JPH08164588A - Composite plastic molding - Google Patents

Abstract

PURPOSE: To obtain a composite plastic molding which has good interlayer adhesion and soft touch, is not sticky, and has good luster, color tone, appearance, etc., by forming a skin layer of an elastic styrene polymer, etc., on the periphery of a thermoplastic resin core material and coating the surface with a paint film. CONSTITUTION: A skin layer of a thermoplastic elastomer composition comprising 20-80 pts.wt. component (A), 80-20 pts.wt. component (B), and 0.01-10 pts.wt. component (C) and/or a component (D) added to 100 pts.wt. total components (A), (B) is formed on the periphery or the surface of a core material layer. The skin layer is coated with a paint film. The component (A) is a hydrogenation product of an elastic styrene-conjugated diene block copolymer; the component (B) is a polyolefin resin; the component (C) is a diene polymer having terminal hydroxyl groups; the component (D) is a copolymer of ethylene and an unsaturated compound having a hydroxyl group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a composite plastic molded article. More specifically, the present invention relates to a composite plastic molded article in which a skin layer made of a thermoplastic elastomer composition is formed on the outer peripheral portion or surface of a core material layer made of a thermoplastic resin, and a coating film is formed on the surface of the skin layer. Is.

[0002]

2. Description of the Related Art Conventionally, a core material layer is molded for the purpose of making it difficult for a thermoplastic resin molded article to be scratched, improving aesthetics (visuality and designability), and obtaining a soft touch. A composite molded article in which a skin layer made of a soft resin is formed on the outer peripheral portion or the surface of the article has been proposed and put into practical use. The core material layer forming resin is generally an olefin resin represented by polyethylene or polypropylene, an AS resin, or an A resin.
A styrene resin represented by a BS resin is used, and a soft polyvinyl chloride or an olefin thermoplastic elastomer is used as a resin for forming a skin layer. The latter is used as a leather or foam sheet in a core material layer. The attached one is used.

On the other hand, recently, in order to reduce the weight and cost of a molded product, an olefin resin has been often used as a core material layer of a composite molded product. The olefin resin is the above-mentioned leather. Or, the adhesiveness with the skin layer made of a foamed sheet is poor, and in order to improve this, a method such as primer treatment or plasma treatment of the surface of the olefin resin molded article is proposed, Deterioration and cost increase are inevitable.

As a method for improving such a defect, for example, a core material layer is inserted into an injection molding die, and a skin layer is formed on the surface of the insert by an injection molding method. JP-A-61-213145, JP-A-63-227313, etc.) have been proposed.

The surface of the composite molded article obtained by the above-mentioned insert molding method has a soft touch property, but has the disadvantages that it is sticky, easily dusty, and the surface feel is insufficient. It had no gloss and poor color tone, and lacked aesthetics (visuality and design). In order to improve such drawbacks, a technique has been proposed in which a styrene-based thermoplastic elastomer containing polybutene is used as a resin for forming a skin layer, and a coating material is applied to the surface of the skin layer (JP-A-64- 22519). However, according to the experiments conducted by the present inventors, the composite molded article produced by this technique has improved stickiness of the skin layer and the feel of the surface, but the adhesion between the skin layer and the coating was not sufficient.

However, when an olefin-based thermoplastic elastomer or a styrene-based thermoplastic elastomer is used as the skin layer forming material, the surface of the composite molded article has a sticky feeling, is easily scratched, and is easily dusty. Therefore, it is absolutely necessary to paint the surface,
There has been a demand for rationalization of the painting process. In order to improve such a defect, it has been attempted to use a modified styrene-based thermoplastic elastomer (JP-A-6-143332), but since the material is soft,
Special paint was essential.

[0007]

The object of the present invention is to provide both excellent adhesive strength between the core material layer and the skin layer, excellent adhesive strength between the surface of the skin layer and the coating film, and excellent soft touch properties. An object of the present invention is to provide a composite plastic molded product which has no stickiness, is excellent in luster, color tone, aesthetics (visuality and design) and has a rationalized coating process.

[0008]

In order to solve the above-mentioned problems, in the invention described in claim 1, a core material layer made of a thermoplastic resin and the following components are provided on the outer peripheral portion or surface of the core material layer. 20 to 80 parts by weight of (A) and 80 parts of the following component (B)
˜20 parts by weight and the following component (C) and / or component (D)
Is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the component (A) and the component (B), and a skin layer made of a thermoplastic elastomer composition is formed on the surface of the skin layer. Means are provided for forming a composite plastic molded product characterized by having a coating film formed thereon. Component (A): Hydrogenated product of elastomeric styrene / conjugated diene block copolymer and / or olefin copolymer rubber Component (B): Olefin resin Component (C): Diene polymer having terminal hydroxyl group or its Hydrogenated Component (D): Copolymer of Ethylene and Unsaturated Compound Having Hydroxyl Group

In the invention described in claim 5,
A core layer made of a thermoplastic resin, and 20 to 80 parts by weight of the following component (A), 80 to 20 parts by weight of the following component (B) and the following component (C) on the outer peripheral portion or surface of the core material layer. as well as/
Alternatively, the total amount of the component (D) of the component (A) and the component (B) is 10
A skin layer made of a thermoplastic elastomer composition formed by blending 0.01 to 10 parts by weight with respect to 0 parts by weight is formed,
A means for producing an automobile part is provided by forming a urethane coating film on the surface of the skin layer. Component (A): Hydrogenated product of elastomeric styrene / conjugated diene block copolymer and / or olefin copolymer rubber Component (B): Olefin resin Component (C): Diene polymer having terminal hydroxyl group or its Hydrogenated Component (D): Copolymer of Ethylene and Unsaturated Compound Having Hydroxyl Group

DETAILED DESCRIPTION OF THE INVENTION The present invention is described in detail below. The composite plastic molded article according to the present invention,
(1) A core material layer made of a thermoplastic resin, (2) a skin layer made of a specific thermoplastic elastomer composition, and (3) a coating film.

[1] Thermoplastic Resin Forming Core Material Layer The thermoplastic resin forms the core material layer of a composite plastic molded product (hereinafter sometimes referred to as "composite molded product"). The thermoplastic resin forming this core material layer is JIS-K7203.
Flexural modulus is 500 MPa or more, preferably 80
A thermoplastic resin of 0 MPa or more, particularly preferably 1,000 MPa or more is suitable. In the case of automobile parts, JIS of thermoplastic resin for composite plastic moldings
The bending elastic modulus according to -K7203 is preferably 1,200 MPa or more, and particularly preferably 1,400 MPa or more.

Examples of the thermoplastic resin include olefin resins, polycarbonate resins, styrene resins, acrylic resins, vinyl chloride resins, modified polyphenylene ether resins, polyamide resins such as nylon 6, nylon 11 and nylon 12, polyethylene terephthalate, Examples thereof include polyester resins such as polybutylene terephthalate. Of these, preferred are olefin resins, polycarbonate resins, styrene resins, acrylic resins,
Vinyl chloride resin and modified polyphenylene ether resin. These thermoplastic resins may be used alone or as a mixture of two or more kinds.

More specifically, examples of the olefin resin include ethylene resin, propylene resin and polybutene resin.
1 resin etc. are mentioned. Examples of ethylene resins include polyethylene, ethylene / α-olefin copolymers, ethylene / vinyl acetate copolymers, ethylene / (meth) acrylic acid copolymers, ethylene / (meth) acrylic acid ester copolymers. be able to. Examples of polyethylene include low-density polyethylene (branched ethylene polymer), medium-density polyethylene, and high-density polyethylene (linear ethylene polymer). As the ethylene / α-olefin copolymer, ethylene / butene-1 copolymer, ethylene / hexene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, ethylene-4-methylpentene-1 copolymer Examples thereof include polymers.

