JPWO2020217813A1 - ウレタン樹脂組成物、発泡ウレタンシート、及び、合成皮革 - Google Patents
ウレタン樹脂組成物、発泡ウレタンシート、及び、合成皮革 Download PDFInfo
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- JPWO2020217813A1 JPWO2020217813A1 JP2020545196A JP2020545196A JPWO2020217813A1 JP WO2020217813 A1 JPWO2020217813 A1 JP WO2020217813A1 JP 2020545196 A JP2020545196 A JP 2020545196A JP 2020545196 A JP2020545196 A JP 2020545196A JP WO2020217813 A1 JPWO2020217813 A1 JP WO2020217813A1
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Abstract
Description
(X)前記ウレタン樹脂組成物を起泡させ起泡液を得、この起泡液を離型紙上に塗布し、乾燥させ、前記基材(i)と貼り合わせる方法、
(Y)前記ウレタン樹脂組成物を起泡させ起泡液を得、この起泡液を、離型紙上に作製した表皮層上に塗布し、乾燥させ、前記基材(i)と貼り合わせる方法、
(Z)前記ウレタン樹脂組成物を起泡させ起泡液を得、この起泡液を前記基材(i)上に塗布し、乾燥させ、必要に応じて、その上に、離型紙上に作製した表皮層(iii)を貼り合わせる方法などが挙げられる。
メチルエチルケトン3,281質量部及びオクチル酸第一錫0.1質量部の存在下、ポリカーボネートポリオール(1,6−ヘキサンジオールを原料とするもの、数平均分子量;2,000)1,000質量部と、2,2−ジメチロールプロピオン酸17質量部と、エチレングリコール47質量部と、ジフェニルメタンジイソシアネート344質量部とを溶液粘度が20,000mPa・sに達するまで70℃で反応させた後、メタノール3質量部を加えて反応を停止させてウレタン樹脂のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル(Hydrophile−Lipophile Balance(以下、「HLB」と略記する);14)70質量部と、トリエチルアミン13質量部を混合させた後に、イオン交換水800質量部を加えて転相乳化させることで前記ウレタン樹脂(A−1)が水に分散した乳化液を得た。
次いで、前記乳化液からメチルエチルケトンを留去することによって、ウレタン樹脂(A−1)50質量%を含むウレタン樹脂組成物を得た。
メチルエチルケトン3,281質量部及びオクチル酸第一錫0.1質量部の存在下、ポリオキシテトラメチレングリコール(数平均分子量;2,000)1,000質量部と、2,2−ジメチロールプロピオン酸17質量部と、エチレングリコール47質量部と、MDIを344質量部とを溶液粘度が20,000mPa・sに達するまで70℃で反応させた後、メタノール3質量部を加えて反応を停止させてウレタン樹脂のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル(HLB;14)70質量部と、トリエチルアミン13質量部を混合させた後に、イオン交換水800質量部を加えて転相乳化させることで前記ウレタン樹脂(A−2)が水に分散した乳化液を得た。
次いで、前記乳化液からメチルエチルケトンを留去することによって、ウレタン樹脂(A−2)50質量%を含むウレタン樹脂組成物を得た。
メチルエチルケトン3,281質量部及びオクチル酸第一錫0.1質量部の存在下、ポリカーボネートポリオール(1,6−ヘキサンジオールを原料とするもの、数平均分子量;2,000)300質量部と、ポリオキシテトラメチレングリコール(数平均分子量;2,000)700質量部と、2,2−ジメチロールプロピオン酸17質量部と、エチレングリコール47質量部と、MDIを344質量部とを溶液粘度が20,000mPa・sに達するまで70℃で反応させた後、メタノール3質量部を加えて反応を停止させてウレタン樹脂のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル(HLB;14)70質量部と、トリエチルアミン13質量部を混合させた後に、イオン交換水800質量部を加えて転相乳化させることで前記ウレタン樹脂(A−3)が水に分散した乳化液を得た。
次いで、前記乳化液からメチルエチルケトンを留去することによって、ウレタン樹脂(A−3)50質量%を含むウレタン樹脂組成物を得た。
