TW202216943A - 黏著劑組成物及表面保護膜 - Google Patents
黏著劑組成物及表面保護膜 Download PDFInfo
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- TW202216943A TW202216943A TW110129946A TW110129946A TW202216943A TW 202216943 A TW202216943 A TW 202216943A TW 110129946 A TW110129946 A TW 110129946A TW 110129946 A TW110129946 A TW 110129946A TW 202216943 A TW202216943 A TW 202216943A
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- meth
- acrylate
- adhesive composition
- film
- monomer
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- 239000000203 mixture Substances 0.000 title claims abstract description 94
- 239000000853 adhesive Substances 0.000 title claims abstract description 81
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 81
- 230000001681 protective effect Effects 0.000 title claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 161
- -1 2-hydroxypropyl Chemical group 0.000 claims description 86
- 239000010410 layer Substances 0.000 claims description 78
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- 239000012948 isocyanate Substances 0.000 claims description 51
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- 239000012790 adhesive layer Substances 0.000 claims description 36
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 35
- 239000011521 glass Substances 0.000 claims description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 150000002513 isocyanates Chemical class 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 239000011159 matrix material Substances 0.000 claims description 16
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- 125000001424 substituent group Chemical group 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-UHFFFAOYSA-N 0.000 claims description 2
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
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Abstract
本發明提出黏著劑組成物及包括彼之表面保護膜,彼等具有低的低速率和高速率剝離力及高的殘留黏著率。
Description
本發明係關於黏著劑組成物和表面保護膜。明確言之,本發明係關於具有高的殘留黏著率之黏著劑組成物和表面保護膜。
相關申請案之交互參照
此申請案主張2020年8月18日向韓國智慧財產辦公室提出申請之韓國專利申請案第10-2020-0103553號之權益,茲將案件全文以引用方式納入本文中。
在製造OLED的程序中,在製造塑膠OLED面板之後,在塑膠OLED面板結合至觸控元件之前,須防止面板表面上的封裝層因為外在污染物和外在刺激而受損。為保護該封裝層,在塑膠OLED製程中,通常使用用於薄膜封裝(TFE)的加工保護膜。
此加工保護膜通常包括基質層和黏著層,及積層於其上之用於保護該黏著層表面的脫模膜。在自具有該脫模膜積層於其上的該加工保護膜剝離該脫模膜之後,該加工保護膜經積層,使得該黏著層與黏著物(如,在程序中須保護其表面的電子組件)的表面接觸。然後,在該程序和須實施的另一程序之後,不再須要保護時,自該黏著物剝離該加工保護膜。
此加工保護膜係積層於該OLED面板的上表面上以保護該OLED裝置的膜。該加工保護膜須具有抗靜電功能以防止OLED裝置因為與製造設備接觸而產生的靜電或剝離該積層的保護膜時可能產生的靜電而受損及防止因為任何殘留的靜電的微弱電荷所引起的面板故障,且須在自彼剝離該脫膜膜時,展現低的剝離電壓。
此外,由於該加工保護膜係用於在製程中暫時保護電力組件的膜,所以在黏著物上須具有優異的潤濕性且在移除該保護膜以進行額外的程序時,展現低的剝離力和低的殘留率,在剝離之後不應留下污染物,且在剝離之後,不應對黏著物引發靜電損傷。據此,該加工保護膜須具有抗靜電性。
依照慣例,塑化劑、低分子量添加劑加至含有胺基甲酸乙酯樹脂的黏著劑組成物以實現較低的剝離力,且提供抗靜電層以實現優異的抗靜電性。但是,該塑化劑加至該黏著劑組成物時,黏著物表面被大量添加的該塑化劑的遷移所污染。
