TWI858080B - 基於水之組合物 - Google Patents
基於水之組合物 Download PDFInfo
- Publication number
- TWI858080B TWI858080B TW109120083A TW109120083A TWI858080B TW I858080 B TWI858080 B TW I858080B TW 109120083 A TW109120083 A TW 109120083A TW 109120083 A TW109120083 A TW 109120083A TW I858080 B TWI858080 B TW I858080B
- Authority
- TW
- Taiwan
- Prior art keywords
- water
- polyol
- isocyanate
- based composition
- reaction product
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229920005862 polyol Polymers 0.000 claims abstract description 60
- 150000003077 polyols Chemical class 0.000 claims abstract description 57
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000012948 isocyanate Substances 0.000 claims description 43
- 150000002513 isocyanates Chemical class 0.000 claims description 42
- 239000002253 acid Substances 0.000 claims description 35
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 25
- -1 ethylenediaminetetraacetic acid compound Chemical class 0.000 claims description 15
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 239000010408 film Substances 0.000 description 34
- 239000000853 adhesive Substances 0.000 description 31
- 230000001070 adhesive effect Effects 0.000 description 31
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 14
- 229920005906 polyester polyol Polymers 0.000 description 13
- 239000013011 aqueous formulation Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000011888 foil Substances 0.000 description 9
- 239000005056 polyisocyanate Substances 0.000 description 9
- 229920001228 polyisocyanate Polymers 0.000 description 9
- 239000001361 adipic acid Substances 0.000 description 8
