JPS6332102B2 - - Google Patents
Info
- Publication number
- JPS6332102B2 JPS6332102B2 JP56012448A JP1244881A JPS6332102B2 JP S6332102 B2 JPS6332102 B2 JP S6332102B2 JP 56012448 A JP56012448 A JP 56012448A JP 1244881 A JP1244881 A JP 1244881A JP S6332102 B2 JPS6332102 B2 JP S6332102B2
- Authority
- JP
- Japan
- Prior art keywords
- light resistance
- color
- polyurethane resin
- halogen
- molded
- 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
- 239000003086 colorant Substances 0.000 claims description 26
- 239000005056 polyisocyanate Substances 0.000 claims description 18
- 229920001228 polyisocyanate Polymers 0.000 claims description 18
- 229920005749 polyurethane resin Polymers 0.000 claims description 17
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 15
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 150000002366 halogen compounds Chemical class 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 239000004604 Blowing Agent Substances 0.000 description 17
- 239000006260 foam Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000009472 formulation Methods 0.000 description 13
- 239000003381 stabilizer Substances 0.000 description 13
- 238000004383 yellowing Methods 0.000 description 10
- 239000012948 isocyanate Substances 0.000 description 9
- 150000002513 isocyanates Chemical class 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 7
- 239000004088 foaming agent Substances 0.000 description 7
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 6
- 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 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- 239000004616 structural foam Substances 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- -1 microcellular Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000010107 reaction injection moulding Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
本発明は密閉型中で成形されたポリウレタン樹
脂の光安定性に関するものであり、さらに詳しく
は着色剤添加による明度の高い淡色成形品表面の
耐候性、すなわち主として紫外線や熱によるポリ
ウレタン樹脂表面の色変化(黄変)およびその劣
化を著しく改良する方法に関するものである。
ポリウレタン樹脂はその配合により軟質から硬
質まで巾広く成形でき優れた特性を有しているた
め車両・輸送・機械関係、家具・事務・電気・音
響機器関係、建材・住宅関係、スポーツ・レジヤ
ー関係など様々な用途に使用されている。これら
は一般にインテグラルスキンドフオーム、ストラ
クチヤルフオーム、マイクロセルラー、ソリツド
(エラストマー)に分類され様々な形に成形され
ている。これら成形品は大気中に暴露放置すると
主として紫外線や熱により成形品表面に色変化
(黄変)が細かなクラツク、ピンホール等の表面
劣化が生じるという問題があつた。そのため一般
には成形品表面に耐光性に優れた塗装を施しそれ
らを解決していた。しかしながら成形品への塗装
は成形品表面の離型剤を落とし乾燥させた後塗装
を施し、これを硬化するため乾燥するなど多くの
工程、設備を必要とする。この他多大な時間、労
力、エネルギーを要しさらに精緻な熟練を必要と
する。そのため大巾なコストアツプとなつており
塗装工程を必要としない、すなわちポリウレタン
樹脂に直接着色剤を添加し着色した成形品それ自
身が耐候性を有するものが強く要求されるように
なつた。
そこで本発明者らはポリウレタン樹脂の耐光性
について種々検討した結果、密閉型で成形するポ
リウレタン樹脂に使用される発泡剤としては従来
かえりみられなかつた揮発性非ハロゲン化合物
(ペンタン、ヘキサン、アセトン、テトラヒドロ
フラン、酢酸メチル、ギ酸メチル等に代表される
飽和炭化水素、活性水素を有さない含酸素化合
物)を発泡剤として使用することにより耐光性に
著しく優れた成形品を得ることを見い出し先に提
案した。この方法ではポリイソシアネートとして
汎用のMDI,TDI及びそれらのプレポリマー、
純MDIカルボジイミド変成ポリイソシアネート
等が使用できた。そしてこれに着色剤を添加し成
形品を着色した場合、着色剤の隠ぺい力により耐
光性は一段と向上する。しかしながら粗MDIの
ごとく、イソシアネートそれ自身が茶褐色である
場合には濃色の着色剤ではイソシアネート自身の
着色をかくしてしまうため所望の色は出せたが、
クリーム、淡黄色、淡緑色等の淡色では淡色着色
剤とイソシアネートの茶褐色が混合した色になつ
てしまい所望の色が出せなかつた。この際ポリイ
ソシアネートの色が無色あるいは淡黄色である
TDI、プレポリマー、XDI(キシリレンジイソシ
アネート)、カルボジイミド変成ポリイソシアネ
ート等を使用することにより淡色着色剤の添加で
所望の色に着色することはできた。しかしながら
それらのポリイソシアネートは耐光性は十分とは
