TW201425491A - 一種可剝離保護膜及其組成物配方 - Google Patents
一種可剝離保護膜及其組成物配方 Download PDFInfo
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- TW201425491A TW201425491A TW101148273A TW101148273A TW201425491A TW 201425491 A TW201425491 A TW 201425491A TW 101148273 A TW101148273 A TW 101148273A TW 101148273 A TW101148273 A TW 101148273A TW 201425491 A TW201425491 A TW 201425491A
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- 230000001681 protective effect Effects 0.000 title claims abstract description 79
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 20
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- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 claims abstract description 16
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 9
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 125000005591 trimellitate group Chemical group 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 10
- 239000010455 vermiculite Substances 0.000 claims description 9
- 229910052902 vermiculite Inorganic materials 0.000 claims description 9
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- MJHNUUNSCNRGJE-UHFFFAOYSA-N trimethyl benzene-1,2,4-tricarboxylate Chemical group COC(=O)C1=CC=C(C(=O)OC)C(C(=O)OC)=C1 MJHNUUNSCNRGJE-UHFFFAOYSA-N 0.000 claims description 8
- KESQFSZFUCZCEI-UHFFFAOYSA-N 2-(5-nitropyridin-2-yl)oxyethanol Chemical compound OCCOC1=CC=C([N+]([O-])=O)C=N1 KESQFSZFUCZCEI-UHFFFAOYSA-N 0.000 claims description 6
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- OMVSWZDEEGIJJI-UHFFFAOYSA-N 2,2,4-Trimethyl-1,3-pentadienol diisobutyrate Chemical compound CC(C)C(=O)OC(C(C)C)C(C)(C)COC(=O)C(C)C OMVSWZDEEGIJJI-UHFFFAOYSA-N 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical class Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 3