- 235000011037 adipic acid Nutrition 0.000 description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011104 metalized film Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- POLIXZIAIMAECK-UHFFFAOYSA-N 4-[2-(2,6-dioxomorpholin-4-yl)ethyl]morpholine-2,6-dione Chemical compound C1C(=O)OC(=O)CN1CCN1CC(=O)OC(=O)C1 POLIXZIAIMAECK-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 229920002799 BoPET Polymers 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
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- 235000015067 sauces Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
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- 230000032798 delamination Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
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- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
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- YBXSYMIDZDBSFD-UHFFFAOYSA-L 3-acetyl-2,4-dioxopentanoate;dibutyltin(2+) Chemical compound CCCC[Sn+2]CCCC.CC(=O)C(C(C)=O)C(=O)C([O-])=O.CC(=O)C(C(C)=O)C(=O)C([O-])=O YBXSYMIDZDBSFD-UHFFFAOYSA-L 0.000 description 1
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- 239000013638 trimer Substances 0.000 description 1
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- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本揭示案之實施例係針對基於水之組合物,其包括藉由使多元醇與胺基聚羧酸化合物反應形成之反應產物。
Description
本揭示案之實施例係針對基於水之組合物,更具體言之,實施例係針對無溶劑組合物,其包括藉由使多元醇與胺基聚羧酸化合物反應形成之反應產物。
基於水之組合物可包括多元醇、異氰酸酯及水以及其他可能之組分。舉例而言,當基於水之組合物用於黏著劑應用時,其可與兩個基板接觸以使得多元醇與異氰酸酯可彼此反應以形成固化產物且在兩個基板之間形成黏結。舉例而言,當基於水之組合物用於塗料應用時,其可與一個基板接觸以使得多元醇與異氰酸酯可彼此反應以形成固化產物。
本揭示案提供基於水之組合物,該等組合物包括:藉由使多元醇與胺基聚羧酸化合物反應所製得之反應產物;異氰酸酯;及水。
本揭示案之以上概述並不意欲描述所揭示之各實施例或本發明之每一實施方式。以下實施方式更具體地舉例說明例示性實施例。在申請案通篇之若干處,經由實例之清單提供指導,該等實例可以不同組合形式使用。在各情況下,所述清單僅用作代表性群組且不應解釋為排他性清單。
多元醇及胺基聚羧酸化合物之反應產物揭示於本文中。反應產物可用於可以合乎需要地提供一或多種改良之特性的基於水之組合物中。
舉例而言,相比於包括與用於製得反應產物之多元醇類似之多元醇的其他組合物,包括反應產物之基於水之組合物可在第7天提供改良之(亦即增加之)T-剝離黏結強度。在第7天之增加的T-剝離黏結強度指示更大黏著
強度,其對於許多應用為所期望的。
另外,相比於包括與用於製得反應產物之多元醇類似之多元醇的其他組合物,包括反應產物之基於水之組合物可提供改良之(亦即增加之)蒸煮袋值。在將用本文所揭示之黏著劑組合物製得的封裝產品與消費型產品結合使用時,改良之蒸煮袋值可指示更大之黏著強度。對於許多應用而言,需要更大黏著強度。
