JP3479167B2 - Method for producing thermoplastic polymer molded article having marble pattern - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing a polymer molding having a marbled appearance. More specifically, the present invention uses an ordinary injection molding machine, an extrusion molding machine, or the like, and has a marble-like surface appearance with a decorative feeling, while maintaining the original surface gloss and mechanical strength of the raw material polymer. The present invention relates to a method for producing a polymer molded body that can be efficiently produced as it is.

[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.

For this reason, various methods have been tried so far in order to impart decorative properties to the thermoplastic polymer molded article. One of them is a method which is performed on the surface of the polymer molded article by secondary processing, for example, a method of forming a flow pattern by a method such as print painting, hot stamping, and ink-washing painting. Although it has a beautiful surface appearance, it has the drawbacks that the manufacturing cost is high, its use is limited, and that the interior ground color appears due to external damage because it is a decoration only on the surface of the molded body.

In addition, 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. Sho 5).
0-105760, JP-A-54-154451, JP-A-54-154454, JP-A-54-
Japanese Patent No. 154456 and Japanese Patent Laid-Open No. 57-207633) have also been proposed. These methods are methods of forming a flow pattern on a polymer molded body by melt-kneading a colored pattern forming material with a base material and molding in a non-uniform state before they are uniformly kneaded. In the method, the range of molding conditions for obtaining a polymer molded product having a marble-like appearance is limited, and in general, the pattern forming material is present in a lump in the base material, or conversely, between the pattern forming material and the base material. In many cases, color mixing occurs and a clear flow pattern cannot be obtained, and in addition, the mechanical strength of the molded product may be reduced, and peeling may occur at the boundary layer between the base material and the pattern forming material.

Further, for example, a method of using colored particles of a thermosetting polymer as a pattern forming material and dispersing the particles in a base material (JP-A-51-123247).
Japanese Patent Laid-Open No. 62-286716 and Japanese Patent Laid-Open No. 2-1152
No. 71, No. 2-103254, No. 3
-200841, JP-A-3-210350, JP-A-5-93091, and JP-A-6-1875.
Japanese Patent Application Laid-Open No. 6-80821). In these methods, even if it is possible to develop a pattern under a relatively wide range of molding conditions, generally, thermosetting is carried out. Since the colored particles of the pattern forming material have to be prepared by pulverizing the functional polymer, there is a problem in that the production of the colored particles is complicated and the cost is inevitable.

As another general surface decoration method, there is a method of performing color mixing or multicolor molding by using a special mold or apparatus, but this method lacks versatility as a production facility, resulting in a low product price. With rise.

In consideration of such a situation, expensive secondary processing,
Alternatively, it is possible to easily and continuously obtain a high-quality and unique surface appearance with a normal extrusion molding machine or injection molding machine without the need to make any work on the mold or molding machine. However, there is a strong demand for a thermoplastic polymer molded product which can obtain the pattern and maintains the mechanical strength of the molded product.

[0008]

DISCLOSURE OF THE INVENTION The present invention overcomes the drawbacks of the conventional method for producing a polymer having a marbled appearance, uses an ordinary extruder, an injection molding machine, and the like, and under a wide range of molding conditions. The object of the present invention is to provide a method for easily and efficiently producing a polymer molded product which can be processed and has a decorative marbled surface appearance.

[0009]

The inventors of the present invention have a marble-like surface appearance with a simple operation while maintaining the properties of various thermoplastic polymers used as materials, for example, surface gloss and mechanical strength. As a result of earnest studies to obtain a polymer molded body, a polymer composition containing a specially prepared pattern forming material and a thermoplastic polymer base material in a predetermined ratio was treated under a specific temperature condition under normal conditions. It was found that a polymer molding having a beautiful marble-like surface appearance can be efficiently obtained by molding by injection molding or extrusion molding method, and the present invention has been completed based on this finding.

