JPH02258247A - Laminated body - Google Patents
Laminated bodyInfo
- Publication number
- JPH02258247A JPH02258247A JP34033789A JP34033789A JPH02258247A JP H02258247 A JPH02258247 A JP H02258247A JP 34033789 A JP34033789 A JP 34033789A JP 34033789 A JP34033789 A JP 34033789A JP H02258247 A JPH02258247 A JP H02258247A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic elastomer
- layer
- crosslinked
- polyolefin resin
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000006260 foam Substances 0.000 claims abstract description 29
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 29
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005977 Ethylene Substances 0.000 claims abstract description 24
- 229920001971 elastomer Polymers 0.000 claims abstract description 24
- 239000005060 rubber Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 22
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 20
- 239000004711 α-olefin Substances 0.000 claims abstract description 20
- -1 polyethylene Polymers 0.000 claims abstract description 19
- 229920001155 polypropylene Polymers 0.000 claims abstract description 11
- 239000004743 Polypropylene Substances 0.000 claims abstract description 10
- 239000004698 Polyethylene Substances 0.000 claims abstract description 8
- 229920000573 polyethylene Polymers 0.000 claims abstract description 8
- 238000004049 embossing Methods 0.000 claims abstract description 7
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003856 thermoforming Methods 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 16
- 239000004800 polyvinyl chloride Substances 0.000 description 8
- 229920000915 polyvinyl chloride Polymers 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920006027 ternary co-polymer Polymers 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、積層体に関する。更に詳しくは、自動車用内
装材などとして有効に使用される積層体に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a laminate. More specifically, the present invention relates to a laminate that is effectively used as an interior material for automobiles.
自動車の床、壁、天井などの内装材としては、表面がエ
ンボス加工され、そこにしぼ付けされた皮革模様を有す
るポリ塩化ビニル層からなり、それが発泡体層および必
要に応じて樹脂骨材層で順次裏打ちされた積層体が従来
から用いられている。Interior materials for automobile floors, walls, ceilings, etc. consist of a polyvinyl chloride layer with a leather pattern embossed on the surface and embossed therein, which is then combined with a foam layer and, if necessary, resin aggregate. Laminates lined with sequential layers are conventionally used.
このような積層体は、次のような各工程を経て製造され
ている：
（１）軟質ポリ塩化ビニルをカレンダー成形してシート
を作製する
（２）このシート表面に、ポリオールとポリイソシアネ
ートとの混合物を塗布し、ウレタン処理することによっ
て艶消処理を行なう
この艶消処理は、後記工程（７）の熱成形時にシート表
面が光沢を帯びてくるのを予め防止することにある
（３）エンボス加工して、しぼ付けされた皮革模様を表
面に形成させる
（４）表面がエンボス加工されたシートの裏面を火炎処
理して溶融させ、別途供給される発泡ポリウレタンシー
トとロールにより圧着させる（５）ポリ塩化ビニルシー
トと発泡ポリウレタンシートとの積層シートの発泡ポリ
ウレタンシート側に、接着剤層を更に設ける
（６）真空成形、圧空成形などの熱成形法により、所定
形状の樹脂骨材を成形する
（７）ポリ塩化ビニル−発泡ポリウレタンー接着剤積層
シートを予備加熱した後、これを樹脂骨材成形品に載置
し、両者を熱成形して一体化するしかるに、こうしたポ
リ塩化ビニルシートおよび発泡ポリウレタンシートを積
層して用いたものと比較して、ポリオレフィン系樹脂と
エチレン・α−オレフィン系共重合体ゴムの部分架橋物
とのブレンド体からなり、表面がエンボス加工された熱
可塑性エラストマー層およびポリエチレンまたはポリプ
ロピレンの発泡体層、好ましくは架橋発泡体１を積層し
た積層体は、その製造上および性゛買上いくつかの点で
著しくすぐれていることが見出された。即ち。Such laminates are manufactured through the following steps: (1) Calender molding of soft polyvinyl chloride to produce a sheet (2) Adding polyol and polyisocyanate to the surface of this sheet. This matte treatment is performed by applying a mixture and treating it with urethane.The purpose of this matte treatment is to prevent the sheet surface from becoming glossy during thermoforming in step (7) described below.(3) Embossing It is processed to form a grained leather pattern on the surface (4) The back side of the sheet with the embossed surface is flame treated and melted, and it is crimped with a separately supplied polyurethane foam sheet using a roll (5) An adhesive layer is further provided on the foamed polyurethane sheet side of the laminated sheet of the polyvinyl chloride sheet and the foamed polyurethane sheet. (6) The resin aggregate is molded into a predetermined shape by a thermoforming method such as vacuum forming or pressure forming. 7) After preheating the polyvinyl chloride-foamed polyurethane-adhesive laminated sheet, it is placed on the resin aggregate molded product, and the two are thermoformed to integrate. Compared to the case where sheets are laminated, a thermoplastic elastomer layer made of a blend of polyolefin resin and a partially crosslinked ethylene/α-olefin copolymer rubber with an embossed surface and a polyethylene layer are used. It has also been found that a laminate in which polypropylene foam layers, preferably crosslinked foam 1, are laminated is significantly superior in several respects in terms of manufacturing and performance. That is.
