JPH03176120A - Polyvinyl chloride resin sheet for vacuum forming - Google Patents
Polyvinyl chloride resin sheet for vacuum formingInfo
- Publication number
- JPH03176120A JPH03176120A JP31671189A JP31671189A JPH03176120A JP H03176120 A JPH03176120 A JP H03176120A JP 31671189 A JP31671189 A JP 31671189A JP 31671189 A JP31671189 A JP 31671189A JP H03176120 A JPH03176120 A JP H03176120A
- Authority
- JP
- Japan
- Prior art keywords
- chloride resin
- vinyl chloride
- vacuum forming
- sheet
- polyvinyl chloride
- 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.)
- Pending
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 98
- 239000011347 resin Substances 0.000 title claims abstract description 98
- 238000007666 vacuum forming Methods 0.000 title claims abstract description 51
- 229920000915 polyvinyl chloride Polymers 0.000 title claims description 30
- 239000004800 polyvinyl chloride Substances 0.000 title claims description 30
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229920001944 Plastisol Polymers 0.000 claims abstract description 37
- 239000004999 plastisol Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 27
- 239000010410 layer Substances 0.000 claims description 22
- 239000006260 foam Substances 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 abstract description 13
- 238000010438 heat treatment Methods 0.000 abstract description 8
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 2
- 229920002554 vinyl polymer Polymers 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 238000009472 formulation Methods 0.000 description 10
- -1 ethylene, propylene, maleate ester Chemical class 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 7
- 238000005187 foaming Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- 239000004135 Bone phosphate Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-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
- 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 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 2
- XWVQUJDBOICHGH-UHFFFAOYSA-N dioctyl nonanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC XWVQUJDBOICHGH-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 2
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- GWOWVOYJLHSRJJ-UHFFFAOYSA-L cadmium stearate Chemical compound [Cd+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GWOWVOYJLHSRJJ-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- QQVHEQUEHCEAKS-UHFFFAOYSA-N diundecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCC QQVHEQUEHCEAKS-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
〔産業上の利用分野〕
本発明は真空成形用の塩化ビニル系樹脂シートに関し、
特にドローダウンの少ない真空成形用ポリ塩化ビニル系
樹脂シートに係るものである。
〔従来技術〕
従来、真空成形用ポリ塩化ビニル系樹脂シートとして、
成形品のソフト化から塩化ビニル系樹脂プラスチゾルを
使用したシートが使用されてきた。
塩化ビニル系樹脂プラスチゾルを使用して絞模様を有す
るシートを形成するには、凹凸模様を有する離型紙に塩
化ビニル系樹脂プラスチゾル組成物を塗布しこれをゲル
化して離型紙から剥離するので、得られる塩化ビニル系
樹脂シートには離型紙の凹凸模様が明確に転写され、絞
の凹凸が微細なものまで含めて充分に表現でき、自動車
等の車輌用内装材用としては好適なものであるが、真空
成形時の加熱によりシートが垂れてしまうドローダウン
の現象が顕著に現れるため、真空成形時の加熱温度を高
くすることができず低温で真空成形しなければならず、