另外,相比於包括與用於製得反應產物之多元醇類似之多元醇的其他組合物,包含反應產物之基於水之組合物可提供改良之(例如更快之)固化。
如所提及,本文揭示多元醇及胺基聚羧酸化合物之反應產物。如本文所用,「胺基聚羧酸化合物」包括其衍生物及/或結構類似物。一或多個實施例規定胺基聚羧酸化合物為乙二胺四乙酸化合物。胺基聚羧酸化合物、衍生物及/或結構類似物之實例包括但不限於乙二胺四乙酸酐、乙二胺四乙酸、二伸乙三胺五乙酸二酐、4,4'-(丙烷-1,2-二基)雙(嗎啉-2,6-二酮)、4,4'-(丙烷-1,3-二基)雙(嗎啉-2,6-二酮)及4,4'-(氧基雙(乙烷-2,1-二基))雙(嗎啉-2,6-二酮)。本揭示案之一或多個實施例規定乙二胺四乙酸化合物可選自乙二胺四乙酸酐、乙二胺四乙酸及其組合。
乙二胺四乙酸二酐可由下式表示:。
本揭示案之實施例規定與胺基聚羧酸化合物反應之多元醇可為聚醚多元醇、聚酯多元醇或其組合。
可藉由已知製程(例如藉由使用已知組分、已知設備及已知反應條件)製備多元醇。可商購獲得多元醇。
市售多元醇之實例包含但不限於以商標名VORANOLTM
、TERCAROLTM
、MOR-FREETM
、PRIPLASTTM
及VORATECTM
以及其他出售之多元醇。
本揭示案之一或多個實施例規定多元醇可包括聚醚多元醇。可藉由已知製程製備聚醚多元醇。舉例而言,可藉由一或多種環氧烷(諸如環氧乙烷、環氧丙烷及環氧丁烷)之陰離子加成聚合來製備聚醚多元醇。可被稱作引發劑之起動化合物為在聚合反應中經烷氧基化之任何有機化合物。引發劑可含有2個或更多個羥基及/或一級或二級胺基。可使用起動化合物/引發劑之混合物。引發劑化合物之實例包括但不限於乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、三丙二醇、1,4-丁二醇、1,6-己二醇、1,8-辛二醇、環己烷二甲醇、甘油、三羥甲基丙烷、三羥甲基乙烷、季戊四醇、山梨醇、蔗糖以及此等中之任一者之烷氧基化物(尤其乙氧化物及/或丙氧基化物)、多元胺或二烷醇胺。
本揭示案之一或多個實施例規定多元醇可包括聚酯多元醇。可由例如具有2至12個碳原子之有機二羧酸(包括具有8至12個碳原子之芳族二羧酸)及多元醇(包括具有2至12個碳原子之二醇)來製備聚酯-多元醇。適合之二羧酸之實例為丁二酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、癸烷二甲酸、順丁烯二酸、反丁烯二酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸及異構萘二甲酸。二羧酸可單獨使用或彼此混合。游離二羧酸可由對應二羧酸衍生物,例如具有1至4個碳原子之醇之二羧酸酯或二羧酸酐置換。一些特定實例可利用二羧酸混合物(其包括呈例如20比35:35至50:20比32重量份之比率的丁二酸、戊二酸及己二酸),及鄰苯二甲酸及/或鄰苯二甲酸酐與己二酸之混合物;鄰苯二甲酸或鄰苯二甲酸酐、間苯二甲酸及己二酸之混合物;或丁二酸、戊二酸及己二酸之二羧酸混合物;及對苯二甲酸及己二酸之混合物;或丁二酸、戊二酸及己二酸之二羧酸混合物。二元醇及多元醇之實例為乙二醇、二乙二醇、1,2-丙二醇及1,3-丙二醇、二丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,10-癸二醇、甘油、三羥甲基丙烷以及其他。一些特定實例規定乙二醇、二乙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇或該等二醇中之至少兩者之混合物,尤其1,4-丁二醇、1,5-戊二醇及1,6-己二醇之混合物。此外,亦可採用由內酯(例如ε-己內酯)或羥基羧酸(例如ω-羥基己酸及氫苯甲酸)製得之聚酯-多元醇。
可藉由例如以1:1至1:1.8(例如1:1.05至1:1.2)之莫耳比將有機聚羧酸及/或其衍生物與多元醇聚縮合來製備聚酯多元醇。
用於製得本文所揭示之反應產物的多元醇之重均分子量可為300至12,000 g/mol。包括300至12,000 g/mol之所有個別值及子範圍;例如多元醇之重均分子量可為自300、400、500、750或1000之下限至12,000、10,000、8000、5000或3000 g/mol之上限。
