JP3439596B2 - Colored resin composition for flow pattern formation - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a colored resin composition for forming a flow pattern which produces a colored flow pattern on an olefin resin.

[0002]

2. Description of the Related Art Conventionally, various methods have been used as a method for imparting a colored pattern or the like to a synthetic resin. For example, a method of obtaining a molded product having various patterns by mixing a synthetic resin with a filler such as a scaly, rod-shaped, fibrous or thread-shaped resin and molding.
One of the poorly compatible resins is mixed with a pigment or the like to be colored, and this colored resin and the other incompatible resin are mixed and molded to obtain a molded product having an incompatible flow pattern. Methods etc. are known. However, in the method of blending and molding the filler, it is difficult to obtain a molded product having a marble-like flow pattern because the filler has a dot-like pattern. On the other hand, in the method of mixing the resins having poor compatibility with each other, the surface of the resin molded product may be peeled off, which is a problem in terms of physical properties of the product.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a thermoplastic resin molded product having a clear flow pattern such as marble or wood grain, which can be easily obtained by a conventional molding machine. It is to provide a colored resin composition for forming.

[0004]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to solve the above-mentioned problems, as a carrier resin for a colored resin composition for forming a flow pattern, a cyclic olefin resin and / or It was found that a polymethylpentene resin is adopted, and that a synthetic rubber and an adhesiveness-imparting resin are mixed in the molded product, and a molded product having a beautiful flow pattern can be obtained without surface peeling from the other resin mixed. Has reached the present invention. That is, the present invention provides a cyclic olefin resin and / or polymethylpentene resin (A) ,
A composition comprising a synthetic rubber (B) , an adhesiveness-imparting resin (C) and a pigment (D) , and based on 100 parts by weight of the component (A).
(B) component 70 to 30 parts by weight, (C) component 30 to 5
Parts by weight of the component (D) of 100 to 0.1 parts by weight
Resin composition, olefin polymer resin, polystyrene resin
Oil, ABS resin, polyester resin, polyphenylene
At least one selected from ether resin and AS resin
1 to 50 parts by weight with respect to 100 parts by weight of the resin
It is a colored resin composition for flow pattern formation characterized by the above.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The cyclic olefin resin as the component (A) used in the present invention is a copolymer obtained by addition-polymerizing an α-olefin and a cyclic olefin, a polymer obtained by ring-opening polymerization of a cyclic olefin, or a copolymer thereof. It is selected from the group consisting of polymers and hydrogenated products thereof. Specific examples of the α-olefin include, for example, ethylene, propylene, 1-butene, 3-
Methyl-1-butene, 4-methyl-1-pentene, 1-
Hexene and the like can be mentioned. Examples of the cyclic olefins used in the present invention include cyclic olefins and cyclic dienes. Specific examples of the cyclic olefin include, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6- Trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-
Ethylidene-2-norbornene, 5-vinylnorbornene, 1,2-dihydrodiclopentadiene, 5-dimethylaminonorbornene, 5-methyl-5-phenyl-bicyclo [2.2.1] hept-2-ene, 5-tolyl. −
Bicyclo [2.2.1] hept-2-ene, 5- (ethylphenyl) -bicyclo [2.2.1] hept-2-ene and the like can be mentioned. Specific examples of cyclic dienes include 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,4-cycloheptadiene, 1,4-cyclooctadiene, dicyclopentadiene and the like can be mentioned.
Examples of the polymethylpentene as the component (A) used in the present invention include 4-methylpentene-1. Examples of the synthetic rubber (B) in the composition of the present invention include styrene / butadiene rubber, chloroprene rubber, butyl rubber, polybutene, ethylene / propylene rubber, nitrile / butadiene rubber, isoprene rubber and isoprene / isobutylene rubber. On the other hand, examples of the adhesion-imparting resin (C) in the composition of the present invention include ethylene-
Examples thereof include vinyl acetate copolymers, acrylic resins, maleic acid resins and epoxy resins. Further, the pigment (D) in the composition of the present invention may be those conventionally used in various resins, and the kind and combination thereof are not particularly limited. For example, insoluble azo pigments, condensed azo pigments, anthraquinone pigments, isoindolinone pigments,
Examples thereof include perylene pigments, perinone pigments, phthalocyanine pigments, quinacridone pigments, dioxazine pigments, complex oxide pigments, titanium oxide, red iron oxide, iron black, navy blue, ultramarine blue, yellow lead, and carbon black. The synthetic rubber (C) as the component (B) with respect to the cyclic olefin resin and / or polymethylpentene resin as the component (A) in the composition of the present invention
Regarding the blending ratio of the adhesiveness-imparting resin as the component and the pigment as the component (D), the amount of the component (B) is 7 per 100 parts by weight of the component (A).
