TW202244223A - 黏合劑組合物及其製造方法 - Google Patents
黏合劑組合物及其製造方法 Download PDFInfo
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- TW202244223A TW202244223A TW111104295A TW111104295A TW202244223A TW 202244223 A TW202244223 A TW 202244223A TW 111104295 A TW111104295 A TW 111104295A TW 111104295 A TW111104295 A TW 111104295A TW 202244223 A TW202244223 A TW 202244223A
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- Prior art keywords
- adhesive composition
- weight
- vinyl aromatic
- maleic anhydride
- aromatic monomer
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 110
- 239000000853 adhesive Substances 0.000 title claims abstract description 94
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 94
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000004908 Emulsion polymer Substances 0.000 claims abstract description 41
- 229920001577 copolymer Polymers 0.000 claims abstract description 36
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 125000005250 alkyl acrylate group Chemical group 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 15
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- 238000003475 lamination Methods 0.000 description 9
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- 239000002518 antifoaming agent Substances 0.000 description 7
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- 239000012948 isocyanate Substances 0.000 description 7
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- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
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- 239000000654 additive Substances 0.000 description 6
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- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical group CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
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- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
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- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- 239000002253 acid Substances 0.000 description 3
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- 150000001340 alkali metals Chemical class 0.000 description 3
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- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 2
- PECUPOXPPBBFLU-UHFFFAOYSA-N 1-ethenyl-3-methoxybenzene Chemical compound COC1=CC=CC(C=C)=C1 PECUPOXPPBBFLU-UHFFFAOYSA-N 0.000 description 2
- CEWDRCQPGANDRS-UHFFFAOYSA-N 1-ethenyl-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(C=C)C=C1 CEWDRCQPGANDRS-UHFFFAOYSA-N 0.000 description 2
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- HSQAWNZCXDAZCC-UHFFFAOYSA-N 2-methoxyhex-1-enylbenzene Chemical compound C(CCC)C(=CC1=CC=CC=C1)OC HSQAWNZCXDAZCC-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
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- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical group CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- 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
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- 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
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Abstract
提供一種黏合劑組合物,其包括:(A)丙烯酸乳液聚合物;及(B)乙烯基芳族單體-順丁烯二酸酐共聚物,其中按該黏合劑組合物之總固體重量計,(B)乙烯基芳族單體-順丁烯二酸酐共聚物以0.1重量%至6.5重量%之量存在。該黏合劑組合物提供就黏結強度及/或熱封效能而言經改善之效能。
Description
本揭示案係關於黏合劑組合物。更特定言之,本揭示案係關於黏合劑組合物、包括其之製品及生產該製品之方法。黏合劑組合物提供就黏結強度及/或熱封效能而言經改善之效能。
黏合劑組合物適用於廣泛多種之目的。舉例而言,黏合劑組合物係用於將諸如聚乙烯、聚丙烯、聚酯、聚醯胺、金屬、紙或賽璐玢(cellophane)之基板黏結在一起以形成複合膜,亦即層製品。黏合劑在不同層壓最終使用應用中之使用一般為已知的。舉例而言,黏合劑可用於製造用於封裝行業中,尤其用於食品封裝之膜/膜及膜/箔層製品。用於層壓應用中之黏合劑或「層壓黏合劑」一般可分為三種類別:基於溶劑、基於水及無溶劑。
幾年來,已研發出許多基於水之層壓黏合劑用於膜/膜(箔)層壓。然而,基於水之層壓黏合劑亦受更廣應用之效能缺點限制。先前技術中基於水之層壓黏合劑傾向於展現較低的針對基於箔之層壓結構之黏結強度及/或不良的熱封效能。因此,期望研發具有就黏結強度及/或熱封效能而言經改善之效能的黏合劑組合物。
在一態樣中,本揭示案提供一種黏合劑組合物,其包括:
(A)丙烯酸乳液聚合物;及
(B)乙烯基芳族單體-順丁烯二酸酐共聚物,
其中按該黏合劑組合物之總固體重量計,(B)乙烯基芳族單體-順丁烯二酸酐共聚物以0.1重量%至6.5重量%之量存在。
在另一態樣中,本揭示案提供一種使用所描述之黏合劑組合物生產層製品之方法,其包括:
(a)提供如上文所描述之黏合劑組合物;
(b)將該黏合劑組合物施用於基板之表面之第一部分上以形成該黏合劑組合物之層;
