JP2000095920A - Molding for automobile and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding using a thermoplastic resin elastomer compsn. which lessen flexural returnability and has low density and excellent in flexibility and processability, and its manufacturing method. SOLUTION: A thermoplastic elastomer compsn. comprises 100 pts.wt. block copolymer comprising two polymer blocks A mainly produced from a vinyl aromatic compd. and a polymer block B mainly produced from a conjugated diene compd. and/or a hydrogenated block copolymer obtd. by hydrogenating the block copolymer, 15-300 pts.wt. non-aromatic rubber softener, 10-150 pts.wt. vinyl aromatic resin, and 1-100 pts.wt. a copolymer of ethylene and a compd. represented by the formula: CH2=C(R1)-COOR2 (R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom of an alkyl group) and a resin contg. at least 30 wt.% copolymer, and it is layered with a protective film layer 7 via a middle adhesive layer 6 and extruded and molded in a body with three molding machines and a metal dice.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to various moldings such as wind moldings, roof moldings, protector moldings and weatherstrip moldings which are mounted on automobiles. The present invention relates to a molding for automobiles in which a portion exposed to the surface is tough and integrally forms a protective layer having excellent scratch resistance, weather resistance and chemical resistance, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a molding material of this kind, a polyvinyl chloride resin having a low bending restoring force and good moldability has been widely and generally used. However, instead of polyvinyl chloride resin, olefin resins, styrene resins, etc. have come to be used instead of polyvinyl chloride resins in terms of weight reduction and environmental measures, but this type of molding requires a long molded product after extrusion molding. Since it is bent and mounted on an automobile, ordinary olefin-based resins and styrene-based resins have a very large bending restoring force, and it is very difficult to bend a molded product and mount it on an automobile. Further, the olefin resin and the styrene resin have problems that the skin layer is very easily damaged and a clean luster cannot be obtained. For example, Utility Model Publication No. 5-32152 and Utility Model Publication No. 7-26.
Use of a hard olefin copolymer for the skin layer of the molding as in No. 217 to improve the scratch resistance, weather resistance, and chemical resistance, but the base has a thermoplastic elastomer composition with low bending restoring force. When the product was used, there was a problem that the product did not firmly fuse with the hard olefin-based copolymer of the skin layer and was easily peeled off.

[0003]

According to the present invention, a thermoplastic elastomer composition having a low bending restoring force and a low specific gravity is used for a base of a molding body, and a protective coating layer exposed on the surface has scratch resistance, weather resistance, and An intermediate adhesive layer of a polar group-containing olefin resin serving as an adhesive layer is provided between the olefin resin composition having excellent chemical properties and a hardness of 90 degrees or more (JIS K7215 A hardness) and the protective coating layer. An object of the present invention is to provide a molding for an automobile in which the whole is strongly and integrally fused by extrusion molding, and a method for manufacturing the same.

[0004]

According to the present invention, as a result of study, styrene, conjugated diene block and / or hydrogenated block copolymer are added to vinyl aromatic resin and softener for non-aromatic rubber. By melting and kneading together, the base of the molding body of the thermoplastic elastomer composition having a low bending restoring force and a low specific gravity is obtained. Further, on the base part of the molding body, on the molding head made of the thermoplastic elastomer composition having a low bending restoring force and a low specific gravity, an intermediate adhesive layer of a polar group-containing olefin resin is provided on the upper part, As a protective layer on top of the adhesive layer, a hardness of 90 degrees or more with excellent scratch resistance, weather resistance, and chemical resistance (JIS K7
By laminating a protective coating layer made of an olefin resin composition having a hardness of 215 A), an automobile molding excellent in scratch resistance, weather resistance, chemical resistance, and surface appearance is provided. Further, a thermoplastic elastomer composition having a small bending restoring force and specific gravity of a molding body, an intermediate adhesive layer of a polar group-containing olefin resin, and a hardness of 90 degrees or more excellent in scratch resistance, weather resistance, and chemical resistance (JIS K7215)
(A hardness) An automotive molding characterized in that the respective materials for the protective coating layer of the olefin-based resin composition and the protective coating layer are separately molded by an extruder and integrally fused and laminated inside one mold die. It is a manufacturing method of.

