JPH11172010A - Colored variegated pattern material for synthetic resin and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To maintain a constant quality over a long period of time by improving a colored variegated pattern material for decoration of synthetic resins. SOLUTION: A colored variegated pattern material for synthetic resins is produced by covering the surface of a fine particle substrate with a colorant. The pattern material has an average particle size of from 0.01 to 1 mm and the difference in density between the pattern material and a synthetic resin for molding is 0.5 g/ml or smaller. Preferably, the fine particle substrate is a polymer bead, and the polymer bead has a weight average molecular weight of 1,000,000 or larger.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored spot pattern material for synthetic resin and a method for producing the same.

[0002]

2. Description of the Related Art In order to add commercial value to synthetic resin molded products, various surface decorations have been conventionally made. Among them, a synthetic resin molded product with a spotted pattern can give the texture of a granite-like natural material. For this reason, the applications are wide ranging from gardening supplies, stationery, toys, daily necessities such as daily necessities, building materials and packaging containers to home appliances and vehicle parts.

[0003] As a material for forming a spot pattern on a synthetic resin molded product, fine particles of inorganic substances such as stone, metal, glass, and the like,
Scale-like substances such as aluminum flakes and mica, pulverized thermosetting resins, fine particles of colored polymers, and colored short fibers have been conventionally proposed.

Among the above materials, fine particles of inorganic substances, flakes such as aluminum flakes and mica have a limited degree of freedom in color tone and low mechanical strength. It has problems such as not appearing. There is also a disadvantage that the screw of the molding machine is worn. When a pulverized thermosetting resin is used, see JP-A-6-27168.
As indicated by 1, it is pointed out that the compatibility with the base resin is poor, and the mechanical strength of the molded product is reduced.

Cases using colored polymers are disclosed in JP-A-48-45549, JP-A-54-154455, JP-A-54-154457, JP-A-57-207633,
It is disclosed in JP-A-50-105760 and JP-A-4-89805. However, as shown in JP-A-2-245037, since the thermal deformation temperatures of the base resin and the coloring resin used for the pattern material are close, the spot pattern is deformed by the shearing force applied during molding, and the mere stripe pattern is formed. There is a problem that it becomes.

[0006] The use of colored short fibers has been increasing in recent years because of convenience such as ease of coloring and variety of color tones. Colored short fibers (generally referred to as a pile) are prepared by bundling long fibers, adjusting the diameter to a desired diameter, and dyeing the bundle (called a tow). It is manufactured by cutting into length or by cutting undyed long fibers and then dyeing.

The above short fibers have various sizes of 1.5 to 150 denier, and are properly used according to the purpose of use. Among them, the 150-denier product having a large diameter has a structure in which fibers having a smaller diameter are bundled, and when kneading into a resin by kneading, a shearing force acts to loosen the bundled fibers. Even if an attempt is made to make a large spot pattern, the spot pattern becomes smaller.

[0008] The dyeing of the colored short fibers is carried out by a method of post-dying with a dye, adding a colorant, and spinning. Colored staple fibers are often added for the purpose of imparting fashionability, and therefore, there is a strong demand for small quantities and many types. In coloring the fiber, a method of post-dying with a dye is generally adopted in consideration of the above situation.

However, the post-dyed colored staple fibers, however, have poor heat resistance and poor weather resistance. Therefore, a colorant prepared by blending the staple fibers is mixed with a resin, and then discolored when molded. Or discoloration during long-term use.

[0010]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above problems, and has as its object the heat resistance and weather resistance which are disadvantages of the conventional colored short fibers used for decoration of synthetic resins. And to maintain a constant quality over a long period of time.

[0011]

In order to solve the above-mentioned problems, the present invention has an average particle diameter of 0.01 to 1 mm and a difference in density between a synthetic resin colorant and a molding synthetic resin of 0.5 g.
/ Ml or less, the colored spot pattern material for synthetic resin takes a measure of coating the surface of the fine particle base material with a coloring agent.