(d)使基板之表面之第二部分與該黏合劑組合物之該層接觸,以使得該黏合劑組合物之該層夾於該第一部分與該第二部分之間;及
(e)乾燥該黏合劑組合物或使其乾燥。
在另一態樣中,本揭示案提供一種層製品,其係藉由使用如本文所描述之生產層製品之方法來製備。
在另一態樣中,本揭示案提供一種層製品,其包括:基板之表面之第一部分、如本文所描述之黏合劑組合物之層及相同或不同基板之表面之第二部分,其中黏合劑組合物之層夾於第一部分與第二部分之間且與其等接觸。
在另一態樣中,本揭示案提供一種乙烯基芳族單體-順丁烯二酸酐共聚物之用途,其用於改善包括丙烯酸乳液聚合物之黏合劑組合物之黏結強度及/或熱封效能。較佳地,按黏合劑組合物之總固體重量計,乙烯基芳族單體-順丁烯二酸酐共聚物以0.1重量%至6重量%之量存在。
除非另外定義,否則本文所使用之所有技術及科學術語均具有與本發明所屬領域之一般技術者通常所理解之含義相同的含義。此外,所有公開案、專利申請案、專利及本文所提及之其他參考文獻均以引用之方式併入。
如本文所揭示,「及/或」意謂「及,或作為替代方案」。除非另外指示,否則所有範圍包含端值。
如本文所揭示,除非另外規定,否則本文提及之所有百分比均按重量計且溫度以℃為單位。
本文中之「水性」組合物或分散液意謂分散於水性介質中之粒子。本文中之「水性介質」意謂水及按介質之重量計0重量%至30重量%諸如醇、二醇、二醇醚、二醇酯或其混合物之(多種)水可混溶性化合物。
如本文所使用之「玻璃轉移溫度」或「Tg」可藉由包含例如微差掃描熱量法(「differential scanning calorimetry,DSC」)之各種技術量測或藉由使用福克斯方程(Fox equation)計算。本文報導之T
g之特定值為藉由使用福克斯方程計算之值(T.G. Fox,美國物理學會會刊(Bull. Am. Physics Soc.), 第1卷, 第3期, 第123頁(1956))。舉例而言,為了計算單體M
1及M
2之共聚物之T
g,
,
其中
T
g (計算值)為共聚物之計算玻璃轉移溫度,
w ( M
1 )為共聚物中之單體M
1之重量分率,
w ( M
2 )為共聚物中之單體M
2之重量分率,
T
g ( M
1 )為單體M
1之均聚物之玻璃轉移溫度,且
T
g ( M
2 )為單體M
2之均聚物之玻璃轉移溫度,所有溫度均以K為單位。均聚物之玻璃轉移溫度可例如見於J. Brandrup及E.H. Immergut編輯之《聚合物手冊(Polymer Handbook)》,Interscience Publishers中。
黏合劑組合物本揭示案之黏合劑組合物包括(A)丙烯酸乳液聚合物;及(B)乙烯基芳族單體-順丁烯二酸酐共聚物,其中按黏合劑組合物之總固體重量計,(B)乙烯基芳族單體-順丁烯二酸酐共聚物以0.1重量%至6.5重量%之量存在。
黏合劑組合物較佳為基於水的。
更佳地,黏合劑組合物為單組分基於水之黏合劑組合物。
丙烯酸乳液聚合物
本發明之丙烯酸乳液聚合物可包括(a)一或多種烯系不飽和離子單體之結構單元。本文中之術語「離子單體」係指在pH=1-14之間攜帶離子電荷之單體。合適的烯系不飽和離子單體之實例包含α、β-烯系不飽和羧酸,包含攜帶酸之單體,諸如甲基丙烯酸、丙烯酸、伊康酸、順丁烯二酸或反丁烯二酸;苯乙烯磺酸鈉(SSS)、乙烯基磺酸鈉(SVS)、2-丙烯醯胺基-2-甲基丙磺酸(AMPS)、2-丙烯醯胺基-2-甲基-1-丙磺酸之鈉鹽、2-丙烯醯胺基-2-甲基-1-丙磺酸之銨鹽;磺酸烯丙醚之鈉鹽;(甲基)丙烯酸磷酸烷酯,諸如(甲基)丙烯酸磷酸乙酯、(甲基)丙烯酸磷酸丙酯、(甲基)丙烯酸磷酸丁酯、其鹽及其混合物;CH
2=C(R
p1)-C(O)-O-(R
p2O)
p-P(O)(OH)
2,其中R
p1=H或CH
3,R
p2=烷基及p=1-10,諸如全部可獲自索爾維(Solvay)之SIPOMER PAM-100、SIPOMER PAM-200及SIPOMER PAM-300;(甲基)丙烯酸磷酸烷氧酯,諸如磷酸乙二醇(甲基)丙烯酸酯、磷酸二乙二醇(甲基)丙烯酸酯、磷酸三乙二醇(甲基)丙烯酸酯、磷酸丙二醇(甲基)丙烯酸酯、磷酸二丙二醇(甲基)丙烯酸酯、磷酸三丙二醇(甲基)丙烯酸酯、磷酸烯丙醚、乙烯基膦酸、其鹽或其混合物。較佳烯系不飽和離子單體為甲基丙烯酸磷酸乙酯(PEM)、丙烯酸(AA)、甲基丙烯酸(MAA)或其混合物。按乳液聚合物之重量計,本發明之丙烯酸乳液聚合物可包括0.1重量%或更多、0.3重量%或更多、0.5重量%或更多、0.75重量%或更多或甚至1重量%或更多且同時8重量%或更少、7重量%或更少、6重量%或更少、5重量%或更少、4.5重量%或更少、4重量%或更少、3.8重量%或更少、3.5重量%或更少或甚至3.3重量%或更少之烯系不飽和離子單體之結構單元。
