JPH06234176A - Laminated composite - Google Patents
Laminated compositeInfo
- Publication number
- JPH06234176A JPH06234176A JP5021053A JP2105393A JPH06234176A JP H06234176 A JPH06234176 A JP H06234176A JP 5021053 A JP5021053 A JP 5021053A JP 2105393 A JP2105393 A JP 2105393A JP H06234176 A JPH06234176 A JP H06234176A
- Authority
- JP
- Japan
- Prior art keywords
- foam
- laminated composite
- skin material
- surface layer
- thickness direction
- 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
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリオレフィン系樹脂
発泡体及び表皮材からなる積層複合体に関し、詳しく
は、表層部分の強度及び柔軟性に優れたポリオレフィン
系樹脂発泡体が表皮材と良好に接着している積層複合体
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated composite comprising a polyolefin resin foam and a skin material, and more specifically, a polyolefin resin foam excellent in strength and flexibility of the surface layer portion can be used as a skin material. The present invention relates to a laminated composite that is adhered.
【０００２】[0002]
【従来の技術】ポリオレフィン系樹脂発泡体は、柔軟
性、断熱性に優れており、従来より、天井、ドア、イン
ストルメントパネル等の車両用内装材として用いられて
いる。これらの内装材は、主にポリオレフィン系樹脂発
泡体に、ポリ塩化ビニル樹脂シート、熱可塑性エラスト
マーシート、布状物、皮革等の表皮材が積層され、真空
成形、圧縮成形等により成形されるが、発泡体の表層部
分の強度が不足すると発泡体が破断してしまうことが多
く、発泡体と表皮材との接着性が低いと得られる内装材
の表面に膨れ、皺等が生じることが多い。2. Description of the Related Art Polyolefin-based resin foams are excellent in flexibility and heat insulation and have been conventionally used as interior materials for vehicles such as ceilings, doors and instrument panels. These interior materials are mainly polyolefin resin foams, laminated with polyvinyl chloride resin sheets, thermoplastic elastomer sheets, cloth-like materials, skin materials such as leather, and molded by vacuum molding, compression molding or the like. When the strength of the surface layer portion of the foam is insufficient, the foam often breaks, and when the adhesiveness between the foam and the skin material is low, the surface of the obtained interior material swells and wrinkles often occur. .
【０００３】そこで、発泡体の表層部分の強度を向上さ
せるために、特開平１−２２２９３７号公報では、表皮
材と積層される面の表層部分の発泡倍率を上げた発泡体
が提案され、特公昭５７−２６２０７号公報では、表層
部分の架橋度を上げた発泡体の製造方法が提案されてい
るが、どちらも表層部分の強度は向上するものの、硬化
し過ぎて発泡体の柔軟性が低下してしまうという欠点が
ある。Therefore, in order to improve the strength of the surface layer of the foam, Japanese Patent Laid-Open No. 1-222937 proposes a foam in which the expansion ratio of the surface layer of the surface laminated with the skin material is increased. Japanese Patent Publication No. 57-26207 proposes a method for producing a foam having an increased degree of cross-linking in the surface layer. In both cases, the strength of the surface layer is improved, but it is too hard and the flexibility of the foam is reduced. There is a drawback that it does.
【０００４】また、発泡体と表皮材との接着性を向上さ
せるために、特開昭６２−１９０２３５号公報では、気
泡の厚さ方向の直径の平均値を限定したポリエチレン系
樹脂発泡体の製造方法が提案され、特開平１−２２２９
２９号公報では、厚さ方向に圧縮されて気泡の厚さ方向
の直径が縮められたポリオレフィン系樹脂発泡体及びそ
の製造方法が提案され、特開平３−６２８３２号公報で
は、長さ方向及び幅方向に延伸されて気泡の厚さ方向の
直径が縮められたポリオレフィン系樹脂発泡体及びその
製造方法が提案されているが、いずれも表皮材との接着
性は向上するものの、発泡体の表層部分の強度は不十分
であるという欠点がある。Further, in order to improve the adhesiveness between the foam and the skin material, in JP-A-62-190235, there is manufactured a polyethylene resin foam in which the average value of the diameters of the cells in the thickness direction is limited. A method has been proposed and is disclosed in JP-A 1-2229
In JP-A No. 29-29632, there is proposed a polyolefin-based resin foam in which the diameter of the bubbles in the thickness direction is compressed by being compressed in the thickness direction, and a manufacturing method thereof. In JP-A-3-62832, a length direction and a width are proposed. Although a polyolefin resin foam in which the diameter in the thickness direction of the cells is contracted by stretching in the direction and a method for producing the same has been proposed, although the adhesion to the skin material is improved, the surface layer portion of the foam is also proposed. Has the disadvantage that its strength is insufficient.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記の欠点
に鑑み、表層部分の強度及び柔軟性に優れたポリオレフ
ィン系樹脂発泡体が表皮材と良好に接着している積層複
合体を提供することを目的とする。In view of the above drawbacks, the present invention provides a laminated composite in which a polyolefin resin foam excellent in strength and flexibility of the surface layer portion is well adhered to the surface material. The purpose is to
【０００６】[0006]
【課題を解決するための手段】本発明で使用されるポリ
オレフィン系樹脂発泡体の見かけ密度は、小さくなると
発泡体の表層部分の強度が低下し、大きくなると発泡体
の柔軟性が低下するため、０．０２〜０．２ｇ／ｃｍ3
に限定される。Since the apparent density of the polyolefin resin foam used in the present invention decreases, the strength of the surface layer portion of the foam decreases, and when the apparent density decreases, the flexibility of the foam decreases. 0.02-0.2g / cm 3
Limited to
【０００７】上記発泡体の１２０℃におけるキシレン抽
出残分値は、小さくなると発泡体の表層部分の強度が低
下し、大きくなると発泡体の柔軟性が低下するため、２
０〜８０重量％に限定される。When the xylene extraction residue value at 120 ° C. of the foam decreases, the strength of the surface layer of the foam decreases, and when it increases, the flexibility of the foam decreases.