いえず経時的に黄変しそれをかくす程淡色着色剤
の隠ぺい力が強くないため所望の色と異なつた色
になつてしまう。このように発泡剤として揮発性
非ハロゲン化合物を用いた場合、マンセル記号で
表わされる明度5未満の濃色の成形品表面着色を
有するものはその着色剤の添加により汎用のポリ
イソシアネートを用いても耐光性は良好であり成
形品の無塗装化は可能である。一方マンセル記号
での明度5以上の表面着色を有する淡色品は紫外
線照射により経時的に色変化を起こし所望の色と
は異なつたものになつてしまうという欠点があつ
た。
本発明はかゝる状況に鑑み鋭意検討の結果なさ
れたものであつて、密閉型中でポリオールとポリ
イソシアネートを反応させて発泡ポリウレタン樹
脂成形品を製造するにさいし、(a)揮発性非ハロゲ
ン化合物(b)イソホロンジイソシアネート及び(c)マ
ンセル記号であらわされる明度5以上の成形品表
面色を有する着色剤を配合することを特徴とする
ものである。
すなわちポリオール、イソホロンジイソシアネ
ート、触媒、着色剤、整泡剤、揮発性非ハロゲン
化合物(発泡剤)、その他必要により安定剤、助
剤よりなる配合系より構成されるポリウレタン樹
脂を密閉型中において成形する方法である。揮発
性非ハロゲン化合物としてはペンタン、ヘキサ
ン、ヘプタン、石油エーテル、アセトン、テトラ
ヒドロフラン、酸化プロピレン、酢酸メチル、ギ
酸メチルに代表される沸点が蒸圧下20〜100℃の
範囲にある飽和炭化水素、活性水素を有しない含
酸素化合物があげられる。これらの発泡剤は2種
類以上併用してもまた水のような化学発泡剤と併
用してもさしつかえない。安定剤としては酸化防
止剤、紫外線吸収剤、加水分解防止剤がありこれ
らの中より選ばれる1種以上を添加し使用するも
のであり、その添加量は0.1〜6重量%が好まし
い。酸化防止剤にはヒンダードフエノール類、フ
エノール類、ヒンダードアミン類、ホスフアイト
類がありこの中で比較的良好なものはヒンダード
フエノール類であり特に2,6ジ―t―ブチル―
4メチルフエノールが良好な結果を示した。紫外
線吸収剤にはベンゾフエノン系、サリチル酸エス
テル系、ベンゾトリアゾール系などがありこの中
でベンゾトリアゾール系が良好であつた。加水分
解防止剤はポリウレタン樹脂の加水分解を抑制あ
るいは防止するためでありそれにはポリメリツク
カルボジイミドがあげられる。これら安定剤は単
独でも2種類以上組合せても使用できその添加量
は0.1〜6重量%が好ましく0.5〜2重量%がより
好ましい。単独添加の場合は効果発現のためその
使用量が多くなり安定剤によりポリウレタン樹脂
の成形性に悪影響を及ぼすことがあるのでその選
択は重要となる。好ましくは2種類以上の添加が
良好でありその場合、添加量は単独添加の場合よ
り少なくて同効果を発揮できる。助剤としては内
部離型剤、難燃剤等があげられるがこれらは必要
に応じ添加することができる。
密閉型中でポリウレタン樹脂を成形する方法は
RIM(Reaction Injection Molding)法が代表的
であり、それは種々の配合によりインテグラルス
キンドフオーム、ストラクチヤルフオーム、マイ
クロセルラー、ソリツド(エラストマー)の形態
で成形される。インテグラルスキンドフオーム、
ストラクチヤルフオーム、マイクロセルーラーは
いずれもその配合中に発泡剤を必要とする。また
ソリツド(エラストマー)は型中に樹脂をオーバ
ーパツクさせる目的で少量、通常0.1〜3部発泡
剤を添加して用いている。これら発泡剤を用いる
ポリウレタン樹脂で耐光性が著しく悪いものはイ
ンテグラルスキンドフオームでありとりわけ硬質
インテグラルスキンドフオーム(ストラクチヤル
フオーム)である。これはフオーム層をはさんで
両側にスキン層を有するインテグラルスキンドフ
オームのスキン層中に発泡剤がとじこめられて存
在し、これが耐光性に大きく影響するためと考え
られる。このことは次の点から明らかである。物
理発泡剤としてフロン11等の含ハロゲン化合物を
使用した場合、耐光性は著しく悪くなり、これに
対し非ハロゲン化合物を使用した場合、耐光性は
著しく改善されること。また含ハロゲン化合物を
使用しても真空処理等によりスキン層中に存在し
ている発泡剤を強制的に除去することにより耐光
性は幾分改良されることによる。ポリウレタン樹
脂の黄変、劣化機構は次のように考えられてい
る。(Advances in Urethane Science and
Technology,Vol6,P103〜172,Technomic
Pub.,1978)
ポリウレタン樹脂の紫外線による分解生成物は
オレフイン、アルデヒド、ケトン等でありその生
成機構は次のように考えられている。
Beachellらは次に示したような反応でポリウ
レタンが解離しイソシアネート(1)が生成しまたウ
レタン基の脱炭酸分解によりアミン(2)が生成し初
基はこのイソシアネートとアミンの酸化により後
期にはポリカルボジイミド(3)とアルコールの反応
生成物が加わり着色が増加するとしている。
SchollenbergerらはTDI,MDIベースポリウ
レタンは主として紫外線によるベンゼン環のキノ
ン、キノンイミド化により黄変すると報告してい
る。
ポリウレタン樹脂の配合面での黄変防止策とし
て従来は(1)紫外線吸収剤や酸化防止剤の添加(2)ベ
ンゼン核と―NCO基との間にアルキレン基を導
入し両者間の共鳴を抑止するようなイソシアネー
ト、例えばXDI(キシリレンジイソシアネート)
を用いる方法。(3)脂環族ポリイソシアネート、例
えば水添MDI、IPDI(イソホロンジイソシアネー
ト)を用いる方法。(4)共軛二重結合を含まぬ脂胞
族ポリイソシアネート、例えばHMDI(ヘキサメ
チレンジイソシアネート)などを用いる方法が一
般的である。(1)は安定剤添加、(2)〜(4)はイソシア
ネートによる耐光性改良方法である。本発明者ら
の実験では(1)の安定剤添加による方法は黄変防止
にそれ程効果がなかつた。そして(2)〜(4)のイソシ
アネートによる方法では発泡剤として含ハロゲン
化合物を用いた場合、黄変防止に大きな効果は認
められず若干の黄変があつた。これはスキン層中
に存在している発泡剤が紫外線により分解しハロ
ゲンを生じそのハロゲンにより酸化反応、ラジカ
ル反応等が起こり黄変するものと思われる。その
ためイソシアネートとしてキノン、キノンイミド
構造をとりにくい構造のものを使用したとしても
前記Beachellらの反応等により黄変は生じるも
のと考えられる。これに対し本発明のように発泡
剤としてハロゲン元素を含有しない紫外線や熱に
対し比較的安定である揮発性非ハロゲン化合物を
用いた場合、黄変化反応を促進するものがなく耐
光性は著しく良好なものとなる。本発明で従来よ
り耐光性配合に公知のイソホロンジイソシアネー
トを用いる場合の効果上の差異は発泡剤として揮
発性非ハロゲン化合物を用いていることにより著
しく耐光性を改善できることにある。またマンセ
ル記号で表わされる明度5以上の淡色形品の耐光
性改良に大きな効果があることである。
以下実施例によりさらに詳しく説明する。
