JP5435695B2 - 脂肪族イソシアネート由来の単位を有するポリウレタンを含むポリエステル−ポリウレタンハイブリッド樹脂の成形用組成物 - Google Patents
脂肪族イソシアネート由来の単位を有するポリウレタンを含むポリエステル−ポリウレタンハイブリッド樹脂の成形用組成物 Download PDFInfo
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- JP5435695B2 JP5435695B2 JP2008527369A JP2008527369A JP5435695B2 JP 5435695 B2 JP5435695 B2 JP 5435695B2 JP 2008527369 A JP2008527369 A JP 2008527369A JP 2008527369 A JP2008527369 A JP 2008527369A JP 5435695 B2 JP5435695 B2 JP 5435695B2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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Description
本発明は一つの観点からはポリウレタン樹脂とポリエステル樹脂とを組み合せたハイブリッド樹脂に関するものであり、別の観点からは脂肪族イソシアネートに由来の単位を含むポリウレタンから成るハイブリッド樹脂に関するものである。
本発明はさらに、上記ハイブリッド樹脂で作られた被覆材料に関するものである。
A.脂肪族多官能性イソシアネート化合物と、フリーラジカル重合開始剤とを含むA部分の組成物、
B.水をほとんど含まないエチレン性不飽和ポリエステルポリオールと、ポリウレタン触媒とを含むB部分の組成物。
ハイブリッド樹脂のA部分の組成物中に用いられる不飽和エチレンモノマーは、ビニル付加重合によって不飽和ポリエステルポリオールを架橋することができる任意の不飽和エチレンモノマーにすることができる。有用な不飽和エチレンモノマーの例としてはスチレン、o−、m−、p−メチルスチレン、メチルアクリレート、メチルメタクリレート、t−ブチルスチレン、ジビニルベンゼン、ジアリルフタレート、トリアリルシアヌレートおよび不飽和モノマーの2種以上の混合物が挙げられる。好ましいモノマーは経済的なモノマー溶液となるスチレンである。
(a)N,N−ジメチルシクロヘキシルアミンのような第三アミン、
(b)トリアルキルホスフィンのような第三ホスフィン、
(c)アルカリおよびアルカリ土類金属水酸化物、アルコキシドおよびフェノキシドのような強塩基、
(d)塩化鉄のような強酸の酸性金属塩、
(e)ジブチル錫ジラウレート、カルボキシル酸ビスマスおよびジルコニウムキレート2,4−ペンタンジオンのような有機金属化合物。
ポリウレタン製造でよく用いられるその他の触媒は下記文献に記載されている。
液体を射出する開放成形法も上記と同じ手順を行なうが、この場合にはハイブリッド樹脂をモールド上に噴霧する。従って、成形部品の片側は周囲雰囲気に曝されている。この成形方法は一般に「吹付け成形」とよばれる。液体を直接注入する成形ではポリオールとポリイソシアネートとを手練りした後、ハイブリッド液体をモールド中または上に注入し、ここで硬化させる。射出と注入の違いは混合時間、混合強度および射出圧力にある。いずれの液体成形法でもポリオールおよび/またはポリイソシアネートは繊維材料、充填材および/またはその他の添加剤を含むことができるが、ゲルコート用途では樹脂は一般的に繊維材料および充填材を全く含まない。
B部分または成分は不飽和ポリエステル樹脂、湿潤剤、均染助剤、促進包装材料、充填材、ポリウレタン触媒、粘度調整剤および顔料を含む。
一つの典型的な配合は下記から成る(重量部):
成分表示 重量部
不飽和ポリエステルポリオール 873.43
黒色顔料分散剤 1.12
鉄黄顔料分散剤 1.80
白色顔料分散剤 92.83
脱泡剤 2.5
クレー(第四アンモニウム処理) 12.48
タルク 12.48
オクタン酸コバルト溶液 0.87
ジブチル錫ジラウレート 1.25
シリコン溶液200cSt-フィッシュアイ除去剤 1.25
以下、本発明の実施例をさらに説明する。以下の実施例の全ての粘度は、粘度計を設定速度で約2分間運転させた後に測定した。
不飽和ポリエステル樹脂の製造