所欲解決技術問題
待本發明解決的技術問題係提出黏著劑組成物和表面保護膜,其展現低的殘留率、低的剝除力和高的殘著黏著率。
解決問題之技術手段
根據本發明的一方面,提出一種含有含羥基的胺基甲酸乙酯樹脂、異氰酸酯系固化劑、和(甲基)丙烯酸酯共聚物之黏著劑組成物,其中該(甲基)丙烯酸酯共聚物係藉含有含羥基的(甲基)丙烯酸酯單體、含氟化的取代基之(甲基)丙烯酸酯單體、具1至10個碳原子的(甲基)丙烯酸烷酯單體和具12至22個碳原子的(甲基)丙烯酸烷酯單體之單體混合物之聚合反應得到。
根據本發明的另一方面,提出一種包含脫模膜和基質膜之表面保護層,其中該基質膜包含:第一基質層;位於該第一基質層的至少一表面上之抗靜電層;和包含該黏著劑組成物的固化產物之黏著層,且該脫模膜和該黏著層彼此直接接觸。
發明對照先前技術之功效
根據本發明的一個實施例之黏著劑組成物的有效之處在於,因為其低的黏著性,所以容易以低速率或高速率自黏著物剝離,且因為沒有殘留物留在該黏著物表面上,所以不會污染該黏著物表面。
根據本發明的另一實施例之表面保護膜的有效之處在於,因為其低的黏著性,所以容易以低速率或高速率自黏著物剝離,且因為沒有殘留物留在該黏著物表面上,所以不會污染該黏著物表面。
本說明書中,瞭解除非另外指明,否則當任何部分指出“包括”任何組份時,其未排除其他組份,而是可以另外包括其他組份。
在本說明書中,術語“重量平均分子量”是指使用具有各種聚合度之單分散的聚苯乙烯(標準樣品)(其為市售之用於分子量測量標準品)作為標準品,藉凝膠滲透層析術(GPC)測得之相關於聚苯乙烯的分子量。該重量平均分子量的單位是g/mol。本說明書中,除非另外指明,否則術語“分子量”是指重量平均分子量。
本說明書中,術語"抗靜電層"是指用以抑制靜電生成的層。
下文中,將更詳細地描述本發明。
根據本發明的一個實施例,提出一種含有含羥基的胺基甲酸乙酯樹脂、異氰酸酯系固化劑、和(甲基)丙烯酸酯共聚物之黏著劑組成物,其中該(甲基)丙烯酸酯共聚物係藉含有含羥基的(甲基)丙烯酸酯單體、含氟化的取代基之(甲基)丙烯酸酯單體、具1至10個碳原子的(甲基)丙烯酸烷酯單體和具12至22個碳原子的(甲基)丙烯酸烷酯單體之單體混合物之聚合反應得到。
根據本發明的一個實施例之黏著劑組成物可以施用和固化於黏著物上而形成黏著層。該黏著層因為其低的剝離力而易自該黏著物剝離,在該黏著物表面留下較少的黏著劑殘留,且可自該黏著物剝離且不會因為其高的殘留黏著率而污染該黏著物表面。
(1) 胺基甲酸乙酯樹脂
根據本發明的一個實施例之黏著劑組成物可含有胺基甲酸乙酯樹脂作為主要組份。“含有胺基甲酸乙酯樹脂作為主要組份”是指該胺基甲酸乙酯樹脂在該黏著劑組成物中的含量為約50重量%或更高,其可高於其他組份的含量。
該胺基甲酸乙酯樹脂含有羥基。隨著該胺基甲酸乙酯樹脂含有羥基,在該黏著劑組成物製成黏著層時,即,當該黏著劑組成物固化形成黏著層時,該胺基甲酸乙酯樹脂的羥基可作為交聯點。因此,使用自多元醇和多官能性異氰酸酯製得的聚胺基甲酸乙酯多元醇樹脂作為上述的該胺基甲酸乙酯樹脂時,該聚胺基甲酸乙酯多元醇樹脂較佳地使用該多元醇和該多官能性異氰酸酯製得,使得該多官能性異氰酸酯中的異氰酸酯基(NCO)的莫耳數與該多元醇中的羥基(OH)的莫耳數的比,(NCO/OH),低於1。
未特別限制根據本發明的一個實施例之黏著劑組成物中所含的該胺基甲酸乙酯樹脂,但可為聚胺基甲酸乙酯多元醇樹脂或聚胺基甲酸乙酯預聚物多元醇,其可藉聚合用於製造胺基甲酸乙酯之含有多元醇和多官能性異氰酸酯的混合物而得。
可以使用一種類型的多元醇、或可以併用二或更多種類型的多元醇作為用於製造聚胺基甲酸乙酯多元醇樹脂的多元醇原料。此外,也可以併用二官能性多元醇和三官能性或更多官能性的多元醇作為多元醇原料,且在此情況中,可以併用一或多種二官能性多元醇和一或多種三官能性或更多官能性的多元醇。
該多元醇原料的例子包括乙二醇、二乙二醇、1,3-丁二醇、1,4-丁二醇、新戊二醇、3-甲基-1,5-戊二醇、2-丁基-2-乙基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇、1,2-己二醇、1,6-己二醇、1,8-辛二醇、1,9-辛二醇、2-甲基-1,8-辛二醇、1,8-癸二醇、十八烷二醇、甘油、三羥甲基丙烷、季戊四醇、己三醇、聚丙二醇等。可使用之酸組份的例子包括丁二酸、甲基丁二酸、己二酸、庚二酸、壬二酸、癸二酸、1,12-十二烷二酸、1,14-十四烷二烷、二聚酸、2-甲基-1,4-環己二羧酸、2-乙基-1,4-環己二羧酸、對酞酸、異酞酸、酞酸、1,4-萘二羧酸、4,4’-聯苯基二羧酸、和其酸酐。
此外,該多元醇原料可含有聚酯多元醇、聚醚多元醇、聚己內酯多元醇、和聚碳酸酯多元醇中之至少一者。其明確例子包括,但不限於,以下所述者。
該聚醚多元醇的例子包括藉環氧烷(如,環氧乙烷、環氧丙烷、環氧丁烷等)與引發劑(如,水);低分子量多元醇(如,丙二醇、乙二醇、甘油、三羥甲基丙烷、或季戊四醇);雙酚(如,雙酚A);或二羥基苯(如,兒茶酚、間苯二酚、或氫醌)之加成聚合反應所得到的聚醚多元醇。該聚醚多元醇的明確例子包括聚乙二醇、聚丙二醇、聚丁二醇等。
該聚己內酯多元醇的例子包括藉環狀酯單體(如,ε-己內酯或σ-戊內酯)的開環聚合反應得到的己內酯系聚酯二醇。
聚碳酸酯多元醇的例子包括:藉多元醇組份和光氣之間的聚縮合反應得到的聚碳酸酯多元醇;藉多元醇組份與二酯碳酸酯(如,碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸二異丙酯、碳酸二丁酯、碳酸乙酯丁酯、碳酸乙二酯、碳酸丙二酯、碳酸二苯酯、或碳酸二苯甲酯)的轉酯化聚縮合反應得到的聚碳酸酯多元醇;藉併用該多元醇組份中之二或多者而得到之共聚的聚碳酸酯多元醇;藉由以含羧基的化合物酯化該上列聚碳酸酯多元醇而得的聚碳酸酯多元醇;藉由以含羥基的化合物醚化該上列聚碳酸酯多元醇而得的聚碳酸酯多元醇;藉由以酯化合物轉酯化該上列聚碳酸酯多元醇而得的聚碳酸酯多元醇;藉由以含羥基的化合物轉酯化該上列聚碳酸酯多元醇而得的聚碳酸酯多元醇;藉上列聚碳酸酯多元醇與二羧酸化合物的聚縮合反應的到的聚酯系聚碳酸酯多元醇;及該上列聚碳酸酯多元醇與環氧烷共聚而得到之共聚的聚醚系聚碳酸酯多元醇。