なお耐光性促進試験は試験片をブラツクパネル
温度63℃のフエードメーター(カーボンアーク)
で行なつた。その評価は試験前後の色を三刺激値
X,Y,Z系で測定しHunter色差を用いて判定
した。色測定は“直読測定色差コンピユーター
CDE―SCH―4A”(スガ試験機)を用いて測定
した。なおHunterの色素△E(Lab)はその値が
小さい程好ましく、3以下では目立たない程度の
色の差を表わす。紫外線長期間暴露による表面劣
化状態は目視により判定した。すなわちある測定
値において成形品表面に細かなクラツク、ピンホ
ールが認められた時に×の記号でまた認められな
い時には〇の記号、そのどちらの状態ともいえな
い中間の状態であるとき△の記号を用いて判定し
た。
参考例 1〜8
参考例1〜8は硬質インテグラルスキンドフオ
ームに関し発泡剤と、ポリイソシアネートが異な
る場合の耐光性の参考例である。参考例1〜4は
発泡剤としてフロン11を使用した場合、参考例5
〜8は発泡剤としてペンタンを使用した場合であ
りそれぞれについてポリイソシアネートとして粗
MDI、純MDIカルボジイミド変成ポリイソシア
ネート、XDI、IPDIを使用した配合である。表
1に示した配合でポリオール成分を予め均一に混
合後、これにポリイソシアネートを加えすばやく
均一になるよう混合し30×30×1cmの金属型(型
温約45℃)に注入し成形板を作製した。これらの
成形板はフオーム層をはさんで両側に厚さ約1mm
のしつかりしたスキン層をもつ全体比重約0.4の
ものであつた。これを2×15×1cmの試験片に切
断し耐光性試験に供した。その結果を第1図に示
した。
The present invention relates to the photostability of polyurethane resin molded in a closed mold, and more specifically, the weather resistance of the surface of a light-colored molded product with high brightness due to the addition of a colorant, that is, the color of the polyurethane resin surface mainly due to ultraviolet rays and heat. It relates to a method for significantly improving yellowing and its deterioration. Polyurethane resin has excellent properties that allow it to be molded into a wide range of shapes from soft to hard depending on its formulation, so it can be used in vehicles, transportation, machinery, furniture, office, electrical and audio equipment, building materials and housing, sports and leisure, etc. It is used for various purposes. These are generally classified into integral skin foam, structural foam, microcellular foam, and solid (elastomer), and are molded into various shapes. When these molded products are left exposed to the atmosphere, there is a problem in that surface deterioration such as color change (yellowing), small cracks, and pinholes occur on the surface of the molded product mainly due to ultraviolet rays and heat. Generally, these problems have been solved by applying a coating with excellent light resistance to the surface of the molded product. However, coating a molded product requires many steps and equipment, such as removing the mold release agent from the surface of the molded product, drying it, applying the paint, and drying it to harden it. In addition, it requires a great deal of time, effort, energy, and even more sophisticated skill. This has led to a significant increase in costs, and there has been a strong demand for molded products that do not require a painting process, that is, molded products that are colored by directly adding a coloring agent to polyurethane resin and that are weather resistant themselves. As a result of various studies on the light resistance of polyurethane resins, the present inventors found that volatile non-halogen compounds (pentane, hexane, acetone, tetrahydrofuran, , saturated hydrocarbons such as methyl acetate and methyl formate, and oxygen-containing compounds without active hydrogen) were used as blowing agents to obtain molded products with outstanding light resistance. . In this method, general-purpose MDI, TDI and their prepolymers are used as polyisocyanates.
