JPH08208919A - Thermoplastic polymer molding having marbled appearance, its production and pattern-forming material used therefor - Google Patents

Abstract

PURPOSE: To obtain a molding having a marbled appearance by common molding by mixing a thermoplastic polymer base material with a pattern-forming material comprising two thermoplastic polymers having a specified relationship between their complex viscosity coefficients and a colorant. CONSTITUTION: This decorative molding having a marbled appearance is obtained by forming a composition comprising 60-99.9 pts.wt. thermoplastic polymer base material (A) and 40-0.1 pts.wt. (the total of components A and B being 100 pts.wt.) pattern- forming material (B) comprising a mixture of 1-95wt.% thermoplastic polymer (B1 ) having a complex viscosity coefficient η1 with 99-5wt.% another thermoplastic polymer (B2 ) having a complex viscosity coefficient of η2 and satisfying the relationship: η1 /η2 >=5 at the same temperature T, or mixture obtained by adding 80wt.%, based on the total weight of the mixture, colorant to the above mixture, and molding the composition at the temperature T under specified conditions. Component A is freely selected from among common thermoplastic polymers. It is suitable that component B1 is a crystalline thermoplastic polymer having a melting point equal to or higher than the molding temperature of a molding. Desirable examples of components B1 and B2 are PET and PC.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polymer molding having a marbled appearance, a method for producing the same, and a pattern molding material used in the production. More specifically, the present invention provides a polymer molded product having a decorative marbled surface appearance, which can be easily obtained by using an ordinary injection molding machine, an extrusion molding machine, or the like, a surface glossiness and a mechanical property inherent to a raw material polymer. TECHNICAL FIELD The present invention relates to a method for efficiently producing a material while maintaining its mechanical strength and a material used for the production.

[0002]

2. Description of the Related Art Many molded articles of thermoplastic polymers are used by being dyed with pigments, and usually,
In these colored moldings, the dyes and pigments are uniformly dispersed in the resin and used as monochromatic moldings. However,
Along with changes in lifestyles, the surface appearance of polymer moldings is required to have a design property. For example, polymer moldings having a marble-like surface appearance are required.

Therefore, various methods have been tried so far for imparting decorative properties to the thermoplastic polymer moldings. One of them is performed on the surface of the polymer molded article by secondary processing, and is a method of forming a flow pattern by a method such as print coating, hot stamping, and ink-wash coating. However, although this method can obtain a high-quality and beautiful surface appearance, it is expensive to manufacture, its use is limited, and the interior ground color appears due to external damage because it is a decoration only on the surface of the molded product. There is a drawback of.

On the other hand, a method of combining a base material made of a thermoplastic polymer with the same type of polymer having a different melt viscosity or another polymer as a pattern forming material (Japanese Patent Laid-Open No.
105760, JP-A-54-154451, JP-A-54-154454, JP-A-54-1.
54456, JP-A-57-207633)
Is proposed. These methods are methods in which a colored pattern forming material is melt-kneaded with a base material and molded in a non-uniform state before they are uniformly kneaded to form a flow pattern on a polymer molded body.

However, in these methods, the range of molding conditions for obtaining a polymer molded product having a marbled appearance is limited, and in general, the pattern forming material is present in a lump form in the base material, or conversely, the pattern forming material is present. In many cases, a clear flow pattern cannot be obtained due to color mixing between the base material and the base material, and in addition, the mechanical strength of the molded body is deteriorated and peeling occurs at the boundary layer between the base material and the pattern forming material. May occur.

As another method, for example, colored thermosetting polymer particles are used as a pattern forming material and dispersed in a base material (JP-A-51-12324).
7, JP-A-62-286716, JP-A-2
-115,271, JP-A-2-103254, JP-A-3-200841, JP-A-3-210
No. 350, No. 5-93091, No. 6
Japanese Patent Laid-Open No. 1875 and Japanese Patent Laid-Open No. 6-80821) have been proposed.

However, in these methods,
It is possible to develop a pattern under a relatively wide range of molding conditions, but generally colored particles of a pattern forming material are obtained by pulverizing a cured thermosetting polymer,
Therefore, it is inevitable that the production of the colored particles becomes complicated and the cost becomes high.

As another surface decoration method, there is a method of performing color mixing or multicolor molding using a special mold or apparatus, but this method lacks versatility as a production facility,
It leads to a rise in product prices. In view of this situation, it is possible to easily and continuously with a normal extrusion molding machine or injection molding machine without the need for expensive secondary processing or modification of molds and molding machines, and a high quality and unique surface appearance. There is a strong demand for a thermoplastic polymer molded article that has the above-mentioned properties and that the pattern can be obtained not only on the surface of the molded article but also on the inside thereof and that the mechanical strength of the molded article is maintained.

[0009]

Under the above circumstances, the present invention can be processed under a wide range of molding conditions by using an ordinary extrusion molding machine, an injection molding machine or the like, and has a decorative marbled tone. The purpose of the present invention is to provide a polymer molded product having a surface appearance simply and efficiently.

[0010]

Means for Solving the Problems The present inventors have made it possible to obtain a marble-like surface appearance with a simple operation while maintaining the characteristics of various thermoplastic polymers used as raw materials, such as surface gloss and mechanical strength. As a result of extensive research to obtain a polymer molded product, a polymer molded product with a beautiful marble-like surface appearance can be obtained by simply performing ordinary injection molding or extrusion molding if a specially prepared pattern forming material is used. It was found that the body can be obtained, and the present invention has been completed based on this finding.

That is, the present invention is based on (A) 60 to 99.9 parts by weight of the thermoplastic polymer base material, and (B)
(B) 1 to 95% by weight of at least one thermoplastic polymer, and (b ') the complex viscosity η _b of (b) at the same temperature.
And the complex viscosity η _b ′ of (b ′), η _b / η _b ′ ≧ 5
A mixture of at least one thermoplastic polymer different from that of (b) with 99 to 5% by weight, or 80% by weight based on the total amount thereof in this mixture.
40 to 0.1 parts by weight of the pattern forming material, which is composed of a mixture of a colorant in an amount not exceeding 1, and the total of (A) and (B) is 1
It is intended to provide a polymer molded product having a marble appearance, which is composed of a polymer composition contained in an amount of 00 parts by weight.

[0012] Such a polymer molded body is based on 60 to 99.9 parts by weight of the thermoplastic polymer base material (A),
(B) (b) at least one thermoplastic polymer 1-9
The relation of η _b / η _b ′ ≧ 5 (I) between 5% by weight and (b ′) complex viscosity η _b of (b) and complex viscosity η _b ′ of (b ′) at the same temperature. From a mixture of 99-5% by weight of at least one thermoplastic polymer different from (b) in which the temperature at which is satisfied is present, or a mixture of coloring agents in an amount not exceeding 80% by weight, based on the total amount of this mixture. 40 to 0.1 parts by weight of the pattern forming material, the total of (A) and (B) is 10
The polymer composition in a proportion equal to 0 parts by weight, wherein _{T m (min) -40 <T} M <T m (max) -1 (II) [ However, T _M is the molding temperature (° C.), T _m (Min) is the melting point (° C.) of the thermoplastic polymer having the lowest melting point in component (b), and T _m (max) is the melting point (° C.) of the thermoplastic polymer having the highest melting point]. It can be manufactured by molding under temperature conditions.