本發明之丙烯酸乳液聚合物可包括(b)一或多種可為單烯系或多烯系不飽和單體之烯系不飽和非離子單體之結構單元。本文中之術語「非離子單體」係指在pH=1-14之間不攜帶離子電荷之單體。合適的單烯系不飽和非離子單體可包含例如乙烯基芳族單體、(甲基)丙烯酸C
1-C
20烷基酯、丙烯腈(AN)、(甲基)丙烯醯胺或其混合物。(甲基)丙烯酸C
1-C
20烷基酯係指含有具有1至20個碳原子之烷基的(甲基)丙烯酸烷基酯。(甲基)丙烯酸C
1-C
20烷基酯可包含(甲基)丙烯酸C
1-C
3烷基酯、(甲基)丙烯酸環烷基酯及不同於(甲基)丙烯酸環烷基酯之(甲基)丙烯酸C
4-C
20烷基酯。合適的(甲基)丙烯酸烷基酯之實例包含(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂醯基酯;(甲基)丙烯酸環烷基酯,諸如(甲基)丙烯酸環己酯、(甲基)丙烯酸甲基環己酯、(甲基)丙烯酸二氫二環戊二烯基酯、(甲基)丙烯酸三甲基環己酯及丙烯酸三級丁酯(甲基)環己酯;羥基官能性(甲基)丙烯酸烷基酯,諸如甲基丙烯酸羥乙酯及甲基丙烯酸羥丙酯;(甲基)丙烯酸縮水甘油酯; 或其混合物。乙烯基芳族單體可包含苯乙烯;經取代之苯乙烯,諸如α-甲基苯乙烯、反式β-甲基苯乙烯、2,4-二甲基苯乙烯、乙基苯乙烯、丁基苯乙烯及對甲氧基苯乙烯;鄰甲氧基苯乙烯、間甲氧基苯乙烯及對甲氧基苯乙烯;及對三氟甲基苯乙烯;或其混合物。較佳的單烯系不飽和非離子單體包含甲基丙烯酸甲酯、苯乙烯、甲基丙烯酸環己酯、丙烯酸2-乙基己酯、丙烯酸丁酯或其混合物。較佳的單烯系不飽和非離子單體包含甲基丙烯酸甲酯、丙烯酸甲酯、苯乙烯、甲基丙烯酸丁酯、丙烯酸丁酯或其混合物。烯系不飽和非離子單體之結構單元之含量可經調整以產生具有期望漢森(Hansen)溶解度參數之所得乳液聚合物。舉例而言,按乳液聚合物之重量計,乳液聚合物可包括量較佳為35重量%或更多、36重量%或更多或甚至37重量%或更多且同時45重量%或更少、44重量%或更少或甚至43重量%或更少之丙烯酸丁酯之結構單元;及量為30重量%或更多、31重量%或更多、32重量%或更多、33重量%或更多或甚至34重量%或更多且同時50重量%或更少、49重量%或更少、48重量%或更少、46重量%或更少或甚至45重量%或更少之苯乙烯之結構單元。可替代地,按乳液聚合物之重量計,乳液聚合物可包括量較佳為30重量%或更多、31重量%或更多或甚至32重量%或更多且同時40重量%或更少、39重量%或更少或甚至38重量%或更少之丙烯酸2-乙基己酯之結構單元;及量為30重量%或更多、31重量%或更多、32重量%或更多、33重量%或更多或甚至34重量%或更多且同時39.5重量%或更少、39重量%或更少、38重量%或更少或甚至37重量%或更少之苯乙烯之結構單元。按乳液聚合物之重量計,乳液聚合物可包括少於19重量%丙烯腈之結構單元,例如少於15重量%、少於10重量%、少於5重量%、少於1重量%或甚至零之丙烯腈之結構單元。適用於本發明之多烯系不飽和非離子單體包含二、三、四或更高多官能性烯系不飽和單體。合適的多烯系不飽和單體可包含例如(甲基)丙烯酸烯丙酯、二乙烯基苯、乙二醇二甲基丙烯酸酯、丁二醇二甲基丙烯酸酯或其混合物。按乳液聚合物之重量計,乳液聚合物可包括零至3.0重量%、0.05重量%至0.8重量%或0.1重量%至0.5重量%多烯系不飽和非離子單體之結構單元。
按乳液聚合物之重量計,丙烯酸乳液聚合物包括
30重量%至50重量%乙烯基芳族單體之結構單元,
50重量%至70重量% (甲基)丙烯酸C
1-C
20烷基酯之結構單元,及
0.1重量%至8重量% (甲基)丙烯酸之結構單元。
可替代地,按乳液聚合物之重量計,丙烯酸乳液聚合物包括
30重量%至50重量%苯乙烯之結構單元,
50重量%至70重量%丙烯酸丁酯之結構單元,及
0.1重量%至8重量%丙烯酸之結構單元。
丙烯酸乳液聚合物中之結構單元之總濃度等於100%。上文所描述之單體之類型及含量可經選擇以提供具有適用於不同應用之玻璃轉移溫度(T
g)的乳液聚合物。丙烯酸乳液聚合物可具有在-20℃至60℃、-15℃至50℃、-10℃至30℃或-5℃至20℃範圍內之T
g。乳液聚合物之T
g值可藉由包含微差掃描熱量法(DSC)之各種技術量測或藉由使用福克斯方程計算。
適用於本發明之丙烯酸乳液聚合物可藉由上文所描述之單體之自由基聚合、較佳乳液聚合來製備。用於製備丙烯酸共聚物之單體之總重量濃度等於100%。單體可以純形式或以於水中之乳液形式添加;或經製備丙烯酸共聚物之反應時段在一或多個添加中或連續地、線性地或非線性地添加。適用於聚合過程之溫度可低於100℃、在30℃至95℃範圍內或在50℃至90℃範圍內。
