TWI837346B - 胺基甲酸酯樹脂組成物、及積層體 - Google Patents
胺基甲酸酯樹脂組成物、及積層體 Download PDFInfo
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- TWI837346B TWI837346B TW109113272A TW109113272A TWI837346B TW I837346 B TWI837346 B TW I837346B TW 109113272 A TW109113272 A TW 109113272A TW 109113272 A TW109113272 A TW 109113272A TW I837346 B TWI837346 B TW I837346B
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- Prior art keywords
- urethane resin
- resin composition
- polyethylene glycol
- range
- mass
- Prior art date
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- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 81
- 239000011342 resin composition Substances 0.000 title claims abstract description 31
- 238000005187 foaming Methods 0.000 claims abstract description 25
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 125000000129 anionic group Chemical group 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 33
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- 239000010410 layer Substances 0.000 description 19
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- 125000000217 alkyl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 2
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Abstract
本發明提供一種胺基甲酸酯樹脂組成物,其係含有胺基甲酸酯樹脂(A)、水(B)、及成膜助劑(C)之胺基甲酸酯樹脂組成物,其特徵為:前述成膜助劑(C)為聚乙二醇(c1)、及/或具有碳原子數為11以下之烷氧基的聚乙二醇(c2)。又,本發明提供一種積層體,其特徵為至少具有基材(i)、及藉由前述胺基甲酸酯樹脂組成物而形成的發泡層(ii)。前述聚乙二醇(c1)及前述聚乙二醇(c2)的重量平均分子量,較佳為100~4,000的範圍。前述胺基甲酸酯樹脂(A),較佳為具有陰離子性基者。
Description
本發明係關於一種胺基甲酸酯(urethane)樹脂組成物。
胺基甲酸酯樹脂因為其機械強度、手感良好,而廣泛利用於合成皮革(包含人工皮革)之製造。在此用途中,至今為止,含有N,N-二甲基甲醯胺(DMF)的溶劑系胺基甲酸酯樹脂為主流。然而,以在歐洲之DMF限制、在中國或台灣之VOC排出限制之強化、因大型服裝製造商所致之DMF限制等為背景,而要求構成合成皮革之各層用的胺基甲酸酯樹脂組成物之去DMF化。