Pure MDI carbodiimide modified polyisocyanate etc. could be used. When a colorant is added to this to color the molded article, the light resistance is further improved due to the hiding power of the colorant. However, when the isocyanate itself is brownish like crude MDI, a dark coloring agent will hide the coloring of the isocyanate itself, so although the desired color could be achieved,
When using light colors such as cream, light yellow, and light green, the color becomes a mixture of the light coloring agent and the brownish brown of the isocyanate, making it impossible to achieve the desired color. In this case, the color of the polyisocyanate is colorless or pale yellow.
By using TDI, prepolymer, XDI (xylylene diisocyanate), carbodiimide-modified polyisocyanate, etc., it was possible to color the desired color by adding a light coloring agent. However, these polyisocyanates do not have sufficient light resistance and turn yellow over time, and the hiding power of the pale coloring agent is not strong enough to hide it, resulting in a color different from the desired color. In this way, when a volatile non-halogen compound is used as a blowing agent, if the surface of the molded product is colored in a dark color with a lightness of less than 5, which is represented by the Munsell symbol, it is possible to use a general-purpose polyisocyanate by adding the colorant. The light resistance is good and it is possible to make molded products without painting. On the other hand, light-colored products having a surface coloring with a lightness of 5 or more in the Munsell symbol have the disadvantage that the color changes over time due to ultraviolet irradiation, resulting in a color different from the desired color. The present invention has been made as a result of intensive studies in view of the above situation, and is based on the following: (a) Volatile non-halogen It is characterized by blending the compound (b) isophorone diisocyanate and (c) a coloring agent having a surface color of a molded article with a lightness of 5 or more expressed by the Munsell symbol. That is, a polyurethane resin composed of a compound system consisting of polyol, isophorone diisocyanate, catalyst, colorant, foam stabilizer, volatile non-halogen compound (foaming agent), and other stabilizers and auxiliary agents as necessary is molded in a closed mold. It's a method. Volatile non-halogen compounds include saturated hydrocarbons with boiling points in the range of 20 to 100°C under vapor pressure, such as pentane, hexane, heptane, petroleum ether, acetone, tetrahydrofuran, propylene oxide, methyl acetate, and methyl formate, and active hydrogen. Examples include oxygen-containing compounds that do not have These blowing agents may be used in combination of two or more types or in combination with a chemical blowing agent such as water. Stabilizers include antioxidants, ultraviolet absorbers, and hydrolysis inhibitors, and at least one selected from these is added and used, and the amount added is preferably 0.1 to 6% by weight. Antioxidants include hindered phenols, phenols, hindered amines, and phosphites. Among these, the relatively good ones are hindered phenols, especially 2,6 di-t-butyl.
4-methylphenol gave good results. Ultraviolet absorbers include benzophenones, salicylic acid esters, benzotriazoles, etc. Among these, benzotriazoles were good. The hydrolysis inhibitor is used to inhibit or prevent hydrolysis of polyurethane resin, and includes polymeric carbodiimide. These stabilizers can be used alone or in combination of two or more, and the amount added is preferably 0.1 to 6% by weight, and more preferably 0.5 to 2% by weight. If added alone, the amount used will be large in order to achieve the effect, and the stabilizer may have an adverse effect on the moldability of the polyurethane resin, so its selection is important. Preferably, the addition of two or more types is good, and in that case, the amount added is smaller than the case of adding only one type, and the same effect can be achieved. Examples of auxiliary agents include internal mold release agents and flame retardants, which can be added as necessary. How to mold polyurethane resin in a closed mold
The RIM (Reaction Injection Molding) method is a typical method, and it molds into integral skin foam, structural foam, microcellular, and solid (elastomer) forms using various formulations. integral skinned form,
Both structural foam and microcellular foam require a blowing agent during their formulation. Solids (elastomers) are used with a small amount, usually 0.1 to 3 parts, of a blowing agent added for the purpose of overpacking the resin in the mold. Polyurethane resins using these blowing agents that have extremely poor light resistance are integral skinned foams, particularly hard integral skinned foams (structural foams). This is thought to be because the foaming agent is trapped in the skin layer of integral skinned foam, which has skin layers on both sides of the foam layer, and this greatly affects the light resistance. This is clear from the following points. When a halogen-containing compound such as Freon 11 is used as a physical foaming agent, the light resistance deteriorates significantly, whereas when a non-halogen compound is used, the light resistance is significantly improved. Further, even if a halogen-containing compound is used, the light resistance can be improved to some extent by forcibly removing the foaming agent present in the skin layer by vacuum treatment or the like. The yellowing and deterioration mechanism of polyurethane resin is thought to be as follows. (Advances in Urethane Science and