攪拌器、凝縮器、温度計および窒素ガス導入管を備えた4リットル容のフラスコ中に、740gのジエチレングリコール、456gのプロピレングリコール、1060gのイソフタル酸を導入した。得られた混合物を酸価が10mg KOH/gに下がるまで210℃で約10時間加熱した。温度を150℃に下げた後、624gの無水マレイン酸を混合物に添加した。酸価が30〜50mg KOH/gになるまで反応を210℃でさらに6時間続けた。生成物を1460gの抑制スチレンとブレンドして4000グラムの清澄な樹脂溶液(樹脂A)を形成した。樹脂溶液の粘度は63%の固形分で約1000mPa.s(cP)である。樹脂粘度はRVT2番のスピンドルを備えたブルックフィールド粘度計によって25℃、20回転/分で測定する。
OH末端を有する不飽和ポリエステル樹脂の製造
攪拌器、凝縮器、温度計および窒素ガス導入管を備えた4リットル容のフラスコ中に、1380gのネオペンチルグリコール、202gのプロピレングリコール、994gのイソフタル酸を導入した。得られた混合物を酸価が10mg KOH/gに下がるまで210℃で約10時間加熱した。温度を150℃に下げた後、587gの無水マレイン酸を混合物に添加した。酸価が5mg KOH/g、OH価が130〜150mg KOH/gになるまで反応を210℃で続けた。生成物を1160gの抑制スチレンとブレンドして4000グラムの清澄な樹脂溶液(樹脂B)を形成した。樹脂溶液の粘度は71%の固形分で700mPa.s(cP)である。
100時間、沸騰水中での積層体の比較
実施例2と実施例4で得られたゲルコートサンプルを用いてゲルコート積層体を製造した。積層体は2つの異なる厚さのゲルコートを有する。ゲルコートの厚い断面(TK)は硬化ゲルコート厚さが約0.762mm(30ミル)で、ゲルコートの薄い断面(TN)は硬化ゲルコート厚さが約0.381mm(15ミル)である。このパネルを沸騰した脱イオン水中に100時間浸漬し、5つの分野で性能を0〜5段階で評価した。0の評価は変化なしを表し、5の評価は極端な変化を表す。この結果から、ポリエステル−ポリウレタンハイブリッドゲルコートは一般的なゲルコートに比べてはるかによい耐水性を有することがわかった。
各種温度での注型機械特性の比較
ゲルコートサンプルを注型品にし、注型品の引張特性をASTM規格D−638に従って測定した。引張特性は周囲温度、−10℃および−30℃で測定した。この結果から、ポリエステル−ポリウレタンハイブリッドゲルコートは一般的なゲルコートに比べて低温での引張伸び率の残率がはるかによいことがわかった。
裏面衝撃強度の比較
ゲルコート積層体の裏面衝撃強度を下記のASTM規格D−3029に従って測定した。各サンプルごとに全部で9回の試験を行い、平均値を報告した。この結果から、ポリエステル−ポリウレタンハイブリッドゲルコートは一般的なゲルコートに比べてはるかによい裏面衝撃強度を有することがわかった。
Claims (20)
- 下記AとBから成る硬化性ハイブリッド樹脂を硬化して得られるゲルコート:
A.脂肪族多官能性イソシアネート化合物と、フリーラジカル重合開始剤とを含み、任意成分としての上記脂肪族多官能性イソシアネート化合物と反応しない溶媒をさらに含むA部分の組成物、
B.水の量が全重量に対して2000ppm以下であるエチレン性不飽和ポリエステルポリオールと、ポリウレタン触媒とを含むB部分の組成物。 - 上記イソシアネート化合物が2,2,4−トリメチルヘキサメチレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネートおよびこれらのビウレットおよび環式トリマー誘導体の少なくとも一つである請求項1に記載のゲルコート。
- 上記イソシアネート化合物がヘキサメチレンジイソシアネートおよび/またはその誘導体である請求項1または2に記載のゲルコート。
- 上記イソシアネートがヘキサメチレンジイソシアネート環式トリマー誘導体である請求項3に記載のゲルコート。
- 上記ポリエステルポリオールが少なくとも一種のジカルボン酸アルケン部分を含む請求項1〜4のいずれか一項に記載のゲルコート。
- 上記ポリエステルポリオールが、{一種または複数の[飽和(ジ−またはポリカルボン酸または無水物)]}および{[不飽和(ジ−またはポリカルボン酸または無水物)}と、(グリコールまたは多価アルコール)との縮合反応によって得られるα,β−不飽和エチレンジカルボン酸化合物のオリゴマーから成る請求項1〜5のいずれか一項に記載のゲルコート。
- 上記フリーラジカル重合開始剤が過酸化物、過硫化物、過ホウ酸塩、過炭酸塩およびアゾ化合物の少なくとも一つである請求項1〜6のいずれか一項に記載のゲルコート。
- 上記ポリウレタン触媒が第三アミン、第三ホスフィン、アルカリおよびアルカリ土類金属水酸化物、アルコキシド、フェノキシド、酸性金属塩および有機金属化合物の少なくとも一つである請求項1〜7のいずれか一項に記載のゲルコート。
