CN107974826A - 一种织物用无氟防水整理乳液及其应用 - Google Patents
一种织物用无氟防水整理乳液及其应用 Download PDFInfo
- Publication number
- CN107974826A CN107974826A CN201711292001.8A CN201711292001A CN107974826A CN 107974826 A CN107974826 A CN 107974826A CN 201711292001 A CN201711292001 A CN 201711292001A CN 107974826 A CN107974826 A CN 107974826A
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- Prior art keywords
- carbon chain
- long carbon
- lotion
- fabric
- floride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004744 fabric Substances 0.000 title claims abstract description 43
- 239000006210 lotion Substances 0.000 title claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 64
- -1 carbon chain carboxylic acids Chemical class 0.000 claims abstract description 41
- 238000004078 waterproofing Methods 0.000 claims abstract description 24
- 239000000839 emulsion Substances 0.000 claims abstract description 22
- 229920003180 amino resin Polymers 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 15
- 239000001993 wax Substances 0.000 claims abstract description 14
- 125000002091 cationic group Chemical group 0.000 claims abstract description 10
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 5
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 21
- 125000001931 aliphatic group Chemical group 0.000 claims description 21
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 20
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 20
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 20
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 claims description 17
- 150000003512 tertiary amines Chemical class 0.000 claims description 16
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- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 8
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical group C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 7
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- 239000000126 substance Substances 0.000 description 7
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- 239000002253 acid Substances 0.000 description 6