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- 230000035939 shock Effects 0.000 claims description 3
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims 2
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 claims 2
- YRXCJAPAMXEMIP-UHFFFAOYSA-N [Zn].[Ca].C1(=CC=CC=C1)O Chemical compound [Zn].[Ca].C1(=CC=CC=C1)O YRXCJAPAMXEMIP-UHFFFAOYSA-N 0.000 claims 1
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 5
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- 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 4
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 2
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- HBMHZKUEKASKNY-UHFFFAOYSA-N 2-nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O.CCCCCCCCCC1=CC=CC=C1O HBMHZKUEKASKNY-UHFFFAOYSA-N 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- LZBCVRCTAYKYHR-UHFFFAOYSA-N acetic acid;chloroethene Chemical compound ClC=C.CC(O)=O LZBCVRCTAYKYHR-UHFFFAOYSA-N 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
一種可剝離保護膜,具有極佳附著能力且不會出現剝離問題,適用於暫時性地保護物品用途,尤其是該保護膜的剝離強度介於35~100g/cm,在與物品撕離過程中可輕易剝離且不會對被膠物留下殘膠,其選用特定配方組成物製成,該組成物的TI值介於2.00~2.20,其成分包括:氯乙烯-醋酸乙烯共聚物、高及低分子量聚氯乙烯乳化聚合粉、苯三酸酯類可塑劑、二異丁酸酯混合可塑劑、無酚鈣鋅安定劑、燻矽石、氫氧化鋁、硫酸鋇及碳酸鈣。
Description
本發明涉及一種可剝離保護膜及其組成物配方,尤指一種中間製程之後可輕易剝離且不留殘膠的可剝離保護膜及其組成物配方。
在現有技術中,可剝離保護膜是一種兼具接著及防塵防刮功能的薄膜產品,經常用於暫時性地保護物品的外觀,或在電子元件或光學元件的中間加工流程中或是儲存期間中,用於暫時性地接著及保護被加工或被儲存的電子元件或光學元件(以下簡稱被膠物),待中間加工流程完畢或正式使用時,可輕易將保護膜從被膠物撕離分開,並且不會傷及到被膠物。
然而,現有技術中的可剝離保護膜,例如美國專利US6211282公開案揭露的一種丙烯酸共聚物保護性薄膜,當接著或貼合到被膠物上時,在高壓水洗下會有剝離的問題,而且,從被膠物撕離保護膜的過程中,保護膜的接著成分經常會形成不易除去的膠層(以下簡稱殘膠)而黏著到被膠物的表面上,有導致需要費時費力清除殘膠的缺陷,故現有技術中的可剝離保護膜仍有改善空間。
