TWI686439B - 不含氟之拒水性組成物 - Google Patents

不含氟之拒水性組成物 Download PDF

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TWI686439B
TWI686439B TW104121331A TW104121331A TWI686439B TW I686439 B TWI686439 B TW I686439B TW 104121331 A TW104121331 A TW 104121331A TW 104121331 A TW104121331 A TW 104121331A TW I686439 B TWI686439 B TW I686439B
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isomers
composition
weight
substrate
monomer
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TW104121331A
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TW201638194A (zh
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沃夫根 克內普
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瑞士商亞克羅瑪智財公司
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Abstract

一種組成物，包含至少組份(A)和(B)及任意地組份(C)至(E)中之至少一者：
(A)組份之聚合反應中得到的聚丙烯酸酯
(M1)CH2=CR3COO-R1和
(M2)CH2=CR3COO-R2和任意地
(M3)CH2=CR3-X-R4；
(B)蠟
(C)嵌段的異氰酸酯
(D)有機聚矽氧烷
(E)三聚氰胺樹脂
其中R1是1至8個碳原子的殘基；R2是含9至40個碳原子的殘基；R3=H、CH3、C2H5；X=COO、CONH； R4=環氧丙基或CH2(CH2)n-OR5，其中n是範圍1-10中的整數，且R5是H或含1至6個碳原子的殘基；以及其中該組成物係基於水和/或有機溶劑且係不含氟。

Description

不含氟之拒水性組成物
本發明係關於一種組成物，其含有由兩種不同的(甲基)丙烯酸酯所製成的聚丙烯酸酯、烷烴蠟(paraffin wax)、及選自嵌段的異氰酸酯、聚矽氧烷和三聚氰胺樹脂之任意的其他組份，係關於製造此組成物之方法，以此組成物處理基材(例如織品)以賦予該基材疏水性(即，拒水性)之方法，及該經處理的基材。該組成物係以不含氟的水性分散液提供。
已知以含水分散液處理紡織品(例如梭織品、針織品或非梭織品)以提供彼等所欲性質。此所欲性質是，例如，拒水效果，即，疏水效果。為了得到織品的拒水性，常使用含氟產物的水性分散液。但是，此含氟的分散液伴隨對環境有害的影響。
為避免使用此環境有害物質，曾建議使用不含氟的組成物提供基材(如織品)疏水性。
DE 10 2013 209 170係關於包含至少矽聚合物 和蠟之組成物。
EP 2 411 575係關於不含氟或N-羥甲基化合物之水性分散液，其包含(甲基)丙烯酸烷酯、苯乙烯或α-甲基苯乙烯、偏二氯乙烯和/或氯乙烯和任意的(甲基)丙烯酸3-氯-2-羥基丙酯和/或(甲基)丙烯酸環氧丙酯之共聚物、熔點範圍為58-80℃的烷烴蠟、和分散劑(較佳地為陽離子性分散劑或陽離子性和非離子性分散劑之混合物)。