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- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 5
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- 239000012188 paraffin wax Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- JVVXZOOGOGPDRZ-SLFFLAALSA-N [(1R,4aS,10aR)-1,4a-dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthren-1-yl]methanamine Chemical compound NC[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 JVVXZOOGOGPDRZ-SLFFLAALSA-N 0.000 description 3
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 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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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- 125000003342 alkenyl group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
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- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明涉及织物防水剂，具体的说是一种织物用无氟防水整理乳液及其应用。无氟防水整理乳液组分按重量份数计(干物质组分)：a)80‑40份长碳链改性的氨基树脂、b)1‑8份阳离子改性的长碳链氨基树脂、c)1‑10份长碳链羧酸的金属络合物、d)10‑55份蜡、e)0.05‑3份阳离子乳化剂、f)0.01‑2份非离子乳化剂和g)0.001‑1.5份有机酸或无机酸。本发明防水剂适用于涤纶、棉、酯、人造板材或造纸及各种混纺织物的防水整理，防水性能优异。
Description
发明领域
本发明涉及织物防水剂，具体的说是一种织物用无氟防水整理乳液及其应用。
背景技术
织物防水剂通常为有机氟化物、有机硅、蜜胺树脂、蜡、聚氨酯、吡啶鎓盐等。其中有机氟化合物效果最好，能防水、防油及防污。但是由于全氟辛烷磺酸PFOS和全氟辛酸PFOA性质非常稳定，降解困难、生物累积性高，对生物有害。欧盟已立法逐步禁用PFOA及其盐类，并于2020年7月开始全面禁止使用PFOA及降解物中含PFOA的物质。其他类型的防水剂防水性能均不及有机氟化物，但是它们的优点在于安全环保性高。例如有机硅类防水剂通常对处理织物的过程条件要求苛刻，否则容易导致织物表面出现斑点。聚氨酯能在织物表面进行覆盖，形成一层防水膜，但阻碍了织物的透气性，舒适感较差。而且聚氨酯的疏水性不是很高，防水性较差。其他类型的防水剂也存在类似问题，因此人们不断对上述类型的防水剂进行改性，以提高防水、透气、手感、耐洗等各项性能，希望尽量达到有机氟化物的防水水平，以减少或替代有机氟化合物的使用。
例如，日本专利EP0632157A1公开了一种丙烯酸酯和甲基丙烯酸酯与有机硅共聚的共聚物，该共聚物使用时以乙醇等为溶剂，使用后能赋予织物防水性及柔软的手感。
美国专利US3374100A公开了一种叔胺、蜡和多价金属盐的组合物乳液。经该乳液处理后的织物具有防水性。
美国专利US3432319A公开了一种以甲基纤维素为乳化剂的石蜡乳液，主要用于纤维板材的防水防潮。
美国专利US7354458B2公开了一种蜡、聚氨酯和乳化剂的组合物乳液。该乳液能赋予织物防水性能。
美国专利WO2013057303A公开了一种由三聚氰胺、甲醛和烷醇制备的交联剂树脂，该树脂能与热敏性底材反应从而赋予底材一定的防水性。
出于环保和操作的便捷性考虑，织物防水剂通常被加工成水乳液，这就需要在防水剂的结构中引入亲水基团或是使用有亲水性的外加乳化剂，从而导致最终产品的防水性下降。因此，常常需要筛选出多种适合主体防水物质的乳化剂，进行合理搭配，发挥协同作用，在保证乳液稳定性的同时保证防水性能。本发明采用了一种阳离子改性的长碳链氨基树脂，该树脂与其他阳离子及非离子乳化剂搭配使用能显著提高本发明涉及乳液的稳定性。
