WO2000006645A1 - Thermoplastic elastomer composition and laminate - Google Patents

Thermoplastic elastomer composition and laminate Download PDF

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Publication number
WO2000006645A1
WO2000006645A1 PCT/JP1999/003952 JP9903952W WO0006645A1 WO 2000006645 A1 WO2000006645 A1 WO 2000006645A1 JP 9903952 W JP9903952 W JP 9903952W WO 0006645 A1 WO0006645 A1 WO 0006645A1
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WIPO (PCT)
Prior art keywords
thermoplastic elastomer
elastomer composition
laminate
weight
composition according
Prior art date
Application number
PCT/JP1999/003952
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French (fr)
Japanese (ja)
Inventor
Makoto Makino
Tatsuo Hamanaka
Original Assignee
Sumitomo Chemical Company, Limited
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Publication date
Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Publication of WO2000006645A1 publication Critical patent/WO2000006645A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins

Definitions

  • the present invention relates to a thermoplastic elastomer composition, a laminate, a laminate for an automobile interior, an automobile interior component, and an instrument panel. More specifically, the present invention provides a thermoplastic elastomer composition which maintains light resistance at a satisfactory high level, does not cause blooming, and has improved fogging resistance, and a thermoplastic elastomer composition comprising the thermoplastic elastomer composition.
  • the present invention relates to a laminated body used, a laminated body for an automobile interior, an automobile interior part, and an instrument panel. Landscape technology
  • thermoplastic elastomer composition used for automobile interior parts is required to be excellent in light resistance and also excellent in fogging resistance.
  • fogging refers to a phenomenon in which various additives contained in the thermoplastic elastomer composition volatilize and adhere to the window glass, causing inconvenience such as deterioration in visibility. From the standpoint of maintaining light resistance at a sufficiently high level and excellent fogging resistance, the thermoplastic elastomer laminate according to the conventional technology is hardly satisfactory.
  • an object of the present invention is to provide a thermoplastic elastomer composition which maintains light resistance at a satisfactory high level, does not involve blooming, and has improved fogging resistance, and a thermoplastic elastomer composition having the same. It is intended to provide a laminate using a product, a laminate for an automobile interior, an automobile interior part, and an instrument panel. That is, the present invention relates to a thermoplastic elastomer composition containing the following (A) to (C).
  • the present invention further provides a laminate obtained by laminating a foam layer on a layer comprising the thermoplastic elastomer composition, a laminate for an automobile interior comprising the laminate, and an instrument comprising the laminate for an automobile interior. It is related to automobile interior parts such as men's panels. BRIEF DESCRIPTION OF THE FIGURES
  • Fig. 1 is a cross-sectional view of a fogging haze measuring device according to ISO 6452. 1. Oil, 2. Oil bath, 3. Cooling plate, 4. Sample, 5. Metal ring, 6. Beaker, 7. Ring packing, 8. Glass plate Best mode for carrying out the invention
  • the olefin-based tree ⁇ meaning ( ⁇ ) used in the present invention is not particularly limited, but is preferably a homopolymer of polypropylene, a copolymer of propylene with a polyolefin having two or more carbon atoms, or polyethylene.
  • monoolefins having two or more carbon atoms include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 1-decene, 3-methyl-11-pentene, 4 —Methyl-1-pentene, 1-octene and the like.
  • these resins can be produced by a known method using a catalyst system such as a zirconate-type catalyst or a meta-opening type catalyst as a catalyst.
  • the melt flow rate (MFR) of the olefin resin ( ⁇ ) is not particularly limited, but is preferably from 0.1 to 500 g / 10 minutes, and more preferably from 0.5 to 300 g / 10 minutes. .
  • the ethylene monoolefin copolymer rubber (B) used in the present invention includes an ethylene monoolefin copolymer rubber and an ethylene monoolefin non-conjugated rubber. Gen copolymer rubber can be mentioned.
  • Propylene among which propylene is preferred.
  • the non-conjugated diene include 1,4-hexadiene, 1,6-butadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,1,5-dibutadiene, 7-methyl-i, 6 —Chain non-conjugated gens such as cyclohexene; cyclohexadiene, dicyclopentene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-12-norbornene, and 5-isopropylene Cyclic non-conjugated gens such as 1-norbornene, 6-chloromethyl-15-isopropenyl-2-norbornene; 2,3-d
  • the ratio (molar ratio) of ethylene / polyolefin in the ethylene-monoolefin copolymer rubber is usually 1 / (0.1 to 10).
  • the content of non-conjugated gen is usually 2 to 25 in terms of iodine value.
  • ethylene monoolefin copolymer rubber an ethylene monoolefin copolymer rubber containing no non-conjugated gen is preferable from the viewpoint of light resistance and fogging resistance, but a partially crosslinked thermoplastic elastomer is preferred.
  • the crosslink density may be insufficient and the mechanical strength may be reduced.
  • a method using N, N, 1 m-phenylene bismaleimide or divinylbenzene as a bridging aid can be cited.
  • an ethylene-unmodified olefin copolymer rubber and an ethylene-unmodified olefin copolymer rubber may be mixed and used.
  • An oil-extended rubber may be used as the ethylene-based copolymer rubber. 100% by weight of rubber component as oil-extended rubber
  • An oil-extended rubber containing 20 to 150 parts by weight of a mineral oil-based softening agent is preferred. If the amount of the mineral oil-based softener is too small, the flexibility and the moldability are not improved by the addition. On the other hand, if the amount of the mineral oil-based softener is too large, the surface of the skin material may stick.
  • ethylene monoolefin copolymer rubber examples include an ethylene-propylene copolymer having a propylene or butene content of 5 to 80% by weight, preferably 10 to 60% by weight, more preferably 15 to 50% by weight.
  • Combined rubber can be given.
  • these rubbers can be produced by a known method using a catalyst system such as a Ziegler-Natta type catalyst or a meta-opening type catalyst.
  • the ethylene-monoolefin copolymer rubber preferably has a viscosity of 100 ° C. (ML 1 + 4 100 ° C.): L50, more preferably 10 to 100. If the viscosity is too low, the mechanical strength may be poor. On the other hand, if the viscosity is too high, the appearance of the molded article may be impaired.
  • (B) may be a cross-linked ethylene monoolefin copolymer rubber obtained by performing dynamic cross-linking in the presence of (A).
  • the degree of crosslinking may be complete or partial, but partial crosslinking is more preferred.
  • the crosslinked (B) and the non-crosslinked (B) for example, those called reactor TP0 produced by polymerization may be used in combination.
  • the weight ratio of (A) / (B) in the thermoplastic elastomer composition is preferably 80/20 to 10/90, more preferably 60/40 to 10/90, and still more preferably 60/40 to 15/85. If (A) is too small ((B) is too large), the fluidity may decrease and sheet workability may be impaired, while if (A) is too large ((B) is too small), flexible thermoplasticity may result. Elastomer may not be obtained. In the present invention, when the oil-extended rubber is used as (B), the quantity viscosity of (B) is based on the value including the mineral oil-based softener.
  • N-alkyl type hindered amine light stabilizer C
  • a light stabilizer other than the N-alkyl-type hindered amine light stabilizer is used according to the conventional technology, the fogging resistance is poor.
  • Preferred (C) is It is an N-methyl type hindered amine light stabilizer, more preferably tetrakis (1: 2,2,6,6-pentamethyl-14-piperidyl) 1,2,3,4-butanetetracarboxylate.
  • the content of (C) is preferably 0.01 to 1.0 part by weight, more preferably 0.05 to 0.5 part by weight, per 100 parts by weight of the total of (A) and (B). 5 parts by weight. If the content of (C) is too small, the light resistance may be poor. On the other hand, if the content of (C) is too large, the fogging resistance is deteriorated, and it is not economically advantageous.
  • the thermoplastic elastomer composition of the present invention is a thermoplastic elastomer composition containing the above (A) to (C).
  • various additives, various auxiliary materials, other rubbers, thermoplastic elastomers, and olefin-based resins can be contained as long as the object of the present invention is not impaired.
  • Various additives include antioxidants, ultraviolet absorbers, lubricants, antistatic agents and the like.
  • Examples of various auxiliary materials include coloring pigments, fillers, and fillers such as calcium carbonate.
  • Rubbers include natural rubber, butyl rubber, black rubber, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butanediene rubber, epichlorohydrin rubber, acrylic rubber, styrene-butadiene rubber, hydrogenated styrene-butadiene rubber. Conjugated rubbers such as butadiene rubber and hydrogenated butadiene rubber.
  • the thermoplastic elastomer include styrene-based butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, styrene-isoprene block copolymers, and hydrogenated styrene-isoprene block copolymers.
  • Plastic elastomers plastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, and the like.
  • resins include olefin monomers such as ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, and maleic anhydride-modified polypropylene. And a polar monomer-modified resin and a polar group-modified resin.
  • thermoplastic elastomer composition can be obtained as a cross-linked composition or a non-cross-linked composition by an ordinary method. Is preferred.