Examples of the propylene resin include polypropylene, propylene / ethylene random copolymer, propylene / ethylene block copolymer and the like. These olefin resins may be used alone or as a mixture of two or more kinds. Among the olefin resins, propylene / ethylene block copolymers are particularly preferable.

As the styrene resin, general-purpose polystyrene (GPPS), rubber-reinforced polystyrene (HIP)
S), AS resin (acrylonitrile / styrene copolymer), ABS resin (acrylonitrile / butadiene / styrene copolymer), AAS resin (acrylonitrile / acrylic rubber / styrene copolymer), ACS resin (acrylonitrile / chlorinated polyethylene) -Styrene copolymer), AES resin (acrylonitrile / EPDM / styrene copolymer), MAS resin (maleimide / styrene copolymer), MBS resin (methyl methacrylate / butadiene / styrene copolymer), and the like, styrene It may be one in which a part of is substituted with α-methylstyrene. These styrene resins can be produced by an emulsion polymerization method, a bulk-suspension polymerization method, a bulk polymerization method, a suspension polymerization method, or the like.

The thermoplastic resin may be blended with a thermoplastic elastomer and various additives. As the thermoplastic elastomer that can be blended, ethylene / propylene copolymer rubber (EPM), ethylene / butene copolymer rubber (EBM), ethylene / propylene / non-conjugated diene copolymer rubber (EPDM), ethylene / propylene / butene copolymer rubber. , Styrene-butadiene copolymer rubber (SB
R), styrene / isoprene copolymer rubber, polybutadiene, and other elastomers. As additives that can be blended, talc, calcium carbonate, fillers such as mica, plasticizers such as paraffin oil, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, neutralizing agents, lubricants, lubricants,
Anti-fog agent, anti-blocking agent, slip agent, dispersant,
Colorants, antibacterial agents, optical brighteners and the like can be mentioned.

[2] Thermoplastic Elastomer Composition for Forming Skin Layer The thermoplastic elastomer composition forms a skin layer on the surface of the core material layer so that the surface of the molded article is not easily scratched, and the appearance (visual property, In addition to enhancing the adhesion with the coating film to improve the design, it also has the function of imparting soft touch. The thermoplastic elastomer composition forming this skin layer has a flexural modulus of 500 M according to JIS-K7203.
Less than Pa and JIS-A according to JIS-K6301
A hardness of more than 50 is preferable. If the flexural modulus exceeds the above range, the coatability is poor, and if the JIS-A hardness is less than the above range, the moldability (release property) is poor. The bending elastic modulus is preferably less than 400 MPa, and more preferably less than 350 MPa within the above range. JIS-A hardness is 55 or more and 10 in the above range.
Those of 0 or less are preferable. The thermoplastic elastomer composition having the above physical properties preferably satisfies the above physical properties, but in addition, the composition has the components (A), (B) and (C) as described in detail below, or It is essential to consist of the component (A), the component (B) and the component (D).

(1) Essential Components The essential components will be described in detail below. The weight average molecular weight of each component for the thermoplastic elastomer composition described below means the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC). An example of measurement by GPC is as follows.

The equipment used is 150C ALC / GP
C (manufactured by MILLIPORE), the column uses three AD80M / S manufactured by Showa Denko KK, the solvent is o-dichlorobenzene, the temperature is 140 ° C., the flow rate is 1 ml / min,
Injection volume 200 μl, concentration 2 mg / ml (2,6-di-t-butyl-p-phenol as an antioxidant 0.2
(Wt% addition), concentration detection is carried out with an infrared spectrophotometer MIRAN 1A manufactured by FOXBORO at a wavelength of 3.42 μm.

Component (A): Component (A) is (a) a hydrogenated product of an elastomeric styrene-conjugated diene block copolymer and / or (b) an olefin copolymer rubber. (A) Hydrogenated substance of elastomeric styrene / conjugated diene block copolymer In the present invention, the hydrogenated substance of styrene / conjugated diene block copolymer means hydrogenated elastomeric block copolymer of styrene and conjugated diene. The preferred conjugated diene is butadiene, isoprene or a mixture thereof. When the conjugated diene is a mixture of isoprene and butadiene, the weight ratio of the mixture (isoprene / butadiene) is 99/1 to 1/99,
Preferably 90/10 to 30/70, particularly preferably 8
It is from 0/20 to 40/60.

As a specific example of (a), styrene-ethylene- which is a hydrogenated product of a styrene-butadiene block copolymer (hereinafter sometimes simply referred to as "hydrogenated S-B-S"). Butylene-styrene copolymer (SEB
S) or a styrene-ethylene-propylene-styrene copolymer (which is a hydrogenated product of a styrene-isoprene block copolymer (hereinafter, may be simply referred to as "hydrogenated S-I-S"). SEPS), hydrogenated products of styrene / butadiene / isoprene block copolymers (hereinafter,
It may be simply abbreviated as "hydrogenated S-BI-S". ) And the like.

The hydrogenated product of the elastomeric styrene / conjugated diene block copolymer (a) is preferably selected in the range of 50,000 to 500,000 in weight average molecular weight. When the weight average molecular weight is less than the above range, rubber elasticity and mechanical strength tend to be poor, and when the weight average molecular weight exceeds the above range, moldability tends to be poor, and both are not preferable. Among the weight average molecular weights in the above range, 60,000 to 400,000 are preferable, and 70,000 to 300,000 are particularly preferable.

(A) The styrene content of the elastomeric styrene / conjugated diene block copolymer is 5 to 50% by weight, preferably 8 to 45% by weight, particularly preferably 10 to
It is 40% by weight. A styrene content of less than 5% by weight is inferior in rubber elasticity and strength, and a styrene content in excess of 50% by weight is inferior in flexibility. In addition, 1,2-
The microstructure is in the range of less than 60%, preferably less than 45%. If the 1,2-microstructure exceeds 60%, the flexibility is poor. The hydrogenation rate of the elastomeric styrene / block copolymer is preferably 95% or more from the viewpoint of weather resistance. The (a) hydrogenated product of the elastomeric styrene / conjugated diene block copolymer preferably has a JIS-A hardness of 98 or less, preferably 95 or less, and particularly preferably 90 according to JIS-K6301.
It is as follows.

As the method for producing the hydrogenated product of the elastomeric styrene / conjugated diene block copolymer (a), for example, the method described in JP-B-40-23798 is used, and it is inert with a lithium catalyst. A styrene / conjugated diene block copolymer was synthesized in a solvent, and then, for example, Japanese Patent Publication Nos. 42-8704 and 43-6.
636, JP-A-59-133203, JP-A-60-
According to the methods described in each of the 79,005 publications, there may be mentioned a method of hydrogenating in the presence of a hydrogenation catalyst in an inert solvent. Further, the hydrogenated S-BI-S can be synthesized by the method described in, for example, JP-A-3-188114.

(B) Olefin-based Copolymer Rubber In the present invention, the olefin-based copolymer rubber is a copolymer of ethylene and another monomer and has rubber-like elasticity. Specific examples of the (b) olefin-based copolymer rubber include ethylene / propylene copolymer rubber (EP
M), ethylene / butene-1 copolymer rubber (EBM),
As non-conjugated dienes, 5-ethylidene norbornene, 5
Examples thereof include ethylene / propylene / non-conjugated diene copolymer rubber (EPDM) using -methylnorbornene, 5-vinylnorbornene, dicyclopentadiene and the like.

[0026] These (b) olefin copolymer rubber
Has a weight average molecular weight of 50,000 to 1,000,000.
It is 0. Rubber with a weight average molecular weight below the above range
Elasticity and mechanical strength tend to be poor, and the weight average molecular weight is
If the amount exceeds the above range, the moldability tends to be poor. Up
The weight average molecular weight within the above range is preferably 60,0.
100 to 800,000, particularly preferably 80,
It is 000 to 500,000.