在製備乳液聚合物之方法中,可使用自由基引發劑。聚合過程可為熱引發或氧化還原引發之乳液聚合。合適的自由基引發劑之實例包含過氧化氫、三級丁基氫過氧化物、氫過氧化異丙苯、過硫酸銨及/或鹼金屬過硫酸鹽、過硼酸鈉、過磷酸及其鹽;高錳酸鉀及過二硫酸之銨或鹼金屬鹽。按用於製備乳液聚合物之單體之總重量計,自由基引發劑可通常以0.01重量%至3.0重量%之含量使用。包括與合適還原劑偶合之上文所描述引發劑之氧化還原系統可用於聚合過程中。合適的還原劑之實例包含甲醛次硫酸鈉、抗壞血酸、異抗壞血酸;含硫的酸之鹼金屬及銨鹽,諸如亞硫酸鈉、亞硫酸氫鹽、硫代硫酸鹽、亞硫酸氫鹽、硫化物、硫氫化物或二亞硫磺酸鹽、甲脒亞磺酸鹽、丙酮亞硫酸氫鹽;乙醇酸、羥甲基磺酸、乙醛酸水合物、乳酸、甘油酸、蘋果酸、酒石酸及前述酸之鹽。鐵、銅、錳、銀、鉑、釩、鎳、鉻、鈀或鈷之金屬鹽可用於催化氧化還原反應。可視情況使用針對金屬之螯合劑。
在製備乳液聚合物之方法中,可使用鏈轉移劑。合適的鏈轉移劑之實例包含3-巰基丙酸、巰基丙酸甲酯、巰基丙酸丁酯、正十二基硫醇、苯硫酚、壬二酸烷基硫醇或其混合物。鏈轉移劑可以有效量使用以控制乳液聚合物之分子量。按用於製備乳液聚合物之單體之總重量計,鏈轉移劑可以零至3重量%、0.01重量%至1重量%或0.1重量%至0.3重量%之量存在。
在製備乳液聚合物之方法中,可使用界面活性劑。可在單體聚合之前、期間或之後或其組合添加界面活性劑。合適的額外界面活性劑之實例包含烷基、芳基或烷芳基硫酸酯、磺酸酯或磷酸酯之鹼金屬或銨鹽;烷基磺酸;磺基丁二酸鹽;脂肪酸;可聚合界面活性劑;乙氧基化醇或苯酚;及其混合物。額外界面活性劑應以不損害水性聚合物分散液之效能的量使用,例如按乳液聚合物之乾重計,以零至1.5重量%、0.1重量%至1重量%、0.2重量%至0.8重量%或0.3重量%至0.6重量%的量使用。
所獲得之水性乳液聚合物分散液之pH值可藉由中和控制為至少5,例如6至10或6.5至9。中和可藉由添加一或多種鹼進行,此舉可引起多階段聚合粒子之離子或潛在離子群之部分或完全中和。合適的鹼之實例包含氨;鹼金屬或鹼土金屬化合物,諸如氫氧化鈉、氫氧化鉀、氫氧化鈣、氧化鋅、氧化鎂、碳酸鈉;一級胺、二級胺及三級胺,諸如三乙胺、乙胺、丙胺、單異丙胺、單丁胺、己胺、乙醇胺、二乙胺、二甲胺、二正丙胺、三丁胺、三乙醇胺、二甲氧基乙胺、2-乙氧基乙胺、3-乙氧基丙胺、二甲基乙醇胺、二異丙醇胺、
啉、乙二胺、2-二乙胺基乙胺、2,3-二胺基丙烷、1,2-丙二胺、新戊烷二胺、二甲胺基丙胺、己二胺、4,9-二氧十二烷-1,12-二胺、聚乙二亞胺或聚乙烯胺;氫氧化鋁;或其混合物。
適用於本發明之乳液聚合物可具有50奈米(nm)至500 nm、80 nm至200 nm或90 nm至150 nm之粒度。本文中之粒度係指Z-平均尺寸且可藉由Brookhaven BI-90增強版粒度分析器來量測。
乙烯基芳族單體-順丁烯二酸酐共聚物
本揭示案之乙烯基芳族單體-順丁烯二酸酐共聚物可包括(a)一或多種乙烯基芳族單體之結構單元。乙烯基芳族單體可包含苯乙烯;經取代之苯乙烯,諸如α-甲基苯乙烯、反式β-甲基苯乙烯、2,4-二甲基苯乙烯、乙基苯乙烯、丁基苯乙烯及對甲氧基苯乙烯;鄰甲氧基苯乙烯、間甲氧基苯乙烯及對甲氧基苯乙烯;及對三氟甲基苯乙烯;或其混合物。按乙烯基芳族單體-順丁烯二酸酐共聚物之重量計,本發明之乙烯基芳族單體-順丁烯二酸酐共聚物可包括20重量%或更多、30重量%或更多或甚至40重量%或更多且同時99重量%或更少、90重量%或更少、80重量%或更少、70重量%或更少或甚至60重量%或更少之乙烯基芳族單體之結構單元。
本揭示案之乙烯基芳族單體-順丁烯二酸酐共聚物可包括(b)順丁烯二酸酐之結構單元。按乙烯基芳族單體-順丁烯二酸酐共聚物之重量計,本發明之乙烯基芳族單體-順丁烯二酸酐共聚物可包括5重量%或更多、10重量%或更多、20重量%或更多、30重量%或更多或甚至40重量%或更多且同時80重量%或更少、70重量%或更少或甚至60重量%或更少之順丁烯二酸酐之結構單元。
本揭示案之乙烯基芳族單體-順丁烯二酸酐共聚物可藉由諸如氨或二甲基伸丙基二胺之胺進行亞胺化。共聚物之亞胺化程度可在50%與100%之間。此等亞胺化乙烯基芳族單體-順丁烯二酸酐共聚物亦可以名稱SMA X10000i、SMA X2000i、SMA X3000i、SMA X4000i及SMA 3000H購自克雷威利(Cray Valley)公司。
本發明之較佳乙烯基芳族單體-順丁烯二酸酐共聚物為苯乙烯與順丁烯二酸酐之共聚物(SMA)。較佳地,苯乙烯與順丁烯二酸酐之比率為1/1至6/1,較佳2/1至4/1。