  • a crosslinked thermoplastic elastomer composition is disclosed in JP-A-48-26838, JP-A-11-10639, and Japanese Patent Application No. 7-249494. It can be obtained by the method disclosed in Japanese Patent Publication No. 2 and the like.
  • the obtained cross-linked composition or non-cross-linked composition may further contain various additives, various auxiliary materials, rubbers, heat, and the like, as necessary, as long as the object of the present invention is not impaired. It is also possible to include a plastic elastomer or an olefin resin.
  • the laminate of the present invention is a laminate obtained by laminating a foam layer on a layer made of the thermoplastic elastomer composition of the present invention.
  • a specific example of a method for manufacturing a laminate will be described.
  • thermoplastic elastomer composition is extruded from an extruder by a T-die method, and the extruded molten sheet-like thermoplastic elastomer is laminated with a polyethylene or polypropylene foam sheet. And heat-fusing through a pair of rolls for production.
  • thermocompression bonding method a method of producing a foam from a thermoplastic elastomer composition by a thermocompression bonding method or an adhesive method using an adhesive or the like can be given.
  • thermoplastic elastomer composition by a powder molding method (see Japanese Patent Application Laid-Open No. 5-4733).
  • the two-layer laminate with the foam described above may be used as a multilayer molded body in which a thermoplastic resin layer is laminated on the foam layer side, or a thermoplastic resin may be used if necessary, as long as the object of the invention is not impaired. It is also possible to apply various primers and top coats on the surface of one layer of elastomer (the side where foam is not laminated).
  • the method for producing a molded article of the thermoplastic elastomer composition is not particularly limited, and examples thereof include an extrusion molding method, a press molding method, a calendar molding method, an injection molding method, and a powder slush molding method.
  • an extrusion molding method a press molding method, a calendar molding method, an injection molding method, and a powder slush molding method.
  • Examples of the foam constituting the foam layer of the laminate of the present invention include a polypropylene foam, a polyethylene foam, and a polyurethane foam obtained by an electron beam cross-linking method. preferable.
  • the laminate of the present invention can be optimally used as a laminate for automobile interiors. That is, it can be processed into an automobile interior part made of the laminate for an automobile interior.
  • the car interior parts It is optimally used as automotive interior parts such as instrument panel parts and door parts.
  • test methods and sheet forming methods used for measuring physical properties in these Examples and Comparative Examples are as follows.
  • EPDM was calculated by the following equation.
  • APHR Oil extension amount per 100 parts by weight of EPDM (parts by weight)
  • Propylene homopolymer and copolymer Temperature 230 °, load 2.16 kg Polyethylene: temperature 190 ° (:, load 2.16 kg
  • a device conforming to ISO 6452, for example, the device shown in Fig. 1 was measured using a windscreen fogging test Yuichi WS F-1 manufactured by Suga Test Instruments Co., Ltd.
  • the oil bath 2 and the cooling plate 3 are provided with temperature control, the metal ring 5 is covered, and the annular notch 7 is made of silicone rubber.
  • the temperature of the oil bath 2 containing oil 1 was adjusted to 100 ⁇ 2 ° (:, the temperature of the cooling plate 3 was adjusted to 20 ⁇ 2 ° C, and the sample 4 was set to 8 Omm0.
  • the thermoplastic elastomer composition layer and the foam layer were measured using a thermometer.
  • the plastic elastomer composition layer is upward (towards the glass plate 8), It is arranged so that the foam layer is located below.
  • the method for calculating the gloss retention is shown below.
  • the gloss of the glass plate after the test is defined as R1, the glass plate is rotated by 90 degrees, the gloss is measured, and the values are defined as R2, R3, and R4. Calculate the average gloss from Rl, R2, R3, and R4, and let this value be R.
  • R (R 1 + R2 + R3 + R4) / 4
  • the gloss retention is the ratio of R to the gloss (R0) of the glass plate before the test. Gloss retention (%)-(R / R 0) X 100
  • the fogging test was carried out in accordance with ISO 6452, and the degree of fogging was visually observed.
  • the gloss retention of less fogging was 60% or more, " ⁇ " (good), and the degree of fogging was less than 60%. Is designated as “x” (bad).
  • the sheet was punched out with a JIS K 6301 JIS No. 3 dumbbell, and the sample was illuminated with a UV fader manufactured by Suga Test Instruments Co., Ltd. (black panel temperature: 83 ° C, no water) for 250 hours.
  • the tensile elongation at break was measured in accordance with JIS K 6301.
  • the JIS No. 3 dumbbell and the pulling speed were 200 mm / min.
  • the elongation retention at tensile break is calculated by the formula below.
  • Elongation at break (%) Tensile elongation at break after aging / Elongation at elongation before light or heat resistance test
  • MFR 10 g / 10min, homopolymer type
  • N, N, 1 m-phenylene bismaleimide (“Sumifine BM” manufactured by Sumitomo Chemical Co., Ltd.) as a cross-linking aid 0.4 part by weight
  • molecular weight 1 177
  • TPO-1 2,5-dimethyl-2,5-di (t-butyloxy) hexane was mixed with 100 parts by weight of the master batch using a Henschel mixer for a uniform blending operation for 3 minutes. went.
  • the obtained blend is subjected to dynamic heat treatment at 240 to 260 ° C for about 30 seconds using a twin-screw extruder (TEX-44HC, manufactured by Nippon Steel Works Ltd.) to obtain a partially crosslinked thermoplastic elastomer.
  • TPO-1 One pellet (hereinafter referred to as “TPO-1”) was obtained.
  • thermoplastic elastomer compositions and laminates Preparation of thermoplastic elastomer compositions and laminates
  • TEX-44HC twin-screw extruder
  • thermoplastic elastomer a sheet of the thermoplastic elastomer was formed using a US V type 25 ⁇ extruder (full-flight type screw, screw rotation speed 40 rpm, T die) manufactured by Union Plastics.
  • the obtained sheet was subjected to bloom evaluation and light resistance test, and the light resistance was evaluated based on the retention of elongation at break after aging. Table 1 shows the evaluation results.
  • the composition was subjected to lamination molding to obtain a laminate.
  • a 0.5 mm t sheet was molded using a 25 mm ⁇ D extruder, and heated and laminated together with PPF (polypropylene foam, Toray PPSM 15030) to obtain an extruded laminated molded product.
  • PPF polypropylene foam, Toray PPSM 15030
  • a fogging test was performed on a sample cut out from this sheet at 8 Omm0. Table 1 shows the evaluation results.
  • thermoplastic elastomer composition was obtained in the same manner as in Example 1, except that LA52 was omitted in the preparation of the thermoplastic elastomer composition and the laminate of Example 1. A light resistance test was performed using this composition. Table 1 shows the evaluation results.
  • a laminated body for an automobile interior which maintains light resistance and the like at a satisfactory high level and has improved fogging resistance, and an automobile interior part comprising the laminated body and the laminated body for an automobile interior are provided. can do.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Instrument Panels (AREA)

Abstract

A thermoplastic elastomer composition comprising the following ingredients (A) to (C); and a laminate comprising a layer of the composition and a foam layer superposed thereon: (A) an olefin resin, (B) an ethylene/α-olefin copolymer rubber, and (C) an N-alkylated hindered amine light stabilizer. The laminate, which is for automotive interior use, retains a satisfactorily high level of light resistance and other properties and has improved fogging resistance. An interior automotive part comprising the laminate can be provided.