用於製備本文所揭示之反應產物之多元醇之平均官能度(亦即羥基官能度)可為1.5至5.0。包括1.5至5.0之所有個別值及子範圍;例如多元醇之平均官能度可為自1.5、1.7或2.0之下限至5.0、4.0或3.0之上限。
可藉由使多元醇及胺基聚羧酸化合物以100:0.5至100:10之多元醇羥基之莫耳數與胺基聚羧酸化合物官能基之莫耳數的莫耳比來反應,製得多元醇及胺基聚羧酸化合物之反應產物。{3}包括100:0.5至100:10之多元醇羥基之莫耳數比胺基聚羧酸化合物官能基之莫耳數之所有個別值及子範圍;例如多元醇可以100:0.5、100:1、100:2、100:3、100:4、100:5、100:6、100:7、100:8、100:9或100:10之多元醇羥基之莫耳數與胺基聚羧酸化合物官能基之莫耳數的莫耳比與胺基聚羧酸化合物反應。胺基聚羧酸化合物官能基包括二酐、單酐二酸、四酸及其組合。
可使用已知設備及反應條件形成反應產物。舉例而言,可將反應物(亦即多元醇及胺基聚羧酸化合物)加熱至任何所需溫度持續足以實現所需化學/物理轉化之規定時間。作為實例,可在50℃至200℃之溫度下形成反應產物;反應可發生(例如維持)約5分鐘至約48小時;且反應可在惰性環境(諸如氮氣環境)中進行。可視情況以催化劑形成反應產物。
多元醇及胺基聚羧酸化合物之反應產物可包括以反應產物之總重量計0.03至10.0重量%之衍生自胺基聚羧酸化合物之單元。包括0.03至10.0重量%之衍生自胺基聚羧酸化合物之單元的所有個別值及子範圍;例如反應產物可包括以反應產物之總重量計自0.03、0.05、0.08或1.0之下限至10.0、8.0、6.0或5.0重量%之上限的衍生自胺基聚羧酸化合物之單元。
本揭示案之實施例提供基於水之組合物,其包括多元醇與胺基聚羧酸化合物之反應產物、及異氰酸酯。可利用已知條件及已知設備製備(例如混合)基於水之組合物,該等已知條件及已知設備可針對不同應用而變化。
異氰酸酯可為聚異氰酸酯。如本文所用,「聚異氰酸酯」係指具有平均大於1.0個異氰酸酯基/分子之分子,例如平均異氰酸酯官能度大於1.0。
異氰酸酯可為例如脂族聚異氰酸酯、環脂族聚異氰酸酯、芳脂族聚異氰酸酯或其組合。異氰酸酯之實例包括但不限於4,4'-二異氰酸酯基二環己基甲烷、異氰酸3-異氰酸酯基甲基-3,3,5-三甲基環己酯(異佛爾酮二異氰酸酯IPDI)、二異氰酸丁二酯、二異氰酸己二酯(HDI)、二異氰酸2-甲基戊二酯、二異氰酸2,2,4-三甲基己二酯(THDI)、二異氰酸十二酯、1,4-二異氰酸酯基環己烷、4,4'-二異氰酸酯基-3,3'-二甲基二環己基甲烷、4,4'-二異氰酸酯基-2,2-二環己基丙烷、3-異氰酸酯基甲基-1-甲基-1-異氰酸醋基環己烷(MCI)、1,3-二異辛基氰酸醋基-4-甲基環己烷、1,3-二異氰酸酯基-2-甲基環己烷、1,4-雙(異氰酸酯基甲基)環己烷、1,3-雙(異氰酸酯基甲基)環己烷及其組合以及其他。除了上文所提及之異氰酸酯之外,可利用包括脲二酮、異氰尿酸酯、碳化二亞胺、脲并亞胺、脲基甲酸酯或縮二脲結構及其組合之部分改質聚異氰酸酯。
異氰酸酯可為聚合的。如本文中所用,在描述異氰酸酯時,「聚合的」係指更高分子量同系物及/或異構體。舉例而言,聚合二異氰酸己二酯(HDI)係指二異氰酸己二酯(HDI)、其二聚體、三聚體或寡聚物或組合之更高分子量同系物及/或異構體。
異氰酸酯可為預聚物。舉例而言,異氰酸酯可為異氰酸酯封端之預聚物,例如異氰酸酯封端之聚胺基甲酸酯預聚物。可藉由使異氰酸酯與多元醇反應來製得預聚物。
如所提及,異氰酸酯之平均官能度可為大於1.0個異氰酸酯基/分子。舉例而言,異氰酸酯之平均官能度可為1.75至3.50。包括1.75至3.50之所有個別值及子範圍;舉例而言,異氰酸酯之平均官能度可為自1.75、1.85或1.95之下限至3.50、3.40或3.30之上限。
異氰酸酯之異氰酸酯當量可為84 g/eq至1000 g/eq。包括84至1000 g/eq之所有個別值及子範圍;舉例而言,異氰酸酯之異氰酸酯當量可為自84、95、115、125、135或145之下限至1000、800、600、500、300、290或280 g/eq之上限。
可藉由已知製程製備異氰酸酯。舉例而言,可藉由以下步驟製備聚異氰酸酯:使相應多元胺光氣化同時形成聚氯化胺甲醯且將其熱解來得到聚異氰酸酯及氯化氫,或藉由無光氣製程(諸如藉由使相應多元胺與尿素及醇反應得到聚胺基甲酸酯)及將其熱解來得到例如聚異氰酸酯及醇。