可以適當地選擇用於胺基甲酸乙酯製造之混合物中所含多元醇原料的數量平均分子量。一個實施例中,該多元醇的數量平均分子量可為約100至40,000,但不在此限。
可以使用可用於胺基甲酸乙酯化反應之任何適當的多官能性異氰酸酯化合物作為多官能性異氰酸酯化合物。此多官能性異氰酸酯化合物的例子包括多官能性脂族異氰酸酯化合物、多官能性脂環族異氰酸酯化合物、和多官能性芳族異氰酸酯化合物。
該多官能性異氰酸酯化合物的例子包括,但不限於,多官能性脂族異氰酸酯、多官能性脂環族異氰酸酯和多官能性芳族異氰酸酯化合物、藉三官能性異氰酸酯修飾聚異氰酸酯而得的三羥甲基丙烷加合物、聚異氰酸酯與水反應而得的縮二脲體、具有三聚異氰酸酯環的三聚體等。
多官能性脂族異氰酸酯化合物的例子包括,但不限於,三伸甲基二異氰酸酯、四伸甲基二異氰酸酯、五伸甲基二異氰酸酯、六伸甲基二異氰酸酯、1,2-伸丙基二異氰酸酯、1,3-伸丁基二異氰酸酯、十二伸甲基二異氰酸酯、2,4,4-三甲基六伸甲基二異氰酸酯等。
多官能性脂環族異氰酸酯化合物的例子包括,但不限於,異佛爾酮二異氰酸酯(IPDI)、1,4-環己烷二異氰酸酯(CHDI)、4,4’-二環己基甲烷二異氰酸酯(HMDI)、雙(異氰酸基甲基)環己烷(HXDI)等。
多官能性芳族異氰酸酯化合物的例子包括,但不限於,甲苯2,4-二異氰酸酯(TDI)、甲苯2,6-二異氰酸酯(TDI)、4,4’-伸甲基二苯基二異氰酸酯(MDI)、2,4’-伸甲基二苯基二異氰酸酯(MDI)、聚合性伸甲基二苯基二異氰酸酯(PMDI)、對-伸苯基二異氰酸酯(PDI)、間-伸苯基二異氰酸酯(PDI)、萘1,5-二異氰酸酯(NDI)、萘2,4-二異氰酸酯(NDI)、對-二甲苯二異氰酸酯(XDI)、1,3-雙(1-異氰酸基-1-甲基乙基)苯(TMXDI)等。
本發明的一個實施例中,二或更多種異氰酸酯化合物可以併用為多官能性異氰酸酯化合物,且在此情況中,可以適當地選擇該二或更多種異氰酸酯化合物的類型和含量。例如,多官能性芳族異氰酸酯化合物和多官能性脂族異氰酸酯化合物可以合併使用作為用於胺基甲酸乙酯製造的混合物中所含的異氰酸酯化合物。
該胺基甲酸乙酯樹脂的重量平均分子量可為50,000至200,000、或100,000至150,000。當使用的胺基甲酸乙酯樹脂的重量平均分子量在以上範圍內時,可以適當地控制該黏著劑層的黏結性和黏著性。
以該黏著劑組成物的總重計,該胺基甲酸乙酯樹脂的含量可為60重量%或更高,較佳為70至90重量%、75至90重量%、80至90重量%、或84至90重量%。即,該胺基甲酸乙酯樹脂係該黏著劑組成物的主要組份且可以以上範圍的量含於該黏著劑組成物中。
適當的添加劑可用於該胺基甲酸乙酯樹脂的製程中。例如,該胺基甲酸乙酯樹脂可藉由添加抗氧化劑、UV吸收劑、光安定劑、抗降解劑等而製得,且可以根據所欲用途,適當地定出該添加劑的類型和含量。較佳地,製得的該胺基甲酸乙酯樹脂可含有抗降解劑,如,抗氧化劑、UV吸收劑和光安定劑。
此外,任何適當的觸媒可用於該胺基甲酸乙酯樹脂的製程。此觸媒的例子包括三級胺系化合物和有機金屬化合物。該有機金屬化合物的例子包括錫系化合物、非錫系化合物等。
該錫系化合物的例子包括二氯化二丁錫、氧化二丁錫、二溴化二丁錫、二馬來酸二丁錫、二月桂酸二丁錫(DBTDL)、二乙酸二丁錫、硫化二丁錫、硫化三丁錫、氧化三丁錫、乙酸三丁錫、乙氧化三乙錫、乙氧化三丁錫、氧化二辛錫、氯化三丁錫、三氯乙酸三丁錫、和己酸2-乙錫。
(2) 異氰酸酯系固化劑
添加該異氰酸酯系固化劑以交聯和固化該黏著劑組成物中所含的該胺基甲酸乙酯樹脂和(甲基)丙烯酸酯共聚物。明確言之,固化劑含有的異氰酸酯基與該胺基甲酸乙酯樹脂和該(甲基)丙烯酸酯共聚物各者中所含的羥基反應,可交聯該胺基甲酸乙酯樹脂和該(甲基)丙烯酸酯共聚物。
可選擇和使用此技術中常用之任何適當的多官能性異氰酸酯化合物作為該異氰酸酯系固化劑,只要其為可用於胺基甲酸乙酯化反應的化合物即可。此外,可以使用選自下列例子中之至少一種多官能性異氰酸酯化合物作為該異氰酸酯系固化劑。
該多官能性異氰酸酯化合物的例子包括,但不限於,多官能性脂族異氰酸酯、多官能性脂環族異氰酸酯和多官能性芳族異氰酸酯化合物、藉三官能性異氰酸酯修飾聚異氰酸酯而得的三羥甲基丙烷加合物、聚異氰酸酯與水反應而得的縮二脲體、具有三聚異氰酸酯環的三聚體等。
該多官能性脂族異氰酸酯化合物的例子包括,但不限於,三伸甲基二異氰酸酯、四伸甲基二異氰酸酯、五伸甲基二異氰酸酯、六伸甲基二異氰酸酯、1,2-伸丙基二異氰酸酯、1,3-伸丁基二異氰酸酯、十二伸甲基二異氰酸酯、2,4,4-三甲基六伸甲基二異氰酸酯等。
該多官能性脂環族異氰酸酯化合物的例子包括,但不限於,異佛爾酮二異氰酸酯(IPDI)、1,4-環己烷二異氰酸酯(CHDI)、4,4’-二環己基甲烷二異氰酸酯(HMDI)、雙(異氰酸基甲基)環己烷(HXDI)等。
多官能性芳族異氰酸酯化合物的例子包括,但不限於,甲苯2,4-二異氰酸酯(TDI)、甲苯2,6-二異氰酸酯(TDI)、4,4’-伸甲基二苯基二異氰酸酯(MDI)、2,4’-伸甲基二苯基二異氰酸酯(MDI)、聚合性伸甲基二苯基二異氰酸酯(PMDI)、對-伸苯基二異氰酸酯(PDI)、間-伸苯基二異氰酸酯(PDI)、萘1,5-二異氰酸酯(NDI)、萘2,4-二異氰酸酯(NDI)、對-二甲苯二異氰酸酯(XDI)、1,3-雙(1-異氰酸基-1-甲基乙基)苯(TMXDI)等。
以100重量份的該胺基甲酸乙酯樹脂計,該異氰酸酯系固化劑的含量可為10至30重量份。該固化劑的含量在以上範圍內時,該黏著劑組成物可經固化以具有適當的硬度,同時可以順利地進行該固化反應,使得該黏著劑組成物的該固化產物展現適當的黏著度。
該異氰酸酯系固化劑中的異氰酸酯基的莫耳數與該胺基甲酸乙酯樹脂中的羥基的莫耳數的比可為0.5或更低。添加該異氰酸酯系固化劑以使得該莫耳數的比在以上範圍內時,該黏著劑組成物可以因為其含有少量未反應的異氰酸酯基而因為高的固化度而展現低的剝離力。
(3) (甲基)丙烯酸酯共聚物
習慣上,塑化劑(一種低分子量添加劑)添加至含有胺基甲酸乙酯樹脂的黏著劑組成物中以實現較低的剝離力和優異的抗靜電性。但是,該塑化劑加至該黏著劑組成物中時,黏著物的表面被大量添加的該塑化劑和該塑化劑的遷移所污染。