When the olefin copolymer rubber is an ethylene / propylene copolymer rubber (EPM), the propylene content is 10 to 60% by weight, preferably 15 to 55% by weight, and the Mooney viscosity ML _{1 + 4} (100 ° C.). ) Is 5-35
It is preferred to use 0, preferably 10-300, copolymer rubber.

The manufacturing method and shape of these (b) olefinic copolymer rubbers are not particularly limited. Also,
It may be one obtained by heat-treating them in the presence of an organic peroxide and crosslinking mainly by radicals.
When component (A) is used in combination with component (A) and component (b), the weight ratio of component (A) and component (b) is 5 / 95-9.
It is preferable to combine them in a ratio of 5/5, and the ratio of 10/90 to 90/10 is particularly preferable.

Component (B): Component (B) is an olefin resin, and includes propylene resin, ethylene resin, crystalline polybutene-1 resin, ethylene / vinyl acetate copolymer, ethylene (meth) acrylic acid copolymer. Coalescence, ethylene (meta)
Examples thereof include ethylene resins such as acrylic acid ester copolymers.

The propylene-based resin is a propylene homopolymer or a copolymer resin containing propylene as a main component, and specific examples thereof include a propylene / ethylene random copolymer and a propylene / ethylene block copolymer. be able to. Among these, a propylene / ethylene block copolymer is preferable from the viewpoint of adhesion to the coating film.

As the ethylene-based resin, a low-density polyethylene resin (branched ethylene polymer) produced by a high-pressure method and a high-density polyethylene resin which is an ethylene homopolymer obtained by a medium- and low-pressure method, produced by a conventional method Examples thereof include (linear ethylene copolymer) and low-density, medium-density, and high-density polyethylene resins which are copolymers of ethylene and a linear α-olefin obtained by the medium- and low-pressure method.

Examples of the linear α-olefin which is a monomer copolymerizable with ethylene include butene-1, pentene-1, hexene-1, 4-methylpentene-1, octene-1 and the like. Also, these may be used in combination of two or more kinds. Conditions for producing an ethylene-based resin by a conventional method are, for example, generally, a pressure of 5 to 2 as described in JP-B-56-18132.
Under the conditions of 500 kg / cm ² and temperature of 50 to 300 ° C.,
A method of copolymerizing ethylene and α-olefin using a Ziegler type catalyst, a vanadium type catalyst, a Kaminsky type catalyst or the like is adopted.

Among the above olefin resins as the component (B), propylene resins are preferable, and melt flow rate (MFR) (JIS-K675) is particularly preferable.
8, 230 ℃, 2.16kg load) 0.01 ~ 100
It is a propylene resin in the range of g / 10 minutes. When the MFR having a MFR less than the above range is used, the injection moldability is deteriorated, and the appearance of the obtained injection-molded product, particularly the generation of flow marks tends to be remarkable. Further, when a material having an MFR exceeding the above range is used, the material strength tends to be lowered, which is not preferable. Among the propylene resins having MFR in the above range, those of 0.05 to 80 g / 10 minutes are preferable, and 0.1 to 60 g / minute is particularly preferable.
It's 10 minutes. The ethylene content of the propylene resin is 0 to 15% by weight, preferably 0 to 13%.
% By weight, particularly preferably 0 to 10% by weight. The ethylene content in the propylene-based resin can be measured by an infrared spectrum analysis method or the like.

As the crystalline butene-1 resin, a monomer mixture containing butene-1 as a main component, which may contain a small amount (20% by weight or less) of other monomers such as ethylene and propylene, is polymerized. Crystalline resin. Regarding the physical properties of this crystalline butene-1 resin, the density is 0.890 to 0.925 g / cm ³ , preferably 0.8.
93 to 0.923 g / cm ³ , particularly preferably 0.90
0 to 0.920 g / cm ³ , and melt flow rate (MFR) (JIS-K6758, 190 ° C, 2.16).
(kg load) is 0.01 to 1,000 g / 10 minutes, preferably 0.05 to 500 g / 10 minutes, and particularly preferably 0.1.
1 to 100 g / 10 minutes, with a crystallinity of 30%
Or more, preferably 30 to 70%, and the weight average molecular weight is 10,000 to 3,000,000, preferably 5
It is in the range of 20,000 to 2,500,000.

Component (C): Component (C) refers to a diene polymer having a hydroxyl group at the terminal or a hydrogenated product thereof, and comprises a skin layer made of a thermoplastic elastomer and a coating film formed on the surface of the skin layer. Functions to improve adhesion. The component (C) is a diene polymer having a hydroxyl group at the terminal or a hydrogenated product thereof, and the diene polymer having a hydroxyl group at the terminal includes, for example, polyhydroxypolybutadiene. Specifically, it has at least one hydroxyl group at the terminal and has a weight average molecular weight of 20.
0 to 100,000, preferably 500 to 50,000
0, particularly preferably 800-10,000, liquid, semi-solid, solid polymers at ambient temperature are included. The average number of hydroxyl groups per molecule is usually from 1 to 10, among which 1.5
To 5 are particularly preferable, and the hydroxyl value is usually 15 to 2.
50, and among them, 25 to 125 (KOHmg / g) is preferable.

The diene polymer having a hydroxyl group at the terminal is
By using 1,3-diene as a raw material, it can be produced by a well-known method such as a radical polymerization method or an anionic polymerization method. Specifically, for example, JP-A-51-71391
The method described in the publication can be cited.

When the diene polymer having a hydroxyl group at the terminal is produced by radical polymerization, it can be easily obtained by polymerizing a diene monomer using hydrogen peroxide as a polymerization initiator. In the case of producing by anionic polymerization, according to a known method, a conjugated diene is obtained by polymerizing with an anion polymerization catalyst, for example, an alkali metal or an organic alkali metal compound, and at least one of both terminals is alkali. A living polymer having a structure in which a metal is bonded may be reacted with, for example, a monoepoxy compound, formaldehyde, acetaldehyde, acetone, halogenoalkylene oxide, polyepoxide, or the like. At least one type of conjugated diene monomer is used as a raw material monomer for these polymers. Examples of the conjugated diene monomer include 1,3-butadiene, 1,3-pentadiene, isoprene, chloroprene, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene and the like.

The hydrogenated product of the diene polymer having a hydroxyl group at the terminal is obtained by hydrogenating the above-mentioned diene polymer having a hydroxyl group at the terminal.
The hydrogenated product of a diene polymer having a hydroxyl group at the terminal is
For example, it can be obtained by an ordinary hydrogenation method as described in JP-A-51-71391. The degree of hydrogenation may be such that the double bonds contained in the polymer are wholly or partially hydrogenated, and the iodine value is usually 0 to 20, especially 0 to 5 (g / 100 g). Those are particularly preferable. These diene polymers having a hydroxyl group at the terminal or hydrogenated products thereof can be used alone or as a mixture of plural kinds.

Component (D): Component (D) is a copolymer containing ethylene, an unsaturated compound having a hydroxyl group, and optionally a third copolymerizable component, and like the component (C), a skin layer. And the function of improving the adhesion to the coating film formed on the surface of the skin layer. For example, a polymer in which ethylene and 2-hydroxyethyl methacrylate are copolymerized randomly or at a certain fixed interval,
Here, from a structural point of view, it refers to all those having a structure in which an unsaturated compound having a hydroxyl group is copolymerized in a branched or regular or irregular manner in the carbon chain.

As for the composition of the copolymer of the component (D), the content of the unsaturated compound having a hydroxyl group is 0.1-5.
It is 0% by weight, preferably 0.5 to 45% by weight, and particularly preferably 1 to 40% by weight. The third copolymerizable component can be selected in the range of 0 to 25% by weight. The weight average molecular weight of the component (D) is preferably selected in the range of 200 to 200,000 from the viewpoint of coatability. If it is out of this range, the coating property is significantly deteriorated, which is not preferable. Within the above range, 500 to
100,000, particularly preferably 800 to 10,
000 range, and includes liquid, semi-solid and solid polymers at room temperature.