It is limited to 0 to 80% by weight.
【０００８】上記残分値は、発泡体を０．１ｇ採取して
その気泡を潰し、温度１２０℃のキシレン５０ｍｌ中で
２４時間保持した後、２００メッシュの金網を透過させ
た残存物の乾燥重量（ｇ）を量り、次式（３）により算
出される。 残分値（重量％）＝（残存物の乾燥重量／０．１）×１００ （３）The above residual value was obtained by collecting 0.1 g of the foam, crushing the bubbles, maintaining the mixture in 50 ml of xylene at a temperature of 120 ° C. for 24 hours, and then allowing it to pass through a wire mesh of 200 mesh to obtain a dry weight of the residue. (G) is weighed and calculated by the following equation (3). Residual value (% by weight) = (dry weight of residue / 0.1) × 100 (3)
【０００９】上記発泡体中表皮材と積層される側の表面
から０．８ｍｍ以内の表層部分に中心が位置している全
気泡の厚さ方向の直径の平均値（ａ）は、小さくなると
隣接する気泡の間隔が小さくなって表層部分の強度が低
下し、大きくなると部分的に間隔の大きいところと小さ
いところができて発泡体の柔軟性が低下するため、０．
０５〜１ｍｍに限定される。なお、表皮材と積層される
側だけでなく、反対側の表層部分の気泡の形状が同様で
あってもよい。If the average value (a) of the diameters in the thickness direction of all the cells, the center of which is located in the surface layer within 0.8 mm from the surface on the side laminated with the skin material in the above-mentioned foam, becomes smaller, it becomes adjacent. Since the gap between the cells is reduced and the strength of the surface layer portion is reduced, and when the gap is increased, a portion with a large gap and a portion with a small gap are partially formed and the flexibility of the foam is reduced.
It is limited to 05 to 1 mm. The shape of the bubbles may be the same not only on the side laminated with the skin material but also on the surface layer portion on the opposite side.
【００１０】上記気泡の大きさを制御する方法として
は、例えば、熱分解型発泡剤を添加し、その分解温度以
上の所定温度に加熱された発泡炉内で樹脂を自由発泡さ
せる方法等が挙げられ、例としてアゾカルボンアミドを
用いる場合、温度が低くなると熱分解速度が遅くなって
気泡が小さくなり、温度が高くなると熱分解速度が速く
なって気泡が大きくなるため、２００〜２６０℃が好ま
しく、より好ましくは２１５〜２５０℃である。As a method of controlling the size of the bubbles, for example, a method of adding a thermal decomposition type foaming agent and free-foaming the resin in a foaming furnace heated to a predetermined temperature higher than the decomposition temperature thereof can be mentioned. In the case of using azocarbonamide as an example, the thermal decomposition rate becomes slower and the bubbles become smaller when the temperature becomes lower, and the thermal decomposition rate becomes faster and the bubbles become larger when the temperature becomes higher. , And more preferably 215 to 250 ° C.
【００１１】上記表層部分に中心が位置している全気泡
のうち、厚さ方向の直径が平均値（ａ）の値の±１５％
の範囲内にある気泡の数は、少なくなると発泡体の柔軟
性が低下するため、８０％以上に限定される。Of all the bubbles whose center is located on the surface layer, the diameter in the thickness direction is ± 15% of the average value (a).
If the number of cells within the range is smaller, the flexibility of the foam decreases, so it is limited to 80% or more.
【００１２】上記気泡の大きさを揃える方法としては、
例えば、粒径の揃った熱分解型発泡剤を用いて樹脂を発
泡させる方法等が挙げられ、その粒径は、小さくなると
発泡剤の熱分解速度が速くなって気泡が大きくなり、大
きくなると熱分解速度が遅くなって気泡が小さくなるた
め、３〜１４μｍが好ましく、より好ましくは４〜１１
μｍである。As a method for making the sizes of the bubbles uniform,
For example, there is a method of foaming a resin by using a pyrolytic foaming agent having a uniform particle size. When the particle size is smaller, the thermal decomposition rate of the foaming agent is faster and the bubbles are larger, and when it is larger, the thermal decomposition rate is higher. Since the decomposition rate becomes slower and the bubbles become smaller, it is preferably 3 to 14 μm, more preferably 4 to 11
μm.
【００１３】気泡の大きさを揃える方法としては、上記
以外にも、ミクロ分散されて強度にむらのない樹脂を用
いて発泡させる方法、両末端の（メタ）アクリロイルオ
キシ間に、好ましくは炭素数２〜１８のアルキレン基を
有する脂肪族２価アルコールのジ（メタ）アクリレー
ト、芳香族多価カルボン酸アリルエステル等の架橋助剤
により均一に架橋された樹脂を用いて発泡させる方法な
どが挙げられる。In addition to the above methods, a method of foaming using a resin that is micro-dispersed and has uniform strength, and a method in which the (meth) acryloyloxy at both ends is preferably carbon number Examples of the method include foaming using a resin uniformly crosslinked with a crosslinking aid such as di (meth) acrylate of an aliphatic dihydric alcohol having 2 to 18 alkylene groups and aromatic polyvalent carboxylic acid allyl ester. .