In this case, the molding temperature (T
_M ) and at least one thermoplastic polymer having a melting point of at least one and / or the formula η _b ( _TM ) / η _A ( _TM ) ≧ 5 (III) [where η _b ( _TM ), η _A (T _M) at least one thermoplastic polymer satisfies each of the processing temperatures (b) is a component and the (a) complex viscosity component] using equation 0.01 ≦ eta _b as (b ') component ′ ( _TM ) / η _A ( _TM ) <15 (IV) η _b ( _TM ) / η _b ′ ( _TM ) ≧ 5 (V) [where η _b ′ ( _TM ) is at the processing temperature The complex viscosity of the component (b '), where η _b ( _TM ) and η _A ( _TM ) are the same as above], a particularly beautiful marble pattern can be obtained by using at least one thermoplastic polymer. A polymer molding having the above is obtained.

The component (A) in the present invention, that is, the thermoplastic polymer used as the base material can be arbitrarily selected from the thermoplastic polymers used as a raw material in ordinary injection molding or extrusion molding. As such, for example, styrene resin, olefin resin, methacrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyamide resin, polyester resin, polyurethane resin, polycarbonate resin, polyacetal resin, polyphenylene ether resin, Examples thereof include fluororesins and various thermoplastic elastomers. Among them, styrene resins, olefin resins, methacrylic resins and polyvinyl chloride resins are preferable.

This styrene resin is generally used for molding, such as styrene homopolymer (PS), and high impact polystyrene (H).
IPS), methyl methacrylate / styrene copolymer (MS), methyl methacrylate / butadiene / styrene copolymer (MBS), styrene / maleic anhydride copolymer (SMA), styrene / methacrylic acid copolymer (S)
MAA), a heat-resistant styrene resin obtained by copolymerizing α-methylstyrene or maleimide, and further, a styrene / acrylonitrile copolymer resin, an α-methylstyrene / acrylonitrile copolymer resin, and the like.

Here, the styrene-acrylonitrile-based copolymer resin is an acrylonitrile-styrene copolymer (A
S), acrylonitrile / styrene / butadiene copolymer (ABS), acrylonitrile / styrene / acrylic rubber copolymer (AAS), acrylonitrile / styrene / chlorinated polyethylene copolymer (ACS), acrylonitrile / styrene / ethylene-propylene rubber Copolymer (AES), acrylonitrile / styrene / ethylene-
It includes a vinyl acetate copolymer, a heat-resistant ABS resin obtained by copolymerizing α-methylstyrene or maleimide, and the α-methylstyrene / acrylonitrile copolymer resin is styrene / acrylonitrile copolymer resin styrene. This represents an α-methylstyrene / acrylonitrile-based copolymer resin in which a part is replaced with α-methylstyrene.

As the olefin resin, those generally used for molding, for example, polyethylene resin such as ultra low density polyethylene, low density polyethylene, linear low density polyethylene, medium low density polyethylene, high density polyethylene, etc., Vinyl acetate unit content is 0.1-2
5 wt% ethylene / vinyl acetate copolymer, acrylic acid unit content 0.1 to 25 wt% ethylene / acrylic acid copolymer, propylene homopolymer, ethylene unit content 2 to 40 mol% Examples thereof include crystalline propylene / ethylene block copolymers, crystalline ethylene / propylene random copolymers having an ethylene unit content of 0.5 to 10 mol%, polybutene, ethylene / propylene rubber, ethylene / propylene / diene rubber. it can.

Examples of the methacrylic resin include methyl methacrylate homopolymer, methyl methacrylate in addition to styrene, α-methylstyrene, acrylonitrile,
A methacrylic resin with various performances improved by copolymerizing other monomers such as various acrylic acid esters and methacrylic acid esters, and a polymer containing acrylate ester or methacrylic acid ester as a main component or butadiene as a main component. Examples thereof include impact-resistant methacrylic resins obtained by graft-copolymerizing methyl methacrylate, styrene, acrylonitrile, and various acrylic acid esters and methacrylic acid esters with the polymer.

Examples of polyvinyl chloride resins include vinyl chloride homopolymers, copolymers obtained by polymerizing vinyl chloride with ethylene, propylene, acrylonitrile, vinylidene chloride, vinyl acetate and the like as comonomers, and polyvinyl chloride resins. Graft copolymers obtained by grafting vinyl chloride with MBS resin, ABS resin, nitrile rubber, chlorinated polyethylene, EVA-PVC, and modified polyvinyl chloride resin with various plasticizers added. You can

The weight average molecular weight (Mw) of these thermoplastic polymers is 10,000 to 1,000,000, preferably 50,000 to 80.
Those in the range of 10,000, particularly those in the range of 100,000 to 500,000 are preferable because they are excellent in moldability. Further, these thermoplastic polymers may be used alone or in combination of two or more kinds.

The base material of the component (A) used in the present invention may be colored. The colorant used for this coloring is not particularly limited, and known pigments, dyes, and decorating materials can be used. This colorant may be used alone or in combination of two or more kinds. The colorant is contained in a proportion of 20 parts by weight or less, preferably 10 parts by weight or less, relative to 100 parts by weight of the thermoplastic polymer base consisting of one or two or more so as not to impair the mechanical properties of the molded product. It is desirable to use.

The base material made of a thermoplastic polymer mixed with a coloring agent is prepared by blending the coloring agent with the thermoplastic polymer in a predetermined ratio, and using an extruder, a Banbury mixer,
It can be performed by melt-kneading using a known kneading device such as a kneader.

This base material is in the form of powder, flakes,
It is convenient to prepare a granular material having a shape such as a bead shape, a spherical shape, a granular shape, a chip shape, or a pellet shape. This granular material has an average particle size of 0.001 to 10 mm, preferably 0.01 to 8 mm, more preferably 0.1 to 5 mm.
Those within the range are preferable. Here, the average particle diameter means the average of the maximum lengths of the granular materials, but when the shape of the granular material is pellet, the value of the diameter is used as the average particle diameter.

Next, the present invention is characterized by the pattern forming material of the component (B), which is (b) at least one thermoplastic polymer of 1 to 95% by weight, and (b ') at the same temperature (b). There is a temperature at which the relationship of η _b / η _b ′ ≧ 5 is satisfied between the complex viscosity η _b of η _b and the complex viscosity η _b ′ of (b ′). It is necessary to use a mixture with 99 to 5% by weight of the plastic polymer or a mixture of this mixture with a colorant in an amount not exceeding 80% by weight, based on the total amount.

This pattern forming material has different complex viscosities.
A mixture of two or more thermoplastic polymers, ie (b) at least one thermoplastic polymer, and (b ') the formula η _b / η _b ′ ≧ 5 (I) where η _b and η _b ′ are The complex viscosity of component (b) and component (b ') at a certain temperature T] is satisfied.] A mixture with at least one thermoplastic polymer different from component (b) where temperature T exists, or It is a granular material composed of a mixture of the above and a coloring agent, and can be used as a pattern forming material in the temperature range corresponding to the above T.

The wider the temperature range corresponding to T is, the better the pattern-forming material of the present invention is because the desired marble-like pattern can be exhibited at a wide range of molding temperatures. Here, η is the dynamic complex elastic modulus (G) obtained from the relationship between the strain (or stress) applied to the thermoplastic polymer to be measured at a constant frequency and the stress (or strain) generated there. The relationship with the angular frequency (ω), that is, η = G / ω = (G ′ ² + G ″ ² ) ^0.5 / ω (VI) [where G ′ is the dynamic storage elastic modulus and G ″ is the dynamic The loss elastic modulus is shown] and can be measured using a commercially available dynamic viscoelasticity measuring device.

