TWI733241B - 黏著劑組成物、黏著層、片及帶 - Google Patents
黏著劑組成物、黏著層、片及帶 Download PDFInfo
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- TWI733241B TWI733241B TW108140102A TW108140102A TWI733241B TW I733241 B TWI733241 B TW I733241B TW 108140102 A TW108140102 A TW 108140102A TW 108140102 A TW108140102 A TW 108140102A TW I733241 B TWI733241 B TW I733241B
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/24—Homopolymers or copolymers of amides or imides
- C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
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Abstract
本發明之目的在於提供一種可保持高接著力，同時並可抑制塑化劑之遷移的黏著劑。本發明之黏著劑組成物，係包含丙烯酸聚合物(A)及交聯劑(B)，前述丙烯酸聚合物(A)為具有源自(甲基)丙烯酸烷基酯(a1)、(甲基)丙烯醯胺單體(a2)及具有羧基之(甲基)丙烯酸單體(a3)之單元者，前述丙烯酸聚合物(A)之重量平均分子量為150萬以下，相對於前述丙烯酸聚合物(A)100質量份，增黏樹脂之含量為未達10質量份。
Description
本發明係有關黏著劑組成物。
黏著片係在從電子機器或汽車等為首之各種製品的製造或電性絶緣材料、顯示/裝飾領域等家庭用至工業用之廣泛領域被使用。尤其，以軟質PVC(氯乙烯樹脂)作為基材之黏著片係因具有高的曲面接著性或印墨固定性，故在顯示、裝飾用領域等廣泛領域中被使用。又，軟質PVC係因其柔軟性或電絶緣性在汽車配線構件中亦被使用，亦較多成為黏著帶之被附體。
相接於自以往所知之PVC的黏著片或帶中，PVC中之塑化劑朝黏著劑層進行遷移，故經時(尤其高溫多溼下)之性能降低(接著力降低、凝集力降低所產生的剝離或浮起)成為問題。相對於此，專利文獻1係已提出一種含有丙烯酸系樹脂及塑化劑，且丙烯酸系樹脂之玻璃轉移溫度為-20℃以上之丙烯酸系黏著劑(參照專利文獻1)。又，專利文獻2係已提出一種黏著劑組成物，其係包含：(甲基)丙烯酸烷基酯、含有羥基之乙烯基單體及含氮之乙烯基單體的共聚物之丙烯酸系共聚物、及具有2個以上之
異氰酸酯基的脂肪族異氰酸酯化合物及其衍生物之至少1種(參照專利文獻2)。
然而，此等之黏著劑雖然可獲得耐塑化劑性，但未達滿足實用上所要求之高接著力。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2016-188282號公報
[專利文獻2]日本特開2016-108399號公報
本發明係有鑑於前述事情而構成者，目的在於保持高接著力，同時並抑制塑化劑之遷移。
本發明人等經過研究，發現使用特定之丙烯酸聚合，使重量平均分子量設為預定範圍，相溶性會提高而可提升黏著層之均勻性，結果，可保持高接著力，同時並抑制塑化劑之遷移。
本發明之黏著劑組成物，其特徵係包含丙烯酸聚合物(A)及交聯劑(B)，前述丙烯酸聚合物(A)為具有源自(甲基)丙烯酸烷基酯(a1)、(甲基)丙烯醯胺單體(a2)及具有羧基之(甲基)丙烯酸單體(a3)之單元者，前述
丙烯酸聚合物(A)之重量平均分子量為150萬以下，且相對於前述丙烯酸聚合物(A)100質量份，增黏樹脂之含量為未達10質量份。
藉由使用本發明之黏著劑組成物，使用氯乙烯樹脂作為基材之情形，可提供一種可維持高接著力，同時並可抑制塑化劑之遷移的黏著帶。