【００１４】更に、気泡の厚さ方向の直径を制御する方
法としては、例えば、熱分解型発泡剤を添加し発泡炉で
樹脂を連続して加熱発泡させる際に、炉内への樹脂の進
入速度に対し比較的小さい延伸比の巻取速度で巻き取る
方法等が挙げられ、巻取速度は、遅くなると直径が長く
なり、速くなると直径が短くなるため、進入速度０．５
〜２．５ｍ／秒に対し１〜５倍の巻取速度が好ましく、
より好ましくは１．５〜４倍である。Further, as a method of controlling the diameter of the bubbles in the thickness direction, for example, when a thermal decomposition type foaming agent is added and the resin is continuously heated and foamed in a foaming furnace, the resin enters the furnace. Examples of the method include a method of winding at a winding speed of a drawing ratio that is relatively small with respect to the speed. When the winding speed becomes slow, the diameter becomes long, and when it becomes fast, the diameter becomes short.
A winding speed of 1 to 5 times is preferable for ~ 2.5 m / sec,
It is more preferably 1.5 to 4 times.
【００１５】上記ポリオレフィン系樹脂発泡体の材料と
しては、例えば、エチレン、プロピレン、ブテン等の単
独重合体；エチレン、プロピレン及び炭素数４以上のα
−オレフィンからなる群より選ばれる２種以上のオレフ
ィンの共重合体；エチレンと、（メタ）アクリル酸、
（メタ）アクリル酸の低級アルキルエステル又は酢酸ビ
ニルとの共重合体等が挙げられ、これらの樹脂が単独で
用いられてもよいし併用されてもよい。Examples of the material of the polyolefin resin foam include homopolymers of ethylene, propylene, butene, etc .; ethylene, propylene and α having 4 or more carbon atoms.
A copolymer of two or more olefins selected from the group consisting of olefins; ethylene and (meth) acrylic acid,
Examples thereof include a lower alkyl ester of (meth) acrylic acid or a copolymer with vinyl acetate, and these resins may be used alone or in combination.
【００１６】上記炭素数４以上のα−オレフィンとして
は、例えば、１−ブテン、１−ペンテン、１−ヘキセ
ン、４−メチル−１ペンテン、１−オクテン等が挙げら
れる。Examples of the α-olefin having 4 or more carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1pentene, 1-octene and the like.
【００１７】上記ポリオレフィン系樹脂のメルトインデ
ックス（ＭＩ）は、小さくなると樹脂の成形性が低下
し、大きくなると得られる発泡体の耐熱性が低下するた
め、例えば、ポリエチレン系樹脂の場合２〜５０ｇ／１
０分が好ましく、より好ましくは３〜３０ｇ／１０分で
ある。また、ポリプロピレン系樹脂の場合０．３〜１２
ｇ／１０分が好ましく、より好ましくは０．５〜５ｇ／
１０分である。When the melt index (MI) of the polyolefin resin is small, the moldability of the resin is low, and when it is high, the heat resistance of the foam is low. 1
It is preferably 0 minutes, more preferably 3 to 30 g / 10 minutes. In the case of polypropylene resin, 0.3 to 12
g / 10 minutes is preferable, and more preferably 0.5 to 5 g /
10 minutes.
【００１８】上記ポリオレフィン系樹脂を発泡させる方
法としては、例えば、所定量のポリオレフィン系樹脂、
熱可塑性樹脂、架橋助剤、熱分解型発泡剤等を押出機に
供給し、溶融混練して押出して樹脂シートを得、得られ
た樹脂シートに電子線を所定量照射して架橋させ、得ら
れた架橋シートを発泡炉に供給して加熱発泡させる方
法、上記所定量の材料を押出機に供給し押出しと同時に
加熱ロールにて発泡させる方法、上記所定量の材料を金
型に供給し加熱してバッチ式に発泡させる方法等の従来
より公知の方法が挙げられる。As a method of foaming the above polyolefin resin, for example, a predetermined amount of polyolefin resin,
A thermoplastic resin, a crosslinking aid, a pyrolytic foaming agent, etc. are supplied to an extruder, melt-kneaded and extruded to obtain a resin sheet, and the obtained resin sheet is irradiated with a predetermined amount of an electron beam to be crosslinked to obtain a resin sheet. A method of supplying the crosslinked sheet thus obtained to a foaming furnace for heating and foaming, a method of supplying the above-mentioned predetermined amount of material to an extruder and foaming with a heating roll simultaneously with extrusion, and supplying the above-mentioned predetermined amount of material to a mold and heating. Then, a conventionally known method such as a method of foaming in a batch system can be used.
【００１９】上記熱可塑性樹脂としては、例えば、ポリ
塩化ビニル樹脂等が挙げられる。Examples of the thermoplastic resin include polyvinyl chloride resin and the like.
【００２０】上記架橋助剤としては、例えば、過酸化ベ
ンゾイル等のラジカル発生剤、ジビニルベンゼン、トリ
メチロールプロパントリ（メタ）アクリレート、１，６
−ヘキサンジオールジ（メタ）アクリレート、１，９−
ノナンジオールジ（メタ）アクリレート等の多官能性モ
ノマーなどが挙げられる。Examples of the crosslinking aid include radical generators such as benzoyl peroxide, divinylbenzene, trimethylolpropane tri (meth) acrylate, and 1,6.
-Hexanediol di (meth) acrylate, 1,9-
Examples thereof include polyfunctional monomers such as nonanediol di (meth) acrylate.
【００２１】上記熱分解型発泡剤としては、例えば、ア
ゾジカルボンアミド、ベンゼンスルホニルヒドラジド、
ジニトロソペンタメチレンテトラミン、トルエンスルホ
ニルヒドラジド、４，４−オキシビス（ベンゼンスルホ
ニルヒドラジド）等が挙げられる。Examples of the thermal decomposition type foaming agent include azodicarbonamide, benzenesulfonyl hydrazide,
Dinitrosopentamethylene tetramine, toluene sulfonyl hydrazide, 4,4-oxybis (benzene sulfonyl hydrazide) etc. are mentioned.