Description

明 細 書 熱可塑性エラストマ一組成物及び積層体 技術分野  Description Thermoplastic elastomer compositions and laminates Technical field
本発明は、 熱可塑性エラストマ一組成物、 積層体、 自動車内装用積層体、 自動車 内装部品及びインストルメンタルパネルに関するものである。更に詳しくは、 本発 明は耐光性を満足できる高い水準に維持し、 ブルームの発生を伴わず、 かつ耐フォ ギング性を改良した熱可塑性エラストマ一組成物、並びに該熱可塑性エラストマ一 組成物を用いた積層体、 自動車内装用積層体、 自動車内装部品及びインストルメン タルパネルに関するものである。 景技術  The present invention relates to a thermoplastic elastomer composition, a laminate, a laminate for an automobile interior, an automobile interior component, and an instrument panel. More specifically, the present invention provides a thermoplastic elastomer composition which maintains light resistance at a satisfactory high level, does not cause blooming, and has improved fogging resistance, and a thermoplastic elastomer composition comprising the thermoplastic elastomer composition. The present invention relates to a laminated body used, a laminated body for an automobile interior, an automobile interior part, and an instrument panel. Landscape technology
インストルメンタルパネル （ダッシュボード） などの自動車内装部品には、 熱可 塑性エラストマ一組成物層に発泡体層を積層してなる積層体が汎用されつつある。 ここで、 自動車内装部品に用いられる熱可塑性エラストマ一組成物は、 耐光性に優 れると共に、 耐フオギング性に優れることが要求される。 ここで、 フオギングとは、 熱可塑性エラストマ一組成物に含有される各種の添加剤が揮散して窓ガラスに付 着し、 視界を悪化させるなどの不都合を生じる現象をいう。 そして、 耐光性を満足 できる高い水準に維持し、 しかも耐フオギング性に優れるという観点からみるとき、 従来の技術による熱可塑性エラストマ一積層体は、十分に満足し得るものとは言い 難いものであった。 発明の開示  For automotive interior parts such as instrument panels (dashboards), laminates composed of a thermoplastic elastomer composition layer and a foam layer are being widely used. Here, the thermoplastic elastomer composition used for automobile interior parts is required to be excellent in light resistance and also excellent in fogging resistance. Here, fogging refers to a phenomenon in which various additives contained in the thermoplastic elastomer composition volatilize and adhere to the window glass, causing inconvenience such as deterioration in visibility. From the standpoint of maintaining light resistance at a sufficiently high level and excellent fogging resistance, the thermoplastic elastomer laminate according to the conventional technology is hardly satisfactory. Was. Disclosure of the invention
かかる現状に鑑み、 本発明の目的は、 耐光性を満足できる高い水準に維持し、 ブ ルームの発生を伴わず、かつ耐フォギング性を改良した熱可塑性エラストマ一組成 物並びに該熱可塑性エラストマ一組成物を用いた積層体、 自動車内装用積層体、 自 動車内装部品及びィンストルメンタルパネルを提供する点に存する。 すなわち、 本発明は、 下記の （A) 〜 （C) を含有する熱可塑性エラストマ一組 成物に係るものである。 In view of this situation, an object of the present invention is to provide a thermoplastic elastomer composition which maintains light resistance at a satisfactory high level, does not involve blooming, and has improved fogging resistance, and a thermoplastic elastomer composition having the same. It is intended to provide a laminate using a product, a laminate for an automobile interior, an automobile interior part, and an instrument panel. That is, the present invention relates to a thermoplastic elastomer composition containing the following (A) to (C).
(A) ：ォレフィン系樹脂  (A): Olefin resin
(B) ：エチレン一ひ一ォレフィン系共重合体ゴム  (B): Ethylene monoolefin copolymer rubber
(C) ： N—アルキル型ヒンダ一ドアミン系光安定剤  (C): N-alkyl type hindered amine light stabilizer
また、 本発明は、 さらに上記熱可塑性エラストマ一組成物からなる層に発泡体層 を積層してなる積層体、 該積層体からなる自動車内装用積層体、該自動車内装用積 層体からなるインストルメン夕ルパネル等の自動車内装部品に係るものである。 図面の簡単な説明  Further, the present invention further provides a laminate obtained by laminating a foam layer on a layer comprising the thermoplastic elastomer composition, a laminate for an automobile interior comprising the laminate, and an instrument comprising the laminate for an automobile interior. It is related to automobile interior parts such as men's panels. BRIEF DESCRIPTION OF THE FIGURES
図 1は I SO 6452の規定に準じたフォギングのヘイズの測定装置の断面図 である。 1. オイル、 2. オイルバス、 3. 冷却板、 4. サンプル、 5. 金属リン グ、 6. ビーカ一、 7. 環状パッキング、 8. ガラス板 発明を実施するための最良の形態  Fig. 1 is a cross-sectional view of a fogging haze measuring device according to ISO 6452. 1. Oil, 2. Oil bath, 3. Cooling plate, 4. Sample, 5. Metal ring, 6. Beaker, 7. Ring packing, 8. Glass plate Best mode for carrying out the invention
本発明で使用されるォレフイン系樹 β旨 （Α) としては、 特に限定されないが、 ポ リプロピレン単独重合体、プロピレンと炭素数が 2個以上のひ一ォレフィンとの共 重合体およびポリエチレンが好ましい。炭素数が 2個以上のひ一ォレフィンとして は、 たとえばエチレン、 1—ブテン、 1—ペンテン、 3—メチル一1—ブテン、 1 一へキセン、 1—デセン、 3—メチル一 1一ペンテン、 4—メチルー 1一ペンテン、 1—ォクテンなどがあげられる。なお、 これらの樹脂は触媒としてチ一グラ一ナツ 夕型触媒またはメタ口セン型触媒等の触媒系を用いて公知の方法で製造すること ができる。  The olefin-based tree β meaning (Α) used in the present invention is not particularly limited, but is preferably a homopolymer of polypropylene, a copolymer of propylene with a polyolefin having two or more carbon atoms, or polyethylene. . Examples of monoolefins having two or more carbon atoms include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 1-decene, 3-methyl-11-pentene, 4 —Methyl-1-pentene, 1-octene and the like. In addition, these resins can be produced by a known method using a catalyst system such as a zirconate-type catalyst or a meta-opening type catalyst as a catalyst.
ォレフィン系樹脂 （Α) のメルトフローレート （MFR) は、 特に限定されない せ、 好ましくは 0. 1〜 500 g/ 10分であり、 より好ましくは 0. 5〜 300 g/10分の範囲である。  The melt flow rate (MFR) of the olefin resin (Α) is not particularly limited, but is preferably from 0.1 to 500 g / 10 minutes, and more preferably from 0.5 to 300 g / 10 minutes. .
本発明で使用されるエチレン一ひ一ォレフィン系共重合体ゴム （B) としては、 エチレン一ひ一ォレフィン共重合体ゴム及びエチレン一ひ一ォレフィン一非共役 ジェン共重合体ゴムをあげることができる。 The ethylene monoolefin copolymer rubber (B) used in the present invention includes an ethylene monoolefin copolymer rubber and an ethylene monoolefin non-conjugated rubber. Gen copolymer rubber can be mentioned.
エチレン一ひ一才レフィンー非共役ジェン共重合体ゴムにおけるひ一才レフィ ンとしては、 たとえばプロピレン、 1—ブテン、 1 一ペンテン、 1 一へキセン、 4 —メチルー 1 一ペンテン、 1—ォクテン、 1ーデセンなどがあげられ、 なかでもプ ロピレンが好ましい。 また、 非共役ジェンとしては、 たとえば 1 , 4一へキサジェ ン、 1 ， 6—才クタジェン、 2—メチルー 1 , 5—へキサジェン、 6—メチル一 1 , 5 一へブタジエン、 7ーメチルー i ， 6—ォク夕ジェンのような鎖状非共役ジェ ン；シクロへキサジェン、 ジシクロペン夕ジェン、 メチルテトラヒドロインデン、 5—ビニルノルボルネン、 5—ェチリデンー 2—ノルボルネン、 5—メチレン一 2 —ノルボルネン、 5—イソプロピリデン一 2—ノルボルネン、 6クロロメチル一 5 —イソプロぺニル一 2—ノルボルネンのような環状非共役ジェン； 2 , 3—ジイソ プロピリデン一 5—ノルボルネン、 2—ェチリデン一 3—イソプロピリデン一 5— ノルボルネン、 2—プロぺニル一 2 , 2—ノルボルナジェン、 1 , 3 , 7—ォク夕 トリェン、 1 ， 4， 9—デカトリェンのようなトリェンがあげられ、 なかでも 5— ェチリデンー 2—ノルボルネン又はジシクロペン夕ジェンが好ましい。  For example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-octene, etc. Propylene, among which propylene is preferred. Examples of the non-conjugated diene include 1,4-hexadiene, 1,6-butadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,1,5-dibutadiene, 7-methyl-i, 6 —Chain non-conjugated gens such as cyclohexene; cyclohexadiene, dicyclopentene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-12-norbornene, and 5-isopropylene Cyclic non-conjugated gens such as 1-norbornene, 6-chloromethyl-15-isopropenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylisopropylidene-5-norbornene , 2-Propenyl-1,2,2-norbornagen, 1,3,7-ok, like Trien, 1,4,9—like Decatrien Toryen. Of these 5 Echiriden 2- norbornene or Jishikuropen evening Jen preferred.
エチレン一ひ一ォレフィン系共重合体ゴムにおけるエチレン/ひ一ォレフィン の比率 （モル比） は通常 1 / ( 0 . 1〜 1 0 ) である。  The ratio (molar ratio) of ethylene / polyolefin in the ethylene-monoolefin copolymer rubber is usually 1 / (0.1 to 10).
エチレン一ひ一ォレフィン—非共役ジェン共重合体ゴムを用いる場合の非共役 ジェンの含有量はヨウ素価で通常 2〜 2 5である。  In the case of using ethylene monoolefin-non-conjugated gen copolymer rubber, the content of non-conjugated gen is usually 2 to 25 in terms of iodine value.