根據本發明的一個實施例之黏著劑組成物藉由含有藉由自含有特定單體的混合物之共聚反應得到的(甲基)丙烯酸酯共聚物解決上述問題。具體言之,該(甲基)丙烯酸酯共聚物藉由包括含有羥基的(甲基)丙烯酸酯單體的聚合單元而含有羥基,且藉由包括含有長鏈烷基的(甲基)丙烯酸酯單體的聚合單元和含有氟化取代基的(甲基)丙烯酸酯的聚合單元而亦含有兩種類型的疏水基。該長鏈烷基係對應於疏水基的烴鏈,而該氟化取代基因為具有氟取代接合至鍵結至丙烯酸酯的該酯之該烷基的碳原子之部分或所有的氫原子並因而具有與該長鏈烷基相仿的疏水性,所以對應於疏水基。在自該黏著劑組成物製造該黏著層的程序中,該(甲基)丙烯酸酯共聚物會藉該疏水基而浮於該黏著層的外表面部分,並藉位於該黏著層的外表面部分(即,以直接接觸方式黏著至該黏著物之表面部分)上的該(甲基)丙烯酸酯共聚物的該疏水基可達到低的剝離力。此外,該(甲基)丙烯酸酯共聚物的該羥基可與該異氰酸酯系固化劑反應並作為與該胺基甲酸乙酯樹脂交聯的交聯點,藉此達成低的剝離力。由於該兩種類型的疏水基和該羥基,所以包括該黏著劑組成物之該黏著層可具有優異的耐久性,即使於高溫度和高濕度環境中亦然,且即使該黏著劑組成物含有塑化劑或剝離力控制劑,也能夠防止該塑化劑或該剝離力控制劑因為其自該黏著層表面遷移至該黏著物表面而污染該黏著物表面。
該(甲基)丙烯酸酯共聚物的重量平均分子量為20,000至70,000、25,000至50,000、27,000至42,000、27,000至41,000、27,000至30,000、或27,000至29,000。重量平均分子量在以上範圍內的(甲基)丙烯酸酯共聚物含於該黏著劑組成物中時,在施用該黏著劑組成物時,其可位於該黏著層表面上,藉此控制該黏著層的剝離力和該黏著劑組成物的固化度。具體言之,此情況中,該表面保護膜在黏著物上的剝離力低且會因為其高的殘留黏著率而留下較少的殘留物。
該(甲基)丙烯酸酯共聚物係藉單體混合物的聚合反應得到。具體言之,該(甲基)丙烯酸酯共聚物可藉各種常用的聚合法(如,溶液聚合反應、整體聚合反應、懸浮聚合反應、乳化聚合反應、和射線固化聚合反應)由單體混合物得到。
該單體混合物含有含羥基的(甲基)丙烯酸酯單體、含氟化的取代基之(甲基)丙烯酸酯單體、具1至10個碳原子的(甲基)丙烯酸烷酯單體和具12至22個碳原子的(甲基)丙烯酸烷酯單體。
該單體混合物可含有超過0至不超過10重量%之該含羥基的(甲基)丙烯酸酯單體。可以考慮藉聚合反應得到的該(甲基)丙烯酸酯共聚物的羥值來控制該含羥基的(甲基)丙烯酸酯單體的含量,且當該(甲基)丙烯酸酯共聚物係藉由聚合該含羥基的(甲基)丙烯酸酯單體之含量在以上範圍內的單體混合物而製得時,則能製備具有適當的剝離力和優異的潤濕性之黏著劑組成物。
該含羥基的(甲基)丙烯酸酯單體可包括(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4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸2-羥基乙二醇酯、和(甲基)丙烯酸2-羥基丙二醇酯中之至少一者。
該單體混合物可含有超過0至不超過10重量%之該含氟化的取代基之(甲基)丙烯酸酯單體。該含氟化的取代基之(甲基)丙烯酸酯單體的聚合單元可對應於該(甲基)丙烯酸酯共聚物中的該疏水基。當該(甲基)丙烯酸酯共聚物係藉由聚合該含氟化的取代基之(甲基)丙烯酸酯單體之含量在以上範圍內的單體混合物而製得時,則能夠將該黏著層的剝離力控制於適當範圍內。
該含氟化的取代基之(甲基)丙烯酸酯單體可包括(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸四氟正丙酯、(甲基)丙烯酸四氟三級戊酯、(甲基)丙烯酸六氟丁酯、(甲基)丙烯酸六氟三級己酯、(甲基)丙烯酸六氟-2,4-雙(三氟甲基)戊酯、(甲基)丙烯酸六氟丁酯、(甲基)丙烯酸六氟異丙酯、(甲基)丙烯酸七氟丁酯、(甲基)丙烯酸八氟戊酯、(甲基)丙烯酸九氟戊酯、(甲基)丙烯酸十二氟庚酯、(甲基)丙烯酸十二氟辛酯、(甲基)丙烯酸十三氟辛酯、(甲基)丙烯酸十三氟庚酯、(甲基)丙烯酸十六氟癸酯、(甲基)丙烯酸十七氟癸酯、(甲基)丙烯酸十八氟十一烷酯、(甲基)丙烯酸十九氟十一烷酯、和(甲基)丙烯酸二十氟十二烷酯中之至少一者。
該單體混合物可含有70至95重量%之該具1至10個碳原子的(甲基)丙烯酸烷酯單體和1至10重量%之該具12至22個碳原子的(甲基)丙烯酸烷酯單體。即,該單體混合物含有(甲基)丙烯酸短鏈烷酯單體和(甲基)丙烯酸長鏈烷酯單體,且特別地,該(甲基)丙烯酸長鏈烷酯單體的該聚合單元可對應於該(甲基)丙烯酸酯共聚物中的另一疏水基。當該(甲基)丙烯酸酯共聚物係藉由聚合(甲基)丙烯酸酯單體之含量在以上範圍內的單體混合物而製得時,則固化含有該(甲基)丙烯酸酯共聚物之該黏著劑組成物而形成的黏著層的可具有適當的剝離力。
該具1至10個碳原子的(甲基)丙烯酸烷酯單體可包括(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-乙基丁酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、和(甲基)丙烯酸異壬酯中之至少一者。
該具12至22個碳原子的(甲基)丙烯酸烷酯單體可包括(甲基)丙烯酸月桂酯、(甲基)丙烯酸十四烷酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸十六烷酯、(甲基)丙烯酸二十二烷酯、和(甲基)丙烯酸二十烷酯中之至少一者。
在不會損及本發明之效果的範圍內,該單體混合物可另外含有可與該(甲基)丙烯酸酯單體聚合的其他單體組份。該其他單體組份的例子包括,但不限於,以下描述者。
該其他(甲基)丙烯酸酯單體的例子包括,但不限於,(甲基)丙烯酸環己酯、苯氧基(甲基)丙烯酸酯、2-乙基苯氧基(甲基)丙烯酸酯、苄基(甲基)丙烯酸酯、苯基(甲基)丙烯酸酯、2-乙基硫代苯基(甲基)丙烯酸酯、2-苯基乙基(甲基)丙烯酸酯、3-苯基丙基(甲基)丙烯酸酯、4-苯基丁基(甲基)丙烯酸酯、2,2-甲基苯基乙基(甲基)丙烯酸酯、2,3-甲基苯基乙基(甲基)丙烯酸酯、2,4-甲基苯基乙基(甲基)丙烯酸酯、2-(4-丙基苯基)乙基(甲基)丙烯酸酯、2-(4-(1-甲基乙基)苯基)乙基(甲基)丙烯酸酯、2-(4-甲氧基苯基)乙基(甲基)丙烯酸酯、2-(4-環己基苯基)乙基(甲基)丙烯酸酯、2-(2-氯苯基)乙基(甲基)丙烯酸酯、2-(3-氯苯基)乙基(甲基)丙烯酸酯、2-(4-氯苯基)乙基(甲基)丙烯酸酯、2-(4-溴苯基)乙基(甲基)丙烯酸酯、2-(3-苯基苯基)乙基(甲基)丙烯酸酯、和2-(4-苄基苯基)乙基(甲基)丙烯酸酯。