如此的環境下,開始探討使胺基甲酸酯樹脂分散於水中的胺基甲酸酯分散液(PUD)作為使以往的溶劑系胺基甲酸酯樹脂濕式凝固而形成之中間多孔層的替代原料。於此替代中,為了賦予與濕式成膜品同等之手感等,而進行種種PUD作成發泡體的探討。
作為得到前述PUD之發泡體的方法,探討例如摻合微膠囊、或者使二氧化碳等氣體分散於PUD摻合液的機械發泡等(參考例如專利文獻1)。然而,摻合微膠囊的方法,得到的發泡體之手感變得不良,或者因微膠囊的膨脹所致之平滑性不良係成為問題。又,使氣體分散的方法,由於在製造發泡體的過程中夾雜於摻合液的氣泡消失等,而難以控制氣泡的尺寸等,且難以穩定地得到手感良好的合成皮革。
因為如此的背景,近年來作為簡便地得到發泡體的方法,探討將PUD以機械攪拌而起泡的機械發泡手法。然而,機械發泡方法,由於在正將PUD的水乾燥時於胺基甲酸酯皮膜產生龜裂(破裂),故有手感、剝離強度、耐彎曲性等之物性表現不穩定的問題。
[先前技術文獻]
[專利文獻]
專利文獻1 日本特開2007-191810號公報
[發明所欲解決的課題]
本發明所欲解決的課題在於提供一種即使進行機械發泡,也可形成具有優異的耐破裂性之皮膜的含有水之胺基甲酸酯樹脂組成物。
[用以解決課題之手段]
本發明提供一種胺基甲酸酯樹脂組成物,其係含有胺基甲酸酯樹脂(A)、水(B)、及成膜助劑(C)之胺基甲酸酯樹脂組成物,其特徵為:前述成膜助劑(C)為聚乙二醇(c1)、及/或具有碳原子數為11以下之烷氧基的聚乙二醇(c2)。又,本發明提供一種積層體,其特徵為至少具有基材(i)、及藉由前述胺基甲酸酯樹脂組成物而形成的發泡層(ii)。
[發明之效果]
本發明的胺基甲酸酯樹脂組成物為含有水者,且為環境對應型。又,本發明的胺基甲酸酯樹脂組成物,即使進行機械發泡,也可形成優異的耐破裂性佳之皮膜。因此,本發明的胺基甲酸酯樹脂組成物,可適合作為合成皮革的材料使用,尤其可適合作為合成皮革的發泡層使用。
[用以實施發明之形態]
本發明的胺基甲酸酯樹脂組成物為含有胺基甲酸酯樹脂(A)、水(B)、及特定的成膜助劑(C)者。
在本發明中,必須含有前述特定的成膜助劑(C)。推測藉由使用特定的成膜助劑(C),可使胺基甲酸酯樹脂組成物中的水之乾燥時的水之揮發速度變得和緩且均勻,因此可抑制皮膜之破裂,得到手感、剝離強度等優異的皮膜。
作為前述成膜助劑(C),必須使用聚乙二醇(c1)、及/或具有碳原子數為11以下之烷氧基的聚乙二醇(c2)。
從得到更優異的耐破裂性之點來看,作為前述聚乙二醇(c2)中之前述烷氧基的碳原子數,較佳為1~5的範圍,更佳為1~3的範圍,進一步更佳為1~2的範圍,特佳為1(甲氧基)。又,前述聚乙二醇(c2)1分子中之前述烷氧基的數為1~2個的範圍,較佳為1個。
從得到更優異的耐破裂性之點來看,作為前述聚乙二醇(c1)及前述聚乙二醇(c2)的重量平均分子量,較佳為100~4,000的範圍,更佳為100~3,000的範圍,進一步更佳為400~2,000的範圍。此外,前述聚乙二醇(c1)及前述聚乙二醇(c2)的重量平均分子量表示藉由凝膠滲透層析(GPC)法測定的數值。
作為前述成膜助劑(C)的使用量,相對於後述的胺基甲酸酯樹脂(A)(=固體成分)100質量份,較佳為0.05~50質量份的範圍,更佳為0.1~20質量份的範圍。
前述胺基甲酸酯樹脂(A)為可分散於後述的水(B)中者,且可使用例如:具有陰離子性基、陽離子性基、非離子性基等親水性基的胺基甲酸酯樹脂;以乳化劑強制地分散於水(B)中的胺基甲酸酯樹脂等。此等胺基甲酸酯樹脂可單獨使用,亦可併用2種以上。從製造穩定性及水分散穩定性之點來看,此等之中,較佳為使用具有親水性基的胺基甲酸酯樹脂,更佳為具有陰離子性基的胺基甲酸酯樹脂。
作為得到前述具有陰離子性基的胺基甲酸酯樹脂之方法,可舉出例如,使用選自包含具有羧基的二醇(glycol)化合物、及具有磺醯基的化合物的群組之1種以上的化合物作為原料之方法。
作為前述具有羧基的二醇化合物,可使用例如:2,2-二羥甲基丙酸、2,2-二羥甲基丁酸、2,2-二羥甲基酪酸、2,2-二羥甲基丙酸、2,2-纈草酸等。此等化合物可單獨使用,亦可併用2種以上。