エチレン一ひ一ォレフィン系共重合体ゴムとしては、耐光性と耐フオギング性の 観点から、非共役ジェンを含有しないエチレン一ひ一ォレフィン共重合体ゴムが好 ましいが、部分架橋型熱可塑性エラストマ一を製造する場合においては架橋密度が 不足し、 機械的強度が低下することがある。 この不都合に対する対策としては、 架 橋助剤として、 N， N， 一m—フエ二レンビスマレイミ ド又はジビニルベンゼンを 用いる方法をあげることができる。なお、 本発明の目的を損じない範囲でエチレン —ひ一才レフィン共重合体ゴムとエチレン一ひ一ォレフィン一非共役ジェン共重 合体ゴムを混合して用いてもよい。 また、 エチレン一ひ一才レフイン系共重合体ゴ ムとしては、 油展ゴムを用いてもよい。 油展ゴムとしては、 ゴム成分 1 0 0重量部 あたり 20〜150重量部の鉱物油系軟化剤を含有する油展ゴムが好ましい。鉱物 油系軟化剤が過少であると添加による柔軟性や成形加工性の向上が少なく、一方、 鉱物油系軟化剤が過多であると表皮材表面にベとつきが生じる場合がある。 As the ethylene monoolefin copolymer rubber, an ethylene monoolefin copolymer rubber containing no non-conjugated gen is preferable from the viewpoint of light resistance and fogging resistance, but a partially crosslinked thermoplastic elastomer is preferred. In the case of manufacturing a product, the crosslink density may be insufficient and the mechanical strength may be reduced. As a countermeasure against this inconvenience, a method using N, N, 1 m-phenylene bismaleimide or divinylbenzene as a bridging aid can be cited. It is to be noted that, as long as the object of the present invention is not impaired, an ethylene-unmodified olefin copolymer rubber and an ethylene-unmodified olefin copolymer rubber may be mixed and used. An oil-extended rubber may be used as the ethylene-based copolymer rubber. 100% by weight of rubber component as oil-extended rubber An oil-extended rubber containing 20 to 150 parts by weight of a mineral oil-based softening agent is preferred. If the amount of the mineral oil-based softener is too small, the flexibility and the moldability are not improved by the addition. On the other hand, if the amount of the mineral oil-based softener is too large, the surface of the skin material may stick.
エチレン一ひ一ォレフィン系共重合体ゴムの好ましい具体例として、プロピレン 又はブテン含有量が 5〜80重量％、 好ましくは 10〜60重量％、 より好ましく は 15〜50重量％のエチレン一プロピレン共重合体ゴムをあげることができる。 また、これらのゴムはチ一グラ一ナッタ型触媒またはメタ口セン型触媒等の触媒 系を用いて公知の方法で製造することができる。  Preferred specific examples of the ethylene monoolefin copolymer rubber include an ethylene-propylene copolymer having a propylene or butene content of 5 to 80% by weight, preferably 10 to 60% by weight, more preferably 15 to 50% by weight. Combined rubber can be given. In addition, these rubbers can be produced by a known method using a catalyst system such as a Ziegler-Natta type catalyst or a meta-opening type catalyst.
エチレン一ひ—ォレフィン系共重合体ゴムは、 100°Cのム一二一粘度（ML 1+4 100°C)力 〜： L 50のものが好ましく、 更に好ましくは 10〜100である。 該ム一二一粘度が過小であると機械的強度に劣ることがあり、 一方、該ム一二一粘 度が過大であると成形品の外観が損なわれることがある。 The ethylene-monoolefin copolymer rubber preferably has a viscosity of 100 ° C. (ML 1 + 4 100 ° C.): L50, more preferably 10 to 100. If the viscosity is too low, the mechanical strength may be poor. On the other hand, if the viscosity is too high, the appearance of the molded article may be impaired.
(B) は、 （A) の共存下で動的架橋を行うことにより得られる架橋されたェチ レン一ひ一ォレフィン系共重合体ゴムであってもよい。更に架橋の程度としては完 全または部分架橋があるが部分架橋がより好ましい。 かかる （B) を用いることに より、力学的物性の向上及び二次成形時の加工性に優れるという利点を得ることが できる。 なお、 架橋した （B) と非架橋の （B) 、 例えば重合で製造されるリアク ター TP 0と称されるもの等を併用しても良い。  (B) may be a cross-linked ethylene monoolefin copolymer rubber obtained by performing dynamic cross-linking in the presence of (A). The degree of crosslinking may be complete or partial, but partial crosslinking is more preferred. By using such (B), it is possible to obtain an advantage that mechanical properties are improved and workability during secondary molding is excellent. In addition, the crosslinked (B) and the non-crosslinked (B), for example, those called reactor TP0 produced by polymerization may be used in combination.
熱可塑性エラストマ一組成物中における （A) / (B) の重量比率は、 80/2 0〜： 10/90であることが好ましく、より好ましくは 60/40〜； 10/90、 更に好ましくは 60/40〜15/85である。 （A) が過少 （ （B) が過多） で あると流動性が低下してシート加工性を損ねることがあり、一方（ A )が過多（（ B ) が過少） であると柔軟な熱可塑性エラストマ一が得られないことがある。 なお、 本 発明において、 （B) として油展ゴムを用いた場合の （B) の量ゃム一二一粘度は、 鉱物油系軟化剤を含めた値を基準とする。  The weight ratio of (A) / (B) in the thermoplastic elastomer composition is preferably 80/20 to 10/90, more preferably 60/40 to 10/90, and still more preferably 60/40 to 15/85. If (A) is too small ((B) is too large), the fluidity may decrease and sheet workability may be impaired, while if (A) is too large ((B) is too small), flexible thermoplasticity may result. Elastomer may not be obtained. In the present invention, when the oil-extended rubber is used as (B), the quantity viscosity of (B) is based on the value including the mineral oil-based softener.
本発明では、 N—アルキル型ヒンダ一ドアミン系光安定剤 （C) を使用すること が必要である。従来の技術に従い、 N—アルキル型ヒンダ一ドアミン系光安定剤以 外の光安定剤を用いた場合には耐フオギング性が劣る。 好ましい (C) としては N—メチル型ヒンダ一ドアミン系光安定剤であり、 より好ましくはテトラキス （ 1： 2， 2 , 6， 6—ペンタメチル一 4—ピペリジル） 1 , 2 , 3 , 4—ブタンテトラ カルボキシラートである。 In the present invention, it is necessary to use an N-alkyl type hindered amine light stabilizer (C). When a light stabilizer other than the N-alkyl-type hindered amine light stabilizer is used according to the conventional technology, the fogging resistance is poor. Preferred (C) is It is an N-methyl type hindered amine light stabilizer, more preferably tetrakis (1: 2,2,6,6-pentamethyl-14-piperidyl) 1,2,3,4-butanetetracarboxylate.
( C ) の含有量は、 （A ) 及び （B ) の合計量 1 0 0重量部あたり 0 . 0 1〜1 . 0重量部であることが好ましく、 更に好ましくは 0 . 0 5〜0 . 5重量部である。 ( C ) が過少であると耐光性に劣る場合があり、 一方、 （C ) が過多であると耐フ ォギング性が悪化したり、 また経済的に有利ではない。  The content of (C) is preferably 0.01 to 1.0 part by weight, more preferably 0.05 to 0.5 part by weight, per 100 parts by weight of the total of (A) and (B). 5 parts by weight. If the content of (C) is too small, the light resistance may be poor. On the other hand, if the content of (C) is too large, the fogging resistance is deteriorated, and it is not economically advantageous.
本発明の熱可塑性エラストマ一組成物は、 上記の （A)〜（C ) を含有する熱可 塑性エラストマ一組成物であるが、 必須成分である （A )〜（C ) の各成分に加え て、 必要に応じて、 本発明の目的を損なわない範囲で、 各種添加剤、 各種副資材、 他のゴム類、熱可塑性エラストマ一およびォレフィン系樹脂等を含有せしめること も可能である。 各種添加剤としては、 酸化防止剤、 紫外線吸収剤、 滑剤、 帯電防止 剤等があげられる。 各種副資材としては、 着色用顔料、 フイラ一、 炭酸カルシウム 等の充填剤があげられる。 ゴム類としては、 天然ゴム、 ブチルゴム、 クロ口プレン ゴム、 アクリロニトリル一ブタジエンゴム、水添ァクリロニトリル一ブ夕ジェンゴ ム、 ェピクロロヒドリンゴム、 アクリルゴム、 スチレン一ブタジエンゴム、 水添ス チレン一ブタジエンゴム、 ブタジエンゴム、 水添ブタジエンゴム等の共役ジェン系 ゴム等があげられる。熱可塑性エラストマ一としては、 スチレン一ブタジエンプロ ック共重合体、水添スチレン一ブタジエンブロック共重合体、 スチレン一イソプレ ンブロック共重合体、水添スチレン一イソプレンブロック共重合体等のスチレン系 熱可塑性エラストマ一、ポリエステル系熱可塑性エラストマ一、 ポリアミ ド系熱可 塑性エラストマ一、 ポリウレタン系熱可塑性エラストマ一等があげられる。樹脂類 としてはエチレン一酢酸ビニル共重合体、エチレン一メチルメタクリレート共重合 体、 エチレン一ェチルァクリレート共重合体、 エチレン一メタクリル酸共重合体、 無水マレイン酸変性ポリプロプレン等、ォレフィン系モノマーと極性モノマーの共 重合体樹脂、 及び極性基で変性されたォレフイン系樹脂等があげられる。  The thermoplastic elastomer composition of the present invention is a thermoplastic elastomer composition containing the above (A) to (C). In addition to the essential components (A) to (C), If necessary, various additives, various auxiliary materials, other rubbers, thermoplastic elastomers, and olefin-based resins can be contained as long as the object of the present invention is not impaired. Various additives include antioxidants, ultraviolet absorbers, lubricants, antistatic agents and the like. Examples of various auxiliary materials include coloring pigments, fillers, and fillers such as calcium carbonate. Rubbers include natural rubber, butyl rubber, black rubber, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butanediene rubber, epichlorohydrin rubber, acrylic rubber, styrene-butadiene rubber, hydrogenated styrene-butadiene rubber. Conjugated rubbers such as butadiene rubber and hydrogenated butadiene rubber. Examples of the thermoplastic elastomer include styrene-based butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, styrene-isoprene block copolymers, and hydrogenated styrene-isoprene block copolymers. Plastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, and the like. Examples of resins include olefin monomers such as ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, and maleic anhydride-modified polypropylene. And a polar monomer-modified resin and a polar group-modified resin.