Strictly speaking, η used here represents the magnitude of the complex viscosity, but for convenience, it is referred to as the complex viscosity in the present invention. As the complex viscosity, a value measured at an angular frequency of 100 rad / sec is used.

In the pattern forming material of the present invention, the thermoplastic polymer in the unmelted state or the hardly fluidized state which is the component (b) is polymerized by the action of the good-flowing thermoplastic polymer which is the component (b '). Since it can be dispersed in a wide range in the molded body, and when a colorant is blended, the color mixture with the base material can be prevented by keeping the colorant in the component (b), Under a wide range of molding conditions,
Particularly under a wide molding temperature condition, a beautiful flow pattern marble-like surface appearance can be easily imparted to the polymer molded body. In addition, since the pattern forming material is spread over a wide area in the polymer molded product, molding defects such as unevenness and peeling do not occur on the molded product, and the original moldability of the base material and the mechanical properties of the molded product are maintained. can do.

When the complex viscosity ratio of the component (b) and the component (b ') constituting the pattern forming material at the temperature T is η _b / η _b ′ <5, the components (b) and (b) are used. Since the respective functions of the component ') are not independently exerted, it becomes impossible to impart a marble-like surface appearance to the molded product.

In order to give the polymer molded article a good marble-like surface appearance, preferably η _b / η _b ′ ≧ 10 (I ′), more preferably η _b / η _b ′ ≧ 50 ( I ″).

Further, in the pattern forming material of the present invention, the component (b) is a dispersed phase, and the average dispersed diameter thereof is 0.1 to 1, 1.
In the case of 000 μm, it is preferably 0.5 to 1
When it is 00 μm, more preferably 0.8 to 10 μm, a polymer molded product having a particularly beautiful and clear marble-like surface appearance can be provided.

Here, the average dispersed diameter of the component (b) means the average particle diameter of the dispersed phase, which is obtained by observing the pattern forming material with a transmission electron microscope or a scanning electron microscope. If the shape of the phase is spherical, the average of its diameter, if it is cylindrical, the average of its diameter, and if the shape is irregular, the average of the major and minor axes of the dispersed phase seen in the micrograph. Shall be represented.

The average dispersion diameter of the component (b) in the pattern forming material is the composition ratio of the component (b) and the component (b '), the combination of the component (b) and the component (b'), and (b ) Component and (b ') component compatibilizer (including reactive compatibilizer),
It can be controlled by the melt viscosity balance between the components (b) and (b '), the kneading conditions (temperature, screw design) when preparing the pattern forming material, and conversely, depending on these factors. It is also possible to control the pattern expression pattern of the polymer molded body by controlling the average dispersion diameter of the component (b).

In the pattern forming material of the present invention, the polymer component is 1 to 95% by weight of the component (b) and the component 99 of the component (b ').
˜5% by weight. If the amount of component (b) is less than 1% by weight, it is not possible to impart a marble-like surface appearance to the molded product, and if it exceeds 95% by weight, the moldability is greatly impaired and the mechanical properties of the molded product are greatly reduced. However, the object of the present invention cannot be achieved. In order to develop a stable marble-like pattern on the molded product under a wide range of molding conditions, the proportion of the component (b) is 5 to 70% by weight, and the proportion of the component (b ') is 95 to 30% by weight. In particular, a proportion of 10 to 50% by weight of the component (b) and 90 to 50% by weight of the component (b ') is preferable.

The pattern forming material of the present invention is the same as the above (b).
The mixture may be a mixture of a thermoplastic polymer composed of the component and the component (b '), or a mixture of the mixture and a colorant. When blending this colorant,
The amount is not more than 80% by weight, preferably 50% by weight or less, more preferably 30% by weight or less, based on the total amount of the thermoplastic polymer mixture. in this way,
By blending the colorant with the pattern forming material, it is possible to provide a polymer molded product having a clearer marble-like surface appearance.

In the pattern forming material of the present invention, as the thermoplastic polymers of the component (b) and the component (b '), those whose complex viscosity ratios satisfy the relation of the above formula (I) are used. The type thereof is appropriately selected depending on the type of the base material in the polymer molded body, as described later.

Regarding the thermoplastic polymer used as the component (b), a thermoplastic polymer having a melting point equal to or higher than the molding temperature (T _M ) when processed into a polymer molded product having a marble appearance, or the formula η _b (T _M ) / η _A (T _M ) ≧ 5 (III) [wherein η _b (T _M ), η _A (T _M ) are the complex viscosity of the (b) component and the (A) component at the molding temperature, respectively. It is preferable to select from those satisfying the relationship of

When a crystalline thermoplastic polymer having a melting point above the molding temperature of the polymer molded body is used as the component (b), a polymer molded body having a clear marble-like surface appearance can be relatively easily prepared. This is convenient because it can be obtained. Here, the melting point is a differential scanning calorimeter (DS
It can be determined from the temperature of the endothermic peak due to the melting of the crystal by the measurement according to C).

In this case, the crystalline thermoplastic polymer used as the component (b) can be selected according to the molding temperature of the base material of the component (A). For example, when a styrene resin, an olefin resin and a methacrylic resin are used as the base material, the thermoplastic polymer having a melting point of 150 to 350 ° C., preferably 200 to 300 ° C. as the component (b). It is preferable to use.

When a polyvinyl chloride resin is used as the base material, the melting point of the component (b) is 1
It is desirable to use a thermoplastic polymer in the range of 00 to 300 ° C, preferably 150 to 250 ° C.

Specific examples of the crystalline thermoplastic polymer which can be used as the component (b) include polyethylene, rigid polyvinyl chloride, polypropylene, isotactic polystyrene, syndiotactic polystyrene, polyvinylidene chloride, polyurethane resin and poly-4. -Methylpentene-
1, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polytetrafluoroethylene, crystalline polycarbonate, polyester resin, polyamide resin, polyacetal resin, polyphenylene sulfide, polyether ether ketone, liquid crystal polymer, etc. It is preferable to use one or two or more types selected from the above, depending on the molding temperature of the thermoplastic polymer as the base material.

Among the above-mentioned crystalline thermoplastic polymers, polyester resins and polyamide resins are particularly preferable because it is easy to control the melting point in a relatively wide range. Here, the polyester resin means at least one aromatic dicarboxylic acid selected from terephthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-biphenyldicarboxylic acid and the like as a dicarboxylic acid component, and diethylene glycol as a diol component. It is a copolyester composed of at least one diol selected from α, ω-diols such as triethylene glycol, 1,4-butanediol and tetraethylene glycol. For example, polyethylene terephthalate (PET, melting point 255 ° C.), polybutylene terephthalate (PBT,
A melting point of 225 ° C.) can be preferably used.

The polyamide resin is a polymer having an amide bond in the main chain, and is a polymer obtained by polycondensation of diamine and dibasic acid, ring-opening polymerization of lactam, polycondensation of aminocarboxylic acid, and the like. . For example, nylon 6 (melting point 225 ° C), nylon 66 (melting point 265 ° C), nylon 610 (melting point 222 ° C), nylon 612 (melting point 224)
℃), nylon 11 (melting point 192 ℃), nylon 12
(Melting point 186 ° C.) can be preferably used.

Further, it is advantageous to use, as the component (b), two or more kinds of crystalline thermoplastic polymers having different melting points, because the temperature range capable of exhibiting a marble-like surface appearance can be further expanded. .