【００２２】上記ポリオレフィン系樹脂には、得られる
発泡体の特性を損なわない範囲内で、フェノール系、リ
ン系、アミン系、イオウ系等の抗酸化剤、金属害防止
剤、難燃剤、充填剤、帯電防止剤、顔料等が添加されて
もよい。The above-mentioned polyolefin-based resin includes phenol-based, phosphorus-based, amine-based, sulfur-based antioxidants, metal-damage-preventing agents, flame-retardants, and fillers as long as the properties of the resulting foam are not impaired. , Antistatic agents, pigments and the like may be added.
【００２３】本発明で使用される表皮材としては、従来
より公知の表皮材が使用可能であり、例えば、ポリ塩化
ビニル樹脂シート、熱可塑性エラストマーシート、布状
物、皮革等が挙げられ、接着剤により接着されたり、熱
ラミネートされたりして発泡体と積層される。As the skin material used in the present invention, conventionally known skin materials can be used, and examples thereof include a polyvinyl chloride resin sheet, a thermoplastic elastomer sheet, a cloth-like material, leather, and the like. It is laminated with the foam by being adhered with an agent or heat laminated.
【００２４】本発明の２で使用される発泡体は、１の発
明と同様に、見かけ密度が０．０２〜０．２ｇ／ｃ
ｍ3 、１２０℃におけるキシレン抽出残分値が２０〜８
０重量％に限定され、発泡体中の表層部分に中心が位置
している全気泡の厚さ方向の平均値（ａ）が０．０５〜
１ｍｍに限定される。The foam used in 2 of the present invention has an apparent density of 0.02 to 0.2 g / c as in the invention of 1.
m 3, 120 xylene extraction residue value at ℃ is 20-8
It is limited to 0% by weight, and the average value (a) in the thickness direction of all the cells whose center is located in the surface layer portion in the foam is 0.05 to
Limited to 1 mm.
【００２５】更に、上記発泡体は、平均値（ａ）と、厚
さ方向にそれぞれ直交している長さ方向及び幅方向の直
径の平均値（ｂ）及び平均値（ｃ）とが、下記式（１）
及び（２）を満たしていることが必要である。 ０．６≦（ａ）／（ｂ）≦１．５ （１） ０．６≦（ａ）／（ｃ）≦１．５ （２）Further, in the foam, the average value (a) and the average value (b) and the average value (c) of the diameters in the length direction and the width direction which are orthogonal to the thickness direction are as follows. Formula (1)
And (2) must be satisfied. 0.6 ≦ (a) / (b) ≦ 1.5 (1) 0.6 ≦ (a) / (c) ≦ 1.5 (2)
【００２６】上記（ａ）／（ｂ）及び（ａ）／（ｃ）の
値は、小さくなると発泡体の表層部分の強度が低下し、
大きくなると発泡体の柔軟性が低下するため、どちらも
上記式（１）及び（２）の範囲に限定される。As the values of (a) / (b) and (a) / (c) become smaller, the strength of the surface layer portion of the foam decreases,
Since the flexibility of the foam decreases as the size increases, both are limited to the ranges of the above formulas (1) and (2).
【００２７】上記（ａ）／（ｂ）及び（ａ）／（ｃ）の
値は、前記気泡の厚さ方向の直径を制御する方法により
制御される。即ち、熱分解型発泡剤を添加し発泡炉で樹
脂を連続して加熱発泡させる際に、炉内への樹脂の進入
速度に対し比較的小さい延伸比の巻取速度で巻き取る方
法等により制御される。The values of (a) / (b) and (a) / (c) are controlled by a method of controlling the diameter of the bubbles in the thickness direction. That is, when a thermal decomposition type foaming agent is added and the resin is continuously heated and foamed in a foaming furnace, it is controlled by a method such as winding at a winding speed that is a relatively small draw ratio with respect to the speed at which the resin enters the furnace. To be done.
【００２８】[0028]
【実施例】次に、本発明の実施例を説明する。なお、
「部」とあるのは「重量部」を意味する。 実施例１ （１）発泡体の製造 エチレン−プロピレン共重合体（エチレン含量３重量
％、メルトインデックス１．５ｇ／１０分）８０部、ポ
リエチレン（密度０．９３５ｇ／ｃｍ3 、メルトインデ
ックス７ｇ／１０分）２０部、架橋助剤としてトリメチ
ロールプロパントリメタクリレート１．５部及び１，９
−ノナンジオールジメタクリレート１．５部、熱分解型
発泡剤としてアゾジカルボンアミド１０部、酸化防止剤
として２，６−ジ−ｔ−ブチル−ｐ−クレゾール０．３
部及びジラウリルチオプロピオネート０．３部、金属害
防止剤としてメチルベンゾトリアゾール０．５部を単軸
押出機（池貝鉄工社製、型式：ＰＣＭ−３０）に供給
し、温度１９０℃で溶融混練して押し出し、厚さ１ｍｍ
の樹脂シートを得た。得られた樹脂シートに加速電圧４
００ｋＶで電子線４Ｍｒａｄを照射して架橋させ、得ら
れた架橋シートを縦型熱風発泡炉に供給し、炉内温度２
７０℃、進入速度１．６ｍ／秒、巻取速度８ｍ／秒で連
続的に延伸して加熱発泡させて発泡体を得た。EXAMPLES Next, examples of the present invention will be described. In addition,
"Parts" means "parts by weight". Example 1 (1) Production of foam 80 parts ethylene-propylene copolymer (ethylene content 3% by weight, melt index 1.5 g / 10 min), polyethylene (density 0.935 g / cm 3 , melt index 7 g / 10) Min) 20 parts, 1.5 parts of trimethylolpropane trimethacrylate as a crosslinking aid and 1,9
-1.5 parts of nonanediol dimethacrylate, 10 parts of azodicarbonamide as a thermal decomposition type foaming agent, and 2,6-di-t-butyl-p-cresol 0.3 as an antioxidant.
