TWI837212B - 聚胺酯樹脂水分散體、塗料、膜構成體、及構造物 - Google Patents
聚胺酯樹脂水分散體、塗料、膜構成體、及構造物 Download PDFInfo
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- TWI837212B TWI837212B TW108140607A TW108140607A TWI837212B TW I837212 B TWI837212 B TW I837212B TW 108140607 A TW108140607 A TW 108140607A TW 108140607 A TW108140607 A TW 108140607A TW I837212 B TWI837212 B TW I837212B
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- Prior art keywords
- polyurethane resin
- coating
- aqueous dispersion
- resin particles
- resin aqueous
- Prior art date
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Abstract
本發明之聚胺酯樹脂水分散體係聚胺酯樹脂粒子於水中分散而成者,且含有40質量%以上之不揮發成分,上述聚胺酯樹脂粒子包含多元醇成分、異氰酸酯成分、及具有1個以上之活性氫基且具有環氧烷之親水性環氧烷成分,上述親水性環氧烷成分相對於聚胺酯樹脂粒子之含量為1~25質量%,上述聚胺酯樹脂粒子之體積平均粒徑為0.3~5 μm。
Description
本發明係關於一種聚胺酯樹脂水分散體、塗料、膜構成體、及構造物。
聚胺酯系樹脂於耐磨耗性、彎曲性、可撓性、柔軟性、加工性、接著性、耐化學品性等諸多物性方面優異,並且對各種加工法之適應性亦優異。因此,被廣泛用作合成仿革(人工皮革與合成皮革之統稱)用材料、各種塗佈劑、油墨、塗料等之黏合劑,或者膜、片材及各種成型物用材料,提出有適用於各種用途之聚胺酯系樹脂。
其中,藉由對樹脂賦予親水性而能夠在水中乳化分散之聚胺酯樹脂水分散體於塗佈後加以乾燥,藉此容易獲得機械物性、耐久性、耐化學品性及耐磨耗性等性能優異之覆膜,從而廣泛用於塗料、接著劑、纖維加工處理劑、紙處理劑及油墨等。迄今為止,該等用途中使用的是溶解於有機溶劑之溶劑系胺酯。然而,由於存在有機溶劑之毒性、火災之危險性、環境污染性等問題,近年來逐漸轉而使用聚胺酯樹脂水分散體代替溶劑系胺酯。
作為聚胺酯樹脂水分散體,已知有與要求特性相應之各種水分散體。例如,於專利文獻1中揭示有一種水系胺酯樹脂,其於分子鏈中含有(A)含有至少50重量%以上環氧乙烷之重複單元之聚氧伸烷基二醇及/或(B)含有至少50重量%以上環氧乙烷之重複單元之單末端聚氧伸烷基
二醇。
專利文獻1:日本專利第3972234號公報
然而,關於先前之具有一液物性之聚胺酯樹脂水分散體,粒徑較小(0.01~0.2μm左右),不揮發成分至多40質量%左右。若聚胺酯樹脂水分散體中之不揮發成分較少,則包含大量水,因此於將其乾燥之步驟中,容易產生向系外排出之水(揮發成分)之量較多之問題、及乾燥步驟所需之能量增加之問題。如此,若考慮到生產性,則較佳為不揮發成分之比率達40質量%左右以上。
可想到增大粒徑以增加不揮發成分之比率,但隨著粒徑變大,粒子之沈澱速度加快,而容易產生沈澱。又,若粒徑較大,則成膜性容易降低,導致產生龜裂等不良情況。