真空成形後のシートの収縮が極めて大きくなるという問
題があり、塩化ビニル系樹脂プラスチゾルから形成した
シートを架橋する方法が提案されてきた。
〔発明が解決しようとする問題点〕
塩化ヒビニル系樹脂プラスチゾルら形成したシトを架橋
することにより、確かにドローダウンは少なくなり、真
空成形温度を高くすることができるようになったが、真
空成形時のシートの伸びが小さくなり真空成形に問題が
あるばかりでなく、架橋による記憶効果のために、真空
成形後のシートの収縮が大きいという問題点をも有して
いるものであった。
本発明は、このような従来技術を背景になされたもので
、真空成形の加熱によってもドローダウンの少ない真空
成形用ポリ塩化ビニル系樹脂シートを提供するものであ
る。
〔課題を解決するための手段］
すなわち本発明は、
（１１塩化ビニル系樹脂１００重量部当たり、ＡＢＳ系
樹脂５〜１００重量部を含有する塩化ビニル系樹脂プラ
スチゾル＆１１威物からなる真空成形用ポリ塩化ビニル
系樹脂シート。
（２）少なくとも表皮層が、塩化ビニル系樹脂１００重
量部当たり、ＡＢＳ系樹脂５〜１００重量部を含有する
塩化ビニル系樹脂プラスチゾル組成物からなり、皮膜層
が塩化ビニル系樹脂プラスチゾル組成物からなる１層以
上の塩化ビニル系樹脂層である真空成形用ポリ塩化ビニ
ル系樹脂シート。
（３）皮膜層が非発泡層である請求項２記載の真空成形
用ポリ塩化ビニル系樹脂シート。
（４）皮ｒｙ、Ｎが発泡層である請求項２記載の真空成
形用ポリ塩化ビニル系樹脂シート。
（５）皮膜層がＡＢＳ系樹脂を含有する塩化ビニル系樹
脂プラスチゾル組成物から形成された請求項２〜４のい
づれかに記載の真空成形用ポリ塩化ビニル系樹脂シート
。
を要旨とするものである。
本発明で使用する塩化ビニル系樹脂としては、塩化ビニ
ル単独、または塩化ビニルと他のビニルモノマー、例え
ば酢酸ビニル、エチレン、プロピレン、マレイン酸エス
テル、メタクリル酸メチル、メタクリル酸エステル、ア
クリル酸エステル、高級ビニルエーテルなどとをエマル
ジョン重合またはマイクロサスベンジョン重合で得られ
る重合体または共重合体が挙げられる。
塩化ビニル系樹脂からプラスチゾルを形成するのに使用
できる液状可塑剤としては、例えばフタル酸ジー２−エ
チルへキシルエステル（ＤＯＰ）、フタル酸ジイソノニ
ルエステル（ＤＩＮＰ）、フタル酸ブチルヘンシルエス
テル（ＢＢＰ）、フタル酸ジイソノニルエステル（ＤＩ
ＤＰ）、フタル酸ジウンデシルエステル（Ｄ［ＪＩ’）
などム二代表される一般のフタル酸エステル系可塑剤、
アジピン酸ジオクチルエステル（ＤＯＡ） 、セバシン
酸ジオクチルエステル（ＤＯ３） 、アゼライン酸ジオ
クチルエステル（ＤＯＺ）に代表される一般の脂肪酸エ
ステル系可塑剤、トリメリット酸トリオクチルエステル
（ＴＯＴＭ）に代表されるトリメリット酸エステル系可
塑剤、トリクレジルフォスフェート（ＴＣＰ）、）リキ
シリルフォスフエート（ＴＸＰ）などに代表されるトリ
アリールフォスフェート系可塑剤のほか、エポキシ化大
豆油などに代表されるエポキシ系可塑剤、ポリプロピレ
ンアジペート等に代表されるポリエステル系可塑剤など
の高分子系可塑剤、塩素化パラフィンなどの一般の可塑
剤が使用できるが、これらの可塑剤は単独で使用しても
良いし、２種以上を併用して使用してもよい。
これらの可塑剤は、目的とする種々の用途に合わせて、
塩化ビニル系樹脂に適宜量添加される。
一般に添加される量は、塩化ビニル系樹脂１００重量部
に対して３０〜１５０重量部程度であるが、本発明にお
いてはこれに限定されるものではない。
本発明においては、塩化ビニル系樹脂に、ＡＢＳ系樹脂
を添加するものであるが、ＡＢＳ系樹脂としでは、−ａ
にアクリロニトリル−ブタジェンスチレン共重合体が使
用されるが、メチルメタクリレ−ドープクジエン−スチ
レン共重合体などのようにアクリロニトリルに代えて他
のアクリル系モノマーを使用した共重合体や、ブタジェ
ンに代えてアクリルゴムを使用した共重合体や、ブタジ
ェンに代えて他のジエン系モノマーを使用した共重合体
や、スチレンに代えて他のスチレン系モノマーを使用し
た共重合体などが使用でき、通常のＡＢＳ共重合体に制
限されるものではない。
これらＡＢＳ系樹脂の添加量は、塩化ビニル系樹脂１０
０重量部当たり５〜１００重量部である。
塩化ビニル系樹脂１００重量部に対して、ＡＢＳ系樹脂
の添加量が５重量部未満になると、得られる真空成形用
ポリ塩化ビニル系樹脂シートは真空成形時の加熱により
、ドローダウンを起こす傾向が強くなり、一方１００重
量部を越えると離型紙へのプラスチゾルの塗布が困難と
なり好ましくない。
また、本発明の塩化ビニル系樹脂には、安定剤として、
例えばステアリン酸鉛、ステアリン酸バリウム、ステア
リン酸亜鉛、ステアリン酸カドミウム、ステアリン酸カ
ルシウム等の金属石鹸、ジブチル錫ジラウレート、ジプ
チル錫マレート、有機錫メルカプチド、有機錫スルホン
アミド等の錫系安定剤、三塩基性硫酸鉛、三塩基性亜燐
酸鉛、三塩基性マレイン酸鉛などが用いられ、これらの
安定剤は単独でまたは２種以上を併用して使用でき、特
に安定剤を制限するものではない。
この安定剤の添加量は、塩化ビニル系樹脂１００重量部
に対して０．５から１０重量部、好ましくは１〜５重量
部程度である。
また、この塩化ビニル系樹脂には、発泡剤を添加して発
泡シートを得ることもできる。発泡させる場合、発泡剤
として例えば塩化ビニル系樹脂の発泡剤であるアゾジカ
ルボンアミド、ジニトロソペンタテトラミン、オキシビ
スベンゼンヒドラジドなどを用いることにより発泡させ
ることができ、また必要に応して発泡促進剤または発泡
抑制剤を添加してもよい。
さらに、本発明の真空成形用ポリ塩化ビニル系樹脂シー
トを得るための塩化ビニル系樹脂プラスチゾルを機械発
泡させて発泡シートを得ることもできるものである。こ
の場合には、整泡剤としてアルキルベンゼンスルホン酸
ナトリウム、アルキルベンゼンスルホン酸カリウム等の
有機界面活性剤やポリジメチルシロキサン、ポリメチル
フェニルシロキサン等のシリコーン油を用いるのが好ま
しい。整泡剤の添加量は塩化ビニル系樹脂プラスチゾル
１００重量部に対して０．１〜５重量部である。
上記以外に、必要に応して三酸化アンチモン、トリアル
コキシアルキルフォスフェートなどの難燃剤、炭酸カル
シウム、タルク、ハイドロタルサイト、炭酸マグネシウ
ム１．水酸化アルミニウム等の充填剤等の他に、加工助
剤、顔料、紫外線吸収剤、帯電防止剤、老化防止剤など
も添加することができる。
本発明においては、ＡＢＳ系樹脂を含有する塩化ビニル
系樹脂のプラスチゾル組成物から得られる塩化ビニル系
樹脂シートを表面層とし、これにＡＢＳ系樹脂を含有し
ないペースト用塩化ビニル系樹脂のプラスチゾル組成物
威物から得られる塩化ビニル系樹脂シートの皮膜層を１