該單體混合物可包括引發劑用於引發聚合反應。可以使用過氧化苯甲醯作為該引發劑,且以總重100重量份的該單體計,該引發劑的含量可為0.5重量份至低於3重量份。
以100重量份的該胺基甲酸乙酯樹脂計,該(甲基)丙烯酸酯共聚物的含量可為0.5至5重量份、0.5至3重量份、1至3重量份、1至2.5重量份、或1.5至2.5重量份。該(甲基)丙烯酸酯共聚物的含量在以上範圍內時,藉固化該黏著劑組成物而形成的黏著層可具有適當剝離力。
(4) 其他
根據本發明的一個實施例之黏著劑組成物除了上述組份以外,可含有其他添加劑。例如,取決於所欲用途,該黏著劑組成物可另含有溶劑、觸媒、固化延遲劑、黏著性樹脂、塑化劑、剝離強度控制劑、光引發劑、水解抑制劑、抗氧化劑、固化加速劑、抗延遲劑等,且這些添加劑的含量亦可經適當選擇。
根據本發明的一個實施例,該黏著劑組成物可以另含溶劑。可以使用已知的適當溶劑作為該溶劑,例如,但不限於,酮系溶劑、乙酸酯系溶劑、或甲苯系溶劑。
根據本發明的一個實施例,該黏著劑組成物可以另含有觸媒。可以考慮本應用的目的而適當地選擇該觸媒,且例如,以該胺基甲酸乙酯聚合物計,其含量可為10 ppm至500 ppm。可以使用錫系觸媒(如,二月桂酸二丁錫(DBTDL)、鐵系觸媒(如,FeAA)、鉛系觸媒、有機和無機酸的鹽、有機金屬衍生物、胺系觸媒、二氮雜二環十一碳烯系觸媒之類作為該觸媒,但該觸媒不限於此。
根據本發明的一個實施例,該黏著劑組成物可以另含有固化延遲劑。可使用任何適當的已知材料作為該固化延遲劑,且可適當地選擇該固化延遲劑的含量。一個實施例中,可使用乙醯基丙酮作為該固化延遲劑。
根據本發明的另一實施例,提出一種包含脫模膜和基質膜之表面保護膜,其中該基質膜包含:第一基質層;位於該第一基質層的至少一表面上之抗靜電層;和包括該黏著劑組成物的固化產物之黏著層,且該脫模膜和該黏著層彼此直接接觸。
該表面保護膜用以在程序中保護黏著物且包括在該表面保護膜接合至該黏著物之前移除的脫模膜。此外,該表面保護膜包括基質膜,該基質膜接合至黏著物並用以保護該黏著物表面。之後自該黏著物表面剝離該基質膜。
圖1係根據本發明之實施例之表面保護膜的截面圖。參照圖1,表面保護膜1000包括脫模膜10和基質膜20,而該基質膜20可包括第一基質層201、抗靜電層503和504、及黏著層301。
(1) 基質膜
該基質膜包括:第一基質層;位於該第一基質層的至少一表面上之抗靜電層;和包括該黏著劑組成物的固化產物之黏著層。
該第一基質層可用以維持該基質膜的形狀,且可包括,但不限於,選自由以下所組成群組中之至少一者:聚對酞酸伸乙酯;聚四氟乙烯;聚乙烯;聚丙烯;聚丁烯;聚丁二烯;氯乙烯共聚物;聚胺基甲酸乙酯;乙烯-乙酸乙烯酯;乙烯-丙烯共聚物;乙烯-丙烯酸乙酯共聚物;乙烯-丙烯酸甲酯共聚物;聚醯亞胺;尼龍;苯乙烯系樹脂或彈料;聚烯烴系樹脂或彈料;其他彈料;聚環氧烷系樹脂或彈料;聚酯系樹脂或彈料;聚氯乙烯系樹脂或彈料;聚碳酸酯樹脂或彈料;聚苯硫醚系樹脂或彈料;烴的混合物;聚醯胺系樹脂或彈料;丙烯酸酯系樹脂或彈料;環氧基系樹脂或彈料;聚矽氧系樹脂或彈料;和液晶聚合物。
可以考慮本發明的目的,適當地選擇該第一基質層的厚度。例如,該第一基質層的厚度可為25 µm至150 µm、50 µm至125 µm、或50 µm至100 µm。
該靜電層可位於該第一基質層的至少一個表面上,即,其一個表面上或兩個表面上。
可藉已知方法形成該靜電層以達到所欲效果。例如,可藉在線塗佈法(in-line coating method)使得該靜電層形成於該第一基質層的一或兩面上。該在線塗佈法係單軸拉伸擠出膜及然後將塗佈層施於彼,接著雙軸拉伸,藉此得到成品膜之方法。該在線塗佈法的優點在於,由於在膜製程中進行塗佈,該塗佈層和該膜之間的黏著性提高,且由於該塗佈層的施用係與膜製造一起進行,所以程序縮短,且製得的該膜可具有可能的最小厚度。
本發明中,可以考慮本發明之目的,自適當的抗靜電劑組成物製得該靜電層。例如,該靜電層可包括含量範圍不會影響本發明之效果的熱固性黏合劑樹脂。
本文中使用的術語,“熱塑性黏合劑樹脂”是指能夠經由適當的加熱或老化程序固化的黏合劑組成物。例如,可以使用選自由以下所組成之群組中之一者或二或多者之混合物作為該熱固性黏合劑樹脂:丙烯酸系樹脂、胺基甲酸乙酯系樹脂、胺基甲酸乙酯-丙烯酸系共聚物、酯系樹脂、醚系樹脂、醯胺系樹脂、環氧系樹脂、和三聚氰胺樹脂,但該熱固性黏合劑樹脂不限於此。
一個例子中,該抗靜電層可包括導電材料。該導電材料可包括,但不限於,導電性聚合物或碳奈米管。
該導電性聚合物的例子包括,但不限於,聚苯胺系聚合物化合物、聚吡咯系聚合物化合物、聚噻吩系聚合物化合物、及其衍生物和共聚物。
該碳奈米管可具有將六個碳原子結合在一起的六角環所構成的石墨片捲起而形成的形狀。該碳奈米管具有優異的剛性和導電性,並因此當該碳奈米管含括於該抗靜電層中時,該抗靜電層的硬度會提高且可增進其抗靜電性能。
各抗靜電層的厚度獨立地為600 nm或更低、10 nm至400 nm、20 nm至300 nm、或20 nm至100 nm。
該黏著層包括該黏著劑組成物的固化產物。關於該黏著劑組成物的細節可以上述者相同。
該黏著層可藉由將該黏著劑組成物施用和固化於該第一基質層的表面上而形成。未特別限制固化該黏著劑組成物的方法,且例如,可以使用藉適當的乾燥、加熱和∕或老化程序固化作為固化該黏著劑組成物的方法。
該抗靜電層位於該第一基質層之背對該黏著層的表面上時,可以根據上述方法,藉由將該黏著劑組成物施用至該抗靜電層而製得該黏著層。
可以考慮本發明的目的,適當地選擇該黏著層的厚度。例如,該黏著層的厚度可為10 µm或更高、30 µm或更高、或45 µm或更高。例如,該黏著層的厚度可為200 µm或更低、150 µm或更低、100 µm或更低、或90 µm或更低。
(2) 脫模膜