專利文獻1之目的在於藉由感熱凝固、尤其是利用蒸汽之感熱凝固來獲得顯著之感熱凝固性,但關於在將不揮發成分之比率設為40質量%以上之同時滿足分散穩定性與製膜性,未作任何揭示。
因此,迄今為止之聚胺酯樹脂水分散體非常難以於將不揮發成分之比率設為40質量%以上之同時滿足分散穩定性與製膜性。
綜上,本發明之目的在於提供一種於將不揮發成分之比率設為40質量%以上之同時滿足分散穩定性與製膜性之聚胺酯樹脂水分散體。
本發明者等人經過銳意研究,結果發現,藉由使構成聚胺酯樹脂粒子之各種成分中含有特定量之具有特定環氧烷之親水性環氧烷成分,可解決上述課題,從而完成本發明。即,本發明如下所述。
[1]一種聚胺酯樹脂水分散體,其係聚胺酯樹脂粒子於水中分散而成者,且含有40質量%以上之不揮發成分,上述聚胺酯樹脂粒子包含多元醇成分、異氰酸酯成分、及具有1個以上之活性氫基且具有環氧烷之親水性環氧烷成分,上述親水性環氧烷成分相對於聚胺酯樹脂粒子之含量為1~25質量%,上述聚胺酯樹脂粒子之體積平均粒徑為0.3~5μm。
[2]如[1]記載之聚胺酯樹脂水分散體,其於25℃下之黏度為3000mPa‧s以下。
[3]一種塗料,其包含如[1]或[2]記載之聚胺酯樹脂水分散體。
[5]一種膜構成體,其包含如[3]或[4]記載之塗料之膜狀物。
[6]一種構造物,其包含如[5]記載之膜構成體作為表皮層、中間層及接著層之至少任一者。
[7]一種構造物,其於表面及內部之至少任一處包含如[3]或[4]記載之塗料。
[8]一種合成仿革,其包含如[6]或[7]記載之構造物。
根據本發明,可提供一種於將不揮發成分之比率設為40質量%以上之同時滿足分散穩定性與製膜性之聚胺酯樹脂水分散體。
以下,對本發明進行詳細說明。再者,於本發明中,所謂聚胺酯樹脂係聚胺酯樹脂及聚胺酯-脲樹脂之統稱。
[聚胺酯樹脂水分散體]
本發明之聚胺酯樹脂水分散體係聚胺酯樹脂粒子於水中分散而成者,並且含有40質量%以上之不揮發成分,聚胺酯樹脂粒子包含多元醇成分、異氰酸酯成分、及具有1個以上之活性氫基且具有環氧烷(聚環氧烷)之親水性環氧烷成分,親水性環氧烷成分相對於聚胺酯樹脂粒子之含量為1~25質量%,上述聚胺酯樹脂粒子之體積平均粒徑為0.3~5μm。
於本發明中,藉由包含具有1個以上之活性氫基且具有環氧烷之親水性環氧烷成分(以下有時簡稱為「親水性環氧烷成分」)作為聚胺酯樹脂粒子之構成成分,即便聚胺酯樹脂粒子之體積平均粒徑為0.3~5μm之相對較大之粒徑,亦可滿足分散穩定性與製膜性。又,由於體積平均粒徑為0.3~5μm,故而容易使不揮發成分達到40質量%以上,由於不揮發成分為40質量%以上,故而可謂具有較迄今為止之聚胺酯樹脂水分散體高之生產性。
此處推測,親水性環氧烷成分於樹脂粒子之表面發揮利用其環氧烷之立體阻礙效應,從而即便大粒徑之樹脂粒子發生沈澱,但由於環氧烷使粒子彼此排斥,故亦防止凝集。其結果,即便為了使不揮發成分達到40質量%以上而將體積平均粒徑設為0.3~5μm,亦可獲得良好之分散穩定性。
再者,本發明中之所謂「不揮發成分」係指下文記述之聚胺酯樹脂粒子或不揮發性之添加劑等,具體而言,指將2g之聚胺酯樹脂
水分散體於120℃下乾燥2小時之情形時獲得之固體成分。
以下,對構成聚胺酯樹脂水分散體所含之聚胺酯樹脂粒子之各成分進行更詳細之說明。
<聚胺酯樹脂粒子>
構成本發明之聚胺酯樹脂粒子之聚胺酯樹脂主要包含多元醇成分、異氰酸酯成分、及具有1個以上之活性氫基且具有環氧烷之親水性環氧烷成分。
[多元醇成分]
作為成為本發明中之多元醇成分的多元醇,可例示以下之(1)~(6)。
(1)聚碳酸酯多元醇
作為聚碳酸酯多元醇,可列舉:聚四亞甲基碳酸酯二醇、聚五亞甲基碳酸酯二醇、聚新戊基碳酸酯二醇、聚六亞甲基碳酸酯二醇、聚(1,4-環己烷二亞甲基碳酸酯)二醇等聚碳酸酯二醇、及該等之無規/嵌段共聚物等。