Polymer beads can be used as the fine particle base material. A crosslinked polymer or a polymer having a weight average molecular weight of 1,000,000 or more is suitable for the polymer beads.

As the coloring agent, pigments and / or dyes are used. For example, those having good heat resistance and weather resistance such as titanium oxide, azo pigments, red iron oxide, titanium yellow, phthalocyanine green, phthalocyanine blue, and ultramarine blue can be used.

The above-mentioned colored spot pattern material for synthetic resin is produced by a method comprising mixing and stirring a composition comprising a fine particle base material, a colorant and a curable resin, and coating the surface of the fine particle base material with a colorant by a curing reaction. It is desirable to do. Polymer beads can be used as the fine particle base.

The speckled material for synthetic resin according to the present invention is fine particles having an average particle size of 0.01 to 1 mm. The average particle size is
It can be measured by a sieving method (JIS K-5101) or an optical sedimentation method. The average particle size is 0.01
mm or less, the spot pattern does not appear clearly,
There are no features in the design. If the average particle diameter is 1 mm or more, the spot pattern material for coloring synthetic resin tends to be clogged at the gate portion during injection molding, which causes a problem in molding.

Further, in the colored spot pattern material for synthetic resin according to the present invention, the difference in density between the colored spot pattern material for synthetic resin and the synthetic resin for molding is 0.5 g / m1 or less. The density of the colored spot pattern material for synthetic resin and the density of synthetic resin for molding are
It can be measured according to JIS K-5101.

The effect of the density difference appears particularly when the density of the colored spot pattern material for synthetic resin is higher than the density of the synthetic resin for molding. That is, when combining the synthetic resin for molding with low density and the colored spot pattern material for synthetic resin with high density, when the density becomes 0.5 g / m1 or more, the colored spot pattern material for synthetic resin and A mixture of synthetic resins,
Since the colored spot pattern material for synthetic resin sinks and is selectively distributed at the lower part, the colored spot pattern is less likely to appear on the surface of the product, which causes a problem in design.

When molding is performed continuously, the appearance of a colored spot pattern is different between the initial stage and the latter stage of molding, which results in uneven color and hinders production of a uniform product. When the density of the colored spot pattern material for the synthetic resin is smaller than the density of the synthetic resin for molding, the colored spot pattern tends to appear on the surface of the product, but when the product is continuously molded, the color unevenness of the product becomes uneven. And it becomes difficult to produce a uniform product.

The particle size of the fine particle base material used in the present invention is appropriately selected according to the purpose of use, and it can be used in any form of one kind or a mixture of two or more kinds of fine particle base materials. Various materials can be used for the fine particle base material in the present invention. Among them, polymer beads are preferably used in terms of performance, availability, and the like. Since the polymer beads are spherical, they are more soft than colored spot pattern materials using pulverized thermosetting resin,
A more natural feel can be created.

In order to form a mottled pattern under the conditions of use of the above polymer beads, it is necessary that the polymer beads do not easily fluidize even at the molding temperature of the base resin. When fluidization occurs, problems occur, such as mixing with the base resin to form a flow pattern, or mixing with the base resin to be diluted and no pattern appear. In order to achieve the object, a polymer bead having a crosslinked structure which does not easily become a fluidized state even at the molding temperature of the base resin, or a polymer bead having a weight average molecular weight of 1,000,000 or more is suitably used.

The polymer beads having a crosslinked structure include a monomer having one unsaturated group in one molecule (monofunctional monomer) and a monomer having two unsaturated groups in one molecule (polyfunctional monomer). Can be produced by polymerization in the presence of Specific examples of monofunctional monomers include acrylates, methacrylates,
Examples include monomers selected from styrene and styrene derivatives. Specific examples of the polyfunctional monomer include:
Examples include diacrylate or dimethacrylate of ethylene glycol, diacrylate or dimethacrylate of 1,4 butanediol, diacrylate or dimethacrylate of tetraethylene glycol, divinylbenzene, and the like.

Polymer fine particles can be obtained by appropriately selecting the above monomers, diluting with a vehicle as needed, adding a catalyst, and using a technique such as suspension polymerization or emulsion polymerization.