On the other hand, as the component (b), the above formula (II
When a thermoplastic polymer satisfying the relationship of I), that is, a non-flowing thermoplastic polymer having a complex viscosity of 5 times or more that of the base material at the molding temperature (T _M ) of the polymer molded body is used, it is clear. In order to obtain such a marble-like surface appearance, a thermoplastic polymer satisfying the relationship of η _b ( _TM ) / η _A ( _TM ) ≧ 10 (III ′), and also the formula η _b ( _TM ) / _A thermoplastic polymer satisfying the relationship of η _A ( _TM ) ≧ 50 (III ″) is more preferable.

Examples of such a non-flowable thermoplastic polymer include polyphenylene ether resin, amorphous polycarbonate resin, polysulfone, polyether sulfone, polyarylate, and a weight average molecular weight of 10.
There may be mentioned various kinds of non-flowing thermoplastic polymers of more than 0,000, or various thermoplastic polymers whose melt viscosity is increased by introducing a partially crosslinked or pseudo-crosslinked structure. These hardly flowable thermoplastic polymers may be used alone or in combination of two or more kinds. Further, it may be used in combination with a crystalline thermoplastic polymer having a melting point above the molding temperature of the polymer molded body.

In the polymer molding of the present invention, (B)
As the component (b ′) constituting the component pattern forming material, the following formula is used: 0.01 ≦ η _b ′ ( _TM ) / η _A ( _TM ) <15 (IV) [where η _b ′ ( _TM )] And η _A (T _M ) are respectively the complex viscosity of the component (b ′) and the component (A) at the molding temperature (T _M ) for processing into a polymer molded body]. . Further, in order to obtain a beautiful and clear marble-like surface appearance, a thermoplastic polymer satisfying the relationship of 0.05 ≦ η _b ′ ( _TM ) / η _A ( _TM ) <10 (IV ′) is Further, a thermoplastic polymer satisfying the relationship of 0.1 ≦ η _b ′ ( _TM ) / η _A ( _TM ) <7 (IV ″) is particularly preferable.

As the thermoplastic polymer of the component (b '), the complex viscosity at the molding temperature (T _M ) is usually in the range of 1 × 10 ³ to 2 × 10 ⁵ poises, although it depends on the base material used. , Preferably 3 × 10 ³ to 1 × 1
Those in the range of 0 ⁵ poise, more preferably 5 × 10 ³
Those in the range of up to 7 × 10 ⁴ poise can be used.

As the component (b ′), η _b ′ (T _M ) / η _A
When a thermoplastic polymer having a ( _TM ) of less than 0.01 is used, a molded product may not have a marble-like surface appearance, and the component (b ') has an extremely low viscosity. In the production of the pattern forming material, there are disadvantages such as a defective kneading of the component (b) and the component (b '), and difficulty in continuously and stably producing the pattern forming material in a uniform shape.

On the other hand, as the (b ′) component, η _b ′ ( _TM )
When a thermoplastic polymer having a / η _A ( _TM ) of 15 or more is used, it becomes difficult for the pattern forming material to disperse in the polymer molded body, and the pattern forming material exists in the polymer molded body while keeping its form. Therefore, the elongation at break and impact strength are remarkably lowered, and the smoothness of the surface of the polymer molded body is lowered.

Examples of the thermoplastic polymer as the component (b ') include styrene resin, olefin resin, polyvinyl chloride resin, polyvinylidene chloride resin, methacrylic resin, polyamide resin, polyester resin, polyurethane resin, polycarbonate. Resins, polyacetal resins, polyphenylene ether resins, fluororesins, various thermoplastic elastomers, and other known thermoplastic polymers can be used.

In the present invention, as the component (b '),
The thermoplastic polymers may be used alone or in combination of two or more. It is also possible to use a thermoplastic polymer having the same composition as the base material. Further, in the present invention, when a thermoplastic elastomer or a mixture of a thermoplastic elastomer and a thermoplastic resin is used as the component (b '), the elongation at break and impact strength of the resulting polymer molded article can be improved. So convenient.

As the thermoplastic elastomer, generally,
Styrene type, olefin type, urethane type, ester type,
Young's modulus classified into amide type, polyvinyl chloride type, 1,2-polybutadiene type, ionomer type, etc. is 5
0-10,000 kgf / cm ² , breaking elongation 100-
Various thermoplastic elastomers having 800% and a tensile strength in the range of 50 to 450 kgf / cm ² can be used.

The styrene-based thermoplastic elastomer is, for example, an aromatic vinyl compound / conjugated diene block copolymer or its hydride, and the olefin-based thermoplastic elastomer is, for example, an ethylene-α-olefin copolymer rubber, Ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid ester copolymer, ethylene / (meth) acrylic acid or its partial metal salt copolymer, ethylene / maleic anhydride / (meth) acrylic acid ester copolymer Various ethylene-based copolymer rubbers such as polymer, ethylene / vinyl alcohol copolymer, ethylene / vinyl acetate / vinyl alcohol copolymer, ethylene / styrene copolymer, propylene / butene rubber, isoprene / butylene rubber, polyisoprene rubber, etc. , As a urethane-based thermoplastic elastomer , For example, diisocyanate and short chain glycol (ethylene glycol, propylene glycol, 1,4-butanediol, bisphenol A, etc.)
Polyurethanes having a polymer chain composed of as a hard segment and a polymer chain composed of a diisocyanate and a long-chain polyol as a soft segment are preferred.

As the ester-based thermoplastic elastomer, for example, a condensate of an aromatic dicarboxylic acid and a short chain glycol is used as a hard segment and a condensate of an aromatic dicarboxylic acid and a polyalkylene glycol, or polycaprolactone is a soft segment. As the amide-based thermoplastic elastomer, for example, a multi-segment polyamide having nylon 6, nylon 66, nylon 11, and nylon 12 as a hard segment, and a polyether or polyester having a soft segment as a soft segment may be used. Examples of the polyvinyl chloride-based thermoplastic elastomer include so-called soft polyvinyl chloride obtained by compounding polyvinyl chloride with NBR.

Further, 0.1 to 10 parts by weight of unsaturated carboxylic acid or its anhydride, unsaturated carboxylic acid derivative, unsaturated carboxylic acid or its anhydride and unsaturated monomer are added to these thermoplastic elastomers. %,Preferably,
0.2-5% by weight, more preferably 0.5-3% by weight
An added modified thermoplastic elastomer can also be preferably used.

In the present invention, the thermoplastic elastomers may be used alone or in combination of two or more, or may be used in combination with other thermoplastic resins.

In the polymer molding of the present invention, in order to prevent molding defects such as peeling and rough skin and maintain mechanical properties, the component (b ') can be the same kind as the base material or can be mixed with the base material. It is preferred to use various thermoplastic polymers. Furthermore, peeling in the polymer molded body,
In order to prevent molding defects such as rough skin and maintain mechanical properties, it is preferable that the components (b) and (b ') are appropriately miscible. For this purpose, it is preferable to combine the miscible components (b) and (b ') into a pattern-forming material. In the pattern-forming material, a compatibilizing agent for the components (b) and (b') is used. Blending with a thermoplastic polymer
A thermoplastic polymer containing a functional group component capable of forming a partial bond between the component (b) and the component (b ′),
The miscibility between the component (b) and the component (b ') can be controlled by using either or both of the component (b').

There are no particular restrictions on the colorant to be added to the pattern-forming material of the component (B), and known pigments and dyes, and decorative materials can be used. For example, monoazo type and condensation type. Organic pigments such as azo, anthraquinone, isoindolinone, heterocyclic, perinone, perylene, quinacridone, thioindigo, dioxazine, phthalocyanine, and anthraquinone, heterocyclic, perinone, thioindigo Dyes such as titanium oxide, red iron oxide, talc, calcium carbonate, zinc oxide, barium sulfate, titanium yellow, iron oxide, ultramarine blue, cobalt blue, inorganic pigments such as calcined pigments, carbon black, and metallic pearls. A special pigment or the like can be used. Further, as a coloring agent, a metal such as aluminum, tin, copper, brass, stainless steel, or iron for expressing a special pattern such as metallic pearl,
Alloys using these metals as substrates, mica, shells, inorganic or organic crystals that cause birefringence, phosphors and the like can be used.

