TW202415732A - 剝離劑組成物、硬剝離紙,及剝離薄膜 - Google Patents
剝離劑組成物、硬剝離紙,及剝離薄膜 Download PDFInfo
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
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- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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Abstract
一種含有
(A)硬度為8~30MPa之醇酸樹脂、
(B)胺基樹脂、及
(C)1分子中具有2個以上可與(A)成分及(B)成分所選出的1個以上之樹脂進行化學鍵結之官能基的有機聚矽氧烷,
且剝離性與重複使用性良好,剝離劑的塗佈皮膜的表面狀態優異之剝離劑組成物。
Description
本發明係關於剝離劑組成物、以及硬剝離紙及剝離薄膜者。
以往藉由在紙或塑膠等之薄片狀基材的表面,塗佈剝離劑,形成硬化皮膜,而對接著性或黏著性物質賦予剝離特性。
剝離紙及剝離薄膜的用途廣泛,有對標籤或貼紙、膠帶般黏著性物質使用之場合、或用於陶瓷層或胺基甲酸酯樹脂等之非黏著性物質的成形步驟的場合,因應用途而要求不同性能。
用於非黏著性物質的成形步驟的例方面,可列舉如合成皮革製造用的工藝紙。合成皮革之製造步驟為在基材上使剝離劑硬化,形成工藝紙,在該工藝紙上塗佈胺基甲酸酯樹脂、氯乙烯樹脂、聚醯胺樹脂、聚胺基酸樹脂等,並使其乾燥。在該乾燥的樹脂上形成接著層,貼合基布,藉由從工藝紙將樹脂剝離,製造合成皮革。
合成皮革有啞光(消光)型與搪瓷(高光澤)型,但在搪瓷型的合成皮革之製造,剝離劑皮膜的表面狀態反映在合成皮革。因此,要求光澤度高且龜裂少的表面狀態良好的剝離劑皮膜。又,為了使合成皮革生產性提高,工藝紙一般被多次使用。因此,以重複使用時剝離性(脫模性)的變化少為佳。
例如,專利文獻1中,揭示含有甲基化三聚氰胺樹脂作為主成分之工藝剝離紙用剝離劑組成物,該甲基化三聚氰胺樹脂係由醇酸樹脂、胺基樹脂、含有與前述醇酸樹脂及前述胺基樹脂具有反應性的官能基的聚矽氧樹脂所構成,且前述胺基樹脂係每三嗪核含有1個以上羥甲基,且記載「可用於高溫的剝離性、光澤、表面狀態、重複使用性優異的工藝剝離紙之製造,可在低溫硬化乾燥」。然而,專利文獻1所記載的剝離劑組成物重複使用性不足,且有工藝剝離紙的重複使用性差的問題點。
專利文獻2中,揭示含有醇酸樹脂、胺基樹脂、具有與前述醇酸樹脂及/或前述胺基樹脂有反應性之官能基的聚矽氧樹脂、陽離子系界面活性劑的剝離劑組成物,且記載「光澤、剝離性、表面狀態優,具有抗靜電性能,重複使用性優異。」。然而,專利文獻2的剝離劑組成物,因界面活性劑的添加而重複使用時的剝離性變化大、需要改善重複使用性。
專利文獻3中,揭示合成皮革製造用工藝紙,其係由含三聚氰胺樹脂、聚矽氧改性醇酸樹脂的剝離劑組成物的硬化物所構成,且前述聚矽氧改性醇酸樹脂的含量相對前述三聚氰胺樹脂而言為特定量。且記載「具有高光澤度且耐刮擦性優異、具有高再現性。」。然而,專利文獻3的剝離劑組成物,需要改善剝離性,且有剝離劑的塗佈皮膜的表面狀態易惡化之缺點。
專利文獻4中,揭示含有丙烯酸樹脂及醇酸樹脂所選出的樹脂、與全乙醚型甲基化三聚氰胺樹脂、羥甲基型甲基化三聚氰胺樹脂、及此等之多聚物所選出的樹脂、與聚矽氧樹脂、與碳數1~8的一元醇之剝離劑組成物,且記載「剝離性與重複使用性良好,低溫的硬化性優異、且保存安定性優異」。然而,專利文獻4的剝離劑組成物,亦有必要改善剝離性,且有剝離劑的塗佈皮膜的表面狀態容易惡化的缺點。