層以上形成した複層構造の真空成形用ポリ塩化ビニル系
樹脂シートとしてもよい。この場合皮膜層は非発泡層で
あっても、発泡層であってもよい。また皮膜層をＡＢＳ
系樹脂を含有する塩化ビニル系樹脂のプラスチゾル組成
物から形成してもよい。
〔作用〕
本発明においては、真空成形用ポリ塩化ビニル系樹脂シ
ートがＡＢＳ系樹脂を含有する塩化ビニル系樹脂のプラ
スチゾル組成物から形成されるので、ＡＢＳ系樹脂を含
有しない塩化ビニル系樹脂のプラスチゾル組成物から形
成されたシートとは異なり、真空成形時の加熱によりド
ローダウンを起こしにくく、また少なくとも表面層がＡ
ＢＳ系樹脂を含有する塩化ビニル系樹脂のプラスチゾル
組成物から形成されていれば、裏面の皮膜層がＡＢＳ系
樹脂を含有しない塩化ビニル系樹脂のブラスヂゾル組成
物から形成されていても表面層の存在によりドローダウ
ンは少なく、自動車等の車輌や、船舶等の乗物の内装に
使用されるインナーパネル、セイフティバソド、リッド
、コンソールボ・７クス、アシストグリップ等に好適で
ある。
（実施例）
以下、本発明の実施例を具体的に説明するが、本発明は
これら実施例ムこ限定されるものではない。
実施例１
第１表に示す配合例１の塩化ビニル樹脂プラスチゾルを
ライカイ機で２０分混練後、革絞状の凹凸模様を有する
離型紙に厚み０．５＋＋＋ｍになるように塗布し、これ
を２００°Ｃで２分間加熱ゲル化して真空成形用ポリ塩
化ビニル樹脂シートを得た。
得られた真空成形用ポリ塩化ビニル樹脂シートは離型紙
に形成された凹凸模様が明確に転写されおり、皮ＴＬ調
の良好な外観を有するものであった。
この真空成形用ポリ塩化ビニル樹脂シートを遠赤外線ヒ
ーターで加熱し、真空成形した結果を第２表に示す。
ドローダウンの試験および収縮率の試験は以下の方法に
従って実施した。[Industrial Application Field] The present invention relates to a vinyl chloride resin sheet for vacuum forming.
In particular, the present invention relates to a polyvinyl chloride resin sheet for vacuum forming with less drawdown. [Prior art] Conventionally, as a polyvinyl chloride resin sheet for vacuum forming,
Sheets using vinyl chloride resin plastisol have been used to make molded products softer. In order to form a sheet with a squeeze pattern using a vinyl chloride resin plastisol, a vinyl chloride resin plastisol composition is applied to a release paper having an uneven pattern, and this is gelled and peeled off from the release paper. The uneven pattern of the release paper is clearly transferred to the vinyl chloride resin sheet produced, and the unevenness of the aperture, even minute ones, can be sufficiently expressed, making it suitable for interior materials for vehicles such as automobiles. Because the heating during vacuum forming causes a noticeable drawdown phenomenon in which the sheet sag, it is not possible to increase the heating temperature during vacuum forming, and vacuum forming must be performed at a low temperature.
There is a problem that the shrinkage of the sheet after vacuum forming becomes extremely large, and a method of crosslinking a sheet formed from a vinyl chloride resin plastisol has been proposed. [Problems to be solved by the invention] By crosslinking the cytos formed from hibinyl chloride resin plastisol, it is true that drawdown can be reduced and the vacuum forming temperature can be increased, but vacuum forming Not only is there a problem with vacuum forming due to the reduced elongation of the sheet during vacuum forming, but there is also the problem of large shrinkage of the sheet after vacuum forming due to the memory effect caused by crosslinking. The present invention has been made against the background of such prior art, and provides a polyvinyl chloride resin sheet for vacuum forming that exhibits less drawdown even when heated during vacuum forming. [Means for Solving the Problems] That is, the present invention provides a vacuum forming polyurethane resin consisting of a vinyl chloride resin plastisol containing 5 