In the pattern forming material of the present invention, these colorants may be used alone or in combination of two or more kinds. The method for preparing the pattern forming material of the present invention is not particularly limited, for example, after mixing the raw materials of the pattern forming material using a Henschel mixer or a tumbler, a Banbury mixer, a roll, a short-axis extruder,
It can be prepared by performing melt-kneading using a known melt-kneading device such as a twin-screw extruder and granulating with various known granulators. It is also possible to omit the mixing of the raw materials by a Henschel mixer, a tumbler, etc., and supply the various raw materials to the melt-kneading device using separate feeders for granulation.

The pattern forming material of the present invention is a granular material, and its shape is not particularly limited, and it is used, for example, in the form of powder, flakes, beads, spheres, granules, chips, pellets and the like. be able to. Further, the average particle diameter is usually 0.01 to 10 mm, preferably 0.1 to 5 mm. Here, the average particle diameter means the average of the maximum lengths of the granular materials, but when the shape of the granular material is pellet, the value of the diameter is used as the average particle diameter.

Next, a preferred example of the embodiment of the present invention will be described. For example, as the base material of the component (A), at least one selected from styrene resins and methacrylic resins is used.
When using a seed or a mixture of this with a colorant,
As the pattern forming material of the component (B), the component (b) has a melting point of 1
At least one crystalline thermoplastic polymer in the range of 50 to 350 ° C., and the component (b ′) is a thermoplastic elastomer or a mixture of a thermoplastic elastomer and a thermoplastic resin, and a colorant is further added to these. By using the above resin, it is possible to obtain a resin molded product having a beautiful and clear marble-like surface appearance and excellent mechanical properties.

Further, as the base material of the component (A), among styrene resins, at least one selected from the group consisting of styrene / acrylonitrile copolymer resins, α-methylstyrene / acrylonitrile copolymer resins and methacrylic resins. When one kind or a mixture of colorants is used, the component (B) is a pattern forming material, the component (b) is a polyethylene terephthalate resin, and the component (b ') is a polycarbonate resin. By using a mixture of the above and a coloring agent, it is possible to obtain a molded product having a beautiful and clear marble-like surface appearance and excellent mechanical properties.

Next, a method for producing the polymer molded article of the present invention having a marble-like surface appearance will be described. First, assuming that the total amount of (A) and (B) is 100 parts by weight, 99.9 to 60 parts by weight of the base material of the granular body which is the component (A) and the pattern forming material 0 of the granular body which is the component (B) 0 1-40
After mixing with 1 part by weight, the mixture can be molded using various molding machines to obtain a polymer molded product having a marble-like surface appearance.

Since this method can be applied to various conventionally known molding processing methods such as injection molding, compression molding, extrusion molding (sheet molding, blow molding), it is practically useful in a wide variety of various shapes. Can make various products. As a method of supplying the base material and the pattern forming material to various molding machines, the base material and the pattern forming material can be mixed in advance and supplied in a lump, but each of them can be molded using various feeders. It is also possible to supply it to the machine.

The shape of the base material and the pattern forming material may be pellets, chips, flakes, granules, powders and the like, but is particularly preferable from the viewpoint of the stability of supply to the molding machine. In the case where both the base material and the pattern forming material are in the form of pellets, the particle diameter of these pellets is preferably in the range of 2 to 5 mm.

If the blending amount of the pattern forming material is less than 0.1 part by weight, the polymer molded article will not have a clear pattern,
If it exceeds 40 parts by weight, the mechanical properties of the polymer molded product will be significantly deteriorated. From the viewpoint of the balance of the surface appearance and mechanical properties of the polymer molded product, the preferable blending ratio of the pattern forming material is 0.5 to 35 parts by weight, particularly 1 to 30 parts by weight.

In the present invention, a polymer molding having a marble-like surface appearance can be obtained under a wide range of molding conditions, but the base material is 99.9 to 60% by weight and the pattern forming material is 0.1 to 40% by weight. % a mixture consisting of the formula _{T m (min) -40 <T} M <T m (max) -1 (II) [ where the thermoplastic is the most low melting point of T _m (min) (b) component Polymer melting point (° C), T _m (max)
Is the melting point (° C.) of the thermoplastic polymer having the highest melting point, and when the crystalline thermoplastic polymer contained in the component (b) is a single component, T _m (min) and T _m (max) are the same. By molding at a molding temperature T _M (° C.) satisfying the relation of “a temperature”, a polymer molded product having a particularly excellent surface appearance can be obtained.

[0069] The molding temperature T _M to obtain this marble tone polymer moldings (° C.), further satisfying the relationship of formula _{T m (min) -30 <T} M <T m (max) -3 (II ') temperature are preferred, the temperature satisfying the relationship of formula _{T m (min) -20 <T} M <T m (max) -5 (II ") are preferred.

Further, in the present invention, a polymer molded body can be obtained by using two or more kinds of pattern forming materials having different hues and colorant concentrations, and by using a plurality of kinds of pattern forming materials at the same time, Polymer moldings having a wide variety of surface appearances can be obtained.

As the component (A), at least one thermoplastic resin selected from the group consisting of styrene / acrylonitrile copolymer resin, α-methylstyrene / acrylonitrile copolymer resin and methacrylic resin, or a granular material thereof 1 to 95% by weight of polyethylene terephthalate resin and polycarbonate resin 99 to 5 with the body as the component (B)
80% based on a mixture with wt.%, Or even its total amount
Particularly excellent polymer moldings can be obtained by using those containing a coloring agent in an amount not exceeding wt%.

Further, in the present invention, various additive components such as a plasticizer, an antistatic agent, a lubricant, a stabilizer, an antioxidant, an ultraviolet absorber, a flame retardant, a release agent and an antibacterial agent may be added, if necessary. Alternatively, a fungicide or the like can be added during the molding process of the polymer molded body. In addition, these additive components are
It is also possible to mix it with the base material, the pattern forming material, or both.

The present invention is preferably applied to extrusion molding or injection molding, and particularly when it is applied to injection molding,
Molding machine screw design, cylinder diameter, L / D,
The surface appearance can be variously changed depending on conditions such as the screw rotation speed, back pressure, and injection speed.

Further, the surface appearance of the molded product can be variously changed by changing the shape and size of the gate of the injection molding die and the thickness of the molded product. Furthermore, in recent years, a plasticizing screw having a high kneading function, for example, Himelta [trade name of Japan Steel Works, Ltd.], UB
Screw [Mitsubishi Heavy Industries, Ltd., trade name], DB Screw [Toshiba Machinery, Ltd. trade name], SF screw [Sumitomo Heavy Industries, Ltd. trade name], pin type, fin type Various molding machines equipped with special mixing elements (such as Dulmaji) and further mixing nozzles (manufactured by Toray Industries, Inc.) have been developed, and the surface appearance of polymer moldings is controlled using these molding machines. You can also

[0075]

INDUSTRIAL APPLICABILITY The present invention provides a granular material comprising a mixture of two or more kinds of thermoplastic polymers having different complex viscosities or a mixture thereof with a colorant as a pattern forming material. , Has a beautiful marble look,
In addition, a polymer molded article having excellent mechanical properties can be easily obtained under a wide range of forming conditions, particularly under a wide range of molding temperatures.