可商購獲得異氰酸酯。可利用之可商購異氰酸酯及/或NCO封端之預聚物之實例包括但不限於可購自陶氏化學公司(The Dow Chemical Company)商標名MOR-FREETM
、VORANATETM
及PAPITM
下之異氰酸酯以及其他可商購異氰酸酯。
可利用異氰酸酯以使得基於水之組合物的異氰酸酯指數在0.9至1.6範圍內。異氰酸酯指數可測定為異氰酸酯之當量除以基於水之組合物的異氰尿酸反應性組分(例如異氰酸酯反應性氫)之總當量,成倍增加。換言之,異氰酸酯指數可測定為異氰酸酯基與異氰酸酯反應性氫之比率。包括0.9至1.6之所有個別值及子範圍;舉例而言,基於水之組合物之異氰酸酯指數可為自0.9、1.0、1.05或1.1之下限至1.6、1.5、1.45或1.4之上限。
基於水之組合物包括水。舉例而言,基於水之組合物可為分散液從而使得水為連續相。如本文所用,「基於水之組合物」係指包括以反應產物、異氰酸酯及水之總重量計至少10重量%之水的組合物。以反應產物、異氰酸酯及水之總重量計,水可為10重量%至80重量%基於水之組合物。包括10重量%至80重量%之所有個別值及子範圍;舉例而言,以反應產物、異氰酸酯及水之總重量計,水可為自10、12或15重量%之下限至80、75或70重量%之上限。
基於水之組合物可包括催化劑,例如用於形成聚胺基甲酸酯之已知催化劑。催化劑之實例包括鋁催化劑、鉍催化劑、錫催化劑、釩催化劑、鋅催化劑、鋯催化劑、鈦催化劑、胺催化劑及其組合。一或多個實施例規定催化劑選自二乙酸二丁基錫、二月桂酸二丁基錫、二乙醯基丙酮酸二丁基錫、二硫醇二丁基錫、二辛酸二丁基錫、二順丁烯二酸二丁基錫、丙酮基丙酮酸二丁基錫、氧化二丁基錫及其組合。當利用催化劑時,以基於水之組合物之總重量計,其可為0.001百萬分率(ppm)至100 ppm。舉例而言,以基於水之組合物之總重量計,催化劑可為0.005 ppm至10 ppm。
本揭示案之實施例規定基於水之組合物可包括一或多種其他組分,諸如與黏著劑組合物一起使用之已知組分及/或與例如塗料組合物一起使用之已知組分。不同其他組分及/或不同量之其他組分可用於各種應用。其他組分之實例包含有機溶劑、多元醇、界面活性劑、螯合劑、交聯劑、擴鏈劑、抗氧化劑及其組合,以及其他已知之組分。
有利地,可將基於水之組合物塗覆於材料。舉例而言,基於水之組合物可塗覆於第一材料且第二材料可與基於水之組合物接觸;隨後,基於水之組合物可經固化以形成層合物。此外,可將基於水之組合物塗覆於第一材料且接著可使組合物固化以形成塗層。可藉由已知製程(例如藉由使用已知組分、已知設備及已知應用條件)(諸如凹版層壓、彈性凸版層壓等)來塗覆基於水之組合物。另外,可將基於水之組合物之組分塗覆於不同基板上且接著層壓在一起。
本文所揭示之基於水之組合物可固化,例如多元醇與胺基聚羧酸化合物之反應產物與異氰酸酯可彼此反應以形成固化產物。已知固化條件(諸如溫度、濕度及持續時間)可用於使本文所揭示之基於水之組合物固化。
有利地,與包括與用於製得反應產物之多元醇類似之多元醇的其他組合物相比,本文所揭示之基於水之組合物可例如在固化時提供改良之在第7天之T-剝離黏結強度。如所提及,在第7天增加之T-剝離黏結強度指示更大黏著
強度。此更大黏著
強度可合乎需要地幫助為用本文所揭示之基於水之組合物製得的產品提供更大密封。
有利地,與包括與用於製得反應產物之多元醇類似的多元醇的其他組合物相比,本文所揭示之基於水之組合物可例如在固化時提供改良之蒸煮袋值。當將以本文所揭示之基於水之組合物製得之封裝產品與諸如醬以及其他之消費型產品結合使用時,改良之蒸煮袋值指示更大之黏著強度。換言之,改良之蒸煮袋值可指示期望改良之消費型產品對封裝失效之抗性。
另外,相比於包括與用於製得反應產物之多元醇類似之多元醇的其他組合物,包括反應產物之基於水之組合物可提供改良之(例如更快之)固化。
如本文所用,與用於製得反應產物之多元醇類似的多元醇係指與用以製得反應產物之多元醇相同的多元醇;或與用以製得反應產物之多元醇相比重均分子量為+
10%且平均羥基官能度為+
10%的多元醇。