此外,現有技術中的可剝離保護膜,在製造過程中需要使用溶劑以及需要經過交聯硬化,以致有廢溶劑的環保
問題,尤其是可剝離保護膜當經過撕離使用過後,卻不能夠回收再利用,需以廢料處理,實不具環境保護意義。
為克服上述缺點,本發明提供一種可剝離保護膜,不使用溶劑以及交聯硬化過程,藉著適當樹脂的組合以及不同可塑劑的搭配,具有尺寸安定、黏度穩定、接著力適度、防水性及熱安定性優異之外,使用時,還兼具可輕易剝離、不破裂且不留殘膠的特點,尤其是不使用溶劑,可以回收循環再使用,具環境保護。
用於製造本發明的可剝離保護膜的組成物,使用下列特定配方成分,基於組成物總重量,包含a)氯乙烯-醋酸乙烯共聚物,K值介於69~71,佔10~65 wt%;其中,醋酸乙烯的含量為1.0~12.5%,優選為4.0~6.9%;b)高分子量聚氯乙烯乳化聚合粉,K值介於77.5~81,佔3~20 wt%;c)低分子量聚氯乙烯乳化聚合粉,K值介於73.0~76.5,佔3~20 wt%;d)苯三酸酯類可塑劑,佔5~40 wt%;e)酜酸混基酯類可塑劑及二異丁酸酯類可塑劑兩種混合使用,佔1~20 wt%;f)無酚鈣鋅安定劑,佔0.5~3 wt%;
g)燻矽石(Fumed silica或稱氣相二氧化矽),佔1~10 wt%;h)氫氧化鋁,佔0.1~10 wt%;i)硫酸鋇,佔0.1~20 wt%。j)碳酸鈣,佔0.1~20 wt%
本發明的可剝離保護膜,具接著及防塵防刮功能外,還滿足下列條件要求,適合製成用於光學元件的可剝離保護膜:1.可剝離保護膜的剝離強度介於35~100g/cm,使用時,在撕離過程中可輕易剝離,且可剝離保護膜的膠層不會對被膠物留下殘膠;2.可剝離保護膜具耐烘烤性,經過180℃烘烤10分鐘,且重複相同步驟連續烘烤3次,可剝離保護膜的膠層仍具有韌性,而且表面乾燥性佳,無黏性問題;3.可剝離保護膜具優良附著力,黏著到被膠物上時,經過下列其中一種或以上測試條件,仍具備不剝離的附著能力:a)在溫度45℃下進行頻率46khz超音波震盪5分鐘;b)以10kg/cm2水壓進行高壓水洗;c)侵入60℃熱水浸泡26分鐘;d)浸入溫度40℃的3.17%NaOH鹼性溶液浸泡2分鐘;或e)浸入溫度46℃的王水系列酸性溶液浸泡2分鐘。
本發明的可剝離保護膜,是使用本發明具特定配方的組成物(下文稱為可剝離組成物)在常溫下經過塗佈加工製成;除具有黏度穩定性、防水性及熱安定性之外,當接著或貼合到被膠物上,還兼具剝離強度介於35~100g/cm的特性,以及可輕易剝離且不留殘膠的特點,尤其是不使用溶劑,可以回收循環再使用。
所使用的可剝離組成物,在25℃室溫下,VT-04黏度計測得的黏度介於400~600ps,使用美國BROOKFIELD公司的DVII+Pro型旋轉黏度計測試(以下簡稱為使用旋轉黏度計測試),具備設定條件為“0.5rpm黏度/2.5rpm黏度”下的搖變性指數(Thixotropy Index,簡稱TI值)介於2.00~2.20的物性,基於組成物總重量,包括下列成分:a)氯乙烯-醋酸乙烯共聚物,K值介於69~71,佔10~65 wt%;其中,醋酸乙烯的含量為1.0~12.5%,優選為4.0~6.9%;b)高分子量聚氯乙烯乳化聚合粉,佔3~20 wt%;其平均聚合度(Average Degree of polymerization,DP),介於1650~1850,K值(Fikentscher’s Constant)介於77.5~81;c)低分子量聚氯乙烯乳化聚合粉,佔3~20 wt%;其平均聚合度介於1350~1550,K值介於73.0~76.5;d)苯三酸酯類可塑劑,佔5~40 wt%;e)二異丁酸酯類可塑劑,佔1~20 wt%;且所述二異丁酸酯
類可塑劑為2,2,4-三甲基-1,3-戊二醇二異丁酸酯(2,2,4-trimethyl-1,3-pentanediol diisobutyrate,TXIB)可塑劑,其中,苯三酸酯類可塑劑與2,2,4-三甲基-1,3-戊二醇二異丁酸酯可塑劑的使用量比值,為1.0~9.0,但以4.0~6.0最佳;f)無酚鈣鋅安定劑,佔0.5~3 wt%;g)燻矽石,佔1~10 wt%;h)氫氧化鋁,佔0.1~10 wt%;i)硫酸鋇,佔0.1~20 wt%;j)碳酸鈣,佔0.1~20 wt%。