to 100 parts by weight of an ABS resin per 100 parts by weight of a 11 vinyl chloride resin and Vinyl chloride resin sheet. (2) At least the skin layer is made of a vinyl chloride resin plastisol composition containing 5 to 100 parts by weight of ABS resin per 100 parts by weight of vinyl chloride resin, and the film layer is made of vinyl chloride resin. A polyvinyl chloride resin sheet for vacuum forming, which is one or more vinyl chloride resin layers made of a resin plastisol composition. (3) The polyvinyl chloride resin sheet for vacuum forming according to claim 2, wherein the film layer is a non-foaming layer. Resin sheet. (4) The polyvinyl chloride resin sheet for vacuum forming according to claim 2, wherein the skin ry and N are foam layers. (5) The film layer is made from a vinyl chloride resin plastisol composition containing an ABS resin. The polyvinyl chloride resin sheet for vacuum forming according to any one of claims 2 to 4 is formed.The vinyl chloride resin used in the present invention includes vinyl chloride alone or vinyl chloride. and other vinyl monomers, such as vinyl acetate, ethylene, propylene, maleate ester, methyl methacrylate, methacrylate ester, acrylic ester, higher vinyl ether, etc., by emulsion polymerization or microsuspension polymerization. Liquid plasticizers that can be used to form plastisols from vinyl chloride resins include, for example, di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), and butyl phthalate. Hensyl ester (BBP), phthalic acid diisononyl ester (DI
DP), phthalic acid diundecyl ester (D[JI')
General phthalate ester plasticizers such as
Common fatty acid ester plasticizers such as dioctyl adipate (DOA), dioctyl sebacate (DO3), and dioctyl azelate (DOZ), and trimellits such as trioctyl trimellitate (TOTM) In addition to acid ester plasticizers, triaryl phosphate plasticizers such as tricresyl phosphate (TCP) and lyxylyl phosphate (TXP), epoxy plasticizers such as epoxidized soybean oil Plasticizers, polymeric plasticizers such as polyester plasticizers such as polypropylene adipate, and general plasticizers such as chlorinated paraffin can be used, but these plasticizers may be used alone, Two or more types may be used in combination. These plasticizers can be used for various purposes,
An appropriate amount is added to the vinyl chloride resin. Generally, the amount added is about 30 to 150 parts by weight per 100 parts by weight of the vinyl chloride resin, but the present invention is not limited to this. In the present invention, an ABS resin is added to a vinyl chloride resin, but as an ABS resin, -a
Acrylonitrile-butadiene-styrene copolymer is used in Copolymers using acrylic rubber, copolymers using other diene monomers instead of butadiene, copolymers using other styrene monomers instead of styrene, etc. can be used, and ordinary ABS It is not limited to copolymers. The amount of these ABS resins added is 10 parts of vinyl chloride resin.
