abrasion of a molding machine, it is preferable to use colored particles of thermosetting resin such as melamine resin, phenol resin and urea resin. No. 51-123247. However, since it itself is hard, when it is used for blow molding, inflation molding, T-die extrusion molding, etc., in which resin is stretched during molding, there is a problem that molding defects such as pinholes occur.

[0004]

The object of the present invention is to solve the drawbacks of the conventional compounding agents that form spot patterns on synthetic resins and to use them for all synthetic resins, depending on molding conditions and molding methods. It is to provide a compounding agent capable of forming a speckled pattern without doing.

[0005]

[Means for Solving the Problems] In the first invention, there are 1 spots.
A spotting pattern molding material for synthetic resin, which is polyurethane particles colored with a dye or pigment in a size of 0 to 200 mesh. The second invention is a spot pattern forming composition comprising the colored polyurethane particles of the first invention, a dispersant and / or a dye / pigment. In the present invention, polyurethane is a foamed urethane which is usually produced as a soft, semi-rigid, hard urethane, and as the polyol, polyester polyol, polyether polyol, polycarbonate carbonate, isocyanate. As tolylene diisocyanate (TDI), methylene diisocyanate (MDI), cludomethylene diisocyanate, ethylene glycol as a crosslinking agent, water and freon as a foaming agent, dibutyltin dilaurate, tin octenoate as a catalyst, etc. Manufactured as a raw material.

This urethane resin is roughly crushed to a size of 1 cm to 3 mm square, and is further crushed to a powder of 10 to 200 mesh by a crusher such as a hammer mill (Hosokawa Micron) or Victory Mill (Hosokawa Micron) and patterned. Used as a molding material. Since the polyurethane resin can be colored with ordinary pigments, it can be colored in various colors. Examples of dyes and pigments include azo-based, anthraquinone-based, phthalocyanine-based, quinacridone-based, isoindolinone-based, perylene-based organic dyes and pigments, titanium dioxide, iron oxide,
Inorganic pigments such as ultramarine, cobalt blue and yellow iron oxide can be used.

Further, since urethane particles have high elasticity, pinholes of molded products can be prevented. The particle diameter of the urethane particles is preferably 10 to 200 mesh, and if it is smaller than 200 mesh, it becomes difficult to recognize as a spot pattern, and if it is larger than 10 mesh, not only a beautiful spot pattern is not formed, but also the moldability is adversely affected. The dispersant in the present invention is necessary for dispersing the urethane particles and the dye / pigment used for the background of pattern formation in the synthetic resin. Examples of the dispersant include waxes such as polyethylene wax, metal soaps such as magnesium stearate, aluminum stearate, zinc stearate and calcium stearate, higher fatty acids such as stearic acid and palmitic acid, and higher grades such as ethylenebisamide and stearylamide. There are fatty acid amides, higher fatty acid esters such as butyl stearate and ethylene glycol monostearate, and higher alcohols such as stearyl alcohol. Liquid dispersants include phthalates such as dioctyl phthalate, dibutyl phthalate, dibenzyl phthalate and dicyclohexyl phthalate. Acid ester, phosphoric acid ester such as triglycyl phosphate, trioctyl phosphate, dibenzyl sebacate dibutoxyethyl sebacate dibutoxyethyl adipate diisoo Fatty dibasic acid esters, triethylene glycol or tetraethylene glycol with fatty acid esters having 6 to 8 carbon atoms such as Chiruajipeito,
Liquid polyesters and polyethylene glycols obtained from dibasic acids such as adipic acid and azelaic acid and diols such as ethylene glycol and diethylene glycol are available.

The composition according to the present invention is of a type which is usually used as a coloring agent for plastics and which is dry color,
It can be supplied as a masterbatch, paste color, etc. When used as a dry color, the proportion of each component of the composition is 0 to 40% by weight of the dispersant and 100 to 100 of the urethane particles.
60% by weight is preferable, and when used as a masterbatch, carrier resin 40 to 90% by weight, dispersant 5 to 30% by weight
-Urethane particles are preferably 5 to 30% by weight. When used as a paste color, the liquid dispersion medium 70-30
% By weight and 10 to 70% by weight of urethane particles are preferable. In addition to the above components, 10% to 1% of colored polyurethane particles
Dyes and pigments can be appropriately blended within a range of 0 to 50% as a coloring component of the molding resin with respect to 00% and a dispersant of 0 to 90%.

When the compounding agent of the present invention is used as a master batch, a carrier resin is compounded as an essential component. As such a carrier resin, thermoplastic resins such as polyethylene, polypropylene, carboxyl group-containing polypropylene, carboxyl group-containing polyethylene, ABS resin, polystyrene, polyvinyl chloride, AS resin can be used.
This masterbatch is generally produced by kneading with a carrier resin / dispersant and, if necessary, a pigment / stabilizer using a kneader such as a single-screw / two-screw extruder / kneader / Banbury mixer to form pellets. Any method is acceptable.

