JPS6156094B2 - - Google Patents
Info
- Publication number
- JPS6156094B2 JPS6156094B2 JP8367982A JP8367982A JPS6156094B2 JP S6156094 B2 JPS6156094 B2 JP S6156094B2 JP 8367982 A JP8367982 A JP 8367982A JP 8367982 A JP8367982 A JP 8367982A JP S6156094 B2 JPS6156094 B2 JP S6156094B2
- Authority
- JP
- Japan
- Prior art keywords
- laminate
- primer layer
- sheet
- weight
- chloroprene
- 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.)
- Expired
Links
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 21
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 16
- 239000006260 foam Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 11
- 229920005672 polyolefin resin Polymers 0.000 claims description 9
- 229920003051 synthetic elastomer Polymers 0.000 claims description 8
- 239000005061 synthetic rubber Substances 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- -1 polyethylene Polymers 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004049 embossing Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Description
【発明の詳細な説明】
本発明は自動車の内装材等として好適に用いら
れる積層体に関する。
従来自動車の天井、ドア等の内装材料は、所定
形状に成形されたレジンフエルト、合成樹脂板、
金属板等の基材に接着剤を塗布し、該基材を型材
として内装材を真空成形、プレス成形等の方法に
より、加熱成形すると共に基材に接着することに
よつて製造されている。上記接着剤としてはクロ
ロプレン系接着剤が使用され、内装材としては軟
質もしくは半硬質塩化ビニルシートとポリオレフ
イン系樹脂発泡シートとの積層体が使用されてお
り、内装材と基材とが確実に接着されるように、
予めポリオレフイン系樹脂発泡シートにプライマ
ー層としてクロロプレン系樹脂層が積層されてい
る。
しかしながら上記積層体は長尺体となされ、ロ
ール状に巻き取つて保管及び輪送されるのである
が、ロール状になされると塩化ビニルシートとク
ロロプレン系樹脂層とは重ね合わされ、塩化ビニ
ルシートに含まれる可塑剤がクロロプレン系樹脂
層に移行し、クロロプレン系樹脂が粘着性を有す
るようになり、積層体同志が相互に接着して、い
わゆるブロツキングを起してしまい、ロール状体
から積層体を剥離するのが困難になり、剥離でき
ても塩化ビニルシートの外観が損なわれると共に
耐熱性、耐候性等が低下するという欠点があつ
た。
又ブロツキングを防止するために離型紙やポリ
エチレンシートをはさんでロール状に巻き取るこ
とも行なわれているが、離型紙やポリエチレンシ
ートは使い捨てなので費用が高くつき、又離型紙
やポリエチレンシートを積層体と共に巻き取る工
程及び積層体から剥離し、除去する工程が必要な
ので作業効率が悪いという欠点があつた。
本発明は上記欠点に鑑み、塩化ビニルシートと
ポリオレフイン系樹脂発泡シートよりなり、自動
車の内装材等として好適に使用される積層体であ
つて、基材と接着する際に確実かつ強固に接着さ
れるように発泡シートにプライヤー層が形成され
ているが、ロール状にして保存してもブロツキン
グをおこさない積層体を提供せんとしてなされた
ものであつて、その要旨は、ポリオレフイン系樹
脂発泡シートの一面に軟質もしくは半硬質塩化ビ
ニルシートが積層され、他面に、クロロプレン系
合成ゴムにアクリル系ビニルモノマーがグラフト
重合されたグラフト化物を主体となるプライマー
層が積層されてなる積層体に存する。
本発明におけるポリオレフイン系樹脂発泡シー
トとは、ポリエチレン、ポリプロピレン等のポリ
オレフイン樹脂、エチレン―酢酸ビニル共重合
体、エチレン―メタクリル酸エステル共重合体、
エチレン―プロピレン共重合体等のオレフインと
他のモノマーの共重合体及びこれらを含む混合物
から製された発泡シートであつて、見掛け密度が
0.02〜0.7ｇ／cm3であり、軟質のものが好まし
い。
本発明における軟質もしくは半硬塩化ビニルシ
ートとは、ポリ塩化ビニル樹脂又は塩化ビニルを
50重量％以上含有する他のモノマーとの共重合体
と、ジオクチルフタレート、ジオクチルアジペー
ト等の可塑剤を主体とする、軟質もしくは半硬質
のシートであり、さらにABS樹脂、メタクリル
酸メチル―ポリブタジエングラフト重合体などの
改質材、充填材、着色剤等が添加されてもよい。
本発明においては上記ポリオレフイン系樹脂発
泡シートは塩化ビニルシートの一面に積層される
のであるが、積層は任意の方法が採用されてよ
く、たとえば熱融着する方法、接着剤で接着する
方法等があげられる。
本発明におけるプライヤー層はクロロプレン系
合成ゴムにアクリル系ビニルモノマーがグラフト
重合されたグラフト化物を主体とする層である。
上記クロロプレン系合成ゴムとは、クロロプレ
ンの単独重合体及びクロロプレンを含む共重合体
であり、アクリレ系ビニルモノマーとしては、た
とえば、アクリル酸メチル、アクリル酸エチル、
メタクリル酸メチルなどのアクリル酸もしはメタ
クリル酸のエステル、アクリルアミド、アクリル
イミド、アクリル酸、メタクリル酸等があげら
れ、アクリル酸ビニルモノマーのグラフトする量
はクロロプレン系合成ゴムとアクリル系ビニルモ
ノマーとよりなるグラフト化物中10〜50重量％で
あるのが好ましい。
そしてグラフト化物は上記クロロプレン系合成
ゴムに上記アクリル系ビニルモノマーをクラフト
重合することによつて得られるが、アクリロニト
リル、スチレン、酢酸ビニル、ビニルピリジン等
の重合性ビニルモノマーをアクリル系ビニルモノ
マーより少量、好ましくは2/3以下の範囲で共重
合せしめてもよい。
本発明においては、プライマー層は上記発泡シ
ートの他面に積層されるのであり、積層方法は任
意の方法が採用されてよいが、上記グラフト重合
を溶液重合もしくはエマルジヨン重合で行い、得
られた重合組成物を発泡シートに塗布乾燥するこ