This polymer molded product has a marble-like surface appearance, does not cause peeling, and can maintain the physical properties such as the surface gloss inherent to the base material, mechanical strength, and moldability. , OA equipment housings, building materials,
It is suitable for a wide range of applications such as vehicle parts, daily necessities, toys and sundries, especially for high-grade molded products.

In particular, when the base material and the pattern forming material are colored in different hues, not only the pattern but also various hues can be combined, so that the base material and the pattern forming material can be suitably applied to a wide variety of parts requiring various appearances. You can. Further, since this polymer molded product can be molded into a high-quality molded product as a finished product only by extrusion molding or injection molding, the cost is low, the productivity is high, and the efficiency is extremely high.

[0078]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, the measurement of each physical property was performed according to the method shown below.

(1) Measurement of Complex Viscosity of Thermoplastic Resin Dynamic Viscoelasticity Measuring Device Dynamic Analyze
r RDAII (trade name, manufactured by Rheometrics, Inc.) was used to measure the complex viscosity at the molding processing temperature of the thermoplastic polymer molding. Angular frequency 100 rad / se
It was measured at c.

(2) Structure observation of pattern forming material The dispersion state and the average dispersion diameter of the component (b) in the pattern forming material were evaluated by observation with a transmission electron microscope or scanning electron microscope. In the transmission electron microscope observation, the pattern forming material is dyed with osmium tetroxide, and a 70-nm-thick transmission electron microscope observation section is cut out with an ultramicrotome to obtain a measurement sample. Made by JEOL Ltd., product name 1200E
X] was used to observe the structure of the pattern forming material at an acceleration voltage of 100 kV. In the scanning electron microscope observation, the pattern forming material was broken in liquid nitrogen, and the fracture surface was subjected to gold vapor deposition to obtain a sample for the scanning electron microscope observation, and the fracture surface was scanned by the scanning electron microscope [JEOL Ltd., Using the trade name JSM-5300], the structure of the pattern forming material was observed at an acceleration voltage of 15 kV. The average dispersed diameter of the component (b) is the average of the diameter of the dispersed phase when it is spherical, the average of the diameter when it is cylindrical, and the maximum length when the shape is irregular. And the average of the minimum length.

(3) Observation of Occurrence of Marble-like Pattern The occurrence of the marble-like pattern in the polymer molded product was evaluated by visually observing the surface of the molded product directly according to the following criteria. ◯: A beautiful marble pattern is observed on the entire polymer molded body. X: A single color or a pattern forming material exists as a granular body in the polymer molded body.

(4) Surface Condition of Polymer Molded Body The presence or absence of molding failure of the polymer molded body was visually evaluated according to the following criteria. ◯: No defective molding is observed. X: Molding defects such as surface roughness, peeling, and unevenness are observed on the surface of the molded product. (5) Izod impact strength It was evaluated according to ASTM D256. The test piece was prepared by using a mixture of a base material and a pattern forming material with an injection molding machine [manufactured by Nissei Jushi Kogyo Co., Ltd., trade name PS40E5A, screw diameter 30].
mm, equipped with a dullimage screw at the tip], and the cylinder was set at the cylinder temperature shown in the table and the mold temperature was 60 ° C.

(6) Tensile Strength and Elongation It was evaluated according to ASTM D638. A test piece was produced by supplying a mixture of a base material and a pattern forming material to an injection molding machine and setting the cylinder temperature and the mold temperature of 60 ° C shown in the table.

The materials used in Examples and Comparative Examples are as follows. Homopolystyrene (PS): [Asahi Kasei Kogyo KK, trade name G8102] High-impact polystyrene (HIPS): [Asahi Kasei Kogyo KK, trade name EXZ13] Transparent HIPS: [Asahi Kasei Kogyo KK, trade name SM0
50] Polymethylmethacrylate (PMMA): [Asahi Kasei Co., Ltd., trade name Delpet 80N] Acrylonitrile / styrene copolymer (AS): [Asahi Kasei Co., Ltd., trade name Stylak AS783] Acrylonitrile butadiene・ Styrene copolymer (A
BS): [Asahi Kasei Kogyo KK, trade name Stylak 220B] Polyphenylene ether (PPE): [Reduced viscosity η
_{SP / C} = 0.51, 0.5 g / dl, chloroform solution,
30 ° C measurement] Polycarbonate (PC): [Teijin Kasei Co., Ltd., trade name Panlite K1400] Polyethylene terephthalate (PET): [Teijin Kasei Co., Ltd., trade name TR8550] Polybutylene terephthalate (PBT): [Mitsubishi] Chemicals Co., Ltd., trade name Novador 5010S] Nylon 6 (PA): [Ube Industries, Ltd., trade name U
BE Nylon 1013B] Ethylene / ethyl acrylate / maleic anhydride terpolymer (modified PE): [Sumitomo Chemical Co., Ltd., trade name Bondine HX8290] Styrene / glycidyl methacrylate copolymer (modified P)
S1): [Nippon Yushi Co., Ltd., trade name Mapproof G
-1010S] Oxazoline group-containing polystyrene (modified PS2): [Nippon Shokubai Kagaku Kogyo KK, trade name RPS-1005] High density polyethylene (HDPE): [Asahi Kasei Kogyo KK
Product name: Suntech-HD S360] Hydrogenated styrene-butadiene-styrene copolymer (SEB
S1): [Asahi Kasei Co., Ltd., trade name Tuftec H
1051] Hydrogenated styrene / butadiene / styrene copolymer (SEB
S2): [Asahi Kasei Co., Ltd., trade name Tuftec H
1081] Maleic anhydride modified SEBS (modified SEBS1): [Asahi Kasei Kogyo KK, trade name Tuftec M1953] Glycidyl methacrylate modified SEBS (modified SEBS)
2) [Asahi Kasei Co., Ltd., trade name Tuftec GX0
73] Ethylene propylene rubber (EPR): [Exxon Chemical Co., Ltd., trade name Vistalon 805] Maleic anhydride-modified ethylene / propylene rubber (modified EPR): [Exxon Chemical Co., trade name Egzero VA1803] block Polypropylene (PP): [Asahi Kasei Co., Ltd.
Manufacture, trade name M8600] Preparation example Preparation of pattern forming materials (B-1) to (B-20) After mixing the components of the types and amounts shown in Tables 1 to 4 with a blender, this mixture was twin-screw extruded. Machine [Ikegai Iron Works Co., Ltd.
Manufactured by trade name PCM45], and melt-kneaded at a kneading temperature shown in the table, and pelletized to prepare white colored pattern forming materials (B-1) to (B-20). Tables 1 to 4 show the structures of the obtained pattern forming materials.

[0085]

[Table 1]

[0086]

[Table 2]

[0087]

[Table 3]

[0088]

[Table 4]

Examples 1 to 10 To 100 parts by weight of each base material polymer shown in Table 5 and Table 6, 0.02 part by weight of carbon black and 0.5 part by weight of titanium dioxide were added and mixed by a blender. After that, the mixture was melt-kneaded with a twin-screw extruder and pelletized to obtain gray-colored base material (A) pellets. The kneading temperature is HIPS, HDPE,
230 each for ABS, AS and PMMA
℃, 230 ℃, 250 ℃, 250 ℃, and 240 ℃.