0 to 30 parts by weight, component (C) 30 to 5 parts by weight, component (D) 1
It must be in the range of 0.00 to 0.1 part by weight.
If the blending amount of the component (B) is less than 30 parts by weight, the flow pattern intended by the present invention will not sufficiently appear, and if it exceeds 70 parts by weight, the rigidity will be significantly lowered, which is not preferable. When the amount of the component (C) is less than 5 parts by weight, the components (A) and (B) cause a peeling phenomenon, and when the amount exceeds 30 parts by weight, high fluidity is not preferable. When the amount of component (D) is less than 0.1 part by weight, the colored pattern does not appear clearly, which is not preferable. Further, if it exceeds 100 parts by weight, the color tone of the pigment itself becomes strong, and it becomes difficult to see the pattern, which is not preferable. The resin composition of the present invention is preferably prepared by melt-kneading, and as a method thereof, a known method, for example, a method of kneading using a Banbury mixer, a mixing roll, a uniaxial or biaxial extruder, or the like. Can be used. In the composition of the present invention, other components such as a filler, a heat stabilizer, an antioxidant, a nucleating agent, a lubricant, an antistatic agent, an anti-UV agent, and other polymers are included as long as the physical properties are not impaired. Etc. can be blended. The colored resin composition for flow pattern formation of the present invention thus obtained is melt-kneaded with a thermoplastic synthetic resin which is usually used for molding, and an extrusion molding machine, an injection molding machine, a hollow molding machine, a film molding machine. Then, a molded product having a flow pattern can be obtained. Examples of the thermoplastic synthetic resin used here include olefin polymer resin, polystyrene resin, AB
Examples thereof include S resin, polyester resin, polyphenylene ether resin, and AS resin, and olefin polymer resin and the like are particularly preferable. The mixing ratio of the resin composition of the present invention to the thermoplastic synthetic resin is 1 to 50 parts by weight, preferably 3 to 30 parts by weight, relative to 100 parts by weight of the thermoplastic synthetic resin. .
If it is less than 1 part by weight, the flow pattern does not appear clearly. On the other hand, if it exceeds 50 parts by weight, the coloring density by the pigment becomes high and the pattern becomes unclear. The resin composition of the present invention and the thermoplastic synthetic resin are mixed by a commonly used blending means,
For example, a mixer such as a tumbler, a V blender, or a Henschel mixer is used.

[0006]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 Polymethylpentene [trade name: TPX MBZ230
Mitsui Petrochemical Co., Ltd.] 60 parts by weight of polybutene [Product name: Polybutene P2000 Mitsui Petrochemical Co., Ltd.]
30 parts by weight of ethylene / methyl acrylate / maleic anhydride copolymer [trade name: Bennet DN-60 Nagase & Co., Ltd. product] 10 parts by weight were mixed, and copper phthalocyanine green pigment [trade name: cyanine green 2GO] was added to this.