該脫模膜可包括:第二基質層;在該第二基質層的至少一表面上的抗靜電層;和脫模層。
根據本發明的一個實施例,該脫模膜用以保護該基質膜的該黏著層直到該表面保護膜接合至電子組件。
參照圖1,該表面保護膜1000可包括該脫模膜10和該基質膜20,和該脫模膜10可包括第二基質層10、抗靜電層501和502、及脫模層401。
該脫模膜的該第二基質層可包括,但不限於,由下列所組成之群組中之至少一者:聚對酞酸伸乙酯;聚四氟乙烯;聚乙烯;聚丙烯;聚丁烯;聚丁二烯;氯乙烯共聚物;聚胺基甲酸乙酯;乙烯-乙酸乙烯酯;乙烯-丙烯共聚物;乙烯-丙烯酸乙酯共聚物;乙烯-丙烯酸甲酯共聚物;聚醯亞胺;尼龍;苯乙烯系樹脂或彈料;聚烯烴系樹脂或彈料;其他彈料;聚環氧烷系樹脂或彈料;聚酯系樹脂或彈料;聚氯乙烯系樹脂或彈料;聚碳酸酯樹脂或彈料;聚苯硫醚系樹脂或彈料;烴的混合物;聚醯胺系樹脂或彈料;丙烯酸酯系樹脂或彈料;環氧基系樹脂或彈料;聚矽氧系樹脂或彈料;和液晶聚合物。
可以考慮本發明的目的,適當地選擇該第二基質層的厚度。例如,該第二基質層的厚度可為25 µm至150 µm、25 µm至125 µm、或25 µm至100 µm。
該脫模膜中所含括之該抗靜電層的相關細節可以與上述該基質膜之該抗靜電層的相關細節相同。
可以考慮本發明的目的,適當地選擇該脫模層的材料。可以使用本發明所屬技術中已知的慣用聚合物膜作為該脫模層的材料。例如,可以使用聚對酞酸伸乙酯膜、聚四氟乙烯膜、聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、氯乙烯共聚物膜、聚胺基甲酸乙酯膜、乙烯-乙酸乙烯酯膜、乙烯-丙烯共聚物膜、乙烯-丙烯酸乙酯共聚物膜、乙烯-丙烯酸甲酯共聚物膜、或聚醯亞胺膜,但該脫模層不在此限。
可以考慮本發明的目的,適當地選擇該脫模層的厚度。例如,該脫模層的厚度可為500 nm或更低,較佳為10 nm至500 nm、10 nm至300 nm、或10 nm至200 nm。
根據本發明之實施例之表面保護膜接合至玻璃之後,以180°的剝離角度和20 m/min的剝離速率測得的剝離力為30 gf/in或更小。
根據本發明之實施例之表面保護膜接合至玻璃之後,以180°的剝離角度和0.3 m/min的剝離速率測得的剝離力為4 gf/in或更小。
根據本發明之實施例之表面保護膜接合至玻璃,在60℃的溫度和90%的相對濕度條件下儲存10天,及接著自該玻璃剝離之後測得的殘留黏著率為70%或更高。
術語"殘留黏著率"是指在剝離之後,該表面保護膜的該黏著層之組份留在該黏著物表面上的程度之參數。殘留黏著率越高代表在剝離之後,該表面保護膜的該黏著層之組份留在該黏著物表面上的量越少。
該殘留黏著率可藉由計算在該表面保護模接合至玻璃,於60℃溫度和90%相對濕度條件下儲存10天,及接著自該玻璃剝離之後,剝離接合至根據本發明之實施例之該表面保護膜的對照黏著膜時測得的黏著性(B)和剝離接合至未事先接合該表面保護膜之玻璃的該對照黏著膜時測得的黏著性(A)的比而測得。
該對照黏著膜在接合至玻璃之後,以180°的剝離角度和0.3 m/min的剝離速率測得的剝離力可為1,600 gf/in至2,400 gf/in。
根據本發明的一個實施例,可以根據以下等式1,由黏著性(A)和(B)的值計算該殘留黏著率。
[等式 1]
殘留黏著率(%) = 100 x (B)/(A)
下文中,將參照實例地詳細描述本發明。但是,根據本發明之實例可被修飾成各種不同的形式,且本發明之範圍之闡釋未受限於以下描述的例子。提出本說明書之實例以更完整地向嫻於此技術者解釋本發明。
[實施方式]
製造例
1
含有89重量份的甲基丙烯酸丁酯、7重量份的甲基丙烯酸硬脂酯、2重量份的丙烯酸羥丁酯、和2重量份的丙烯酸十三氟辛酯之單體混合物引至含有回流氮氣且配備易於調整溫度的冷卻裝置之1-L反應器中,且接著引入作為溶劑的甲苯。在該混合物均勻混合之後,該反應器溫度維持於120℃,且以100重量份的該單體混合物,作為反應引發劑的苯甲醯基過氧化物(BPO)以1.6重量份的量加至該混合物中,之後反應約4小時。反應完全之後,該反應溶液另以甲苯稀釋,藉此製造重量平均分子量為27,000 g/mol的(甲基)丙烯酸酯共聚物。
製造例
2
至
13
以與製造例1相同的方式製造甲基(丙烯酸酯)共聚物,但使用以下表1中所示的組份和含量製備單體混合物,且該引發劑的含量控制於以下表1中所示者。此外,該製得的共聚物的分子量示於以下的表1中。
表1中,(A) BMA代表甲基丙烯酸丁酯,(B) STMA代表甲基丙烯酸硬脂酯,STA代表丙烯酸硬脂酯,BHA代表丙烯酸丙烯酸二十二烷酯,(C) HBA代表丙烯酸羥丁酯,和(D) V13F代表丙烯酸十三氟辛酯。此外,該含量的重量份單位係以100重量份的該單體混合物計。
實例
1
藉混合100重量份的胺基甲酸乙酯樹脂(重量平均分子量:120,000;SH-101,Toyochem Co., Ltd.)和1.5重量份在製造實例1中製造的該(甲基)丙烯酸酯共聚物、及15重量份含有三聚異氰酸酯異氰酸酯三聚物和異佛爾酮二異氰酸酯之重量比為7:3的單體混合物(DR7030X, Samyoung Ink Co., Ltd.)(作為多官能性異氰酸酯固化劑)以製備黏著劑組成物。
該黏著劑組成物施用至其兩面上已具有抗靜電層的PET膜的一個表面上,並在Mathis烘箱中於140℃乾燥約3分鐘以形成黏著層,及將脫模膜(RF02ASW, SKC)積層於該黏著層上。然後,所得膜結構在烘箱中於40℃老化約5天,藉此製造表面保護膜。
實例
2
至
9
及比較例
1
至
7
以與實例1相同的方式製造表面保護膜,但組份和含量改為以下表2中所示者。
以上的表2中,該含量(重量份)係以100重量份的該胺基甲酸乙酯樹脂計的值,而ATBC代表乙醯基三丁基檸檬酸酯(ATBC, Asahi Kasei Corp.),其作為剝離力控制劑。
實驗例1:低速率剝離力之測量
實例1至9和比較例1至7各者中製造的表面保護膜切成25 mm(寬) x 250 mm(長)的尺寸,且自彼剝離該脫模膜。使用乙醇清理已剝離其脫模膜的各個表面保護膜的黏著表面並藉2-kg滾輪接合至已於100℃乾燥20分鐘的玻璃(Corning)。然後,所得材料於50℃和5 atm儲存20分鐘,及之後於25℃的溫度儲存24小時。然後,使用紋理分析儀(Stable Micro Systems Inc., UK)測量以0.3 m/min的剝離速率和180°的剝離角度自該玻璃剝離該表面保護膜時,各個表面保護膜的剝離力。