The unsaturated compound having a hydroxyl group is 2
-Hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, poly (ethylene glycol) monomethacrylate, etc. may be mentioned. As the third copolymerizable component, unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate and methyl methacrylate; vinyl compounds such as styrene, α-methylstyrene and vinyltoluene; nitrile compounds such as acrylonitrile, 2 -Vinyl pyridine, vinyl pyridine such as 4-vinyl pyridine; methyl vinyl ether,
Vinyl ether such as 2-chloroethyl vinyl ether; acrylamide and the like. These unsaturated compounds may be used alone or as a mixture of two or more. And the copolymer which comprises a component (D) may be individual or may be a mixture of several.

The copolymer of ethylene and an unsaturated compound having a hydroxyl group can be produced by a known method, for example, a high pressure radical polymerization method, using an unsaturated compound having an ethylene and a hydroxyl group as a raw material. When this copolymer is produced by a high-pressure radical polymerization method, ethylene, an unsaturated compound having a hydroxyl group and a radical reaction initiator are added, for example, at a pressure of 1,000 to 3,000 kg / c.
m ² and the temperature in the reaction zone kept at 90 to 280 ° C., the ratio of ethylene: unsaturated compound having a hydroxyl group was adjusted to 1: 0.
According to the method of continuously feeding while maintaining the range of 0001 to 1: 0.02, changing 3 to 20% of the raw material ethylene to the above copolymer, and continuously taking out the copolymer from the reaction zone. Good.

(2) Mixing ratio of essential components: The mixing ratio of each essential component constituting the thermoplastic elastomer composition is as follows. First, as for the component (A) and the component (B), 20 is added to the total amount of the component (A) and the component (B).
˜80 wt%, and the component (B) is 80 to 20 wt% with respect to the total amount of the component (A) and the component (B). If the blending ratio of the component (A) is less than the above range, the coatability of the obtained skin layer will be inferior, and if the blending ratio of the component (A) exceeds the above range, the molded article will have a mold release property. The property becomes poor and neither is preferable. The above component (A)
In the range of the mixing ratio of the component (B) and the component (B), the preferable ratio is 25 to 75% by weight of the component (A) and 75 to the component (B).
25% by weight, and particularly preferable blending ratio is 30 to 70% by weight of component (A) and 70 to 30% by weight of component (B).
Is.

Further, the component (C) and / or the component (D)
Is preferably blended in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the total of the components (A) and (B). When the amount of the component (C) and / or the component (D) is less than the above range, the adhesion between the surface of the skin layer and the coating film becomes insufficient,
If it exceeds the above range, peeling between the core material layer and the skin layer tends to occur, which is not preferable. Among the above blending ratios of the component (C) and / or the component (D), preferred is 0.
05 to 9 parts by weight, and particularly preferably 0.1 to 8 parts by weight. The component (C) and the component (D) can be used in combination, but in the range of 0.01 to 10 parts by weight with respect to the total 100 parts by weight of the component (A) and the component (B) when used in combination. It is good to mix.

(3) Coating Property Improving Component In addition to the above essential components, the thermoplastic elastomer composition forming the skin layer further comprises the following components (E) to (G) in order to improve the coating property. Of these, one kind or two or more kinds can be blended.

Component (E): Component (E) is a copolymer containing ethylene and a carboxyl group (including acid anhydride) -containing unsaturated compound, and optionally a third copolymerizable component,
It functions to improve the adhesion between the surface of the skin layer and the coating film formed on this surface. Examples of the copolymer of ethylene as the component (E) and a carboxyl group (including acid anhydride) -containing unsaturated compound include, for example, ethylene and acrylic acid copolymerized randomly or at certain intervals. This is a polymer that has a branched structure or a structure in which an unsaturated compound containing a carboxyl group (including acid anhydride) is copolymerized in a branched or irregular manner in the carbon chain from a structural viewpoint. Refers to all things that have.

With respect to the composition of the copolymer of component (E), the content of the unsaturated compound containing a carboxyl group (including acid anhydride) is preferably in the range of 0.01 to 50% by weight. Among them, 0.1 to 40% by weight is preferable, and 1 to 30% by weight is particularly preferable. The weight average molecular weight of the copolymer of component (E) is from 200 to 2 from the viewpoint of coatability.
A range of 0,000 is preferred. If the weight average molecular weight is out of the above range, the coating property is significantly deteriorated, which is not preferable. Among them, 500 to 100,000 is preferable, 800 to 10,000 is particularly preferable, and liquid, semi-solid, and solid polymers at room temperature are included.

The unsaturated compound containing a carboxyl group (including acid anhydride) is an unsaturated carboxylic acid having 3 to 8 carbon atoms, specifically acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, maleic acid. Monomethyl ester,
Maleic acid monoethyl ester etc. can be mentioned.

As the third copolymerizable component, methyl acrylate, ethyl acrylate, butyl acrylate,
Unsaturated carboxylic acid esters such as methyl methacrylate; vinyl compounds such as styrene, α-methylstyrene, vinyltoluene; nitrile compounds such as acrylonitrile; vinylpyridines such as 2-vinylpyridine and 4-vinylpyridine; methyl vinyl ether, 2-chloro. Vinyl ether such as ethyl vinyl ether; acrylamide and the like. A plurality of these may be mixed and used.

These copolymers can be used alone or as a mixture of a plurality of them. The copolymer of ethylene and a carboxyl group (including an acid anhydride) -containing unsaturated compound can be prepared by a known method using ethylene and a carboxyl group (including an acid anhydride) -containing unsaturated compound as a raw material, for example, high pressure. It can be produced by a radical polymerization method or the like.

When this copolymer is produced by the high-pressure radical polymerization method, ethylene, a carboxyl group (including acid anhydride) -containing unsaturated compound, and a radical reaction initiator are added, for example, at a pressure of 1,000-. 3,000 kg / cm
^{2. In} the reaction zone kept at a temperature of 90 to 280 ° C., the ratio of ethylene: carboxyl group (including acid anhydride) -containing unsaturated compound is adjusted to the range of 1: 0.0001 to 1: 0.02. Continuously supply while maintaining 3-20% of the raw material ethylene
The above method may be changed to the above copolymer, and the copolymer may be continuously taken out from the reaction zone.

Component (F): The component (F) has the following formula (I):
Is an organotin compound represented by the formula (1), and has the function of improving the adhesion between the surface of the skin layer and the coating film formed on the surface of the skin layer, particularly the urethane coating film.

[0053]

Embedded image

In the formula (I), R ¹ , R ² , R ³ and R
⁴ is a saturated hydrocarbon group having 1 to 12 carbon atoms, which may be the same or different, preferably 3 to 12 carbon atoms.
12 saturated hydrocarbon groups. X ¹ is an oxygen atom, a sulfur atom, maleic acid or the like, preferably an oxygen atom or maleic acid. Y ¹ and Y ² are fatty acids, maleic acid derivatives,
Examples thereof include mercaptan and mercapto acid, which may be the same or different and are preferably fatty acid and maleic acid derivatives. n is an integer of 0 to 30, preferably an integer of 0 to 25, and particularly preferably an integer of 0 to 20.

Specific examples of the organotin compound represented by the formula (I) include monobutyl tin trimethyl malate, monobutyl tin trioctyl malate, dibutyl tin dilaurate, dibutyl tin laurate, methyl malate. , Dibutyl tin dioleyl maleate, dibutyl tin dimethyl maleate, dibutyl
Tin malate, dibutyl tin methoxymethyl malate, dibutyl tin dioctyl malate, dibutyl tin dioctyl thioglycolate, dibutyl tin dilauryl mercaptide, tribenzyl tin octyl malate, tribenzyl trimethyl Malate etc. can be mentioned. These organotin compounds may be used alone or as a mixture of plural kinds.