5 to 100 parts by weight per 0 parts by weight. If the amount of ABS resin added to 100 parts by weight of vinyl chloride resin is less than 5 parts by weight, the resulting polyvinyl chloride resin sheet for vacuum forming tends to cause drawdown due to heating during vacuum forming. On the other hand, if it exceeds 100 parts by weight, it becomes difficult to apply plastisol to the release paper, which is not preferable. In addition, the vinyl chloride resin of the present invention includes, as a stabilizer,
For example, metal soaps such as lead stearate, barium stearate, zinc stearate, cadmium stearate, calcium stearate, tin stabilizers such as dibutyltin dilaurate, diptyltin malate, organotin mercaptide, organotin sulfonamide, tribasic Lead sulfate, tribasic lead phosphite, tribasic lead maleate, etc. are used, and these stabilizers can be used alone or in combination of two or more, and there are no particular restrictions on the stabilizers. The amount of the stabilizer added is about 0.5 to 10 parts by weight, preferably about 1 to 5 parts by weight, per 100 parts by weight of the vinyl chloride resin. A foamed sheet can also be obtained by adding a foaming agent to this vinyl chloride resin. In the case of foaming, foaming can be carried out by using a foaming agent such as azodicarbonamide, dinitrosopentatetramine, oxybisbenzene hydrazide, etc., which are foaming agents for vinyl chloride resin, and a foaming accelerator, if necessary. Alternatively, a foaming inhibitor may be added. Furthermore, a foamed sheet can also be obtained by mechanically foaming the vinyl chloride resin plastisol for obtaining the polyvinyl chloride resin sheet for vacuum forming of the present invention. In this case, it is preferable to use an organic surfactant such as sodium alkylbenzenesulfonate or potassium alkylbenzenesulfonate or a silicone oil such as polydimethylsiloxane or polymethylphenylsiloxane as the foam stabilizer. The amount of the foam stabilizer added is 0.1 to 5 parts by weight per 100 parts by weight of the vinyl chloride resin plastisol. In addition to the above, flame retardants such as antimony trioxide and trialkoxyalkyl phosphate, calcium carbonate, talc, hydrotalcite, and magnesium carbonate may be used as necessary.1. In addition to fillers such as aluminum hydroxide, processing aids, pigments, ultraviolet absorbers, antistatic agents, antiaging agents, and the like can also be added. In the present invention, a vinyl chloride resin sheet obtained from a plastisol composition of vinyl chloride resin containing an ABS resin is used as the surface layer, and a plastisol composition of vinyl chloride resin for paste that does not contain an ABS resin is added to the surface layer. 1 film layer of vinyl chloride resin sheet obtained from Umono
It may also be a polyvinyl chloride resin sheet for vacuum forming with a multilayer structure formed of more than one layer. In this case, the coating layer may be a non-foamed layer or a foamed layer. Also, the film layer is made of ABS.