Next, the base material (A) pellets and the pattern forming material (B) pellets obtained in the preparation example were mixed with a blender in the blending ratios shown in Tables 5 and 6, and then the injection molding machine [ Product name PS40E5 manufactured by Nissei Plastic Industry Co., Ltd.
A, screw diameter 30 mm, with tip dullage screw] at a molding temperature shown in the table at a mold temperature of 60
Injection molding was performed at 0 ° C. to prepare a 90 mm × 50 mm × 3 mm flat plate.

Tables 5 and 6 show the occurrence of the marbled pattern and the surface appearance of this polymer molded body together with the complex viscosity and the ratio of each polymer.

Η _A , η _b and η _b ′ in each table below
Are respectively the complex viscosities of the base material (A), the pattern forming material (b) component, and the pattern forming material (b ') component at the molding temperature (T _M ) of the polymer molded body. In the table, when the complex viscosity is α × 10β, it is expressed as αEβ (for example, 0.95 × 10 ⁴ is 0.95E4.
Will be written).

Further, η _b / η _b ′, η _b / η _A and η _b ′ /
η _A is the ratio of the complex viscosities of the component (b) and the component (b ′) of the pattern forming material at the molding temperature (T _M ) of the polymer molded product, the component (b) of the pattern forming material and the base material (A), respectively. ) And the ratio of the complex viscosity of the pattern forming material (b ') component to the base material (A).

[0094]

[Table 5]

[0095]

[Table 6]

As can be seen from Table 5 and Table 6, Example 1
All of the polymer moldings obtained in Nos. 10 to 10 had a high-quality marbled surface appearance.

Comparative Example 1 The pellets of the colored base material (HIPS) used in Example 1 and the pellets of the pattern forming material (B-12) obtained in the Preparation Example were mixed at the compounding ratio shown in Comparative Example 1 of Table 7. Then, a polymer molded body was produced from the mixture in the same manner as in Example 1 under the conditions of a molding temperature of 210 ° C. and a mold temperature of 60 ° C. Table 7 shows the generation state of the marble pattern and the surface appearance of this polymer molded body together with the complex viscosity and the ratio of each polymer.

When the thermoplastic polymer constituting the pattern forming material is PBT only, the pattern forming material does not disperse in the molded body but exists in the form of granules, and the molded body has a spot-like shape made of the pattern forming material. A pattern was obtained. In addition, unevenness was observed on the surface of the polymer molded body and the smoothness was poor.

Comparative Example 2 The pellets of the colored base material (ABS) used in Example 8 and the pellets of the pattern forming material (B-13) obtained in the Preparation Example were mixed at the compounding ratio shown in Comparative Example 2 in Table 7. Then, a polymer molded body was produced from the mixture in the same manner as in Example 8 under the conditions of a molding temperature of 245 ° C. and a mold temperature of 60 ° C. Table 7 shows the generation state of the marble pattern and the surface appearance of this polymer molded body together with the complex viscosity and the ratio of each polymer.

When the thermoplastic polymer constituting the pattern forming material was only PC, the obtained polymer molding had a uniform gray color, and a marble-like surface appearance was not obtained.

Comparative Example 3 The colored base material (HIPS) pellets used in Example 1 and the pattern forming material (B-15) pellets obtained in the Preparation Example were mixed at the compounding ratio shown in Comparative Example 3 of Table 7. Then, a polymer molded body was produced from the mixture in the same manner as in Example 1 under the conditions of a molding temperature of 210 ° C. and a mold temperature of 60 ° C. Table 7 shows the generation state of the marble pattern and the surface appearance of this polymer molded body together with the complex viscosity and the ratio of each polymer.

In this example, η _{b at} 210 ° C.
The values of / η _b ′ and η _b / η _A are 2.00 and 1.
32, both smaller than 5. The polymer molded product obtained at this time had a gray uniform color, and a marble-like surface appearance was not obtained.

Comparative Example 4 Pellets of the colored base material (HIPS) used in Example 1 and the pellets of the pattern forming material (B-2) obtained in Preparation Example were mixed at the compounding ratio shown in Comparative Example 4 of Table 7. After that, the mixture is injection-molded from the mixture at a molding temperature of 240 ° C and a mold temperature of 60 ° C.
A polymer molded body was produced under the conditions of.

Table 7 shows the occurrence of the marbled pattern and the surface appearance of this polymer molded product together with the complex viscosity and the ratio of each polymer. The values of η _b / η _b ′ and η _b / η _A at 240 ° C., which is higher than the melting point (225 ° C.) of PBT, are both 1.67 and smaller than 5. The polymer molded product obtained at this time had a gray uniform color, and a marble-like surface appearance was not obtained.

Comparative Example 5 The pellets of the colored base material (HIPS) used in Example 1 and the pellets of the pattern forming material (B-5) obtained in the Preparation Example were mixed at the compounding ratio shown in Comparative Example 5 in Table 7. After that, the mixture is injection-molded from the mixture at a molding temperature of 210 ° C and a mold temperature of 60 ° C.
A polymer molded body was produced under the conditions of. Table 7 shows the generation state of the marble pattern and the surface appearance of this polymer molded body together with the complex viscosity and the ratio of each polymer. In this example, the polymer molded product had a marble-like surface appearance, but the surface peeling was remarkable.

[0106]

[Table 7]

Examples 11 to 14 Pellets of the colored base material (HIPS) used in Example 1 and the pattern forming materials (B-16) to (B-1) obtained in the preparation example.
9) The pellets of 9) were mixed at the compounding ratios shown in Examples 11 to 14 of Table 8, and the mixture was molded by injection molding at a molding temperature of 21.
90 mm x 50 mm x under conditions of 0 ° C and mold temperature of 60 ° C
A 3 mm flat plate and test pieces for evaluating various physical properties were prepared. Table 8 shows each physical property of this polymer molded body together with the complex viscosity of each polymer and its ratio. Examples 11 to 1
Each of the polymer molded products of No. 4 had a clear and high-quality marbled surface appearance.

Further, as shown in Table 8, Examples 11 to 14
The polymer molded body of is a colored base material (HIPS) described later.
In comparison with a polymer molding composed of a single material (Comparative Example 6),
Although the Izod impact strength was improved and the elongation at break was lowered, the degree of decrease was smaller than that in the case of using a pattern forming material made of PBT described later (Comparative Example 7). As described above, the polymer moldings obtained in Examples 11 to 14 were excellent polymer moldings in which the mechanical appearance was maintained in addition to the beautiful marble-like surface appearance.

Example 15 A mixture of pellets of gray-colored block polypropylene (PP) obtained by mixing in the mixing ratio shown in Example 15 of Table 8 and pellets of the pattern forming material (B-20) obtained in Preparation Example. From the above, a polymer molded body was produced by injection molding under the conditions of a molding temperature of 210 ° C. and a mold temperature of 60 ° C. The obtained polymer molded product had a clear and high-quality marble-like surface appearance. Table 8 shows each physical property of this polymer molded body together with the complex viscosity of each polymer and its ratio.

The Izod impact strength of the polymer molded article of Example 15 was the Izod impact strength (5.5 kg · cm / c) of the polymer molded article composed of the colored base material (PP) alone.
m), and the breaking elongation of the polymer molded product composed of the colored base material alone (200%).
%) Was small. Thus, Example 1
The polymer molded product obtained in No. 5 was an excellent polymer molded product in which the mechanical appearance was maintained in addition to the beautiful marble-like surface appearance.