作為前述具有磺醯基的化合物,可使用例如:3,4-二胺基丁烷磺酸、3,6-二胺基-2-甲苯磺酸、2,6-二胺基苯磺酸、N-(2-胺乙基)-2-胺基磺酸、N-(2-胺乙基)-2-胺乙基磺酸、N-2-胺基乙烷-2-胺基磺酸、N-(2-胺乙基)-β-丙胺酸;此等之鹽等。此等化合物可單獨使用,亦可併用2種以上。
作為使用為了製造前述具有陰離子性基的胺基甲酸酯樹脂而使用的原料時的使用量,從得到更優異的水分散穩定性之點來看,較佳為胺基甲酸酯樹脂的原料之合計質量中0.1~5質量%的範圍,更佳為0.5~4質量%的範圍,進一步更佳為1~3質量%的範圍。
前述羧基及磺醯基,在胺基甲酸酯樹脂組成物中,也可一部分或全部被鹼性化合物中和。作為前述鹼性化合物,可使用例如:氨、三乙胺、吡啶、啉等有機胺;單乙醇胺、二甲基乙醇胺等烷醇胺;包含鈉、鉀、鋰、鈣等之金屬鹼化合物等。
作為得到前述具有陽離子性基的胺基甲酸酯樹脂之方法,可舉出例如,使用具有胺基的化合物之1種或2種以上作為原料的方法。
作為前述具有胺基的化合物,可使用例如:三伸乙四胺、二伸乙三胺等具有一級及二級胺基的化合物;N-甲基二乙醇胺、N-乙基二乙醇胺等N-烷基二烷醇胺、N-甲基二胺基乙胺、N-乙基二胺基乙胺等N-烷基二胺基烷胺等具有三級胺基的化合物等。此等化合物可單獨使用,亦可併用2種以上。
作為可在得到前述強制地分散於水(B)中的胺基甲酸酯樹脂之際使用的乳化劑,可使用例如:聚氧伸乙基壬基苯醚、聚氧伸乙基月桂醚、聚氧伸乙基苯乙烯基苯醚、聚氧伸乙基山梨糖醇四油酸酯、聚氧伸乙基・聚氧伸丙基共聚物等非離子性乳化劑;油酸鈉等脂肪酸鹽、烷基硫酸酯鹽、烷基苯磺酸鹽、烷基磺基琥珀酸鹽、萘磺酸鹽、聚氧伸乙基烷基硫酸鹽、烷磺酸鈉鹽、烷基二苯醚磺酸鈉鹽等陰離子性乳化劑;烷基胺鹽、烷基三甲基銨鹽、烷基二甲基苯甲基銨鹽等陽離子性乳化劑等。此等乳化劑可單獨使用,亦可併用2種以上。
作為前述胺基甲酸酯樹脂(A),具體而言,可使用例如,聚異氰酸酯(a1)、多元醇(a2)、及前述為了製造具有親水性基的胺基甲酸酯樹脂而使用的原料之反應物。
作為前述聚異氰酸酯(a1),可使用例如:苯二異氰酸酯、甲苯二異氰酸酯、二苯甲烷二異氰酸酯、苯二甲基二異氰酸酯、萘二異氰酸酯、聚亞甲基聚苯基聚異氰酸酯(polymethylene polyphenyl polyisocyanate)、碳二亞胺化二苯甲烷聚異氰酸酯等芳香族聚異氰酸酯;六亞甲基二異氰酸酯、離胺酸二異氰酸酯、環己烷二異氰酸酯、異佛爾酮二異氰酸酯、二環己基甲烷二異氰酸酯、苯二甲基二異氰酸酯、四甲基苯二甲基二異氰酸酯、二聚酸二異氰酸酯、降莰烯二異氰酸酯(norbornene diisocyanate)等脂肪族聚異氰酸酯或脂環式聚異氰酸酯等。此等聚異氰酸酯可單獨使用,亦可併用2種以上。
從製造穩定性、及得到之皮膜的機械物性之點來看,作為前述聚異氰酸酯(a1)的使用量,較佳為前述胺基甲酸酯樹脂(A)的原料之合計質量中5~40質量%的範圍,更佳為10~30質量%的範圍。
作為前述多元醇(a2),可使用例如:聚醚多元醇、聚酯多元醇、聚丙烯酸多元醇、聚碳酸酯多元醇、聚丁二烯多元醇等。此等多元醇可單獨使用,亦可併用2種以上。
作為前述多元醇(a2)的數量平均分子量,從得到之皮膜的機械強度之點來看,較佳為500~50,000的範圍,更佳為800~10,000的範圍。此外,前述多元醇(a2)的數量平均分子量表示藉由凝膠滲透管柱層析(GPC)法測定的數值。
前述多元醇(a2)中,視需要也可併用數量平均分子量小於500(較佳為50~450的範圍)的鏈伸長劑(a2-1)。作為前述鏈伸長劑(a2-1),可使用例如:乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、六亞甲二醇、蔗糖、甲二醇、丙三醇、山梨糖醇、雙酚A、4,4’-二羥基二苯基、4,4’-二羥基二苯醚、三羥甲基丙烷等具有羥基的鏈伸長劑;乙二胺、1,2-丙二胺、1,6-六亞甲二胺、哌、2,5-二甲基哌、異佛爾酮二胺、1,2-環己二胺、1,3-環己二胺、1,4-環己二胺、4,4’-二環己基甲二胺、3,3’-二甲基-4,4’-二環己基甲二胺、1,4-環己二胺、胼等具有胺基的鏈伸長劑等。此等鏈伸長劑可單獨使用,亦可併用2種以上。