It may be formed from a plastisol composition of a vinyl chloride resin containing a vinyl chloride resin. [Function] In the present invention, since the polyvinyl chloride resin sheet for vacuum forming is formed from a plastisol composition of vinyl chloride resin containing ABS resin, plastisol composition of vinyl chloride resin that does not contain ABS resin. Unlike sheets formed from compositions, drawdown is less likely to occur due to heating during vacuum forming, and at least the surface layer is
If it is formed from a plastisol composition of a vinyl chloride resin containing a BS resin, the presence of a surface layer will occur even if the back film layer is formed from a plastisol composition of a vinyl chloride resin that does not contain an ABS resin. As a result, drawdown is small, making it suitable for inner panels, safety baths, lids, console boxes, assist grips, etc. used in the interior of vehicles such as automobiles and vehicles such as ships. (Examples) Hereinafter, examples of the present invention will be specifically described, but the present invention is not limited to these examples. Example 1 After kneading the vinyl chloride resin plastisol of Formulation Example 1 shown in Table 1 for 20 minutes in a Laikai machine, it was applied to a release paper having a leather-like uneven pattern to a thickness of 0.5 +++ m. The mixture was gelatinized by heating at °C for 2 minutes to obtain a polyvinyl chloride resin sheet for vacuum forming. The obtained polyvinyl chloride resin sheet for vacuum forming had a good appearance with a leather TL tone, in which the uneven pattern formed on the release paper was clearly transferred. This polyvinyl chloride resin sheet for vacuum forming was heated with a far infrared heater and vacuum formed. The results are shown in Table 2. The drawdown test and shrinkage rate test were conducted according to the following method.
得られた真空成形用ポリ塩化ビニル樹脂シートを１辺が
７０ｃｍの正方形の枠に固定し遠赤外線ヒーターで加熱
し、下方に１０ｃｍドローダウンしたときのシート温度
を測定した。
この温度が高いほどドローダウンが少ないものである。The obtained polyvinyl chloride resin sheet for vacuum forming was fixed to a square frame with one side of 70 cm, heated with a far infrared heater, and the sheet temperature was measured when the sheet was drawn down 10 cm downward. The higher the temperature, the less the drawdown.
得られた真空成形用ポリ塩化ビニル樹脂シートを真空成
形し、１００％伸長された部分の２４時間放置後の収縮
率を測定した。この収縮率が小さいほど好ましいもので
ある。
実施例２〜４、比較例１〜３
配合例２〜７の塩化ビニル樹脂プラスチゾルを使用し、
実施例１と同様にして真空成形用ポリ塩化ビニル樹脂シ
ートを得た。この真空成形用ポリ塩化ビニル樹脂シート
について実施例１と同様の試験を行なった。その結果に
ついては第２表に示す。
実施例５〜６、比較例４
配合例２．５．７の塩化ビニル樹脂プラスチゾルを使用
し、配合例２と配合例５、配合例２と配合例７、配合例
５と配合例７との組合せで離型紙上に２Ｎ引きする以外
は実施例１と同様にして真空成形用ポリ塩化ビニル樹脂
シートを得た。この真空成形用ポリ塩化ビニル樹脂シー
トについて実施例１と同様の試験を行なった。その結果
については第２表に示す。
比較例５
配合例８の塩化ビニル樹脂プラスチゾルを使用し、実施
例１と同様にして真空成形用ポリ塩化ビニル樹脂シート
を得た。この真空成形用ポリ塩化ビニル樹脂シートにつ
いて実施例１と同様の試験を行なった。その結果につい
ては第２表に示す。
（以下余白）
第
表
第
表
第２表から明らかなように本発明の真空成形用ポリ塩化
ビニル系樹脂シートは、塩化ビニル系樹脂１００重量部
当たり、ＡＢＳ系樹脂５〜１００重量部を含有する塩化
ビニル系樹脂プラスチゾル組成物からなるので、ドロー
ダウンが少なく、したがって真空成形時の加熱温度を上
げることができ、真空成形後の成形品の収縮も小さいこ
とがわかる。また、２層以上の積層シートの場合には、
１層が塩化ビニル系樹脂１００重量部当たり、ＡＢＳ系
樹脂５〜１００重量部を含有する塩化ビニル系樹脂プラ
スチゾル組成物からなるものであれば、同様の効果を有
することが明らかである。
一方、塩化ビニル系樹脂１００重量部当たり、ＡＢＳ系
樹脂５重量部未満を含有する塩化ビニル系樹脂プラスチ
ゾル組放物や、ＡＢＳ系樹脂を含有しない塩化ビニル系
樹脂プラスチゾル組成物なる真空底形用シートは、比較
例１〜４に見られるようにドローダウンが大きいばかり
でなく、収縮率も大きく真空成形に適さないものである
ことがわかる。
また、比較例５においては、塩化ビニル系樹脂プラスチ
ゾルから形成したシートを架橋することにより、確かに
ドローダウンは少なくなり、真空成形温度を高くするこ