(2)聚醚多元醇
作為聚醚多元醇,可列舉:使環氧烷(環氧乙烷、環氧丙烷、環氧丁烷等)及雜環式醚(四氫呋喃等)之任一者進行聚合或共聚合而獲得者。具體而言,可列舉:聚丙二醇、聚乙二醇-聚四亞甲基二醇(嵌段或無規)、聚四亞甲基醚二醇及聚六亞甲基二醇等。
再者,聚醚多元醇中之環氧乙烷(EO)含有比率設為未達50質量%。
(3)聚酯多元醇
作為聚酯多元醇,可列舉:使脂肪族系二羧酸(例如:琥珀酸、己二酸、癸二酸、戊二酸及壬二酸等)及芳香族系二羧酸(例如:間苯二甲酸及
對苯二甲酸等)之至少任一者、與低分子量二醇類(例如:乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-六亞甲基二醇、新戊二醇及1,4-雙羥基甲基環己烷等)進行縮聚合而獲得者。
具體而言,可列舉:聚己二酸乙二酯二醇、聚己二酸丁二酯二醇、聚六亞甲基己二酸酯二醇、聚己二酸新戊酯二醇、聚己二酸乙二酯/丁二酯二醇、聚己二酸新戊酯/己酯二醇、聚-3-甲基戊烷己二酸酯二醇及聚間苯二甲酸丁二酯二醇等。
(4)聚內酯多元醇
作為聚內酯多元醇,可列舉:聚己內酯二醇及聚-3-甲基戊內酯二醇等。
(5)聚烯烴多元醇
作為聚烯烴多元醇,可列舉:聚丁二烯二醇及聚異戊二烯二醇、或其氫化物等。
(6)聚甲基丙烯酸酯二醇
作為聚甲基丙烯酸酯二醇,可列舉:α,ω-聚甲基丙烯酸甲酯二醇及α,ω-聚甲基丙烯酸丁酯二醇等。
多元醇之數量平均分子量只要為500以上,則並無特別限制,較佳為500~4,000左右,更佳為1000~3000左右。該等多元醇可單獨使用或將2種以上組合使用,但就長期耐久性之觀點而言,較佳為包含聚碳酸酯二醇。
再者,數量平均分子量係聚苯乙烯換算之數量平均分子量,通常可藉由凝膠滲透層析法(GPC)之測定求出。
[異氰酸酯成分]
作為成為本發明中之異氰酸酯成分的異氰酸酯,並無特別限定,較佳為脂肪族二異氰酸酯、脂環族二異氰酸酯、芳香族二異氰酸酯等二官能之聚異氰酸酯。
聚異氰酸酯之具體例為:甲苯二異氰酸酯、4-甲氧基-1,3-苯二異氰酸酯、4-異丙基-1,3-苯二異氰酸酯、4-氯-1,3-苯二異氰酸酯、4-丁氧基-1,3-苯二異氰酸酯、2,4-二異氰酸酯-二苯醚、均三甲苯二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、伸荰基二異氰酸酯、1,5-萘二異氰酸酯、聯苯胺二異氰酸酯、鄰硝基聯苯胺二異氰酸酯、4,4-二異氰酸二苄酯、1,4-四亞甲基二異氰酸酯、1,5-五亞甲基二異氰酸酯、1,6-六亞甲基二異氰酸酯、1,10-十亞甲基二異氰酸酯、1,4-環己二異氰酸酯、二甲苯二異氰酸酯、4,4'-亞甲基雙(異氰酸環己酯)、1,5-四氫萘二異氰酸酯、異佛爾酮二異氰酸酯、二環己基甲烷4,4'-二異氰酸酯等。其中,較佳為至少包含二環己基甲烷4,4'-二異氰酸酯。
再者,於如車輛用途或淺色系用途等需要柔軟性、機械物性及耐變色性之情形時,較佳為將4,4'-二苯基甲烷二異氰酸酯與脂肪族二異氰酸酯或脂環族二異氰酸酯併用。
聚異氰酸酯成分之異氰酸基當量相對於全部成分之羥基當量的比較佳為1.1~2.2,更佳為1.2~1.9。若NCO/OH為1.2~1.9,則柔軟性及耐久性均更良好。
[具有1個以上之活性氫基且具有環氧烷之親水性環氧烷成分]
具有1個以上之活性氫基且具有環氧烷之親水性環氧烷成分對聚胺酯樹脂粒子賦予水分散性。水分散性變得良好之原因尚不明確,但推測如
下:環氧烷以自聚胺酯樹脂粒子之表面伸出之方式突出至水中,藉此,其發揮阻礙其他聚胺酯樹脂粒子接近之立體阻礙效應。
於親水性環氧烷成分中,所謂活性氫係指會與異氰酸酯之異氰酸基反應之氫原子,可列舉:羥基、巰基、胺基等中之氫原子,該等之中,較佳為羥基之氫原子。