That is, the present invention comprises (A) 60 to 99.9 parts by weight of a thermoplastic polymer base material, and (B) (b).
1-95% by weight of at least one crystalline thermoplastic polymer, and (b ') a complex viscosity [[eta] _b ' at temperature T _M.
(T _M)] is the total amount thereof in the mixture or the mixture of 99 to 5 weight% different at least one thermoplastic polymer and said (b) component in the range of 1 × 10 ³ ~2 × 10 ⁵ poise A polymer containing 40 to 0.1 parts by weight of a pattern forming material composed of a colorant in an amount of not more than 80% by weight based on 100 parts by weight of the components (A) and (B). the composition, the formula _{T m (min) -40 <T} M <T m (max) -1 and _{T M + 1 ≦ T N <} T m (max) +50 [ However, T _M is the molding machine cylinder temperature ( ℃),
T _N is the nozzle set temperature (° C.) of the molding machine, T _m (min) is the melting point (° C.) of the thermoplastic polymer having the lowest melting point of component (b), and T _m (max) is the highest melting point. It is the melting point (° C.) of the thermoplastic polymer having the above]. The present invention also provides a method for producing a polymer molded product having a marble pattern, which is characterized in that it is molded under a temperature condition represented by

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polymer used as the component (A), that is, the base material in the method of the present invention, can be arbitrarily selected from the thermoplastic polymers used as raw materials in ordinary injection molding and extrusion molding. it can. 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 copolymer resin means acrylonitrile / styrene copolymer (AS), 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-vinyl acetate copolymer, α-methylstyrene or maleimide A heat-resistant ABS resin obtained by polymerization is included, and α-methylstyrene / acrylonitrile-based copolymer resin is a styrene / acrylonitrile-based copolymer resin in which the styrene portion is replaced with α-methylstyrene.
-Methylstyrene / acrylonitrile copolymer resin.

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 of the impact-resistant methacrylic resin obtained by graft-copolymerizing methyl methacrylate, styrene, acrylonitrile, various acrylic acid esters, methacrylic acid esters and the like to 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. MBS resin, ABS resin, nitrile rubber, chlorinated polyethylene, EVA-PVC graft copolymer, and modified polyvinyl chloride resin obtained by adding various plasticizers to vinyl chloride can be mentioned.

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 method of 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 an amount 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 material composed of one or more kinds 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. Advantageously, the particles have an average particle size of 0.001 to 10 mm, preferably 0.01 to 8 mm, and more 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, of the component (B) used in the method of the present invention,
The pattern forming material is (b) at least one crystalline thermoplastic
1 to 95% by weight of polymer and (b ') molding temperature (molding machine
Cylinder set temperature T_M) Complex viscosity η_b′
(T_M) Is 1 × 10³~ 2 x 10 ^FiveBefore in the Poise Range
At least one type of thermoplastic poly-carbon different from the component (b)
It is necessary to use a mixture with 99 to 5% by weight
It

The component (B) may be colored in a color tone different from that of the component (A), if desired. This coloring is
It is carried out by blending a colorant in an amount of not more than 80% by weight based on the total amount of the mixture of the components (b) and (b ').

Here, the complex viscosity η is a dynamic complex elasticity 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. Rate (G) and measured angular frequency (ω)
, That is, η = G / ω = (G ′ ² + G ″ ² ) ^0.5 / ω [where G ′ is the dynamic storage elastic modulus and G ″ is the dynamic loss elastic modulus] It 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 the sake of convenience, it means the complex viscosity in the present invention. Also, this complex viscosity has an angular frequency of 1
The value measured at 00 rad / sec is used.

In the pattern forming material of the present invention, the non-melting crystalline thermoplastic polymer which is the component (b) is prepared by the action of the good-flowing thermoplastic polymer which is the component (b ').
It can be dispersed in a wide range in the polymer molded body, and when a colorant is blended, since the colorant is held in the component (b), color mixing with the base material can be prevented. In a wide range of molding conditions, particularly in a wide range of molding temperature conditions, it is possible to easily impart a beautiful flow pattern-like marble-like surface appearance to the polymer molded body. Further, since the pattern forming material is diffused in a wide range in the polymer molded body, molding defects such as unevenness and peeling do not occur in the molded body, and the original moldability of the base material and the mechanical properties of the molded body are improved. Can be maintained.

Further, the pattern forming material in the present invention is
When the component (b) is a dispersed phase and the average dispersed diameter thereof is 0.05 to 1,000 μm, it is preferably 0.1 to 100 μm, more preferably 0.5 to 1 μm.
When it is 0 μm, a polymer molded product having a particularly beautiful and clear marbled surface appearance can be provided.