乙烯基芳族單體-順丁烯二酸酐共聚物之數目分子量係在500與20,000之間,較佳在2,000與5,000之間。
乙烯基芳族單體-順丁烯二酸酐共聚物可藉由任何已知方法,例如根據US 3,444,151 A中所描述之方法來製備。
按黏合劑組合物之總固體重量計,乙烯基芳族單體-順丁烯二酸酐共聚物(B)以0.1重量%或更多、0.5重量%或更多、0.8重量%或更多、1.0重量%或更多、1.2重量%或更多、1.5重量%或更多且同時6.5重量%或更少、6.0重量%或更少或5.5重量%或更少、5.0重量%或更少、4.5重量%或更少之量存在。
視情況選用之組分
本揭示案之黏合劑組合物可視情況包括一或多種選自由異氰酸酯交聯劑、流變改質劑、消泡劑、矽烷及其他添加劑組成之群組之組分。
(多種)異氰酸酯交聯劑
本揭示案之黏合劑組合物可視情況包括異氰酸酯交聯劑。異氰酸酯交聯劑包含異氰酸酯單體、聚異氰酸酯、異氰酸酯加合物及其混合物或碳化二亞胺。
在本揭示案之黏合劑組合物中,按黏合劑組合物之總固體重量計,(多種)異氰酸酯交聯劑可以0.1-20重量%、較佳1-15重量%、更佳1-8重量%且再更佳3-7重量%之量存在。
流變改質劑
本揭示案之黏合劑組合物可進一步包括流變改質劑。流變改質劑可包含、不限於非離子胺基甲酸酯聚合物、纖維素、纖維素醚、聚乙二醇、澱粉醚、聚乙烯醇、聚醯亞胺、膠、麵粉及其混合物。流變改質劑較佳選自諸如纖維素醚之非締合增稠劑。
按黏合劑組合物之總固體重量計,流變改質劑可以一般0.1重量%至5.0重量%、0.2重量%至3重量%或0.5重量%至2.0重量%或0.4重量%至1.0重量%之量存在。
消泡劑
本揭示案之黏合劑組合物可進一步包括一或多種消泡劑。本文中之「消泡劑」係指減少及阻礙發泡體形成之化學添加劑。消泡劑可為基於聚矽氧之消泡劑、基於礦物油之消泡劑、基於環氧乙烷/環氧丙烷之消泡劑或其混合物。合適的市售消泡劑包含例如均可獲自TEGO之TEGO Airex 902 W及TEGO Foamex 1488聚醚矽氧烷共聚物乳液、可獲自BYK之BYK-024聚矽氧消泡劑、可獲自NOPCO之NOPCO NXZ消泡劑或其混合物。按黏合劑組合物之總固體重量計,消泡劑可一般以0.01%至2%、0.02%至1.5%或0.04%至0.5%或0.04%至0.1%之量存在。
矽烷
對於一些應用,需要具有高黏度(例如> 20, 000 cP)及高固體含量(例如> 70%)之黏合劑組合物。在此等情況下,為了提供充足適用期,將限制NCO交聯劑之負載量,且使用矽烷作為添加劑以補償NCO交聯劑,由此傳遞充足適用期及黏合效能。本揭示案之矽烷可為環氧官能矽烷。
適用於本發明之環氧官能矽烷化合物通常為具有環氧基之飽和烷氧基化矽烷。環氧官能矽烷化合物可具有至少一種可水解矽烷基。較佳的環氧官能矽烷化合物具有通式(I):
,
其中各R
3獨立地表示具有一個至6個碳原子之烷基;各OR
3基團獨立地表示具有一個至6個碳原子之烷氧基,包含例如甲氧基、乙氧基或其組合;R
4表示分子量為200或更小之二價有機基團,較佳地,R
4為C
1-C
10、C
1-C
5或C
1-C
3伸烷基;R
5表示氫原子或具有一個至20個碳原子之烷基、芳基或芳烷基;且q為一、2或3。合適的環氧官能矽烷化合物之實例包含3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷或其混合物。市售環氧官能矽烷化合物可包含來自邁圖高新材料公司(Momentive Performance Materials Inc.)之Silquest A-187 γ-縮水甘油氧基丙基三甲氧基矽烷。
按黏合劑組合物之總固體重量計,適用於本揭示案之環氧官能矽烷可以零或更多、0.05%或更多、0.1%或更多、0.15%或更多、0.2%或更多、0.25%或更多、0.3%或更多或甚至0.35%或更多且同時5%或更少、4%或更少、3%或更少、2.5%或更少、2%或更少、1.5%或更少、1.2%或更少、1%或更少、0.8%或更少或甚至0.5%或更少之合併量存在。
其他添加劑
除上文所描述之組分以外,本發明之黏合劑組合物可進一步包括以下添加劑中之任一者或組合:分散劑、緩衝劑、中和劑、保濕劑、防黴劑、殺生物劑、著色劑、流動劑、抗氧化劑、塑化劑、調平劑、觸變劑、助黏劑及研磨媒劑。當存在時,按黏合劑組合物之總固體重量計,此等添加劑可以0重量%至5重量%或0.1重量%至3重量%或0.5重量%至1.5重量%之合併量存在。
本發明之黏合劑組合物可用黏合劑領域中已知之技術製備,該等技術包含將丙烯酸乳液聚合物與乙烯基芳族單體-順丁烯二酸酐共聚物及如上文所描述之其他視情況選用之組分混合。黏合劑組合物中之組分可按任何次序混合以得到本發明之黏合劑組合物。亦可將以上所提及之視情況選用之組分中之任一者在混合期間或之前添加至組合物中以形成黏合劑組合物。