Component (G): The component (G) is a tertiary amine compound and improves the adhesion between the surface of the skin layer and the coating film formed on the surface of the skin layer, especially the urethane coating film. Fulfill the function of causing. The tertiary amine compound as the component (G) includes a low molecular compound having a tertiary amine structure and a high molecular compound.

(I) Low molecular weight compound having a tertiary amine structure The low molecular weight compound having a tertiary amine structure is one having a molecular weight of about 1,000 or less. In particular,
Triethylamine, dimethylaminopropylamine, diethylaminopropylamine, tetraguanidine, 1,
8-diazabicyclo- (5,4,0) -7-undecene, N, N-bis (2-hydroxyethyl) laurylamine, and tetrakis (M-methyl-2,2,6,6)
-Tetramethyl-4-pyridyl) -1,2,3,4-butanetetracarboxylate and the like.

(Ii) Polymer Compound Having a Tertiary Amine Structure As a polymer compound having a tertiary amine structure (sometimes referred to as “tertiary amino group”),
It has at least one primary amine structure and a molecular weight of about 1,0.
Polymers up to about 00 to 500,000 are included.
Structurally, a tertiary amine structure may be present in the branched or linear molecular chain or at the terminal of the molecular chain,
Refers to all structures having a pendant group having a primary amine structure. The form at room temperature may be liquid, semi-solid or solid.

Specifically, (a) a homopolymer obtained by addition polymerization or condensation polymerization of a tertiary amine structure-containing polymerizable compound (hereinafter sometimes referred to as "tertiary amino group-containing unsaturated compound"). A polymer (homopolymer), (b) a copolymer of a tertiary amino group-containing unsaturated compound and another polymerizable monomer, and (c) a tertiary amine structure at the side chain or molecular chain end Examples thereof include graft modified polymers.

Here, the term "tertiary amine structure-containing polymerizable compound (tertiary amino group-containing unsaturated compound)" means the third
A compound having at least one secondary amine structure (tertiary amino group) and at least one unsaturated group capable of addition polymerization or functional group capable of condensation polymerization. Examples of the tertiary amino group-containing unsaturated compound include vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine, and compounds represented by the following formula (II).

[0061]

Embedded image

In the formula (II), R ¹¹ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrogen atom or a saturated hydrocarbon group having 1 to 2 carbon atoms. X ² is a carbonyl group, an aromatic ring, an aliphatic ring or an alkyl chain having 1 to 12 carbon atoms, preferably a carbonyl group, an aromatic ring or an aliphatic ring, particularly preferably a carbonyl group. R ¹² is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxyl group having an oxygen atom on the X ² group side having 1 to 12 carbon atoms, a sulfur atom or —NR ¹⁵
R ¹⁶ - and is, preferably an alkoxyl group or -NR with oxygen atoms in X ² group side of 1 to 12 carbon atoms ¹⁵ R ¹⁶ -
And particularly preferably an alkoxyl group having an oxygen atom on the X ² group side having 1 to 12 carbon atoms.

R ¹³ and R ¹⁴ are substituents having an alkyl chain having 1 to 12 carbon atoms, a polyalkylene glycol chain having a glycol unit having 1 to 6 carbon atoms, an aliphatic ring and an aromatic ring structure, An alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is particularly preferable. Further, where R ^13, R1 ⁴ may be the same or different. R ¹⁵ is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, preferably a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms, particularly preferably a hydrocarbon group having 1 to 4 carbon atoms. R ¹⁶ is a hydrocarbon group having 2 to 12 carbon atoms,
It is preferably a hydrocarbon group having 2 to 6 carbon atoms, particularly preferably a saturated hydrocarbon group having 2 to 6 carbon atoms.

Examples of preferable unsaturated compounds containing a tertiary amino group include 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl acrylate, and 2
-(Dimethylamino) ethyl methacrylate, 2- (diethylamino) ethyl methacrylate, 2- [di (t-
Butyl) amino] ethyl acrylate, 2- [di (t-
Butyl) amino] ethyl metalylate, 3- (dimethylamino) -propylacrylamide, 3- (dimethylamino) -propylmethacrylamide and the like can be mentioned.

The above third step for obtaining the copolymer (b)
Examples of the monomer copolymerizable with the unsaturated compound containing a primary amino group include α-olefins, vinyl aromatic compounds, unsaturated carboxylic acid compounds, and nitrile compounds when the copolymer is obtained by addition polymerization. , Vinyl ethers, vinyl esters, conjugated dienes, vinyl halides, and acrylamides. Examples of the olefin-based monomer component include α such as ethylene, propylene, and 1-butene.
-Olefins can be mentioned, and among these, ethylene is particularly preferable.

When the copolymer (b) is obtained by condensation polymerization, the monomers include diol compounds, polyol compounds, dicarboxylic acid compounds, polycarboxylic acid (including acid anhydride) compounds, Examples thereof include diamine compounds, diimino compounds, lactam rings, lactones and formaldehydes.

In the case of the copolymer (b), the content of the tertiary amine structure-containing polymerizable compound is 0.01 to 50% by weight, preferably 0.1 to 40% by weight, particularly preferably 0.1. It is 1 to 30% by weight. The solution viscosity of the copolymer (b) is 1 to 100 cps, preferably 1 to 50 cps,
Particularly preferably, it is 1 to 30 cps. Here, the solution viscosity means that the copolymer (b) is dissolved in toluene heated to 80 ° C. to a concentration of 5% by weight, completely dissolved, and then left to cool to room temperature (23 ° C.), This is measured by a B-type viscometer.

When the polymer compound having a tertiary amine structure is the graft-modified polymer of (c), the backbone polymer is an olefin polymer, styrene polymer, acrylic polymer, diene polymer. Examples include coalesced materials, polyamides, polyimides, polyesters, polyurethanes, polyethers and polyketones.

Examples of the olefin polymer include olefin resins such as ethylene resins and propylene resins, olefin elastomers, styrene elastomers, and copolymer resins containing non-conjugated dienes.
Among these, ethylene resin, propylene resin,
It is preferable to use an olefin elastomer and a styrene elastomer. The trunk polymer may be a single kind or a mixture of plural kinds.

The graft modified polymer of the above (c) is prepared by a known method, for example, high pressure radical, in the presence of the above-mentioned tertiary amine structure-containing polymerizable compound and, if necessary, other copolymerizable monomer. It can be produced by a polymerization method, an impregnation graft polymerization method, a kneading graft method or the like.

When the high-pressure radical polymerization method is used, ethylene, a tertiary amine structure-containing polymerizable compound and a radical polymerization initiator are added under a pressure of, for example, 1,000 to 3,000 atm.
In the reaction zone kept at a temperature of 90 to 300 ° C., the ratio of ethylene: tertiary amine structure-containing polymerizable compound was 1: 0.
Supply continuously while maintaining 0001 to 1: 0.1,
It is produced by converting an ethylene copolymer at a conversion rate of 3 to 20% and continuously taking out this copolymer from the reaction zone.

In the case of production by the impregnation graft polymerization method, pellets of an olefinic polymer, a tertiary amino group-containing unsaturated compound and a radical polymerization initiator are suspended in an aqueous solvent to prepare a tertiary amino group. It is produced by impregnating a pellet of an olefinic polymer with a group-containing unsaturated compound and an initiator, then heating the pellet to a decomposition temperature of the initiator, causing a graft reaction in the pellet, and modifying the pellet.

Further, in the case of production by the kneading and grafting method, for example, an olefin resin, a copolymer resin containing a non-conjugated diene, or an elastomer is dry-blended with a tertiary amino group-containing unsaturated compound, Then, it can be produced by melt-kneading in an extruder using an organic peroxide as a reaction initiator and setting the temperature at 80 to 250 ° C.