Here, the average dispersion 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 the component (b). Ingredient and (b ')
Blending of compatibilizers (including reactive compatibilizers) between the components,
It can be controlled by the melt viscosity balance of the components (b) and (b '), the kneading conditions (temperature, screw design, screw rotation speed) when preparing the pattern forming material, and vice versa. By controlling the average dispersion diameter of the component (b) by these factors, it is possible to control the pattern expression state of the polymer molded product.

In the pattern forming material of the component (B),
The polymer component comprises 1 to 95% by weight of the component (b) and (b ')
It is necessary to consist of 99 to 5% by weight of the components.
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 preferably 5 to 70% by weight and the ratio of the component (b ') is 95 to 30% by weight, and particularly preferably 10 to 50% by weight of component (b) and 90% of component (b ').
A proportion of -50% by weight is suitable.

The pattern forming material may be a mixture of thermoplastic polymers comprising the above-mentioned components (b) and (b '), or may be a mixture of a colorant with this mixture. Good. When this colorant is compounded, the amount thereof does not exceed 80% by weight, preferably 50% by weight or less, more preferably 3% based on the total amount of the mixture of the thermoplastic polymers.
It is blended in a proportion of 0% by weight or less. Thus, by blending the colorant with the pattern forming material, it is possible to provide a polymer molded product having a more clear marbled surface appearance.

The crystalline thermoplastic polymer used as the component (b) of the pattern forming material used in the present invention is a crystalline thermoplastic polymer having a melting point above the molding temperature (T _M ) of the polymer molded article. The melting point can be determined from the temperature of the endothermic peak due to the melting of crystals by measurement with a differential scanning calorimeter (DSC). The molding temperature (T _M ) mentioned here indicates the set temperature of the cylinder portion of the molding machine.

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 component (b) has a melting point of 15
It is desirable to use a thermoplastic polymer in the range of 0 to 350 ° C, preferably 200 to 300 ° C.

When a polyvinyl chloride resin is used as the base material, the component (b) has a melting point of 100.
It is desirable to use a thermoplastic polymer in the range of -300 ° C, preferably 150-250 ° C.

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, 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, particularly polyester resins and polyamide resins are advantageous in that the melting point can be easily controlled in a relatively wide range.

Here, the polyester resin means at least one aromatic dicarboxylic acid selected from terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid as a dicarboxylic acid component, and a diol component. Is a copolymerized polyester comprising at least one diol selected from α, ω-diols such as diethylene glycol, triethylene glycol, 1,4-butanediol, and tetraethylene glycol, and is, for example, polyethylene terephthalate (PET). ,
Melting point 255 ° C), polybutylene terephthalate (PB
T, melting point 225 ° C.) and the like.

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. Yes, 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 ° C.), nylon 11 (melting point 192 ° C.), nylon 12 (melting point 186 ° C.) and the like.

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

In the method of the present invention, the component (b ') constituting the pattern forming material of the component (B) has the formula 0.01≤η _b ′ ( _TM ) / η _A ( _TM ) <15 [where , Η _b ′ (T _M ) and η _A (T _M ) are the complex viscosities of the (b ′) component and the (A) component at the molding temperature (T _M ) when processing into a polymer molded body, respectively.] Thermoplastic polymers that satisfy the relationship are preferred. Further, in order to obtain a beautiful and clear marble-like surface appearance, a thermoplastic polymer satisfying the relation of the formula 0.05 ≦ η _b ′ ( _TM ) / η _A ( _TM ) ≦ 10 is preferable, and particularly the formula 0 _A thermoplastic polymer satisfying the relationship of 1 ≦ η _b ′ ( _TM ) / η _A ( _TM ) ≦ 7 is suitable.

The thermoplastic polymer as the component (b ') usually has a complex viscosity at a molding temperature (T _M ) in the range of 1 × 10 ³ to 2 × 10 ⁵ poises, although it depends on the base material used. Must be, preferably 3 × 1
Those in the range of 0 ³ to 1 × 10 ⁵ poise, and more preferably those in the range of 5 × 10 ^{3 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 that the component (b) and the component (b ') are not kneaded properly, and it is difficult to continuously and stably produce 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 resins, olefin resins, polyvinyl chloride resins, polyvinylidene chloride resins, methacrylic resins, polyamide resins, polyester resins, polyurethane resins, polycarbonates. It can be arbitrarily selected from known thermoplastic polymers and thermoplastic elastomers such as resins, polyacetal resins, polyphenylene ether resins, fluororesins, and various thermoplastic elastomers.