從得到之皮膜的機械強度之點來看,作為使用前述鏈伸長劑(a2-1)時的使用量,較佳為胺基甲酸酯樹脂(A)的原料之合計質量中0.5~5質量%的範圍,更佳為1~3質量%的範圍。
作為前述胺基甲酸酯樹脂(A)之製造方法,可舉出例如,將前述多元醇(a2)、前述為了製造具有親水性基的胺基甲酸酯樹脂而使用的原料、前述鏈伸長劑(a2-1)、及前述聚異氰酸酯(a1)一次性添加,並進行反應的方法。此等之反應,可舉出例如,在50~100℃進行3~10小時。
作為製造前述胺基甲酸酯樹脂(A)之際的前述多元醇(a2)所具有之羥基、前述為了製造具有親水性基的胺基甲酸酯樹脂而使用的原料所具有的羥基及胺基、以及前述鏈伸長劑(a2-1)所具有的羥基及胺基之合計與前述聚異氰酸酯(a1)所具有的異氰酸酯基之莫耳比[異氰酸酯基/(羥基及胺基)],較佳為0.8~1.2的範圍,更佳為0.9~1.1的範圍。
在製造前述胺基甲酸酯樹脂(A)之際,較佳為使殘存於前述胺基甲酸酯樹脂(A)的異氰酸酯基去活化。在使前述異氰酸酯基去活化時,較佳為使用甲醇等具有1個羥基的醇。作為前述醇的使用量,相對於胺基甲酸酯樹脂(A)100質量份,較佳為0.001~10質量份的範圍。
又,在製造前述胺基甲酸酯樹脂(A)之際,亦可使用有機溶劑。作為前述有機溶劑,可使用例如:丙酮、甲基乙基酮等酮化合物;四氫呋喃、二烷等醚化合物;乙酸乙酯、乙酸丁酯等乙酸酯化合物;乙腈等腈化合物;二甲基甲醯胺、N-甲基吡咯啶酮等醯胺化合物等。此等有機溶媒可單獨使用,亦可併用2種以上。此外,前述有機溶劑,較佳為最後藉由蒸餾法等去除。
於可穩定地保持藉由後述的機械發泡而產生的氣泡,使發泡層(ii)的密度成為較佳的範圍,且穩定地得到優異的手感之點,作為前述胺基甲酸酯樹脂(A)的流動起始溫度,較佳為80℃以上,更佳為80~220℃的範圍。
作為調整前述胺基甲酸酯樹脂(A)的流動起始溫度之方法,主要可舉出後述之藉由為胺基甲酸酯樹脂(A)的原料之多元醇(a2)的種類、鏈伸長劑(a2-1)的使用量、及聚異氰酸酯(a1)的種類而調整的方法。作為將前述流動起始溫度調高的方法,可舉出例如:使用如聚碳酸酯多元醇之結晶性高的多元醇作為多元醇(a2);增加鏈伸長劑(a2-1)的使用量;使用如4,4’-二苯甲烷二異氰酸酯、二環己基甲烷二異氰酸酯之結晶性高的聚異氰酸酯作為聚異氰酸酯(a1)等。又,作為將前述流動起始溫度調低的方法,可舉出例如:使用如聚氧丙二醇之結晶性低的多元醇作為多元醇(a2);減少鏈伸長劑(a2-1)的使用量;使用如甲苯二異氰酸酯、異佛爾酮二異氰酸酯之結晶性低的聚異氰酸酯作為聚異氰酸酯(a1)等。因此,藉由適當選擇此等方法,可調整前述胺基甲酸酯樹脂(A)的流動起始溫度。
此外,作為前述胺基甲酸酯樹脂(A)的流動起始溫度之測定方法,可舉出例如,將胺基甲酸酯樹脂組成物塗布於脫模紙(塗布厚度150μm),以熱風乾燥機,在70℃乾燥4分鐘,接著在120℃乾燥2分鐘,藉以得到乾燥物,並將此乾燥物,使用島津製作所股份有限公司製流動試驗機「CFT-500A」(使用口徑1mm、長度1mm的模具,荷重98N,升溫速度3℃/分鐘)進行測定的方法。
作為前述水(B),可使用例如:離子交換水、蒸餾水、自來水等。此等之中,較佳為使用雜質少的離子交換水。從作業性、塗布性、及保存穩定性之點來看,作為前述水(B)的含量,較佳為胺基甲酸酯樹脂組成物中20~90質量%的範圍,更佳為40~80質量%的範圍。
從水分散穩定性及作業性之點來看,作為前述胺基甲酸酯樹脂(A)與前述水(B)之質量比[(A)/(B)],較佳為5/95~70/30的範圍,更佳為10/90~60/40的範圍。
本發明的胺基甲酸酯樹脂組成物含有前述胺基甲酸酯樹脂(A)、水(B)、及成膜助劑(C)作為必須成分,但視需要亦可含有其它的添加劑。