[0005]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail with reference to the drawings, taking wind molding as an example. FIG.
A wind molding body (1) is mounted between a vehicle body panel (9) of a vehicle (19) and a window glass (8). The molding main body (1) has a molding head (2), a lower insertion leg (3), a glass insertion groove (4), and a glass support piece (5) formed integrally at a lower end thereof. Reference numeral (10) indicates an adhesive with the window glass (8). FIG. 2 is a schematic view of a method of bending and attaching a molded product. FIG. 3 is a part of a cross-sectional view taken along the line AA of FIG. 1, and FIG. 4 is a view showing only the wind molding. FIG. 5 is a drawing showing the protective coating layer (7), the intermediate adhesive layer (6), and the base of the molding body (1) on the surface of the wind molding. The molding body (1) of the wind molding shown in FIG. 4 is composed of (a) a vinyl aromatic compound at the base of the molding body (1) shown in FIG. A block copolymer consisting of at least two polymer blocks A mainly made of at least one polymer block B mainly made of a conjugated diene compound, and / or a hydrogenated block copolymer obtained by hydrogenating the same. 100 parts by weight, (b) 15 to 300 parts by weight of a softener for non-aromatic rubber, (c) 10 to 150 parts by weight of vinyl aromatic resin,

[0006]

Embedded image CH ₂ ＣC (R ₁ ) —COOR ₂ (d) ethylene and a general formula (wherein R ₁ represents hydrogen or a methyl group, and R ₂ represents hydrogen or an alkyl group having 1 to 10 carbon atoms) ), And 1-100 parts by weight of a resin containing at least 30% by weight of the copolymer. As for the bending restoring force of the thermoplastic elastomer, the recovery time is preferably 15 seconds or more in a test method described later. Further, when oil resistance and heat resistance are required, it is preferable to carry out a crosslinking treatment. As the intermediate adhesive layer of the polar group-containing olefin resin of FIG. 5,

[0007]