- B部分の組成物がその全重量に対して1000ppm以下の水を含む請求項1〜8のいずれか一項に記載のゲルコート。
- B部分の組成物が第三炭素上の水素、エーテルグリコールおよびテレフタル酸残基を含まない請求項1〜10のいずれか一項に記載のゲルコート。
- 下記(1)と(2)とから成る硬化性ハイブリッド樹脂組成物を硬化して得られるゲルコート:
(1)請求項1〜10のいずれか一項に記載のA部分の組成物 10〜50重量%、
(2)請求項1〜10のいずれか一項に記載のB部分の組成物 50〜90重量%。 - B部分の組成物の酸価が10以下、固体に対するヒドロキシル価が120〜170である請求項1〜11のいずれか一項に記載のゲルコート。
- B部分の固体に対するヒドロキシルヒドロキシル価が130〜160である請求項13に記載のゲルコート。
- A部分の組成物中の脂肪族多官能性イソシアネートのNCO含有率が5〜50%である請求項1〜12のいずれか一項に記載のゲルコート。
- A部分の組成物中の脂肪族多官能性イソシアネートのNCO含有率が10〜35%である請求項14に記載のゲルコート。
- 脂肪族ポリイソシアネートが少なくとも2つの官能基を有し且つB部分の組成物のポリエステルポリオールと反応可能である請求項1〜15のいずれか一項に記載のゲルコート。
- B部分の組成物のポリエステルポリオールにチキソトロピック剤を加える請求項1〜16のいずれか一項に記載のゲルコート。
- シリカ、脂肪酸アミド、クレーの中から選択されるチキソトロープ剤をB部分の組成物の重量に対して0.2〜5%の重量含有率で添加して上記ハイブリッド樹脂をチキソトロピックにした請求項17に記載のゲルコート。
- 請求項1〜18のいずれか一項に記載のゲルコートのハイブリッド樹脂または不飽和ポリエステル樹脂(UPR)またはビニルエステルまたはその他任意の熱硬化性樹脂で作られた複合成形品の基材上に塗布された請求項1〜18のいずれか一項に記載のゲルコート。
- 請求項1〜19のいずれか一項に記載のゲルコートを有する物品。
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DK (1) | DK1917286T3 (ja) |
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FR2903412B1 (fr) * | 2006-07-07 | 2012-10-05 | Cray Valley Sa | Pre-polymere urethane - polyester insature et ses applications |
EP2048172A1 (en) * | 2007-10-09 | 2009-04-15 | Cray Valley Ltd | Crosslinkable and foaming polyester-polyurethane (hybrid) resin moulding compositions, with foaming characteristics for closed mould applications |
US20110059319A1 (en) * | 2007-10-11 | 2011-03-10 | Tse Industries, Inc. | Method for spray forming high modulus polyurethane structures |
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CL2009000032A1 (es) * | 2008-01-11 | 2009-06-12 | Sherwin Williams Co | Composicion de revestimiento que comprende un sistema de resina que contiene al menos un poliol de poliester insaturado libre de resina acrilica y un agente de curado, adecuada para su aplicacion directa a los sustratos de metal; metodo para la imprimacion de un sustrato de metal; y composicion imprimadora. |