（ａ）このような積層体は、ポリオレフィン系樹脂とエ
チレン・α−オレフィン系共重合体ゴムの部分架橋物と
のブレンド体を約１５０〜２５０℃の押出機から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、好ましくはポリエチレン
またはポリプロピレンの架橋発泡体シートと積層させた
状態で一対のロール間を通し、その際熱可塑性エラスト
マーシートはロール温度的６０〜７０℃のエンボス加工
用ロール側に、また架橋発泡体シートは加熱されていな
い通常ロール側に接触させるようにして製造される。(a) Such a laminate is produced by extruding a blend of a polyolefin resin and a partially crosslinked ethylene/α-olefin copolymer rubber from an extruder at about 150 to 250°C using a T-die method. The thermoplastic elastomer sheet in a molten state is passed between a pair of rolls, preferably in a laminated state with a crosslinked foam sheet of polyethylene or polypropylene, with the thermoplastic elastomer sheet being heated at a temperature of 60 to 70°C at a temperature of the rolls. The cross-linked foam sheet is produced in contact with the embossing roll at 0.degree. C., and the crosslinked foam sheet is brought into contact with the unheated normal roll.
この結果、軟質ポリ塩化ビニルを用いた場合の前記工程
（１）〜（４）に相当する工程がわずか一工程で行われ
、そこに表面がエンボス加工された積層体を与える。即
ち、この積層体は、後で行われる骨材成形品との加熱に
よる一体成形時に艶を生ずることがないので、前記工程
（２）の如き艶消し工程を特に設ける必要がない、また
、これに関連して、ポリ塩化ビニルの場合には、艶消し
処理をするために、前記工程（１）の如く予めそれをシ
ート状に成形しておくことを必要としているが１本発明
にあっては熱可塑性エラストマーのシート状への押出し
と同時に（引続いて）架橋発泡体シートへの融着を行な
うことができ、このことは前記工程（４）にみられるよ
うな発泡ポリウレタンシートとの接着のためのポリ塩化
ビニルシートの火炎処理の如き工程をも不必要とさせる
。しかも、熱可塑性エラストマーシートのエンボス加工
は、架橋発泡体シートとの積重時に同時に行なうことが
でき。As a result, the steps corresponding to steps (1) to (4) described above when using soft polyvinyl chloride are performed in just one step, thereby providing a laminate with an embossed surface. That is, since this laminate does not become glossy when integrally molded by heating with the aggregate molded product, which is performed later, there is no need to provide a matting process such as the above-mentioned step (2). In relation to this, in the case of polyvinyl chloride, it is necessary to form it into a sheet shape in advance as in step (1) above in order to apply the matte treatment, but one aspect of the present invention is that The thermoplastic elastomer can be extruded into a sheet and simultaneously (successively) fused to a crosslinked foam sheet, which is similar to the bonding with a foamed polyurethane sheet as seen in step (4) above. It also eliminates the need for processes such as flame treatment of polyvinyl chloride sheets. Moreover, the embossing of the thermoplastic elastomer sheet can be carried out at the same time as stacking with the crosslinked foam sheet.
前記工ａ（３）の如きエンボス加工工程を特に別に設け
る必要もない。There is no need to provide a separate embossing process such as step a(3).