CH ₂ ＣC (R ₁ ) —COOR ₂ (d) Ethylene and a general formula (wherein R ₁ represents hydrogen or a methyl group, and R ₂ represents hydrogen or an alkyl group having 1 to 10 carbon atoms). 100% by weight of a resin containing at least 30% by weight of the copolymer, and (e) a polyethylene polymer or an ethylene-based copolymer polymerized with a single-site catalyst. 30 to 300 parts by weight. The hardness of 90 degrees or more in FIG. 5 (JIS K72)
An olefin resin composition having a hardness of 15 A or more (JI hardness: 90 A or more) having excellent scratch resistance, weather resistance and chemical resistance.
(SK7215A hardness). Preferred are ethylene / acrylate copolymers, metal salts thereof, and compositions thereof. For example, as an ethylene / acrylate copolymer, Nuclel N0903H manufactured by DuPont-Mitsui Co., Ltd.
C, and a metal salt thereof is Himilan 1554 (zinc-based) manufactured by DuPont-Mitsui. As shown in FIG. 5, the method of manufacturing the molding body (1) will be described.
The thermoplastic elastomer composition is injected into a first extruder (11) for molding the base of the molding body. Next, a polar group-containing olefin-based resin for forming an intermediate adhesive layer (6) for molding is injected into the second extruder (12). Next, the third extruder (1)
In 3), an olefin resin composition having a hardness of 90 degrees or more (JIS K7215 A hardness) for forming a protective coating layer (7) for molding is injected. Then, the three extrusion molding machines are operated at the same time, and each of the melted resins passes through the flow pipes (18) (18)... To form the molding body (1) inside one mold die (14). After the base is formed, an intermediate adhesive layer (6) is formed on the surface of the base, and a protective coating layer (7) is formed on the surface of the intermediate adhesive layer (6) in that order to integrally form the base. Thereafter, the formed molding body (1) advances and passes through the cooling water tank (15), and is cut into a predetermined size by a fixed-size cutting machine (17) via a take-off machine (16). Next, as an example of the extrusion molding, the thermoplastic elastomer of the molding base is charged into the first extrusion molding machine (11) and heated to 160 to 240 ° C., and the second extrusion molding machine (12) is heated to an intermediate temperature. The adhesive resin is charged and heated to 160 to 240 ° C, and the third extruder (13) is charged with a hard olefin resin for forming the protective layer and heated to 160 to 240 ° C, and simultaneously extrudes three units. By operating the molding machine, one die (1
In 4), they are integrally formed. Each component in the composition of the present invention will be described. Component (a): Block copolymer The block copolymer is mainly made of a vinyl aromatic compound (hereinafter sometimes referred to as a vinyl aromatic compound as a main component).
And a block copolymer comprising at least one polymer block B mainly made of a conjugated diene compound (hereinafter sometimes referred to mainly as a conjugated diene compound) or obtained by hydrogenating the block copolymer. Yes, for example, ABA, BABA, ABBABA
Or a conjugated diene compound block copolymer having such a structure, or obtained by hydrogenating the same. This block copolymer contains 5 to 60% by weight, preferably 20 to 5% by weight of a vinyl aromatic compound as a whole.
0% by weight. The aggregate block A mainly composed of a vinyl aromatic compound accounts for 50% by weight or more, preferably 70% by weight.
Homopolymers or polymer blocks made from the above vinyl aromatic compounds and optional components, for example, conjugated diene compounds. The polymer block B mainly composed of a conjugated diene compound is a homopolymer or a polymer block made of 50% by weight or more, preferably 70% by weight or more of a conjugated diene compound and an optional component such as a vinyl aromatic compound. is there. Further, in the polymer block A mainly composed of the vinyl aromatic compound or the polymer block B mainly composed of the conjugated diene compound, the distribution of units derived from the conjugated diene compound or the vinyl aromatic compound in the molecular chain is random. ,
It may be tapered (the monomer component increases or decreases along the molecular chain), partially block-shaped, or any combination thereof. When there are two or more polymer A mainly composed of vinyl aromatic compound or polymer block B mainly composed of conjugated diene compound, each polymer block has a different structure even if each has the same structure. There may be. As the vinyl aromatic compound constituting the block copolymer, one or more kinds can be selected from, for example, styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene and the like, and among them, styrene is preferable. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3