Next, the polymer beads constituting the factor of the present invention are polymers having a weight average molecular weight of 1,000,000 or more.
If the weight-average molecular weight is 1,000,000 or less, the melt viscosity of the polymer beads decreases, the fluidity increases, and the polymer beads mix with the base resin, making it difficult to form a spot pattern.

When a polymer having a weight average molecular weight of 1,000,000 or more is subjected to a polymerization reaction in a system comprising a monomer, a catalyst and, if necessary, a vehicle, polymerization conditions are set so that a polymerization termination reaction does not occur intentionally. Can be produced. Ultra-high molecular weight polyethylene is a specific example thereof, and can be produced by setting production conditions so that the molecular weight becomes a desired ultra-high molecular weight according to a normal production process.

For the coloring of the speckled pattern material, a method of dyeing uncolored polymer beads with a dye, a method of producing colored beads by polymerizing in the presence of a dye or a pigment, and the like have been conventionally known. In the method by the above-mentioned dyeing, there is a problem that the spotted pattern material is not deeply dyed, an aesthetic effect is hardly obtained, and the dye is transferred, so that the base color of the molded product is dyed to the color of the pattern material. The method of performing polymerization in the presence of a dye or a pigment requires the polymerization to be performed each time the color changes, and is not suitable for a small amount of a variety of spotted pattern materials.

In the colored spot pattern material for synthetic resin according to the present invention, a fine particle base material is coated with a coloring agent. The coating is performed by reacting a composition comprising a fine particle base material and a coloring agent selected from a pigment and a dye and a curable resin and, if necessary, a vehicle, mixing and stirring, and curing the pigment and dye onto the fine particle base material by a curing reaction. It can be carried out by being fixed to.

In the present invention, pigments and / or dyes are used as colorants. When the colorant is fixed with a cured resin, migration of the dye is improved as compared with the case where the polymer beads are dyed with the dye. However, since migration may occur depending on the properties of the dye, the type of the synthetic resin for molding, the processing conditions, and the like, the pigment is considered to be more preferable in the present invention.

The method of coloring the fine particle base material by the method is such that the polymer particles of the fine particle base material have an extremely high melt viscosity and are extremely difficult to process using a general processing machine.
This is because coloring by extrusion kneading using an extruder cannot be easily performed.

The colorant component used in the present invention can be appropriately selected from pigments and dyes according to the purpose of use. Among them, pigments are preferably used in terms of heat resistance and weather resistance. Specifically, titanium oxide (white), azo pigment (red), red iron oxide (brown), titanium yellow (yellow),
And phthalocyanine green (green), phthalocyanine blue (blue), and ultramarine (blue).

The curable resin used as a varnish in the present invention is a phenol resin, a urea resin, an epoxy resin, an epoxy acrylate resin, an amino resin, an alkyd resin,
It can be appropriately selected from curable resins such as unsaturated polyester resins and urethane resins.

The vehicle used in the present invention is selected from solvents such as water, hydrocarbons, halogenated hydrocarbons, alcohols, esters and ketones in consideration of solubility, boiling point and the like. The amount of the vehicle used is determined in consideration of the type of the fine particle base material, the type and amount of the colorant component, the reaction conditions, and the like. Curing conditions can be appropriately selected in consideration of the type of the curable resin, the composition of the composition, and the like.

The synthetic resin for molding which can be used in the present invention can be selected from the resins used for injection molding and extrusion molding, and includes polyethylene, polypropylene, polystyrene, acrylonitrile / styrene copolymer, acrylonitrile / butadiene / Styrene copolymer, polymethyl methacrylate, polycarbonate, polyacetal,
Examples include various resins such as polybutylene terephthalate, polyethylene terephthalate, polyarylate, polyamide, polyphenylene ether, polyphenylene sulfide, and polyether sulfone.