发明内容
本发明目的在于提供一种织物用无氟防水整理乳液及其应用。
为实现上述目的，本发明采用技术方案为：
一种织物用无氟防水整理乳液，无氟防水整理乳液组分按重量份数计(干物质组分)：a)80-40份长碳链改性的氨基树脂、b)1-8份阳离子改性的长碳链氨基树脂、c)1-10份长碳链羧酸的金属络合物、d)10-55份蜡、e)0.05-3份阳离子乳化剂、f)0.01-2份非离子乳化剂和g)0.001-1.5份有机酸或无机酸。
所述无氟防水整理乳液中固含量为20-40wt％，优选为30-40％，更优选为40％。
所述组分a)长碳链改性的氨基树脂为六羟甲基三聚氰胺或六羟甲基三聚氰胺的短碳链醇醚化物与脂肪族长碳链醇、脂肪族长碳链羧酸或脂肪族长碳链N-羟甲基酰胺反应获得。
进一步的说是由1mol六羟甲基三聚氰胺或者其短碳链醇醚化物与6mol长碳链醇或羧酸、羟甲基酰胺反应获得，得到的产物可为长碳链醚、酯或酰胺。这类物质由于结构的外围分布着大量疏水基团，所以具有良好的防水性。
现以六羟甲基三聚氰胺或者其短碳链醇醚化物与长碳链醇反应制备组分a)为例，反应式如下：
基团R1为H或C1-C8烷基，优选碳数为C1-C4烷基，R2为C12-C40烷基、C12-C40烯基或C12-C40炔基，优选碳数为C12-C22烷基、C12-C22烯基或C12-C22炔基。
组分a长碳链改性的氨基树脂由1mol六羟甲基三聚氰胺或者其短碳链醇醚化物与6mol长碳链醇或羧酸、羟甲基酰胺反应获得，得到的产物可为长碳链醚、酯或酰胺。上述短碳链醇一般指碳数小于4的脂肪醇，使用最多的为甲醇。由于三聚氰胺上的>N(CH2OH)2基团活性较高，羟甲基三聚氰胺单体间容易发生交联，所以该反应最好使用短碳链醚化的羟甲基三聚氰胺。制备过程为：将短碳链醚化的羟甲基三聚氰胺与长碳链醚或羧酸、羟甲基酰胺混合，加热融化，加入0.1-0.5％盐酸或硫酸等作催化剂，升温到90℃反应1.5h，再升温到140℃反应2小时，反应过程中始终加真空脱除低沸物。所得产物即为组分a。值得注意的是，当使用羟甲基酰胺与短碳链醚化的羟甲基三聚氰胺反应时，反应较为剧烈，且由于物料粘稠，体系在真空减压时容易冲料，应小心控制真空度。
所述组分b)阳离子改性的长碳链氨基树脂是由六羟甲基三聚氰胺或六羟甲基三聚氰胺短碳链醇醚化物与季铵盐或叔胺反应后再与脂肪族长碳链醇或脂肪族长碳链羧酸或脂肪族长碳链N-羟甲基酰胺反应制得。
进一步的说，由1mol六羟甲基三聚氰胺或者其短碳链醇醚化物与5mol长碳链醇(或羧酸、羟甲基酰胺等)和1mol带一个羟基的季铵盐或叔胺反应制得。该化合物由于主体结构与组分a相似，其疏水部分能很好的嵌入组分a中，亲水基则伸入水相，从而具有一定的表面活性作用。
现以六羟甲基三聚氰胺或者其短碳链醇醚化物与长碳链醇和带羟乙基的季铵盐反应制备组分b)为例，反应式如下：
制备过程为：将1mol短碳链醚化的羟甲基三聚氰胺与1mol带羟基的季铵盐或叔胺混合，加热融化，加入0.1-0.5％盐酸或硫酸等作催化剂，升温到90℃反应1.5h，再加入5mol长碳链醚或羧酸、羟甲基酰胺，继续于90℃反应2h，反应过程中始终加真空脱除低沸物。所得产物即为组分b。
上述反应式中季铵盐的负离子为Cl-，季铵盐的负离子除氯离子外还可以是溴离子、硫酸甲酯基等。
上述反应式中所列举的例子为六羟甲基三聚氰胺或者其短碳链醇醚化物与长碳链醇和带羟乙基的季铵盐反应制备组分b，而使用六羟甲基三聚氰胺或者其短碳链醇醚化物与长碳链醇和带羟乙基的叔胺反应制备组分b的过程和原理与使用季铵盐时相同，不再重复描述。
所述六羟甲基三聚氰胺的短碳链醇醚化物为六羟甲基三聚氰胺与C1-C8的脂肪醇反应获得；
所述脂肪族长碳链醇、脂肪族长碳链羧酸或脂肪族长碳链N-羟甲基酰胺所含碳数均为C12-C20，优选C12-C18。如月桂醇、十八醇、棕榈酸、油酸、N-羟甲基十八酰胺等。
所述季铵盐或叔胺的结构中分别含有一个羟基、一个松香类基团；或一个羟基和C12-C20的脂肪族长碳链。
其中，松香类基团包括松香酸基团和脱氢松香胺基团
其中，松香酸基团的典型结构为：
由于松香是多种树脂酸的混合物，上述结构只是松香中的主要成分松香酸的结构，实际使用的松香类表面活性剂还包括松香树脂中的其他组分，如左旋海松酸、长叶松酸、脱氢松酸、新枞酸、二氢松酸、四氢松酸等。
脱氢松香胺的典型结构为：
同样，脱氢松香胺也包括由松香树脂中其他组分制得的脱氢松香胺。
所述含松香类基团的季铵盐为Ⅰ所示的季铵盐或式Ⅱ所示季铵盐
式Ⅰ
式中，R8,R9＝C1-C20烷基、R6为松香酸基团；
式Ⅱ
式中，R8,R9＝C1-C20烷基、R7为脱氢松香胺基团；
所述含松香类基团的叔胺为Ⅲ所示的叔胺或式Ⅳ所示叔胺，
式Ⅲ
式中，R8＝C1-C20烷基、R6为松香酸基团；
式Ⅳ
式中，R8＝C1-C20烷基、R7为脱氢松香胺基团。