One or two of dimethyl-1,3-butadiene and the like;
At least one species is selected, and among them, butadiene, isoprene and a combination thereof are preferred. In the polymer block B mainly composed of a conjugated diene compound, its microstructure can be arbitrarily selected. For example, in a polybutadiene block, the 1,2-microstructure has 20 to 50% by weight, preferably 25 to 45% by weight. is there. In the polyisoprene block, 70 to 100% by weight of isoprene is 1,4.
Preference is given to those having a microstructure and at least 90% of the aliphatic double bonds derived from isoprene being hydrogenated. More preferably, hydrogenation obtained by hydrogenating a block copolymer consisting of at least two polymer blocks A mainly made of a vinyl aromatic compound and at least one polymer block B mainly made of a conjugated diene compound is used. A block copolymer, wherein polymer block B comprises a polyisoprene block, 70-100% by weight of isoprene has a 1,4-microstructure,
Further, it is a hydrogenated block copolymer in which at least 90% of aliphatic double bonds derived from isoprene are hydrogenated. The above is, for example, Septon 40 from Kuraray
It is commercially available under the trade name of 77. The number average molecular weight of the block copolymer is preferably from 5,000 to 1,000,000.
00, more preferably 10,000-500,000,
More preferably, it is in the range of 100,000 to 300,000, and the molecular weight distribution is 10 or less. The molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof. Component (b): As the vinyl aromatic resin, polystyrene, rubber-modified polystyrene (high-impact polystyrene),
Styrene-α-methylstyrene copolymer, (styrene-
Examples thereof include a paramethylstyrene copolymer, a styrene-acrylic rubber-acrylonitrile copolymer, and a styrene-maleic anhydride copolymer, and one or more of these can be selected. The rubber component of the rubber-modified polystyrene contains 2 to 15%. Among them, polystyrene is preferable. Also, the melt flow rate is 0.5 to 6
It is preferably 0 g / 10 min. Further, those having a weight average molecular weight of 10 ³ to 10 ⁷ are preferred. When the component (b) is used, it is 10 parts by weight or more, preferably 30 parts by weight or more and 150 parts by weight or less, 100 parts by weight or less, preferably 80 parts by weight or less based on 100 parts by weight of the component (a). Use in the amount of 1
If the amount exceeds 50 parts by weight, the hardness of the obtained elastomer composition becomes too high, the flexibility is lost, and a rubber-like product cannot be obtained. Also, when the amount is less than 10 parts by weight, the elastomer composition has a problem that the bending restoring force becomes large and a good feel cannot be obtained. Component (c): Non-aromatic Rubber Softener The non-aromatic rubber softener is a non-aromatic mineral oil or a liquid or low molecular weight synthetic softener. A mineral oil softener generally used for rubber is a mixture of an aromatic ring, a naphthene ring and a paraffin chain in which the number of carbon atoms is 50% or more of the total number of carbon atoms. System, naphthene ring carbon number is 30 ~
Those with 40% are called naphthenics, and those with 30% or more of aromatic carbons are called aromatics. The mineral oil-based rubber softener used as the component (c) of the present invention includes:
Paraffinic and naphthenic in the above category,
Aromatic softeners are not preferred in terms of dispersibility with component (a). In particular, as the component (c) of the present invention, a paraffin-based component is preferable, and a paraffin-based component having a small aromatic ring component is particularly suitable. The properties of these non-aromatic rubber softeners are such that the dynamic viscosity at 37.8 ° C. is 20 to 500 cst, and the pour point is −10 to −15.
° C and a flash point (COC) of 170-300 ° C are preferred. The amount of the component (c) is 15 parts by weight or more, preferably 30 parts by weight or more, and 300 parts by weight or less, preferably 150 parts by weight or less based on 100 parts by weight of the component (a). If the amount exceeds 300 parts by weight, the softener tends to bleed out, which may give tackiness to the final product, and also deteriorates the mechanical properties. If the amount is less than 15 parts by weight, the moldability becomes difficult, and the flexibility of the obtained composition is lost. Component (d): ethylene-acrylic copolymer