[先前技術文獻]
[專利文獻]
[專利文獻1] 特開2000-095929號公報
[專利文獻2] 特許第4827282號公報
[專利文獻3] 特許第6707795號公報
[專利文獻4] 國際公開第2020/153281號
[發明所欲解決之課題]
本發明係有鑑於上述情況而成者,以提供剝離性與重複使用性良好,剝離劑的塗佈皮膜的表面狀態優異之剝離劑組成物為目的。
[用以解決課題之手段]
本發明者為了達成上述目的,努力檢討結果,發現藉由以特定之質量比含有(A)硬度為8~30MPa之醇酸樹脂、(B)胺基樹脂、(C)具有可與(A)成分及(B)成分的1個以上之樹脂進行化學鍵結之官能基的有機聚矽氧烷之剝離劑組成物,可得到剝離性與重複使用性良好,塗佈剝離劑,形成塗佈皮膜時,在塗佈皮膜不易產生龜裂,塗佈面的光澤度優異,表面狀態優異之剝離劑組成物。
因此,本發明提供下述發明。
1. 一種剝離劑組成物,其含有
(A)硬度為8~30MPa之醇酸樹脂、
(B)胺基樹脂、及
(C)1分子中具有2個以上可與(A)成分及(B)成分所選出的1個以上之樹脂進行化學鍵結之官能基的有機聚矽氧烷。
2. 如上述1記載之剝離劑組成物,其中(A)成分的羥基價為120~150mgKOH/g。
3. 如上述1或2記載之剝離劑組成物,其中(A)成分相對於(B)成分的質量比(A)/(B)為66/34~38/62。
4. 如上述1~3之任一記載之剝離劑組成物,其中(C)成分相對於(B)成分的質量比(C)/(B)為1/99~20/80。
5. 一種剝離紙或剝離薄膜,其係具有基材與形成於該表面的剝離層的硬剝離紙或剝離薄膜,且上述剝離層係由上述1~4之任一記載之剝離劑組成物的硬化物所構成。
[發明之效果]
本發明之剝離劑組成物,可提供剝離性與重複使用性良好,形成剝離層時,其剝離層的表面狀態優異之剝離劑組成物。
[實施發明之最佳形態]
以下詳細說明本發明。
[(A)成分]
本發明之(A)成分為硬度8~30MPa之醇酸樹脂,可1種單獨或2種以上組合使用。醇酸樹脂係藉由多元醇及多元酸與脂肪酸或脂肪油之縮聚及酯交換反應得到的合成樹脂。醇酸樹脂,可藉由例如,特開2007-308658號公報所記載般以往習知方法合成,亦可使用市售者。
形成醇酸樹脂的單體中,多元醇的具體例方面,可舉例如,乙二醇、聚乙二醇、二乙二醇、三乙二醇、丙二醇、聚丙二醇、1,3-丁二醇、2,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,4-環己烷二甲醇、2,2-二甲基-1,3-丙二醇(新戊二醇)、2,2-二烷基-1,3-丙二醇、2,4,4-三甲基-1,3-戊二醇、丁二醇、氫化雙酚A、雙酚A的氧化乙烯的加成物、雙酚A的環氧丙烷的加成物等之二元醇、甘油、三羥甲基乙烷、三羥甲基丙烷、季戊四醇、參-(2-羥基乙基)異氰脲酸酯等之三價以上之多元醇等。此等之多元醇可種單獨或2種以上適宜組合使用。其中,以二元醇為必須多元醇成分,且因應必要併用三價以上之多元醇為佳。
形成醇酸樹脂的單體中,多元酸的具體例方面,可舉例如,鄰苯二甲酸酐、對苯二甲酸、琥珀酸、己二酸、癸二酸等之飽和多元酸;馬來酸、馬來酸酐、富馬酸、伊康酸、無水檸康酸、間苯二甲酸及無水偏苯三羧酸等之不飽和多元酸;環戊二烯-馬來酸酐加成物、萜烯-馬來酸酐加成物、及松香-馬來酸酐加成物等之狄耳士-阿爾德反應的多元酸等。又,除上述多元酸外,可併用一元酸之安息香酸。