EP2414424B1 (en) | 2009-04-03 | 2018-12-19 | Polynt Composites USA Inc. | Thermosetting compositions containing isocyanurate rings |
CN101649176B (zh) * | 2009-08-25 | 2012-11-07 | 东华大学 | 不饱和脂肪族聚酯型聚氨酯粘合剂 |
US9371468B2 (en) | 2013-01-16 | 2016-06-21 | Composites Intellectual Holdings, Inc. | Co-cured gel coats, elastomeric coatings, structural layers, and in-mold processes for their use |
US10239265B2 (en) | 2013-03-15 | 2019-03-26 | Composites Intellectual Holdings, Inc. | Structural composite preform wet-out and curing system and method |
US10329763B2 (en) | 2016-02-24 | 2019-06-25 | Wabash National, L.P. | Composite floor structure and method of making the same |
US10815330B2 (en) * | 2016-04-22 | 2020-10-27 | Covestro Deutschland Ag | Thermolatently catalysed two-component system |
JP6697631B2 (ja) * | 2017-03-09 | 2020-05-20 | 富士フイルム株式会社 | 音響レンズ用樹脂材料、音響レンズ、音響波プローブ、音響波測定装置、超音波診断装置、光音響波測定装置および超音波内視鏡 |
CN108774393B (zh) * | 2018-06-22 | 2020-08-18 | 天津市中科众晟医疗科技有限责任公司 | 一种女性乳腺自查手套 |
CN111138845A (zh) * | 2020-01-19 | 2020-05-12 | 南京聚发新材料有限公司 | 一种片状模塑料、纤维增强复合材料及其制备方法和应用 |
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US20070049686A1 (en) | 2007-03-01 |
CA2620015A1 (en) | 2007-03-01 |
CA2620015C (en) | 2014-05-06 |
AU2006284121B2 (en) | 2011-12-15 |
DE602006007014D1 (de) | 2009-07-09 |
EP1917286A2 (en) | 2008-05-07 |
DK1917286T3 (da) | 2009-09-14 |
EP1917286B1 (en) | 2009-05-27 |
KR101318682B1 (ko) | 2013-10-16 |
US8742054B2 (en) | 2014-06-03 |
MX2008002450A (es) | 2008-04-03 |
AU2006284121A1 (en) | 2007-03-01 |
PL1917286T3 (pl) | 2009-10-30 |
KR20080039456A (ko) | 2008-05-07 |
MY141205A (en) | 2010-03-31 |
CN101243116A (zh) | 2008-08-13 |
CN101243116B (zh) | 2012-07-18 |
WO2007022932A2 (en) | 2007-03-01 |
ES2327449T3 (es) | 2009-10-29 |
SI1917286T1 (sl) | 2009-10-31 |
JP2009506146A (ja) | 2009-02-12 |
ATE432305T1 (de) | 2009-06-15 |
BRPI0615711A2 (pt) | 2011-05-24 |
ZA200801005B (en) | 2008-11-26 |
WO2007022932A3 (en) | 2007-05-03 |
BRPI0615711B1 (pt) | 2021-10-13 |
PT1917286E (pt) | 2009-08-24 |
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