とができるようになったが、真空成形後のシートの収縮
が大きいという問題点を有していることが明らかである
。
〔発明の効果〕
本発明は、このようにペースト用塩化ビニル系樹脂１０
０重量部当たり、ＡＢＳ系重合体５〜１００重量部を含
有する塩化ビニル系樹脂プラスチゾル組成物からなる真
空底形用ポリ塩化ビニル樹脂シートであるため、真空成
形時の加熱によっても、ドローダウンが極めて少なく、
従って真空成形時の加熱温度を上げることができ、でき
た真空成形品の収縮も極めて少なく、ソフトで手触り感
の優れた真空成形品を得ることができるものである。The obtained polyvinyl chloride resin sheet for vacuum forming was vacuum formed, and the shrinkage rate of the 100% elongated portion after being left for 24 hours was measured. The smaller this shrinkage rate is, the more preferable it is. Examples 2 to 4, Comparative Examples 1 to 3 Using the vinyl chloride resin plastisol of Formulation Examples 2 to 7,
A polyvinyl chloride resin sheet for vacuum forming was obtained in the same manner as in Example 1. The same tests as in Example 1 were conducted on this polyvinyl chloride resin sheet for vacuum forming. The results are shown in Table 2. Examples 5 to 6, Comparative Example 4 Using the vinyl chloride resin plastisol of Formulation Examples 2.5.7, the combinations of Formulation Example 2 and Formulation Example 5, Formulation Example 2 and Formulation Example 7, and Formulation Example 5 and Formulation Example 7 were used. A polyvinyl chloride resin sheet for vacuum forming was obtained in the same manner as in Example 1, except that the combination was pulled 2N onto a release paper. The same tests as in Example 1 were conducted on this polyvinyl chloride resin sheet for vacuum forming. The results are shown in Table 2. Comparative Example 5 Using the vinyl chloride resin plastisol of Formulation Example 8, a polyvinyl chloride resin sheet for vacuum forming was obtained in the same manner as in Example 1. The same tests as in Example 1 were conducted on this polyvinyl chloride resin sheet for vacuum forming. The results are shown in Table 2. (Left below) As is clear from Table 2, the polyvinyl chloride resin sheet for vacuum forming of the present invention contains 5 to 100 parts by weight of ABS resin per 100 parts by weight of vinyl chloride resin. Since it is made of a vinyl chloride resin plastisol composition, there is little drawdown, so it is possible to increase the heating temperature during vacuum forming, and the shrinkage of the molded product after vacuum forming is also small. In addition, in the case of a laminated sheet with two or more layers,
It is clear that similar effects can be obtained if one layer is made of a vinyl chloride resin plastisol composition containing 5 to 100 parts by weight of ABS resin per 100 parts by weight of vinyl chloride resin. On the other hand, a vacuum bottom sheet made of a vinyl chloride resin plastisol composition containing less than 5 parts by weight of ABS resin per 100 parts by weight of vinyl chloride resin, or a vinyl chloride resin plastisol composition containing no ABS resin. As seen in Comparative Examples 1 to 4, not only the drawdown was large but also the shrinkage rate was large, making it unsuitable for vacuum forming. In addition, in Comparative Example 5, by crosslinking the sheet formed from vinyl chloride resin plastisol, drawdown was certainly reduced and the vacuum forming temperature could be increased, but after vacuum forming, It is clear that the problem is that the sheet shrinks significantly. [Effects of the Invention] As described above, the present invention provides the vinyl chloride resin 10 for paste.