熱可塑性エラストマ一組成物は、 通常の方法により、 架橋型組成物又は非架橋型 組成物として得ることができる力 自動車内装用組成物としては架橋型組成物の方 が好ましい。 たとえば、 架橋型の熱可塑性エラストマ一組成物は、 特開昭 4 8— 2 6 8 3 8号公報、 特開平 1一 1 0 3 6 3 9号公報、特願平 7— 2 4 9 4 4 2号公報 などに開示されている方法により得ることができる。 また、得られた架橋型組成物 又は非架橋型組成物に、すでに述べたように必要に応じて本発明の目的を損なわな い範囲で、 さらに各種添加剤、 各種副資材、 ゴム類、 熱可塑性エラストマ一、 ォレ フィン系樹脂を含有せしめることも可能である。 The thermoplastic elastomer composition can be obtained as a cross-linked composition or a non-cross-linked composition by an ordinary method. Is preferred. For example, a crosslinked thermoplastic elastomer composition is disclosed in JP-A-48-26838, JP-A-11-10639, and Japanese Patent Application No. 7-249494. It can be obtained by the method disclosed in Japanese Patent Publication No. 2 and the like. As described above, the obtained cross-linked composition or non-cross-linked composition may further contain various additives, various auxiliary materials, rubbers, heat, and the like, as necessary, as long as the object of the present invention is not impaired. It is also possible to include a plastic elastomer or an olefin resin.
本発明の積層体は、本発明の熱可塑性エラストマ一組成物からなる層に発泡体層 を積層してなる積層体である。 以下、 積層体の製造法の具体例を述べる。  The laminate of the present invention is a laminate obtained by laminating a foam layer on a layer made of the thermoplastic elastomer composition of the present invention. Hereinafter, a specific example of a method for manufacturing a laminate will be described.
第一に、熱可塑性エラストマ一組成物を押出機から Tダイ法によって押出し、押 出された溶融状態にあるシート状の熱可塑性エラストマーをポリェチレン又はポ リプロピレンの発泡シ一トと積層させた状態で一対のロール間を通して熱融着さ せて製造する方法をあげることができる。  First, a thermoplastic elastomer composition is extruded from an extruder by a T-die method, and the extruded molten sheet-like thermoplastic elastomer is laminated with a polyethylene or polypropylene foam sheet. And heat-fusing through a pair of rolls for production.
第二に、 熱可塑性エラストマ一組成物からなる成形体に、 発泡体を熱圧着法又は 接着剤などを用いた接着法によって製造する方法をあげることができる。  Second, a method of producing a foam from a thermoplastic elastomer composition by a thermocompression bonding method or an adhesive method using an adhesive or the like can be given.
第三に、 熱可塑性エラストマ一組成物を粉末成形法（特開平 5— 4 7 3号公報な ど参照） によって一体的に製造する方法をあげることができる。  Third, there is a method for integrally producing a thermoplastic elastomer composition by a powder molding method (see Japanese Patent Application Laid-Open No. 5-4733).
また、先述の発泡体との二層積層体はその発泡層側に熱可塑性樹脂層を積層され てなる多層成形体として用いたり、必要に応じて本発明の目的を損なわない範囲で、 熱可塑性エラストマ一層の表面 （発泡体を積層していない面)に各種プライマ一、 トップコートを塗布することも可能である。  In addition, the two-layer laminate with the foam described above may be used as a multilayer molded body in which a thermoplastic resin layer is laminated on the foam layer side, or a thermoplastic resin may be used if necessary, as long as the object of the invention is not impaired. It is also possible to apply various primers and top coats on the surface of one layer of elastomer (the side where foam is not laminated).
熱可塑性エラストマ一組成物の成形体の製造方法は、特に限定されるものではな く、 たとえば押出成形法、 プレス成形法、 カレンダ一成形法、 射出成形法、 粉末ス ラッシュ成形法等などがあげられる。  The method for producing a molded article of the thermoplastic elastomer composition is not particularly limited, and examples thereof include an extrusion molding method, a press molding method, a calendar molding method, an injection molding method, and a powder slush molding method. Can be
本発明の積層体の発泡体層を構成する発泡体としては、電子線架橋法により得ら れたポリプロピレン発泡体、 ポリエチレン発泡体、 ポリウレタン発泡体などがあげ られ、 ポリプロピレン発泡体及びポリエチレン発泡体が好ましい。  Examples of the foam constituting the foam layer of the laminate of the present invention include a polypropylene foam, a polyethylene foam, and a polyurethane foam obtained by an electron beam cross-linking method. preferable.
本発明の積層体は、 自動車内装用積層体として最適に使用され得る。すなわち、 該自動車内装用積層体からなる自動車内装部品に加工され得る。該自動車内装部品 としては、ィンストルメントパネル部品やドア部品などの自動車内装部品として最 適に使用される。 The laminate of the present invention can be optimally used as a laminate for automobile interiors. That is, it can be processed into an automobile interior part made of the laminate for an automobile interior. The car interior parts It is optimally used as automotive interior parts such as instrument panel parts and door parts.
次に、 本発明を実施例によって具体的に説明する。 なお、 これらの実施例及び比 較例における物性測定に用いた試験方法及びシート成形加工法は以下のとおりで ある。  Next, the present invention will be described specifically with reference to examples. The test methods and sheet forming methods used for measuring physical properties in these Examples and Comparative Examples are as follows.
(1) ム一ニー粘度 （ML 1+4100°C) (1) Mooney viscosity (ML 1 +4 100 ° C)
ASTM D 927 - 57 Tに準拠して測定した。 E P D Mについては下記の式 で算出した。  Measured according to ASTM D 927-57T. EPDM was calculated by the following equation.
1 o g(ML 1/ML 2) = 0. 0066(APHR)  1 o g (ML 1 / ML 2) = 0.0066 (APHR)
ML 1： EPDMのム一二一粘度  ML 1: EPDM viscosity
ML 2：油展 EP DMのム一ニー粘度  ML 2: Oil extension EP DM's viscosity
APHR： EPDM 100重量部あたりの油展量 （重量部）  APHR: Oil extension amount per 100 parts by weight of EPDM (parts by weight)
(2) メルトフ口一レート （MFR)  (2) Meltov mouth rate (MFR)
J I S K-7210に準拠し、 下記の条件にて測定した。  It was measured under the following conditions in accordance with JIS K-7210.
プロピレン単独重合体および共重合体：温度 230° 荷重 2. 16kg ポリエチレン ：温度 190 ° (：、 荷重 2. 16kg  Propylene homopolymer and copolymer: Temperature 230 °, load 2.16 kg Polyethylene: temperature 190 ° (:, load 2.16 kg
(3) フオギング試験法  (3) Fogging test method
I SO 6452の規定に準じた装置、 たとえば図 1に示す装置をいい、 スガ試験 機（株）社製 ウィンドスクリーンフオギングテス夕一 WS F— 1を用いて測定し た。 ここで、 オイルバス 2、 冷却板 3は温度コントロール付き、 金属リング 5がク 口一ムメヅキ済み、 環状ノ ツキン 7はシリコンゴム製である。  A device conforming to ISO 6452, for example, the device shown in Fig. 1 was measured using a windscreen fogging test Yuichi WS F-1 manufactured by Suga Test Instruments Co., Ltd. Here, the oil bath 2 and the cooling plate 3 are provided with temperature control, the metal ring 5 is covered, and the annular notch 7 is made of silicone rubber.