本發明組成物多,含有固、液態原料,投料順序會影響黏度變化,為控制組成物黏度穩定,且不使用溶劑調整之下,先以可塑劑溶解氯乙烯-醋酸乙烯共聚粉、低分子量聚氯乙烯乳化聚合粉,接著溶解高分子量聚氯乙烯乳化聚合粉,注意不可先投入高分子量乳化聚合粉,以防黏度遽升,攪拌40分鐘後靜置2小時以上,使共聚粉、乳化聚合粉充分膨潤,確保黏度穩定,燻矽石及氫氧化鋁均會大幅提高黏度,在慢速攪拌下最後投入,其製造方法投料順序如下述:(1)先將苯三酸酯類可塑劑投入混合機,接著投入二異丁酸酯可塑劑,然後投入綜合安定劑;啟動攪拌葉,慢速攪拌並依序緩緩投入氯乙烯-醋酸乙烯共聚物,接著投入低分
子量聚氯乙烯乳化聚合粉,最後投入高分子量聚氯乙烯乳化聚合粉,攪拌40分鐘後靜置2小時以上;(2)啟動攪拌葉並提高攪拌速度,依序投入硫酸鋇,碳酸鈣;(3)攪拌5分鐘後降速攪拌,最後投入燻矽石及氫氧化鋁;(4)攪拌30±5分鐘後測量黏度,在25℃下黏度為400~600ps,攪拌時間視黏度而延長或縮短。
所述氯乙烯-醋酸乙烯共聚物(Vinyl Chloride-Vinyl Acetate copolymers)是由氯乙烯及醋酸乙烯兩種單體共同聚合而成,且醋酸乙烯的含量愈高,氯乙烯-醋酸乙烯共聚物的接著強度則隨之愈高,考慮成膜附著性佳又容易剝離,醋酸乙烯的含量應適當,不可偏高或太低。因此,所述氯乙烯-醋酸乙烯共聚物擁有氯乙烯的高韌性和抗腐蝕性以及醋酸乙烯的強黏性和可塑性,塗佈加工製成薄膜尺寸安定性佳,可耐高溫烘烤及熱水浸泡,而且所製得的薄膜,具備耐酸又耐鹼、防潮又防水、不易燃及不助燃的特性。
所述高分子量聚氯乙烯乳化聚合粉具備低黏度及低溫加熱可膠化的特性,在常溫下可塗佈加工製成薄膜。而且,所製得的薄膜,具備耐水性及防靜電的特性。
所述低分子量聚氯乙烯乳化聚合粉具備適當黏度,製
成薄膜時具有良好的脫膜性。
本發明的可剝離保護膜組成物中,包含氯乙烯-醋酸乙烯共聚物與不同平均聚合度的聚氯乙烯乳化聚合粉一起搭配使用,在不使用溶劑的條件下,選取適量的氯乙烯-醋酸乙烯共聚物,再配合使用適量的高、低分子量的聚氯乙烯乳化聚合粉,可製得具備最適當接著強度、拉力強度及韌性的可剝離保護膜,當作為保護膜使用用途時,兼具可輕易剝離、不破裂且不留殘膠的特點,同時,三者混合組成膠之搖變性指數(TI值)最穩定,變異小有利塗佈加工。
所述苯三酸酯類可塑劑可選自苯三酸三甲酯(Trimethyl trimellitate,TMTM),苯三酸己酯(Triethyl trimellitate,TETM),苯三酸三己酯(Trihexyl trimellitate,THTM),苯三酸異三辛酯(Trisooctyl trimellitate,TIOTM)或苯三酸三辛酯(Tri(2-ethylhexyl)trimellitate,TOTM)的其中一種單獨使用或一種以上混合並用,高溫100~180℃烘烤之下具低移型性,可保有表面乾燥性,而無黏性,且仍保有優良韌性。
所述2,2,4-三甲基-1,3-戊二醇二異丁酸酯(TXIB),是一種不含苯環的無毒環保型可塑劑,與氯乙烯-醋酸乙烯共聚物容易混合,除了能夠降低本發明的可剝離組成物的黏度之外,並且能夠提升本發明的可剝離組成物的流動特性,使得本發明的可剝離組成物的黏度穩定且不易混入氣泡,最適合用於塗佈加工製得薄膜;而且,所製得的薄膜成品
外表平滑,其表面具抗污及抗磨損能力(或稱耐刮性),使用時,不易出現刮痕。