とによつて形成する方法が採用されるのが好まし
い。尚重合組成物の固形分濃度は５〜25重量％に
なされるのが好ましい。
又この場合プライマー層が上記発泡シートに対
してより強固に接着され、ブロツキング性をより
低下せしめるために、重合組成物に多官能性イソ
シアネートが添加されるのが好ましい。該イソシ
アネートはイソシアネート基の含有量が多くなつ
たり、添加量が多くなると、プライマー層の熱活
性が低下するので、イソシアネート基を25〜60重
量％含有する多官能性イソシアネートが好まし
く、その添加量はグラフト化物100重量部に対し
１〜15重量部であるのが好ましい。
上記多官能性イソシアネートとしては、たとえ
ばトルエンジイソシアネート、ジフエニルメタン
―４，4′―ジイソシアネート、トリフエニル―メ
タン―トリイソシアネート、チオリン酸トリス
（Ｐ―イソシアネートフエニル）エステル等があ
げられる。
又プライマー層には、さらに粘着付与剤、充填
材、抗酸化剤等が添加されてもよい。
又さらにプライマー層のブロツキング性を低下
せしめるために、プライマー層及び発泡シートに
エンボス加工を施こしても良い。尚エンボス加工
を施すと基材に対する接着性も低下するので、本
発明の積層体を基材に加熱成形して接着する際の
加熱温度でエンボス加工した部分が平滑に戻るよ
うに該加熱温度よりも低い温度でエンボス加工は
施されるのが好ましい。
本発明の積層体の構成は上述の通りであり、グ
ラフト化物はクロロプレン系合成ゴムの部分とア
クリル系重合体の部分を有し、クロロプレン系合
成ゴムはポリオレフイン系樹脂発泡体及びクロロ
プレン系接着剤との接着性がすぐれ、アクリル系
重合体は可塑剤の移行性が極めて少ないので、プ
ライマー層はポリオレフイン系樹脂発泡シートに
強固に接着されており、クロロプレン系接着剤と
の接着性がすぐれ、ロール状に巻いておいても塩
化ビニルシートから可塑剤が移行せずブロツキン
グをおこさない。
従つて本発明の積層体はロール状にして保存し
てもブロツキングをおこさず、離型紙、ポリエチ
レンシート等を積層しておく必要がないので作業
性よく使用することができ、又塩化ビニルシート
の外観が損なわれたり、耐熱性、耐候性等が低下
することがなく、クロロプレン系接着剤によつて
基材に容易かつ確実に接着することができるか
ら、自動車の内装材等として好適に使用される。
次に本発明を実施例を参照して説明する。
実施例及び比較例
塩化ビニル樹脂（重合度1200）100重量部、ジ
オクチルフタレート40重量部、錫系安定剤２重量
部及び顔料0.5重量部よりなる、厚さ0.35mmの軟
質塩化ビニルシートと、厚さ３mm、見掛密度
0.035ｇ／cm3のポリエチレン発泡シートをウレタ
ン系接着剤で接着して積層シートを得、次に下記
の如くプライマー層を積層して試料を得た。尚試
料１及び２が比較例であり、試料３〜５が実施例
である。
試料 １
上記積層シートの発泡シートに、クロロプレン
系接着剤（エスダイン2017P、積水化学社製）を
塗布し、50℃で５分間乾燥して５ｇ／m2のプライ
マー層を形成し積層体を得た。プライマー層は無
色で、少し粘着性を有していた。
試料 ２
上記層シートの発泡シートに、ウレタン系接着
剤（ボスチツク7662、ボスチツク日本社製）100
重量部とトリイソシアネート（デスモジユール
Ｒ、バイエル社製）３重量部よりなる配合物を20
ｇ／m2（ウエツト）塗布し、30℃で24時間熟成し
てプライマー層を形成し、積層体を得た。プライ
マー層は透明であり、表面はさらさらであつた。
試料 ３
上記積層シートの発泡シートにポリクロロプレ
ンにメタクリル酸メチルが40重量％グラフト重合
されたグラフト化物の固形分濃度が15重量％の重
合組成物（溶剤はトルエン）を25ｇ／m2（ウエツ
ト）塗布し、50℃で15分間乾燥してプライマー層
を形成し本発明の積層体を得た。プライマー層は
うすい黄色であり、粘着性はなかつた。
試料 ４
上記積層シートの発泡シートに、上記重合組成
物100重量部にトリイソシアネート（デスモジユ
ールＲ、バイエル社製）３重量部を添加した配合
物を25ｇ／m2（ウエツト）塗布し、30℃で24時間
熟成してプライマー層を形成し、本発明の積層体
を得た。プライマー層はうすい赤色であり、粘着
性はなかつた。
試料 ５
上記積層シートの発泡シートに、試料４で使用
した配合物を25ｇ／m2（ウエツト）塗布し、50℃
で２分間乾燥し、210℃で５秒間加熱し、次に90
℃で絹目のエンボス加工を行つて、プライマー層
を形成し、本発明の積層体を得た。プライマー層
はうすい赤色であり、粘着性はなかつた。
上記試料１〜５について、プライマー層の接着
試験、ブロツキングテスト、及び積層体とレジン
フエルトとの接着試験を行い結果を第１表に示し
た。
尚、プライマー層の接着試験は積層シートとプ
ライマー層を手で剥離し、剥離状態を観察した。
ブロツキングテストは積層体を100mm×100mmの大
きさに切断し、プライマー層と軟質塩化ビニルシ
ートを重ね合せ、20ｇ／cm2の荷重を加え、50℃で
24時間放置した後プライマー層と軟質塩化ビニル
シートを剥離し、ブロツキング状態を観察した。
又積層体とレジンフエルトとの接着試験はレジン
フエルトにクロロプレン系接着剤（エスダイン
271、積水化学社製）を200ｇ／cm2（ウエツト）塗
布し、乾燥し、積層体のプライマー層を120℃で
加熱圧着し、冷却後積層体とレジンフエルトを手
で剥離し、剥離状態を観察した。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a laminate suitable for use as an interior material for automobiles. Traditionally, interior materials for automobile ceilings, doors, etc. are made of resin felt molded into a predetermined shape, synthetic resin plates,
It is manufactured by applying an adhesive to a base material such as a metal plate, using the base material as a molding material, and heat-forming the interior material by a method such as vacuum forming or press molding, and adhering it to the base material. A chloroprene adhesive is used as the above adhesive, and a laminate of a soft or semi-hard vinyl chloride sheet and a polyolefin resin foam sheet is used as the interior material, ensuring reliable adhesion between the interior material and the base material. To be,