フオギングの測定において、 オイル 1の入ったオイルバス 2は 100±2° (：、 冷 却板 3は 20±2°Cの温度範囲で調整され、 サンプル 4は 8 Omm0とする。サン プル 4を 20時間ビーカー 6内で加熱し、 取り出した後、 23±2°C、 50%RH の環境下で 1±0. 1時間後にガラス板 8の光沢度を測定する。光沢度は、 スガ試 験機（株）社製デジタル変角光沢計を用い、 J I S K7105の 60度鏡面光沢 度に準拠して測定される。 なお、 測定に際しては、 熱可塑性エラストマ一組成物層 と発泡体層について、 熱可塑性エラストマ一組成物層が上方 （ガラス板 8の方） に、 発泡体層が下方に位置するように配置する。 In the fogging measurement, the temperature of the oil bath 2 containing oil 1 was adjusted to 100 ± 2 ° (:, the temperature of the cooling plate 3 was adjusted to 20 ± 2 ° C, and the sample 4 was set to 8 Omm0. After heating in a beaker 6 for 20 hours, take it out, and measure the gloss of the glass plate 8 after 1 ± 0.1 hour in an environment of 23 ± 2 ° C and 50% RH. It is measured in accordance with JIS K7105 60-degree specular gloss using a digital gonio-gloss meter manufactured by Kiki Co., Ltd. In the measurement, the thermoplastic elastomer composition layer and the foam layer were measured using a thermometer. The plastic elastomer composition layer is upward (towards the glass plate 8), It is arranged so that the foam layer is located below.
(4) 光沢度保持率  (4) Gloss retention
光沢度保持率の算出法を次に示す。試験後のガラス板の光沢度を R 1とし、 その ガラス板を 90度づっ回転させ、 それぞれ光沢度を測定し、 その値を R 2、 R3、 R4とする。 Rl、 R2、 R3、 及び R 4より平均の光沢度を計算し、 この値を R とする。  The method for calculating the gloss retention is shown below. The gloss of the glass plate after the test is defined as R1, the glass plate is rotated by 90 degrees, the gloss is measured, and the values are defined as R2, R3, and R4. Calculate the average gloss from Rl, R2, R3, and R4, and let this value be R.
R= (R 1 +R2+R3+R4) /4  R = (R 1 + R2 + R3 + R4) / 4
光沢度保持率は試験前のガラス板の光沢度 （R0) に対する Rの割合とする。 光沢度保持率 （％) - (R/R 0 ) X 100  The gloss retention is the ratio of R to the gloss (R0) of the glass plate before the test. Gloss retention (%)-(R / R 0) X 100
(5) 耐フオギング性  (5) Fogging resistance
I SO 6452に準拠してフォギング試験を行ったガラス板の曇り具合を目 視し、 曇りが少ない光沢度保持率 （前述） が 60%以上を 「〇」 （良好） 、 曇りが 大きな 60%未満を 「x」 （不良） とした。  The fogging test was carried out in accordance with ISO 6452, and the degree of fogging was visually observed. The gloss retention of less fogging (described above) was 60% or more, "〇" (good), and the degree of fogging was less than 60%. Is designated as “x” (bad).
( 6 ) 耐光性試験  (6) Light fastness test
シートを J I S K 6301 J I S 3号ダンベルで打ち抜き、そのサンプルを スガ試験機（株）製の UVフェードメ一夕一 （ブラックパネル温度 83°C、 水無し の条件下） で 250時間照した。  The sheet was punched out with a JIS K 6301 JIS No. 3 dumbbell, and the sample was illuminated with a UV fader manufactured by Suga Test Instruments Co., Ltd. (black panel temperature: 83 ° C, no water) for 250 hours.
(7)破断伸び保持率  (7) Break elongation retention
J I S K 6301に準拠し、 引張破断点伸びを測定した。 なお、 J I S 3号ダ ンベル、 引張速度 200 mm/分とした。 引張破断点伸び保持率は、 下記の式に基 さ算山し/こ。  The tensile elongation at break was measured in accordance with JIS K 6301. The JIS No. 3 dumbbell and the pulling speed were 200 mm / min. The elongation retention at tensile break is calculated by the formula below.
破断伸び保持率（％) =経時後の引張破断点伸び値/耐光又は耐熱テスト前の引 張破断点伸び値  Elongation at break (%) = Tensile elongation at break after aging / Elongation at elongation before light or heat resistance test
(8) ブルーム性  (8) Bloom property
シート成形で得られたシートサンプルを 23±2°C、 50%RHの環境下に 30 日保存後、 シート表面のブルームを目視し、 ブルームしていない場合を 「〇」 （良 好） 、 ブルームしていた場合を 「X」 （不良） とした。  After storing the sheet sample obtained by sheet molding in an environment of 23 ± 2 ° C and 50% RH for 30 days, visually check the bloom on the sheet surface, and when the bloom is not blooming, “〇” (good), bloom If it did, it was marked “X” (bad).
実施例 1 熱可塑性エラストマ一ペレツ 卜の調製 Example 1 Preparation of thermoplastic elastomer pellets
( 1 ) TPO- 1  (1) TPO-1
EPM- 1 (エチレン一プロピレン共重合体ゴム、 プロピレン含有量 =22重 量％、 ML 1+4100°C= 35) 70重量部とポリプロピレン一 1 (MFR= 10 g/10分、 ホモポリマータイプ） 30重量部及び架橋助剤として N, N，一 m— フエ二レンビスマレイミ ド （住友化学工業 （株） 製 「スミファイン BM」 ） 0. 4重量部、 更に光安定剤としてスミソ一ブ 300 {2- (2—ヒドロキシー 3— t —ブチルー 5—メチルフエニル） 一 5—クロ口べンゾトリアゾ一ル、 分子量二 31 6 ：住友化学工業 （株） 製 } 0. 05重量部、 熱安定剤としてィルガノックス 10 10 {ペン夕エリスリチルーテトラキス 〔3— （3, 5—ジ一 t—ブチル一 4ーヒ ドロキシフエニル） プロピオネート〕 、 分子量 = 1 177、 チバ 'ガイギ一社製 } 0. 1重量部をバンバリ一ミキサーで 170〜200°Cx 7分混練した後、押出機 を用いてペレツト状マスタ一バッチを作製した。次いで該マスタ一バッチ 100重 量部あたり 0. 04重量部の 2， 5—ジメチル— 2, 5—ジ （t—ブチルバ一ォキ シ）へキサンをヘンシェルミキサーを用いて均一プレンド操作を 3分間行った。得 られたブレンド物を二軸押出機 （日本製鋼所 （株）製 TEX— 44HC) を用い て、 240〜260°Cで約 30秒間動的熱処理を行ない、 部分架橋してなる熱可塑 性エラストマ一ペレツト （以下 「TPO— 1」 と記す。 ） を得た。 EPM-1 (Ethylene-propylene copolymer rubber, propylene content = 22% by weight, ML 1 + 4 100 ° C = 35) 70 parts by weight and polypropylene-1 (MFR = 10 g / 10min, homopolymer type) ) 30 parts by weight and N, N, 1 m-phenylene bismaleimide (“Sumifine BM” manufactured by Sumitomo Chemical Co., Ltd.) as a cross-linking aid 0.4 part by weight, and Sumisoub 300 { 2- (2-hydroxy-3-t-butyl-5-methylphenyl) -1-5-benzobenzotriazole, molecular weight 316: manufactured by Sumitomo Chemical Co., Ltd.} 0.05 parts by weight, ilganox 10 as heat stabilizer 10 {Penyu erythrityl-tetrakis [3- (3,5-di-t-butyl-14-hydroxyphenyl) propionate], molecular weight = 1 177, Ciba-Geigy Corporation} 0.1 parts by weight After kneading with a mixer at 170-200 ° C for 7 minutes, use an extruder To prepare a Retsuto shaped master one batch. Then, 0.04 parts by weight of 2,5-dimethyl-2,5-di (t-butyloxy) hexane was mixed with 100 parts by weight of the master batch using a Henschel mixer for a uniform blending operation for 3 minutes. went. The obtained blend is subjected to dynamic heat treatment at 240 to 260 ° C for about 30 seconds using a twin-screw extruder (TEX-44HC, manufactured by Nippon Steel Works Ltd.) to obtain a partially crosslinked thermoplastic elastomer. One pellet (hereinafter referred to as “TPO-1”) was obtained.