上述反应过程中适合的含一个羟基的直链脂肪烃基季铵盐或叔胺的例子有N,N-二甲基-N-羟乙基-N-十八烷基硫酸甲酯铵，N-甲基-N-羟乙基-N,N-双十八烷基硫酸甲酯铵，N-甲基-N-羟乙基-N-十八烷基胺，N-甲基-N-羟乙基-N-十四烷基胺，N,N-双十八烷基-N-羟乙基胺，N,N-双十二烷基-N-羟乙基胺。
上述反应过程中适合的含一个羟基和松香类基团的季铵盐的例子有N,N-二甲基-N-羟乙基-N-松香酸羧甲氧甲基氯化铵，N,N-二甲基-N-羟乙基-N-脱氢松香基氯化铵。适合的含一个羟基和松香类基团的叔胺的例子有N-甲基-N-羟乙基-N-松香酸羧甲氧甲基胺，N-甲基-N-羟乙基-N-脱氢松香基胺。
所述组分c)长碳链羧酸金属络合物为(RCOO)nM，其中，R为C12-C20直链脂肪族羧酸或C12-C20的含有1-3个不饱和双键或三键的羧酸，n为1-4，M为金属离子。
进一步的说，组分c长碳链羧酸金属络合物，为碳数C12-C20直链脂肪族羧酸或含1-3个不饱和双键或三键的羧酸，优选碳数为C12-C18的直链脂肪族羧酸或含1-3个不饱和双键或三键的羧酸，上述羧酸与Ca2+、Mg2+、Al3+、Zr4+、Ba2+等金属离子的水溶性盐形成的络合物，可选用的金属盐有氯化钙、氯化镁、氯化铝、氯化钡、醋酸锆、硫酸镁、硫酸铝等，优选的金属盐为氯化钙、硫酸铝和醋酸锆，更优选的为硫酸铝和醋酸锆。可使用的羧酸金属络合物的例子有硬脂酸钙、硬脂酸铝、硬脂酸镁、硬脂酸锆、油酸镁、油酸铝、油酸锆等，优选硬脂酸铝和硬脂酸锆。
所述组分d)中的蜡为熔点在40-85℃的蜡中的一种或几种的混合。
进一步的说，组分d为熔点在40-85℃的蜡，优选50-75℃，更有选为50-65℃。可选用的天然动植物性蜡包括但不限于小烛树蜡、巴西棕榈蜡、白虫蜡、鲸蜡、蜂蜡等。石蜡可选用精炼或半精炼石蜡。适合的蜡组分还包括微晶蜡、聚乙烯蜡等合成蜡。优选的蜡为精炼石蜡和微晶蜡，更优选的为精炼石蜡。
乳液制备过程中使用的乳化剂有阳离子乳化剂(e)和非离子乳化剂(f)，它们同组分b一起混合使用能很好的稳定乳液。
所述组分e)中的阳离子乳化剂为C8-C20季铵盐型阳离子乳化剂优选碳数为C16-C18的长碳链，其中，季铵盐的负离子为氯离子或硫酸甲酯基；组分f)中的非离子乳化剂为C8-C20的聚氧乙烯醚、吐温和司盘。
所述阳离子乳化剂可选用为椰油基三甲基氯化铵、十四烷基三甲基氯化铵、十六烷基三甲基氯化铵、十八烷基三甲基氯化铵、十四烷基苄基二甲基氯化铵、双十八烷基二甲基氯化铵、棕榈羧乙基羟乙基硫酸甲酯铵、月桂酰丙基三甲基硫酸甲酯铵、二硬脂酰乙基二甲基氯化铵、丙撑基-双(十八烷基二甲基)二铵、三鲸脂基甲基氯化铵、双十八烷基聚氧乙烯基双季铵盐等。
所述非离子乳化剂为长碳链起始的聚氧乙烯醚、吐温和司盘等。聚氧乙烯醚的长碳链端碳数为C8-C20，优选C12-C18；聚合的乙氧基数为3-20，优选3-15，更优选为5-12。可选择的聚氧乙烯醚的例子有AEO-10、硬脂酸聚氧乙烯(15)醚、蓖麻油酸聚氧乙烯(20)醚、异构醇聚氧乙烯(10)醚等。
本专利制备的防水剂乳液pH范围在4-6，可使用无机酸或有机酸调节pH。无机酸可选择盐酸、硫酸、磷酸、亚磷酸等。有机酸可选择甲酸、乙酸、柠檬酸等。优选有机弱酸，如乙酸。
乳化时先将所有物料混合，加热到约95℃，然后加入95℃左右的水，用高速分散机分散均匀，使粒径小于1μ，再在75-85℃下用高压均质机处理，得到粒径约400nm的稳定乳液。为使乳液颗粒足够小，高速分散机工作时的圆周线速度不小于15m/s，高压均质机工作压力不小于800bar。
一种织物用无氟防水整理乳液的应用，其特征在于：所述乳液在作为混纺织物、人造板材或造纸的制备过程中防水剂的应用。适用于涤纶、棉、酯及各种混纺织物、人造板材或造纸的防水整理，防水性能优异。本发明所具有的优点：
本发明乳液在三聚氰胺分子中引入长碳链疏水基，起到防水的作用。同时在三聚氰胺分子中引入少量阳离子结构，目的是在保证防水性的同时保证防水剂可以顺利乳化且乳液存储稳定。
本发明无氟防水乳液，包括以蜡和长碳链改性氨基树脂为主的防水组分，与长碳链改性氨基树脂结构类似并带有阳离子亲水基团的氨基树脂、季铵盐和非离子表面活性剂，以及其他辅助成分等。本发明防水乳液中包含一种长碳链改性的阳离子氨基树脂，该树脂主体结构与具有防水性能的长碳链改性氨基树脂相似，不同点在于引入了阳离子的亲水基。引入了阳离子亲水基的氨基树脂能与原氨基树脂很好的相融，对乳液的稳定性有很大的帮助。本发明采用阳离子改性的长碳链氨基树脂，该树脂与其他阳离子及非离子乳化剂搭配使用能显著提高本发明涉及乳液的稳定性。进而本发明组合物适用于涤纶、棉、酯及各种混纺织物、人造板材或造纸的防水整理，初次防水性能优异。本发明制备的乳液与聚氨酯乳液配合使用还能提供多次洗涤防水性。
具体实施方式
下面结合实施例对本发明作进一步的解释说明。
实施例1.