脂肪酸或脂肪油的具體例方面,如辛基酸、月桂酸、棕櫚酸、硬脂酸、油酸、亞麻油酸、次亞麻酸、桐油酸、蓖麻油酸、以及脫水蓖麻油酸、亞麻仁油、大豆油、紅花油、中國桐油、大麻籽油、紫蘇籽油、妥爾油、米糠油、蓖麻油、脫水蓖麻油、菜種油、綿實油、椰子油、魚油、魷魚肝油等之動植物油、及此等之脂肪酸等,以使用椰子油、大豆油、蓖麻油、脫水蓖麻油為佳。
醇酸樹脂可使用已知者。例如,動植物油或動植物油脂肪酸、或使用各種飽和脂肪酸等所製造者。此等之醇酸樹脂的油長以0~65為佳、25~55更佳、27~45再佳、29~40特別佳。其中,以使用棕櫚油改性醇酸樹脂、大豆油改性醇酸樹脂、蓖麻油改性醇酸樹脂為佳、棕櫚油改性醇酸樹脂特別佳。又,在不損及本發明之效果範圍,亦可於此等醇酸樹脂以丙烯酸樹脂、聚酯樹脂、環氧樹脂、酚樹脂等改性或混合使用。
醇酸樹脂的硬度為8~30MPa,以9~25MPa為佳、10~20MPa更佳。硬度比8MPa小,則塗佈面易產生龜裂,表面狀態惡化。另一方面,硬度比30MPa大,則醇酸樹脂的合成變得困難。
又,本說明書中提到的硬度係指,以納米壓痕法測定者,例如,使用納米壓痕儀(Hysitron Inc公司製 Triboindenter TI-950),在室溫23℃環境下,將伯科維奇型壓頭(Berkovich-type indenter)在醇酸樹脂,以最大壓痕深度100nm押入時的測定數據,用測定裝置附帶的專用軟體(triboscan)進行解析結果得到的值。
醇酸樹脂的重量平均分子量以40,000~300,000為佳、60,000~280,000更佳、80,000~260,000再佳、100,000~240,000特別佳。重量平均分子量在上述範圍內,則表面狀態更良好。
又,本說明書中提到的重量平均分子量係指,藉由下述條件的膠體滲透層析法(GPC),以聚苯乙烯為標準物質得到的值。
[測定條件]
GPC:HLC-8320(東曹公司製)
展開溶劑:四氫呋喃(THF)
流量:0.6mL/min
偵測器:示差折射率偵測器(RI)
管柱:TSK Guardcolomn SuperH-L
TSKgel SuperHM-N(6.0mmI.D.×15cm×1)
TSKgel SuperH2500(6.0mmI.D.×15cm×1)
(皆為東曹公司製)
管柱溫度:40℃
試料注入量:50μL(濃度0.5重量%之THF溶液)
醇酸樹脂的羥基價,以100~165mgKOH/g為佳、120~150mgKOH/g更佳。羥基價在上述範圍內,則剝離性與重複使用性更良好。又,上述羥基價值方面,為藉由JIS K0070:1922規定之電位差滴定法所測定的值。
[(B)成分]
本發明使用的胺基樹脂,為藉由具有胺基的化合物與甲醛之縮合反應而得到的樹脂,作為與(A)成分及/或(C)成分反應之交聯劑的角色,可使用1種或2種以上。胺基樹脂,例如,可依據特開昭53-061684號公報所記載般習知方法合成,亦可使用市售者。
胺基樹脂的例方面,例如尿素S樹脂、三聚氰胺樹脂、苯胺樹脂、胍胺樹脂,但由硬化性的觀點,以三聚氰胺樹脂為佳。
三聚氰胺樹脂為三聚氰胺與甲醛進行縮合而得到的合成樹脂,為單聚物或2聚物以上之多聚物所構成的縮合物。為包含三嗪環的周圍透過3個氮原子鍵結有官能基的構造者,可舉例如1分子中具有亞胺基、羥甲基或烷氧基甲基作為官能基,因官能基而有為全乙醚型、羥甲基型、亞胺基型、羥甲基/亞胺基型。
又,三聚氰胺樹脂以烷氧基甲基的種類區分,可舉例如烷氧基甲基全部為甲氧基甲基之甲基化三聚氰胺樹脂、烷氧基甲基全部為n-丁氧基甲基之n-丁基化三聚氰胺樹脂、烷氧基甲基中混合有甲氧基甲基及n-丁氧基甲基之甲基化/n-丁基化三聚氰胺樹脂。