實施例規定可將基於水之組合物與各種材料(例如基板)一起使用。可與本文所揭示之基於水之組合物一起使用之材料之實例包括聚合材料,諸如聚對苯二甲酸伸乙酯、聚乙烯、聚丙烯及其組合。聚合材料可為例如膜。實施例規定可與基於水之組合物一起使用之材料可包括金屬,例如箔或金屬化膜。箔及金屬化膜為熟知的。舉例而言,可在金屬化之前預處理(諸如藉由電暈處理及電漿處理)聚合材料。接著,可藉由物理氣相沈積製程來進行金屬化。在此類製程中,加熱金屬且將其在真空下蒸發。金屬接著在聚合材料上冷凝以形成金屬化膜。適合金屬之實例包括但不限於鋁、鎳、鉻及其組合。實施例規定可將基於水之組合物用於例如膜對膜層壓及膜對箔層壓。
實例
在實例中,使用材料之各種術語及名稱,包括例如以下:
胺基聚羧酸化合物(乙二胺四乙酸二酐;獲自奧德里奇(Aldrich));
三乙胺(獲自奧德里奇);
MOR-FREE CR9-101(異氰酸酯;獲自陶氏化學公司);
MOR-FREE C-33(脂族異氰酸酯;獲自陶氏化學公司);
VORANOL P-425(聚醚多元醇;獲自陶氏化學公司);
POLYSTEP B-5-N(界面活性劑;獲自陶氏化學公司);
VERSENOL 120(螯合劑;獲自陶氏化學公司);
金屬化PET膜(金屬化48 g PET膜;獲自Filmquest Group);PET膜(48 LBT;聚酯膜[聚(乙二醇-對苯二甲酸酯)];獲自杜邦公司(DuPont));PET/箔層壓膜(PET鋁箔膜;獲自FILM TECH公司);低密度聚乙烯膜(GF-19膜;高潤滑低密度膜;厚度1.5 mil;獲自柏利塑膠公司(Berry Plastics Corp)。
如下製得實驗室合成之聚酯多元醇。在氮氣氛圍下向容器中添加1,6-己烷二醇(1012.3公克;獲自奧德里奇)、新戊二醇(494.9公克;獲自奧德里奇)及己二酸(1492.8公克;獲自奧德里奇);在攪拌之同時,將容器之內容物自約25℃緩慢加熱至約100℃。接著,將容器之內容物緩慢加熱至約190℃且保持在該溫度下直至酸值為大約10 mg KOH/g。接著,將容器之內容物冷卻至約125℃且將異丙醇鈦(0.03公克;獲自奧德里奇)添加至容器中且將容器之內容物維持在約125℃下30分鐘。接著,將容器之內容物緩慢加熱至約190℃且保持在該溫度下直至酸值為約1 mg KOH/g;如需減小酸值則施加真空(435 mm Hg)。接著,將容器之內容物冷卻至約125℃並過濾以提供實驗室合成之聚酯多元醇。
如下製得實例1,多元醇與乙二胺四乙酸二酐之反應產物。將實驗室合成之聚酯多元醇(99公克)添加至容器中且在流動氮氣下在大約105℃下乾燥60分鐘。接著,將乙二胺四乙酸二酐(1公克)添加至容器中,且將容器之內容物緩慢加熱至170℃且維持在該溫度下約3小時;其後,將容器之內容物緩慢加熱至180℃且維持在該溫度下約30分鐘。接著,將容器之內容物冷卻至約90℃且過濾,得到實例1。實例1包括以實例1之總重量計1.0重量%之衍生自乙二胺四乙酸二酐之單元。
測定實例1及實驗室合成之聚酯多元醇之多種特性。根據ASTM E 1899-08測定OH數目;根據ASTM D4274-16測定酸值;經由SEC分析如下描述數均分子量(Mn)及重均分子量(Mw)。將各個樣品(0.01公克)溶解於四氫呋喃(4.0 mL)中以得到樣品濃度(2.5 mg/mL)。分離模組:沃特世(Waters)e2695;管柱:聚合物實驗室PL凝膠混合E管柱(Polymer Labs PLGel Mixed E column)×2,3 µm粒度及混合C管柱×1,5 µm粒度;管柱溫度:40℃;溶離劑:四氫呋喃(不穩定的);流率:1 mL/min;注射體積:50 µL;分析時間:40分鐘;檢測器:沃特世2414折射率檢測器(Waters 2414 Refractive Index Detector)(40℃);校準:安捷倫技術聚苯乙烯(PS)-介質EasiVials(Agilent Technologies Polystyrene(PS)-Medium EasiVials),批號0006386106;軟件:安捷倫(Agilent)OpenLAB CDS(EZChrome版)A.04.06型。
結果報導於表1中
表1
| 實例1 | 實驗室合成之聚酯多元醇 | |
| OH數目 (mg KOH/g) | 66 | 67 |
| 酸值 (mg KOH/g) | 4.8 | 0.4 |
| 數均分子量 | 1840 | 1680 |
| 重均分子量 | 2700 | 3420 |
| 分子量分散度 (Mw /Mn ) | 2.01 | 2.04 |
表1之數據說明對於實例1,製得多元醇及乙二胺四乙酸二酐之反應產物。
