JP2000191794A - Coloring agent for marble-like pattern-having thermoplastic resin molding and molded product therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coloring agent for thermoplastic resins that can develop marble-like (flow) patterns on the surfaces of thermoplastic resin moldings by containing a specific coloring agent, a polybutene resin or the like and a poly(methylpentene) resin. SOLUTION: The objective coloring agent comprises (A) 0.1-60 pts.wt. of a colorant of 5-80 wt.% pigment content, (B) 1-50 pts.wt. of a polybutene resin or a butene-α-olefin copolymer, preferably having a molecular weight of 800,000-3,500,000, a density of 0.900-0.930, an MI value (according to JIS K6760) of 0.2-20, and (C) 5-90 pts.wt. of a poly(methylpentene) resin, preferably having an MI value (according to JIS D-1238 at 260 deg.C at a load of 5 kg) or 1-100 and a density of 0.82-0.85 with stereoregularity. Two or more kinds of these colorants different in hue are used and combined with a thermoplastic resin, kneaded to give molded products having marble-like patterns. The component A is prepared in the form of a color master batch, a color compound and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colorant for molding a marble-patterned thermoplastic resin for producing a marble-like (flow) pattern having a flow pattern on the surface of a molded article using a thermoplastic resin, and a molded article thereof. .

[0002]

2. Description of the Related Art Conventionally, FRP (fiber reinforced resin) molded articles using an unsaturated polyester resin which is a thermosetting resin have been actively manufactured and sold in daily necessities such as bathtubs and kitchenware provided with a marble pattern. I have. However, the marble pattern of the FRP molded product is manufactured by applying and curing a thermosetting resin on the surface of a synthetic resin sheet or a laser printed to obtain a beautiful marble patterned product. In this case, products are manufactured using a large amount of liquid resin or organic solvent, and the working environment is poor and the work is complicated, which is not preferable. For this reason, in recent years, in order to eliminate the above-mentioned complicated work, production of a molded article in which a fibrous substance or a flaky substance is mixed in advance in an unsaturated polyester resin has been attempted, but a satisfactory marble pattern molded article has been attempted. It is not preferable because it cannot be obtained.

[0003] On the other hand, in a molded article using a thermoplastic resin,
2. Description of the Related Art A molded article having a spot-like pattern in which a resin film, a fibrous substance, or the like is mixed in a thermoplastic resin is manufactured and sold. However, the mottled molded product is inferior in aesthetic sense as compared with the FRP molded product having a marble pattern on its surface, and no satisfactory product has yet been found. Furthermore, in recent years, it has been proposed to use two or more kinds of thermoplastic resins having poor compatibility at the time of coloring molding and blend them with a pigment. However, the obtained thermoplastic molded product is not only inferior in beauty than the marble pattern obtained in the FRP molded product, but also may have a surface exfoliated on the surface of the resin molded product, resulting in mechanical properties of the product (eg: There is a problem in terms of impact resistance).

[0004]

[Problems to be solved by the present invention]
In order to easily obtain a beautiful molded product that is comparable to the marble tone of an FRP molded product using an unsaturated polyester resin in a molded product using a thermoplastic resin, the softening point is used as a carrier resin to be used when producing a colorant. Therefore, the development of a colorant obtained by mixing and using two kinds of polyolefin resins different from each other, that is, a polymethylpentene resin and a polybutene resin or a butene-α-olefin copolymer was studied.

[0006]

That is, the invention of claim 1 of the present invention provides a colorant having a pigment content of 5 to 80% by weight of 0.1 to 60 parts by weight (A), a polybutene resin or a butene-α-olefin copolymer. A colorant for molding a marble-patterned thermoplastic resin, comprising 1 to 50 parts by weight of polymer (B) and 5 to 90 parts by weight of polymethylpentene resin (C). The present invention has two major features, the first being a polybutene resin or a butene-α-olefin copolymer (hereinafter referred to as a polybutene resin), which is a polyolefin-based resin having a different melting temperature as a carrier resin. (B) and the two components of polymethylpentene resin (C). The second feature is that the colorant (A) produced in advance is blended and used in (B) and (C), whereby the coloring which exhibits an excellent marble-like (flow) pattern is achieved. An agent is obtained.