實驗例2:高速率剝離力之測量
實例1至9和比較例1至7各者中製造的表面保護膜切成25 mm(寬) x 250 mm(長)的尺寸,且自彼剝離該脫模膜。使用乙醇清理已剝離該脫模膜的各個表面保護膜的黏著表面並藉2-kg滾輪接合至已於100℃乾燥20分鐘的玻璃(Corning)。然後,所得材料於50℃和5 atm儲存20分鐘,及之後於25℃的溫度儲存24小時。然後,使用高速率剝離試驗機(Peel Tester SJTA-034SD, Samjitech)測量以20 m/min的剝離速率和180°的剝離角度自該玻璃剝離該表面保護膜時,各個表面保護膜的剝離力。
實驗例3:儲存於高溫度和高濕度環境中之後,殘留黏著率之評估
製備對照的黏著膜(50-µm厚的丙烯酸系黏著層和50-µm厚的PET基質膜,LG Chem Co., Ltd.),在接合至玻璃之後,其以0.3 m/min的剝離速率和180°的剝離角度自玻璃剝離時,測得其剝離力為2,000±400 gf/in。
黏著性(A)之測定
該對照的黏著膜切成25 mm(寬) x 250 mm(長)的尺寸,自彼剝離該脫模膜。使用乙醇清理已剝離該脫模膜之該對照的黏著膜並接合至已於100℃乾燥20分鐘的玻璃(Corning)。然後,該所得材料在烘箱中於40℃儲存1小時,及之後於25℃儲存4小時。然後,使用紋理分析儀(Stable Micro Systems Inc., UK)測量以0.3 m/min的剝離速率和180°的剝離角度自該玻璃剝離該對照的黏著膜時的剝離力。將該測得的剝離力視為黏著性(A)。
黏著性(B)之測定
剝離實例1至9和比較例1至7各者中製得之該表面保護膜的該脫模膜。使用乙醇清理各個表面保護膜的黏著表面並藉2-kg滾輪接合至已於100℃乾燥20分鐘的玻璃(Corning)。然後,所得材料於50℃和5 atm儲存20分鐘,及之後於25℃的溫度儲存24小時,然後在溫度為60℃且相對濕度為90%的恆溫恆濕器中儲存10天。然後,取出有該表面保護膜接合至彼的各個玻璃並留置於25℃24小時,之後自該玻璃剝離各個表面保護膜。
該對照的黏著膜切成25 mm(寬) x 250 mm(長)的尺寸,自彼剝離該脫模膜。然後,該對照的黏著膜接合至已移除該表面保護膜的玻璃表面。所得材料在烘箱中於40℃儲存1小時,及之後25℃儲存4小時。然後,使用紋理分析儀(Stable Micro Systems Inc., UK)測量以0.3 m/min的剝離速率和180°的剝離角度自該玻璃剝離該對照的黏著膜時的剝離力。將該測得的剝離力視為黏著性(B)。
殘留黏著率之計算
根據以下等式1,自黏著性(A)和黏著劑(B)計算殘留黏著率。
[等式 1]
殘留黏著率(%) = 100 x (B)/(A)
以下的表3列出實例1至9和比較例1至7之表面保護膜的低速率剝離力和高速率剝離力,該殘留黏著率係於在高溫度和高濕度環境中儲存之後剝離該表面保護膜時測得。
參照以上的表3,能夠確認實例1至9之表面保護膜即使在高溫度和高濕度環境中儲存之後,仍具有高的殘留黏著率,同時其在玻璃上的該低速率剝離力和該高速率剝離力低。即,能夠確認幾乎沒有殘留物留在該玻璃上。
另一方面,能夠確認,在比較例1的情況中,該殘留黏著率略高,但該低速率剝離力和該高速率剝離力高。
此外,能夠確認,在比較例2的情況中,該殘留黏著率非常低,並因而該表面保護膜的該黏著層在該玻璃上留下大量的殘留物,且該低速率剝離力和該高速率剝離力亦高。
此外,能夠確認,在比較例3的情況中,該殘留黏著率非常低,並因而該表面保護膜的該黏著層在該玻璃上留下大量的殘留物,且該高速率剝離力高。
此外,能夠確認,在比較例4至6的情況中,該殘留黏著率高,並因而各表面保護膜的該黏著層少量留在該玻璃上,但該高速率剝離力高。
此外,能夠確認在比較例7的情況中,該低速率剝離力和該高速率剝離力低,但該殘留黏著率低,並因而該表面保護膜的該黏著層在該玻璃上留下大量的殘留物。
1000:表面保護膜
10:脫模膜
20:基質膜
101:第二基質層
201:第一基質層
301:黏著層
401:脫模層
501,502,503,504:抗靜電層
[圖1]係根據本發明的一個實施例之表面保護膜的截面圖示。
10:脫模膜
20:基質膜
101:第二基質層
201:第一基質層
301:黏著層
401:脫模層
501,502,503,504:抗靜電層
1000:表面保護膜
Claims (15)
- 一種含有含羥基的胺基甲酸乙酯樹脂、異氰酸酯系固化劑、和(甲基)丙烯酸酯共聚物之黏著劑組成物, 其中該(甲基)丙烯酸酯共聚物係藉含有含羥基的(甲基)丙烯酸酯單體、含氟化的取代基之(甲基)丙烯酸酯單體、具1至10個碳原子的(甲基)丙烯酸烷酯單體和具12至22個碳原子的(甲基)丙烯酸烷酯單體之單體混合物之聚合反應得到。
- 如請求項1之黏著劑組成物,其中該胺基甲酸乙酯樹脂的重量平均分子量為50,000至200,000。
- 如請求項1之黏著劑組成物,其中以100重量份的該胺基甲酸乙酯樹脂計,該異氰酸酯系固化劑的含量為10至30重量份。
- 如請求項1之黏著劑組成物,其中該(甲基)丙烯酸酯共聚物的重量平均分子量為20,000至70,000。
- 如請求項1之黏著劑組成物,其中該單體混合物含有超過0至不超過10重量%之該含羥基的(甲基)丙烯酸酯單體、超過0至不超過10重量%之該含氟化的取代基之(甲基)丙烯酸酯單體、70至95重量%之該具1至10個碳原子的(甲基)丙烯酸烷酯單體、和1至10重量%之該具12至22個碳原子的(甲基)丙烯酸烷酯單體。
- 如請求項1之黏著劑組成物,其中該含羥基的(甲基)丙烯酸酯單體包含(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4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸2-羥基乙二醇酯、和(甲基)丙烯酸2-羥基丙二醇酯中之至少一者。