本發明之黏著劑組成物係包含丙烯酸聚合物(A)及交聯劑(B)。
前述丙烯酸聚合物(A)係具有：源自(甲基)丙烯酸烷基酯(a1)、(甲基)丙烯醯胺單體(a2)及具有羧基之(甲基)丙烯酸單體(a3)之單元。
(甲基)丙烯酸烷基酯(a1)係可舉出烷基鍵結於酯鍵之(甲基)丙烯酸烷基酯。前述烷基之碳數較佳係1以上，更佳係3以上，再更佳係4以上，較佳係20以下，更佳係15以下，再更佳係12以下，又再更佳係10以下，特別佳係8以下。
前述(甲基)丙烯酸烷基酯(a1)較佳係包含碳數3以上(較佳係4以上)之烷基鍵結於酯鍵之(甲基)丙烯酸烷基酯(a1-1)。前述(甲基)丙烯酸烷基酯(a1-1)之含有率係在(甲基)丙烯酸烷基酯(a1)中，較佳係50質量%以上，更佳係60質量%以上，再更佳係70質量%以上，較佳係100質量%以下。
前述(甲基)丙烯酸烷基酯(a1)亦較佳係包含碳數2以下之烷基鍵結於酯鍵之(甲基)丙烯酸烷基酯(a1-2)。包含前述(甲基)丙烯酸烷基酯(a1-2)之情形，其含有率較佳係1質量%以上，更佳係2質量%以上，較佳係50質量%以下，更佳係40質量%以下，再更佳係30質量%以下。
前述烷基係可舉出甲基、乙基、正-丙基、正-丁基、正-戊基、正-己基、正-庚基、正-辛基、正-壬基等之直鏈狀烷基；異丙基、異丁基、異戊基、新戊基、異己基、異庚基、異辛基、2-乙基己基等之分支鏈狀烷基等。
前述(甲基)丙烯酸烷基酯(a1)係以丙烯酸烷基酯為較佳。
前述(甲基)丙烯酸烷基酯(a1)係可使用1種或2種以上，可舉出例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯等。
前述丙烯酸聚合物(A)中，源自前述(甲基)丙烯酸烷基酯(a1)之單元的含有率較佳係50質量%以上，更佳係70質量%以上，較佳係99質量%以下，更佳係95質量%以下。
在前述(甲基)丙烯醯胺化合物中，取代成醯胺鍵所含之氮原子的基係可舉出氫原子、烴基(較佳係脂肪族烴基)、烴基(較佳係脂肪族烴基)所含之-CH2-取代成-CO-，及/或該烴基(較佳係脂肪族烴基)所含之氫原子取代成羥基之基等，2個以上之基取代成氮原子之情形，此等之基係可互相鍵結而形成含有氮原子之環。
取代成前述醯胺鍵所含之氮原子的烴基(較佳係脂肪族烴基)之碳數較佳係1以上，較佳係10以下，更佳係6以下。
前述(甲基)丙烯醯胺單體(a2)係可使用1種或2種以上。前述(甲基)丙烯醯胺單體係可為(甲基)丙烯醯胺、N-1取代(甲基)丙烯醯胺化合物、N,N-2取代(甲基)丙烯醯胺化合物之任一者。
前述(甲基)丙烯醯胺化合物係可使用1種或2種以上，可舉出例如(甲基)丙烯醯胺；N-異丙基(甲基)丙烯醯胺、N-(1,1-二甲基-3-氧丁基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-甲氧基甲基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、N-(2-羥基甲基)丙烯醯胺、N-(2-羥基乙基)丙烯醯胺等之N-1取代(甲基)丙烯醯胺化合物；N-(甲基)丙烯醯基嗎啉、N-(甲基)丙烯醯基哌啶酮、N-(甲基)丙烯醯基哌啶、N-(甲基)丙烯醯基吡咯啶、N-(甲基)丙烯醯基-4-哌啶酮、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N,N-亞甲基雙(甲基)丙烯醯胺、N,N-二甲基胺基丙基(甲基)丙烯醯胺等之N-2取代(甲基)丙烯醯胺化合物等。
其中，前述(甲基)丙烯醯胺單體(a2)較佳係含有式(1)所示之單體者。
[式(1)中，R1係表示氫原子或甲基。R2及R3係分別獨立地表示氫原子或碳數1至20之烴基，該烴基所含之-CH2-係可取代成-CO-或-O-，該烴
基所含之氫原子係可取代成羥基，R2及R3係可互相鍵結而形成含有氮原子之環。]