Parts and 0.3 parts of dilauryl thiopropionate and 0.5 parts of methylbenzotriazole as a metal damage inhibitor are supplied to a single-screw extruder (manufactured by Ikegai Tekko KK, model: PCM-30) at a temperature of 190 ° C. Melt kneading and extruding, thickness 1mm
A resin sheet of was obtained. The resulting resin sheet has an accelerating voltage of 4
Electron beam 4Mrad was irradiated at 00kV to crosslink, and the obtained crosslinked sheet was supplied to a vertical hot air foaming furnace to obtain an internal temperature of 2
A foamed body was obtained by continuously stretching at 70 ° C., an entry speed of 1.6 m / sec and a winding speed of 8 m / sec, and heat-foaming.
【００２９】（２）積層複合体の製造 得られた発泡体の表面をコロナ放電処理し、２液硬化型
ポリエステル系接着剤（ポリエステル：日立化成ポリマ
ー社製、商品名：ハイボン；イソシアネート：住友バイ
エルウレタン社製、商品名：ＤｅｓｍｏｄｕｒＲ）を用
い、厚さ０．６５ｍｍの塩化ビニル樹脂及びアクリロニ
トリル−ブタジエン−スチレン共重合樹脂の混合系シー
トと接着して積層複合体を得た。(2) Manufacture of Laminated Composite The surface of the obtained foam is subjected to corona discharge treatment, and a two-component curable polyester adhesive (polyester: manufactured by Hitachi Chemical Polymer Co., Ltd., trade name: Hibon; isocyanate: Sumitomo Bayer) Using a urethane company, trade name: Desmodur R), a 0.65 mm-thick vinyl chloride resin and an acrylonitrile-butadiene-styrene copolymer resin mixed sheet were adhered to obtain a laminated composite.
【００３０】実施例２ 実施例１と同様にして得られた発泡体を厚さ０．６５ｍ
ｍの熱可塑性ポリオレフィンシートと熱ラミネートして
積層複合体を得た。Example 2 A foam obtained in the same manner as in Example 1 had a thickness of 0.65 m.
m was laminated with a thermoplastic polyolefin sheet to obtain a laminated composite.
【００３１】実施例３及び４ 表１に示した所定量（部）の組成分を用い、所定量（Ｍ
ｒａｄ）の電子線を照射したこと以外は実施例１と同様
にして、発泡体及び積層複合体を得た。Examples 3 and 4 Using a predetermined amount (part) of the composition shown in Table 1, a predetermined amount (M
A foam and a laminated composite were obtained in the same manner as in Example 1 except that the electron beam (rad) was applied.
【００３２】[0032]
【表１】 [Table 1]
【００３３】実施例５ 上記表１に示した所定量（部）の組成分を６インチロー
ルに供給し、温度１７０℃、２０ｒｐｍで５分間混練し
た後、プレス成形機（神藤金属工業所製、型式：ＮＳＦ
−３７）にて温度１８０℃、圧力１００kg/cm2でプレス
成形し、厚さ１ｍｍの樹脂シートを得た。得られた樹脂
シートに加速電圧４００ｋＶで電子線３．２Ｍｒａｄを
照射して架橋させ、得られた架橋シートをオーブンに入
れ、温度２４０℃で６分間自由発泡させて発泡体を得
た。得られた発泡体を用い、実施例１と同様にして積層
複合体を得た。Example 5 A predetermined amount (part) of the composition shown in Table 1 above was supplied to a 6-inch roll and kneaded at a temperature of 170 ° C. and 20 rpm for 5 minutes, and then a press molding machine (manufactured by Shinto Metal Industry Co., Ltd., Model: NSF
-37) was press-molded at a temperature of 180 ° C. and a pressure of 100 kg / cm 2 to obtain a resin sheet having a thickness of 1 mm. The obtained resin sheet was irradiated with an electron beam of 3.2 Mrad at an acceleration voltage of 400 kV to be crosslinked, and the obtained crosslinked sheet was placed in an oven and freely foamed at a temperature of 240 ° C. for 6 minutes to obtain a foam. Using the obtained foam, a laminated composite was obtained in the same manner as in Example 1.
【００３４】比較例１及び２ 表２に示した所定量（部）の組成分を用い、所定量（Ｍ
ｒａｄ）の電子線を照射したこと以外は実施例１と同様
にして、発泡体及び積層複合体を得た。Comparative Examples 1 and 2 Using the predetermined amount (part) of the composition shown in Table 2, a predetermined amount (M
A foam and a laminated composite were obtained in the same manner as in Example 1 except that the electron beam (rad) was applied.
【００３５】[0035]
【表２】 [Table 2]
【００３６】比較例３ 実施例１と同様にして得られた架橋シートをオーブンに
入れ、温度３００℃で５分間自由発泡させて発泡体を得
た。得られた発泡体を用い、実施例１と同様にして積層
複合体を得た。Comparative Example 3 The crosslinked sheet obtained in the same manner as in Example 1 was placed in an oven and allowed to freely foam at a temperature of 300 ° C. for 5 minutes to obtain a foam. Using the obtained foam, a laminated composite was obtained in the same manner as in Example 1.