EP 1 899 391係關於聚合物稀釋劑(polymer extender)組成物，其包含經共聚的單體，其中該單體選自各種(甲基)丙烯酸酯、(甲基)丙烯酸醯胺、偏二氯乙烯、氯乙烯、乙酸乙烯酯、或其混合物。
EP 1 485 533係關於以水和/或有機溶劑為底之製劑及其作為紡織品上的塗料之用途。該製劑包含以蠟為底的疏水性組份，及藉組份與未經保護或經部分保護的二-、三-或聚異氰酸酯之反應而製得的反應產物。
EP 2 152 957係關於以水和/或有機溶劑為底之不含氟的組成物及其於織物應用之用途，其基於藉組份與未經保護或經部分保護的二-、三-或聚異氰酸酯之反應而製得的反應產物、及含C8-C28-烷基的有機聚矽氧烷。
EP 1 424 433係關於包含正烷烴(n-paraffin)和以丙烯酸或甲基丙烯酸的C1-12酯為底的丙烯酸系聚合物之含水系統。
發明目的
本發明的目的係提供賦予基材(如織品)耐久的拒水性且對環境無害之組成物。
發明概述
以包含至少組份(A)和(B)之不含氟的組成物達到此目的，其中組份(A)係聚合兩種不同的(甲基)丙烯酸酯而得到的聚丙烯酸酯，而組份(B)係蠟，並包含水和/或有機溶劑。
據此，第一態樣中，本發明係關於組成物，其包含至少組份(A)和(B)及任意地組份(C)至(E)中之至少一者：(A)單體之聚合反應中得到的聚丙烯酸酯(M1)CH2=CR3COO-R1和(M2)CH2=CR3COO-R2和任意地(M3)CH2=CR3-X-R4；(B)蠟；(C)嵌段的異氰酸酯；(D)有機聚矽氧烷；(E)三聚氰胺樹脂；其中R1是單體(M1)中之含1至8個碳原子的醇部分；R2是單體(M2)中之含9至40個碳原子的醇部分；R3是H、CH3、或C2H5； X是COO或CONH；R4是環氧丙基或CH2(CH2)n-OR5，其中n是範圍1-10中的整數，且R5是H或含1至6個碳原子的殘基；及其中該組成物係基於水和/或有機溶劑且係不含氟。
一個實施態樣中，R1含1至6個碳原子，R2含12至40個碳原子。
進一步的實施態樣中，R1是支鏈或非支鏈或環狀C1-C6烷基，且R2是支鏈或非支鏈或環狀C12-C40烷基。
進一步的實施態樣中，R1選自由下列所組成的群組中之一或多者：甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊基和其異構物、正己基和其異構物、環丙基、環丁基、環戊基、環己基；且R2選自由下列所組成的群組中之一或多者：正十二基(月桂基)和其異構物、正十三基和其異構物、正十四基(肉豆蔻基)和其異構物、正十五基和其異構物、正十六基(鯨蠟基)和其異構物、正十七基和其異構物、正十八基(硬脂基)和其異構物、正十九基和其異構物、正二十基和其異構物、正二十一基和其異構物、正二十二基(山萮基)(behenyl)和其異構物、正二十三基和其異構物、正二十四基和其異構物、正二十五基和其異構物、正二十六基(蠟 基)和其異構物、正二十七基和其異構物、正二十八基和其異構物、正二十九基和其異構物、正三十基(蜜蠟基)和其異構物。
進一步的實施態樣中，(A)係基於(A)總量(=100重量%)，在5至45重量%單體(M1)與55至95重量%單體(M2)之聚合反應中得到；或基於(A)總量(=100重量%)，在5至44重量%單體(M1)與55至94重量%單體(M2)和0.1至20重量%(M3)之聚合反應中得到。
進一步的實施態樣中，該蠟具有在50至130℃或60至90℃範圍內的熔點。
進一步的實施態樣中，該蠟係烷烴蠟。