前述R2及R3所示之烴基係可為1種或2種以上，可舉出例如直鏈狀或分支鏈狀之飽和脂肪族烴基；直鏈狀或分支鏈狀之不飽和脂肪族烴基等。其中，以直鏈狀或分支鏈狀之飽和脂肪族烴基為較佳，以分支鏈狀之飽和脂肪族烴基為更佳。R2及R3之至少一者係以氫原子為較佳。
前述(甲基)丙烯醯胺單體(a2)較佳係包含R2及R3之至少一者為碳數1至20之烴基所含的-CH2-取代成-CO-之基的(甲基)丙烯醯胺單體(a2-1)。包含前述(甲基)丙烯醯胺單體(a2-1)之情形，源自(甲基)丙烯醯胺單體(a2-1)之單元的含有率係前述丙烯酸聚合物(A)中，較佳係3質量%以上，更佳係5質量%以上，較佳係30質量%以下，更佳係25質量%以下。
前述(甲基)丙烯醯胺單體(a2)較佳係包含R2及R3之一者為氫原子，另一者為前述烴基之(甲基)丙烯醯胺單體(a2-2)。包含前述(甲基)丙烯醯胺單體(a2-2)之情形，源自(甲基)丙烯醯胺單體(a2-2)之單元的含有率係前述丙烯酸聚合物(A)中，較佳係3質量%以上，更佳係5質量%以上，較佳係30質量%以下，更佳係25質量%以下。
前述(甲基)丙烯醯胺單體(a2)亦較佳係包含R2及R3之兩者為前述烴基之(甲基)丙烯醯胺單體(a2-3)。包含前述(甲基)丙烯醯胺單體(a2-3)之情形，源自(甲基)丙烯醯胺單體(a2-3)之單元的含有率係前述丙烯酸聚合物(A)中，較佳係3質量%以上，更佳係5質量%以上，較佳係30質量%以下，更佳係25質量%以下。
前述丙烯酸聚合物(A)中，源自前述丙烯醯胺單體(a2)之單元的含有率較佳係1質量%以上，較佳係40質量%以下，更佳係30質量%以下，再更佳係25質量%以下。
前述具有羧基之(甲基)丙烯酸單體(a3)係可使用1種或2種以上，可舉出例如(甲基)丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、(甲基)丙烯酸β-羧基乙酯等之不飽和單羧酸等。
前述丙烯酸聚合物(A)中，源自前述具有羧基之(甲基)丙烯酸單體(a3)的單元之含有率較佳係0.1質量%以上，更佳係0.5質量%以上，再更佳係1質量%以上，較佳係20質量%以下，更佳係10質量%以下，再更佳係7質量%以下。
前述丙烯酸單體(A)係亦可具有源自前述(甲基)丙烯酸烷基酯(a1)、(甲基)丙烯醯胺單體(a2)及具有羧基之(甲基)丙烯酸單體(a3)以外之其他之單體(ax)的單元。
前述其他之單體(ax)係可使用1種或2種以上，可舉出例如具有羥基之(甲基)丙烯酸單體；(甲基)丙烯酸縮水甘油酯等之含有環氧基環的(甲基)丙烯酸單體；(甲基)丙烯酸環己酯等之含有脂環的(甲基)丙烯酸單體；苯乙烯、鄰甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、乙基乙烯基苯、α-甲基苯乙烯、對甲氧基苯乙烯、對三級丁基苯乙烯、對苯基苯乙烯、鄰氯苯乙烯、間氯苯乙烯、對氯苯乙烯、對羥基苯乙烯等之芳香族乙烯基單體；N-乙烯基吡咯啶酮、N-乙烯基己內醯胺、(甲基)丙烯醯基嗎啉等之含有雜環的乙烯基單體；具有2個以上之乙烯基的單體；(甲基)丙烯腈、(甲基)丙烯酸三級丁基胺基乙酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙
烯酸二乙基胺基乙酯等之具有含有氮原子的官能基(例如胺基、1取代胺基、2取代胺基、腈基等)的(甲基)丙烯酸酯化合物等。
前述具有羥基之(甲基)丙烯酸單體係可舉出羥基鍵結於(甲基)丙烯酸烷基酯之烷基的化合物；(甲基)丙烯酸聚烷二醇酯等，較佳係羥基鍵結於(甲基)丙烯酸烷基酯之烷基的化合物，更佳係羥基鍵結於(甲基)烷基酸烷基酯之烷基的末端之化合物。
前述具有羥基之(甲基)丙烯酸單體所含的羥基之數較佳係1個。
又，前述具有羥基之(甲基)丙烯酸單體係以具有羥基之丙烯酸單體為較佳。
前述丙烯酸烷基酯係可舉出與例示作為前述(甲基)丙烯酸烷基酯(a1)之化合物為同樣之化合物。
前述具有羥基之(甲基)丙烯酸單體係可使用1種或2種以上，可舉出例如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等之(甲基)丙烯酸羥基烷基酯；聚乙二醇(甲基)丙烯酸酯等。