又,環氧烷成為表現出親水性之親水性基,助益於聚胺酯樹脂粒子之水分散性。該環氧烷之碳數較佳為例如2~12,具體而言,可列舉:環氧乙烷、1,2-或1,3-環氧丙烷、1,2-、2,3-或1,3-環氧丁烷、四氫呋喃、3-甲基四氫呋喃、α-氧化烯烴、氧化苯乙烯及表鹵醇(表氯醇等)等。其中,較佳為包含環氧乙烷作為環氧烷。
於具有環氧烷之親水成分中,較佳為含有至少50質量%以上之環氧乙烷之重複單元,更佳為含有70質量%以上,進而較佳為環氧烷即為環氧乙烷。
作為成為親水性環氧烷成分之化合物,可列舉:聚乙二醇、聚氧乙烯-聚氧丙烯共聚物二醇、聚氧乙烯-聚氧丁烯共聚物二醇、聚氧乙烯-聚氧伸烷基共聚物二醇,及該等之甲醚、***、丁醚等單烷基醚類,對該等之單烷基醚類加成1,3-二醇之類的二醇而成之聚伸烷基二醇單烷基醚之二醇加成體。
其中,較佳為聚乙二醇;聚乙二醇單甲醚及聚乙二醇單***等之類的聚乙二醇單烷基醚;對聚乙二醇單烷基醚加成1,3-二醇之類的二醇而成之聚乙二醇單烷基醚之二醇加成體等。
尤其就不僅進一步提高分散穩定性,亦使再分散性變得良好,發揮優異之耐熱性之觀點而言,更佳為聚乙二醇單烷基醚及聚乙二醇
單烷基醚之二醇加成體,進而較佳為聚乙二醇單烷基醚之二醇加成體。
推測於聚胺酯樹脂粒子中,該等取得適於發揮分散性及熱穩定性之形態。
成為親水性環氧烷成分之化合物之數量平均分子量較佳為500~3000,更佳為700~2000。
作為聚乙二醇之市售品,例如可列舉:日油股份有限公司製造之「PEG#200」、「PEG#300」、「PEG#400」、「PEG#600」、「PEG#1000」、「PEG#1500」、「PEG#1540」、「PEG#2000」等。
作為聚乙二醇單甲醚之市售品,例如可列舉:日油股份有限公司製造之「Uniox M-400」、「Uniox M-550」、「Uniox M-1000」、「Uniox M-2000」等。
作為聚乙二醇單烷基醚之二醇加成體之市售品,例如可列舉:Evonic公司製造之「TEGOMER D3403」等。
以上為較佳之成分之例示,本發明並不限定於該等。因此,不僅是上述之例示,其他之目前在售之容易自市場購入之化合物均可使用。
親水性環氧烷成分相對於聚胺酯樹脂粒子之含量為1~25質量%,較佳為3~20質量%,更佳為5~10質量%。若含量未達1質量%,則分散穩定性降低,或製膜性降低、產生龜裂。若超過25質量%,則有機械物性降低、水分散體增黏之可能性,導致作業性降低或不揮發成分減少。
又,藉由含有1~20質量%之親水性環氧烷成分,可減慢成膜時之乾燥(水分之蒸發)速度,抑制龜裂產生。
[聚胺酯樹脂粒子之體積平均粒徑]
本發明之聚胺酯樹脂粒子之體積平均粒徑為0.3~5μm。若聚胺酯樹脂粒子之體積平均粒徑未達0.3μm,則水分散體之黏度上升,致使必須減少不揮發成分。另一方面,若體積平均粒徑超過5μm,則粒子容易沈澱。
就此觀點而言,聚胺酯樹脂粒子之體積平均粒徑較佳為0.3~5.0μm,更佳為0.3~3.0μm,進而較佳為0.3~1.5μm。
[聚胺酯樹脂水分散體之黏度]
聚胺酯樹脂水分散體於25℃下之黏度較佳為3000mPa‧s以下,更佳為2000mPa‧s以下。藉由使黏度為2000mPa‧s以下,於製造時容易實施異物去除(過濾等),可提高生產效率。
[聚胺酯樹脂水分散體之製造方法]
作為本發明中之聚胺酯樹脂水分散體之製造方法,例如可列舉:方法(1),其係經過反應步驟與乳化及高分子量化步驟之方法,該反應步驟係使多元醇、成為親水性環氧烷成分之化合物及異氰酸酯進行反應,該乳化及高分子量化步驟係於反應後添加界面活性劑等,添加離子交換水與二胺等之混合液而一面乳化一面高分子化,其中,將乳化及高分子量化步驟中之添加有界面活性劑等時之攪拌設為100~300rpm左右之慢攪拌,將添加有離子交換水與二胺等之混合液時之攪拌設為4000~6000rpm左右之強攪拌;以及方法(2),其於具有槽內循環用攪拌翼與剪力賦予用攪拌翼之攪拌槽中,至少使多元醇、異氰酸酯及成為親水性環氧烷成分之化合物進行反應並進行乳化。