進一步的實施態樣中，該組成物包含5-90重量%(A)；5-90重量%(B)；0-40重量%(C)；0-40重量%(D)；0-40重量%(E)；0.1-90重量%水和/或有機溶劑；此係基於組成物總量(=100重量%)。
進一步的實施態樣中，該組成物另含有包含了兩性結構的組份(例如甜菜鹼和/或胺N-氧化物(組份F))。
進一步的實施態樣中，該組成物包含5-90重量%(A)； 5-90重量%(B)；0-40重量%(C)；0-40重量%(D)；0-40重量%(E)；0.1-90重量%水和/或有機溶劑；0.1至3重量%包含了兩性結構的組份[組份(F)]；此係基於組成物總量(=100重量%)。
進一步的實施態樣中，該組成物不含有包含N-羥甲基或氯基之化合物。
第二態樣中，本發明係關於一種製造先前申請專利範圍任一項中定義之組成物之方法，其至少包含步驟(C1)至(C2)：(C1)令至少包含單體(M1)和(M2)、和組份(B)、及水和/或有機溶劑之混合物均質化；(C2)聚合步驟(C1)中得到的混合物。
第三態樣中，本發明係關於一種處理基材之方法，其至少包含步驟(S1)：(S1)令基材與第一態樣或文中揭示的任何實施態樣定義之組成物接觸，或令基材與根據第二態樣中定義之方法製得的組成物接觸。
一個實施態樣中，基材係紡織品、纖維、織品、紙、非梭織品、皮革、或其中二或更多者之組合。
一個實施態樣中，本發明係關於第一態樣中定義之組成物用於或作為任何紡織品的修整劑之用途，其 中該紡織品為線性形成形式(例如細線和絲)、平面形成形式(例如織物、針織品、網羅織物、非梭織物、毛氈)、或立體形成形式(例如軟管及供女性、男性和孩童用的外衣)。
進一步的實施態樣中，本發明係關於蠟之用途，以蠟總量計(=100重量%)，該蠟包含下列者或由下列者所組成：75至95重量%正烷烴(n-paraffin)和5至25重量%異烷烴(isoparaffin)和/或環烷烴(cycloparaffin)和/或芳族化合物，其中該正烷烴具20至60個碳原子，較佳地，其中該正烷烴具有300至600的分子量；其用於或作為任何紡織品(線性形成形式(如細線和絲)、平面形成形式(如織物、針織品、網羅織物、非梭織物、毛氈)、或立體形成形式(如軟管及女性、男性和孩童的外衣))的修整物。
第四態樣中，本發明係關於一種基材，其至少包含第一態樣中定義之組份(A)和(B)。
一個實施態樣中，基材是或經第三態樣中定義之方法處理。
一個實施態樣中，該基材為線性形成形式(如細線和絲)、平面形成形式(如織物、針織品、網羅織物(knotted fabric)、非梭織物(non-woven fabric)、毛氈)、或立體形成形式(如軟管及女性、男性和孩童的外衣)；或該基材係紡織品、纖維、織品、紙、非梭織品、皮革、或其中的二或更多者之組合。
第一態樣：根據本發明之組成物
第一態樣中，本發明係關於一種組成物，其包含至少組份(A)和(B)及任意地組份(C)至(E)中之至少一者：(A)單體之聚合反應中得到的聚丙烯酸酯(M1)CH2=CR3COO-R1和(M2)CH2=CR3COO-R2和任意地(M3)CH2=CR3-X-R4；(B)蠟；(C)嵌段的異氰酸酯；(D)有機聚矽氧烷；(E)三聚氰胺樹脂；其中R1是含1至8個碳原子的殘基；R2是含9至40個碳原子的殘基；R3是H、CH3、或C2H5；X是COO或CONH；R4是環氧丙基或CH2(CH2)n-OR5，其中n是範圍1-10中的整數，且R5是H或含1至6個碳原子的殘基；以及其中該組成物係基於水和/或有機溶劑且係不含氟。
組份(A)
組份(A)係單體(M1)與單體(M2)之聚合反應所得的反應產物。任意地，可另利用單體(M3)於單體(M1)和(M2)。