（ｂ）本発明に係るこの積層体は、予備加熱された後所
定形状に成形されたポリオレフィン系樹脂骨材成形品に
載置し、両者を熱成形して一体化することができ、その
際前記工程（５）の如き接着剤層を必要とはしない。(b) This laminate according to the present invention can be placed on a polyolefin resin aggregate molded product that has been preheated and molded into a predetermined shape, and can be integrated by thermoforming the two. There is no need for an adhesive layer as in step (5).
（ｃ）積層体の性質についていえば、この積層体は軽量
性、柔軟性および表面の耐傷付性の点ですぐれ、また可
塑剤含有軟質ポリ塩化ビニルを用いた場合のような表面
のべとつき感もなく、更に熱可塑性エラストマーおよび
架橋発泡体はいずれも耐熱性にすぐれているので、積層
体全体としても耐熱性にすぐれ、このため特に夏季に室
内が高温となる自動車の内装材などとして有効に使用す
ることができる。(c) Regarding the properties of the laminate, this laminate has excellent lightness, flexibility, and surface scratch resistance, and also has a sticky surface that does not occur when soft polyvinyl chloride containing a plasticizer is used. In addition, thermoplastic elastomers and crosslinked foams both have excellent heat resistance, so the laminate as a whole also has excellent heat resistance, making it an effective material for the interior of automobiles, where the interior gets hot, especially in the summer. can be used.
積層体の表皮層を形成する、ポリオレフィン系樹脂とエ
チレン・α−オレフィン系共重合体ゴムの部分架橋物と
のブレンド体からなる熱可塑性エラストマーとしては１
次のようなものが示される。As a thermoplastic elastomer consisting of a blend of a polyolefin resin and a partially crosslinked product of ethylene/α-olefin copolymer rubber, which forms the skin layer of the laminate, 1
The following will be shown:
（ｉ）エチレンまたはプロピレンの単独重合体または少
量の他の重合性単量体との共重合体によって代表される
各種ポリオレフィン系樹脂およびエチレンと炭素数３〜
１４のα−オレフィンとの２元共重合体ゴムまたはこれ
に各種ポリエン化合物を更に共重合させた３元共重合体
ゴムであるエチレン・α−オレフィン系共重合体ゴムの
部分架橋物のブレンド体からなる熱可塑性組成物（例え
ば、特公昭５３−２１０２１号公報および特開昭５５−
７１７３８号公報参照）
（３ｉ）ポリオレフィン系樹脂とエチレン・α−オレフ
ィン系共重合体ゴムとのブレンド体を動的に熱処理して
得られた熱可塑性組成物（例えば特公昭５３−３４２１
０号公報、特開昭５３−１４９２４０号公報および同５
３−１４９２４１号公報参照）
（ｉｉｉ）ポリオレフィン系樹脂とエチレン・α−オレ
フィン系共重合体ゴムとのブレンド体を動的に熱処理し
て得られたものに、更にポリオレフィン系樹脂をブレン
ドして得られた熱可塑性組成物（例えば特開昭５３−１
４５８５７号公報および同５４−１６５５４号公報参照
）
（神）エチレンの単独重合体または少量の他の重合性単
量体との共重合体によって代表されるペルオキシド架橋
型ポリオレフィン系樹脂、プロピレンの単独重合体また
は少量の他の重合性単量体との共重合体によって代表さ
れるペルオキシド非架橋型ポリオレフィン系樹脂および
エチレン・α−オレフィン系共重合体ゴムのブレンド体
を動的に熱処理した得られた熱可塑性組成物（例えば特
開昭５５−７１７３９号公報参照）
これら各種の熱可塑性エラストマーにおいて、ポリオレ
フィン系樹脂とエチレン・α−オレフィン系共重合体ゴ
ムの部分架橋物とは、 ８０／２０〜２０／８０゜好ま
しくは７０／３０〜３０／７０の重量比となるようにブ
レンドして用いられる。ポリオレフィン系樹脂としては
、シート成形時の成形し易さ、シートの耐傷付性などの
点からポリエチレン、特に低密度ポリエチレンとポリプ
ロピレンとを１０／９０〜７０／３０の重量比で混合し
て用いることが好ましい、また、部分架橋さるべきエチ
レン・α−オレフィン系共重合体ゴムとしては、主とし
て強度的な理由から、エチレンとα−オレフィンとが５
０１５０〜９０／１０、好ましくは７０／３０〜８５／
１５のモル比で、またムーニー粘度ＭＬ１−．（１２１
℃）が約２０以上、好ましくは約４０〜８０のものが使
用されることが望ましい、そして。(i) Various polyolefin resins represented by homopolymers of ethylene or propylene or copolymers with small amounts of other polymerizable monomers, and ethylene and carbon atoms of 3 to 3
A partially crosslinked blend of ethylene/α-olefin copolymer rubber, which is a binary copolymer rubber with 14 α-olefins or a ternary copolymer rubber obtained by further copolymerizing various polyene compounds with this rubber. thermoplastic compositions (for example, Japanese Patent Publication No. 53-21021 and Japanese Patent Application Laid-open No. 55-1989)