- 如請求項1之黏著劑組成物,其中該含氟化的取代基之(甲基)丙烯酸酯單體包含(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸四氟正丙酯、(甲基)丙烯酸四氟三級戊酯、(甲基)丙烯酸六氟丁酯、(甲基)丙烯酸六氟三級己酯、(甲基)丙烯酸六氟-2,4-雙(三氟甲基)戊酯、(甲基)丙烯酸六氟丁酯、(甲基)丙烯酸六氟異丙酯、(甲基)丙烯酸七氟丁酯、(甲基)丙烯酸八氟戊酯、(甲基)丙烯酸九氟戊酯、(甲基)丙烯酸十二氟庚酯、(甲基)丙烯酸十二氟辛酯、(甲基)丙烯酸十三氟辛酯、(甲基)丙烯酸十三氟庚酯、(甲基)丙烯酸十六氟癸酯、(甲基)丙烯酸十七氟癸酯、(甲基)丙烯酸十八氟十一烷酯、(甲基)丙烯酸十九氟十一烷酯、和(甲基)丙烯酸二十氟十二烷酯中之至少一者。
- 如請求項1之黏著劑組成物,其中該具1至10個碳原子的(甲基)丙烯酸烷酯單體包含(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-乙基丁酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、和(甲基)丙烯酸異壬酯中之至少一者。
- 如請求項1之黏著劑組成物,其中該具12至22個碳原子的(甲基)丙烯酸烷酯單體包含(甲基)丙烯酸月桂酯、(甲基)丙烯酸十四烷酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸十六烷酯、(甲基)丙烯酸二十二烷酯、和(甲基)丙烯酸二十烷酯中之至少一者。
- 如請求項1之黏著劑組成物,其中以100重量份的該胺基甲酸乙酯樹脂計,該(甲基)丙烯酸酯共聚物含量為0.5至5重量份。
- 一種包含脫模膜和基質膜之表面保護膜, 其中該基質膜包含:第一基質層;位於該第一基質層的至少一表面上之抗靜電層;和包含如請求項1之黏著劑組成物的固化產物之黏著層,且 該脫模膜和該黏著層彼此直接接觸。
- 如請求項11之表面保護膜,其中該脫模膜包含:第二基質層;位於該第二基質層的兩個表面上之抗靜電層;和脫模層。
- 如請求項11之表面保護膜,其在接合至玻璃之後,以180°的剝離角度和20 m/min的剝離速率測得的剝離力為30 gf/in或更小。
- 如請求項11之表面保護膜,其在接合至玻璃之後,以180°的剝離角度和0.3 m/min的剝離速率測得的剝離力為4 gf/in或更小。
- 如請求項11之表面保護膜,其在該表面保護膜接合至玻璃,在60℃的溫度和90%的相對濕度條件下儲存10天,及接著自該玻璃剝離之後測得的殘留黏著率為70%或更高。
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KR102129543B1 (ko) * | 2013-07-03 | 2020-07-03 | 삼성디스플레이 주식회사 | 점착 필름 및 그 제조 방법과 상기 점착 필름을 포함하는 표시 장치 |
JP6479540B2 (ja) | 2015-04-01 | 2019-03-06 | ニッタ株式会社 | 感温性粘着剤 |
JP6319331B2 (ja) * | 2016-01-12 | 2018-05-09 | 三菱ケミカル株式会社 | 積層ポリエステルフィルム |
JP6790865B2 (ja) | 2017-01-23 | 2020-11-25 | 東洋インキScホールディングス株式会社 | 感圧式接着剤及び接着フィルム |
JP6856395B2 (ja) * | 2017-02-03 | 2021-04-07 | 日東電工株式会社 | 粘着剤組成物、粘着剤層、表面保護フィルム、及び、光学部材 |
CN113166595B (zh) | 2019-01-25 | 2023-02-21 | 株式会社Lg化学 | 表面保护膜和用于制造有机发光电子装置的方法 |
TWI730606B (zh) | 2019-01-25 | 2021-06-11 | 南韓商Lg化學股份有限公司 | 表面保護膜及製造有機發光電子裝置之方法 |
JP6590099B1 (ja) | 2019-02-25 | 2019-10-16 | 住友電気工業株式会社 | 樹脂組成物成形体および直流電力ケーブル |
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2021
- 2021-08-13 CN CN202180024330.2A patent/CN115335483A/zh active Pending
- 2021-08-13 JP JP2022560505A patent/JP7391462B2/ja active Active
- 2021-08-13 EP EP21858532.1A patent/EP4130188A4/en active Pending
- 2021-08-13 KR KR1020210107388A patent/KR20220022460A/ko unknown
- 2021-08-13 TW TW110129946A patent/TW202216943A/zh unknown
- 2021-08-13 WO PCT/KR2021/010769 patent/WO2022039445A1/ko active Application Filing
- 2021-08-13 US US18/022,086 patent/US20240010875A1/en active Pending
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JP7391462B2 (ja) | 2023-12-05 |
WO2022039445A1 (ko) | 2022-02-24 |
EP4130188A4 (en) | 2023-09-20 |
KR20220022460A (ko) | 2022-02-25 |
EP4130188A1 (en) | 2023-02-08 |
JP2023521070A (ja) | 2023-05-23 |
US20240010875A1 (en) | 2024-01-11 |
CN115335483A (zh) | 2022-11-11 |
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