藉由該製造方法,可以上述較高之不揮發性成分濃度高效率地製造具有上述體積平均粒徑之聚胺酯樹脂粒子。又,可成為所需之黏度。
關於方法(2),具體而言,可藉由如下方式進行製造:於具備可達成均一化且亦可應對超高黏度液之攪拌翼之反應容器(上述攪拌槽)中使多元醇、視需要添加之短鏈二醇、異氰酸酯、及成為親水性環氧烷成分之化合物進行反應,其後,添加短鏈二胺等鏈伸長劑或鏈伸長終止劑、界面活性劑、作為分散介質之離子交換水,進行乳化並進行反應。
再者,於方法(1)中亦可適當添加短鏈二醇或短鏈二胺等鏈伸長劑或鏈伸長終止劑等。
又,作為上述攪拌槽,例如可列舉:於攪拌槽內具有2個以上之攪拌翼,例如具有2個以槽內循環為目的之攪拌翼、1個以對槽內賦予高剪力為目的之剪力賦予用攪拌翼之攪拌裝置,其中,較佳為於反應容器內之上部、底部、及上部與底部之中間部這3個位置具有攪拌翼之攪拌裝置。具體而言,可列舉:高黏度高剪切複合攪拌裝置(製品名:NANOVisK,Sumitomo Heavy Industries Process Equipment股份有限公司製造)、或真空乳化攪拌裝置(MIZUHO INDUSTRIAL股份有限公司製造)。
於上述(1)及(2)之製造方法中,若需要,則亦可使用有機溶劑進行反應,繼而進行減壓,藉此去除有機溶劑,而製造聚胺酯樹脂水分散體。
作為有機溶劑,例如可列舉:酮系溶劑(丙酮、甲基乙基酮、甲基異丁基酮、環己酮等)、芳香族系烴溶劑(甲苯、二甲苯、Swasol(Cosmo Oil股份有限公司製造之芳香族系烴溶劑)、Solvesso(Exon Chemical股份有限公司製造之芳香族系烴溶劑)等)、脂肪族系烴溶劑(正己烷等)。該等之中,就操作性之觀點而言,較佳為甲基乙基酮、丙酮及四氫呋喃等。
作為界面活性劑,可列舉:非反應性之非離子性界面活性劑。
作為上述非離子性界面活性劑,例如可列舉:聚氧乙烯烷基醚等二醇醚、及乙炔二醇等。
作為短鏈二胺,可列舉:乙二胺、三亞甲基二胺、六亞甲基二胺及八亞甲基二胺等脂肪族二胺化合物;苯二胺、3,3'-二氯-4,4'-二胺基二苯基甲烷、4,4'-亞甲基雙(苯基胺)、4,4'-二胺基二苯醚及4,4'-二胺基二苯碸等芳香族二胺化合物;環戊烷二胺、環己二胺、4,4-二胺基二環己基甲烷、1,4-二胺基環己烷及異佛爾酮二胺等脂環式二胺化合物;肼、甲二醯肼、己二酸二醯肼、癸二酸二醯肼、鄰苯二甲酸二醯肼等肼類等。該等之中,更佳為肼(水合肼)。
短鏈二醇為數量平均分子量未達500之化合物,可列舉:乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇及新戊二醇等脂肪族二醇類及其環氧烷低莫耳加成物(數量平均分子量未達500)、二乙二醇、三乙二醇、二丙二醇等伸烷基醚二醇;1,4-雙羥基甲基環己烷及2-甲基-1,1-環己烷二甲醇等脂環式系二醇類及其環氧烷低莫耳加成物(數量平均分子量未達500)、苯二甲醇等芳香族二醇類及其環氧烷低莫耳加成物(數量平均分子量未達500)、雙酚A、硫代雙酚及磺化雙酚等雙酚類及其環氧烷低莫耳加成物(數量平均分子量未達500)、及C1~C18之烷基二乙醇胺等烷基二烷醇胺類等化合物。該等之中,較佳為脂肪族二醇類。
<聚胺酯樹脂水分散體中之不揮發成分之量>
於本發明中,由於聚胺酯樹脂水分散體中之不揮發成分為40質量%