(2) ΤΡΟ- 2  (2) ΤΡΟ-2
TP 0— 1の製造法において、 EPM— 1の代わりに EPDM— 1 (エチレン— プロピレン一 5—ェチリデン一 2—ノルボルネン共重合体ゴム、ヨウ素化 = 12、 プロピレン含有量 =28重量％、 ML 1+4100°C= 242) の 5重量％へキサン 溶液中に、 EPDM— 1 100重量部あたり鉱物油系軟化剤 （出光興産 （株） 製 「ダイアナプロセスオイル PW— 380」） 100重量部を添加し、 その後スチ一 ムストリッピングで脱溶媒にて得られた油展 EPDM— 1 (ML 1+4100°C= 5 3) 85重量部とポリプロピレン一 2 (MFR = 1 g/10分、 プロピレン一ェチ レンランダム共重合体、 エチレン含量 5重量％) 15重量部及び架橋助剤として N, N，一 m—フエ二レンビスマレイミ ド 0. 4重量部、 更に光安定剤としてスミ ソープ 300を 0. 2重量部、 熱安定剤としてィルガノックス 1010を 0. 15 重量部、 滑剤としてニュートロン S ( エル力酸アミ ド、 日本精化 （株） 製） 0. 1 重量部に変更した以外は T P 0 _ 1と同様に製造し、部分架橋してなる熱可塑性ェ ラストマ一ペレツト （以下 「TPO— 2」 と記す。 ） を得た。 In the production process of TP 0-1, EPDM-1 (ethylene-propylene-15-ethylidene-12-norbornene copolymer rubber, iodination = 12, propylene content = 28% by weight, ML 1 +4 100% by weight of mineral oil-based softener ("Diana Process Oil PW-380" manufactured by Idemitsu Kosan Co., Ltd.) per 100 parts by weight of EPDM-1 in a 5% by weight hexane solution of 100 ° C = 242) Oil-extended EPDM-1 (ML 1 + 4 100 ° C = 53) obtained by steam stripping and then solvent removal.85 parts by weight of polypropylene and 2 of polypropylene (MFR = 1 g / 10 min, propylene 15% by weight of ethylene random copolymer, ethylene content 5% by weight) 0.4% by weight of N, N, 1m-phenylenebismaleimide as a crosslinking aid, and Sumi as a light stabilizer 0.2 parts by weight of Soap 300, 0.15 parts by weight of Irganox 1010 as a heat stabilizer, and 0.1 parts by weight of Neutron S (Eluonic acid amide, Nippon Seika Co., Ltd.) as a lubricant A thermoplastic elastomer pellet (hereinafter referred to as “TPO-2”) which was produced in the same manner as in TP 0 _ 1 and partially crosslinked was obtained.
熱可塑性エラストマ一組成物及び積層体の調製 Preparation of thermoplastic elastomer compositions and laminates
上記 TP〇一 1を 56重量部、 TP 0—2を 24重量部、 ポリエチレン {MFR =2、 熱安定剤としてィルガノックス ® 1076 {ォク夕デシルー 3— (3， 5— ジ一 t—ブチルー 4—ヒドロキシフエニル） プロピオネート、 分子量 =530、 チ バ .ガイギ一社製 } 0. 15重量部、 ィルガフォス ®168 〔トリス （2， 4ージ 一 t—ブチルフエニル） フォスファイ ト、 分子量 =647、 チバ 'ガイギ一社製〕 0. 12重量部を含む。 ） 20重量部と、 ヒンダ一ドアミン系光安定剤として LA 52 {テトラキス （1 , 2， 2， 6， 6—ペン夕メチル一4ーピペリジル） 1 , 2， 3, 4—ブタンテトラカルボキシラート、 分子量 =847 旭電化 （株） 製 } を 0. 3重量部とをヘンシヱルミキサーでブレンドした後、 二軸押出機（日本製鋼所社製 TEX— 44HC)を用いて、 240〜260°Cで約 30秒間動的熱処理を行い、 ペレツト化して熱可塑性エラストマ一組成物を得た。次いで、ユニオンプラスチヅ ク社製 US V型 25πιπιΦ押出機（フルフライ トタイプスクリユー、 スクリュー回 転数 40 rpm、 Tダイ） を使用し、 該熱可塑性エラストマ一のシート成形を行つ た。得られたシートでブルーム評価と耐光テス卜を行い、 経時後の破断伸びの保持 率で耐光性を評価した。 評価結果を表 1に示す。  56 parts by weight of the above TP-11, 24 parts by weight of TP0-2, polyethylene {MFR = 2, irganox ® 1076 as a heat stabilizer {octyldecyl 3- (3,5-di-t-butyl-4) —Hydroxyphenyl) propionate, molecular weight = 530, Ciba. Geigy One Co., Ltd.} 0.15 parts by weight, Irgafos®168 [Tris (2,4-di-t-butylphenyl) phosphite, molecular weight = 647, Ciba ' 0.1% by weight. 20 parts by weight, LA 52 {tetrakis (1,2,2,6,6-pentanemethyl-1-piperidyl) 1,2,3,4-butanetetracarboxylate as a hindered amine light stabilizer, molecular weight = 847 manufactured by Asahi Denka Co., Ltd.) was blended with 0.3 parts by weight using a Hensile mixer, and then mixed at about 240-260 ° C using a twin-screw extruder (TEX-44HC manufactured by Nippon Steel Works). A dynamic heat treatment was performed for 30 seconds, and the mixture was pelletized to obtain a thermoplastic elastomer composition. Next, a sheet of the thermoplastic elastomer was formed using a US V type 25πιπιΦ extruder (full-flight type screw, screw rotation speed 40 rpm, T die) manufactured by Union Plastics. The obtained sheet was subjected to bloom evaluation and light resistance test, and the light resistance was evaluated based on the retention of elongation at break after aging. Table 1 shows the evaluation results.
また、 この組成物について積層成形を行い積層体を得た。積層成形に際しては、 25mm<D押出機を使用し 0. 5 mm tのシートを成形し、 PPF (ポリプロピレ ン発泡体、東レ PPSM 15030) と共に加熱積層を行い押出積層成形品を得た。 このシートから 8 Omm0で切り抜いたサンプルで、 フオギング試験を行った。評 価結果を表 1に示す。  The composition was subjected to lamination molding to obtain a laminate. At the time of lamination molding, a 0.5 mm t sheet was molded using a 25 mm <D extruder, and heated and laminated together with PPF (polypropylene foam, Toray PPSM 15030) to obtain an extruded laminated molded product. A fogging test was performed on a sample cut out from this sheet at 8 Omm0. Table 1 shows the evaluation results.
比較例 1 Comparative Example 1
実施例 1の熱可塑性エラストマ一組成物及び積層体の調製において、 LA52の かわりに、 サノール LS— 770 〔ビス （2 , 2 , 6， 6—テトラメチル一 4ーピ ペリジル） セバケ一卜、 分子量 = 4 8 1、 三共社製〕 を 0 . 3重量部追添した以外 は実施例 1と同様に実施して熱可塑性エラストマ一組成物及び積層体を得た。この 組成物を用いて耐光性試験、積層体を用いてフォギング試験を行った。評価結果を 表 1に示す。 In the preparation of the thermoplastic elastomer composition and laminate of Example 1, SANOL LS-770 [bis (2,2,6,6-tetramethyl-1-pi) was used instead of LA52. Peridyl) (Sebacel, molecular weight = 481, manufactured by Sankyo Co., Ltd.) was added in the same manner as in Example 1 to obtain a thermoplastic elastomer composition and a laminate. A light resistance test was performed using this composition, and a fogging test was performed using the laminate. Table 1 shows the evaluation results.
比較例 2 Comparative Example 2
実施例 1の熱可塑性エラストマ一組成物及び積層体の調製において、 L A 5 2を 除いた以外は実施例 1と同様に実施して熱可塑性エラストマ一組成物を得た。この 組成物を用いて耐光性試験を行った。 評価結果を表 1に示す。 A thermoplastic elastomer composition was obtained in the same manner as in Example 1, except that LA52 was omitted in the preparation of the thermoplastic elastomer composition and the laminate of Example 1. A light resistance test was performed using this composition. Table 1 shows the evaluation results.
実施例 1 比較例 1 比較例 2 配合 （重量部） Example 1 Comparative Example 1 Comparative Example 2 Formulation (parts by weight)
(A)ォレフィン系樹脂 40.4 40.4 40.4 (A) Olefin resin 40.4 40.4 40.4
(B)エチレン-ひ-ォレフィン系共重合体： rム 59.6 59.6 59.6(B) Ethylene-co-olefin copolymer: r 59.6 59.6 59.6
(C)LA-52 *1 0.3 0 0 (C) LA-52 * 1 0.3 0 0
LS-770 *2 0 0.3 0 評価  LS-770 * 2 0 0.3 0 Evaluation
(1)フォキ、、ンク、、試験  (1) Foki, Nku, Test
光沢度保持率 ％ 61 45  Gloss retention rate% 61 45
耐フォキ'、ンク 生 〇 X  Foki-resistant, Nku 〇 X
(2) 耐光性試験  (2) Light fastness test
破断伸び保持率 % 79 77 3  Elongation at break% 79 77 3
(3) フ、、ルーム性 〇 X 〇  (3) H, room 性 X 〇
* 1 L A— 5 2 ：テトラキス （ 1， 2， 2 , 6 , 6 —ペンタメチルー 4—ピペリ ジル） 1， 2， 3 , 4—ブタンテトラカルボキシラート  * 1 L A—52: Tetrakis (1,2,2,6,6—pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate
* 2 L S— 7 7 0 : ビス （2 , 2 , 6， 6—テトラメチルー 4—ピペリジル） セ バケート 産業上の利用可能性  * 2 L S—770: Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate Industrial applicability
以上説明したとおり、 本発明により、 耐光性などを満足できる高い水準に維持し、 かつ耐フォギング性を改良した自動車内装用積層体及び該及び該自動車内装用積 層体からなる自動車内装部品を提供することができる。  As described above, according to the present invention, a laminated body for an automobile interior, which maintains light resistance and the like at a satisfactory high level and has improved fogging resistance, and an automobile interior part comprising the laminated body and the laminated body for an automobile interior are provided. can do.