メチルエチルケトン3,281質量部及びオクチル酸第一錫0.1質量部の存在下、ポリカーボネートポリオール(1,6−ヘキサンジオールを原料とするもの、数平均分子量;2,000)500質量部と、ポリオキシテトラメチレングリコール(数平均分子量;2,000)500質量部と、2,2−ジメチロールプロピオン酸17質量部と、エチレングリコール47質量部と、MDIを344質量部とを溶液粘度が20,000mPa・sに達するまで70℃で反応させた後、メタノール3質量部を加えて反応を停止させてウレタン樹脂のメチルエチルケトン溶液を得た。このウレタン樹脂溶液にポリオキシエチレンジスチレン化フェニルエーテル(HLB;14)70質量部と、トリエチルアミン13質量部を混合させた後に、イオン交換水800質量部を加えて転相乳化させることで前記ウレタン樹脂(A−4)が水に分散した乳化液を得た。
次いで、前記乳化液からメチルエチルケトンを留去することによって、ウレタン樹脂(A−4)50質量%を含むウレタン樹脂組成物を得た。
合成例1で得られたウレタン樹脂(A−1)組成物30質量部及び合成例2で得られたウレタン樹脂(A−2)組成物70質量部に、増粘剤(Borchers社製「Borchi Gel ALA」)2質量部、ステアリン酸アンモニウム0.5質量部、架橋剤(日本触媒株式会社製「エポクロスWS−700」)4質量部を加え、メカニカルミキサーを使用して2,000rpmで1分間撹拌し、起泡させ、1.5倍の体積にした起泡液を得た。
これを離型紙に塗布し、80℃で3分間、さらに120℃で2分間乾燥させることで、発泡ウレタンシートを製造した。
実施例1において、ウレタン樹脂(A−1)の配合量を50質量部、ウレタン樹脂(A−2)の配合量を50質量部に変更した以外は、実施例1と同様にして、発泡ウレタンシートを得た。
実施例1において、ウレタン樹脂(A−1)の配合量を80質量部、ウレタン樹脂(A−2)の配合量を20質量部に変更した以外は、実施例1と同様にして、発泡ウレタンシートを得た。
合成例3で得られたウレタン樹脂(A−3)組成物100質量部に、増粘剤(Borchers社製「Borchi Gel ALA」)2質量部、ステアリン酸アンモニウム0.5質量部、架橋剤(日本触媒株式会社製「エポクロスWS−700」)4質量部を加え、メカニカルミキサーを使用して2,000rpmで1分間撹拌し、起泡させ、1.5倍の体積にした起泡液を得た。
これを離型紙に塗布し、80℃で3分間、さらに120℃で2分間乾燥させることで、発泡ウレタンシートを製造した。
合成例4で得られたウレタン樹脂(A−4)組成物100質量部に、増粘剤(Borchers社製「Borchi Gel ALA」)2質量部、ステアリン酸アンモニウム0.5質量部、架橋剤(日本触媒株式会社製「エポクロスWS−700」)4質量部を加え、メカニカルミキサーを使用して2,000rpmで1分間撹拌し、起泡させ、1.5倍の体積にした起泡液を得た。
これを離型紙に塗布し、80℃で3分間、さらに120℃で2分間乾燥させることで、発泡ウレタンシートを製造した。
合成例1で得られたウレタン樹脂(A−1)組成物30質量部及び合成例2で得られたウレタン樹脂(A−2)組成物70質量部に、増粘剤(Borchers社製「Borchi Gel ALA」)2質量部、ドデシルベンゼンスルホン酸ナトリウム1.5質量部、架橋剤(日本触媒株式会社製「エポクロスWS−700」)4質量部を加え、メカニカルミキサーを使用して2,000rpmで1分間撹拌し、起泡させ、1.5倍の体積にした起泡液を得た。
これを離型紙に塗布し、80℃で3分間、さらに120℃で2分間乾燥させることで、シートを製造した。
合成例1で得られたウレタン樹脂(A−1)組成物100質量部に、増粘剤(Borchers社製「Borchi Gel ALA」)2質量部、ステアリン酸アンモニウム0.5質量部、架橋剤(日本触媒株式会社製「エポクロスWS−700」)4質量部を加え、メカニカルミキサーを使用して2,000rpmで1分間撹拌し、起泡させ、1.5倍の体積にした起泡液を得た。
これを離型紙に塗布し、80℃で3分間、さらに120℃で2分間乾燥させることで、発泡ウレタンシートを製造した。
合成例2で得られたウレタン樹脂(A−2)組成物100質量部に、増粘剤(Borchers社製「Borchi Gel ALA」)2質量部、ステアリン酸アンモニウム0.5質量部、架橋剤(日本触媒株式会社製「エポクロスWS−700」)4質量部を加え、メカニカルミキサーを使用して2,000rpmで1分間撹拌し、起泡させ、1.5倍の体積にした起泡液を得た。
これを離型紙に塗布し、80℃で3分間、さらに120℃で2分間乾燥させることで、発泡ウレタンシートを製造した。
合成例で用いたポリオール等の数平均分子量は、ゲル・パーミエーション・カラムクロマトグラフィー(GPC)法により、下記の条件で測定した。