Daiichi Seika Kogyo Co., Ltd.] 0.3 parts by weight and 0.2 parts by weight of magnesium stearate were added and mixed with a Henschel mixer, and the mixture was mixed with an extrusion granulator (diameter 40 mmφ, L /
D = 32) was melt-kneaded at 250 ° C. to obtain a green colored resin composition. On the other hand, 100 parts by weight of polypropylene resin [trade name: Hypol J600 Mitsui Petrochemical Co., Ltd. product] and 0.5 parts by weight of titanium dioxide pigment were kneaded in advance. 2 parts by weight of the resin composition was blended, and a molded plate was molded at a molding temperature of 210 ° C. using an inline screw type injection molding machine. The obtained molded plate had a beautiful flow pattern of green on a white background. The surface of the molded plate was a smooth surface, and the cellophane adhesive tape was attached to the surface of the molded plate and peeled off. As a result, no surface peeling occurred. Example 2 Polymethylpentene [trade name: TPX MBZ230
Mitsui Petrochemical Co., Ltd.] 65 parts by weight of polyisoprene rubber [Product name: JSR IR2200 Nippon Synthetic Rubber]
Products Co., Ltd.] 25 parts by weight, ethylene / ethyl acrylate / maleic anhydride copolymer (trade name: Bondine TX
8030 Sumika CDF Chemical Co., Ltd. product) 10 parts by weight are mixed, and copper phthalocyanine green pigment [Product name: Cyanine Green 2GO Dainichiseika Kogyo Co., Ltd. product]
0.3 parts by weight of magnesium stearate and 0.2 parts by weight of magnesium stearate were added and mixed in a Henschel mixer, which was melt-kneaded at 250 ° C. in an extrusion granulator (bore diameter 40 mmφ, L / D = 32). A green colored resin composition was obtained. Polypropylene resin [Product name: Hipol J600 Mitsui Petrochemical
Products Co., Ltd.] 2 parts by weight of the green colored resin composition obtained above was mixed with 100 parts by weight, and a molded plate was molded at a molding temperature of 210 ° C. using an inline screw type injection molding machine. The resulting molded plate had a beautiful semi-transparent background color and a beautiful green flow pattern. The surface of the molded plate was a smooth surface, and the cellophane adhesive tape was attached to the surface of the molded plate and peeled off. As a result, no surface peeling occurred. Example 3 Norbornene polymer [trade name: Nosolex Nippon Zeon Co., Ltd. product] 60 parts by weight, polybutene [trade name: Polybutene P2000 Mitsui Petrochemical Co., Ltd. product] 30 parts by weight, ethylene / ethyl acrylate / maleic anhydride copolymer 10 parts by weight of a polymer [trade name: Bondine TX8030 Sumika Chemical Industries, Ltd. product] was mixed, and a polyazo pigment [trade name: Chromo Fine Yellow 5980] was added to this.
Dainichi Seika Kogyo Co., Ltd.] 0.35 parts by weight and 0.2 parts by weight of magnesium stearate were added and mixed with a Henschel mixer, which was then extruded and granulated (a diameter of 40 mmφ, L
/ D = 32) and melt-kneaded at 145 ° C. to obtain a yellow colored resin composition. On the other hand, polypropylene resin [Product name: Hipol J600 Mitsui Petrochemical Co., Ltd. product] 10
2 parts by weight of the brown colored resin composition obtained above was mixed with 100 parts by weight of a white polypropylene resin composition prepared by previously kneading 0.5 parts by weight of a titanium dioxide pigment with 0 parts by weight, and an in-line screw type injection molding machine was used. Molding temperature 210
Molded plates were molded at ° C. The obtained molded plate had a beautiful flow pattern of yellow on a white background. The surface of the molded plate was a smooth surface, and the cellophane adhesive tape was attached to the surface of the molded plate and peeled off. As a result, no surface peeling occurred. Example 4 Cyclic olefin copolymer [trade name: Apel APL6
509 Mitsui Petrochemical Co., Ltd. product] 60 parts by weight, polybutene [trade name: Polybutene P2000 Mitsui Petrochemical Co., Ltd.