如下製得包括如上文所論述之實例1之水性調配物1。將實例1添加至容器中且加熱至70℃。接著,將表2中所指示之組分及量添加至容器中,且經由在1800 RPM下之FlackTek高速混合器(FlackTek High Speed Mixer)混合容器之內容物3分鐘。其後,將去離子水(70℃)添加至容器中且再在1800 RPM下混合容器之內容物15分鐘。
與水性調配物1一樣來製得包括如上文所論述之實驗室合成之聚酯多元醇之水性調配物A,組分及量之變化指示於表2中。
與水性調配物1一樣來製得包括如上文所論述之實驗室合成之聚酯多元醇之水性調配物B,組分及量之變化指示於表2中。
用Nanotrac Ultra(麥奇客公司(Microtrac, Inc.))測定表2中所報導之特性。
表2
| 水性調配物1 | 水性調配物A | 水性調配物B | |
| 實例1 | 20.17 (公克) | - | - |
| 實驗室合成之聚酯多元醇 | - | 20.05 (公克) | 20.07 (公克) |
| 三乙胺 | 0.29 (公克) | 0.29 (公克) | 0.47 (公克) |
| VORANOL P-425 | 0.25 (公克) | 0.25 (公克) | 0.24 (公克) |
| POLYSTEP B-5-N | 0.0057 (公克) | 0.0062 (公克) | 0.0061 (公克) |
| VERSENOL 120 | - | - | 0.56 (公克) |
| 甲乙酮 | 6.05 (公克) | 6.04 (克) | 6.01 (公克) |
| 去離子水 | 34.62 (公克) | 30.70 (公克) | 30.08 (公克) |
| 固體含量 (公%) | 33.7 | 35.9 | 37.2 |
| 平均直徑(強度分佈) | 2655 (nm) | 4220 (nm) | 3240 (nm) |
| 平均直徑(數量分佈) | 177 (nm) | 3790 (nm) | 3150 (nm) |
| 平均直徑 (面積分佈) | 469 (nm) | 4070 (nm) | 3210 (nm) |
| 多分散性指數 | 2.431 | 0.0809 | 0.0146 |
如下製得實例2,一種基於水之組合物。將表3中所指示之組分及量添加至容器且混合。
與實例2一樣,製得比較實例A,組分及量之變化指示於表3中。
表3
| 實例2 | 比較實例A | |
| 水性調配物1 | 57.38公克 | - |
| 水性調配物A | - | 57.33公克 |
| MOR-FREE CR9-101 | 5.42公克 | 5.41公克 |
| MOR-FREE C-33 | 5.43公克 | 5.41公克 |
| 固體含量 (重量%) | 46.2 | 46.1 |
| 異氰酸酯指數 | 1.2 | 1.2 |
如下利用實例2製備層合物。利用油加熱滾筒手動層壓機(夾持溫度為150℉;運行速度為20英尺/分鐘)及約1.05磅/令之塗佈重量。一片片製備具有約12吋×10吋塗佈面積之層合物。將實例3調配為含35重量%固體之乙酸乙酯,且接著塗佈至一級膜上;將經塗佈之一級膜烘箱乾燥(90℃;約1分鐘)。接著以油加熱之滾筒手動層壓機(約40 psi)將經塗佈之一級膜層壓至二級膜上;接著在約20℃下固化層合物七天。
如上文所論述,利用比較實例A製備層合物。
對層合物進行T-剝離黏結強度測試及蒸煮袋測試。結果報導於表4中。
在英斯特朗公司(Instron)拉力測試儀上用50 N負載單元以10英吋/分鐘之速率對1英吋條帶量測T剝離黏結強度。測試各層合物之三個條帶,且記錄高強度及平均強度以及失效模式。在膜撕裂及膜拉伸之情況下,報告高值,且在其他失效模式中,報告平均T剝離黏結強度。
如下進行層合物之蒸煮袋測試。將固化之層壓物(9吋×11吋)摺疊以形成雙層,從而一層PE膜與另一層PE膜接觸。接著用切紙機修整邊緣以獲得摺疊片(約5吋×7吋)。接著熱密封邊緣以形成內部大小為4吋×6吋之袋。接著經由開放邊緣向袋填充100 mL等重量份番茄醬、醋及植物油之醬摻合物。在填充之後,以使袋內部之空氣截留降到最小的方式將袋密封。接著將經填充之袋小心地置放於沸水中且保持浸沒於水中30分鐘或60分鐘。當完成時,將穿隧、分層或洩露之程度與明顯的預先存在之缺陷進行比較。
表4
| 實例2 | 比較 實例A | |