【００３７】比較例４ 実施例１と同様にして得られた樹脂シートに加速電圧４
００ｋＶで電子線１０Ｍｒａｄを照射して架橋させ、得
られた架橋シートをオーブンに入れ、温度２７０℃で５
分間自由発泡させて発泡体を得た。得られた発泡体を用
い、実施例１と同様にして積層複合体を得た。Comparative Example 4 An acceleration voltage of 4 was applied to a resin sheet obtained in the same manner as in Example 1.
Irradiate with electron beam 10 Mrad at 00 kV to crosslink, and put the obtained crosslinked sheet in an oven at 270 ° C. for 5
A foam was obtained by free foaming for a minute. Using the obtained foam, a laminated composite was obtained in the same manner as in Example 1.
【００３８】得られた発泡体の残分値（重量％）、見か
け密度 (ｇ／ｃｍ3)及び厚さ（ｍｍ）を測定し、その結
果を表３及び４に示した。The residual value (% by weight), apparent density (g / cm 3 ) and thickness (mm) of the resulting foam were measured, and the results are shown in Tables 3 and 4.
【００３９】[0039]
【表３】 [Table 3]
【００４０】[0040]
【表４】 [Table 4]
【００４１】更に、得られた発泡体の表層部分にある気
泡の厚さ方向の切片をとり、この切片を走査型電子顕微
鏡（日立製作所製、型式：Ｓ−２３００）にて倍率５０
倍で写真撮影して観察した。写真観察は、発泡体の表面
から０．８ｍｍ以内の表層部分の所定位置での一定面積
（１．８９ｍｍ2 ）中にある全気泡について、個数を数
え、厚さ方向の直径（ｍｍ）を測定してその平均値
（ａ）を計算し、平均値（ａ）±１５％の範囲内にある
気泡数（ｎ）の、全気泡数（Ｎ）に対する割合（％）を
計算し、得られた結果を上記表３及び４に示した。Furthermore, a slice in the thickness direction of the cells in the surface layer portion of the obtained foam was taken, and this slice was taken with a scanning electron microscope (Hitachi, model: S-2300) at a magnification of 50.
I took a picture with double and observed. In the photograph observation, the total number of all the bubbles in a certain area (1.89 mm 2 ) at a predetermined position of the surface layer within 0.8 mm from the surface of the foam is counted, and the diameter (mm) in the thickness direction is measured. Then, the average value (a) was calculated, and the ratio (%) of the number of bubbles (n) within the range of the average value (a) ± 15% to the total number of bubbles (N) was calculated and obtained. The results are shown in Tables 3 and 4 above.
【００４２】次に、得られた積層複合体を用い、外観を
観察して評価した後、Ｈ／Ｄ値を測定して発泡体の表層
部分の強度及び柔軟性を評価し、剥離強度を測定して発
泡体と表皮材との接着性を評価し、得られた結果を表５
に示した。Next, using the obtained laminated composite, the appearance was observed and evaluated, and then the H / D value was measured to evaluate the strength and flexibility of the surface layer portion of the foam, and the peel strength was measured. The adhesiveness between the foam and the skin material was evaluated, and the obtained results are shown in Table 5.
It was shown to.
【００４３】[0043]
【表５】 [Table 5]
【００４４】上記外観は、目視にて、膨れ、へこみ、表
面荒れ等が観察されない場合は○、１箇所でも観察され
る場合は×とした。The above appearance was evaluated as ◯ when swelling, dents, surface roughness and the like were not visually observed, and was evaluated as x when even one spot was observed.
【００４５】上記Ｈ／Ｄ値は、得られた積層複合体を遠
赤外線ヒーターで加熱して発泡体の表層部分の温度を１
５０〜１６０℃に昇温し、直径１００ｍｍの円柱状メス
型金型を用いて真空成形し、得られた成形品の深さＨ
（ｃｍ）及び直径Ｄ（ｃｍ）を測定してその比Ｈ／Ｄを
計算した。The above H / D value was obtained by heating the obtained laminated composite with a far-infrared heater and setting the temperature of the surface layer of the foam to 1
The temperature is raised to 50 to 160 ° C., vacuum molding is performed using a cylindrical female die having a diameter of 100 mm, and the depth H of the obtained molded product is H.
(Cm) and diameter D (cm) were measured, and the ratio H / D was calculated.
【００４６】上記剥離強度は、得られた積層複合体を切
断して製造した幅２５ｍｍ、長さ１００ｍｍの試験片を
用い、オートグラフ（島津製作所製、型式：ＤＣＳ−５
０００）にて温度２０℃又は１２０℃で５分間保持した
後、同一温度で剥離させた際の強度（ｋｇ／２５ｍｍ）
を測定した。The peel strength was measured by using a test piece having a width of 25 mm and a length of 100 mm produced by cutting the obtained laminated composite, and using an autograph (manufactured by Shimadzu Corporation, model: DCS-5).
000) at 20 ° C or 120 ° C for 5 minutes and then peeled at the same temperature (kg / 25mm)
Was measured.
【００４７】実施例６ 表６に示した所定量（部）の組成分を用い、加速電圧５
００ｋＶで所定量（Ｍｒａｄ）の電子線を照射したこと
以外は実施例１と同様にして発泡体を得、得られた発泡
体を用い、実施例１と同様にして積層複合体を得た。な
お、実際に用いた電子線照射量（Ｍｒａｄ）、縦型熱風
発泡炉の炉内温度（℃）、架橋シートの進入速度（ｍ／
秒）及び発泡体の巻取速度（ｍ／秒）を表７に示した。Example 6 Using a predetermined amount (part) of the composition shown in Table 6, an accelerating voltage of 5
A foam was obtained in the same manner as in Example 1 except that a predetermined amount (Mrad) of electron beam was irradiated at 00 kV, and the obtained foam was used to obtain a laminated composite in the same manner as in Example 1. In addition, the electron beam irradiation amount (Mrad) actually used, the furnace temperature (° C.) of the vertical hot air foaming furnace, the cross-linking sheet entry speed (m / m)
Second) and the winding speed (m / sec) of the foam are shown in Table 7.