[0010]

EXAMPLES Examples will be described below. In the examples, “part” means “part by weight” and “%” means “% by weight”. Example 1 20 parts of carbon black (Mitsubishi Carbon # 45, manufactured by Mitsubishi Kasei) and polyether polyol (Sannicks
PG-3000, manufactured by Sanyo Kasei Co.)
The meat is kneaded with a main roll to obtain a black paste. 5 parts of this paste, 100 parts of Sannix GP-3000, 1.0 part of silicone oil (Toray Silicone SH-190, made from Toray Silicone), 0.4 parts of octenoic acid.
Parts and 40 parts of water were uniformly stirred and mixed, and tolylene diisocyanate was added at an index of 105 to perform free foaming to obtain a black urethane foam. After crushing this urethane foam with Victory Mill, sieving it for 40-8
A 0 mesh urethane powder was obtained. This is designated as Sample 1.

Samples 1 and 4 parts, titanium oxide (Taipec C
R-80, made by Ishihara Sangyo) 2 parts, and magnesium stearate 4 parts are uniformly mixed with a high-speed stirrer. This mixture is polyethylene (HIZEX 5100B, manufactured by Mitsui Petrochemical)
When 0.3 part was added to 100 parts and uniformly mixed and then a blow bottle was prepared by a blow molding machine (manufactured by Placo), a bottle having a uniform spot pattern was obtained. The evaluation results are shown in Table 1. Comparative Example 1 Colored aluminum flakes (ASTRO Flake # 40, manufactured by Fukuda Metal Industry Co., Ltd.) were used instead of the sample 1 of Example 1 to obtain a spotted pattern colored bottle of colored aluminum flakes.

The evaluation results are shown in Table 1. In Example 1, a normal molded product was obtained, whereas in the aluminum flake, cracks occurred at the flake portion. Comparative Example 2 Instead of the sample 1 of Example 1, a commercially available phenol resin plate was roughly crushed and sieved to obtain 40 to 80 mesh phenol resin particles. Molding was performed using this to obtain a spotted colored bottle of phenol resin. In Example 1, a normal molded product was obtained, whereas in the phenol resin, peeling of the pattern was observed.

The evaluation results are shown in Table 1. Example 2 45 parts of iron oxide (Toda Color 120ED, manufactured by Toda Kogyo),
Mitsubishi Carbon # 45, 5 parts and polyether polyol (Sumiphen 3900, Sumitomo Bayer Urethane) 50
After mixing the parts, the mixture is kneaded with 3 rolls to obtain a brown paste. 10 g of this paste, 3900 Sumifene
100 parts, 1,4-butanediol 10 parts, triethylenediamine 1 part, DBTDL 0.05 part, and trichlorofluoromethane 4 parts were stirred and mixed uniformly, and then Crude MDI (Millionate MR-200, made by Nippon Polyurethane) was used as an index. Then, 105 was added and put into a mold to obtain a urethane sheet. This urethane sheet was crushed with a Victory mill and then sieved to obtain a urethane portion of 40 to 80 mesh. This is designated as Sample 2.

500 parts of Sample 2 and 500 parts of unsaturated polyester (Polymer 6409, manufactured by Takeda Chemical Industries) are uniformly dispersed by a disperser such as a dissolver to obtain a paste. Further, as a coloring component, Taipaque CR-80, 58.
5 parts, Mitsubishi Carbon # 45, 0.5 parts, Toda Color 12
OED (1.0 part) and polymer (6409, 40 parts) were kneaded with a three-roll mill to obtain an ivory-colored paste. 2 parts of paste of spot pattern component, 2 parts of paste of coloring component, Polymer 6409, 26.8 parts, Low shrinkage imparting agent (Polymer 9965, Takeda Pharmaceutical Co., Ltd.) 10 parts, Calcium carbonate (NS100, Nitto Koki Co., Ltd.) 36 .4 parts, zinc stearate 0.7 parts, magnesium oxide (Kyowa mug # 1
00, Kyowa Chemical Co., Ltd.) 0.7 part, polymerization initiator (Perbutyl Z, NOF CORPORATION) 0.4 part Glass fiber (CS13E-2)
Twenty-five parts (27 SB, Nitto Boseki) are thoroughly stirred with a lab mixer to adjust the coloring compound. After this compound was left in an oven at 45 ° C for 48 hours, it was placed in a mold kept at 140 ° C and press-molded to obtain a molded plate having a uniform spot pattern.

The evaluation results are shown in Table 2. Comparative Example 3 Instead of the sample 2 of Example 2, 20-40 mesh cobalt-containing synthetic mica (manufactured by Topy Industries, Ltd.) was used for coloring to obtain a speckled pattern forming plate of colored mica. In Example 2, a molded product having a uniform pattern was obtained, whereas in synthetic mica, the molded product was separated in a sedimented form. The evaluation results are shown in Table 2. Comparative Example 4 Instead of the sample 2 of Example 2, a green rayon fiber having a length of 3 mm and a denier of 5 mm was used for coloring to obtain a spotted pattern forming plate of the fiber.

The evaluation results are shown in Table 2.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

Industrial Applicability According to the present invention, there can be provided a compounding agent which can be used for any synthetic resin and can form a speckled pattern without depending on molding conditions and molding methods.

Claims (2)

[Claims] 1. A speckle pattern molding material for synthetic resin, characterized in that it is polyurethane particles colored with dyes and pigments in a size of 10 to 200 mesh. 2. A spot pattern forming composition comprising the colored polyurethane particles according to claim 1, a dispersant, and / or a dye / pigment.