Technology, Vol6, P103-172, Technomic
Pub., 1978) The decomposition products of polyurethane resins caused by ultraviolet rays are olefins, aldehydes, ketones, etc., and the mechanism of their formation is thought to be as follows. In the reaction shown by Beachell et al., polyurethane dissociates to produce isocyanate (1), and amine (2) is produced by decarboxylation of the urethane group. It is said that the reaction product of polycarbodiimide (3) and alcohol is added and the coloring increases. Schollenberger et al. reported that TDI and MDI-based polyurethanes yellow mainly due to the conversion of benzene rings into quinone and quinone imidization by ultraviolet rays. Conventional measures to prevent yellowing in the formulation of polyurethane resin include (1) adding ultraviolet absorbers and antioxidants, and (2) introducing an alkylene group between the benzene nucleus and -NCO group to suppress resonance between the two. Isocyanates such as XDI (xylylene diisocyanate)
method using (3) A method using an alicyclic polyisocyanate, such as hydrogenated MDI or IPDI (isophorone diisocyanate). (4) A common method is to use a lipophilic polyisocyanate that does not contain conjoint double bonds, such as HMDI (hexamethylene diisocyanate). (1) is a method of improving light resistance by adding a stabilizer, and (2) to (4) is a method of improving light resistance by using an isocyanate. In experiments conducted by the present inventors, the method (1) of adding a stabilizer was not very effective in preventing yellowing. In the methods (2) to (4) using isocyanates, when a halogen-containing compound was used as a blowing agent, no great effect was observed in preventing yellowing, and some yellowing occurred. This is thought to be because the foaming agent present in the skin layer is decomposed by ultraviolet rays to produce halogen, and the halogen causes oxidation reactions, radical reactions, etc., resulting in yellowing. Therefore, even if an isocyanate having a structure that is difficult to form a quinone or quinone imide structure is used, yellowing is thought to occur due to the reaction of Beachell et al. mentioned above. On the other hand, when a volatile non-halogen compound that does not contain a halogen element and is relatively stable against ultraviolet rays and heat is used as a blowing agent as in the present invention, there is nothing that promotes the yellowing reaction and the light resistance is extremely good. Become something. The difference in effectiveness when conventionally known isophorone diisocyanate is used in the light resistance formulation in the present invention is that the light resistance can be significantly improved by using a volatile non-halogen compound as a blowing agent. It is also highly effective in improving the light resistance of light-colored products with a brightness of 5 or more as represented by the Munsell symbol. This will be explained in more detail below with reference to Examples. For accelerated light resistance testing, test pieces were tested using a fade meter (carbon arc) at a black panel temperature of 63°C.
I did it at The evaluation was made by measuring the color before and after the test using a tristimulus value X, Y, Z system, and using Hunter color difference. Color measurement is done using “direct reading measurement color difference computer”
Measured using "CDE-SCH-4A" (Suga Test Instruments).For Hunter's dye ΔE (Lab), the smaller the value, the better; 3 or less indicates an inconspicuous color difference.Long-term UV rays The state of surface deterioration due to exposure was determined by visual inspection.In other words, when small cracks or pinholes were observed on the surface of the molded product in a certain measurement value, they were marked with an x symbol, and when they were not observed, they were marked with an ○ symbol. Reference examples 1 to 8 Reference examples 1 to 8 are reference examples of light resistance when the blowing agent and polyisocyanate are different for hard integral skinned foam. Yes.Reference Examples 1 to 4 use Freon 11 as a blowing agent, and Reference Example 5
-8 are cases where pentane is used as a blowing agent, and each is treated as a crude polyisocyanate.
This is a formulation using MDI, pure MDI carbodiimide modified polyisocyanate, XDI, and IPDI. After uniformly mixing the polyol components in advance with the formulation shown in Table 1, add polyisocyanate to this and quickly mix until uniform, then pour into a 30 x 30 x 1 cm metal mold (mold temperature approximately 45°C) and form a molded plate. Created. These molded plates are approximately 1mm thick on both sides with a foam layer in between.
It had a firm skin layer and an overall specific gravity of approximately 0.4. This was cut into test pieces of 2 x 15 x 1 cm and subjected to a light resistance test. The results are shown in Figure 1.