本發明的可剝離組成物中,包含苯三酸酯類可塑劑與二異丁酸酯可塑劑一起搭配使用,且不使用溶劑,藉兩者不同使用量的調配,其中,苯三酸酯類可塑劑與2,2,4-三甲基-1,3-戊二醇二異丁酸酯可塑劑的使用量比值,為1.0~9.0,但以4.0~6.0最佳;可以達到對所述可剝離組成物適當地調整其黏度以及確保具備黏度穩定性,不但有助於將所述可剝離組成物加工製成薄膜,並且使得所製得的薄膜具備優異柔軟性、韌性及防刮性,尤其經過180℃ 10分鐘烘烤3次,仍保有韌性,其乾燥性亦佳,當保護膜第一面100~120℃預烘烤3分鐘後,印第二面時,第一面與印刷檯面無黏性,更適合作為可剝離保護膜之用途,且在撕離可剝離保護膜的過程中,可確保可剝離保護膜不會發生破裂。
所述無酚鈣鋅安定劑是不含壬基酚(Nonyl Phenol)、不含雙酚A(Bis-Phenol-A)、不含酚(Phenol)三種溶劑之安定劑,其目的是製程不含酚溶劑而且提高本發明的可剝離組成物的耐熱性能。
所述燻矽石的用途,是作為調黏劑使用,用於調整本發明的可剝離組成物的黏度,防止垂流亦可防止填充料沉澱。所述燻矽石的結構,優選為粒徑介於5~50nm,表面積
介於50~600m2/g。
為防止黏度隨時間劇變,配合燻矽石使用氫氧化鋁調黏具有增稠效果,同時氫氧化鋁具有兩性特性,既能與酸反應又能與鹼反應,發揮耐酸、鹼的功用,亦是本發明的特點。燻矽石用量為氫氧化鋁之2~6倍為佳,該兩物用量可調整控制組成物之搖變值TI(Thixotripic Index)在2.00~2.20為佳。
此外,本發明的可剝離組成物中的二異丁酸酯類可塑劑,是一種非離子表面活性劑,既具有親油基團,又具有親水基團。而所述氫氧化鋁具有兩性,既能與酸反應又能與鹼反應。因此,本發明的可剝離組成物中,將所述氫氧化鋁與所述二異丁酸酯可塑劑一起搭配使用,可以促進所述非離子表面活性劑形成膠團,並藉此增強表面活性劑的表面張力,使得本發明的可剝離組成物達到增黏的效果。
所述硫酸鋇的用途,用於改善本發明的可剝離組成物的性能,包括改善電氣絕緣性、耐熱變形性、耐光性及熱穩定性,減小線膨脹係數和收縮率,增加導熱性,提高膠層穩定性,增加耐熱性和機械強度,改變膠狀的可剝離組成物的流動性或調節可剝離組成物的黏度等。本發明硫酸鋇的結構,優選為平均粒徑介於1~50nm,用於提高可剝離保護膜的耐磨性、耐酸性。
所述碳酸鈣的結構,優選為平均粒徑介於30~100nm,
用於提高本發明的可剝離組成物的韌性,以及降低所製得的可剝離保護膜的收縮率、增進所述可剝離保護膜的表面光滑度及耐刮特性。尤其是本發明的可剝離組成物使用奈米膠質碳酸鈣作為填充劑時,則本發明的可剝離組成物具備更佳的熱安定性及分散性,更適合製成用於光學元件的可剝離保護膜。
在不使用溶劑之下,本發明的可剝離組成物,具備TI值(在0.5rpm黏度/2.5rpm黏度條件下)介於2.00~2.20的物性,搖變性小,黏度穩定,最適合塗佈加工。而且,在塗佈加工的過程中,本發明的可剝離組成物,具抗垂流性,不會出現垂流現象。
而且,根據本發明的可剝離組成物以塗佈加工製得的可剝離保護膜,可滿足下列條件要求:1.可剝離保護膜的剝離強度介於35~100g/cm,優選為介於45~80g/cm,在撕離過程中可輕易剝離,且可剝離保護膜的膠層不會對被膠物留下殘膠;2.可剝離保護膜具耐烘烤性,經過180℃烘烤10分鐘,且重複相同步驟連續烘烤3次,可剝離保護膜的膠層仍具有韌性;3.可剝離保護膜具優良附著力,黏著到被膠物上時,經過下列測試條件後,仍不會有剝離問題:在溫度45℃條件下進行頻率46khz超音波震盪5分鐘、在壓
力10kg/cm2條件下進行高壓水洗、侵入60℃熱水浸泡26分鐘、浸入溫度40℃的(3.17%NaOH)鹼性溶液浸泡2分鐘、浸入溫度46℃的(王水系列)酸性溶液浸泡2分鐘。
以下列舉實施例及比較例具體說明本發明的可剝離組成物適用於製成一種可剝離保護膜。實施例及比較例使用的可剝離組成物及所製得的可剝離保護膜,依據下述評估方法測試其物性及特性。
在溫度25℃條件下,使用日本RION公司的VT-04F型黏度計測試可剝離組成物的黏度。
在溫度25℃條件下,使用美國BROOKFIELD公司的DVII+Pro型旋轉黏度計測試可剝離組成物的TI值。
測量方法:在2.5 rpm轉速下,使可剝離組成物的黏度穩定後,等待約3分鐘,測其黏度為V1;在0.5 rpm轉速下,使可剝離組成物的黏度穩定後,同樣等待約3分鐘,測其黏度為V2。其中,TI值=10V2/V1。