Product] 30 parts by weight, ethylene / ethyl acrylate / maleic anhydride copolymer [Brand name: Bondine TX80
30 Sumika CDF Chemical Co., Ltd. product] 10 parts by weight was added to this, and a petal pigment [trade name: Tarox T-10
-A Titanium Industry Co., Ltd. product] 0.5 parts by weight and 0.2 parts by weight of magnesium stearate were added and mixed with a Henschel mixer, and this was mixed with an extrusion granulator (bore diameter 40 mmφ,
L / D = 32) and melt-kneaded at 260 ° C. to obtain a brown colored resin composition. On the other hand, polypropylene resin [Product name: Hipol J600 Mitsui Petrochemical Co., Ltd. product] 10
2 parts by weight of the yellow colored resin composition obtained above was mixed with 100 parts by weight of a white polypropylene resin composition obtained by previously kneading 0.5 parts by weight of a titanium dioxide pigment with 0 parts by weight, and using an in-line screw type injection molding machine. Molding temperature 210
Molded plates were molded at ° C. The obtained molded plate had a white background color and a beautiful brown flow pattern. The surface of the molded plate was a smooth surface, and the cellophane adhesive tape was attached to the surface of the molded plate and peeled off. As a result, no surface peeling occurred. Example 5 Cyclic olefin copolymer [trade name: Apel APL6
509 Mitsui Petrochemical Co., Ltd. product] 55 parts by weight, polybutadiene rubber [trade name: JSR BR01 Japan Synthetic Rubber
Products] 10 parts by weight, polybutene [Product name: Polybutene P2000 Mitsui Petrochemical Co., Ltd. products] 20 parts by weight, ethylene / vinyl acetate copolymer [Product name: Ultracene 5
41 Tosoh Co., Ltd. product] 15 parts by weight, and copper phthalocyanine green pigment [trade name: Cyanine Green 2GO Dainichiseika Chemicals Co., Ltd. product] 0.3 parts by weight, magnesium stearate 0.2 parts by weight Was added and mixed with a Henschel mixer, and this was mixed with an extrusion granulator (caliber 40
mmφ, L / D = 32) and melt-kneaded at 260 ° C. to obtain a green colored resin composition. On the other hand, 100 parts by weight of polypropylene resin [trade name: Hypol J600 Mitsui Petrochemical Co., Ltd. product] and 0.5 parts by weight of titanium dioxide pigment were kneaded in advance. 2 parts by weight of the resin composition is blended,
A molded plate was molded at a molding temperature of 210 ° C. using an in-line screw type injection molding machine. The obtained molded plate had a beautiful flow pattern of green on a white background. The surface of the molded plate was a smooth surface, and the cellophane adhesive tape was attached to the surface of the molded plate and peeled off. As a result, no surface peeling occurred.

Comparative Example 1 Polymethylpentene [trade name: TPX MBZ230
Mitsui Petrochemical Co., Ltd. product] 100 parts by weight, copper phthalocyanine pigment [trade name: Cyanine Green 2GO Dainichiseika Kogyo Co., Ltd. product] 0.5 parts by weight, magnesium stearate 0.2 parts by weight are added. Was mixed with a Henschel mixer, and this was extruded granulator (diameter 40 mmφ, L / D = 32)
Was melt-kneaded at 250 ° C. to obtain a green colored resin composition. Polypropylene resin [Product name: High Pole J60
0 Mitsui Petrochemical Co., Ltd.] 2 parts by weight of the green colored resin composition obtained above was mixed with 100 parts by weight, and a molded plate was molded at a molding temperature of 210 ° C. using an in-line screw type injection molding machine. The obtained molded plate had a semi-transparent background color and a green flow pattern, but the surface smoothness of the molded plate was poor. Further, the cellophane adhesive tape was attached to the surface of the molded plate and peeled off, resulting in surface peeling. Comparative Example 2 Cyclic olefin copolymer [trade name: Apel APL6
509 Mitsui Petrochemical Co., Ltd. product] 100 parts by weight of polyazo pigment [trade name: Chromofine Yellow 5980 Dainichiseika Chemicals Co., Ltd. product] 0.35 parts by weight, magnesium stearate 0.2 parts by weight, Is mixed with a Henschel mixer, and this is granulated by an extruder (diameter 40 mmφ, L / D
= 32), the mixture was melt-kneaded at 260 ° C. to obtain a yellow colored resin composition. On the other hand, 100 parts by weight of a polypropylene resin [trade name: Hypol J600, a product of Mitsui Petrochemical Co., Ltd.] and 0.5 parts by weight of a titanium dioxide pigment were kneaded in advance. 2 parts by weight of the resin composition was blended, and a molded plate was molded at a molding temperature of 210 ° C. using an inline screw type injection molding machine. The obtained molded plate had a white background color with a yellow flow pattern, but the surface smoothness of the molded plate was poor. Further, the cellophane adhesive tape was attached to the surface of the molded plate and peeled off, resulting in surface peeling. Comparative Example 3 Polybutene [trade name: Polybutene P2000 Mitsui Petrochemical Co., Ltd. product] 100 parts by weight, copper phthalocyanine pigment [trade name: Cyanine Green 2GO Dainichiseika Kogyo Co., Ltd.]