(3i) A thermoplastic composition obtained by dynamically heat-treating a blend of a polyolefin resin and an ethylene/α-olefin copolymer rubber (for example, Japanese Patent Publication No. 53-3421)
Publication No. 0, Japanese Patent Application Laid-open No. 149240/1983, and Japanese Patent Application Laid-Open No. 1983-149240
(Refer to Publication No. 3-149241) (iii) A blend obtained by dynamically heat treating a blend of a polyolefin resin and an ethylene/α-olefin copolymer rubber, and further blending a polyolefin resin. thermoplastic compositions (e.g., JP-A-53-1)
45857 and 54-16554)) Peroxide crosslinked polyolefin resins represented by ethylene homopolymers or copolymers with small amounts of other polymerizable monomers, propylene homopolymers A blend of a peroxide non-crosslinked polyolefin resin represented by a polymer or a copolymer with a small amount of other polymerizable monomer and an ethylene/α-olefin copolymer rubber is dynamically heat-treated. Thermoplastic compositions (see, for example, JP-A-55-71739) Among these various thermoplastic elastomers, partially crosslinked products of polyolefin resin and ethylene/α-olefin copolymer rubber are 80/20 to 20. /80° Preferably, they are blended at a weight ratio of 70/30 to 30/70. As the polyolefin resin, polyethylene, especially low density polyethylene and polypropylene should be mixed in a weight ratio of 10/90 to 70/30 for ease of molding during sheet molding and scratch resistance of the sheet. It is preferable that ethylene and α-olefin copolymer rubber be partially crosslinked, mainly for strength reasons.
0150-90/10, preferably 70/30-85/
15 and a Mooney viscosity ML1-. (121
C) is about 20 or more, preferably about 40 to 80.
これらのエチレン・α−オレフィン系共重合体ゴムの部
分架橋は、一般に熱可塑性エラストマー形成に際して用
いられる被処理物［前記（ｉ）の場合にはエチレン・α
−オレフィン系共重合体ゴム、また（ｉｔ）〜（ｔｖ）
の場合にはブレンド体と表示されたもの１１００重量部
に対し約０．１〜２重量部の有機ペルオキシドを用いて
、ジビニルベンゼンなどの多官能性化合物の存在下に動
的に熱処理して行われる。Partial crosslinking of these ethylene/α-olefin copolymer rubbers is generally performed on the treated material used in forming thermoplastic elastomers [in the case of (i) above, ethylene/α-olefin copolymer rubber is
- Olefin copolymer rubber, also (it) ~ (tv)
In the case of 1100 parts by weight of the blend, about 0.1 to 2 parts by weight of organic peroxide is used to dynamically heat-treat in the presence of a polyfunctional compound such as divinylbenzene. be exposed.
そして、これらの熱可塑性エラストマー中には、必要に
応じてポリイソブチレン、ブチルゴムなどによって代表
されるペルオキシド非架橋型炭化水素系ゴム状物質およ
びｌまたは鉱物油系軟化剤を混合することもできる。These thermoplastic elastomers may also be mixed with peroxide non-crosslinked hydrocarbon rubber-like substances such as polyisobutylene, butyl rubber, etc. and lubricant or mineral oil-based softeners, if necessary.