Further, according to a second aspect of the present invention, a marble-patterned thermoplastic resin obtained by blending the component (C) with the previously obtained kneaded product comprising the components (A) and (B) according to the first aspect. It is a molding colorant. The feature of claim 2 is that when the component (A) and the component (B) are kneaded in advance and then the component (C) is blended, the combination of the component (B) and the component (C) described in the above claim 1 is obtained. The effect of the marble pattern is more remarkably exhibited. According to a third aspect of the present invention, there is provided a marble pattern molded product obtained by mixing and kneading a thermoplastic resin with two or more types of the marble pattern thermoplastic resin molding colorants having different colors according to the first embodiment. Accordingly, a molded article exhibiting a more beautiful marble pattern can be obtained. In this case, it is preferable to knead about 30 to 200 parts by weight of the thermoplastic resin with respect to 1 part by weight of the marble-patterned thermoplastic resin molding colorant of the present invention since the marble pattern is remarkably expressed. Further, in the invention of claim 4, two or more kinds of the marble-patterned thermoplastic resin molding colorants having different colors according to claim 2 are used,
By producing a marble pattern molded product obtained by blending and kneading a thermoplastic resin with the mixture, a molded product having a rich marble pattern and a beautiful marble pattern can be obtained. At this time, it is preferable to knead about 30 to 200 parts by weight of the thermoplastic resin with respect to 1 part by weight of the coloring agent for molding a marble pattern thermoplastic resin of the present invention, since the marble pattern is remarkably expressed.

In the present invention, when manufacturing a marble-patterned molded article, two or more kinds of colorants for forming a marble-patterned thermoplastic resin of the present invention which are mixed in different colors (tones) are used in molding. According to the invention, a more beautiful marble pattern molded product can be obtained. By adjusting the amount of the coloring agent to be used at this time, a marble-shaped molded article with a great variety can be obtained. In particular, the molded article obtained in claim 4 gives a very excellent marble pattern molded article,
It is much more aesthetically pleasing than a P marble product. As described above, the invention of claim 4 is a method of kneading the component (A) and the component (B) of the present invention, and then using two or more kinds of different colors as the component (C), and mixing them with a thermoplastic resin. To obtain a marble pattern molded product by kneading
A very beautiful marble (flow) pattern is exhibited, and the effect is more beautiful than FRP molded products. (A) used in the present invention
Examples of the form of the colorant of the component include color master batch and color compound conventionally used as colorants for thermoplastic resins. These colorants are obtained by blending a metal soap, wax, or the like as a dispersant with a pigment.

The pigment may be any pigment that has been conventionally used for coloring a thermoplastic resin. Examples thereof include phthalocyanine-based, quinacridone-based, anthraquinone-based, and azo-based organic pigments, titanium oxide, chromium oxide, and oxide pigments. Iron, car
And inorganic pigments such as bon black. (A)
The content of the pigment in the component is preferably from 5 to 80% by weight, and if it is less than 5% by weight, the marble pattern coloring effect, which is a feature of the present invention, is not sufficiently exhibited. Not only does not change the coloring effect, but also deteriorates the mechanical properties of the obtained molded article.
When the amount of the component (A) is 0.1 to 60 parts by weight, less than 0.1 part by weight is not preferable because the marble pattern is not sufficiently exhibited, and when it is more than 60 parts by weight, the marble pattern is obtained. It is not preferable because the mechanical properties are reduced. still,
If the content of the pigment in the component (A) is less than 5% by weight, the marble pattern is not sufficiently exhibited, which is not preferable.
If the amount is more than the weight percentage, the mechanical properties of the obtained molded article are undesirably reduced.

