JP5196088B1 - 皮革様シート及びその製造方法 - Google Patents
皮革様シート及びその製造方法 Download PDFInfo
- Publication number
- JP5196088B1 JP5196088B1 JP2012546286A JP2012546286A JP5196088B1 JP 5196088 B1 JP5196088 B1 JP 5196088B1 JP 2012546286 A JP2012546286 A JP 2012546286A JP 2012546286 A JP2012546286 A JP 2012546286A JP 5196088 B1 JP5196088 B1 JP 5196088B1
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- JP
- Japan
- Prior art keywords
- urethane resin
- skin layer
- leather
- sheet
- resin composition
- 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.)
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- 239000011342 resin composition Substances 0.000 claims abstract description 69
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 43
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- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
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- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
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- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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Abstract
本発明は、少なくとも1つの末端に2個以上の水酸基を有するウレタン樹脂(A)、及び、水性媒体(B)を含有するウレタン樹脂組成物を用いて形成される表皮層(C)と、接着層(D)と、支持体層(E)とを有することを特徴とする皮革様シートである。
【選択図】なし
Description
前記3級アミノ基の一部又は全てを中和する際に使用することができる酸としては、例えば、酢酸、プロピオン酸、乳酸、マレイン酸などの有機酸類や、スルホン酸、メタンスルホン酸等の有機スルホン酸類、及び、塩酸、硫酸、オルトリン酸、オルト亜リン酸等の無機酸等を単独または2種以上を組み合わせて使用してもよい。
前記工程1は、前記ポリオール(a1)とポリイソシアネート(a2)と必要に応じて鎖伸長剤(a3)とを反応させることによって末端にイソシアネート基を有するウレタンプレポリマーを製造する工程である。具体的には、無溶剤下または有機溶剤の存在下、前記ポリオール(a1)と前記ポリイソシアネート(a2)と、必要に応じて鎖伸長剤(a3)とを混合し、50℃〜100℃で概ね3時間〜10時間程度反応させることによって製造することができる。また、前記ポリオール(a1)と前記ポリイソシアネート(a2)とを前記と同様の方法で反応させた後に、前記反応物と鎖伸長剤(a3)とを混合し、更に反応することによって、目的とする末端にイソシアネート基を有するウレタンプレポリマーを製造することもできる。
工程2は、前記工程1で得られたイソシアネート基含有ウレタンプレポリマーまたはその有機溶剤溶液と、ポリアルカノールアミンとを混合し反応させることによって、得られるウレタン樹脂(A)中に存在する1以上の末端に、2個以上の水酸基を導入する工程である。
メチルエチルケトン1221g及びオクチル酸第一錫0.1gの存在下、ポリカーボネートジオール(ニッポランN980R;日本ポリウレタン工業(株):数平均分子量2000)1000gと、ジメチロールプロピオン酸34gと、ジシクロヘキシルメタンジイソシアネート(HMDI)187gとを、イソシアネート基が消失するまで70℃で反応させることによって、末端に水酸基を有するウレタン樹脂のメチルエチルケトン溶液を得た。