The amount of the colored spot pattern material for a synthetic resin according to the present invention can be arbitrarily determined according to the purpose of use, but from the viewpoint of design and economy, is preferably about 0.1% to 5%. Used for

Hereinafter, the present invention will be specifically illustrated. However, the content of the present invention is not limited to the following specific examples.

Example 11 1) Preparation of Colored Spotting Material for Synthetic Resin As a varnish, bisphenol-based epoxy resin (Sumiepoxy ELA-128, manufactured by Sumitomo Chemical Co., Ltd.) 100
A mixture of 125 parts of a dimer-acid-modified polyamide (Tomide 215X manufactured by Fuji Kasei Kogyo Co., Ltd.) and 75 parts of a mixed solvent of isopropyl alcohol / toluene = 1/1 part by volume was prepared.

To 100 parts of crosslinked polymethyl methacrylate resin beads having a density of 1.20 / ml and 30 parts of the above varnish are added to 10 parts of ultramarine blue, mixed well, the solvent is removed under reduced pressure, and the mixture is reacted at 60 ° C. for 2 hours. Thus, a colored spot pattern material for synthetic resin having an average particle diameter of 0.1 mm was obtained.

The density of the obtained colored spot pattern material for synthetic resin was 1.29 g / ml.

2) Production of Molded Article Polypropylene (J-150G manufactured by Nippon Polyolefin Co., Ltd., density = 0.90 g / ml) was used as a synthetic resin for molding.
00 parts, white pigment masterbatch (manufactured by Clariant)
A mixture of 1 part of Remafin White EEF 90) and 1 part of the above-mentioned colored spot pattern material was subjected to 50 mm × 9 at 210 ° C. using a 1 oz. Injection molding machine manufactured by Yamashiro Seiki Co., Ltd.
A plate having a thickness of 0 mm and a thickness of 3 mm was molded.

The density difference between the colored spot pattern material for synthetic resin and the synthetic resin for molding was 0.39 g / ml.

The molded article was a beautiful one having a blue spot pattern on a white background.

Example 2 The varnish of Example 1 was replaced with 100 parts of an ortho-unsaturated polyester resin (Rigolac 2260 manufactured by Showa Polymer Co., Ltd.) and a catalyst (methyl ethyl ketone peroxide) 1.2.
Parts, a mixture consisting of 0.5 parts of an accelerator (cobalt naphthenate) and a density of 1.20 g / ml in 40 parts of the mixture.
Cross-linked polymethyl methacrylate resin beads 100
Parts, 10 parts of carbon black, and then mixed and stirred at room temperature for 30 minutes, and cured to obtain an average particle size of 0.1 m.
m of colored spot pattern material for synthetic resin was obtained.

The density of the obtained colored spot pattern material for synthetic resin was 1.24 g / ml.

Using the colored spot pattern material for a synthetic resin, a plate was molded according to the method of Example 1, and a beautiful molded product having a black spot pattern was obtained.

The density difference between the colored spot pattern material for synthetic resin and the synthetic resin for molding was 0.34 g / ml.

Example 3 The varnish of Example 1 was replaced with a urea resin (manufactured by Mitsui Toatsu Chemicals, Inc.).
Euroid 701) 100 parts, ammonium chloride 1 part,
Change to 30 parts of water and add 20 parts of the mixture to a density of 1.20 g /
ml of crosslinked polymethyl methacrylate resin beads 100
Parts and 10 parts of phthalocyanine green, heated at 100 ° C. to evaporate water, allowed to undergo a curing reaction, and mixed and stirred for several hours to give an average particle size of 0.08 m
m of colored spot pattern material for synthetic resin was obtained.

The density of the obtained colored spot pattern material for synthetic resin was 1.26 g / ml.

Using the colored spot pattern material for a synthetic resin, a plate was molded according to the method of Example 1, and a beautiful molded product having a green spot pattern was obtained.

The density difference between the colored spot pattern material for synthetic resin and the synthetic resin for molding was 0.36 g / ml.