前述丙烯酸聚合物(A)中，源自前述具有羥基之(甲基)丙烯酸單體的單元之含有率較佳係0.01質量%以上，更佳係0.02質量%以上，再更佳係0.03質量%以上，較佳係10質量%以下，更佳係5質量%以下，再更佳係1質量%以下。
前述丙烯酸聚合物(A)中，源自其他之單體(ax)的單元之含有率較佳係0質量%以上，更佳係0質量%以上，再更佳係0.01質量%以
上，較佳係20質量%以下，更佳係10質量%以下，再更佳係5質量%以下。
前述丙烯酸聚合物(A)之重量平均分子量較佳係10萬以上，更佳係20萬以上，再更佳係30萬以上，較佳係100萬以下，更佳係90萬以下，再更佳係80萬以下。
在本說明書中，前述丙烯酸聚合物(A)之數平均分子量、重量平均分子量係表示以聚苯乙烯作為標準試料，並使用凝膠滲透層分析法(GPC)所測定之換算值者。
在本發明之黏著劑組成物中，前述丙烯酸聚合物(A)之含有率在不揮發分中，較佳係30質量%以上，更佳係50質量%以上，再更佳係60質量%以上，較佳係100質量%以下。
本說明書中，所謂黏著劑組成物之不揮發分係表示黏著劑組成物依照需要而除去所含之溶劑成分的部分者。
前述丙烯酸聚合物(A)係可藉由使前述(甲基)丙烯酸烷基酯(a1)、(甲基)丙烯醯胺單體(a2)、具有羧基之(甲基)丙烯酸單體(a3)及依需要而使用之其他的單體(ax)在聚合起始劑之存在下共聚合而製造。
前述聚合起始劑係可使用1種或2種以上之熱聚合起始劑，可舉出例如過氧化苯甲醯基或過氧化月桂醯基等之過氧化物起始劑、偶氮雙異丁基腈等之偶氮起始劑等。
本發明之黏著劑組成物係包含交聯劑(B)。交聯劑係可使用1種或2種以上，可舉出例如異氰酸酯交聯劑(較佳係芳香族異氰酸酯交聯劑)、環氧基交聯劑、氮丙啶交聯劑、多價金屬鹽交聯劑、金屬螯合劑交聯
劑、酮/聯胺交聯劑、唑啉(oxazoline)交聯劑、碳二醯亞胺交聯劑、矽烷交聯劑、縮水甘油基(烷氧基)環氧基矽烷交聯劑等。
其中，以異氰酸酯交聯劑(較佳係芳香族異氰酸酯交聯劑)、環氧基交聯劑、唑啉交聯劑、碳二醯亞胺交聯劑、縮水甘油基(烷氧基)環氧基矽烷交聯劑為較佳，以異氰酸酯交聯劑(較佳係芳香族異氰酸酯交聯劑)、環氧基交聯劑、碳二醯亞胺交聯劑為更佳，以異氰酸酯交聯劑(較佳係芳香族異氰酸酯交聯劑)為特佳。
前述異氰酸酯交聯劑之含有率係在前述交聯劑(B)中，較佳係30質量%以上，更佳係50質量%以上，再更佳係80質量%以上，更加佳係90質量%以上，較佳係100質量%以下。
前述交聯劑(B)之含有率係相對於前述丙烯酸聚合物(A)100質量份，較佳係0.1質量份以上，更佳係0.3質量份以上，再更佳係0.5質量份以上，較佳係10質量份以下，更佳係7質量份以下，再更佳係5質量份以下。
本發明之黏著劑組成物係以含有溶劑(D)為較佳。前述溶劑(D)係可使用1種或2種以上，可舉出例如甲苯、二甲苯等之芳香族烴溶劑；乙酸乙酯、乙酸丁酯等之酯溶劑；丙酮、甲基乙基酮等之酮溶劑；己烷等之脂肪族烴溶劑等。其中，以含有酯溶劑為較佳。
前述酯溶劑之含有率係在前述溶劑(D)中，較佳係50質量%以上，更佳係80質量%以上，再更佳係90質量%以上，較佳係100質量%以下。
前述溶劑(D)之含有率係在前述黏著劑組成物中，較佳係10質量%以上，更佳係30質量%以上，再更佳係50質量%以上，較佳係90質量%以下，更佳係70質量%以下，再更佳係65質量%以下。
在本發明之黏著劑組成物係為了維持低黃變性，以降低增黏樹脂之含量為較佳，相對於前述丙烯酸聚合物100質量份，較佳係未達10質量份，更佳係8質量份以下，再更佳係3質量份以下，更加佳係1質量份以下，以0質量份為較佳。使用具有特定組成及重量平均分子量之丙烯酸聚合物(A)，且採用不含有增黏樹脂之構成，可維持黏著層之低黃變性，同時在高溫/高濕條件下，可保持高接著力，抑制塑化劑之遷移。