窒素雰囲気、オクチル酸第一錫0.1gの存在下、80℃に加温したポリカーボネートジオール(ニッポランN980R;日本ポリウレタン工業(株):数平均分子量2000)100gとジシクロヘキシルメタンジイソシアネート(HMDI)14gをメカニカルミキサーを用いて2000rpm、2分間撹拌し、次いで真空脱泡機を用いて脱泡することによって無溶剤接着剤(d1−2)を得た。
メチルエチルケトン710g及びオクチル酸第一錫0.1gの存在下、ポリカーボネートジオール(ニッポランN981;日本ポリウレタン工業(株):数平均分子量1000)1000gと、ジメチロールプロピオン酸67gと、ジシクロヘキシルメタンジイソシアネート(HMDI)590gとを、NCO%が2.7質量%に達するまで70℃で反応させることによって、末端イソシアネート基含有ウレタンプレポリマー(A’−1)のメチルエチルケトン溶液を得た。なお、前記NCO%は、前記ポリウレタンの製造に使用した原料の合計質量に対する、そのうちポリイソシアネートが有するイソシアネート基の質量の割合である。
一方、前記実施例1で使用した表皮層形成用のウレタン樹脂組成物〔I−1〕の100質量部を、離型紙(155T フラット 大日本印刷(株)製)上に、塗布後の膜厚が150μmとなるように塗布した。
メチルエチルケトン710g及びオクチル酸第一錫0.1gの存在下、ポリエステルジオール(プラクセル210、ダイセル化学(株)分子量約1000)1000gと、ジメチロールプロピオン酸67gと、ジシクロヘキシルメタンジイソシアネート(HMDI)590gとを、NCO%が2.7質量%に達するまで70℃で反応させることによって、末端イソシアネート基含有ウレタンプレポリマー(A’−2)のメチルエチルケトン溶液を得た。
メチルエチルケトン710g及びオクチル酸第一錫0.1gの存在下、ポリカーボネートジオール(ニッポランN981;日本ポリウレタン工業(株):数平均分子量1000)1000gと、ポリエチレングリコール(PEG1000、日油(株))50gと、ポリエチレングリコールモノメチルエーテル(ユニオックスM1000:日油(株))50gと、ジシクロヘキシルメタンジイソシアネート(HMDI)590gとを、NCO%が2.7質量%に達するまで70℃で反応させることによって、末端イソシアネート基含有ウレタンプレポリマー(A’−3)のメチルエチルケトン溶液を得た。
メチルエチルケトン630g及びオクチル酸第一錫0.1gの存在下、ポリカーボネートジオール(ニッポランN980R;日本ポリウレタン工業(株):数平均分子量2000)1000gと、ジメチロールプロピオン酸67gと、ジシクロヘキシルメタンジイソシアネート(HMDI)390gとを、NCO%が2.0質量%に達するまで70℃で反応させることによって、末端イソシアネート基含有ウレタンプレポリマー(A’−4)のメチルエチルケトン溶液を得た。
前記表皮層形成用のウレタン樹脂組成物〔I−1〕の代わりに、前記表皮層形成用のウレタン樹脂組成物〔IV−1〕100質量部を使用すること以外は、実施例1と同様の方法で皮革様シート〔V−2〕を得た。
メチルエチルケトン710g及びオクチル酸第一錫0.1gの存在下、ポリカーボネートジオール(ニッポランN981;日本ポリウレタン工業(株):数平均分子量1000)1000gと、ジメチロールプロピオン酸67gと、ジシクロヘキシルメタンジイソシアネート(HMDI)590gとを、NCO%が2.7質量%に達するまで70℃で反応させることによって、末端イソシアネート基含有ウレタンプレポリマー(A’−1)のメチルエチルケトン溶液を得た。
前記表皮層形成用のウレタン樹脂組成物〔I−1〕の代わりに、前記表皮層形成用のウレタン樹脂組成物〔V−1〕100質量部を使用すること以外は、実施例1と同様の方法で皮革様シート〔V−2〕を得た。
メチルエチルケトン710g及びオクチル酸第一錫0.1gの存在下、ポリカーボネートジオール(ニッポランN981;日本ポリウレタン工業(株):数平均分子量1000)1000gと、ジメチロールプロピオン酸67gと、ジシクロヘキシルメタンジイソシアネート(HMDI)590gとを、NCO%が2.7質量%に達するまで70℃で反応させることによって、末端イソシアネート基含有ウレタンプレポリマー(A’−1)のメチルエチルケトン溶液を得た。
メチルエチルケトン710g及びオクチル酸第一錫0.1gの存在下、ポリカーボネートジオール(ニッポランN981;日本ポリウレタン工業(株):数平均分子量1000)1000gと、ジメチロールプロピオン酸67gと、ジシクロヘキシルメタンジイソシアネート(HMDI)590gとを、NCO%が2.7質量%に達するまで70℃で反応させることによって、末端イソシアネート基含有ウレタンプレポリマー(A’−1)のメチルエチルケトン溶液を得た。