Example 4 The crosslinked polymethyl methacrylate resin beads of Example 1 were changed to ultra high molecular weight polyethylene having a density of 0.93 g / ml and a molecular weight of 3.4 million, and the varnish was epoxy resin (ELA-128 manufactured by Sumitomo Chemical Co., Ltd.). A varnish consisting of 100 parts, 80 parts of nadic anhydride and 1 part of benzyldimethylamine was reacted at 80 ° C. for 4 hours and at 150 ° C. for 15 hours to obtain a colored spot pattern material for synthetic resin having an average particle size of 0.16 mm. Obtained.

The density of the obtained colored spot pattern material for synthetic resin was 1.10 g / ml.

Using the colored spot pattern material for synthetic resin, a plate was molded according to the method of Example 1, and it was beautiful having a blue spot pattern on a white background.

The density difference between the colored spot pattern material for synthetic resin and the synthetic resin for molding was 0.20 g / ml.

Example 5 As a varnish, 100 parts of urea melamine resin (Euroid 350 manufactured by Mitsui Toatsu Chemicals, Inc.) and ammonium chloride 1 were used.
Parts, 30 parts of water and 30 parts of the mixture at a density of 1.2
100 g of 0 g / ml crosslinked polymethyl methacrylate resin beads and 10 parts of phthalocyanine blue,
Heat at ℃ to evaporate the water and at the same time cure reaction,
By mixing and stirring for several hours, an average particle size of 0.0
An 8 mm colored spot pattern material for synthetic resin was obtained.

The density of the obtained colored spot pattern material for synthetic resin was 1.24 g / ml.

One part of the colored spot pattern material for synthetic resin, polystyrene (CR-4500G, density =
1.05 g / ml) The mixture consisting of 100 parts was subjected to 50 m at 220 ° C. using a 1 oz. Injection molding machine manufactured by Yamashiro Seiki Co., Ltd.
An mx 90 mm, 3 mm thick plate was molded.

The density difference between the colored spot pattern material for synthetic resin and the synthetic resin for molding was 0.19 g / ml.

The molded product was a beautiful one having a blue spot pattern.

Example 6 As varnishes, 100 parts of a polyol (Desmophen 1200 manufactured by Sumitomo Bayer Urethane) and a prepolymer (Desmodur manufactured by Sumitomo Bayer Urethane) 7
5 parts and 30 parts of a varnish consisting of 50 parts of methyl / isobutyl / ketone were thoroughly mixed with 100 parts of crosslinked polymethyl methacrylate resin beads having a density of 1.20 g / ml and 10 parts of phthalocyanine blue, reacted at 40 ° C. for 2 hours, and stirred. The mixture was mixed to obtain a colored spot pattern material for synthetic resin having an average particle diameter of 0.1 mm.

The density of the obtained colored spot pattern material for synthetic resin was 1.24 g / ml.

A plate was molded using the colored spot pattern material for a synthetic resin according to the method of Example 1, and a beautiful molded product having a blue spot pattern was obtained.

The density difference between the colored spot pattern material for synthetic resin and the synthetic resin for molding was 0.34 g / ml.

Comparative Example 1 A colored spot pattern material for synthetic resin having an average particle size of 0.005 mm was obtained in the same manner as in Example 1 except that the particle size of the crosslinked polymethyl methacrylate resin beads of Example 1 was changed. Was prepared and a plate was prepared according to the method of Example-1.

In the molded product, a speckle pattern was not clearly developed, and the molded product was unsatisfactory in design.

Comparative Example 2 A synthetic resin having an average particle size of 0.3 mm was prepared according to the method of Example 1, except that the crosslinked polymethyl methacrylate resin beads of Example 1 were changed to silica sand having a density of 2.6 g / ml. A colored spot pattern material was manufactured and 100 plates were molded using a 3 oz. Horizontal injection molding machine.

The density of the colored spot pattern material for synthetic resin was 2.29 g / ml. The density difference between the colored spot pattern material for synthetic resin and the synthetic resin for molding was 1.39 g / ml.