A chloroprene resin layer is laminated as a primer layer on a polyolefin resin foam sheet in advance. However, the above-mentioned laminate is made into a long body and is wound up into a roll for storage and transportation, but when it is made into a roll, the vinyl chloride sheet and the chloroprene resin layer are overlapped, and the vinyl chloride sheet and the chloroprene resin layer are overlapped. The contained plasticizer migrates to the chloroprene resin layer, the chloroprene resin becomes sticky, and the laminates adhere to each other, causing so-called blocking, which makes it difficult to remove the laminate from the roll. It becomes difficult to peel it off, and even if it can be peeled off, the appearance of the vinyl chloride sheet is impaired and its heat resistance, weather resistance, etc. are reduced. In order to prevent blocking, release paper or polyethylene sheets are also sandwiched and wound into rolls, but release paper and polyethylene sheets are disposable and are expensive, and release paper and polyethylene sheets are laminated. Since the process of winding up the laminate together with the laminate and the process of peeling it off and removing it from the laminate are required, the work efficiency is low. In view of the above-mentioned drawbacks, the present invention is a laminate consisting of a vinyl chloride sheet and a polyolefin resin foam sheet, which is suitably used as an interior material for automobiles, etc. Although a plier layer is formed on a foam sheet as shown in the figure, this was done in an attempt to provide a laminate that does not cause blocking even when stored in a roll form. It consists of a laminate in which a soft or semi-hard vinyl chloride sheet is laminated on one side, and a primer layer mainly composed of a grafted product obtained by graft polymerizing an acrylic vinyl monomer to a chloroprene synthetic rubber is laminated on the other side. The polyolefin resin foam sheet in the present invention refers to polyolefin resins such as polyethylene and polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid ester copolymer,
A foam sheet made from a copolymer of olefin such as ethylene-propylene copolymer and other monomers, or a mixture containing these, with an apparent density of
It is 0.02 to 0.7 g/cm 3 and preferably soft. In the present invention, the soft or semi-hard vinyl chloride sheet refers to polyvinyl chloride resin or vinyl chloride.
It is a soft or semi-rigid sheet mainly composed of a copolymer with other monomers containing 50% by weight or more and a plasticizer such as dioctyl phthalate or dioctyl adipate, and also contains ABS resin, methyl methacrylate-polybutadiene graft polymer. Modifiers such as coalescents, fillers, colorants, etc. may be added. In the present invention, the polyolefin resin foam sheet is laminated on one side of the vinyl chloride sheet, but any method may be used for lamination, such as heat-sealing, adhesive bonding, etc. can give. The plier layer in the present invention is a layer mainly composed of a grafted product obtained by graft polymerizing an acrylic vinyl monomer onto a chloroprene synthetic rubber. The above-mentioned chloroprene-based synthetic rubber refers to a chloroprene homopolymer and a copolymer containing chloroprene, and examples of the acrylate-based vinyl monomer include methyl acrylate, ethyl acrylate,