【表】
これより耐光性は発泡剤により大きく影響され
ることは明らかであり、含ハロゲン化合物のフロ
ン11を発泡剤として使用した場合耐光性は著しく
悪い。これに対し揮発性非ハロゲン化合物の場合
は耐光性が著しく改善される。耐光性に優れてい
るといわれる公知のXDI、IPDI(イソホロンジイ
ソシアネート)でもフロン11を使用した場合耐光
性は悪くなる。そしてIPDIの場合、耐光性の評
価上用いた色差△E(Lab)は8前後でありそれ
は目視感覚では“muck”(多いに)で表現され、
最初の色と多いに異なつた色になることを示す。
△E(Lab)は3以下が良好でありそれは最初の
色に対し目立たない程度であることを示す。
IPDIに対しペンタンの使用は△E(Lab)が3〜
4であり良好な耐光性を示す。
比較例1〜11および実施例1〜5
比較例1〜11および実施例1〜5は硬質インテ
グラルスキンドフオームに関し着色剤が異なる場
合の比較例および実施例である。比較例1〜8は
純MDIカルボジイミド変成ポリイソシアネート
およびペンタンを用いて着色剤が異なる場合の比
較例である。これはイソシアネート自身の色が淡
黄色であり、これに淡色着色剤を添加して所望の
色が出せるものである。比較例9〜11はイソホロ
ンジイソシアネート、およびフロン11を用いて淡
色着色剤を添加した比較例である。実施例1〜5
はイソホロンジイソシアネート、およびペンタン
を用いて淡色着色剤を添加した実施例である。表
2に示した配合でポリオール成分を予め均一に混
合後、これにポリイソシアネートを加えすばやく
均一になるよう混合し30×30×1cmの金属型(型
温約45℃)に注入し成形板を作製した。これらの
成形板はフオーム層をはさんで両側に厚さ約1mm
のしつかりしたスキン層をもつ全体比重約0.4の
ものであつた。これを2×15×1cmの試験片に切
断し耐光性試験に供した。その結果を第2図およ
び第3図に示した。比較例1〜8のカルボジイミ
ド変成ポリイソシアネート、ペンタン、着色剤よ
り成る系では耐光性は大きく3つに分類される。
1つは紫外線照射200hysまで色差△E(Lab)が
3以下のもの。1つは色差△E(Lab)が8〜10
のもので他の1つは色差△E(Lab)が20以上と
なるものである。これらは着色剤によつて異なつ
ており着色剤の明度の高いもの程、すなわち淡色
なもの程耐光性は悪くなつている。マンセル記号
で表わされる明度5未満の濃色なものは着色剤の
陰ぺい力が強いこともあり耐光性は△E(Lab)
が3以下と良好である。しかしながらマンセル記
号での明度5以上のものはその値が高くなる程耐
光性は悪く色差△E(Lab)の値が大きくなり初
期の色とはかけ離れた色になつてしまう。このマ
ンセル記号で表わされる明度5以上の淡色着色剤
添加による成形品表面をもつ成形品の耐光性は実
施例1〜5に示したようにイソホロンジイソシア
ネート、ペンタン、着色剤の系で良好な結果を示
す。この場合比較例9〜11で示したように発泡剤
としてフロン11を用いた場合は耐[Table] It is clear from this that the light resistance is greatly affected by the blowing agent, and when the halogen-containing compound Freon 11 is used as the blowing agent, the light resistance is extremely poor. In contrast, in the case of volatile non-halogen compounds, the light resistance is significantly improved. Even with the well-known XDI and IPDI (isophorone diisocyanate), which are said to have excellent light resistance, the light resistance deteriorates when Freon 11 is used. In the case of IPDI, the color difference △E (Lab) used for evaluating light resistance is around 8, which is expressed visually as "muck".
Indicates that the color will be much different from the initial color.
A value of ΔE (Lab) of 3 or less is good, indicating that it is not noticeable compared to the original color.
When using pentane for IPDI, △E (Lab) is 3 ~
4, indicating good light resistance. Comparative Examples 1 to 11 and Examples 1 to 5 Comparative Examples 1 to 11 and Examples 1 to 5 are comparative examples and examples in which different colorants are used for hard integral skinned foams. Comparative Examples 1 to 8 are comparative examples in which pure MDI carbodiimide-modified polyisocyanate and pentane were used and different colorants were used. The color of the isocyanate itself is pale yellow, and a desired color can be produced by adding a pale coloring agent to this. Comparative Examples 9 to 11 are comparative examples in which isophorone diisocyanate and Freon 11 were used to add a light coloring agent. Examples 1-5
This is an example in which isophorone diisocyanate and pentane were used to add a light coloring agent. After uniformly mixing the polyol components in advance with the formulation shown in Table 2, add polyisocyanate to this and quickly mix until uniform, then pour into a 30 x 30 x 1 cm metal mold (mold temperature approximately 45°C) and form a molded plate. Created. These molded plates are approximately 1mm thick on both sides with a foam layer in between.
It had a firm skin layer and an overall specific gravity of approximately 0.4. This was cut into test pieces of 2 x 15 x 1 cm and subjected to a light resistance test. The results are shown in FIGS. 2 and 3. In the systems of Comparative Examples 1 to 8 consisting of carbodiimide-modified polyisocyanate, pentane, and colorant, the light resistance is broadly classified into three types.
One type has a color difference △E (Lab) of 3 or less up to 200hys of ultraviolet irradiation. One is color difference △E (Lab) of 8 to 10.