Other copolymerizable monomer components that can be used in the production of the (c) graft modified polymer include unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, and methyl metallate. Acid esters; vinyl aromatic compounds such as styrene, α-methylstyrene and vinyltoluene; nitrile compounds such as acrylonitrile and methacrylonitrile; vinylpyridines such as 2-vinylpyridine and 4-vinylpyridine; methyl vinyl ether, Examples thereof include vinyl ethers such as 2-chloroethyl vinyl ether; vinyl halides such as vinyl chloride and vinyl bromide; vinyl esters such as vinyl acetate; acrylamide. These may be used alone or as a mixture of plural kinds. Among the tertiary amine compounds of the component (G) mentioned above, it is preferable to use the high molecular compound of (b) rather than the low molecular compound of (a).

The components (E), (F) and (G) are
0.01 to 10 parts by weight of at least one of these three kinds is blended with respect to a total of 100 parts by weight of the component (A), the component (B), and the component (C) and / or the component (D). Good to do. When at least one of these is blended in the thermoplastic elastomer composition within the above range, the adhesion between the surface of the skin layer and the coating film, especially the urethane coating film is enhanced, but if it exceeds this range, the Not just an economy,
The blended components bleed out from the skin layer, and the adhesion strength between the surface of the skin layer and the coating film decreases, which is not preferable. When two or more of the components (E) to (G) are used in combination, 0.01 to 10 parts by weight is preferably added to 100 parts by weight of the total of the components (A) to (D). Good.

(4) Additional compounding material The above-mentioned thermoplastic elastomer composition may be used in accordance with the purpose.
Conventionally known compounding materials for thermoplastic elastomers and various additives for thermoplastic resins can be compounded. Examples of compounding materials and additives include softeners for hydrocarbon rubber, various plasticizers, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, neutralizing agents, lubricants, antifog agents, and antiblocking agents. Examples include agents, slip agents, crosslinking agents, crosslinking aids, colorants, flame retardants, dispersants, antistatic agents, and the like.

Further, within the range that the effects of the present invention are not significantly impaired, various thermoplastic resins such as polyethylene resin, polypropylene resin, crystalline butene-1 resin, various elastomers such as olefinic thermoplastic elastomer, various inorganic fillers and the like. A resin compound material can be compounded. Below, among the compounding materials and additives, a softening agent for hydrocarbon rubber,
The inorganic filler and the thermoplastic resin will be described.

(I) Hydrocarbon Rubber Softener {Component (H)} The hydrocarbon rubber softener functions to adjust the hardness of the thermoplastic elastomer composition and to control the melt fluidity during molding. . As a hydrocarbon-based softening agent for a rubber used as an additional component in the present invention, a mixture in which an aromatic ring, a naphthene ring and a paraffin ring are appropriately combined is known. This component (H) has a weight average molecular weight of 300 to
Those in the range of 2,000, and those in the range of 500 to 1,500 are preferable.

Those in which the number of carbons in the paraffin chain accounts for 50% or more of the total carbons are called paraffinic oils, and those in which the number of naphthene ring carbons is 30 to 45% are called naphthenic oils, and the number of aromatic carbons is Those with more than 30% are classified as aromatic oils. Examples of the paraffin oil include those having a weight average molecular weight of 300 to 2,000, preferably 500 to 1,500. Regarding other physical properties, the kinematic viscosity at a temperature of 40 ° C. is 20 to 800 cSt, preferably 50 to 600 cSt.
St, pour point is 0 to -40 ° C, preferably 0 to -30
Oils having a temperature of 200 ° C. and a flash point (COC) of 200 to 400 ° C., preferably 250 to 350 ° C. are suitably used.
Among the above three kinds of oil, paraffinic oil is preferable from the viewpoint of weather resistance.

The amount of the component (H) added is 0 to 250 parts by weight, preferably 5 to 200 parts by weight, particularly preferably 10 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B).
It is preferable to mix it in an amount of 150 parts by weight. Ingredient (H)
The component (A) may be added to the component (A) in advance before the thermoplastic elastomer composition is prepared, or may be added when the thermoplastic elastomer composition is prepared.

(Ii) Inorganic filler {component (I)} The inorganic filler is the hardness of the thermoplastic elastomer composition,
It functions to adjust the density and gloss of molded products. Examples of the inorganic filler used as an additional component in the present invention include talc, mica, glass fiber, whiskers, carbon fiber, calcium carbonate, glass balloon and the like.

Among these, plate-like inorganic fillers such as talc and mica, and fibrous inorganic fillers such as glass fibers, whiskers and carbon fibers, when the composite molded article is used, shrinkage of the molded article, warpage due to shrinkage, and point of sink mark. Is preferred. Preferred talc has a specific surface area of 37,000 cm ² / g or more, preferably 40,000 cm ² / g or more, a length of substantially 15 μm or less, preferably 10 μm or less, and an average particle size of 1.0 to 3. 0 μm, preferably 0.8 to 2.5 μm
m and an average aspect ratio of 5 or more, preferably 6 or more.

Here, the term "substantially" the length of talc means that most of the talc particles are in this range.
The average particle size is a value measured by using a laser light scattering type particle size distribution meter. As such a measuring device, for example, LA-500 manufactured by Horiba Ltd. has excellent measurement accuracy. desirable. Further, the diameter, length, aspect ratio and the like are values measured with a microscope or the like.

The talc having the above-mentioned characteristics is obtained by, for example, crushing talc raw stones with an impact type crusher or a micro type crusher, further finely crushing with a micron mill or jet type crusher, and then classifying with a cyclone or micron separator. It can be adjusted and manufactured. The amount of component (I) added is the same as that of component (A)
0 to 20 per 100 parts by weight of the total amount of the component (B) and
The amount is 0 parts by weight, preferably 5 to 150 parts by weight, and particularly preferably 10 to 150 parts by weight.

(Iii) Thermoplastic resin other than component (B) {component (J)} The thermoplastic resin is a thermoplastic resin other than component (B) for the purpose of adjusting the rigidity of the thermoplastic elastomer composition. It can be blended. The thermoplastic resin other than the component (B) has the same meaning as that already described for the thermoplastic resin forming the core layer. This component (J) may be a single kind or a mixture of plural kinds.

The content of the component (J) is generally 1 to 30 with respect to 100 parts by weight of the total amount of the components (A) and (B).
It is preferable to add the compound in an amount of 0 part by weight, preferably 20 to 250 parts by weight. Ingredient (H) -Ingredient (J)
Can be used alone or as a mixture of plural kinds. The mixing timing of the above components (H) to (J) is not particularly limited, and a method may be used in which predetermined amounts of each of the components (A) to (C) are weighed, and these are mixed and kneaded, or the components ( A method of blending and kneading with A) or the component (B) may be used.

[3] Composite Plastic Molded Article A composite plastic molded article (or “composite molded article”) according to the present invention comprises the above [1] thermoplastic resin and the above [2] thermoplastic elastomer composition as raw materials. Manufactured as.
The method for producing the composite molded article is not particularly limited, and it is a conventionally known method for molding a thermoplastic resin, such as T-die laminate molding method, co-extrusion molding method, blow molding method, injection molding method (insert injection molding method). , Two-color injection molding method, core back injection molding method, sandwich injection molding method, injection press molding method, gas injection molding method, etc.). Among them, the injection molding method is preferable.

Among the above-mentioned molding methods, the sandwich injection molding method means that a thermoplastic elastomer composition for forming a skin layer is first injected from a gate, and a thermoplastic resin for forming a core material layer is injected after or while the injection is completed. Is injected at the same time, and the thermoplastic resin for forming the core material layer is made to flow over almost the entire region of the molded product. In addition, the insert injection molding method means that a core layer made of a thermoplastic resin is molded in advance by an injection molding method, the core layer is inserted into a mold cavity for manufacturing a final product, and then the core layer surface and metal It is a molding method of forming a skin layer by injecting a thermoplastic elastomer composition into a void formed by the surface of a mold cavity.