本發明之黏著劑組成物係就添加劑而言，亦可含有用以調整pH之鹼(氨水等)或酸；發泡劑；塑化劑；軟化劑；抗氧化劑；玻璃或塑膠製之纖維/中空玻璃珠/金屬粉末等之填充劑；顏料/染料等之著色劑；pH調整劑；皮膜形成補助劑；調平劑；增黏劑；撥水劑；消泡劑；酸觸媒；酸產生劑等。
藉由將前述黏著劑組成物塗佈於支撐體上，並使其乾燥，可形成黏著層。前述支撐體係可為剝離片及黏著片等之基材的任一者。
前述塗佈方法係可使用刮刀塗佈器、逆輥式塗佈器、模縫塗佈器、唇模塗佈器、狹縫模頭塗佈器、凹版塗佈器、簾幕塗佈器等之方法。
前述黏著層之厚度較佳係5μm以上，更佳係10μm以上，再更佳係15μm以上，較佳係100μm以下，更佳係70μm以下，再更佳係50μm以下。
本發明之黏著片或黏著帶係具有前述黏著層及前述基材。前述基材係可為薄膜狀、片狀、帶狀、板狀、立體形狀等之任一者，前述基材之材質係可舉出聚酯樹脂、聚丙烯樹脂、聚乙烯樹脂、聚醯亞胺樹脂、氯乙烯樹脂、胺甲酸乙酯樹脂等之塑膠；橡膠；不織布；金屬箔；紙等，以塑膠為較佳，以氯乙烯樹脂為更佳。又，前述基材係可為表面平滑者，亦可為纖維質基材、發泡基材等之表面具有凹凸者。
前述基材之厚度較佳係0.1μm以上，較佳係1,000μm以下。
[實施例]
以下，舉出實施例而更具體說明本發明。
[合成例1]
<丙烯酸樹脂(A)之合成>
於具備攪拌機、回流冷卻管、氮導入管、溫度計之反應容器中，裝填丙烯酸丁酯580重量份、丙烯酸15重量份、二丙酮丙烯醯胺(DAAM)100重量份、丙烯酸甲酯300重量份、丙烯酸4-羥基乙酯5重量份、乙酸乙酯1000重量份，在攪拌下，一邊吹入氮一邊升溫至70℃。1小時後，添加預先以乙酸乙酯溶解之2,2’-偶氮雙(2-甲基丁腈)溶液10份(固體成分5%)。其後，攪拌下在70℃保持8小時之後，冷卻內容物，以200篩目金屬網進行過濾，獲得不揮發分50質量%、黏度27000mPa‧s、重量平均分子量60萬之丙烯酸樹脂(A)。
[實施例1]
相對於合成例1所得到之丙烯酸樹脂(A)100重量份，藉由將聚異氰酸酯系交聯劑(FINETACK硬化劑D-40；DIC股份有限公司製)1.2重量份攪拌混合成均勻，獲得丙烯酸黏著組成物。
[實施例2至7]
在實施例1中，將丙烯酸樹脂之丙烯酸單體變更成表1所示以外，其餘係與實施例1同樣方式而獲得黏著劑組成物。
前述分子量係使用以下之條件測定，並換算出聚苯乙烯之值。
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之管柱串聯連接而使用。「TSKgel GMHxL」(7.8mmI.D.×30cm)×4根
檢測器：RI(微差折射器)，RI溫度40℃
管柱溫度：40℃
溶析液：四氫呋喃(THF)
流速：1.0mL/分
注入量：100μL
濃度：(試料)4mg/mL之四氫呋喃溶液
(標準聚苯乙烯)1mg/mL之四氫呋喃溶液
標準試料：使用下述之標準聚苯乙烯而作成檢量線。
(標準聚苯乙烯)
Tosoh股份有限公司製「標準聚苯乙烯 A-500」
Tosoh股份有限公司製「標準聚苯乙烯 A-1000」
Tosoh股份有限公司製「標準聚苯乙烯 A-2500」
Tosoh股份有限公司製「標準聚苯乙烯 A-5000」
Tosoh股份有限公司製「標準聚苯乙烯 F-1」
Tosoh股份有限公司製「標準聚苯乙烯 F-2」
Tosoh股份有限公司製「標準聚苯乙烯 F-4」
Tosoh股份有限公司製「標準聚苯乙烯 F-10」
Tosoh股份有限公司製「標準聚苯乙烯 F-20」
Tosoh股份有限公司製「標準聚苯乙烯 F-40」
Tosoh股份有限公司製「標準聚苯乙烯 F-80」
Tosoh股份有限公司製「標準聚苯乙烯 F-128」
Tosoh股份有限公司製「標準聚苯乙烯 F-288」
Tosoh股份有限公司製「標準聚苯乙烯 F-550」
Tosoh股份有限公司製「標準聚苯乙烯 F-850」
[比較例1至5]
將丙烯酸樹脂之組成、分子量、增黏劑之量變更成表1所示以外，其餘係與實施例1同樣方式而獲得黏著劑組成物。
(在比較例4中，因樹脂之黏度(分子量)高，且無法塗佈，故無法評估。)