[0008]

Embedded image CH ₂ ＣC (R ₁ ) —COOR ₂ Ethylene and a general formula (wherein R ₁ represents hydrogen or a methyl group, and R ₂ represents hydrogen or an alkyl group having 1 to 10 carbon atoms). It is a resin containing at least 30% by weight of a copolymer with the represented monomer. Here, the monomer represented by (wherein, R ₁ represents hydrogen or a methyl group, and R ₂ represents hydrogen or an alkyl group having 1 to 10 carbon atoms) includes methyl methacrylate and methyl acrylate , Ethyl methacrylate, methacrylic acid, acrylic acid and the like. Of these, methacrylic acid is preferred. Two or more types of R ₁ and / or two or more types of R ₂ may be combined. In the copolymer with ethylene, the above monomer is contained in an amount of 3 to 20% by weight, particularly 4 to 1% by weight.
It preferably accounts for 5% by weight. Preferred is an ethylene-methacrylic acid copolymer having a methacrylic acid content of 3 to 20% by weight, particularly 4 to 15% by weight. If the amount of the monomer is less than 3% by weight, there is a problem that the adhesive strength of the obtained composition to the intermediate adhesive layer becomes insufficient, and if it exceeds 20% by weight, there is a problem that the bending restoring force becomes large. is there. The copolymer preferably has a melt flow rate of 0.5 to 15 g / 10 min (measured at 190 ° C. under a load of 2160 g according to JIS K 6760). The resin layer contains at least 30% by weight, preferably 50 to 100% by weight, particularly 70% by weight of the above-mentioned ethylene-acrylic copolymer.
-100% by weight. Here, the optional second resin component includes an ethylene-vinyl acetate copolymer and an ethylene-α-olefin copolymer. A mixture of three or more resins can also be used. When used for the surface layer, it is an ionic copolymer having ionic cross-linking, specifically, a copolymer with ethylene and an unsaturated organic acid such as acrylic acid or methacrylic acid, Is preferably completely or partially neutralized to form a salt. The cation of the acid is usually an alkali metal, zinc or the like. Component (e): polyethylene-based polymer As the polyethylene or ethylene-based olefin-based polymer, high-density polyethylene (low-pressure polyethylene), low-density polyethylene (high-pressure polyethylene), linear low-density polyethylene (ethylene and a small amount) Is preferably
1 to 10 mol% of a copolymer with an α-olefin such as butene-1, hexene-1 and octene-1); Particularly preferred is an ethylene octene copolymer produced using a metallocene catalyst (single-site catalyst) having a density of 0.90 g / cm ³ or less. The thermoplastic elastomer composition can be heat-treated in the presence of an organic peroxide and a crosslinking aid. The organic peroxides and crosslinking aids used are as follows. Component (f): Organic peroxide Examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, and 2,5.
-Dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (ter
t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (Tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-
Chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide, and the like, These may be used alone or in combination of two or more. Among them, 2,5-dimethyl-2,2 is preferred in terms of odor, coloring, and scorch stability.
5-di- (tert-butylperoxy) hexane,
2,5-Dimethyl-2,5-di (tret-butylperoxy) hexyne-3 is most preferred. The amount of component (f) is 0.1 to 3 parts by weight based on 100 parts by weight of component (a). Ingredient (g): Crosslinking Aid As crosslinking aids, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate And a polyfunctional vinyl monomer such as vinyl butyrate or vinyl stearate as a crosslinking aid. With such a compound, a uniform and efficient crosslinking reaction can be expected. Component (g) is added in an amount of 0.1 or more with respect to 100 parts by weight of component (a).
It is at most 10 parts by weight, preferably at most 5 parts by weight. The composition of the present invention has various antiblocking agents, sealant improvers, heat stabilizers, antioxidants, antioxidants, ultraviolet absorbers, lubricants, coloring agents, etc., depending on the application, in addition to the above components. It is also possible.