[Product] 0.5 parts by weight of magnesium stearate and 0.2 parts by weight of magnesium stearate were added and mixed in a Henschel mixer, and the mixture was mixed with an extrusion granulator (bore diameter 40 mmφ, L / D = 32) to 1
The mixture was melt-kneaded at 40 ° C. to obtain a green colored resin composition. 2 parts by weight of the green colored resin composition obtained above was mixed with 100 parts by weight of a polypropylene resin [trade name: Hypol J600, a product of Mitsui Petrochemical Co., Ltd.], and the molding temperature was 210 ° C. using an in-line screw type injection molding machine. The molded plate was molded with. The obtained molded plate had good surface smoothness and did not cause surface peeling by the cellophane adhesive tape, but no flow pattern appeared. Comparative Example 4 Polymethylpentene [trade name: TPX MBZ230
Mitsui Petrochemical Co., Ltd. product] 50 parts by weight, polybutene [Product name: Polybutene P2000 Mitsui Petrochemical Co., Ltd. product] 5
0.5 parts by weight of copper phthalocyanine pigment [trade name: Cyanine Green 2GO, product of Dainichiseika Kogyo Co., Ltd.] in 0 parts by weight,
0.2 parts by weight of magnesium stearate was added and mixed with a Henschel mixer, which was melt-kneaded at 250 ° C. with an extrusion granulator (caliber 40 mmφ, L / D = 32) to give a green colored resin composition. I got a thing. Polypropylene resin [trade name: Hypol J600 Mitsui Petrochemical Co., Ltd. product] 100 parts by weight of the green colored resin composition 2 obtained above
Parts by weight were blended and a molded plate was molded at a molding temperature of 210 ° C. using an inline screw type injection molding machine. The obtained molded plate had good surface smoothness and a slight amount of surface peeling by the cellophane adhesive tape, but the appearance of the flow pattern was not satisfactory.

[0008]

EFFECTS OF THE INVENTION The colored resin composition for flow pattern formation of the present invention is blended in a small amount with a ground color molding resin such as a polyolefin resin which is generally used as a molding resin, and a molded article is prepared based on this composition. By obtaining the above, a molded product having a beautiful flow pattern can be easily obtained. The obtained molded product having a flow pattern has excellent surface smoothness, and the phenomenon of surface peeling between the colored resin composition for flow pattern formation and the background color forming resin does not occur. The colored resin composition for flow pattern formation of the present invention is particularly effective for obtaining a marble-like or natural stone-like synthetic resin composition.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 35/00 C08L 35/00 45/00 45/00 101/00 101/00 (56) Reference JP-A-56-20053 ( JP, A) JP 54-102344 (JP, A) JP 6-329882 (JP, A) JP 9-31207 (JP, A) JP 2000-191794 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (5)

(57) [Claims] 1. A cyclic olefin resin and / or polymethylpentene resin (A) , a synthetic rubber (B) , and an adhesiveness-imparting resin.
A composition comprising (C) and a pigment (D) , and (A)
70 to 30 parts by weight of component (B) with respect to 100 parts by weight of component
Parts, (C) component 30 to 5 parts by weight, (D) component 100 to
0.1 parts by weight of the resin composition was added to the olefin polymer.
Combined resin, polystyrene resin, ABS resin, polyester
Resin, polyphenylene ether resin and AS resin
For 100 parts by weight of at least one selected resin
And 1 to 50 parts by weight of the resin composition are mixed together to form a flow pattern-forming colored resin composition. 2. The colored resin composition for flow pattern formation according to claim 1, wherein the cyclic olefin resin is polynorbornene, a copolymer of ethylene and 2-norbornene, or dicyclopentadiene. 3. The colored resin composition for flow pattern formation according to claim 1, wherein the polymethylpentene resin is a polymer of 4-methylpentene-1. 4. The synthetic rubber is styrene-butadiene rubber, chloroprene rubber, butyl rubber, polybutene, ethylene.
A propylene rubber, a nitrile-butadiene rubber, an isoprene rubber, or an isoprene-isobutylene rubber.
A colored resin composition for forming a flow pattern as described above. 5. The adhesion-imparting resin is an ethylene-vinyl acetate copolymer, an ethylene / ethyl acrylate / maleic anhydride copolymer, an ethylene / methacrylate / maleic anhydride copolymer, a maleic acid resin or an epoxy resin. A colored resin composition for flow pattern formation according to claim 1.