[評論：由於修正了比較例，故修正了編號。]
[黏著薄膜之加工方法]
表面經離型處理之厚度25μm的聚對苯二甲酸乙二酯薄膜(離型PET25)之表面，以溶劑乾燥後之膜厚成為25μm之方式塗佈實施例及比較
例所得到之黏著劑組成物，在80℃乾燥機中使溶劑揮發3分鐘之後，貼合軟質PVC基材。
[接著力之測定方法]
將以前述之方法作成之黏著薄膜切成25mm寬度者作為試驗片。設為使被附體以SUS304不銹鋼板表面精加工BA(冷間壓延後、光輝熱處理)之不銹鋼板、或PP(聚丙烯)板，以2kg輥×2往返貼附於被附體。貼附1小時後，在23℃、50%RH之環境下測定180度剝離強度，作為接著力。將結果表示於表1中。
[耐塑化劑性之評估方法]
如以下，評估接著力保持率。將結果表示於表1中。
[數1]
[耐黃變性之評估方法]
以前述之方法作成之黏著薄膜切成5cm×5cm者作為試驗片。使軟質PVC基材側密著於色彩計量儀之光源部，以反射測定條件測定黃變度b＊。將結果表示於表1中。
[表1]
表1中，BA係表示丙烯酸正丁酯，MA係表示丙烯酸甲酯，CHA係表示丙烯酸環己酯，NIPAM係表示N-異丙基丙烯醯胺，DMAA係表示二甲基丙烯醯胺，NVP係表示N-乙烯基吡咯啶酮，DMAEA係表示丙烯酸二甲胺乙酯。又，A-100係表示「SUPERESTER A-100」(荒川化學工業股份有限公司製)、D-135係「PENSEL D-135」(荒川化學工業股份有限公司製)。
實施例1至7係本發明之實施例，認為藉由使用併用(甲基)丙烯醯胺單體與具有羧基之(甲基)丙烯酸單體而成之丙烯酸聚合物，兩者會氫鍵性地相互作用，塑化劑難以從PVC基材遷移。
又，比較例1至3係不含有源自(甲基)丙烯醯胺單體之單元的例，無法使高接著力化及耐塑化劑遷移性併存。比較例4係丙烯酸聚合物之重量平均分子量超過150萬之例，對PVC基材之塗佈性並非充分。比較例5係相對於丙烯酸聚合物100質量份而增黏樹脂之含量超過10質量份之例，黏著層之透明性並不充分。
Claims (5)
- 一種黏著劑組成物，係包含丙烯酸聚合物(A)及交聯劑(B)；前述丙烯酸聚合物(A)為具有源自(甲基)丙烯酸烷基酯(a1)、(甲基)丙烯醯胺單體(a2)及具有羧基之(甲基)丙烯酸單體(a3)之單元者；前述丙烯酸聚合物(A)中，源自前述(甲基)丙烯酸烷基酯(a1)之單元的含有率係50質量%以上99質量%以下，源自前述丙烯醯胺單體(a2)之單元的含有率係1質量%以上40質量%以下，源自前述具有羧基之(甲基)丙烯酸單體(a3)的單元之含有率係0.1質量%以上20質量%以下；前述(甲基)丙烯醯胺單體(a2)為包含下述式(1)所示之單體者，
- 如申請專利範圍第1項所述之黏著劑組成物，其中，源自前述(甲基)丙烯醯胺單體(a2)之單元及源自具有羧基之(甲基)丙烯酸單體(a3)之單元的質量比[(a2)/(a3)]為0.25以上7.5以下。
- 如申請專利範圍第1或2項所述之黏著劑組成物，其係更含有溶劑(D)者。
- 一種黏著層，係由申請專利範圍第1至3項中任一項所述之黏著劑組成物所形成。
- 一種片或帶，係具有氯乙烯樹脂基材及申請專利範圍第4項所述之黏著層。
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| JP7422641B2 (ja) * | 2020-10-20 | 2024-01-26 | 綜研化学株式会社 | 粘着剤組成物および粘着シート |
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| JPH059450A (ja) * | 1991-07-03 | 1993-01-19 | Nichiban Co Ltd | マスキングテープ用アクリル系感圧接着剤組成物 |
| JP2017106000A (ja) * | 2015-11-30 | 2017-06-15 | 積水化学工業株式会社 | 粘着剤組成物及び粘着シート |