[0009]

EXPERIMENTAL EXAMPLE Next, a method for producing the above-described composition of the present invention will be described. The production method is not particularly limited, and the above-described composition of the present invention can be produced by melt-kneading the components at once. Any of conventional melt-kneading techniques and apparatuses (single-screw, twin-screw and multi-screw extruders, rolls, Banbury mixers, various kneaders) can be used. Specifically, in Examples and Comparative Examples, the components shown in Table 1 were melt-kneaded at once. Melt kneading conditions were as follows. Using a twin screw extruder (L / D = 47), the kneading temperature is 180 ~
The test was performed at 220 ° C. with a screw rotation of 100 rpm. 1. Specific Gravity According to JIS K 6301, the test piece was measured using a 6.3 mm thick pressed sheet. 2. Hardness According to JIS K 6301, a 6.3 mm thick press sheet was used as a test piece. The hardness after 15 seconds was measured. 3. Tensile strength According to JIS K 6301, a test piece was prepared by extracting a 1 mm thick press sheet into a dumbbell No. 3 mold. The tensile speed was 500 mm / min. 4. 100% elongation stress According to JIS K 6301, a 1 mm thick press sheet of a dumbbell No. 3 was used as a test piece. The tensile speed was 500 mm / min. 5. Tensile Elongation According to JIS K 6301, a test piece was prepared by extracting a 1 mm thick press sheet into a dumbbell No. 3 mold. The tensile speed was 500 mm / min. 6. Compression set According to JIS K 6262, a 6.3 mm thick press sheet was used as a test piece. The measurement was performed at 70 ° C. for 72 hours under a condition of 25% deformation. 7. Tear strength According to JIS K 6301, a test piece was prepared by punching a 2.5 mm thick pressed sheet into a dumbbell No. 3 mold.
The tensile speed was 500 mm / min. 8. Adhesive force between base material, adhesive resin layer, and surface layer Each base material, adhesive resin, and surface resin are 2 mm in size using an injection molding machine.
A strip-shaped test piece having a thickness, a width of 25 mm and a length of 150 mm was prepared. The test pieces were overlapped by 100 mm in the length direction, and the test pieces were arranged in a metal mold having a thickness of 3 mm, and pressed from the upper surface. (Pressure conditions; preheating time: 30 seconds, preheating temperature:
8. 180 ° C., pressurization time: 10 seconds, pressure 50 kg / cm ² ) Bending restoring force Metal plate (20) shown in FIG. 7 (thickness: 10 mm, width: 5)
0 mm, length: 150 mm, roundness at the tip: R ₁ ) were left in an atmosphere at the measurement temperature for 30 minutes, and then the test piece (21)
(Thickness: 3mm, width: 10mm, length: 150mm)
Is fixed so that the center part (75 mm from the end) and the tip of the tip part coincide as shown in FIG. 8, and a 2.0 kg weight is applied from above to the test piece (21) so that a uniform load is applied to the entire test piece (21). did. The metal plate (20) and the test piece (2
After leaving 1) at a predetermined temperature (25 ° C.) for 3 minutes, FIG.
The time required for the test piece to return to an angle of 100 degrees by releasing the load as described above was measured. Component (a): (a-1) Septon 4077 manufactured by Kuraray Co., Ltd., styrene content: 30% by weight, isoprene content: 70% by weight, number average molecular weight: 260,000, weight average molecular weight:
320,000, molecular weight distribution: 1.23, hydrogenation rate:
90% or more (a-2) Hibler VS-1, manufactured by Kuraray Co., Ltd. Styrene content: 20% by weight, isoprene content: 70% by weight, hydrogenation rate: 90% or more Component (b): Diana Process manufactured by Idemitsu Kosan Co., Ltd. Oil PW-90, type: paraffinic oil Component (c): polystyrene homopolymer, GP-1 manufactured by Denki Kagaku Kogyo, melt index (measurement temperature 200
° C, measurement load 5 kg): 6.4 g / 10 min Component (d) (d-1) Ethylene-acrylic acid copolymer, Nuclell N0903HC, manufactured by Mitsui DuPont, content of 9.0% MAA (methacrylic acid), density : 0.93 g / cm ³ ,
Melting point 99 ° C, melt index (measuring temperature 190 ° C,
(Measurement load 2.16 kg): 1.3 g / 10 min (d-2) Ethylene-acrylic acid copolymer, Himilan 1554, manufactured by DuPont-Mitsui, MAA (methacrylic acid) content 9.0%, density: 0.94 g / Cm ³ , melting point 99 ° C., melt index (measuring temperature 190 ° C., measuring load 2.16 kg): 1.3 g / 10 min, ion-crosslinked metal salt: zinc component (e): (e-1) ethylene- Octene copolymer, Engage EG8150, manufactured by Dow Chemical Japan, density: 0.1.
868 g / cm ³ , melt index (measurement temperature 19
0 ° C, measurement load 2.16 kg): 0.5 g / 10 min (e-2) Ethylene-octene copolymer, Engage EG8440 manufactured by Dow Chemical Japan, density: 0.
897 g / cm ³ , melt index (measurement temperature 19
0 ° C., measurement load 2.16 kg): 1.6 g / 10 minutes Peroxide: Nippon Oil & Fats Co., Ltd.
(2,5-dimethyl-2,5- (t-butylperoxy) -hexane) Crosslinking aid: NK ester 3G, manufactured by Shin-Nakamura Chemical Co., Ltd., Type:
Triethylene glycol dimethacrylate

[0010]

[Table 1]

[0011]

The present invention can contribute to weight reduction and environmental problems by changing various moldings to the conventional vinyl chloride resin, and can use the hard olefin resin composition for the protective coating layer to provide scratch resistance. Excellent in heat resistance, weather resistance, chemical resistance, appearance surface, remarkably small return by the restoring force to the bending of the base of the molding, and bending the long molding by using a mild thermoplastic elastomer, There is an effect that each part bending portion can be easily and reliably formed. Furthermore, since the intermediate adhesive layer was used, both the protective coating layer and the molding base were firmly and integrally fused together without using an adhesive or the like, and the protective coating layer was never peeled off. There is no effect. If the intermediate adhesive layer is made of a softer material than the protective coating layer and the molding base, the intermediate adhesive layer has a buffering effect, so that there is an effect that the scratch resistance is further improved.
Also in the manufacturing method, since it is possible to mold with one mold die using three extrusion molding machines, it is possible to omit the steps of applying the adhesive and the like, and it is possible to mold with a very simple process. There is. As described above, the present invention has an effect that mounting is extremely easy and stability is improved particularly when used for molding for automobiles. Also, when used in fields requiring heat resistance and oil resistance, such as molding of automobiles, there is an effect of exhibiting a very excellent effect.