合成组分a1：在一500mL四口烧瓶中投入39g，0.1mol六甲氧基亚甲基三聚氰胺和162g，0.6mol十八醇，加热使物料融化，再加入0.4g浓盐酸，继续升温到90℃。当体系开始有回流时，加真空蒸出甲醇。在90℃反应1.5h后升温到140℃反应2小时，产物为无色透明的粘稠物，冷却后为蜡状固体。
实施例2.
合成组分a2：在一500mL四口烧瓶中投入39g，0.1mol六甲氧基亚甲基三聚氰胺和170g，0.6mol十八酸，加热使物料融化，再加入0.4g浓盐酸，继续升温到90℃。当体系开始有回流时，加真空蒸出甲醇。在90℃反应1.5h后升温到140℃反应2小时，产物为无色透明的粘稠物，冷却后为蜡状固体。
实施例3.
合成组分a3：在一500mL四口烧瓶中投入39g，0.1mol六甲氧基亚甲基三聚氰胺和188g，0.6mol十八醇，加热使物料融化，再加入0.4g浓盐酸，继续升温到90℃。当体系开始有回流时，加真空蒸出甲醇，注意控制真空度防止冲料。在90℃反应1.5h后升温到140℃反应2小时，产物为淡黄色色透明的粘稠物，冷却后为蜡状固体。
实施例4.
合成组分b1：在一250mL四口烧瓶中投入18g，0.05mol六甲氧基亚甲基三聚氰胺和22.5g，0.05molN,N-二甲基-N-羟乙基-N-松香酸羧甲氧甲基氯化铵，加热使物料融化，再加入0.4g浓盐酸，继续升温到90℃反应1.5h，再加入67.5g，0.25mol十八醇，继续于90℃反应2h。反应在开始有回流后加真空脱除低沸物。产物为无色透明的粘稠物，冷却后为蜡状固体。
实施例5.
合成组分b2：在一250mL四口烧瓶中投入18g，0.05mol六甲氧基亚甲基三聚氰胺和22.6g，0.05mol N,N-二甲基-N-羟乙基-N-十八烷基硫酸甲酯铵，加热使物料融化，再加入0.4g浓盐酸，继续升温到90℃反应1.5h，再加入67.5g，0.25mol十八醇，继续于90℃反应2h。反应在开始有回流后加真空脱除低沸物。产物为无色透明的粘稠物，冷却后为蜡状固体。
实施例6.
合成组分b3：在一250mL四口烧瓶中投入18g，0.05mol六甲氧基亚甲基三聚氰胺和13.5g，0.05mol N-甲基-N-羟乙基-N-十四烷基胺，加热使物料融化，再加入0.4g浓盐酸，继续升温到90℃反应1.5h，再加入67.5g，0.25mol十八醇，继续于90℃反应2h。反应在开始有回流后加真空脱除低沸物。产物为无色透明的粘稠物，冷却后为蜡状固体。
实施例7-例17.