熱可塑性エラストマーから形成される表皮層に裏打ちさ
れるポリエチレンまたはポリプロピレンの発泡体、好ま
しくは架橋発泡体は、例えば特公昭３９−２５５００号
公報、同４０−２５３５１号公報および同４゜−２５３
５２号公報などにアジド架橋剤を用いた架橋発泡体の製
造法が記載されており、この他に放射線による架橋発泡
体なども知られており、またこれらの架橋発泡体は市販
もされているので、それをそのまま使用することもでき
る。これらの発泡体は、積層体を自動車用内装材として
用いる場合には、約１０〜５０程度度の発泡倍率である
ことが望ましい。Polyethylene or polypropylene foams, preferably crosslinked foams, which are lined with a skin layer formed from a thermoplastic elastomer, are described, for example, in Japanese Patent Publication No. 39-25500, Japanese Patent Publication No. 40-25351 and Japanese Patent Publication No. 40-253.
A method for producing a crosslinked foam using an azide crosslinking agent is described in Publication No. 52, etc. In addition, crosslinked foams using radiation are also known, and these crosslinked foams are also commercially available. So you can use it as is. These foams desirably have a foaming ratio of about 10 to 50 degrees when the laminate is used as an interior material for an automobile.
膏剤を成形するのに用いられるポリオレフィン系樹脂中
には、要求される物性を損わない範囲において、あるい
は物性を更に改善する目的で、木粉、繊維片、無機充填
剤などを混合することができる。これらのポリオレフィ
ン系樹脂骨材は、例えば一般にレジンボード、プラスチ
ックダンボール、レジンフェルトなどの状態で所定形状
に成形される。Wood flour, fiber pieces, inorganic fillers, etc. may be mixed into the polyolefin resin used to form plasters, to the extent that the required physical properties are not impaired, or for the purpose of further improving the physical properties. I can do it. These polyolefin resin aggregates are generally molded into a predetermined shape, for example, in the form of resin board, plastic cardboard, resin felt, or the like.
このような骨材成形品と一体成形される積層体の熱可塑
性エラストマー層と発泡体層との厚さは。What is the thickness of the thermoplastic elastomer layer and foam layer of the laminate that is integrally molded with such an aggregate molded product?
積層体成形品の用途によって異なり、例えば自動車用内
装材として用いられる場合には、一般に前者は約０．１
〜２１■、また後者は約１〜３０ｍｍ程度であり、その
ような用途の場合においても、表皮層の厚さは天井材で
は比較的薄く、ダツシュボード。It varies depending on the use of the laminate molded product; for example, when used as an interior material for an automobile, the former is generally about 0.1
~21■, and the latter is about 1 to 30 mm, and even in such applications, the thickness of the skin layer is relatively thin for ceiling materials, and the thickness of the skin layer is relatively thin for ceiling materials.
ホイルハウスカバー、各種ピラー、シートなどでは比較
的厚いものが用いられる。Relatively thick materials are used for foil house covers, various pillars, sheets, etc.
次に、実施例について本発明を説明する。Next, the present invention will be explained with reference to examples.
実施例
（Ａ成分）エチレン・プロピレン・５−エチリデン−２
−ノルボルネン３元共重合体ゴム；エチレン単位／プロ
ピレン単位（モル比）ニア８／２２゜ヨウ素価ｔＳ、ム
ーニー粘度（ＭＬ工゛、、 １２１℃）６１
（Ｂ成分）アイソタクチックポリプロピレン樹脂；メル
トインデックス１３ｇ／１０分（２３０℃）（Ｃ成分）
１，３−ビス（第３ブチルペルオキシイソプロビル）ベ
ンゼン２０重量％、ジビニルベンゼン３０重量％および
パラフィン系鉱油５０重量算よりなる混合物
上記（Ａ成分）７０重量部、（Ｂ成分）３０重量部およ
び（Ｃ成分）１重量部をヘンシェル・ミキサーで混合し
。Example (component A) ethylene/propylene/5-ethylidene-2
-Norbornene ternary copolymer rubber; ethylene unit/propylene unit (molar ratio) near 8/22° iodine value tS, Mooney viscosity (ML process, 121°C) 61 (Component B) Isotactic polypropylene resin; melt Index 13g/10min (230℃) (C component)
A mixture consisting of 20% by weight of 1,3-bis(tert-butylperoxyisopropyl)benzene, 30% by weight of divinylbenzene, and 50% by weight of paraffinic mineral oil. 70 parts by weight of the above (component A), 30 parts by weight of (component B), and (Component C) 1 part by weight was mixed using a Henschel mixer.