【００４８】[0048]
【表６】 [Table 6]
【００４９】[0049]
【表７】 [Table 7]
【００５０】実施例７ 実施例６と同様にして得られた発泡体を用い、実施例２
と同様にして積層複合体を得た。Example 7 Using the foam obtained in the same manner as in Example 6, Example 2
A laminated composite was obtained in the same manner as in.
【００５１】実施例８ 上記表６に示した所定量（部）の組成分を用い、上記表
７に示した所定の電子線照射量（Ｍｒａｄ）、炉内温度
（℃）、進入速度（ｍ／秒）及び巻取速度（ｍ／秒）の
条件を用いたこと以外は実施例６と同様にして発泡体を
得た。得られた発泡体を用い、実施例１と同様にして積
層複合体を得た。Example 8 Using the prescribed amount (part) of the composition shown in Table 6 above, the prescribed electron beam irradiation dose (Mrad), furnace temperature (° C.) and entry speed (m) shown in Table 7 above were used. / Sec) and a winding speed (m / sec) were used to obtain a foam in the same manner as in Example 6. Using the obtained foam, a laminated composite was obtained in the same manner as in Example 1.
【００５２】実施例９ 実施例６と同様にして得られた架橋シートをオーブンに
入れ、温度２５０℃で長さ方向に５ g/cm2の荷重をかけ
ながら５分間発泡させて発泡体を得た。得られた発泡体
を用い、実施例１と同様にして積層複合体を得た。Example 9 The crosslinked sheet obtained in the same manner as in Example 6 was placed in an oven and foamed for 5 minutes at a temperature of 250 ° C. while applying a load of 5 g / cm 2 in the longitudinal direction to obtain a foamed product. It was Using the obtained foam, a laminated composite was obtained in the same manner as in Example 1.
【００５３】実施例１０ 厚さ方向に５ g/cm2の荷重をかけながら発泡させたこと
以外は実施例９と同様にして発泡体を得た。得られた発
泡体を用い、実施例１と同様にして積層複合体を得た。Example 10 A foam was obtained in the same manner as in Example 9 except that foaming was performed while applying a load of 5 g / cm 2 in the thickness direction. Using the obtained foam, a laminated composite was obtained in the same manner as in Example 1.
【００５４】比較例５〜７ 上記表７に示した所定の電子線照射量（Ｍｒａｄ）、炉
内温度（℃）、進入速度（ｍ／秒）及び巻取速度（ｍ／
秒）の条件を用いたこと以外は実施例６と同様にして発
泡体を得た。得られた発泡体を用い、実施例１と同様に
して積層複合体を得た。Comparative Examples 5 to 7 Predetermined electron beam irradiation dose (Mrad), furnace temperature (° C), penetration speed (m / sec) and winding speed (m /) shown in Table 7 above.
A foam was obtained in the same manner as in Example 6 except that the condition of (sec) was used. Using the obtained foam, a laminated composite was obtained in the same manner as in Example 1.
【００５５】比較例８ 厚さ方向に４０ g/cm2の荷重をかけながら発泡させたこ
と以外は実施例９と同様にして発泡体を得た。得られた
発泡体を用い、実施例１と同様にして積層複合体を得
た。Comparative Example 8 A foam was obtained in the same manner as in Example 9 except that foaming was performed while applying a load of 40 g / cm 2 in the thickness direction. Using the obtained foam, a laminated composite was obtained in the same manner as in Example 1.
【００５６】得られた発泡体の残分値（重量％）、見か
け密度 (ｇ／ｃｍ3)及び厚さ（ｍｍ）を測定し、その結
果を表８及び９に示した。The residual value (% by weight), apparent density (g / cm 3 ) and thickness (mm) of the obtained foam were measured, and the results are shown in Tables 8 and 9.
【００５７】[0057]
【表８】 [Table 8]
【００５８】[0058]
【表９】 [Table 9]
【００５９】更に、得られた発泡体の表層部分にある気
泡の厚さ方向及び厚さ方向に直交する方向の切片をそれ
ぞれとり、この切片を走査型電子顕微鏡（日立製作所
製、型式：Ｓ−２３００）にて倍率６０倍で写真撮影し
て観察した。写真観察は、発泡体の表面から０．８ｍｍ
の表層部分の所定位置で一定面積（１．８９ｍｍ2 ）中
にある全気泡について、厚さ方向の直径、厚さ方向と直
交している長さ方向及び幅方向の直径をそれぞれ測定
し、厚さ方向の直径の平均値（ａ）、長さ方向の直径の
平均値（ｂ）及び幅方向の直径の平均値（ｃ）並びに平
均値の比（ａ）／（ｂ）及び（ａ）／（ｃ）を計算し、
得られた結果を上記表８及び９に示した。Further, a section in the thickness direction of the cells in the surface layer portion of the obtained foam and a section in the direction orthogonal to the thickness direction were respectively taken, and these sections were taken with a scanning electron microscope (manufactured by Hitachi Ltd., model: S- 2300) and photographed at a magnification of 60 times and observed. The photograph is 0.8 mm from the surface of the foam.
The thickness in the thickness direction and the diameters in the length and width directions orthogonal to the thickness direction are measured for all the bubbles in a certain area (1.89 mm 2 ) at the predetermined position of the surface layer of Mean value of diameter in the depth direction (a), mean value of diameter in the length direction (b) and mean value of diameter in the width direction (c), and ratio of mean values (a) / (b) and (a) / Calculate (c),
The obtained results are shown in Tables 8 and 9 above.