[Brief description of the drawings]

FIG. 1 is an overall perspective view of the present invention mounted on a window glass of an automobile or the like.

FIG. 2 is a schematic view of a method for bending and attaching a molded article according to the present invention.

FIG. 3 is a vertical sectional side view taken along the line 1A-A of the present invention.

FIG. 4 is a perspective view of the molding body of the present invention with a part thereof being omitted.

FIG. 5 is a partially cutaway oblique view of the molding body of the present invention covering a protective coating layer.

FIG. 6 is a vertical sectional side view showing a molding step of the molding of the present invention.

FIG. 7 is a schematic view showing the shape of a bending restoring force measuring jig and the shape of a test piece according to the present invention.

FIG. 8 is a schematic diagram in which a test piece is fixed to a metal plate.

FIG. 9 is a schematic diagram in which the load on the test piece is released.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Molding main body 2 Mold head 3 Insertion leg part 4 Glass insertion groove 6 Intermediate adhesive layer 7 Protective coating layer 8 Wind glass 9 Car body panel 11 First extrusion molding machine 12 Second extrusion molding machine 13 Third extrusion molding machine 14 Mold Dice 15 Cooling water tank 20 Metal plate 21 Test piece

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 23/08 C08L 23/08 25/02 25/02 33/06 33/06 51/04 51/04 // B29K 21 : 00 23:00 B29L 9:00 31:30 (72) Inventor Naohisa Miyagawa 261-5 Kawai, Shirai-cho, Inba-gun, Chiba Prefecture Toki Wake Chemical Industry Co., Ltd. 1-18, Kagaoka Ground 12

Claims (4)

[Claims] 1. In various moldings mounted on an automobile, the various molding bodies use a thermoplastic elastomer composition having a small bending restoring force and a low specific gravity, and the thermoplastic elastomer composition comprises: (a) a vinyl aromatic compound; A block copolymer consisting of at least two polymer blocks A mainly made of a compound and at least one polymer block B mainly made of a conjugated diene compound, and / or a hydrogenated block obtained by hydrogenating the block copolymer 100 parts by weight of copolymer, (b) 15 to 300 parts by weight of softener for non-aromatic rubber, (c) 10 to 150 parts by weight of vinyl aromatic resin, CH ₂ 【C (R ₁ ) —COOR ₂ (d) ethylene and a general formula (wherein R ₁ represents hydrogen or a methyl group, and R ₂ is hydrogen or alkyl having 1 to 10 carbons) A resin represented by the following formula: and a resin containing at least 30% by weight of the copolymer. 2. The base of the molding main body is composed of a thermoplastic elastomer composition having a small bending restoring force and a low specific gravity, and the molding head made of the thermoplastic elastomer composition is provided with a polar group-containing olefin resin at the top. An intermediate adhesive layer having a hardness of 90 degrees or more (JIS) having excellent scratch resistance, weather resistance, and chemical resistance is provided on the intermediate adhesive layer.
2. The molding for automobiles according to claim 1, wherein a protective coating layer made of an olefin resin composition having a K7215 A hardness) is laminated. 3. An intermediate adhesive layer of a polar group-containing olefin resin comprising: CH ₂ ＣC (R ₁ ) —COOR ₂ (d) ethylene and a general formula (where R ₁ is hydrogen or methyl And R ₂ represents hydrogen or an alkyl group having 1 to 10 carbon atoms), and 100 parts by weight of a resin containing at least 30% by weight of the copolymer; (e) a single-site catalyst A polyethylene polymer or a copolymer mainly composed of ethylene
3. The molding according to claim 2, comprising 0 parts by weight. 4. The base of the molding body has an intermediate adhesive layer of a thermoplastic elastomer composition having a low bending restoring force and a low specific gravity and a polar group-containing olefin resin, and has excellent scratch resistance, weather resistance, and chemical resistance. Hardness 90 degrees or more (JIS
3. An extruder for extruding each material with a protective coating layer of an olefin-based composition (K7215A hardness) into a single die, and integrally fusing and laminating the same within a single die. And 3. The method for producing a molding for an automobile according to claim 3.