以上,故而於乾燥步驟中藉由揮發向系外排出之揮發成分之量較少,可削減乾燥所需之能量。
於本發明中,就削減乾燥步驟中使用之能量之觀點而言,聚胺酯樹脂水分散體中之不揮發成分之量較佳為41質量%以上,更佳為45質量%以上。上限值並無特別限定,例如為70質量%左右。
本發明之聚胺酯樹脂水分散體如上所述揮發成分之量較少,因此與先前相比可容易地去除揮發成分,藉由經過乾燥步驟,能夠使聚胺酯樹脂粒子融合而膜化。此處,所謂膜化係指例如於離型紙上以膜厚度成為40μm之方式塗佈本發明之聚胺酯樹脂水分散體,於120℃下乾燥5分鐘後,可保持膜形態地自剝離紙上剝離。
<添加劑>
本發明之聚胺酯樹脂水分散體視需要可含有添加劑。作為添加劑,例如可列舉:消光劑、抗氧化劑(受阻酚系、亞磷酸酯系、硫醚系等)、光穩定劑(受阻胺系等)、紫外線吸收劑(二苯甲酮系、苯并***系等)、氣體變色穩定劑(肼系等)、金屬減活劑等。
作為消光劑,可列舉:樹脂粒子、二氧化矽粒子、滑石、氫氧化鋁、硫酸鈣、矽酸鈣、碳酸鈣、碳酸鎂、碳酸鋇、氧化鋁矽酸鹽、分子篩、高嶺土、雲母及雲母(mica)等。於本發明之聚胺酯樹脂水分散體含有消光劑之情形時,可使作為表皮材之覆膜呈現消光色調。
[塗料]
本發明之塗料可由上文記述之本發明之聚胺酯樹脂水分散體獲得。即,本發明之塗料係包含聚胺酯樹脂水分散體者,由於不揮發成分較多,故可削減乾燥所需之能量。
於提高機械物性及/或耐久性之情形時,本發明之塗料較佳為除聚胺酯樹脂水分散體以外亦包含選自由異氰酸酯系交聯劑、碳二亞胺系交聯劑、唑啉系交聯劑及環氧系交聯劑所組成之群中之至少一種,更佳為包含選自由異氰酸酯系、碳二亞胺系、唑啉系交聯劑所組成之群中之至少一種。
若交聯劑之使用量過多,則可能引起膜脆化、或未反應之交聯劑導致之塑化等不良情況。因此,相對於聚胺酯樹脂100質量份,交聯劑之使用量以交聯劑固體成分換算計,較佳為設為10質量份以下,進而較佳為設為1.0~7.5質量份。
[膜構成體、構造物]
本發明之膜構成體包含由上文記述之本發明之塗料所獲得之膜狀物。即,本發明之膜構成體係包含本發明之塗料之膜狀物者,本發明之構造物包含上述膜構成體作為表皮層、中間層及接著層之至少任一者。
作為膜構成體,包括:單獨之膜、至少包含該膜並進而將該膜或其他層積層而成之積層體等各種態樣。
又,本發明之構造物較佳為於表面及內部之至少任一處包含本發明之塗料之構造物。作為該構造物,可列舉合成仿革,作為合成仿革所使用之合成仿革用基材,可列舉:織物、不織布、海綿。
上述合成仿革例如包含本發明之構造物,藉由如下方式製造。首先,於離型紙上利用缺角輪塗佈、刀式塗佈、輥式塗佈等公知方法塗佈本發明之聚胺酯樹脂水分散體作為用以形成表皮層之水系表皮劑。將其適當乾燥而形成表皮層。於該表皮層上藉由缺角輪塗佈、刀式塗佈、輥式塗佈等公知方法塗佈公知之水系聚胺酯樹脂接著劑作為水系接著劑。將
其乾燥後,與合成仿革用基材進行壓接。進而,實施熟化等,自離型紙剝離而獲得合成仿革。
作為膜構成體或構造物之一例,就於基材塗佈本發明之聚胺酯樹脂水分散體而製作該等之方法進行說明。
<基材>
作為上述基材,可列舉使用如下所述之樹脂之膜或合成皮革。又,基材可為發泡基材。
作為樹脂,可列舉:聚氯乙烯樹脂、聚乙烯系樹脂、聚丙烯系樹脂、熱塑性聚烯烴等烯烴系樹脂、乙烯丙烯二烯系樹脂、苯乙烯丙烯腈系樹脂、聚碸系樹脂、聚苯醚系樹脂、丙烯酸系樹脂、矽酮系樹脂、氟系樹脂、聚酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚苯乙烯系樹脂、聚胺酯系樹脂、聚碳酸酯系樹脂、降烯系樹脂、纖維素系樹脂、聚乙烯醇系樹脂、聚乙烯醇縮甲醛系樹脂、聚乙烯醇縮丁醛系樹脂、聚乙烯吡咯啶酮系樹脂、聚乙烯醇縮醛系樹脂、聚乙酸乙烯酯系樹脂、工程塑膠、生物降解性塑膠等。