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| DE102004061611A1 (de) * | 2004-12-17 | 2006-07-06 | Basf Ag | Vernetzbarer Haftklebstoff für wiederablösbare Weich-PVC-Träger |
| JP4931197B2 (ja) * | 2006-08-24 | 2012-05-16 | リケンテクノス株式会社 | 粘着剤組成物およびそれを用いた粘着シート部材 |
| US20120315476A1 (en) * | 2011-06-08 | 2012-12-13 | Hiroshi Ogawa | Adhesive composition and surface protection film using the same |
| DE102012211075A1 (de) * | 2012-06-27 | 2014-05-08 | Tesa Se | Haftklebemasse insbesondere zur Verklebung von Druckklischees auf Druckzylindern für den Flexodruck |
| JP6013898B2 (ja) * | 2012-12-17 | 2016-10-25 | 藤森工業株式会社 | 粘着剤層、及び粘着フィルム |
| JP2017533289A (ja) * | 2014-09-04 | 2017-11-09 | スリーエム イノベイティブ プロパティズ カンパニー | ナノ結晶性セルロース含有感圧性接着剤 |
| KR20180090980A (ko) * | 2015-12-21 | 2018-08-14 | 세키스이가가쿠 고교가부시키가이샤 | 점착제 조성물 및 점착 테이프 |
| CN105505263B (zh) * | 2016-01-13 | 2017-12-05 | 3M创新有限公司 | 压敏胶组合物及其制品 |
| JP6872869B2 (ja) * | 2016-08-10 | 2021-05-19 | 日東電工株式会社 | 粘着シート |
| CN112105701A (zh) * | 2018-06-15 | 2020-12-18 | Dic株式会社 | 粘合剂组合物 |
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Patent Citations (2)
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| JPH059450A (ja) * | 1991-07-03 | 1993-01-19 | Nichiban Co Ltd | マスキングテープ用アクリル系感圧接着剤組成物 |
| JP2017106000A (ja) * | 2015-11-30 | 2017-06-15 | 積水化学工業株式会社 | 粘着剤組成物及び粘着シート |
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| US20210403773A1 (en) | 2021-12-30 |
| JPWO2020095878A1 (ja) | 2021-02-25 |
| JP6863535B2 (ja) | 2021-04-21 |
| CN112955517B (zh) | 2022-09-02 |
| WO2020095878A1 (ja) | 2020-05-14 |
| CN112955517A (zh) | 2021-06-11 |
| TW202031842A (zh) | 2020-09-01 |
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