The other one has a color difference ΔE (Lab) of 20 or more. These differ depending on the colorant, and the brighter the colorant, that is, the lighter the color, the worse the light resistance. Dark colors with a lightness of less than 5, represented by the Munsell symbol, have a strong shade of colorant, so their light resistance is △E (Lab).
is 3 or less, which is good. However, the higher the lightness value of 5 or more in the Munsell symbol, the worse the light fastness becomes, and the value of the color difference ΔE (Lab) increases, resulting in a color that is far different from the initial color. As shown in Examples 1 to 5, good results were obtained for the light resistance of molded products whose surface was created by adding a light colored colorant with a brightness of 5 or more expressed by the Munsell symbol. show. In this case, as shown in Comparative Examples 9 to 11, when Freon 11 is used as a foaming agent, the
【表】
光性は著しく悪化しイソホロンジイソシアネート
使用の意味をなさなくなる。
比較例12〜16および実施例6〜9
比較例12〜16および実施例6〜9は硬質インテ
グラルスキンドフオームに関し安定剤の種類およ
び発泡剤が異なる場合である。
比較例12〜16は比較例9の配合に安定剤を添加
したものであり、実施例6〜10は実施例1の配合
に安定剤を添加したものである。それらの配合を
表3に示した。これらの配合により前回と同様に
して成形板を作製し耐光性試験[Table] The optical property deteriorates significantly and the use of isophorone diisocyanate becomes meaningless. Comparative Examples 12 to 16 and Examples 6 to 9 Comparative Examples 12 to 16 and Examples 6 to 9 are cases in which the types of stabilizers and blowing agents are different regarding rigid integral skinned foams. Comparative Examples 12 to 16 were obtained by adding a stabilizer to the formulation of Comparative Example 9, and Examples 6 to 10 were obtained by adding a stabilizer to the formulation of Example 1. Their formulations are shown in Table 3. Using these formulations, molded plates were made in the same manner as before and a light resistance test was carried out.
【表】
を行いその表面劣化状態を観察しその結果を表4
に示した。[Table] The surface deterioration state was observed and the results are shown in Table 4.
It was shown to.
【表】
〓 の。
これより安定剤の添加は紫外線長期間暴露によ
る成形品表面の劣化状態を著しく改善でき、発泡
剤として揮発性非ハロゲン化合物を使用するとさ
らに改善される。また安定剤は単独添加より組合
せて使用した方が効果的である。
以上詳述したように本発明により成形されたポ
リウレタン樹脂は、耐光性を補うための塗装を必
要とせず、マンセル記号で表わされる明度5以上
の淡色成形品表面色を有するものでも耐光性は優
れている。さらにこの配合に安定剤を添加するこ
とにより紫外線長期間暴露による細かなクラツ
ク、ピンホール等の表面状態の劣化を著しく改善
することができる。[Table] 〓.
The addition of a stabilizer can significantly improve the deterioration of the surface of a molded article due to long-term exposure to ultraviolet rays, and the use of a volatile non-halogen compound as a blowing agent further improves this. In addition, it is more effective to use stabilizers in combination than to add them singly. As detailed above, the polyurethane resin molded according to the present invention does not require painting to supplement light resistance, and has excellent light resistance even if the surface color of the molded product is a light color with a lightness of 5 or more expressed by the Munsell symbol. ing. Furthermore, by adding a stabilizer to this formulation, it is possible to significantly improve surface deterioration such as fine cracks and pinholes caused by long-term exposure to ultraviolet rays.
第1図はポリイソシアネート、発泡剤が異なる
硬質インテグラルスキンドフオームの紫外線照射
による照射時間と色差△E(Lab)の関係を示す
線図、第2図はカルボジイミド変成ポリイソシア
ネートによる着色剤が異なる硬質インテグラルス
キンドフオームの紫外線照射による照射時間と色
差△E(Lab)の関係を示す線図、第3図はイソ
ホロンジイソシアネートによる淡色着色剤、発泡
剤が異なる硬質インテグラルスキンドフオームの
紫外線照射による照射時間と色差△E(Lab)の
関係を示す線図である。
Figure 1 is a diagram showing the relationship between the irradiation time and color difference △E (Lab) due to ultraviolet irradiation of hard integral skin foams using different polyisocyanates and blowing agents. Figure 2 is a diagram showing the relationship between color difference △E (Lab) using different coloring agents using carbodiimide-modified polyisocyanates. A diagram showing the relationship between irradiation time and color difference △E (Lab) due to ultraviolet irradiation of hard integral skinned foam. Figure 3 shows ultraviolet ray irradiation of hard integral skinned foam with different foaming agents and light coloring agent using isophorone diisocyanate. FIG. 3 is a diagram showing the relationship between irradiation time and color difference ΔE (Lab).