尤其作為汽車用之內裝材用,可列舉:聚氯乙烯樹脂、熱塑性聚烯烴、聚胺酯、聚丙烯等。
又,於基材為發泡基材之情形時,可使用氯乙烯樹脂之類的基材。
基材之厚度較佳為0.2~1.5mm,於基材為發泡基材而使其發泡之情形時,發泡後之厚度較佳為0.3~4.5mm。
<製造方法>
於基材塗佈本發明之聚胺酯樹脂水分散體,在80~140℃下乾燥,並視需要進行交聯,藉此形成覆膜,而製造膜構成體或構造物。
於基材為發泡基材之情形時,例如於聚氯乙烯樹脂基材片材之情形時,包括藉由加熱使氯乙烯發泡層組合物中之發泡劑發泡而形成氯乙烯發泡層之步驟(發泡步驟)。例如,於該步驟之前,於基材片材上藉由噴霧塗裝或凹版塗裝等塗敷本發明之聚胺酯樹脂水分散體而形成塗膜。其後,於80~140℃下乾燥1~3分鐘而成為覆膜後,於130~230℃下實施發泡處理。進而,為了賦予設計性,使雕刻有花紋之壓紋輥於表面經加熱(100~190℃)之狀態下壓抵於該表面處理層側,藉此製成表面形成有花紋之合成樹脂表皮材(例如汽車用之座席片材)(花紋形成步驟)。
再者,於在接著性較差之熱塑性樹脂基材塗佈本發明之聚胺酯樹脂水分散體之情形時,為了提高與塗料之密接性,可進行底塗處理。
又,發泡步驟及花紋形成步驟分別可於形成塗膜之步驟之前進行,亦可於表面處理層形成步驟之後進行。即,有於發泡前之基材塗佈聚胺酯樹脂水分散體後再進行加熱發泡之方法、及於發泡後之基材塗佈聚胺酯樹脂水分散體之方法,基於表面處理層之均勻塗敷性及接著強度提高之原因,較佳為塗佈聚胺酯樹脂水分散體後再進行發泡之方法。
藉由以上方式形成之覆膜之膜厚較佳為2~30μm。
[實施例]
以下,列舉實施例及比較例對本發明進行更具體之說明,但本發明並不限定於此。又,以下出現之「份」表示質量份、「%」表示質量%。
<作為聚胺酯樹脂水分散體之PUD1~12及比較PUD1~8之製作>
[含末端NCO基之胺酯預聚物合成步驟]
對具備攪拌機、回流冷卻管、溫度計、氮氣吹送管及人孔之反應容器進行氮氣置換後,按照表1及表2中記載之調配,添加多元醇、鏈伸長劑、成為親水性環氧烷成分之化合物、異氰酸酯,一面攪拌一面升溫,於95℃下反應,藉此獲得末端具有NCO基之胺酯預聚物。
再者,聚異氰酸酯成分之異氰酸基當量相對於全部成分之羥基當量的比(NCO/OH)設為1.5。
[乳化及高分子量化反應]
將所獲得之含末端NCO基之胺酯預聚物移至不鏽鋼容器內,使用裝配有直徑50mm之分散翼之T.K.勻相分散機(特殊機化工工業公司製造)以100~300rpm緩慢攪拌5分鐘。繼而,以表1及2中記載之調配添加界面活性劑,於比較PUD7、8之情形時亦添加中和劑,並進行攪拌直至變得均勻。確認到系內均勻後,以4000~6000rpm強力攪拌10分鐘,並以表1及2中記載之調配添加離子交換水與二胺之混合液,進行乳化並進行高分子量化,藉此獲得作為聚胺酯樹脂水分散體之PUD1~12及比較PUD1~8。
<聚胺酯原料>
‧多元醇A:宇部興產股份有限公司製造之UH-100(聚碳酸酯二醇;數量平均分子量1000)
‧成為親水性環氧烷成分之化合物B:日油股份有限公司製造之PEG1000(聚乙二醇;數量平均分子量1000)
‧成為親水性環氧烷成分之化合物C:Evonic公司製造之TEGOMER D 3403(聚乙二醇單甲醚-1,3-二醇;數量平均分子量1000)
‧成為親水性環氧烷成分之化合物D:日油股份有限公司製造之
Uniox M-1000(聚氧乙烯單甲醚;數量平均分子量1000)
‧親水成分E:Bis-MPA(二羥甲基丙酸)
‧鏈伸長劑F:1,4-丁二醇
‧異氰酸酯G:Sumika Covestro Urethane股份有限公司製造之Desmodur W(二環己基甲烷4,4'-二異氰酸酯)