カラム:東ソー株式会社製の下記のカラムを直列に接続して使用した。
「TSKgel G5000」(7.8mmI.D.×30cm)×1本
「TSKgel G4000」(7.8mmI.D.×30cm)×1本
「TSKgel G3000」(7.8mmI.D.×30cm)×1本
「TSKgel G2000」(7.8mmI.D.×30cm)×1本
検出器:RI(示差屈折計)
カラム温度:40℃
溶離液:テトラヒドロフラン(THF)
流速:1.0mL/分
注入量:100μL(試料濃度0.4質量%のテトラヒドロフラン溶液)
標準試料:下記の標準ポリスチレンを用いて検量線を作成した。
東ソー株式会社製「TSKgel 標準ポリスチレン A−500」
東ソー株式会社製「TSKgel 標準ポリスチレン A−1000」
東ソー株式会社製「TSKgel 標準ポリスチレン A−2500」
東ソー株式会社製「TSKgel 標準ポリスチレン A−5000」
東ソー株式会社製「TSKgel 標準ポリスチレン F−1」
東ソー株式会社製「TSKgel 標準ポリスチレン F−2」
東ソー株式会社製「TSKgel 標準ポリスチレン F−4」
東ソー株式会社製「TSKgel 標準ポリスチレン F−10」
東ソー株式会社製「TSKgel 標準ポリスチレン F−20」
東ソー株式会社製「TSKgel 標準ポリスチレン F−40」
東ソー株式会社製「TSKgel 標準ポリスチレン F−80」
東ソー株式会社製「TSKgel 標準ポリスチレン F−128」
東ソー株式会社製「TSKgel 標準ポリスチレン F−288」
東ソー株式会社製「TSKgel 標準ポリスチレン F−550」
合成例で得られたウレタン樹脂組成物を離型紙に塗布し(塗布厚さ150μm)、熱風乾燥機にて70℃、4分間、次いで120℃で2分間乾燥することで乾燥物を得た。この乾燥物を、株式会社島津製作所製フローテスター「CFT−500A」(口径1mm、長さ1mmのダイスを使用、荷重98N、昇温速度3℃/分)を使用して、流動開始温度を測定した。
得られた発泡ウレタンシートを手で触り、以下のように評価した。
「A」:柔軟性に富む。
「B」:やや柔軟性がある。
「C」:柔軟性が劣る。
「D」:硬い。
実施例及び比較例で得られた発泡ウレタンシートを、不織布に貼り合わせることで合成皮革を得た。得られた合成皮革を幅50mm、長さ50mmに裁断したものを試験片とした。この試験片を80℃でオレイン酸に24時間浸漬した後取り出し、表面に付着したオレイン酸を紙ウエスで軽く拭き取った。オレイン酸浸漬前後の外観変化を目視観察し、以下のように評価した。
「T」:外観変化なし。
「F」:合成皮革が膨張、及び/又は、変形している。
実施例及び比較例で得られた発泡ウレタンシートを、不織布に貼り合わせることで合成皮革を得た。得られた合成皮革をフレキソメーター(株式会社安田精機製「低温フレキシオメーター」)で屈曲性試験(−30℃、100回/毎分)を行い、合成皮革の表面に我が生じるまでの回数を測定し、以下のように評価した。
「A」:15,000回以上
「B」:10,000回以上15,000回未満
「C」:10,000回未満
Claims (6)
- ウレタン樹脂(A)、水(B)、及び、芳香環を有さず、かつ炭素原子数が10以上の疎水部を有する界面活性剤(C)を含有するウレタン樹脂組成物であり、前記ウレタン樹脂組成物が、ウレタン樹脂(A)に由来する、カーボネート構造(X)とオキシアルキレン構造(Y)とを有することを特徴とするウレタン樹脂組成物。
- 前記カーボネート構造(X)と前記オキシアルキレン構造(Y)との質量比[X/Y]が、10/90〜90/10の範囲である請求項1記載のウレタン樹脂組成物。
- 前記界面活性剤(C)が、ステアリン酸塩である請求項1又は2記載のウレタン樹脂組成物。
- 前記ウレタン樹脂(A)が、アニオン性基を有するものである請求項1〜3のいずれか1項記載のウレタン樹脂組成物。
- 請求項1〜4のいずれか1項記載のウレタン樹脂組成物により形成された、密度が200〜1,000kg/m3であることを特徴とする発泡ウレタンシート。
- 少なくとも、基材(i)、及び、ポリウレタン層(ii)を有する合成皮革であって、
前記ポリウレタン層(ii)が、請求項5記載の発泡ウレタンシートにより形成されているものであることを特徴とする合成皮革。
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JP2019112564A (ja) * | 2017-12-25 | 2019-07-11 | 日華化学株式会社 | 発泡体形成用組成物、発泡体、発泡体の製造方法及び皮革用材 |
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