作為前述其它的添加劑,可使用例如:界面活性劑(D)、交聯劑、中和劑、增黏劑、胺基甲酸酯化觸媒、填充劑、顏料、染料、阻燃劑、調平劑、抗結塊劑(antiblocking agent)等。此等添加劑可單獨使用,亦可併用2種以上。
從防止藉由機械發泡而產生的泡消失,且得到更優異的耐破裂性及手感之點來看,作為前述界面活性劑(D),較佳為使用具有碳原子數為10以上之疏水部的界面活性劑(D)。
作為前述界面活性劑(D),可使用例如:下述式(2)所示之界面活性劑;脂肪酸鹽、琥珀酸鹽、磺基琥珀酸鹽、十八基磺基琥珀酸鹽、磺基琥珀酸酯等。此等之界面活性劑可單獨使用,亦可併用2種以上。
(式(2)中,R表示碳原子數10~20之直鏈或分支狀的烷基,X表示Na、K、NH4
、啉、乙醇胺、三乙醇胺。)
從得到更優異的氣泡保持性之點來看,作為前述界面活性劑(D),前述者之中,較佳為使用前述式(2)所示之界面活性劑,更佳為表示碳原子數為13~19之直鏈的烷基者,特佳為使用硬脂酸鹽。
從得到更優異的氣泡保持性之點來看,作為使用前述界面活性劑(D)時的使用量,相對於前述胺基甲酸酯樹脂(A)(=固體成分)100質量,較佳為0.01~30質量份的範圍,更佳為0.1~20質量份的範圍。
作為前述交聯劑,係以發泡層(ii)的機械強度之提升等為目的而使用者,且可使用例如:聚異氰酸酯交聯劑、環氧交聯劑、三聚氰胺交聯劑、唑啉交聯劑等。此等交聯劑可單獨使用,亦可併用2種以上。作為使用前述交聯劑時的使用量,例如,相對於前述胺基甲酸酯樹脂(A)(=固體成分)100質量份,較佳為0.01~100質量份的範圍,更佳為0.1~50質量份的範圍,進一步更佳為0.5~30質量份的範圍。
接著,針對本發明的積層體進行說明。
前述積層體為至少具有基材(i)、及藉由前述胺基甲酸酯樹脂組成物而形成的發泡層(ii)者。
作為前述基材(i),可使用例如:聚酯纖維、聚乙烯纖維、耐綸纖維、丙烯酸纖維、聚胺基甲酸酯纖維、乙酸酯纖維、嫘縈纖維、聚乳酸纖維、綿、麻、絹、羊毛、玻璃纖維、碳纖維、利用彼等之混紡纖維等的不織布、織布、編織物等纖維基材;對前述不織布含浸聚胺基甲酸酯樹脂等樹脂者;進一步於前述不織布設置多孔質層者;熱塑性胺基甲酸酯(TPU)等樹脂基材等。
接著,針對本發明的積層體之製造方法進行說明。
作為前述積層體之製造方法,可舉出例如:
(X)使前述胺基甲酸酯樹脂組成物起泡,得到起泡液,將此起泡液塗布於脫模紙上,並進行乾燥,與前述基材(i)貼合的方法;
(Y)使前述胺基甲酸酯樹脂組成物起泡,得到起泡液,將此起泡液,塗布於在脫模紙上製作的表皮層上,並進行乾燥,與前述基材(i)貼合的方法;
(Z)使前述胺基甲酸酯樹脂組成物起泡,得到起泡液,將此起泡液塗布於前述基材(i)上,並進行乾燥,且視需要,於其上貼合在脫模紙上製作的表皮層(iii)之方法等。
作為使前述胺基甲酸酯樹脂組成物起泡,得到起泡液之方法,可舉出例如:利用手之攪拌、使用機械式混合機等混合機之機械發泡等。從簡便地得到起泡液之點來看,此等之中,較佳為使用混合機的方法。在使用混合機時,可舉出例如,以500~3,000rpm進行10秒鐘~10分鐘攪拌的方法。此時,從得到手感良好的發泡層(ii)之點來看,在起泡之前後,較佳係成為1.3~7倍之體積,更佳係成為1.2~2倍之體積。
作為將得到的起泡液塗布於基材(i)等的方法,可舉出例如,使用輥塗布機、刀塗布機、缺角輪塗布機(comma coater)、塗抹器(applicator)等的方法。
作為前述塗布物的乾燥方法,可舉出例如,在60~130℃的溫度進行30秒鐘~10分鐘乾燥的方法。
作為藉由以上的方法得到的發泡層(ii)之厚度,例如為5~300μm。
從得到更優異的手感之點來看,作為前述發泡層(ii)的密度,較佳為200~1,000kg/m3
,更佳為400~800kg/m3
的範圍。此外,前述發泡層(ii)的密度表示將自每10cm見方的積層體之重量減去每10cm見方的基材(i)之重量的數值,除以發泡層(ii)之厚度所得的數值。