Since this polyvinyl chloride resin sheet for vacuum bottom molding is made of a vinyl chloride resin plastisol composition containing 5 to 100 parts by weight of ABS polymer per 0 parts by weight, drawdown will not occur even when heated during vacuum forming. extremely few,
Therefore, it is possible to raise the heating temperature during vacuum forming, and the shrinkage of the vacuum-formed product is extremely small, making it possible to obtain a vacuum-formed product that is soft and has an excellent feel to the touch.
Claims (5)
樹脂５〜１００重量部を含有する塩化ビニル系樹脂プラ
スチゾル組成物からなる真空成形用ポリ塩化ビニル系樹
脂シート。(1) A polyvinyl chloride resin sheet for vacuum forming made of a vinyl chloride resin plastisol composition containing 5 to 100 parts by weight of ABS resin per 100 parts by weight of vinyl chloride resin.
量部当たり、ＡＢＳ系樹脂５〜１００重量部を含有する
塩化ビニル系樹脂プラスチゾル組成物からなり、皮膜層
が塩化ビニル系樹脂プラスチゾル組成物からなる１層以
上の塩化ビニル系樹脂層である真空成形用ポリ塩化ビニ
ル系樹脂シート。(2) At least the skin layer is made of a vinyl chloride resin plastisol composition containing 5 to 100 parts by weight of ABS resin per 100 parts by weight of vinyl chloride resin, and the film layer is made of a vinyl chloride resin plastisol composition. A polyvinyl chloride resin sheet for vacuum forming that has one or more vinyl chloride resin layers.
用ポリ塩化ビニル系樹脂シート。(3) The polyvinyl chloride resin sheet for vacuum forming according to claim 2, wherein the film layer is a non-foamed layer.
ポリ塩化ビニル系樹脂シート。(4) The polyvinyl chloride resin sheet for vacuum forming according to claim 2, wherein the coating layer is a foam layer.
脂プラスチゾル組成物から形成された請求項２〜４のい
づれかに記載の真空成形用ポリ塩化ビニル系樹脂シート
。(5) The polyvinyl chloride resin sheet for vacuum forming according to any one of claims 2 to 4, wherein the film layer is formed from a vinyl chloride resin plastisol composition containing an ABS resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31671189A JPH03176120A (en) | 1989-12-06 | 1989-12-06 | Polyvinyl chloride resin sheet for vacuum forming |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31671189A JPH03176120A (en) | 1989-12-06 | 1989-12-06 | Polyvinyl chloride resin sheet for vacuum forming |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03176120A true JPH03176120A (en) | 1991-07-31 |
Family
ID=18080051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31671189A Pending JPH03176120A (en) | 1989-12-06 | 1989-12-06 | Polyvinyl chloride resin sheet for vacuum forming |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03176120A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05253968A (en) * | 1992-03-13 | 1993-10-05 | Nakajima Urethane:Kk | Method for printing surface of molded product |
| JP2019177681A (en) * | 2018-03-30 | 2019-10-17 | 大日本印刷株式会社 | Decorative sheet for molding |
-
1989
- 1989-12-06 JP JP31671189A patent/JPH03176120A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05253968A (en) * | 1992-03-13 | 1993-10-05 | Nakajima Urethane:Kk | Method for printing surface of molded product |
| JP2019177681A (en) * | 2018-03-30 | 2019-10-17 | 大日本印刷株式会社 | Decorative sheet for molding |
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