“單體(M1)與單體(M2)及任意的單體(M3)之聚合反應中得到的聚丙烯酸酯”是指該聚丙烯酸酯[組份(A)]包含自單體(M1)和單體(M2)及任意的單體(M3)衍生的部分或者由彼所組成(下文中，括弧中的所有詞彙定義為本發明之中之意義)。
單體(M1)和(M2)係彼此不同的丙烯酸酯。“彼此不同”是指(M1)和(M2)至少構成單體的酯部分不相同。
單體(M1)
根據本發明，單體(M1)係丙烯酸酯CH2=CR3COO-R1，其中R1代表含1至8個碳原子的殘基。R3選自由下列組成的群組：H、CH3或C2H5。
單體(M1)定義中所用的“殘基”是指酯或單體(M1)的醇部分。
一個實施態樣中，R1係飽和或不飽和的支鏈或非支鏈或環狀C1-C8烷基。
較佳地，R1選自由下列組成的群組：甲基、乙基、正丙基、異丙基、正丁基、二級丁基、異丁基、三級丁基、正戊基和其異構物、正己基和其異構物、正庚基 和其異構物、正辛基和其異構物、環丙基、環丁基、環戊基、環己基、環庚基和環辛基。
亦可以使用不同單體(M1)之混合物。
與R1相關之“異構物”涵蓋位置異構物。
一個實施態樣中，R1代表殘基，即，酯的醇部分，其含1至6個碳原子。
一個實施態樣中，R1係支鏈或非支鏈或環狀C1至C6烷基，其係飽和或不飽和。
較佳地，R1選自由下列組成的群組中之一或多者：甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊基和其異構物、正己基和其異構物、環丙基、環丁基、環戊基、環己基。
單體(M2)
根據本發明，單體(M2)係丙烯酸酯CH2=CR3COO-R2，其中R2代表殘基，即，酯的醇部分，含有9至40個碳原子。R3選自由下列組成的群組：H、CH3或C2H5。
單體(M2)定義中所用的“殘基”是指酯或單體(M2)的醇部分。
一個實施態樣中，R2是支鏈或非支鏈或環狀C9至C40烷基，其係飽和或不飽和。
較佳地，R2選自由下列組成的群組中之一或多者：正壬基和其異構物、正癸基和其異構物、正十一基 和其異構物、正十二基(月桂基)和其異構物、正十三基和其異構物、正十四基(肉豆蔻基)和其異構物、正十五基和其異構物、正十六基(鯨蠟基)和其異構物、正十七基和其異構物、正十八基(硬脂基)和其異構物、正十九基和其異構物、正二十基和其異構物、正二十一基和其異構物、正二十二基(山萮基)和其異構物、正二十三基和其異構物、正二十四基和其異構物、正二十五基和其異構物、正二十六基(蠟基)和其異構物、正二十七基和其異構物、正二十八基和其異構物、正二十九基和其異構物、正三十基(蜜蠟基)和其異構物。
亦可施用不同單體(M2)之混合物。
與R2相關之“異構物”涵蓋位置異構物。
一個實施態樣中，R2代表殘基，即，酯的醇部分，其含12至40個碳原子。
一個實施態樣中，R2是飽和或不飽和的支鏈或非支鏈或環狀C12至C40烷基。
較佳地，R2選自由下列組成的群組中之一或多者：正十二基(月桂基)和其異構物、正十三基和其異構物、正十四基(肉豆蔻基)和其異構物、正十五基和其異構物、正十六基(鯨蠟基)和其異構物、正十七基和其異構物、正十八基(硬脂基)和其異構物、正十九基和其異構物、正二十基和其異構物、正二十一基和其異構物、正二十二基(山萮基)和其異構物、正二十三基和其異構物、正二十四基和其異構物、正二十五基和其異構物、正二十六 基(蠟基)和其異構物、正二十七基和其異構物、正二十八基和其異構物、正二十九基和其異構物、正三十基(蜜蠟基)和其異構物。
一個實施態樣中，單體(M1)中的R1係支鏈或非支鏈或環狀C1至C6烷基，R2係飽和或未飽和的支鏈或非支鏈或環狀C12至C40烷基。