三聚氰胺樹脂,由剝離性的觀點,以全乙醚型甲基化三聚氰胺樹脂、全乙醚型甲基化/n-丁基化三聚氰胺樹脂、羥甲基型甲基化三聚氰胺樹脂、羥甲基型甲基化/n-丁基化三聚氰胺樹脂為佳、全乙醚型甲基化三聚氰胺樹脂、羥甲基型甲基化三聚氰胺樹脂更佳、全乙醚型甲基化三聚氰胺樹脂又更佳。
市售的三聚氰胺樹脂方面,可舉例如,Cymel300、Cymel301、Cymel303LF(以上,Allnex Japan Co., Ltd.製、全乙醚型甲基化三聚氰胺樹脂)、Cymel350、Cymel370N(以上,Allnex Japan Co., Ltd.製、羥甲基型甲基化三聚氰胺樹脂)、Cymel325、Cymel327(以上,Allnex Japan Co., Ltd.製、亞胺基型甲基化三聚氰胺樹脂)、Cymel232、Cymel235(以上,Allnex Japan Co., Ltd.製、全乙醚型甲基化/n-丁基化三聚氰胺樹脂)、Cymel251(以上,Allnex Japan Co., Ltd.製、羥甲基型甲基化/n-丁基化三聚氰胺樹脂)等。
(A)成分相對於(B)成分的質量比(A)/(B),以66/34~38/62為佳、62/38~40/60更佳、58/42~43/57再佳、55/45~46/54特別佳。(A)成分相對於(B)成分的質量比(A)/(B)在上述範圍內,則重複使用性與表面狀態更良好。(A)~(C)成分的合計中(B)成分的比例雖不特別限制,可為10~90質量%、以20~80質量%為佳、35~60質量%更佳。
[(C)成分]
本發明之(C)成分,為1分子中具有2個以上可與(A)成分及(B)成分所選出的1個以上之樹脂進行化學鍵結之官能基的有機聚矽氧烷,可1種單獨或2種以上適宜組合使用。有機聚矽氧烷,必須為1分子中具有2個以上可與由(A)成分及(B)成分所選出的1個以上之樹脂進行化學鍵結之官能基。藉由此,由形成剝離層的(A)成分及(B)成分與脫模成分之聚矽氧樹脂在剝離層中化學鍵結之構造,可抑制聚矽氧樹脂移動至黏著劑層。如此之官能基方面,可舉例如羥基、胺基、羧基、環氧基、異氰酸酯基、矽烷醇基、胺基矽烷基等,以胺基、羥基、環氧基為佳、羥基更佳。
有機聚矽氧烷,在可發揮本發明之作用效果範圍內,可為直鏈狀或分支鏈狀任一構造,但以下述平均組成式(1)所表示者為佳。
(式中,R
1可為相同或相異之碳數1~20的未取代或取代的有機基,且為1分子中具有2個以上具有羥基、胺基、羧基、環氧基或異氰酸酯基的可被雜原子取代的碳數1~20的有機基。a為2以上,b為1以上,c為0以上,d為0以上之整數,且5≦a+b+c+d≦500。)
上述碳數1~20的有機基的較佳者,具體上例如甲基、乙基、丙基、丁基等碳數1~6的烷基、環己基等之碳數5~8的環烷基、苯基、甲苯基等之碳數6~10的芳基、苄基等之碳數7~10的芳烷基。或可舉例如鍵結在此等之基的碳原子之氫原子的一部份或全部被聚醚基、烷氧基烷基、鹵素原子等取代的羥基丙基、1-氯丙基、3,3,3-三氟丙基等所選出的碳數1~10的烷基。其中,由剝離性的觀點,以甲基、苯基更佳。
上述具有羥基、胺基、羧基、環氧基或異氰酸酯基的可被雜原子取代的碳數1~20的有機基方面,可舉例如羥基甲基、羥基乙基、羥基丙基、羥基丁基、羥基戊基、羥基己基、羥基庚基、羥基辛基等之羥基烷基、
-(CH
2)
3-(OCH
2CH
2)
n-OH所表示之聚乙二醇基、
-(CH
2)
3-(OCH
2CH
2CH
2)
n-OH所表示之聚丙二醇基、3-胺基丙基、N-2-(胺基乙基)-3-胺基丙基、羧基辛基、3-環氧丙氧基丙基、2-(3,4-環氧基環己基)乙基、3-異氰酸酯丙基。其中,由硬化性的觀點,以羥基烷基、聚乙二醇基、聚丙二醇基更佳。