Examples include esters of acrylic acid or methacrylic acid such as methyl methacrylate, acrylamide, acrylimide, acrylic acid, methacrylic acid, etc., and the amount of vinyl acrylate monomer grafted is determined by the amount of chloroprene-based synthetic rubber and acrylic vinyl monomer. It is preferably 10 to 50% by weight in the grafted product. The grafted product can be obtained by craft polymerizing the acrylic vinyl monomer to the chloroprene synthetic rubber, but by adding a small amount of a polymerizable vinyl monomer such as acrylonitrile, styrene, vinyl acetate, or vinyl pyridine to the acrylic vinyl monomer. Preferably, the amount of copolymerization may be 2/3 or less. In the present invention, the primer layer is laminated on the other surface of the foam sheet, and any method may be used as the lamination method, but the graft polymerization is performed by solution polymerization or emulsion polymerization, and the resulting It is preferable to adopt a method of forming the composition by applying the composition to a foam sheet and drying it. The solid content concentration of the polymer composition is preferably 5 to 25% by weight. In this case, it is preferable to add a polyfunctional isocyanate to the polymer composition in order to more firmly adhere the primer layer to the foamed sheet and further reduce blocking properties. When the isocyanate has a large content of isocyanate groups or is added in a large amount, the thermal activity of the primer layer decreases, so a polyfunctional isocyanate containing 25 to 60% by weight of isocyanate groups is preferable, and the amount added is The amount is preferably 1 to 15 parts by weight per 100 parts by weight of the grafted material. Examples of the polyfunctional isocyanate include toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, triphenylmethane-triisocyanate, and tris(P-isocyanate phenyl) phosphoric acid ester. Further, a tackifier, a filler, an antioxidant, etc. may be further added to the primer layer. Furthermore, in order to further reduce the blocking property of the primer layer, the primer layer and the foamed sheet may be embossed. Note that embossing also reduces the adhesiveness to the base material, so the temperature at which the laminate of the present invention is heated and bonded to the base material is lowered so that the embossed area returns to a smooth surface. It is preferable that the embossing is performed at a low temperature. The structure of the laminate of the present invention is as described above, in which the grafted material has a chloroprene synthetic rubber part and an acrylic polymer part, and the chloroprene synthetic rubber has a polyolefin resin foam and a chloroprene adhesive. Since