在溫度25℃條件下,將可剝離組成物靜置於無塵室中24hr後,使用美國BROOKFIELD公司的DVII+Pro型旋轉黏度計測試可剝離組成物的黏度。
膠狀可剝離組成物經塗佈後,無垂流現象。
在溫度100~120℃條件下,將可剝離保護膜的第一面表面預烘烤3分鐘後,將可剝離保護膜置於印刷檯面上對其第二面表面進行印刷,則可剝離保護膜的第一面表面需滿足與印刷檯面無黏性。
在溫度180℃條件下,將可剝離保護膜烘烤10分鐘後,再重複烘烤3次,可剝離保護膜的膠層仍具有韌性。
將可剝離保護膜與3M膠帶(tape)貼合後,將3M膠帶剝除,3M膠帶需沒有殘膠出現。
將組成物塗佈於被膠物,經150℃×2分鐘成膜後,可剝離保護膜附著到被膠物,再以下列5種方法測試可剝離保護膜的附著能力。經過測試後,再目測觀察可剝離保護膜是否會與被膠物剝離,沒有出現剝離問題,代表可剝離保護膜具有極佳的附著能力:
a.超音波震盪:在溫度45℃條件下,以頻率46kHz超音波對附著可剝離保護膜的被膠物震盪5分鐘。
b.高壓水柱衝擊:
以壓力10kg/cm2的水柱對附著到被膠物的可剝離保護膜進行沖洗。
c.熱水浸泡:在水溫60℃條件下,將附著可剝離保護膜的被膠物浸泡26分鐘。
d.耐鹼性:在溫度40℃且濃度3.17%的氫氧化納(NaOH)溶劑中,將附著可剝離保護膜的被膠物浸泡2分鐘。
e.耐酸性:在溫度46℃的王水系列溶劑中,將附著可剝離保護膜的被膠物浸泡2分鐘。
取寬度1公分的可剝離保護膜,從其所貼合的被膠物剝離時,測量其180度方向的剝離強度。
可剝離保護膜的剝離強度介於35~100g/cm的條件下,可剝離保護膜在撕離過程中不會出現殘膠。
按照表1的配方(數字為重量份),分別調製成實施例1-6的可剝離組成物,再分別測量其物性,包括黏度、TI值、黏度穩定性及抗垂流性,測量結果如表2所示。
將所調製的可剝離組成物以塗佈加工分別製成可剝離保
護膜,再分別測量其特性,包括耐烘烤性、剝除性、附著性及剝離強度,測量結果如表3所示。
按照表1的配方(數字為重量份),分別調製成比較例1-4的可剝離組成物,再分別測量其物性,包括黏度、TI值、黏度穩定性及抗垂流性,測量結果如表2所示。
將所調製的可剝離組成物以塗佈加工分別製成可剝離保護膜,再分別測量其特性,包括耐烘烤性、剝除性、附著性及剝離強度,測量結果如表3所示。
註7:可剝離保護膜的膠層經烘烤後仍具有韌性,以優、佳、可、劣為評量等級。
註8:浸入溫度40℃且濃度3.17%的氫氧化納(NaOH)溶劑中2分鐘,以優、佳、可、劣為評量耐鹼性附著不剝離等級。
註9:浸入溫度46℃王水系列溶劑中2分鐘,以優、佳、可、劣為評量耐酸性附著不剝離等級。
1.比較例1-4的可剝離組成物配方,只選用氯乙烯-醋酸乙烯共聚物或高、低分子量聚氯乙烯乳化聚合粉的其中一至二種與單一種類的可塑劑搭配使用,而且不使用具調黏劑用途的燻矽石及氫氧化鋁。
而實施例1-6的可剝離組成物,選用將氯乙烯-醋酸乙烯共聚物與高、低分子量的聚氯乙烯乳化聚合粉一起搭配使用,並且搭配選用苯三酸酯類可塑劑與二異丁酸酯可塑劑一起使用,再調配其它特定成分配方,例如有添加具調黏劑用途的燻矽石及氫氧化鋁等成分。
相較之下,在表現可剝離組成物的黏度、TI值、黏度穩定性及抗垂流性方面,根據表2所示,實施例1-6的可剝離組成物的物性,均較比較例1-4的可剝離組成物優異許多。
尤其是實施例1-6的可剝離組成物的TI值,介於2.05~2.16,搖變性小,黏度穩定,有利於塗佈加工,對所製得的可剝離保護膜亦有利於放置及儲存。
2.實施例1-6製得的可剝離保護膜,根據表3所示,具備剝離強度介於50~80g/cm特性,滿足當可剝離保護膜的剝離強度介於35~100g/cm時在撕離過程中不會出現殘膠的條件。
比較例1-4製得的可剝離保護膜,根據表3所示,其剝離強度則沒有落在35~100g/cm的範圍之內。比較例3全量氯乙烯-醋酸乙烯共聚物,比較例4高含量醋酸乙烯之保護膜剝離強度偏高,不易剝離。