In the method of the present invention, the thermoplastic polymer may be used alone as the component (b '), or 2
You may use it in combination of 2 or more types. It is also possible to use a thermoplastic polymer having the same composition as the base material.

Further, in the method of the present invention, (b ')
The use of a thermoplastic elastomer or a mixture of a thermoplastic elastomer and a thermoplastic resin as a component is advantageous because the breaking elongation and impact strength of the obtained polymer molded article can be improved.

As the thermoplastic elastomer, generally,
Styrene type, olefin type, urethane type, ester type,
Young's modulus classified into amide type, PVC type, 1,2-polybutadiene type, ionomer type, etc. is 50 to 1
50,000 kgf / cm ² , elongation at break 100-800
%, Various thermoplastic elastomers having a tensile strength of 50 to 450 kgf / cm ² can be used.

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

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 used as a soft segment. Examples of amide thermoplastic elastomers such as multi-segment polyester include nylon 6, nylon 66, nylon 1
Examples of the polyvinyl chloride thermoplastic elastomer include, for example, polyvinyl chloride compounded with a plasticizer or NBR, such as a multi-segment polyamide having 1 and nylon 12 as hard segments and polyether or polyester as soft segments. Soft polyvinyl chloride etc.

Further, 0.1 to 10 unsaturated monomers such as unsaturated carboxylic acid or its anhydride, unsaturated carboxylic acid derivative, unsaturated carboxylic acid or its anhydride are added to these thermoplastic elastomers. A modified thermoplastic elastomer added with wt%, preferably 0.2 to 5 wt%, more preferably 0.5 to 3 wt% can also be suitably 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 method of the present invention, in order to prevent molding defects such as peeling and rough skin and maintain mechanical properties, the component (b ') is of the same type as the base material or a thermoplastic resin miscible with the base material. Preference is given to using polymers.

Further, in order to prevent molding defects such as peeling and rough skin in the polymer molded body 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').

Next, there is no particular limitation on the colorant to be added to the pattern forming material of the component (B), if desired, and known pigments and dyes and decorative materials can be used. Organic pigments such as condensed azo type, anthraquinone type, isoindolinone type, heterocyclic type, perinone type, perylene type, quinacridone type, thioindigo type, dioxazine type, phthalocyanine type, anthraquinone type, heterocyclic type, perinone type, thioindigo type Like dyes such as titanium oxide, red iron oxide, red iron oxide, talc, calcium carbonate, zinc oxide, barium sulfate, titanium yellow, iron oxide, ultramarine blue, cobalt blue, calcined pigments, carbon black, and metallic pearls. Special pigments can be used.

Further, metals such as aluminum, tin, copper, brass, stainless steel, and iron, alloys using these metals as a substrate, mica, shells, and birefringence are generated in order to develop a special pattern such as metallic pearl. Inorganic or organic crystals, phosphors, etc. can also be used.

In the pattern forming material used in the method 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 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 single screw 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 used in the method of the present invention is a granular body, and its shape is not particularly limited.
For example, it can be used in the form of powder, flakes, beads, spheres, granules, chips, pellets and the like. Further, the average particle diameter is usually 0.01 to 10 m.
m, preferably 0.1 to 5 mm. here,
The average particle diameter means the average of the maximum lengths of the particles, but when the shape of the particles is pellet, the value of the diameter is used as the average particle diameter.

The thermoplastic polymer molding obtained by the production method of the present invention is a polymer having a marble-like surface appearance obtained by allowing a pattern-forming material to flow in a wide range in a base material without causing color mixing. A molded product, wherein the pattern forming material is the component (b), that is, a crystalline thermoplastic polymer having a melting point above the molding temperature and the component (b '),
That is, it is characterized in that it is a granular body of a polymer composition composed of a thermoplastic polymer having a complex viscosity in a specific range.