the acrylic polymer has extremely low plasticizer migration, the primer layer is firmly adhered to the polyolefin resin foam sheet, and has excellent adhesion to the chloroprene adhesive, making it easy to roll. The plasticizer does not migrate from the vinyl chloride sheet and does not cause blocking even if it is wrapped around the vinyl chloride sheet. Therefore, the laminate of the present invention does not cause blocking even when stored in roll form, and there is no need to laminate release paper, polyethylene sheets, etc., so it can be used with good workability. It is suitable for use as interior materials for automobiles because it can be easily and reliably bonded to substrates with chloroprene adhesives without damaging its appearance or reducing its heat resistance and weather resistance. Ru. Next, the present invention will be explained with reference to examples. Examples and Comparative Examples A soft vinyl chloride sheet with a thickness of 0.35 mm, consisting of 100 parts by weight of vinyl chloride resin (degree of polymerization 1200), 40 parts by weight of dioctyl phthalate, 2 parts by weight of a tin-based stabilizer, and 0.5 parts by weight of a pigment; 3mm, apparent density
A 0.035 g/cm 3 polyethylene foam sheet was adhered with a urethane adhesive to obtain a laminated sheet, and then a primer layer was laminated as described below to obtain a sample. Note that samples 1 and 2 are comparative examples, and samples 3 to 5 are examples. Sample 1 A chloroprene-based adhesive (ESDINE 2017P, manufactured by Sekisui Chemical Co., Ltd.) was applied to the foamed sheet of the above laminated sheet, and dried at 50°C for 5 minutes to form a 5 g/m 2 primer layer to obtain a laminate. . The primer layer was colorless and slightly tacky. Sample 2 Urethane adhesive (Bostik 7662, manufactured by Bostik Nippon Co., Ltd.) 100%
20 parts by weight and 3 parts by weight of triisocyanate (Desmodyur R, manufactured by Bayer AG)
g/m 2 (wet) and aged at 30° C. for 24 hours to form a primer layer and obtain a laminate. The primer layer was transparent and the surface was smooth. Sample 3 25 g/m 2 (wet) of a polymer composition (solvent: toluene) with a solid content concentration of 15 wt %, which was obtained by graft polymerizing 40 wt % methyl methacrylate to polychloroprene, was applied to the foamed sheet of the above laminated sheet. A primer layer was formed by coating and drying at 50° C. for 15 minutes to obtain a laminate of the present invention. The primer layer was pale yellow and non-tacky. Sample 4 A mixture of 100 parts by weight of the above polymer composition and 3 parts by weight of triisocyanate (Desmodyur R, manufactured by Bayer AG) was applied at 25 g/m 2 (wet) on the foamed sheet of the above laminated sheet, and the mixture was heated at 30°C. A primer layer was formed by aging for 24 hours to obtain a laminate of the present invention. The primer layer was pale red and non-tacky. Sample 5 25g/m 2 (wet) of the compound used in Sample 4 was applied to the foamed sheet of the above laminated sheet, and the mixture was heated at 50°C.