その後混合物を１２０〜１４０℃に予熱された密閉型バ
ンバリー・ミキサー中に移し、１８０〜１９０℃で１０
分間混線および架橋反応を行なった。The mixture was then transferred to a closed Banbury mixer preheated to 120-140°C and heated to 180-190°C for 10
Mixing and crosslinking reactions were carried out for minutes.
このようにして得られた部分架橋処理物７０重量部と低
密度ポリエチレン［密度０．９１７ｇ／ａＪ、メルト・
インデックス６．５ｇ／１０分（１９０℃）］３３０重
量とを押出機中で混合し、ポリオレフィン（ポリプロピ
レン＋低密度ポリエチレン）と部分架橋ゴムとが５１７
４９の重量比のブレンド体からなる熱可塑性エラストマ
ーを製造した。70 parts by weight of the partially crosslinked product thus obtained and low density polyethylene [density 0.917 g/aJ, melt
index 6.5 g/10 minutes (190°C)] and 330 weight in an extruder, polyolefin (polypropylene + low density polyethylene) and partially crosslinked rubber
A thermoplastic elastomer consisting of a blend with a weight ratio of 49 was produced.
このようにして製造された熱可塑性エラストマーを、東
芝製９０ｍｍψＴ−ダイ押出成形機を用いて、スクリュ
ーがフルフライト、Ｌ／Ｄ２２、押出温度２２０℃、■
−ダイがコートハンガーダイ、引取速度２．５ｍ１分で
シート状に押出し、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エチレンの架橋発泡体シ
ート（積木化学製品“ソフトロン″、発泡倍率３０倍、
厚さ３■鳳）と積層させた状態で一対のロール間を通し
、その際熱可塑性エラストマーシートはロール温度６０
℃のエンボス加工用ロール側に、また架橋発泡体シート
は加熱されていない通常ロール側に接触させるようにし
、表皮層が０．３ｍｍの厚さを有する積層体を製造した
。The thermoplastic elastomer thus produced was molded using a Toshiba 90 mm ψ T-die extrusion molding machine, with the screw in full flight, L/D 22, extrusion temperature 220°C,
- The die is a coat hanger die, and the sheet is extruded at a take-up speed of 2.5 m/min, and the extruded thermoplastic elastomer in the molten state is converted into a polyethylene crosslinked foam sheet (building block chemical product "Softlon", foaming ratio 30 times,
The thermoplastic elastomer sheet is passed between a pair of rolls in a laminated state with a thickness of 3 cm) at a roll temperature of 60°C.
The crosslinked foam sheet was brought into contact with the embossing roll at 0.degree. C., and the crosslinked foam sheet was brought into contact with the unheated normal roll to produce a laminate having a skin layer with a thickness of 0.3 mm.
これとは別に、タルクを３０％充填したポリプロピレン
から成形したプラスチックダンボール（ピッチ１０鳳■
、厚さ３■鳳）から自動車の天井材用骨材を成形するた
めに、雄型および雌型のホットプレスを用い、９５℃、
２Ｋｇ／ｄの加熱加圧条件下で４０秒間のプレス成形を
行ない、その間に１７０℃に予備加熱された前記積層体
を骨材成形品上に載置し、再度プレスして両者を熱成形
一体化させると、表面に艶のない天井材が得られた。こ
のようにして熱成形される積層体成形品において、熱可
塑性エラストマーを形成するブレンド体成分のエチレン
・α−オレフィン系共重合体ゴムとして非架橋物を用い
るとある程度の艶がその表面にみられ、またエチレン・
酢酸ビニル共重合体よりなる表皮層を設けたものでは艶
がはっきりと認められた。Separately, a plastic cardboard box (pitch 10 porcelain) made of polypropylene filled with 30% talc
, 3cm thick) to form aggregate for automobile ceiling materials, using male and female hot presses at 95°C.