[0111]

[Table 8]

Examples 16 to 20 The pellets of the colored base material (ABS) used in Example 8 and the pellets of the pattern-forming materials (B-9) to (B-11) obtained in Preparation Example were used as shown in Table 9. Mixing was carried out at the compounding ratios shown in Examples 16 to 20, and the mixture was injection molded at a molding temperature of 210 ° C.
90mm × 50mm × 3mm under the condition of mold temperature 60 ℃
And a test piece for evaluation of various physical properties were prepared. Table 9 shows each physical property of this polymer molded body together with the complex viscosity of each polymer and its ratio.

[0113]

[Table 9]

All of the polymer moldings obtained had a clear and high-quality marbled surface appearance. Table 9
As shown in FIG. 6, the polymer molded articles of Examples 16 to 20 have large values for both the Izod impact strength and the elongation at break, as compared with the case where the pattern forming material made of PET described below is used (Comparative Example 9). Was obtained. Thus, Examples 16-2
The polymer molded product obtained in No. 0 was an excellent polymer molded product in which the mechanical appearance was maintained in addition to the beautiful marble-like surface appearance.

Comparative Example 6 From the pellets of the colored base material (HIPS) used in Example 1, a molding temperature of 210 ° C. and a mold temperature of 6 were obtained by injection molding.
A polymer molded body was prepared under the condition of 0 ° C. The obtained polymer molded body had a single gray color. Table 10 shows each physical property of this polymer molded body together with the complex viscosity of each polymer and its ratio.

Comparative Example 7 A pattern forming material (B-1 comprising the pellets of the colored base material (HIPS) used in Example 1 and the PBT obtained in Preparation Example (B-1)
The pellets of 2) were mixed at the compounding ratio shown in Comparative Example 7 of Table 10, and the mixture was injection-molded at a molding temperature of 210 ° C.
A polymer molded body was produced under the condition that the mold temperature was 60 ° C. A speckled pattern composed of a pattern forming material appeared on the obtained polymer molded product, and a marble-like surface appearance was not obtained.
Table 10 shows each physical property of this polymer molded body together with the complex viscosity of each polymer and its ratio.

Comparative Example 8 From the pellets of the colored base material (ABS) used in Example 8, a molding temperature of 250 ° C. and a mold temperature of 60 were obtained by injection molding.
A polymer molded body was prepared under the condition of ° C. The obtained polymer molded body had a single gray color. Table 10 shows each physical property of this polymer molded body together with the complex viscosity of each polymer and its ratio.

Comparative Example 9 A pattern forming material (B-14) comprising pellets of the colored base material (ABS) used in Example 8 and PET obtained in the preparation example.
The pellets of No. 1 were mixed at the compounding ratio shown in Comparative Example 9 in Table 10, and a polymer molded body was produced from the mixture by injection molding under the conditions of a molding temperature of 250 ° C and a mold temperature of 60 ° C. A speckled pattern composed of a pattern forming material appeared on the obtained polymer molded product, and a marble-like surface appearance was not obtained. Table 10 shows each physical property of this polymer molded body together with the complex viscosity of each polymer and its ratio.

[0119]

[Table 10]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location C08L 69/00 LPN (72) Inventor Yuki Saijo 3-2-184-101 Takanedai, Funabashi City, Chiba Prefecture

Claims (8)

[Claims] 1. (A) Thermoplastic polymer base material 60 to
With respect to 99.9 parts by weight, (B) (b) 1 to 95% by weight of at least one thermoplastic polymer, and (b ') the complex viscosity η _b of (b) and (b') at the same temperature. There exists a temperature at which the relationship of η _b / η _b ′ ≧ 5 is satisfied between the complex viscosity η _b ′ and at least one thermoplastic polymer different from (b) and a mixture with 99 to 5 wt% of this thermoplastic polymer. 40 to 0.1 parts by weight of a pattern forming material composed of a mixture containing a colorant in an amount not exceeding 80% by weight based on the total amount thereof, and the total of (A) and (B) is 100 parts by weight. A polymer molded product having a marbled appearance, which is composed of a polymer composition contained in a ratio. 2. The component (b) is at least one crystalline thermoplastic polymer having a melting point in the range of 150 to 350 ° C., and the component (b ') has a complex viscosity of 10 ³ to 2 × 10 ⁵ poises. The polymer molding according to claim 1, which is at least one thermoplastic polymer within the range. 3. The component (b) is at least one crystalline thermoplastic polymer having a melting point in the range of 150 to 350 ° C., and the component (b ′) is a thermoplastic elastomer or a thermoplastic elastomer and a thermoplastic resin. The polymer molded article according to claim 1, which is a mixture of 4. A granular body comprising component (A), which is composed of at least one thermoplastic resin selected from styrene resins and methacrylic resins or colored products thereof.
The polymer molded product according to any one of 1. 5. The component (A) comprises at least one thermoplastic resin selected from styrene / acrylonitrile copolymer resin, α-methylstyrene / acrylonitrile copolymer resin and methacrylic resin, or a colored product thereof. And (B) component is 1 to 95 parts by weight of polyethylene terephthalate resin and 99 to 5 of polycarbonate resin.
3. A granular material comprising a mixture of 100 parts by weight and 100 parts by weight, or a mixture containing a colorant in an amount not exceeding 80% by weight based on the total amount. Polymer molding. 6. (A) Thermoplastic polymer base material 60 to
With respect to 99.9 parts by weight, (B) (b) 1 to 95% by weight of at least one thermoplastic polymer, and (b ') the complex viscosity η _b of (b) and (b') at the same temperature. There exists a temperature at which the relationship of η _b / η _b ′ ≧ 5 is satisfied between the complex viscosity η _b ′ and at least one thermoplastic polymer different from (b) and a mixture with 99 to 5 wt% of this thermoplastic polymer. 40 to 0.1 parts by weight of a pattern forming material composed of a mixture containing a colorant in an amount not exceeding 80% by weight based on the total amount thereof, and the total of (A) and (B) is 100 parts by weight. the polymer compositions containing in a ratio, wherein _{T m (min) -40 <T} M <T m (max) -1 [ However, T _M is the molding temperature _{(℃), T m (min} ) is the component (b) melting point of the thermoplastic polymer with the lowest melting point in the _{(℃), T m (max} ) is the highest melting point Heat at a temperature indicated by the melting point (℃) which is on the thermoplastic polymer, method for producing a polymer molded body according to claim 1, wherein the molding with. 7. The component (b) is at least one thermoplastic polymer having a melting point equal to or higher than the molding temperature ( _TM ) and / or the formula η _b ( _TM ) / η _A ( _TM ) ≧ 5 [wherein _{η b (T M), η} a (T M) is at least one thermoplastic polymer satisfy the in each processing temperature (b) is a component and the (a) complex viscosity component], (b ′) Component is _expressed by the equation 0.01 ≦ η _b ′ ( _TM ) / η _A ( _TM ) <15 η _b ( _TM ) / η _b ′ ( _TM ) ≧ 5 [where η _b ′ ( _TM ) Is the complex viscosity of the component (b ') at the processing temperature, and η _b ( _TM ) and η _A ( _TM ) are the same as the above], which is at least one thermoplastic polymer. 6. The manufacturing method according to 6. 8. (B) (b) 1 to 95% by weight of at least one thermoplastic polymer, and (b ') the complex viscosity η _b of (b) and the complex viscosity of (b') at the same temperature. η _b ′
There is a temperature at which the relationship of η _b / η _b ′ ≧ 5 is satisfied, and a mixture with 99-5% by weight of at least one thermoplastic polymer different from (b) or based on the total amount thereof in this mixture A pattern forming material for forming a marble pattern on a thermoplastic polymer molded product, which comprises a colorant in an amount not exceeding 80% by weight.