Dry for 2 minutes at 210℃, heat for 5 seconds at 210℃, then heat at 90℃ for 5 seconds.
Texture embossing was performed at ℃ to form a primer layer to obtain a laminate of the present invention. The primer layer was pale red and non-tacky. Samples 1 to 5 were subjected to a primer layer adhesion test, a blocking test, and an adhesion test between the laminate and resin felt, and the results are shown in Table 1. In addition, in the primer layer adhesion test, the laminated sheet and the primer layer were peeled off by hand, and the peeled state was observed.
For the blocking test, the laminate was cut into a size of 100 mm x 100 mm, the primer layer and soft vinyl chloride sheet were overlapped, a load of 20 g/cm 2 was applied, and the layer was heated at 50°C.
After standing for 24 hours, the primer layer and soft vinyl chloride sheet were peeled off and the blocking state was observed.
In addition, an adhesion test between the laminate and resin felt was performed using a chloroprene adhesive (ESDINE) on the resin felt.
271 (manufactured by Sekisui Chemical Co., Ltd.) at 200g/cm 2 (wet), dried, heat-pressed the primer layer of the laminate at 120℃, and after cooling, peeled the laminate and resin felt by hand to check the peeling condition. Observed. 【table】
Claims (1)
質もしくは半硬質塩化ビニルシートが積層され、
他面に、クロロプレン系合成ゴムにアクリル系ビ
ニルモノマーがグラフト重合されたグラフト化物
を主体とするプライマー層が積層されてなる積層
体。 ２ プライマーがグラフト化物100重量部と、イ
ソシアネート基を25〜60重量％含有する多官能性
イソシアネート１〜15重量部よりなる特許請求の
範囲第１項記載の積層体。[Claims] 1. A soft or semi-hard vinyl chloride sheet is laminated on one side of a polyolefin resin foam sheet,
A laminate in which, on the other side, a primer layer mainly composed of a grafted product obtained by graft polymerizing an acrylic vinyl monomer onto a chloroprene synthetic rubber is laminated. 2. The laminate according to claim 1, wherein the primer comprises 100 parts by weight of a grafted product and 1 to 15 parts by weight of a polyfunctional isocyanate containing 25 to 60% by weight of isocyanate groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8367982A JPS58199137A (en) | 1982-05-17 | 1982-05-17 | Laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8367982A JPS58199137A (en) | 1982-05-17 | 1982-05-17 | Laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58199137A JPS58199137A (en) | 1983-11-19 |
| JPS6156094B2 true JPS6156094B2 (en) | 1986-12-01 |
Family
ID=13809161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8367982A Granted JPS58199137A (en) | 1982-05-17 | 1982-05-17 | Laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58199137A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59169844A (en) * | 1983-03-17 | 1984-09-25 | 大日精化工業株式会社 | Composite sheet |
| JPS61100442A (en) * | 1984-10-22 | 1986-05-19 | 豊田合成株式会社 | Mounting structure of lace |
| JPS61164828A (en) * | 1985-01-17 | 1986-07-25 | 豊田合成株式会社 | Mounting structure of lace |
| JPS61100443A (en) * | 1984-10-22 | 1986-05-19 | 豊田合成株式会社 | Mounting structure of lace |
-
1982
- 1982-05-17 JP JP8367982A patent/JPS58199137A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58199137A (en) | 1983-11-19 |
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