Press molding was carried out for 40 seconds under heating and pressurizing conditions of 2 kg/d, during which time the laminate preheated to 170°C was placed on the aggregate molded product, and pressed again to thermoform the two into one piece. When oxidized, a ceiling material with a matte surface was obtained. In the laminate molded product that is thermoformed in this way, if a non-crosslinked ethylene/α-olefin copolymer rubber is used as the blend component that forms the thermoplastic elastomer, a certain degree of gloss may be observed on the surface. , and ethylene.
Gloss was clearly observed in those provided with a skin layer made of vinyl acetate copolymer.
また、前記積層体を３０ｃｍ Ｘ ３０ｃｍの大きさの
シートにカットし、それを１００℃のオーブン中に２時
間入れると、その収縮率は１．５％の値を示すにすぎな
いが、エチレン・α−オレフィン系共重合体の非架橋物
を用いたものおよびエチレン・酢酸ビニル共重合体の表
皮層を設けたものは、いずれも軟質ポリ塩化ビニルの表
皮層を設けたもの程ではないが。Furthermore, when the laminate is cut into a sheet of 30 cm x 30 cm and placed in an oven at 100°C for 2 hours, the shrinkage rate is only 1.5%. Both those using a non-crosslinked α-olefin copolymer and those with a skin layer of ethylene/vinyl acetate copolymer are not as good as those with a skin layer of soft polyvinyl chloride.
表面の溶融およびカール現象が認められる。Surface melting and curling phenomena are observed.
Claims (1)
に際して用いられる被処理物１００重量部当り０．１〜
２重量部の有機ペルオキシドを用い、多官能性化合物の
存在下に動的に熱処理して得られたエチレン・α−オレ
フィン系共重合体ゴムの部分架橋物とのブレンド体から
なり、表面がエンボス加工された熱可塑性エラストマー
層およびポリエチレンまたはポリプロピレンの発泡体層
を積層してなる積層体。 ２、熱可塑性エラストマー層が、ポリオレフィン系樹脂
とエチレン・α−オレフィン系共重合体ゴムの部分架橋
物を８０／２０〜２０／８０の重量比でブレンドしたブ
レンド体から形成された層である特許請求の範囲第１項
記載の積層体。 ３、発泡体層が架橋発泡体から形成された層である特許
請求の範囲第１項記載の積層体。 ４、熱可塑性エラストマー層および発泡体層の積層時に
エンボス加工用ロールを用いて熱可塑性エラストマー層
表面にエンボス加工を施した特許請求の範囲第１項記載
の積層体。 ５、ポリオレフィン系樹脂と熱可塑性エラストマー形成
に際して用いられる被処理物１００重量部当り０．１〜
２重量部の有機ペルオキシドを用い、多官能性化合物の
存在下に動的に熱処理して得られたエチレン・α−オレ
フィン系共重合体ゴムの部分架橋物とのブレンド体から
なり、表面がエンボス加工された熱可塑性エラストマー
層、ポリエチレンまたはポリプロピレンの発泡体層およ
びポリオレフィン系樹脂骨材層を順次積層してなる積層
体。 ６、熱可塑性エラストマー層が、ポリオレフィン系樹脂
とエチレン・α−オレフィン系共重合体ゴムの部分架橋
物を８０／２０〜２０／８０の重量比でブレンドしたブ
レンド体から形成された層である特許請求の範囲第５項
記載の積層体。 ７、発泡体層が架橋発泡体から形成された層である特許
請求の範囲第５項記載の積層体。 ８、ポリオレフィン系樹脂骨材を所定形状に成形し、成
形された骨材成形品に予備加熱された熱可塑性エラスト
マーと架橋発泡体との積層体を載置し、両者を熱成形し
て一体化した特許請求の範囲第５項記載の積層体。[Claims] 1. 0.1 to 100 parts by weight of the material to be treated used in forming the polyolefin resin and thermoplastic elastomer.