That is, in the method of the present invention, the total amount of the components (A) and (B) is 100 parts by weight, and 99.9 to 60 parts by weight of the granular base material which is the component (A) and (B).
After mixing 0.1 to 40 parts by weight of the granular pattern forming material as an ingredient, the mixture is molded using various molding machines.

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 all at once. It is also possible to supply it to various molding machines.

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 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 method of the present invention, the base material 99.9
The mixture consisting of 60 wt% and pattern forming material 0.1 to 40 wt%, wherein _{T m (min) -40 <T} M <T m (max) -1 and _{T M + 1 ≦ T N <} T m (Max) +50 [where T _M is the cylinder setting temperature (° C) of the molding machine,
T _N is the nozzle set temperature (° C.) of the molding machine, T _m (min) is the melting point (° C.) of the thermoplastic polymer having the lowest melting point of component (b), and T _m (max) is the highest melting point. It is the melting point (° C.) of the thermoplastic polymer having the above], and a polymer molded product having an excellent surface appearance can be obtained by molding under the temperature condition.

In the method of the present invention, it is necessary to set the nozzle set temperature (T _N ) of the molding machine 1 ° C. higher than the cylinder set temperature (T _M ). That is, in the production of the polymer molded product according to the method of the present invention, in order to inject the component (b) into the molding die in an unmelted state, the cylinder set temperature ( _TM ) of the molding machine is less than the melting point of the component (b). However, since the component (b) is in an unmelted state, the poor flowability of the molten polymer is liable to occur, which often causes nozzle clogging and molding defects such as rough skin on the polymer molded body. .

However, by setting the set temperature (T _N ) of the nozzle portion of the molding machine within the range of the formula T _M + 1 ≦ T _N <T _m (max) +50, the injection into the mold becomes smooth. A good polymer molding can be manufactured extremely efficiently and stably. In this case, the nozzle set temperature may be higher than the melting point of the component (b), but since the molten resin passes through the nozzle portion for an extremely short time, the unmelted state of the component (b) is maintained. Since the molten resin can be poured into the mold as it is, the polymer molded product can be molded without impairing the pattern development.

This molding temperature T _M (° C.) is [T _m (mi
n) -40] or less, the moldability of the polymer molded article is greatly impaired, and the pattern-forming material is present in the polymer molded body in a lump form without being dispersed. The appearance is greatly reduced. On the other hand, T _M is [T _m
In the case of (max) -1] or more, since the component (b) may be melted, the formation of the marble pattern becomes incomplete.

From the aspects of moldability, mechanical properties of the molded product, surface appearance, and marble pattern impartability, the molding temperature T
_{As M} (° C.), a temperature satisfying the relationship of the formula T _m (min) −30 ≦ T _M ≦ T _m (max) −3, in particular, the formula T _m (min) −20 ≦ T _M ≦ T _m (max) ) -5 is preferable.

On the other hand, the nozzle set temperature T _N (° C.) is [T
_{In the case of m} (max) +50] or more, since the component (b) is melted, a marble pattern is not imparted to the polymer molded body, and if it is less than [T _M +1], nozzle clogging may occur as described above. As a result, the injection into the mold is not smooth.

Marble pattern imparting property and injection into a mold
From the aspects such as performance, the nozzle set temperature T _N(℃)
formula T_M+ 1≤T_N≤T_m(Max) +30 The temperature that satisfies the relationship of T_M+ 1≤T_N≤T_m(Max) +20 The temperature satisfying the relationship of is preferable.

Further, in the method of the present invention, a polymer molded article 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. Moreover, polymer moldings having a wide variety of surface appearances can be obtained.

In the method of the present invention, if necessary, 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. Agents, antifungal agents and the like can be added during the molding process of the polymer molded body. Further, these additive components may be mixed in advance with the base material, the pattern forming material, or both.

In the method of the present invention, when extrusion molding or injection molding is carried out, particularly when injection molding is carried out, the screw design of the molding machine, cylinder diameter, L / D, screw rotation speed, back pressure, injection speed, etc. It is advantageous because the surface appearance can be variously changed depending on the conditions.

The surface appearance of the molded body can be changed in various ways depending on the shape and size of the gate of the injection molding die, and further, the thickness of the molded body.