本发明提供了多种乳液制备实例，部分实例列于表1中。
表1.实施例7-17
1631：十六烷基三甲基氯化铵，D1821：双十八烷基二甲基氯化铵，TC-90：三鲸脂基甲基氯化铵，E1310：异构十三醇聚氧乙烯(10)醚
*：乳液在2300G离心15min后固体分离率
织物防水整理过程：使用去离子水将乳液稀释到1％浓度，将织物浸渍在工作液中，轧去多余液体，上液率60％左右。轧好的布料在100-120℃烘60-120s，然后在160℃烘60-120s。根据GB/T 4745-2012沾水法评价织物经防水乳液处理后的防水性能(参见表2)。
表2.处理后织物的初次防水性
从上述实验数据可以看出，添加了阳离子改性三聚氰胺的乳液比不添加的乳液更稳定，乳液在2300G时离心15min的固体分离率明显降低。而且通过不同物质间的合理搭配，乳液的防水性能没有影响。
实施例18-19
本发明提供的防水乳液能为织物提供良好的初次防水性能，可满足不需化学清洗剂洗涤的防水应用。但经本发明制备的防水乳液处理后的布料的洗涤防水性较差，为提高洗涤防水性，可将乳液与阳离子或非离子型聚氨酯乳液复配使用，能显著提高织物的洗涤防水性。通常聚氨酯乳液的用量占复合整理剂的5-20％。以下实施例中使用的聚氨酯乳液为上海雅运纺织助剂有限公司提供的FP-BA，用量为10％。表3.为添加聚氨酯前后织物防水性能比较。
表3.添加聚氨酯前后织物防水性能比较
IN SR：初次防水，5HL IR SR：5次家用洗涤熨平
从表3中数据可以看出，本发明提供的防水乳液与聚氨酯乳液复配使用能显著提高织物的洗涤防水性，尤其对于聚酯类织物效果更明显。
Claims (10)
1.一种织物用无氟防水整理乳液，其特征在于：无氟防水整理乳液组分按重量份数计(干物质组分)：a)80-40份长碳链改性的氨基树脂、b)1-8份阳离子改性的长碳链氨基树脂、c)1-10份长碳链羧酸的金属络合物、d)10-55份蜡、e)0.05-3份阳离子乳化剂、f)0.01-2份非离子乳化剂和g)0.001-1.5份有机酸或无机酸。
2.按权利要求1所述的织物用无氟防水整理乳液，其特征在于：所述无氟防水整理乳液中固含量为20-40wt％。
3.按权利要求1所述的织物用无氟防水整理乳液，其特征在于：所述组分a)长碳链改性的氨基树脂为六羟甲基三聚氰胺或六羟甲基三聚氰胺的短碳链醇醚化物与脂肪族长碳链醇、脂肪族长碳链羧酸或脂肪族长碳链N-羟甲基酰胺反应获得。
4.按权利要求1所述的织物用无氟防水整理乳液，其特征在于：所述组分b)阳离子改性的长碳链氨基树脂是由六羟甲基三聚氰胺或六羟甲基三聚氰胺短碳链醇醚化物与季铵盐或叔胺反应后再与脂肪族长碳链醇或脂肪族长碳链羧酸或脂肪族长碳链N-羟甲基酰胺反应制得。
5.按权利要求3或4所述的织物用无氟防水整理乳液，其特征在于：所述六羟甲基三聚氰胺的短碳链醇醚化物为六羟甲基三聚氰胺与C1-C8的脂肪醇反应获得；
所述脂肪族长碳链醇、脂肪族长碳链羧酸或脂肪族长碳链N-羟甲基酰胺所含碳数均为C12-C20。
6.按权利要求4所述的织物用无氟防水整理乳液，其特征在于：所述季铵盐或叔胺的结构中分别含有一个羟基、一个松香类基团；或一个羟基和C12-C20的脂肪族长碳链。
7.按权利要求6所述的织物无氟防水整理乳液，其特征在于：所述含松香类基团的季铵盐为Ⅰ所示的季铵盐或式Ⅱ所示季铵盐
式Ⅰ
式中，R8,R9＝C1-C20烷基、R6为松香酸基团；
式Ⅱ
式中，R8,R9＝C1-C20烷基、R7为脱氢松香胺基团；
所述含松香类基团的叔胺为Ⅲ所示的叔胺或式Ⅳ所示叔胺，
式Ⅲ
式中，R8＝C1-C20烷基、R6为松香酸基团；
式Ⅳ
式中，R8＝C1-C20烷基、R7为脱氢松香胺基团。
8.按权利要求1所述的织物用无氟防水整理乳液，其特征在于：所述组分c)长碳链羧酸金属络合物为(RCOO)nM，其中，R为C12-C20直链脂肪族羧酸或C12-C20的含有1-3个不饱和双键或三键的羧酸，n为1-4，M为金属离子。
9.按权利要求1所述的织物用无氟防水整理乳液，其特征在于：所述组分e)中的阳离子乳化剂为C8-C20季铵盐型阳离子乳化剂，其中，季铵盐的负离子为氯离子或硫酸甲酯基；组分f)中的非离子乳化剂为C8-C20的聚氧乙烯醚、吐温和司盘。
10.一种权利要求1所述的织物用无氟防水整理乳液的应用，其特征在于：所述乳液在作为混纺织物、人造板材或造纸的制备过程中防水剂的应用。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108560275A (zh) * | 2018-06-22 | 2018-09-21 | 深圳市骏鼎达新材料股份有限公司 | 应用于航空高温环境的线束保护套管及制备方法 |