作為前述表皮層(iii),可藉由周知的材料並以周知的方法形成,可使用例如:溶劑系胺基甲酸酯樹脂、水系胺基甲酸酯樹脂、聚矽氧樹脂、聚丙烯樹脂、聚酯樹脂等。重視柔軟的手感、及耐熱性、耐水解性時,較佳為使用聚碳酸酯系胺基甲酸酯樹脂。又,為了在環境對應下之DMF減低化,更佳為使用水系聚碳酸酯系胺基甲酸酯樹脂。
在前述表皮層(iii)上,視需要,以耐擦傷性提升、賦予光澤性等為目的,也可進一步設置表面處理層(iv)。作為前述表面處理層(iv),可藉由周知的材料並以周知的方法形成。
以上本發明的胺基甲酸酯樹脂組成物為含有水者,且為環境對應型。又,本發明的胺基甲酸酯樹脂組成物,即使進行機械發泡,也可形成優異的耐破裂性佳之皮膜。因此,本發明的胺基甲酸酯樹脂組成物,可適合作為合成皮革的材料使用,尤其可適合作為合成皮革的發泡層使用。
[實施例]
以下使用實施例,更詳細地說明本發明。
[實施例1]
加入聚醚系聚胺基甲酸酯分散液(DIC股份有限公司製「HYDRAN WLS-120AR」,固體成分50質量%,以下簡稱為「PUD(A-1)」)100質量份、增黏劑(Borchers公司製「Borch Gel ALA」)2質量份、硬脂酸銨2質量份、交聯劑(Nisshinbo Chemical股份有限公司製「Carbodilite SV-02」)4質量份、甲氧基聚乙二醇(日油股份有限公司製「UNIOX M-550」,重量平均分子量:550,以下簡稱為「甲氧基PEG(1)」)5質量份,使用機械式混合機,以2,000rpm攪拌,使其包含空氣,藉以得到相對於初期的體積而成為1.5倍之體積的起泡液。
將其塗布於脫模紙,於80℃乾燥3分鐘,藉以形成厚度300μm的胺基甲酸酯發泡層,且將其與聚酯纖維的不織布貼合,藉以得到合成皮革。
[實施例2~5、比較例1]
將使用的胺基甲酸酯樹脂(A)之種類、以及成膜助劑(C)之種類及/或使用量,如表1所示進行變更,除此以外係與實施例1同樣進行,得到合成皮革。
[數量平均分子量・重量平均分子量之測定方法]
成膜助劑(C)的重量平均分子量等係表示藉由凝膠滲透層析(GPC)法,以下述的條件測定的數值。
測定裝置:高速GPC裝置(Tosoh股份有限公司製「HLC-8220GPC」)
管柱:將Tosoh股份有限公司製之下述的管柱串聯使用。
「TSKgel G5000」(7.8mmI.D.×30cm)×1支
「TSKgel G4000」(7.8mmI.D.×30cm)×1支
「TSKgel G3000」(7.8mmI.D.×30cm)×1支
「TSKgel G2000」(7.8mmI.D.×30cm)×1支
檢測器:RI(示差折射計)
管柱溫度:40℃
沖提液:四氫呋喃(THF)
流速:1.0mL/分鐘
注入量:100μL(試料濃度0.4質量%的四氫呋喃溶液)
標準試料:使用下述的標準聚苯乙烯,作成檢量線。
(標準聚苯乙烯)
Tosoh股份有限公司製「TSKgel標準聚苯乙烯A-500」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯A-1000」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯A-2500」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯A-5000」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-1」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-2」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-4」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-10」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-20」