本揭示案亦提供一種使用如本文所描述之黏合劑組合物生產層製品之方法,其包括:
(a)提供如上文所描述之黏合劑組合物;
(b)將該黏合劑組合物施用於基板之表面之第一部分上以形成該黏合劑組合物之層;
(c)使基板之表面之第二部分與該黏合劑組合物之該層接觸,以使得該黏合劑組合物之該層夾於該第一部分與該第二部分之間;及
(d)乾燥該黏合劑組合物或使其乾燥。
在一些實施例中,該方法可包括將黏合劑組合物施用於基板(例如膜)之表面之第一部分上以形成黏合劑組合物之層。如本文所使用之「基板之表面之第一部分」可指表面之一部分或整個表面。在一些實施例中,表面之第一部分可為表面之一部分或整個表面。在一些實施例中,黏合劑組合物之塗層重量可為0.5至5.0 g/m
2、0.5至4.0 g/m
2、0.5至3.0 g/m
2、0.5至2.0 g/m
2、0.5至1.0 g/m
2、0.8至4.0 g/m
2、0.8至3.0 g/m
2、1.0至3.0 g/m
2、1.5至3.0 g/m
2或1.5至2.0 g/m
2。在一些實施例中,基板可由選自由以下組成之群組之材料製成:聚乙烯、聚丙烯、聚酯、聚醯胺、金屬、紙、賽璐玢及其組合。在一些實施例中,基板可呈膜形式。
「膜」可指具有0.5 mm或更小之厚度之材料層。在一些實施例中,膜可為在一個維度中為0.5 mm或更小且在其他兩個維度兩者中為1 cm或更大的結構。在一些實施例中,聚合物膜為由聚合物或聚合物混合物製成之膜。在一些實施例中,施用於膜之黏合劑組合物之層之厚度為1至5 µm。合適的膜包含紙、織造及非織造織物、金屬箔、聚合物及經金屬塗佈之聚合物。膜視情況具有上面用油墨印刷有影像之表面;該油墨可與黏合劑組合物接觸。在一些實施例中,膜為聚合物膜及經金屬塗佈之聚合物膜,更佳為聚合物膜。聚合物膜可為PE或PET膜。
在一些實施例中,該方法可包括使基板(例如膜)之表面之第二部分與黏合劑組合物之層接觸,以使得黏合劑組合物之層夾於第一部分與第二部分之間以形成層製品。如本文所使用之「基板之表面之第二部分」可指表面之一部分或整個表面。一般而言,第二部分不同於如上文所描述之第一部分。在一些實施例中,第一部分及第二部分可為相同或不同表面上之部分。在一些實施例中,第一部分及第二部分可為相同或不同基板之相同或不同表面之部分。在一些實施例中,表面之第一部分可為表面之一部分或整個表面。在一些實施例中,表面之第二部分可為表面之一部分或整個表面。
在一些實施例中,該方法可包括乾燥黏合劑組合物或使其乾燥。在一些實施例中,層製品可經受壓力,例如藉由穿過可經加熱或可不經加熱之軋輥。在一些實施例中,層製品可經加熱(例如,在30℃至90℃,例如30℃至60℃之溫度下)以加速乾燥過程。
在另一態樣中,本揭示案提供一種層製品,其係藉由使用如本文所描述之生產經固化層製品之方法來製備。
在另一態樣中,本揭示案提供一種層製品,其包括:基板之表面之第一部分、如本文所描述之黏合劑組合物之層及相同或不同基板之表面之第二部分,其中黏合劑組合物之層夾於第一部分與第二部分之間且與其等接觸。
實例
本發明之一些實施例現將描述於以下實例中,其中除非另外規定,否則所有份數及百分比均按重量計。然而,本揭示案之範疇當然不限於此等實例中所闡述之調配物。更確切而言,實例對本揭示案而言僅為發明性的。
1.原材料
實例中所使用之原材料之資訊列於下表1中。
表1:原材料
原材料 | 描述 | 供應商 |
ROBOND™L-80D | 丙烯酸丁酯/苯乙烯/丙烯酸共聚物,固體=45% | 陶氏(Dow) |
SMA-3000H | 苯乙烯/順丁烯二酸酐共聚物分散液,固體含量15%,PH值約8-9,Mn=3800 | 克雷威利S. A. |
2.準備程序:
根據表2中所列出之調配物製備樣本。對ROBOND™ L-80D及SMA-3000H進行稱重且在玻璃反應器中小心混合,隨後將其置於25℃水浴中。開啟旋轉器,且在50RM下控制旋轉速度且監測整個過程。0.5小時後,將產物裝入100 ml HDPE瓶中。
表2:黏合劑組合物調配物
註:按黏合劑組合物之總固體重量計藉由SMA-3000H乾重量測之SMA-3000H(%)。
樣本編碼 | ROBOND™ L-80D(G) | SMA-3000H(G) | SMA-3000H固體含量(%) |
C-1 | 100 | 0 | 0 |
I-1 | 100 | 2 | 0.71% |
I-2 | 100 | 5 | 1.75% |
I-3 | 100 | 10 | 3.45% |
I-4 | 100 | 15 | 5.08% |