‧二胺H:60%水合肼
‧界面活性劑I:日本乳化劑股份有限公司製造之Newcol 2306-Y(聚氧伸烷基烷基醚;EOPO非離子系界面活性劑)
‧中和劑J:三乙基胺
‧分散介質K:離子交換水
<評估方法>
(粒子分散穩定性)
於1000ml之量筒(內徑80mm)中添加1000ml所合成之聚胺酯樹脂水分散體,於25℃之環境下靜置。經過1個月後,去除未沈澱之聚胺酯樹脂水分散體,計測沈澱堆積物之厚度。
◎:沈澱堆積物厚度未達30mm
○:沈澱堆積物厚度30以上且未達50mm
△:沈澱堆積物厚度50以上且未達100mm
×:沈澱堆積物厚度100mm以上
(龜裂抑制效果)
於PET膜上以100μm之塗敷厚度(縱橫為A4尺寸)塗佈所合成之聚胺酯樹脂水分散體,繼而於120℃/5分鐘之條件下進行加熱乾燥,藉此獲得膜。目視確認於膜上有無龜裂產生。
○:無龜裂產生
×:有龜裂產生
(不揮發成分測定)
使用電子天平計測不鏽鋼容器之重量(g0),稱取所獲得之各聚胺酯水分散體2g至不鏽鋼容器中(g1)。繼而,將裝有所稱取之聚胺酯水分散體之不鏽鋼容器於120℃下乾燥2小時,計測乾燥後之重量(g2)。根據所獲得之各重量及以下式(1),測定不揮發成分。
不揮發成分(質量%)=(g2-g0)/(g1-g0)×100式(1)
(體積平均粒徑測定)
利用離子交換水稀釋所獲得之聚胺酯樹脂水分散體使不揮發成分成為0.1質量%後,使用動態光散射式(DLS)粒徑分佈測定裝置[Nanotrac WaveII(MicrotracBEL製造)]進行測定。
(黏度)
利用B型黏度計(型式:BM型,2號轉子/60rpm或3號轉子/30rpm,東京計器製造所股份有限公司製造)測定求出25℃下之黏度。
(酸值)
比較PUD7、8之酸值係根據親水成分等之調配量,以計算值之方式算出。
(再分散性)
稱取500g所獲得之聚胺酯樹脂水分散體至1L聚乙烯瓶中(AS ONE股份有限公司製造),於25℃之環境下靜置3天。繼而,使用裝配有直徑40mm之分散翼之T.K.勻相分散機(特殊機化工工業公司製造)以任意轉速攪拌10分鐘,經聚乙烯篩網(MS-100目,目數83/64)進行過濾後,確認有無
凝集物或沈澱物,評估再分散性。
◎:於轉速未達3000rpm之情況下無凝集物或沈澱物
○:於轉速3000以上且未達5000rpm之情況下無凝集物或沈澱物
△:於轉速5000rpm以上之情況下無凝集物或沈澱物
×:凝集物或沈澱物無法再分散
再者,表1、2中之調配之數值為質量份。
聚胺酯樹脂水分散體PUD1~12於粒子分散穩定性、龜裂抑制及再分散性之各方面均優異。再者,比較PUD2、4、6、7雖然該等方面亦良好,但不揮發成分未達40質量%,乾燥時所需之熱量增加,因此於生產性方面較差。
Claims (7)
- 一種聚胺酯樹脂水分散體,其係聚胺酯樹脂粒子於水中分散而成者,且含有40.3質量%以上之不揮發成分,包含界面活性劑,於25℃下之黏度為2100mPa‧s以下,上述聚胺酯樹脂粒子包含多元醇成分、異氰酸酯成分、及具有1個以上之活性氫基且具有環氧烷之親水性環氧烷成分,上述親水性環氧烷成分相對於聚胺酯樹脂粒子之含量為1~25質量%,上述聚胺酯樹脂粒子之體積平均粒徑為0.3~5μm。
- 一種塗料,其包含如請求項1之聚胺酯樹脂水分散體。
- 一種膜構成體,其包含如請求項2或3之塗料之膜狀物。
- 一種構造物,其包含如請求項4之膜構成體作為表皮層、中間層及接著層之至少任一者。
- 一種構造物,其於表面及內部之至少任一處包含如請求項2或3之塗料。
- 一種合成仿革,其包含如請求項5或6之構造物。
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