Consists of a blend with a partially crosslinked ethylene/α-olefin copolymer rubber obtained by dynamic heat treatment in the presence of a polyfunctional compound using 2 parts by weight of organic peroxide, and has an embossed surface. A laminate comprising a processed thermoplastic elastomer layer and a polyethylene or polypropylene foam layer. 2. A patent in which the thermoplastic elastomer layer is formed from a blend of partially crosslinked polyolefin resin and ethylene/α-olefin copolymer rubber in a weight ratio of 80/20 to 20/80. A laminate according to claim 1. 3. The laminate according to claim 1, wherein the foam layer is a layer formed from a crosslinked foam. 4. The laminate according to claim 1, wherein the surface of the thermoplastic elastomer layer is embossed using an embossing roll when the thermoplastic elastomer layer and the foam layer are laminated. 5. 0.1 to 100 parts by weight of the material to be treated used in forming polyolefin resin and thermoplastic elastomer
Consists of a blend with a partially crosslinked ethylene/α-olefin copolymer rubber obtained by dynamic heat treatment in the presence of a polyfunctional compound using 2 parts by weight of organic peroxide, and has an embossed surface. A laminate formed by sequentially laminating a processed thermoplastic elastomer layer, a polyethylene or polypropylene foam layer, and a polyolefin resin aggregate layer. 6. A patent in which the thermoplastic elastomer layer is formed from a blend of partially crosslinked polyolefin resin and ethylene/α-olefin copolymer rubber in a weight ratio of 80/20 to 20/80. The laminate according to claim 5. 7. The laminate according to claim 5, wherein the foam layer is a layer formed from a crosslinked foam. 8. Molding polyolefin resin aggregate into a predetermined shape, placing a laminate of preheated thermoplastic elastomer and crosslinked foam on the molded aggregate, and thermoforming the two to integrate them. A laminate according to claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34033789A JPH02258247A (en) | 1980-07-11 | 1989-12-28 | Laminated body |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9489880A JPS5720344A (en) | 1980-07-11 | 1980-07-11 | Laminate |
| JP34033789A JPH02258247A (en) | 1980-07-11 | 1989-12-28 | Laminated body |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9489880A Division JPS5720344A (en) | 1980-07-11 | 1980-07-11 | Laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02258247A true JPH02258247A (en) | 1990-10-19 |
| JPH0325346B2 JPH0325346B2 (en) | 1991-04-05 |
Family
ID=26436130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34033789A Granted JPH02258247A (en) | 1980-07-11 | 1989-12-28 | Laminated body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02258247A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0699522A1 (en) | 1994-09-05 | 1996-03-06 | Mitsui Petrochemical Industries, Ltd. | Lining sheet for vehicle ceiling and laminate using the same |
| US6331576B1 (en) | 1998-06-25 | 2001-12-18 | Nhk Spring Co Ltd | Surface-decorated foam skin of cross-linked rubbery soft olefin resin |
| US7144623B2 (en) | 2002-04-19 | 2006-12-05 | Mitsubishi Chemical Corporation | Thermoplastic elastomer composition and sheet, and laminate |
| US9260577B2 (en) | 2009-07-14 | 2016-02-16 | Toray Plastics (America), Inc. | Crosslinked polyolefin foam sheet with exceptional softness, haptics, moldability, thermal stability and shear strength |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5720344A (en) * | 1980-07-11 | 1982-02-02 | Mitsui Petrochemical Ind | Laminate |
-
1989
- 1989-12-28 JP JP34033789A patent/JPH02258247A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5720344A (en) * | 1980-07-11 | 1982-02-02 | Mitsui Petrochemical Ind | Laminate |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0699522A1 (en) | 1994-09-05 | 1996-03-06 | Mitsui Petrochemical Industries, Ltd. | Lining sheet for vehicle ceiling and laminate using the same |
| US6331576B1 (en) | 1998-06-25 | 2001-12-18 | Nhk Spring Co Ltd | Surface-decorated foam skin of cross-linked rubbery soft olefin resin |
| US7144623B2 (en) | 2002-04-19 | 2006-12-05 | Mitsubishi Chemical Corporation | Thermoplastic elastomer composition and sheet, and laminate |
| US9260577B2 (en) | 2009-07-14 | 2016-02-16 | Toray Plastics (America), Inc. | Crosslinked polyolefin foam sheet with exceptional softness, haptics, moldability, thermal stability and shear strength |
| US10301447B2 (en) | 2009-07-14 | 2019-05-28 | Toray Plastics (America), Inc. | Crosslinked polyolefin foam sheet with exceptional softness, haptics, moldability, thermal stability and shear strength |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0325346B2 (en) | 1991-04-05 |
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