Furthermore, the two-color injection molding method is a method in which two or more injection molding machines are used to first mold a core material layer with a thermoplastic resin, and then the mold is rotated or moved to form a mold. The cavity is exchanged, a void is formed between the surface of the core material layer and the surface of the mold cavity, and the thermoplastic elastomer composition is injected into the void to form the skin layer.

Furthermore, the core back injection molding method is
Using one injection molding machine and one die, first inject the thermoplastic resin with the die cavity reduced to form the core layer, and then expand the cavity volume of the die. The molding method comprises forming a void between the surface of the core material layer and the surface of the mold cavity, and injecting the thermoplastic elastomer composition into the void to form the skin layer.

The conditions for manufacturing the core material layer of the composite molded product by the injection molding method depend on the kind of the thermoplastic resin, the size of the core material layer, the structure, etc., but the molding temperature is 100 to 3
00 ° C., preferably 150-280 ° C., injection pressure 50
~ 1,000 kg / cm ² , preferably 100-800
It is selected in the range of kg / cm ² .

The conditions for forming the skin layer on the surface of the core layer depend on the kind of the thermoplastic elastomer composition, the thickness of the skin layer, the size of the skin layer, the structure, etc., but the molding temperature is It is important to select in the range of 150 to 260 ° C, preferably 160 to 250 ° C. If the upper limit is exceeded, abnormal appearance of the composite molded article is likely to occur, and if the temperature is lower than the lower limit, the heat fusion property between the core layer and the skin layer is deteriorated, which is not preferable. The injection pressure is 50 to 1,000 kg.
/ Cm ² , preferably 100 to 800 kg / cm ² .

The skin layer of the composite molded article has an average thickness of 0.5 although it depends on the application, size, structure, etc. of the composite molded article.
It is important that the thickness is in the range of up to 3 mm. If it exceeds the above range, the rigidity of the molded product is poor, and if it is less than the above range, the heat fusion property between the core material layer and the skin layer is poor and the soft touch is obtained. It is not preferable because the property is not improved.

[4] Coating film The composite plastic molded article according to the present invention has a coating film formed on the surface of the skin layer. The coating film has a function of improving the stickiness of the surface of the molded product, the easiness of getting dust, the easiness of being scratched, etc., and at the same time, improving the luster, color tone, and aesthetics (visuality and designability).

The paint used to form the coating film may be any paint generally available on the market, and is cured using an isocyanate compound such as an acrylic / urethane-based paint or a polyester / urethane-based paint. Examples of the melamine-based paint that causes a curing reaction include urethane-based paints, acrylic-melamine-based paints, polyester-melamine-based paints, and other N-alkyl group-containing compounds that react. Among these paints,
From the viewpoints of adhesion to the surface of the skin layer, flexibility of the coating film, soft touch property, susceptibility to cracks, etc., urethane-based paints are preferable.

Among urethane-based paints, chlorinated urethane polyols, chlorinated polyester acrylic polyols,
Chlorinated polyols such as chlorinated acrylic polyols; urethane polyols modified with chlorinated polypropylene, polyester acrylic polyols modified in the same manner, chlorinated polypropylene modified polyols such as acrylic polyols modified in the same manner; maleated urethane polyols, Maleated polyester acrylic polyol, maleated acrylic polyol, and other maleated polyols; chlorinated polypropylene, chlorinated polyethylene, and other chlorinated polyolefins; maleated polypropylene, maleated polyethylene, and other maleated polyolefins; styrene / conjugated diene blocks A coating material containing a resin such as a hydrogenated product of a copolymer or a maleated product thereof is preferable. The hydrogenated product of the styrene / conjugated diene block copolymer or its maleated product can improve the adhesion to the skin layer.

The coating film can be formed on the surface of the skin layer by a well-known coating method, of which the spray method is preferable. The thickness of the coating film formed on the surface of the skin layer depends on the use, size, structure, etc. of the composite molded article, but is generally 1 to
A range of 200 μm can be selected.

When a coating film is formed on the surface of the skin layer, the coating material may be directly applied to the surface of the skin layer without applying a primer or pretreatment such as plasma treatment. it can. This is because the skin layer is made of a specific thermoplastic elastomer composition, so that the adhesive force between the surface of the skin layer and the coating film is improved. Prior to forming a coating film on the surface of the skin layer, alcohol such as isopropyl alcohol, an alkaline aqueous solution, or an acidic aqueous solution, water, air, or nitrogen gas is used for the purpose of removing dirt such as dust or machine oil. The surface of the skin layer may be washed.

[5] Uses of Composite Plastic Molded Article The composite plastic molded article according to the present invention can be used as various industrial parts. Specifically, vehicle interior parts such as instrument panels, center panels, center console boxes, glow boxes, door trims, pillars, armrests, assist grips, handles, airbag covers, automotive exterior parts such as bumpers, malls, protectors, etc., It can be used for housings of vacuum cleaners, various key tops of OA equipment, various parts, home electric appliances such as housings, various cover parts, and the like.

[0100]

EXAMPLES The present invention will be described in more detail with reference to the following examples.
The present invention is not limited to the following description example. In the examples described below, the properties of the raw material thermoplastic resin, the thermoplastic elastomer composition, the appearance of the molded article, the paintability of the paint, and the like were evaluated by the methods described below.

(1) JIS-A hardness Using an in-line screw type injection molding machine (small injection molding machine manufactured by Toshiba Machine Co., Ltd .; IS90B), the cylinder temperature is 210 ° C., the mold temperature is 40 ° C., and the injection pressure is 500.
A sheet having a size of 120 mm × 80 mm × 2 mm was formed under the condition of kg / cm ² . Using this sheet, JIS
JIS-A hardness was measured according to -K6301. (2) Flexural modulus From the sheet molded by the method described in (1) above, JIS
A test piece according to K7203 was prepared by a punching method. The flexural modulus of the obtained test piece was measured according to JIS-K7203.

(3) Appearance of molded product Two-color injection molding machine {manufactured by Takahashi Seiki Co., Ltd .; KS-2C
-680} or a sandwich injection molding machine {manufactured by Nissei Plastic Co., Ltd .; FS360S100ASED},
Use the raw materials listed below to increase the cylinder temperature to 220
A core material layer having a temperature of 300 mm × 300 mm × 2 mm was formed, and then a skin layer having a thickness of 2 mm was formed on the surface of the core material layer. However, in Comparative Example 6, the molding was carried out at a cylinder temperature of 280 ° C. When a composite molded product is manufactured according to the procedure described above, if there is no mold release defect or short shot, and there is no significant external appearance defect (delamination, bleed-out, etc.), the molded product appearance is "good". Judgment, "defective" when a defective phenomenon occurs
It was determined.

(4) Coatability The surface of the composite molded article obtained by the method described in (3) above was lightly wiped with absorbent cotton impregnated with isopropyl alcohol for a few times, and then an air spray gun was used. After applying a commercially available two-component urethane-based paint so that the thickness of the coating film will be about 30 μm and baking and drying it, 48 at room temperature.
After leaving for a time, a cross-cut adhesion test was performed. The peel peel strength test was carried out by the same procedure as above, with a coating film having a thickness of about 100 μm being formed on the surface of the composite molded article.

(Cross-cut Adhesion Test Method) A cross-cut was made by drawing 11 parallel and 11 horizontal and vertical parallel lines with a single-edged razor on the surface of the skin layer of a composite molded article having a coating film with a thickness of about 30 μm. I made 100 pieces. Place the cellophane adhesive tape (JIS-Z1522) on the part where this grid is formed and press it to adhere it, and maintain it so that the surface of the coating film and the adhesive surface of the adhesive tape form an angle of about 30 degrees. On the other hand, it was peeled off at once, and the number of crosses where the coating film remained on the surface of the skin layer in the part surrounded by the crosses was counted.