| CN112400044A (zh) * | 2018-07-18 | 2021-02-23 | 普莱玛有限公司 | 透气抗流体静力结构 |
| CN114318939A (zh) * | 2022-01-17 | 2022-04-12 | 佛山市桥通化工科技有限公司 | 一种疏水防水乳液及其制备方法 |
| CN114960199A (zh) * | 2021-07-07 | 2022-08-30 | 上海允继化工新材料有限公司 | 一种纺织品用无氟防水剂及其制备方法 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060135678A1 (en) * | 2004-12-16 | 2006-06-22 | Atsuya Kato | Aqueous amino resin dispersions and thermosetting water-based paint compositions |
| CN101724116A (zh) * | 2009-12-08 | 2010-06-09 | 南京工业大学 | 一种聚合物乳液及其制备方法 |
| CN105671970A (zh) * | 2016-03-16 | 2016-06-15 | 广州恒锦化工科技有限公司 | 纺织品用无氟防水剂及其制备方法 |
| CN106810650A (zh) * | 2017-01-20 | 2017-06-09 | 北京中纺化工股份有限公司 | 一种具有立体硅烷结构的无氟防水剂及其制备方法 |
| CN107011534A (zh) * | 2017-03-14 | 2017-08-04 | 华南理工大学 | 一种超疏水超亲油三聚氰胺泡沫及其制备方法与应用 |
-
2017
- 2017-12-08 CN CN201711292001.8A patent/CN107974826B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060135678A1 (en) * | 2004-12-16 | 2006-06-22 | Atsuya Kato | Aqueous amino resin dispersions and thermosetting water-based paint compositions |
| CN101724116A (zh) * | 2009-12-08 | 2010-06-09 | 南京工业大学 | 一种聚合物乳液及其制备方法 |
| CN105671970A (zh) * | 2016-03-16 | 2016-06-15 | 广州恒锦化工科技有限公司 | 纺织品用无氟防水剂及其制备方法 |
| CN106810650A (zh) * | 2017-01-20 | 2017-06-09 | 北京中纺化工股份有限公司 | 一种具有立体硅烷结构的无氟防水剂及其制备方法 |
| CN107011534A (zh) * | 2017-03-14 | 2017-08-04 | 华南理工大学 | 一种超疏水超亲油三聚氰胺泡沫及其制备方法与应用 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108560275A (zh) * | 2018-06-22 | 2018-09-21 | 深圳市骏鼎达新材料股份有限公司 | 应用于航空高温环境的线束保护套管及制备方法 |
| CN108560275B (zh) * | 2018-06-22 | 2024-03-19 | 深圳市骏鼎达新材料股份有限公司 | 应用于航空高温环境的线束保护套管及制备方法 |
| CN112400044A (zh) * | 2018-07-18 | 2021-02-23 | 普莱玛有限公司 | 透气抗流体静力结构 |
| CN114960199A (zh) * | 2021-07-07 | 2022-08-30 | 上海允继化工新材料有限公司 | 一种纺织品用无氟防水剂及其制备方法 |
| CN114960199B (zh) * | 2021-07-07 | 2023-11-03 | 上海允继化工新材料有限公司 | 一种纺织品用无氟防水剂及其制备方法 |
| CN114318939A (zh) * | 2022-01-17 | 2022-04-12 | 佛山市桥通化工科技有限公司 | 一种疏水防水乳液及其制备方法 |
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