メチルエチルケトン710g及びオクチル酸第一錫0.1gの存在下、ポリカーボネートジオール(ニッポランN981;日本ポリウレタン工業(株):数平均分子量1000)1000gと、ジメチロールプロピオン酸67gと、ジシクロヘキシルメタンジイソシアネート(HMDI)590gとを、NCO%が2.7質量%に達するまで70℃で反応させることによって、末端イソシアネート基含有ウレタンプレポリマー(A’−1)のメチルエチルケトン溶液を得た。
実施例及び比較例で得た皮革様シートを構成する表皮層の表面に、1インチ幅のホットメルト布テープ(サン化成株式会社製)を130℃で5秒間かけて接着した後、JIS K6854−2に準拠して、テンシロン(ヘッドスピード=200mm/分)を用いて、温度23℃及び相対湿度65%の状態での剥離強度を測定した。前記皮革様シートを構成する表皮層の剥離強度が3.0kg/cm以上であれば、前記表皮層が前記支持体に対して実用上十分な密着性を有するものであると判断した。
前記実施例及び比較例で得た皮革様シートを構成する表皮層上に、乾燥濾紙の質量と同質量のオレイン酸を浸みこませた濾紙を載せた状態で、24時間、80℃加熱した。
前記実施例及び比較例で得た皮革様シートをオレイン酸に浸漬させ、3日間、25℃の環境下に放置した。
A;摩擦回数が5000回で皮革様シートの表皮層が剥離しなかった。
B;摩擦回数が5000回で皮革様シートの表皮層が剥離し基材が露出した。
C;摩擦回数が4000回で皮革様シートの表皮層が剥離し基材が露出した。
D;摩擦回数が3000回で皮革様シートの表皮層が剥離し基材が露出した。
E;擦過以前または摩擦回数が5回以内で皮革様シートの表皮層が剥離、基材が露出した。
前記実施例及び比較例で得た皮革様シートを構成する表皮層上に、乾燥濾紙の質量と同質量のサンオイル(BUG SUN;COPPERTORN社)を浸みこませた濾紙を載せた状態で、24時間、70℃で加熱した。
B;サンオイルを付着させる前と比較して、外観上、ごく一部で若干の膨潤(表皮層のフクレ)が見られたが、実用上問題ないレベルであり、表皮層の剥離も見られなかった。
C;サンオイルを付着させる前と比較して、外観上、明確に確認できる膨潤(表皮層のフクレ)が見られたが、表皮層の剥離も見られなかった。
D;サンオイルを付着させる前と比較して、外観上、明確に確認できる膨潤(表皮層のフクレ)が見られ、かつ、表皮層の部分的な剥離が見られた。
E;表皮層の大半が剥離または溶解した。
屈曲試験機(フレキソメーター)を使用して、−10℃の条件下で皮革様シート表面に亀裂が発生するまでの回数を測定した。
A;屈曲回数が100000回の時点で皮革様シート表面に亀裂が発生しなかった。
B;屈曲回数が75000回の時点で皮革様シート表面に亀裂が発生した。
C;屈曲回数が50000回の時点で皮革様シート表面に亀裂が発生した。
D;屈曲回数が25000回の時点で皮革様シート表面に亀裂が発生した。
E;屈曲回数が10000回の時点で皮革様シート表面に亀裂が発生した。
Claims (5)
- 少なくとも1つの末端に2個以上の水酸基を有するウレタン樹脂(A)、及び、水性媒体(B)を含有するウレタン樹脂組成物を用いて形成される表皮層(C)と、接着層(D)と、支持体層(E)とを有することを特徴とする皮革様シート。
- 前記ウレタン樹脂(A)が、ポリカーボネートポリオールを含むポリオール(a1)と、ポリイソシアネート(a2)と、必要に応じて鎖伸長剤(a3)とを反応させることによって両末端にイソシアネート基を有するウレタンプレポリマーを得て、次いで、前記ウレタンプレポリマーの有するイソシアネート基と、ポリアルカノールアミンの有するアミノ基とを反応させることによって得られるものである請求項1に記載の皮革様シート。
- 前記接着層(D)が、水酸基を有する化合物(d−1)と、イソシアネート基を有する化合物(d−2)とを含有する接着剤(d)を用いて形成されるものである請求項1に記載の皮革様シート。
- 前記化合物(d−2)のイソシアネート基の一部または全部と、前記表皮層(C)に含まれる前記ウレタン樹脂(A)が有する水酸基とが反応しウレタン結合を形成したものである請求項3に記載の皮革様シート。
- 離型紙上に、少なくとも1つの末端に2個以上の水酸基を有するウレタン樹脂(A)、及び、水性媒体(B)を含有するウレタン樹脂組成物を塗布し、乾燥した後、前記塗布面に前記接着剤(d)を塗布し、次いで、前記接着剤(d)の塗布面に支持体を載置し、加熱することを特徴とする皮革様シートの製造方法。
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