The polybutene resin of component (B) used in this component is not a conventionally used amorphous or viscous solution having a small molecular weight of, for example, about 150 to 50,000, but has a high purity as a monomer. Butene-1 is a crystalline thermoplastic resin having an ultra-high molecular weight and isotacticity obtained by regular polymerization, having a molecular weight of 800,000 to 3.5 million, a density of 0.900 to 0.930, and an MI value of 0.2 to 20 ( JIS-K-67
60) resin. The amount of the component (B) is 1 to 50.
If the amount is less than 5 parts by weight, the components (A) and (C) cannot be sufficiently blended, and the resulting molding is liable to peel off. If it is more than 50 parts by weight, the components (A) and ( C) The kneading of the components is facilitated, but it is difficult to obtain the effect of the marble pattern, which is not preferable.

As the polymethylpentene as the component (C), a homopolymer of 4-methylpentene-1 or 4-methylpentene-1 and an aliphatic hydrocarbon vinyl compound such as ethylene, propylene and butene-1, styrene, It is a copolymer with an aromatic hydrocarbon vinyl compound such as para-divinylbenzene and α-methylstyrene, and has an MI value of 1 to 100 (D-1238, 260
This resin has stereoregularity with a density of 0.82 to 0.85. The amount of component (C) used is 5 to 90 parts by weight. When the amount is less than 5 parts by weight, a marble pattern cannot be obtained, which is not preferable. When the amount is more than 50 parts by weight, kneading of the components (A) and (B) becomes insufficient, and the effect of the marble pattern is hardly obtained, which is not preferable.

[0012] The product of the present invention can be used, if necessary, as various thermoplastic resins such as olefin resin, polystyrene resin, AB
S resin, polyester resin or the like may be used as the diluting resin. However, when an olefin resin is used, a marble pattern is most clearly exhibited on the surface of the obtained molded product, which is optimal. A filler, a nucleating agent, a lubricant, an antioxidant, a heat stabilizer, an antistatic agent, and the like may be added to the product of the present invention as long as the physical properties are not impaired. In addition, the colorant for molding a marble-patterned thermoplastic resin of the present invention may be mixed with a colorant conventionally used or a color compound during the production of a molded article to produce a molded article. Further, one of the coloring agents for molding a marble-patterned thermoplastic resin having different colors according to the present invention.
Even if the seed or two or more kinds are mixed and diluted and kneaded with the thermoplastic resin, a marble-patterned molded article can be produced. In the production of a molded article using the marble-patterned thermoplastic resin molding colorant of the present invention, the mixture is melt-kneaded with a thermoplastic resin usually used for molding, and the marble-patterned molded article is produced by an extrusion molding machine, an injection molding machine, and a hollow molding machine. Can be obtained. Examples and comparative examples are described below.

Example 1 25% by weight of Karamasta batch (A) having a pigment content of 65% and a polybutene resin (BL: manufactured by Mitsui Chemicals, Inc .: BL
-7000) 30 parts by weight (B) and 45 parts by weight of polymethylpentene (manufactured by Mitsui Chemicals, Inc .: TPX-MX001) were mixed with a Henschel mixer, and then mixed using an extruder.
The mixture is melted and kneaded at ℃ to obtain a colorant for molding a marble-patterned thermoplastic resin of the present invention having a pigment content of 16.25%. 100 parts by weight of a polypropylene resin having a density of 0.91 is mixed with 2 parts by weight of the colorant for molding a marble-patterned thermoplastic resin, and the mixture is molded using an injection molding machine at a molding temperature of 210 ° C. and the flow pattern is brown 90 * 50 * 2.0.
mm test piece was prepared, and the following evaluation tests (a) and (b) were performed using the test piece. The results are shown in Table 1. Hereinafter, the same evaluation test was performed for Examples 1 to 4 and Comparative Examples 1 to 6, and the results are shown in Table 1.

(A) Observation of marble (flow) pattern A test piece of 150 * 120 * 2.0 mm was prepared, and the surface of the test piece was visually observed to judge the marble pattern according to the following criteria.