Claims (1)
を反応させて発泡ポリウレタン樹脂成形品を製造
するにさいし、(a)揮発性非ハロゲン化合物(b)イソ
ホロンジイソシアネート及び(c)マンセル記号であ
らわされる明度5以上の成形品表面色を有する着
色剤を配合することを特徴とするポリウレタン樹
脂成形品の光安定化法。 2 揮発性非ハロゲン化合物が常圧下20℃〜100
℃の沸点を有する飽和炭化水素および/または活
性水素を有しない酸素含有炭化水素より選ばれる
化合物である特許請求の範囲第1項記載のポリウ
レタン樹脂成形品の光安定化法。[Claims] 1. When producing a foamed polyurethane resin molded product by reacting a polyol and a polyisocyanate in a closed mold, (a) a volatile non-halogen compound, (b) isophorone diisocyanate, and (c) Munsell symbol. 1. A method for photostabilizing polyurethane resin molded products, which comprises blending a colorant having a surface color of the molded product with a lightness of 5 or more. 2. Volatile non-halogen compounds at normal pressure from 20℃ to 100℃
The method for photostabilizing polyurethane resin molded articles according to claim 1, wherein the compound is selected from saturated hydrocarbons having a boiling point of 0.degree. C. and/or oxygen-containing hydrocarbons having no active hydrogen.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56012448A JPS57126815A (en) | 1981-01-29 | 1981-01-29 | Stabilization of polyurethane resin molding against light |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56012448A JPS57126815A (en) | 1981-01-29 | 1981-01-29 | Stabilization of polyurethane resin molding against light |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57126815A JPS57126815A (en) | 1982-08-06 |
JPS6332102B2 true JPS6332102B2 (en) | 1988-06-28 |
Family
ID=11805611
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP56012448A Granted JPS57126815A (en) | 1981-01-29 | 1981-01-29 | Stabilization of polyurethane resin molding against light |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS57126815A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2237024A (en) * | 1989-10-18 | 1991-04-24 | British Vita | Flexible polyurethane foam |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE1001853A7 (en) * | 1988-06-28 | 1990-03-20 | Recticel | Process for the preparation of flexible polyurethane foam. |
JP2735102B2 (en) * | 1988-09-28 | 1998-04-02 | 三井東圧化学株式会社 | Method for producing rigid polyurethane foam |
ZA902976B (en) | 1989-04-24 | 1991-01-30 | Wilhelm Huetzen Hans | Polyurethane foam material free of halogenated hydrocarbons and process for producting the same |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5036597A (en) * | 1973-06-18 | 1975-04-05 |
-
1981
- 1981-01-29 JP JP56012448A patent/JPS57126815A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5036597A (en) * | 1973-06-18 | 1975-04-05 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2237024A (en) * | 1989-10-18 | 1991-04-24 | British Vita | Flexible polyurethane foam |
Also Published As
Publication number | Publication date |
---|---|
JPS57126815A (en) | 1982-08-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0176013B1 (en) | Process for the preparation of foamed polyurethanes that are fitted with or covered by another material | |
CN102746485B (en) | Flexible polyurethane foam and manufacturing method thereof | |
CA2065910C (en) | Water blown integral skin polyurethane foams | |
DE3721058A1 (en) | METHOD FOR THE PRODUCTION OF COLD-CURING POLYURETHANE SOFT MOLDING FOAMS | |
DE2334259A1 (en) | POLYURETHANE FOAM WITH A FIRE-RESISTANT COMPLETE SKIN | |
EP2867268B1 (en) | Method for making skinned polyurethane foam composites | |
EP1117718A1 (en) | Mixture containing isocyanates as well as organic and/or inorganic acid anhydrides | |
EP0826706A2 (en) | Foamable polyurethane compositions with a good flow behaviour and process for the preparation of foamed polyurethane mouldings | |
JPS6332102B2 (en) | ||
EP0758659A1 (en) | Process for the preparation of low emission polyurethane moulding and composite materials and their use | |
EP0472080B1 (en) | Process for the preparation of rigid polyurethane foams | |
JPS6084319A (en) | Resin composition | |
US4542166A (en) | Steering wheel composed of a non-yellowing semi-rigid polyurethane foam | |
US3836487A (en) | High impact rigid self-skinned polyurethane foam and method | |
EP0512347B1 (en) | Process for the preparation of urethane groups-containing polyurea elastomers | |
EP0490145A1 (en) | Polyvinylchloride-Polyurethane foam laminates, method for their manufacture and for the production of liquid polyisocyanate mixtures containing urethane groups for the manufacture of the polyurethane foams | |
KR101329058B1 (en) | Polyurethane resin composition for casting for the upper of shoes having excellent workability | |
EP0017060B1 (en) | Process for preparing polyurethane elastomers | |
EP2365013A1 (en) | New weather-resistant polyurethane casting masses, method for their production and use | |
EP1127913A2 (en) | Process for preparing polyurethane foams | |
DE4013712A1 (en) | Environmentally-friendly mfr. of foam-backed plastics parts - using polyurethane lacquer to protect plastic from partly-halogenated blowing agent used in polyurethane foam backing mixt. | |
JPH01145110A (en) | Manufacture of polyurethane/polyurea molded product | |
US9517607B2 (en) | Skinned substrates with highly crosslinked polyurethane layer | |
JPH0759648B2 (en) | Polyurethane / Polyurea molded products Painted products | |
JPS595040A (en) | Manufacture of trim goods for vehicle |