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-40」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-80」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-128」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-288」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-550」
[耐破裂性的評價方法]
觀察實施例及比較例所得到的合成皮革之外觀,確認破裂之有無。將沒有破裂者評價為「T」,將確認破裂者評價為「F」。
[手感之評價方法]
以手觸摸實施例及比較例所得到的合成皮革,如以下進行評價。
「T」:有柔軟性與彈力
「F」:柔軟性差,硬。
[剝離強度的評價方法]
在實施例及比較例所得到的合成皮革之表面,載置2.5cm寬的熱熔膠帶(SAN CHEMICALS股份有限公司製「BW-2」),於150℃加熱30秒鐘,將熱熔膠帶接著。沿著熱熔膠帶的寬而裁切試料。將此試料之一部分剝離,且將基材與熱熔膠帶以夾具夾持,使用島津Autograph「AG-1」(島津製作所股份有限公司製),以滿刻度5kg、測試頭速度20mm/分鐘的條件,測定剝離強度,並換算為1cm寬。在剝離強度為3kgf/cm以上的情況,評價為「T」,除此以外的情況評價為「F」。
[表1]
表1 | 實施例1 | 實施例2 | 實施例3 | 實施例4 | 實施例5 | 比較例1 |
胺基甲酸酯樹脂(A) | PUD(A-1) | PUD(A-1) | PUD(A-2) | PUD(A-3) | PUD(A-1) | PUD(A-1) |
成膜助劑(C) | 甲氧基 PEG(1) | 甲氧基 PEG(2) | 甲氧基 PEG(1) | PEG(1) | PEG(2) | |
重量平均分子量 | 550 | 1000 | 550 | 400 | 1000 | |
(C)的使用量 (相對於(A)固體成分100質量份) | 10 | 10 | 15 | 10 | 8 | 0 |
耐破裂性的評價 | T | T | T | T | T | F |
手感的評價 | T | T | T | T | T | F |
剝離強度的評價 | T | T | T | T | T | F |
表1中之縮寫為以下者。
「PUD(A-2)」:聚碳酸酯系聚胺基甲酸酯分散液(DIC股份有限公司製「HYDRAN WLS-110AR」,固體成分50質量%)
「PUD(A-3)」:酯系聚胺基甲酸酯分散液(DIC股份有限公司製「HYDRAN ADS-110」,固體成分50質量%)
「甲氧基PEG(2)」:甲氧基PEG(重量平均分子量:1,000)
「PEG(1)」:聚乙二醇(重量平均分子量:400)
「PEG(2)」:聚乙二醇(重量平均分子量:1,000)
可知為本發明之胺基甲酸酯樹脂組成物的實施例1~5,可得到具有優異的耐破裂性、手感、及剝離強度之合成皮革。
另一方面,比較例1為未使用成膜助劑(C)的態樣,但耐破裂性、手感、及剝離強度均不良。
無。
無。
無。
Claims (3)
- 一種胺基甲酸酯樹脂組成物,其係含有具有陰離子性基的胺基甲酸酯樹脂(A)、水(B)、成膜助劑(C)、及包含硬脂酸鹽的的界面活性劑(D)之胺基甲酸酯樹脂組成物,其特徵為:該成膜助劑(C)為聚乙二醇(c1)、及/或具有碳原子數為1~2之烷氧基的聚乙二醇(c2),該聚乙二醇(c1)及該聚乙二醇(c2)的重量平均分子量為100~4,000的範圍。
- 一種積層體,其特徵為至少具有基材(i)、及藉由如請求項1之胺基甲酸酯樹脂組成物而形成的發泡層(ii)。
- 如請求項2之積層體,其中該發泡層(ii)係藉由將該胺基甲酸酯樹脂組成物進行機械發泡而形成者。
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