上述官能基R
1中,以具有芳基、芳烷基5~50mol%為佳、具有8~45mol%更佳、具有11~40mol%再佳、具有14~35mol%特別佳。若在上述範圍內,則剝離性更良好。
上述式(1)中之a、b、c、d,a為2以上,較佳為2~30的整數、b為1以上,較佳為1~500的整數、c為0以上,較佳為0~10的整數、d為0以上,較佳為0~10的整數,且5≦a+b+c+d≦500,較佳為10≦a+b+c+d≦400、更佳為20≦a+b+c+d≦300。
(C)成分的具體例方面,可舉例如以下者,但不限於此等。又,下述式中之Me、Ph,各自表示甲基、苯基,各矽氧烷單位的鍵結順序非被下述所限制者。
(C)成分相對於(B)成分的質量比(C)/(B),以1/99~20/80為佳、1.5/98.5~16/84更佳、2/98~12/88再佳、2.5/97.5~10/90特別佳。(C)成分相對於(B)成分的質量比(C)/(B)在上述範圍內,則剝離性更良好。
[(D)成分]
本發明之組成物中,(D)成分方面,可含有1種單獨或2種以上之任意量的溶劑。藉由以溶劑稀釋,操作性及塗佈作業性被改善。
可使用的溶劑,可舉例如甲苯、二甲苯等之芳香族烴系化合物、己烷、庚烷、異液態石蠟等之脂肪族烴系化合物、丙酮、甲基乙基酮、甲基異丁基酮等之酮化合物、乙酸乙酯、乙酸丁酯等之酯化合物、二異丙基醚、1,4-二噁烷等之醚化合物、甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇等之醇化合物,以芳香族烴系化合物、酮化合物、酯化合物、醇化合物為佳、甲苯、二甲苯、丙酮、甲基乙基酮、乙酸乙酯、乙酸丁酯、甲醇、1-丁醇特別佳,可為任何可使其溶解的化合物即可。
搭配(D)成分時的搭配量,相對於(A)~(C)成分的合計100質量份,以20~10,000質量份為佳、50~5,000質量份更佳。
[(E)成分]
本發明之組成物中,由促進(A)成分、(B)成分、(C)成分之交聯反應的觀點,可使用酸性觸媒。酸性觸媒可1種單獨或2種以上組合使用。酸性觸媒方面,可舉例如,鹽酸、硫酸、磷酸、硼酸等之無機酸類、乙酸、單氯乙酸、二氯乙酸、酪酸等之羧酸、苯磺酸、p-甲苯磺酸、二甲苯磺酸、p-酚磺酸、甲磺酸、乙烷磺酸、十二基苯磺酸等之有機磺酸等所選出的有機酸,以使用有機酸為佳、p-甲苯磺酸、十二基苯磺酸更佳。
搭配酸性觸媒時的搭配量,可為促進反應之觸媒量,例如,相對於(A)~(C)成分的合計100質量份,以0.1~20質量份為佳、1~10質量份更佳。若在上述範圍內,則硬化性優異、剝離性與重複使用性良好。搭配(D)~(E)成分之場合,本發明之剝離劑組成物中(A)~(E)成分的合計量宜選自80~100質量%之範圍。
[其其他任意成分]
本發明之剝離劑組成物,在不損及本發明之效果範圍,可進一步添加上述成分以外的任意成分。任意成分方面,可使用例如,酚系、醌系、胺系、磷系、亞磷酸酯系、硫系、硫醚系等之抗氧化劑;三唑系、二苯甲酮系等之光安定劑;磷酸酯系、鹵素系、磷系、銻系等之難燃劑;染料;顏料;消泡劑;充填劑;平坦劑;增黏劑;界面活性劑等。此等可種單獨或2種以上適宜組合使用。又,本發明之剝離劑組成物中,由重複耐久性的觀點來看,陽離子性界面活性劑的搭配量以少為佳,亦可不搭配。任意成分的量為在不損及本發明之效果範圍雖不特別限制,以剝離劑組成物中20質量%以下為佳。
[製造方法]
本發明之組成物的調製,將(A)~(C)成分、因應必要之(D)、(E)成分及任意成分混合即可,但以將(A)、(B)、(C)、(D)及任意成分預先均勻混合後,使用前再添加(E)成分之方法,在保存安定性的面上為佳。混合方法等不特別限制,可使用習知方法。