| 一級膜:PET/箔層壓膜(塗佈箔側) 二級膜:聚乙烯膜 | ||
| T-剝離黏結強度 (第7天) | 253+ 17 g/25mm | 153+ 6 g/25mm |
| 失效模式 | 黏著劑轉移 (關於一級膜之黏著劑) | 黏著劑轉移 (關於一級膜之黏著劑) |
| 蒸煮袋 (30分鐘) | 39+ 4 g/25mm | 18+ 2 g/25mm |
| 蒸煮袋 失效模式 | 黏著劑轉移 (關於二級膜之黏著劑) | 黏著劑轉移 (關於二級膜之黏著劑)及分層 |
表4之數據說明對於包括金屬化膜之層合物,實例2與比較實例A相比有利地在第7天具有改良之T-剝離黏結強度。
另外,表4之數據說明對於包括金屬化膜之層合物,實例2與比較實例A相比有利地在30分鐘具有改良之蒸煮袋值。改良之蒸煮袋值有利地說明所測試之醬摻合物之更大黏著強度。
如下製得實例3,一種基於水之組合物。將表5中所指示之組分及量添加至容器且混合。
與實例3一樣,製得比較實例B-C,組分及量之變化指示於表5中。
表5
| 實例3 | 比較實例B | 比較實例C | |
| 水性調配物1 | 56.85公克 | - | - |
| 水性調配物A | - | 57.24公克 | - |
| 水性調配物B | - | - | 57.43公克 |
| MOR-FREE CR9-101 | 12.23公克 | 12.46公克 | 12.35公克 |
| 固體含量 (重量%) | 47.8 | 47.7 | 48.3 |
| 異氰酸酯指數 | 1.2 | 1.2 | 1.2 |
如上文所論述,利用實例3及比較實例B-C製備層合物。
如上文所論述,對層合物進行T-剝離黏結強度測試及蒸煮袋測試。結果報導於表6中。
表6
| 實例3 | 比較 實例B | 比較 實例C | |
| 一級膜:PET/箔層壓膜(塗佈箔側) 二級膜:聚乙烯膜 | |||
| T-剝離黏結強度 (第7天) | 235+ 4 g/25mm | 170+ 16 g/25mm | 74+ 11 g/25mm |
| 失效模式 | 黏著劑轉移 (關於一級膜之黏著劑) | 黏著劑轉移 (關於一級膜之黏著劑) | 黏著劑轉移 (關於一級膜之黏著劑) |
| 蒸煮袋 (30分鐘) | 63+ 8 g/25mm | 10+ 5 g/25mm | 0 g/25mm |
| 蒸煮袋 失效模式 | 黏著劑轉移 (關於二級膜之黏著劑) | 黏著劑轉移 (關於二級膜之黏著劑)及分層 | 分層 |
| 一級膜:金屬化PET膜 二級膜:PET膜 | |||
| T-剝離黏結強度 (第7天) | 76+ 12 g/25mm | 53+ 3 g/25mm | 29+ 12 g/25mm |
| 失效模式 | 黏著劑轉移 (關於一級膜之黏著劑) | 黏著劑轉移 (關於一級膜之黏著劑) | 黏著劑轉移 (關於一級膜之黏著劑) |
表6之數據說明對於包括金屬化膜之層合物,實例3與比較實例B-C相比有利地在第7天具有改良之T-剝離黏結強度。
另外,表6之數據說明對於包括金屬化膜之層合物,實例3與比較實例B-C相比有利地在30分鐘後具有改良之蒸煮袋值。改良之蒸煮袋值有利地說明所測試之醬摻合物之更大黏著強度。
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Claims (8)
- 一種基於水之組合物,其包含:藉由使多元醇與胺基聚羧酸化合物反應製得之反應產物;異氰酸酯;及水。
- 如請求項1之基於水之組合物,其中該胺基聚羧酸化合物為乙二胺四乙酸化合物。
- 如請求項1之基於水之組合物,其中該胺基聚羧酸化合物選自乙二胺四乙酸酐、乙二胺四乙酸及其組合。
- 如請求項1之基於水之組合物,其中該反應產物具有以該反應產物之總重量計0.03至10.0重量%之衍生自該胺基聚羧酸化合物之單元。
- 如請求項1之基於水之組合物,其中該多元醇之重均分子量為300至12,000g/mol。
- 如請求項1之基於水之組合物,其中該基於水之組合物之異氰酸酯指數在1.0至1.6範圍內。
- 如請求項1之基於水之組合物,其中以該反應產物、該異氰酸酯及水之總重量計,該水為該基於水之組合物之10重量%至80重量%。
- 一種層合物,其由如請求項1至6中任一項之基於水之組合物形成。
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