Furthermore, in recent years, a plasticizing screw having a high kneading function, for example, Himelta [manufactured by Japan Steel Works,
Product name], UB screw [made by Mitsubishi Heavy Industries, Ltd., product name], DB screw [made by Toshiba Machine Co., Ltd., product name],
SF screw [Sumitomo Heavy Industries, Ltd. product name]
Alternatively, various types of molding machines equipped with pin-type and fin-type [Dulmaji, etc.] special mixing elements, and further mixing nozzles (manufactured by Toray Industries, Inc.) have been developed, and polymer molding is performed using these molding machines. You can also control the surface appearance of the body.

[0075]

EFFECTS OF THE INVENTION According to the method of the present invention, as a pattern forming material, a granular body of a polymer composition comprising a crystalline thermoplastic polymer having a melting point above the molding temperature and a thermoplastic polymer having a complex viscosity in a specific range is used. By using
A polymer molded product having a beautiful marbled appearance and excellent mechanical properties can be easily obtained under a wide range of molding conditions, particularly 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 in a wide range of fields such as vehicle parts, daily necessities, toys, and sundries, especially for the production of 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 used for various parts which require a wide variety of appearances. .

Furthermore, 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.

[0079]

EXAMPLES Next, 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
Using r RDA II (trade name, manufactured by Rheometrics), the complex viscosity at the molding processing temperature of the thermoplastic polymer molded article was measured. 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 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 directly observing the surface of the molded product and observing 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, with tip dullage screw], and the molding temperature (cylinder setting temperature), nozzle setting temperature, and mold temperature of 60 ° C. shown in the table.

(6) Tensile Strength, Elongation at Break Evaluated according to ASTM D638. As a test piece, a mixture of a base material and a pattern forming material was supplied to an injection molding machine, and a molding temperature, a nozzle setting temperature, and a mold temperature of 60 ° C shown in the table.
It was made in.

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 Kogyo KK, trade name Delpet 80N] Acrylonitrile-butadiene-styrene copolymer (A
BS): [Asahi Kasei Co., Ltd., trade name Stylak 220B] Polycarbonate (PC): [Teijin Kasei Co., Ltd., trade name Panlite K1300] Polyethylene terephthalate (PET): [Teijin Kasei Co., Ltd. Trade name TR8550] Polybutylene terephthalate (PBT): [Mitsubishi Kasei Co., Ltd., trade name Novador 5010S] Oxazoline group-containing polystyrene (modified PS): [Nippon Shokubai Kagaku Kogyo Co., Ltd., trade name RPS-1005] Water Styrene / butadiene / styrene copolymer (SEB
S): [Asahi Kasei Kogyo KK, trade name Tuftec H1
051] Maleic anhydride-modified SEBS (modified SEBS): [Asahi Kasei Kogyo KK, trade name Tuftec M1953] Polyester elastomer (PEs-R): [TOYOBO KK, trade name Perprene P40H]

Preparation Example After mixing the components of the types and amounts shown in Tables 1 and 2 with a blender, the mixture was mixed with a twin-screw extruder [manufactured by Ikegai Tekko KK,
Pellets of the pattern forming materials (B-1) to (B-10) colored in white were prepared by melt-kneading at a kneading temperature shown in the table using a product name PCM45] and pelletizing. The structures of the obtained pattern forming materials are shown in Tables 1 and 2.

[0088]

[Table 1]

[0089]

[Table 2]

Examples 1 to 10 To 100 parts by weight of each base material polymer shown in Tables 3 and 4, 0.02 part by weight of carbon black and 0.5 part by weight of titanium dioxide were added and mixed with 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 was 230 ° C, 250 ° C, and 240 ° C for HIPS, ABS, and PMMA, respectively.

Next, the base material (A) pellets and the pattern forming material (B) pellets obtained in the preparation examples were mixed with a blender in the blending ratios shown in Tables 3 and 4, and then the injection molding machine [Nissei] was used. Resin Industry Co., Ltd., trade name PS40E5
A, screw diameter 30 mm, with tip dullage screw], injection molding at the molding temperature (cylinder setting temperature), nozzle setting temperature, and mold temperature 60 ° C shown in the table, and a 90 mm × 50 mm × 3 mm flat plate , And test pieces for evaluation of various physical properties were prepared. Table 3 and Table 4 show the occurrence of a marble pattern and the surface appearance of this polymer molded body together with the complex viscosity of each polymer and its ratio.