Claims

請 求 の 範 囲 The scope of the claims
1. 下記の （A) 〜 （C) を含有する熱可塑性エラストマ一組成物。 1. A thermoplastic elastomer composition containing the following (A) to (C).
(A) ：ォレフィン系樹脂  (A): Olefin resin
(B) ：エチレン一ひ一ォレフィン系共重合体ゴム  (B): Ethylene monoolefin copolymer rubber
(C) ： N—アルキル型ヒンダ一ドアミン系光安定剤  (C): N-alkyl type hindered amine light stabilizer
2. (A)がポリプロピレン及び/又はポリエチレンである請求項 1記載の熱可 塑性エラストマ一組成物。  2. The thermoplastic elastomer composition according to claim 1, wherein (A) is polypropylene and / or polyethylene.
3. (B)がエチレン一ひ一ォレフィン共重合体ゴム又はエチレン一ひ一ォレフ ィン—非共役ジェン共重合体ゴムである請求項 1または 2記載の熱可塑性エラス トマ一組成物。  3. The thermoplastic elastomer composition according to claim 1, wherein (B) is an ethylene monoolefin copolymer rubber or an ethylene monoolefin-nonconjugated gen copolymer rubber.
4. (B)の α—才レフインがプロピレンである請求項 1— 3のいずれかに記載 の熱可塑性エラストマー組成物。  4. The thermoplastic elastomer composition according to claim 1, wherein the α-olefin of (B) is propylene.
5. (Β) 力 ゴム成分 100重量部あたり 20〜150重量部の鉱物油系軟化 剤を含有する油展ゴムである請求項 1一 4のいずれかに記載の熱可塑性エラスト マー組成物。  5. (Β) Force The thermoplastic elastomer composition according to any one of claims 14 to 14, which is an oil-extended rubber containing 20 to 150 parts by weight of a mineral oil-based softener per 100 parts by weight of a rubber component.
6. (Β) 力 (A) の共存下で動的架橋を行うことにより架橋しているェチレ ン— α—ォレフィン系共重合体ゴムである請求項 1— 5のいずれかに記載の熱可 塑性エラストマ一組成物。  6. (Β) The heat-treatable rubber according to any one of claims 1 to 5, which is an ethylene-α-olefin copolymer rubber crosslinked by performing dynamic crosslinking in the presence of force (A). Plastic elastomer composition.
7. (A) / (Β) の重量比率が 80/20〜； L 0/90である請求項 1—6の いずれかに記載の熱可塑性エラストマ一組成物。  7. The thermoplastic elastomer composition according to any one of claims 1 to 6, wherein the weight ratio of (A) / (Β) is from 80/20 to L / 90.
8. (A) / (Β) の重量比率が 60/40-10/90である請求項 7記載の 熱可塑性エラストマ一組成物。  8. The thermoplastic elastomer composition according to claim 7, wherein the weight ratio of (A) / (Β) is 60 / 40-10 / 90.
9. (C) 力 N—メチル型ヒンダ一ドアミン系光安定剤である請求項 1—8の いずれかに記載の熱可塑性エラストマ一組成物。  9. (C) The thermoplastic elastomer composition according to any one of claims 1 to 8, which is an N-methyl type hindered amine light stabilizer.
10. (C) 力 s、 テトラキス （ 1， 2， 2 , 6, 6—ペン夕メチル一4—ピベリジ ル） 1， 2 , 3, 4—ブタンテトラカルボキシラートである請求項 1—9のいずれ かに記載の熱可塑性エラストマ一組成物。 10. (C) Force s, Tetrakis (1,2,2,6,6-pentanemethyl-1-piberidyl) 1,2,3,4-butanetetracarboxylate according to any one of claims 1 to 9 A thermoplastic elastomer composition according to any one of the above.
11. (A)及び （B)の合計量 100重量部あたりの （C)の含有量が 0. 01 〜 1.0重量部である請求項 1― 10のいずれかに記載の熱可塑性エラストマ一組 成物。 11. The thermoplastic elastomer composition according to claim 1, wherein the content of (C) is 0.01 to 1.0 part by weight per 100 parts by weight of the total amount of (A) and (B). object.
12.請求項 1— 11のいずれかに記載の熱可塑性エラストマ一組成物からなる層 に発泡体層を積層してなる積層体。  12. A laminate obtained by laminating a foam layer on a layer comprising the thermoplastic elastomer composition according to any one of claims 1 to 11.
13.発泡体層がポリプロピレン、 ポリェチレン又はポリウレタンの発泡体からな る請求項 12記載の積層体。  13. The laminate according to claim 12, wherein the foam layer is made of a foam of polypropylene, polyethylene, or polyurethane.
14. 請求項 12または 13記載の積層体からなる自動車内装用積層体。  14. A laminate for an automobile interior, comprising the laminate according to claim 12 or 13.
15. 請求項 14記載の自動車内装用積層体からなる自動車内装部品。  15. An automobile interior part comprising the laminate for an automobile interior according to claim 14.
16.請求項 14記載の自動車内装用積層体からなるインストルメンタルパネル。  16. An instrument panel comprising the laminate for an automobile interior according to claim 14.
PCT/JP1999/003952 1998-07-28 1999-07-23 Thermoplastic elastomer composition and laminate WO2000006645A1 (en)

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JP5042459B2 (en) * 2004-03-12 2012-10-03 オリヱント化学工業株式会社 Laser light transmitting composition and laser welding method
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5720344A (en) * 1980-07-11 1982-02-02 Mitsui Petrochemical Ind Laminate
JPH03220248A (en) * 1989-08-02 1991-09-27 Himont Inc Method for stabilizing polyolefin and product thereby obtained
JPH03265638A (en) * 1990-03-14 1991-11-26 Sumitomo Chem Co Ltd Stabilized polypropylene resin composition
JPH03275746A (en) * 1990-03-23 1991-12-06 Asahi Denka Kogyo Kk Polyolefinic resin composition
JPH05279524A (en) * 1992-03-31 1993-10-26 Sumitomo Chem Co Ltd Elastomer composition for light-resistant facing material and light-resistant facing material for industrial part comprising said composition
JPH06240054A (en) * 1993-02-19 1994-08-30 Asahi Denka Kogyo Kk Stabilized thermoplastic elastomer composition
JPH0987394A (en) * 1995-09-27 1997-03-31 Sumitomo Chem Co Ltd Olefinic thermoplastic elastomer sheet, and laminate comprising the same and its use
JPH09165477A (en) * 1995-12-15 1997-06-24 Ube Ind Ltd Polypropylene resin composition for automobile component part
JPH09278955A (en) * 1996-04-10 1997-10-28 Showa Denko Kk Propylene resin composition and its laminate
JPH10120847A (en) * 1996-06-18 1998-05-12 Montell North America Inc Brittling-resistant polyolefin composition and flexible article produced therefrom

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5720344A (en) * 1980-07-11 1982-02-02 Mitsui Petrochemical Ind Laminate
JPH03220248A (en) * 1989-08-02 1991-09-27 Himont Inc Method for stabilizing polyolefin and product thereby obtained
JPH03265638A (en) * 1990-03-14 1991-11-26 Sumitomo Chem Co Ltd Stabilized polypropylene resin composition
JPH03275746A (en) * 1990-03-23 1991-12-06 Asahi Denka Kogyo Kk Polyolefinic resin composition
JPH05279524A (en) * 1992-03-31 1993-10-26 Sumitomo Chem Co Ltd Elastomer composition for light-resistant facing material and light-resistant facing material for industrial part comprising said composition
JPH06240054A (en) * 1993-02-19 1994-08-30 Asahi Denka Kogyo Kk Stabilized thermoplastic elastomer composition
JPH0987394A (en) * 1995-09-27 1997-03-31 Sumitomo Chem Co Ltd Olefinic thermoplastic elastomer sheet, and laminate comprising the same and its use
JPH09165477A (en) * 1995-12-15 1997-06-24 Ube Ind Ltd Polypropylene resin composition for automobile component part
JPH09278955A (en) * 1996-04-10 1997-10-28 Showa Denko Kk Propylene resin composition and its laminate
JPH10120847A (en) * 1996-06-18 1998-05-12 Montell North America Inc Brittling-resistant polyolefin composition and flexible article produced therefrom

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