[Table 1] It was shown to. ◎: Appears sufficiently, ○: Appears slightly, ×: Does not appear at all. (B) Impact resistance Measure according to JIS-K-7121. The evaluation is made according to the following criteria when used as a household item. ◎… Excellent, ○… Practical limit, ×… There is a problem in use

Example 2 In Example 1, after the components (A) and (B) were kneaded in advance using an extruder, (C) was added thereto and kneaded using an extruder to obtain a pigment content. This gives 16.25% of the inventive marbled thermoplastic resin colorant. Subsequent operations are the same as in the first embodiment. Example 3 The marble pattern of the present invention having a pigment content of 10% of two different colors, brown and white, using the production method of Example 1 and separately using, as component (A), brown pigment and titanium oxide as the pigment. A colorant for molding a thermoplastic resin is obtained. Using 1 part by weight of each of the above two types of marble-patterned thermoplastic resin colorants, 100 parts by weight of a polypropylene resin having a density of 0.91 were mixed, and the flow pattern was brown and white using an injection molding machine. 90 * 50 * 2.0mm test piece consisting of the following test pieces were prepared, and evaluation tests (a) and (b) were performed.
It describes in.

Example 4 Using the production method of Example 2 and separately using, as the component (A), brown pigment and titanium oxide as the component (A), two kinds of brown and white pigments having different pigment contents of 10% each having a pigment content of 10% were used. An inventive marble patterned colorant for thermoplastic resin molding is obtained. Using 1 part by weight of each of the above two types of marble-patterned thermoplastic resin colorants, 100 parts by weight of a polypropylene resin having a density of 0.91 were mixed, and the flow pattern was brown and white using an injection molding machine. 90 * 50 * 2.0mm test piece consisting of the following test pieces were prepared, and evaluation tests (a) and (b) were performed.
It describes in.

Comparative Example 1 The procedure of Example 2 was the same as Example 2 except that the amount of the coloring agent (A) used was 0.05 part by weight. Comparative Example 2 Example 2 was the same as Example 2 except that the amount of the coloring agent (A) used was 80 parts by weight. Comparative Example 3 Example 2 was the same as Example 2 except that the amount of component (B) used was 0.5 part by weight.

Comparative Example 4 Example 2 was the same as Example 2 except that the amount of component (B) used was 70 parts by weight. Comparative Example 5 Example 2 was the same as Example 2 except that the amount of component (C) used was 2 parts by weight. Comparative Example 6 Example 2 was the same as Example 2 except that the amount of component (C) used was 100 parts by weight.

[0019]

[Table 1]

[0020]

In the production of the colorant for molding a marble-patterned thermoplastic resin of the present invention, a dilute resin is obtained by mixing and using two kinds of polyolefin resins, a polybutene resin and a polymethylpentene resin, as a carrier resin. When molded by using a thermoplastic resin, a molded product exhibiting a beautiful marble pattern not found in conventional FRP molded products can be obtained. In particular, when an olefin resin is used as a diluting resin, a marble pattern is further superior to that of a conventional FRP molded product using an unsaturated polyester resin, and a molded product comparable to natural marble can be obtained. In addition, the obtained molded article is excellent in surface smoothness and mechanical properties, and can be obtained as a molded article sufficiently usable for applications such as household goods and building materials.

Claims (4)

[Claims] 1. A colorant having a pigment content of 5 to 80% by weight 0.1 to 60 parts by weight (A), a polybutene resin or butene.alpha.-olefin copolymer-1 to 50 parts by weight (B), and polymethylpentene A colorant for forming a marble-patterned thermoplastic resin, comprising 5 to 90 parts by weight (C) of a resin. 2. A marble-patterned thermoplastic resin molding colorant obtained by blending the component (C) with the kneaded product comprising the components (A) and (B) according to claim 1. 3. A marble pattern molded product obtained by blending and kneading a thermoplastic resin with two or more of the colorants for molding a marble pattern thermoplastic resin having different colors according to claim 1. 4. A marble-pattern molded product obtained by mixing and kneading two or more types of the marble-pattern thermoplastic resin molding colorants of different colors according to claim 2 with the thermoplastic resin.