較佳地，R1選自由下列組成的群組中之一或多者：甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊基和其異構物、正己基和其異構物、環丙基、環丁基、環戊基、環己基；R2選自正十二烷基(月桂基)和其異構物、正十三烷基和其異構物、正十四烷基(肉豆蔻基)和其異構物、正十五烷基和其異構物、正十六烷基(鯨蠟基)和其異構物、正十七烷基和其異構物、正十八烷基(硬脂基)和其異構物、正十九烷基和其異構物、正二十烷基和其異構物、正二十一烷基和其異構物、正二十二烷基(山萮基)和其異構物、正二十三烷基和其異構物、正二十四烷基和其異構物、正二十五烷基和其異構物、正二十六烷基(蠟基)和其異構物、正二十七烷基和其異構物、正二十八烷基和其異構物、正二十九烷基和其異構物、正三十烷基(蜜蠟基)和其異構物。
一個實施態樣中，單體(M1)中的R1係支鏈或非支鏈或環狀C1至C5烷基，R2係飽和或不飽和的支鏈或非支鏈或環狀C14至C40烷基。
較佳地，R1選自由下列組成的群組中之一或 多者：甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊基和其異構物、環丙基、環丁基、環戊基；R2選自由下列組成的群組：正十四烷基(肉豆蔻基)和其異構物、正十五烷基和其異構物、正十六烷基(鯨蠟基)和其異構物、正十七烷基和其異構物、正十八烷基(硬脂基)和其異構物、正十九烷基和其異構物、正二十烷基和其異構物、正二十一烷基和其異構物、正二十二烷基(山萮基)和其異構物、正二十三烷基和其異構物、正二十四烷基和其異構物、正二十五烷基和其異構物、正二十六烷基(蠟基)和其異構物、正二十七烷基和其異構物、正二十八烷基和其異構物、正二十九烷基和其異構物、正三十烷基(蜜蠟基)和其異構物。
根據本發明之組成物中，聚丙烯酸酯(A)較佳地得自5至45重量%單體(M1)與55至95重量%單體(M2)之聚合反應，此以(A)總量(=100重量%)計；或得自20至40重量%單體(M1)與60至80重量%單體(M2)之聚合反應，此以(A)總量(=100重量%)計。
單體(M3)
根據本發明，此組成物可以在單體(M3)(其為單體CH2=CR3-X-R4)存在下製得。
一個實施態樣中，單體(M3)是丙烯酸的環氧丙酯(X=COO，R4=環氧丙基)。
另一實施態樣中，單體(M3)是丙烯酸酯，其 中酯部分帶有醚基(X=COO，R4=CH2(CH2)n-OR5)，其中n是範圍1至10的整數，R5是H或含1至6個碳原子的殘基，較佳地為支鏈或非支鏈或環狀烷基。較佳地，n由範圍1至4且R5是H或1至4個碳原子的殘基，較佳地為支鏈或非支鏈或環狀烷基。
一個較佳的實施態樣中，若R4=CH2(CH2)n-OR5，則n是範圍1至4的整數且R5是H或正丁基或異丁基。
一個實施態樣中，單體(M3)是(甲基)丙烯酸羥乙酯。“(甲基)丙烯酸酯”涵蓋丙烯酸酯和甲基丙烯酸酯二者。
另一實施態樣中，單體(M3)是丙烯酸醯胺的環氧丙酯(X=CONH，R4=環氧丙基)。
另一實施態樣中，單體(M3)是丙烯酸醯胺的酯，其中酯部分帶有醚基(X=CONH，R4=CH2(CH2)n-OR5，其中n是1至10的整數，R5是H或含1至6個碳原子的殘基，較佳地為支鏈或非支鏈或環狀烷基。較佳地，n由1至4，R5是H或含1至4個碳原子的殘基，較佳地為支鏈或非支鏈或環狀烷基。
亦可施用不同單體(M3)之混合物。
在丙烯酸酯或丙烯酸醯胺的較佳實施態樣中，若R4=CH2(CH2)n-OR5，則n是1至4的整數，R5是H或正丁基或異丁基。
帶環氧丙基的單體(M3)可賦予帶有會與該環 氧丙基反應之基團(如羥基或胺基)的基材提高的黏著性。
若單體(M3)存在，則(A)較佳地得自5至44重量%單體(M1)與55至94重量%單體(M2)和0.1至20重量%(M3)之聚合反應，此以(A)總量(=100重量%)計。