[剝離紙或剝離薄膜(塗佈物)]
本發明為提供具有基材與形成於該其表面的剝離層的硬剝離紙或剝離薄膜,且上述剝離層由上述剝離劑組成物的硬化物所構成。剝離紙或剝離薄膜,可藉由將剝離劑組成物塗佈於基材後,進行加熱,形成硬化皮膜而得到。
具體上,例如,藉由將上述剝離劑組成物直接、或以上述稀釋用的溶劑進一步稀釋為上述範圍後,使用缺角輪塗佈機、唇口塗佈機、輥塗佈機、模具塗佈機、刀式塗佈機、刮刀塗佈機、棒式塗佈機、吻塗機、凹版塗佈機、鋼絲棒塗布等之塗佈、網版塗佈、浸漬塗佈、鑄塗型塗佈等之塗佈方法,在紙或薄膜等之薄片狀基材的單面或兩面上塗佈0.01~100g/m
2後,在50~200℃,進行1~120秒鐘加熱,於基材上形成硬化皮膜,形成剝離層。
塗佈量以0.01~100g/m
2為佳、0.03~20g/m
2更佳,乾燥時的溫度以50~200℃為佳、70~180℃更佳。乾燥時的時間以1~120秒為佳、5~90秒更佳。在基材兩面製作剝離層之場合,以在基材單面分別進行硬化皮膜(剝離層)的形成操作為佳。
薄片基材之例方面,可舉例如聚乙烯層合紙、玻璃紙、高品質紙張、牛皮紙、黏土銅版紙、鏡面銅版紙等各種銅版紙、YUPO等合成紙、聚乙烯薄膜、CPP或OPP等之聚丙烯薄膜、聚對苯二甲酸乙二醇酯薄膜等之聚酯薄膜、聚醯胺薄膜、聚醯亞胺薄膜、聚乳酸薄膜、多酚薄膜、聚碳酸酯薄膜等。為了使此等之基材與剝離層之密著性提升,亦可使用在基材面施以電暈處理、蝕刻處理或電漿處理者。
[實施例]
以下為實施例及比較例,將本發明具體說明,但本發明不限於下述實施例。
<使用原料>
(A成分)
(A-1)棕櫚油改性醇酸樹脂(50質量%二甲苯溶液、羥基價133mgKOH/g)10.9
(A-2)棕櫚油改性醇酸樹脂(50質量%二甲苯溶液、羥基價139mgKOH/g)12.5
(A-3)棕櫚油改性醇酸樹脂(50質量%二甲苯溶液、羥基價125mgKOH/g)16.4
(A-4)棕櫚油改性醇酸樹脂(50質量%二甲苯溶液、羥基價142mgKOH/g)8.6
(A-5)比較品、哈里夫塔爾732-60(播磨化成製、棕櫚油改性醇酸樹脂的60質量%二甲苯溶液、羥基價130 mgKOH/g)4.1
(A-6)比較品、阿爾西迪亞J-524-A(DIC製、棕櫚油改性醇酸樹脂的60質量%二甲苯溶液、羥基價126mgKOH/g) 6.8
(B成分)
(B-1)
Cymel303LF(Allnex Japan製:全乙醚型甲基化三聚氰胺樹脂)
(C成分)
(C-1)
一般式(3)所表示之聚有機矽氧烷:下述式中之Me、Ph,各自表示甲基、苯基,各矽氧烷單位的鍵結順序不限於下述者。
(C-2)
一般式(4)所表示之聚有機矽氧烷:下述式中之Me、Ph,各自表示甲基、苯基,各矽氧烷單位的鍵結順序不限於下述者。
(D成分)
甲苯及二甲苯的混合溶液(質量比50:50)
(E成分)
p-甲苯磺酸
[硬度]
(A)成分的硬度係以使用納米壓痕儀(Hysitron Inc公司製 Triboindenter TI-950)的納米壓痕法測定。以(A)成分的固形分成為10g之方式,在直徑6cm、深度1cm的圓形鋁製培養皿秤取(A)成分,並在150℃的熱風乾燥機中加熱5小時,使溶劑揮發。進一步在室溫23℃的環境下放冷24小時,得到測定樣本。
使得到的樣本以(A)成分面與壓頭接觸,固定在專用的樣本固定台,在室溫23℃環境下,使伯科維奇型壓頭(Berkovich-type indenter)在(A)成分的表面以壓痕速度約17nm/sec、壓痕深度約100nm推擠時,得到的數據以專用軟體(triboscan)分析,而求出硬度。對各樣本中相異5點,進行同樣操作,以求出硬度,其平均值記載於表1、2。