【００６０】次に、得られた積層複合体を用い、実施例
１と同様にして外観、発泡体の表層部分の強度及び柔軟
性、発泡体と表皮材との接着性を評価し、得られた結果
を表１０に示した。Next, using the obtained laminated composite, the appearance, the strength and flexibility of the surface layer portion of the foam, and the adhesiveness between the foam and the skin material were evaluated in the same manner as in Example 1 to obtain the product. The results are shown in Table 10.
【００６１】[0061]
【表１０】 [Table 10]
【００６２】[0062]
【発明の効果】本発明の積層複合体の構成は上述の通り
であるから、発泡体の表層部分の強度及び柔軟性に優
れ、発泡体と表皮材とが良好に接着しており、表面に膨
れ、皺等のない成形品が得られる。The structure of the laminated composite of the present invention is as described above, and therefore the strength and flexibility of the surface layer portion of the foam are excellent, the foam and the skin material are well adhered, and A molded product free from swelling and wrinkles can be obtained.
Claims (2)
3 、１２０℃におけるキシレン抽出残分値２０〜８０重
量％のポリオレフィン系樹脂発泡体及び表皮材からなる
積層複合体であって、上記発泡体は、少なくとも表皮材
と積層される側の表面から０．８ｍｍ以内の表層部分に
中心が位置している全気泡の厚さ方向の直径の平均値
（ａ）が０．０５〜１ｍｍであり、上記気泡のうち、厚
さ方向の直径が平均値（ａ）の値の±１５％の範囲内に
ある気泡の数が８０％以上であることを特徴とする積層
複合体。1. Apparent density 0.02-0.2 g / cm
3. A laminated composite comprising a polyolefin resin foam having a xylene extraction residue value of 20 to 80% by weight at 120 ° C. and a skin material, wherein the foam is at least 0 from the surface on the side laminated with the skin material. The average value (a) of the diameters in the thickness direction of all the bubbles whose center is located in the surface layer portion within 0.8 mm is 0.05 to 1 mm, and the diameter in the thickness direction of the bubbles is the average value ( A laminated composite characterized in that the number of bubbles within the range of ± 15% of the value of a) is 80% or more.
3 、１２０℃におけるキシレン抽出残分値２０〜８０重
量％のポリオレフィン系樹脂発泡体及び表皮材からなる
積層複合体であって、上記発泡体は、少なくとも表皮材
と積層される側の表面から０．８ｍｍ以内の表層部分に
中心が位置している全気泡の厚さ方向の直径の平均値
（ａ）が０．０５〜１ｍｍであり、平均値（ａ）と、厚
さ方向にそれぞれ直交している長さ方向及び幅方向の直
径の平均値（ｂ）及び平均値（ｃ）とが、下記式（１）
及び（２）を満たしていることを特徴とする積層複合
体。 ０．６≦（ａ）／（ｂ）≦１．５ （１） ０．６≦（ａ）／（ｃ）≦１．５ （２）2. Apparent density 0.02-0.2 g / cm
3. A laminated composite comprising a polyolefin resin foam having a xylene extraction residue value of 20 to 80% by weight at 120 ° C. and a skin material, wherein the foam is at least 0 from the surface on the side laminated with the skin material. The average value (a) of the diameters in the thickness direction of all the bubbles whose center is located in the surface layer portion within 0.8 mm is 0.05 to 1 mm, and the average value (a) is orthogonal to the thickness direction. The average value (b) and the average value (c) of the diameters in the length direction and the width direction are expressed by the following formula (1).
And (2) are satisfied, The laminated composite characterized by the above-mentioned. 0.6 ≦ (a) / (b) ≦ 1.5 (1) 0.6 ≦ (a) / (c) ≦ 1.5 (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2105393A JP2914839B2 (en) | 1993-02-09 | 1993-02-09 | Laminated composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2105393A JP2914839B2 (en) | 1993-02-09 | 1993-02-09 | Laminated composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06234176A true JPH06234176A (en) | 1994-08-23 |
| JP2914839B2 JP2914839B2 (en) | 1999-07-05 |
Family
ID=12044172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2105393A Expired - Lifetime JP2914839B2 (en) | 1993-02-09 | 1993-02-09 | Laminated composite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2914839B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012214626A (en) * | 2011-03-31 | 2012-11-08 | Sekisui Chem Co Ltd | Cross-linked polyolefin-based resin foamed sheet and adhesive tape using the same |
| JP2013177630A (en) * | 2003-04-11 | 2013-09-09 | Sekisui Chem Co Ltd | Crosslinked polyolefin-based resin foamed sheet and adhesive tape |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01259936A (en) * | 1988-04-12 | 1989-10-17 | Toray Ind Inc | Laminated molded product and its manufacture |
| JPH02102034A (en) * | 1988-10-07 | 1990-04-13 | Toray Ind Inc | Interior molding form for vehicle |
-
1993
- 1993-02-09 JP JP2105393A patent/JP2914839B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01259936A (en) * | 1988-04-12 | 1989-10-17 | Toray Ind Inc | Laminated molded product and its manufacture |
| JPH02102034A (en) * | 1988-10-07 | 1990-04-13 | Toray Ind Inc | Interior molding form for vehicle |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013177630A (en) * | 2003-04-11 | 2013-09-09 | Sekisui Chem Co Ltd | Crosslinked polyolefin-based resin foamed sheet and adhesive tape |
| JP2012214626A (en) * | 2011-03-31 | 2012-11-08 | Sekisui Chem Co Ltd | Cross-linked polyolefin-based resin foamed sheet and adhesive tape using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2914839B2 (en) | 1999-07-05 |
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