In the tables, η _A , η _b and η _b ′ are the base material (A), the pattern forming material (b) component, and the pattern forming, respectively, at the molding temperature (T _M ) of the polymer molded body. This is the complex viscosity of the material (b ') component. In the table, when the complex viscosity is α × 10 ^n, it is abbreviated as αEn (for example, 5.25 × 10 ³ is 5.25E3).

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 3]

[0095]

[Table 4]

As can be seen from Tables 3 and 4, Example 1
All of the polymer moldings obtained in Nos. 10 to 10 had a high-quality marbled surface appearance.

Further, as shown in Examples 7 and 9, (b ')
When the thermoplastic elastomer was used as the component, the Izod impact strength was improved as compared with the polymer moldings (Comparative Examples 8 and 7) consisting of the colored base materials (ABS and HIPS) alone described below. Also, although the elongation at break is reduced, the degree of reduction is lower than when a pattern forming material made of only PBT is used (Comparative Example 1) or a pattern forming material made of PET only is used (Comparative Example 2). Was a small polymer, and it was an excellent polymer molded product with a beautiful marbled surface appearance and mechanical properties maintained.

Comparative Example 1 The pellets of the colored base material (HIPS) used in Example 1 and the pellets of the pattern forming material (B-9) obtained in the Preparation Example were mixed at the compounding ratio shown in Comparative Example 1 of Table 5. Molding temperature 210 ° C, nozzle setting temperature 220 ° C, mold temperature 6
90mm x 50mm x using an injection molding machine at 0 ° C
A 3 mm flat plate and test pieces for evaluating various physical properties were prepared. Table 5 shows the generation state of the marble pattern and the surface appearance of this polymer molded body together with the complex viscosity of each polymer and its ratio. When the thermoplastic polymer forming the pattern forming material is only PBT, the pattern forming material does not disperse in the molded body but exists in the form of particles, and a speckled pattern made of the pattern forming material is obtained in the molded body. Was given. 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 5 and the pellets of the pattern forming material (B-10) obtained in the Preparation Example were mixed at the compounding ratio shown in Comparative Example 2 in Table 5. Molding temperature 250 ° C, nozzle setting temperature 270 ° C, mold temperature 6
90mm x 50mm x using an injection molding machine at 0 ° C
A 3 mm flat plate and test pieces for evaluating various physical properties were prepared. Table 5 shows the generation state of the marble pattern and the surface appearance of this polymer molded body together with the complex viscosity of each polymer and its ratio. When the thermoplastic polymer forming the pattern forming material is only PET, the pattern forming material does not disperse in the molded body but exists in the form of particles, and a speckled pattern made of the pattern forming material is obtained in the molded body. Was given. In addition, unevenness was observed on the surface of the polymer molded body and the smoothness was poor.

Comparative Example 3 Pellets of the colored base material (HIPS) used in Example 1 and the pellets of the pattern forming material (B-1) obtained in the Preparation Example were mixed in the compounding ratio shown in Comparative Example 3 of Table 5. Molding temperature 210 ° C, nozzle setting temperature 230 ° C, mold temperature 6
90mm x 50mm x using an injection molding machine at 0 ° C
A 3 mm flat plate and test pieces for evaluating various physical properties were prepared. Table 5 shows the occurrence state of the marble pattern of the polymer molded product, the surface appearance and each physical property together with the complex viscosity of each polymer and the ratio thereof. The molding temperature of this example is PE
The temperature is 40 ° C. or more lower than the melting point of T (255 ° C.). The polymer molded product obtained at this time had a poor dispersibility in the pattern forming material, and a flow pattern-like surface appearance was not obtained. Also,
Unevenness was found on the surface of the polymer molded body and the smoothness was poor.