C-2 | 100 | 20 | 6.67% |
3.塗佈及層壓過程:
塗佈及層壓過程係在SDC Labo-Combi 400機器中進行。在整個層壓過程期間,層壓速度保持在100 m/min速度下。塗層重量為1.8-2.0 g/m
2。隨後,在測試之前,在室溫(23-25℃)下或在烘箱中固化層壓膜。
4.測試方法:
T型剝離(90°)黏結強度(手工輔助T型剝離)
在乾燥之後,將層壓膜切割成15 mm寬條帶以用於在Instron 5943機器中以250 mm/min十字頭速度進行T型剝離測試。測試三個條帶以獲取平均值。在測試期間,由手指輕微拉動條帶之尾部以確保尾部與剝離方向保持90度。
熱封強度:
在140℃密封溫度及300 N壓力下,將層製品在可獲自Brugger公司之HSG-C熱封機器中熱封1秒,接著將其冷卻且切割成15 mm寬條帶以使用可獲自英斯特朗公司(Instron Corporation)之5940系列單管柱台面系統在250 mm/min十字頭速度下進行熱封強度測試。各樣本測試三個條帶且計算平均值。結果係以N/15 mm為單位。
5.效能評估結果
黏結強度(BS)及熱封強度(HS)特性概述於表3中。結果表明,使用SMA-3000H將改善PET/PE及箔/PE之黏結強度及熱封強度。然而,當SMA-3000H含量增加至5.08乾重%時,PET/PE及箔/PE之黏結強度開始降低。當SMA-3000H含量進一步增加至6.67%時,黏結強度甚至變得低於原始ROBOND™L-80D之效能。
表 3
BS-(N/15MM) | HS-N/15MM | ||||
PET/PE | 箔/PE | PET/PE | 箔/PE | ||
C-1 | ROBOND™L-80D | 1.21 | 1.86 | 18.23 | 16.4 |
I-1 | SMA-1 | 1.39 | 1.94 | 23.81 | 19.6 |
I-2 | SMA-2 | 2.05 | 3.2 | 27.31 | 24.2 |
I-3 | SMA-3 | 2.21 | 3.43 | 32.23 | 25.34 |
I-4 | SMA-4 | 2.08 | 2.54 | 30.21 | 23.42 |
C-2 | SMA-5 | 1.08 | 1.72 | 28.89 | 22.11 |
無
無
Claims (11)
- 一種黏合劑組合物,其包括: (A)丙烯酸乳液聚合物;及 (B)乙烯基芳族單體-順丁烯二酸酐共聚物, 其中按該黏合劑組合物之總固體重量計,(B)乙烯基芳族單體-順丁烯二酸酐共聚物以0.1重量%至6.5重量%之量存在。
- 如請求項1之黏合劑組合物,其中該丙烯酸乳液聚合物包括(a)一或多種烯系不飽和離子單體之結構單元及(b)一或多種烯系不飽和非離子單體之結構單元。
- 如請求項1之黏合劑組合物,其中按該乳液聚合物之重量計,該丙烯酸乳液聚合物包括 30重量%至50重量%乙烯基芳族單體之結構單元, 50-70重量% (甲基)丙烯酸C 1-C 20烷基酯之結構單元,及 0.1重量%至8重量% (甲基)丙烯酸之結構單元。
- 如請求項1之黏合劑組合物,其中該乙烯基芳族單體-順丁烯二酸酐共聚物包括(a)一或多種乙烯基芳族單體之結構單元及(b)順丁烯二酸酐之結構單元。
- 如請求項1之黏合劑組合物,其中按該黏合劑組合物之總固體重量計,該乙烯基芳族單體-順丁烯二酸酐共聚物(B)以0.5重量%或更多且同時6.0重量%或更少之量存在。
- 如請求項1之黏合劑組合物,其中該黏合劑組合物為單組分基於水之黏合劑組合物。
- 一種使用所描述之黏合劑組合物生產層製品之方法,其包括: (a)提供如請求項1至6中任一項之黏合劑組合物; (b)將該黏合劑組合物施用於基板之表面之第一部分上以形成該黏合劑組合物之層; (d)使基板之表面之第二部分與該黏合劑組合物之該層接觸,以使得該黏合劑組合物之該層夾於該第一部分與該第二部分之間;及 (e)乾燥該黏合劑組合物或使其乾燥。
- 一種層製品,其係藉由使用如請求項7之生產層製品之方法來製備。
- 一種層製品,其包括基板之表面之第一部分、如請求項1至6中任一項之黏合劑組合物之層及相同或不同基板之表面之第二部分,其中該黏合劑組合物之該層夾於該第一部分與該第二部分之間且與其等接觸。
- 一種乙烯基芳族單體-順丁烯二酸酐共聚物之用途,其用於改善包括丙烯酸乳液聚合物之黏合劑組合物之黏結強度及/或熱封效能。
- 如請求項10之用途,其中按該黏合劑組合物之總固體重量計,該乙烯基芳族單體-順丁烯二酸酐共聚物以0.1重量%至6重量%之量存在。
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