(Peel Peel Strength Test Method) A 1 cm wide straight line cut was made with a single-edged razor on the surface of the composite molded article having a coating film having a thickness of about 100 μm, and the coating film was peeled off from the surface of the skin layer. , The peeled coating layer portion and the peeled skin layer portion are sandwiched between chucks of opposing tensile testers so that a straight line is formed between them (inverted by 180 °). Was pulled at a speed of 50 mm / min, and the load at which the coating film peeled off was read.

[1] Thermoplastic Resin for Core Material Layer In the examples and comparative examples, details of the types and characteristics of the thermoplastic resin forming the core material layer are as follows. PP: "Mitsubishi Polypro BC03C" manufactured by Mitsubishi Chemical Corporation
And the flexural modulus according to JIS-K7203 is 1,500.
Of MPa. PPC-1: "Mitsubishi Polypro BC03C" and Talc (MT-7 manufactured by Fuji Talc Co., Ltd.) in a weight ratio of 7: 3.
The mixture was mixed at a ratio of, and kneaded by a twin-screw extruder and pelletized. The flexural modulus according to JIS-K7203 was 3,80.
0 MPa. PPC-2: "Mitsubishi Polypro BC03C", EPM
The three components (EP07P manufactured by Nippon Synthetic Rubber Co., Ltd.) and talc (same as above) were mixed in a weight ratio of 7: 1: 2,
Kneaded and pelletized by a twin-screw extruder, JIS-K
Bending elastic modulus according to 7203 of 2,600 MPa.

[2] Skin Layer-Forming Thermoplastic Elastomer Composition In Examples and Comparative Examples, the types and characteristics of each component of the skin layer forming thermoplastic elastomer composition are described in Table-1 to Table- This is as shown in 10.

[0108]

[Table 1]

[0109]

[Table 2]

[0110]

[Table 3]

[0111]

[Table 4]

[0112]

[Table 5]

[0113]

[Table 6]

[0114]

[Table 7]

[0115]

[Table 8]

[0116]

[Table 9]

[0117]

[Table 10]

[Examples 1 to 26, Comparative Examples 1 to 6] A thermoplastic elastomer composition for forming a skin layer was prepared as follows. First, the raw materials shown in Table-1 to Table-10 are
~ Weighed to the blending composition (parts by weight) shown in Table-14. 0.1 parts by weight of a phenolic antioxidant (trade name "Irganox 1010") was added to 100 parts by weight of the total composition of the formulations shown in Tables 11 to 14 to prepare a cylinder having a cylinder diameter of 45 mm. Using a screw extruder (L / D = 33), the mixture was melt-kneaded under the condition of a preset temperature of 200 ° C. to obtain a thermoplastic elastomer composition pellet. With respect to the obtained pellets, various physical properties, appearances of molded articles and the like were evaluated by the methods described above.

In Example 18, the blending composition (parts by weight) shown in Table 12 was weighed and kneaded in advance with a Banbury mixer at a temperature of 170 ° C. for 6 minutes, then formed into a sheet, and this sheet was prepared. It was cut into pellets. Then, the pellets were added in a total amount of 10
0.1 part by weight of a phenolic antioxidant (trade name "Irganox 1010") and 0,25 parts by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane as a peroxide -3 (Product name "Kaya Hexa A
D ”) 0.3 part by weight and divinylbenzene 0.2 part by weight as a crosslinking aid are added, and the temperature is set to 220 ° C. by a twin-screw extruder (L / D = 33) having a cylinder diameter of 45 mm. Was heat-treated (crosslinking treatment) to obtain pellets of the partially crosslinked thermoplastic elastomer composition. With respect to the obtained pellets, various physical properties, appearances of molded articles and the like were evaluated by the methods described above. The evaluation results are shown in Table-11 to Table-14.

[0120]

[Table 11]

[0121]

[Table 12]

[0122]

[Table 13]

[0123]

[Table 14]

From Table-11 to Table-14, the following is clarified. (1) The composite molded article according to claim 1 of the present invention is excellent in both the appearance of the molded article and the coatability (determined by a cross-cut adhesion test and a peel peel strength test). (2) On the other hand, none of the composite molded articles of Comparative Examples are excellent in appearance and coatability of the molded article, and either one is inferior.

[0125]

As described above, the present invention has the following advantageous effects, and its industrial utility value is extremely large. 1. The composite plastic molded product according to the present invention has the skin layer formed on the surface of the core material layer, and thus has excellent soft touch properties. 2. In the composite plastic molded product according to the present invention, since the skin layer is composed of the thermoplastic elastomer composition having the specific composition, the adhesive property between the core layer and the skin layer is excellent. 3. Since the composite plastic molded article according to the present invention has a coating film formed on the surface of the skin layer, there is no stickiness,
Therefore, dust is unlikely to adhere to the surface of the molded product. 4. The composite plastic molded article according to the present invention, the skin layer is composed of a thermoplastic elastomer composition of a specific composition, so that the surface of the skin layer is not subjected to any special surface treatment such as primer treatment or plasma treatment. The coating film can be formed directly on the surface of the layer. 5. The composite plastic molded article according to the present invention, the skin layer is composed of a thermoplastic elastomer composition of a specific composition, excellent adhesion between the surface of the skin layer and the coating film,
It is difficult to peel off, and the appearance of molded products is excellent.

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Claims (5)

[Claims] 1. A core material layer made of a thermoplastic resin, and 20 to 80 of the following component (A) on the outer peripheral portion or surface of the core material layer.
By weight, 80 to 20 parts by weight of the following component (B) and 0.01 to 100 parts by weight of the following components (C) and / or component (D) are added to 100 parts by weight of the total amount of the components (A) and (B). A composite plastic molded article, characterized in that a skin layer made of a thermoplastic elastomer composition mixed in 10 parts by weight is formed, and a coating film is formed on the surface of the skin layer. Component (A): Hydrogenated product of elastomeric styrene / conjugated diene block copolymer and / or olefin copolymer rubber Component (B): Olefin resin Component (C): Diene polymer having terminal hydroxyl group or its Hydrogenated Component (D): Copolymer of Ethylene and Unsaturated Compound Having Hydroxyl Group 2. A thermoplastic elastomer composition further containing at least one of the following components (E) to (G) in the following proportion with respect to 100 parts by weight of the thermoplastic elastomer composition. Characterized by being
The composite plastic molded product according to claim 1 or 2. Component (E): Copolymer of ethylene and carboxyl group (including acid anhydride) -containing unsaturated compound: 0.01 to 10 parts by weight Component (F): Organotin compound: 0.01 to 10 parts by weight Component (G): tertiary amine compound ... 0.01 to 10 parts by weight 3. A thermoplastic elastomer composition according to JIS
-The bending elastic modulus according to K7203 is less than 500 MPa,
And, JIS-A hardness according to JIS-K6301 is 50.
The composite plastic molded article according to any one of claims 1 to 3, characterized in that 4. The composite plastic molded article according to any one of claims 1 to 3, wherein the coating film formed on the surface of the skin layer is a urethane-based paint. . 5. A core layer made of a thermoplastic resin, and 20 to 80 of the following component (A) on the outer peripheral portion or surface of the core layer.
80 parts by weight of the following component (B) and 0.01 to 20 parts by weight of the following component (C) and / or component (D) per 100 parts by weight of the total amount of the components (A) and (B). An automotive part comprising a skin layer formed of a thermoplastic elastomer composition containing 10 parts by weight, and a urethane coating film formed on the surface of the skin layer. Component (A): Hydrogenated product of elastomeric styrene / conjugated diene block copolymer and / or olefin copolymer rubber Component (B): Olefin resin Component (C): Diene polymer having terminal hydroxyl group or its Hydrogenated Component (D): Copolymer of Ethylene and Unsaturated Compound Having Hydroxyl Group