Comparative Example 4 The pellets of the colored base material (HIPS) used in Example 1 and the pellets of the pattern forming material (B-2) obtained in the Preparation Example were mixed at the compounding ratio shown in Comparative Example 4 in Table 5. Molding temperature 250 ° C, nozzle setting temperature 250 ° C, mold temperature 6
90mm x 50mm x using an injection molding machine at 0 ° C
A 3 mm flat plate and test pieces for evaluating various physical properties were prepared. Table 5 shows the occurrence state of the marble pattern of the polymer molded product, the surface appearance and each physical property together with the complex viscosity of each polymer and the ratio thereof. At the molding temperature of this example, the PBT in the pattern forming material was completely melted, and η _b / η _b ′
And η _b / η _A are 1.35 and 1.40, respectively. The molded product obtained at this time had a uniform gray color, and a marble-like surface appearance was not obtained.

Comparative Example 5 90 mm × 50 mm × 3 mm using an injection molding machine under the same conditions as in Example 6 except that the nozzle setting temperature was 210 ° C.
And a test piece for evaluation of various physical properties were prepared. Table 5 shows the occurrence state of the marble pattern of the polymer molded product, the surface appearance and each physical property together with the complex viscosity of each polymer and the ratio thereof. When the nozzle set temperature was 210 ° C., the obtained polymer molded article had a flow pattern-like surface appearance, but rough skin appeared and the surface smoothness was poor.

Comparative Example 6 90 mm × 50 mm × 3 mm using an injection molding machine under the same conditions as in Example 8 except that the nozzle setting temperature was 320 ° C.
And a test piece for evaluation of various physical properties were prepared. Table 6 shows the generation state of the marble pattern of this polymer molded product, the surface appearance and each physical property together with the complex viscosity and the ratio of each polymer. When the nozzle setting temperature was 320 ° C., the obtained molded product had a uniform gray color, and a marble-like surface appearance was not obtained.

Comparative Example 7 A polymer molding was produced from the pellets of the colored base material (HIPS) used in Example 1 by injection molding under the conditions of molding temperature 210 ° C., nozzle setting temperature 220 ° C., and mold temperature 60 ° C. did. The obtained polymer molded body had a single gray color. Table 6 shows the physical properties of the polymer molded body together with the complex viscosity of each polymer and the ratio thereof.

Comparative Example 8 From the pellets of the colored base material (ABS) used in Example 8, a polymer molding was prepared by injection molding under the conditions of molding temperature of 250 ° C., nozzle setting temperature of 270 ° C., and mold temperature of 60 ° C. did. The obtained polymer molded body had a single gray color. Table 6 shows the physical properties of the polymer molded body together with the complex viscosity of each polymer and the ratio thereof.

[0106]

[Table 5]

[0107]

[Table 6]

─────────────────────────────────────────────────── --Continued from the front page (56) Reference JP-A-8-208919 (JP, A) JP-A-62-18232 (JP, A) JP-A-62-4727 (JP, A) JP-A-6- 1857 (JP, A) JP 50-105760 (JP, A) JP 58-69027 (JP, A) JP 6-184447 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08J 5/00-5/24 C08L 1/00-101/14 B29C 45/00-45/84

Claims (2)

(57) [Claims] 1. (A) Thermoplastic polymer base material 60 to
99.9 parts by weight, and (B) (b) at least one and 1 to 95 wt% crystalline thermoplastic polymer, (b ') a complex viscosity at a temperature _{T M [η b' (T} M)] is 1 x 10 ³ ~
40-0.1 parts by weight of a pattern-forming material composed of a mixture with 99-5% by weight of at least one thermoplastic polymer different from component (b) in the range of 2 × 10 ⁵ poises as component (A). (B) the total polymer composition containing such that 100 parts by weight of the components, wherein _{T m (min) -40 <T} M <T m (max) -1 and _{T M + 1 ≦ T N <} T m (Max) +50 [where T _M is the cylinder setting temperature (° C) of the molding machine,
T _N is the nozzle set temperature (° C.) of the molding machine, T _m (min) is the melting point (° C.) of the thermoplastic polymer having the lowest melting point of component (b), and T _m (max) is the highest melting point. It is the melting point (° C.) of the thermoplastic polymer having the above]. The method for producing a polymer molded product having a marble pattern, wherein the molding is performed under a temperature condition. 2. The production method according to claim 1, wherein a pattern forming material colored with a colorant different from that of the component (A) is used as the component (B).