[實施例1~6、比較例1~4]
使用上述所示之(A)~(C)成分作為原料,用以下的過程調製塗佈用組成物。將(A)、(B)、(C)成分依照表1、2之搭配比,取至燒瓶,使固形分濃度成為40質量%之方式,添加(D)成分,並均勻混合。在得到的溶液,添加(E)成分使其相對於(A)~(C)成分的合計100質量份,為5質量份,並攪拌混合而得到剝離劑組成物。使用該組成物,用後述方法,調製具有剝離層之剝離紙,且進行下述評估。結果一併記如表中。
又,(A)成分含有溶劑,但表中之搭配量為除去溶劑的純分量。
[剝離強度]
在厚度165μm的鏡面銅版紙,使得到的剝離劑組成物以棒塗佈機塗佈為塗附量5.0g/m
2,在170℃的熱風式乾燥機中進行60秒加熱,形成剝離劑層後,於其硬化皮膜表面塗佈一液型聚胺基甲酸酯溶液〔克里斯本5516S(大日本油墨化學工業(股)製)〕使其塗膜的厚度成為30μm,在130℃進行2分鐘熱處理,使聚胺基甲酸酯層形成。接著,在該處理面貼合日東31B膠帶,以2Kg輥進行1次往復壓接,在25℃進行20小時老化後,使試料切斷為寬3cm,使用拉伸試驗機,以180°之角度、剝離速度0.3m/分鐘,測定拉伸、剝離貼合膠帶所需要之力(gf/30mm)。設該數值為第1次剝離強度,依據下述指標進行評估。
○:第1次剝離強度為20gf/30mm以下
△:第1次剝離強度為超過20gf/30mm且30gf/30mm以下
×:第1次剝離強度為超過30gf/30mm
[重複使用性]
與上述剝離強度試驗同樣地,在形成剝離劑層後,塗佈聚胺基甲酸酯溶液,使聚胺基甲酸酯層形成。重複3次聚胺基甲酸酯的剝離,將第3次測定值作為第3次剝離強度。
由(第3次剝離強度-第1次剝離強度)/第1次剝離強度×100(%)的式,求出重複使用場合的剝離力的增加率。增加率愈少,顯示重複使用性愈優,並依據下述指標進行評估。
○:增加率為20%以下
△:增加率為超過20%且50%以下
×:增加率為超過50%
[表面狀態(龜裂)]
將上述剝離強度試驗所形成的塗佈皮膜表面(400cm
2)用目視觀察,測定龜裂個數。龜裂數愈少,表面狀態愈良好,並依據下述指標進行評估。
○:龜裂數為0~2個
△:龜裂數為3~5個
×:龜裂數為6個以上
[表面狀態(光澤度)]
將以上述剝離強度試驗所形成的塗佈皮膜表面的60度之鏡面光澤度,使用日本電色工業公司的光澤計VG7000進行測定。鏡面光澤度愈高,表面狀態愈良好,並依據下述指標進行評估。
○:鏡面光澤度為96%以上
△:鏡面光澤度為92%以上且未達96%
×:鏡面光澤度未達92%
Claims (5)
- 一種剝離劑組成物,其係含有 (A)硬度為8~30MPa之醇酸樹脂、 (B)胺基樹脂、及 (C)1分子中具有2個以上可與(A)成分及(B)成分所選出的1個以上之樹脂進行化學鍵結之官能基的有機聚矽氧烷。
- 如請求項1記載之剝離劑組成物,其中,(A)成分的羥基價為120~150mgKOH/g。
- 如請求項1記載之剝離劑組成物,其中,(A)成分相對於(B)成分的質量比(A)/(B)為66/34~38/62。
- 如請求項1記載之剝離劑組成物,其中,(C)成分相對於(B)成分的質量比(C)/(B)為1/99~20/80。
- 一種剝離紙或剝離薄膜,其係具有基材與形成於其表面的剝離層之硬剝離紙或剝離薄膜,且上述剝離層係由請求項1~4中任1項記載之剝離劑組成物的硬化物所構成。
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