The color tone of the spot pattern on the plate was beautiful, but the spot pattern did not appear on the surface of the plate, and the design was unsatisfactory. Further, the density of the spot pattern of the product was not uniform, the product immediately after molding had a high density of the spot pattern, and the product before the completion of molding had a low density of the spot pattern, and a uniform molded product was not obtained.

Comparative Example 3 In place of the crosslinked polymethyl methacrylate resin beads of Example 1, non-crosslinked polymethyl methacrylate resin beads (weight average molecular weight: 150,000) were used, and the average particle size was determined according to the method of Example 1. A colored spot pattern material for synthetic resin of 0.12 mm was manufactured, and a plate was prepared according to the method of Example-1.

In the molded product, no spot pattern appeared, and the plate was a mixture of blue streaks on a white base.

Comparative Example 4 In place of the ultrahigh molecular weight polyethylene having a density of 0.93 g / ml and a molecular weight of 3.4 million in Example-4, a high density polyethylene having a molecular weight of 300,000 was used and the method of Example 1 was used.
A colored spot pattern material for synthetic resin having an average particle diameter of 0.15 mm was manufactured, and a plate was prepared according to the method of Example-1.

The molded product had no spot pattern and the plate had a slightly bluish color tone with a white base.

Example 7 A plate was manufactured under the same conditions as in Example 1 except that the molding conditions for the plate of Example 1 were changed to 240 ° C.

The molded product was beautiful having a blue spot pattern on a white background.

Comparative Example 5 Instead of the colored spot pattern material for synthetic resin of Example-7, a pile obtained by dyeing a cellulose fiber having a fiber diameter of 3 denier blue was used under the same molding conditions as in Example-7. Was manufactured.

The plate was a product having an unsatisfactory color tone, in which the blue color of the spotted pattern turned brownish.

Example 8 The weather resistance test of the plates of Examples-1 to 7 was carried out by using a xenon
Weatherometer (63 ° C., 60 W / m ² , irradiation 108
Min / shower 12 min cycle) for 100 hours.

The plate after the weather resistance test was not particularly different from that before the irradiation, and a beautiful state having colorful spots of each color on a white background was maintained.

COMPARATIVE EXAMPLE 6 Instead of the colored spot pattern material for synthetic resin of Example 1, a pile obtained by dyeing cellulose fibers having a fiber diameter of 3 denier blue was used under the same molding conditions as in Example 1. Was manufactured.

The plate was subjected to a weather resistance test under the same conditions as in Example-8. On the plate after the weather resistance test, the blue spot pattern turned yellow, and the product had a problem with the color tone.

Claims (7)

[Claims] 1. A colored spot pattern material for synthetic resin comprising a fine particle base material coated on its surface with a coloring agent, wherein the average particle size is 0.1%.
A colored spot pattern material for a synthetic resin, wherein the density difference between the colored pattern material and the molding synthetic resin is 0.5 g / ml or less. 2. The colored spot pattern material for a synthetic resin according to claim 1, wherein the fine particle base material is a polymer bead. 3. The colored spot pattern material for a synthetic resin according to claim 2, wherein the polymer beads are a crosslinked polymer. 4. The polymer beads having a weight average molecular weight of 10
The colored spot pattern material for a synthetic resin according to claim 2, which is a polymer of not less than 10,000. 5. The colored spot pattern material for a synthetic resin according to claim 1, wherein the colorant is a pigment and / or a dye. 6. The coloring for a synthetic resin according to claim 5, wherein the coloring agent comprises a material having good heat resistance and weather resistance such as titanium oxide, azo pigment, red iron oxide, titanium yellow, phthalocyanine green, phthalocyanine blue and ultramarine blue. Spotted pattern material. 7. An average particle diameter of 0.01 to 1 mm, and a density difference between the colored pattern material and the synthetic resin for molding is 0.5 g / m.
A method for producing a colored pattern material having a particle size of 1 or less, characterized in that a fine particle substrate, a composition comprising a colorant and a curable resin are mixed and stirred, and the surface of the fine particle substrate is coated with a colorant by a curing reaction. A method for producing a colored spot pattern material for synthetic resin.