相較之下,實施例1-6的可剝離保護膜,具備可輕易剝離且不會對被膠物留下殘膠的優異特點。
3.同前項說明,在表現可剝離保護膜的耐烘烤性、剝除性及附著性能力,尤其是耐震盪、耐沖洗、耐水性、耐酸性、耐鹼性方面,根據表3所示,實施例1-6製得的可剝離保護膜的物性,均較比較例1-4的可剝離保護膜優異。
據此,實施例1-6的可剝離保護膜具有極佳的附著能力,當附著到被膠物上作為暫時性地保護用途使用時,不會出現剝離的問題。
4.實施例4-6的耐酸性、耐鹼性附著不剝離,優於實施例1-3更優於比較例1-4,顯示氫氧化鋁及硫酸鋇的影響效果佳。
Claims (8)
- 一種可剝離保護膜的組成物,其特徵在於:不使用溶劑之下,使用特定醋酸乙烯含量的氯乙烯-醋酸乙烯共聚物與高、低分子量聚氯乙烯乳化聚合粉配合特殊可塑劑共同組成,以旋轉黏度計測試,具備設定條件為0.5rpm黏度/2.5rpm黏度下的TI值介於2.00~2.20的物性,基於組成物總重量,包含以下成分:a)氯乙烯-醋酸乙烯共聚物,K值介於69~71,佔10~65 wt%;其中,醋酸乙烯的含量為1.0~12.5%,優選為4.0~6.9%;b)高分子量聚氯乙烯乳化聚合粉,其平均聚合度介於1650~1850,K值介於77.5~81,佔3~20 wt%;c)低分子量聚氯乙烯乳化聚合粉,其平均聚合度介於1350~1550,K值介於73,0~76.5;佔3~20 wt%;d)苯三酸酯類可塑劑,佔5~40 wt%;e)2,2,4-三甲基-1,3-戊二醇二異丁酸酯(TXIB)可塑劑,佔1~20 wt%;其中,苯三酸酯類可塑劑與2,2,4-三甲基-1,3-戊二醇二異丁酸酯可塑劑的使用量比值,為1.0~9.0,但以4.0~6.0最佳;f)無酚鈣鋅安定劑,佔0.5~3 wt%;g)燻矽石,佔1~10 wt%;h)氫氧化鋁,佔0.1~20 wt%; i)硫酸鋇,佔0.1~20 wt%,其中,所述硫酸鋇的平均粒徑,介於1~50nm;j)碳酸鈣,佔0.1~20 wt%,其中,所述碳酸鈣的平均粒徑,介於30~100nm。
- 如申請專利範圍第1項所述之組成物,其中,所述氯乙烯-醋酸乙烯共聚物的醋酸乙烯含量為4.0~6.9%。
- 如申請專利範圍第1項所述之組成物,其中,所述苯三酸酯類可塑劑選自苯三酸三甲酯(TMTM)、苯三酸己酯(TETM)、苯三酸三己酯(THTM)、苯三酸異三辛酯(TIOTM)或苯三酸三辛酯(TOTM)的其中一種單獨使用或一種以上混合並用。
- 如申請專利範圍第1項所述之組成物,其中組成物投料順序為:(1)先將苯三酸酯類可塑劑投入混合機,接著投入二異丁酸酯可塑劑,然後投入綜合安定劑;啟動攪拌葉,慢速攪拌並依序緩緩投入氯乙烯-醋酸乙烯共聚物,接著投入低分子量聚氯乙烯乳化聚合粉,最後投入高分子量聚氯乙烯乳化聚合粉,攪拌40分鐘後靜置2小時以上;(2)啟動攪拌葉並提高攪拌速度,依序投入硫酸鋇、碳酸鈣;(3)攪拌5分鐘後降速攪拌,依序投入燻矽石、氫氧化鋁; (4)攪拌30±5分鐘後測量黏度,在25℃下黏度為400~600ps,攪拌時間視黏度而延長或縮短。
- 如申請專利範圍第1項所述之組成物,其中,所述燻矽石的粒徑介於5~50nm,表面積介於50~600m2/g。
- 一種使用申請專利範圍第1項之組成物製成的可剝離保護膜,其特徵在於,具備剝離強度介於35~100g/cm的特性。
- 如申請專利範圍第6項所述之可剝離保護膜,具備剝離強度介於45~80g/cm的特性。
- 如申請專利範圍第6項或第7項所述之可剝離保護膜,經過下列其中一種或以上測試條件,仍具備不剝離的附著能力:a)在溫度45℃下進行頻率46khz超音波震盪5分鐘;b)以10kg/cm2水壓進行高壓水洗;c)侵入60℃熱水浸泡26分鐘;d)浸入溫度40℃的3.17%NaOH鹼性溶液浸泡2分鐘;或e)浸入溫度46℃的王水系列酸性溶液浸泡2分鐘。
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