組份(B)
根據本發明，組份(B)是蠟，較佳地，具疏水性(如拒水性)的蠟。
基本上，所有已知的蠟可用於根據本發明之組成物，即，天然蠟、經化學改質的蠟和合成蠟，只要其具有疏水性即可。此處所謂“蠟”是指期刊“Römpp Chemielexikon,9th edition,vol.6,4972頁中指出的定義。
據此，天然蠟可基於植物蠟、動物蠟、礦物蠟、石化蠟。
植物蠟係如棕櫚蠟，動物蠟係如蜂蠟。
礦物蠟係如地蠟。
亦可使用石化蠟，如礦脂、烷烴蠟和微晶蠟。
經化學改質的蠟係蠟，如褐煤酯蠟和sasol蠟。
合成蠟係基於聚伸烷和聚伸乙二醇的蠟。
較佳實施態樣中，選用的蠟具有在50至100℃，更佳60至90℃，又更佳60至80℃範圍內的熔點。此熔點係根據ASTM D 938-05/DIN ISO 2207：1983測定。
包含沸點範圍低於50℃的蠟之根據本發明之組成物有時較不適合提供待以根據本發明之含水分散液處理的織品拒水性。熔點範圍高於100℃的蠟會使得織品得到可接受的拒水性和耐洗性，但會導致含水分散液的黏度提高，使得這些分散液技術上較不易操作。因此，基本上，熔點在100至130℃範圍內的蠟亦適用於根據本發明之組成物中。
因此，通常，根據成分(B)之蠟的熔點可在50至130℃的範圍內。
較佳地，此蠟是烷烴蠟。
烷烴蠟係含有具20至60個碳原子的正烷烴作為主要組份和含有少量異烷烴和/或環烷烴和/或芳族化合物之混合物。正烷烴較佳地具有300至600的分子量。
分子量係使用凝膠穿透層析法測定。正烷烴、異烷烴、環烷烴和芳族化合物之分佈可使用13C NMR光譜術定出。
一個實施態樣中，蠟包含75至95重量%正烷烴和5至25重量%異烷烴和/或環烷烴和/或芳族化合物，或由以上者所組成，此基於蠟總量(=100重量%)。
如，具68℃至74℃之熔點範圍的烷烴蠟可為市售品(CAS No.8002-74-2)。
此適當的蠟可為市售品，如Sasolwax 8775、Sasolwax 7040、Sasolwax 3971、Sasolwax 6805、或Sasolwax 2222。
組份(C)(任意的)
根據本發明，組成物可以任意地含有嵌段或部分嵌段的異氰酸酯。
所謂“嵌段的異氰酸酯”含括單-、二-或聚異氰酸酯，其中異氰酸酯基已與嵌段劑反應，於加熱時釋出異氰酸酯和嵌段劑。適當的嵌段劑為此技術中已知者，如胺、醯胺、具有活性氫原子的化合物或醇。若該加熱在具有能夠與該異氰酸酯基反應的官能基(如適當基材(如纖維)的羥基或胺基)的化合物存在下進行，則可得到改良的黏著性。
據此，存在於根據本發明之組成物中之嵌段的異氰酸酯，特別是嵌段的聚異氰酸酯，會賦予與帶有基團(如可與該嵌段的異氰酸酯反應的胺或羥基)的基材提高的黏著性。
組分(C)存在量可由0至40重量%，以此組成物總量(=100重量%)計。
此適當之嵌段的異氰酸酯可為市售品，如Arkophob DAN、Arkophob SR、和Cassurit FF(皆Archroma)；Phobol XAN(Huntsman)和Ruco-Guard WEB(Rudolf)。
組份(D)(任意的)
根據本發明，組成物可任意地含有有機聚矽 氧烷樹脂。
所謂“有機聚矽氧烷”涵蓋化合物，其中帶有烷基或芳基之矽原子的至少一部分可經取代。此聚矽氧烷可為環狀、直鏈或支鏈。
可以使用此技術中已知提供基材拒水性的任何有機聚矽氧烷樹脂。適當產品由如DE 10 2013 209 170和EP 2 152 957得知。
組份(D)存在量可由0至40重量%，以此組成物總量(=100重量%)計。
此聚矽氧烷調合物為市售品，如Ceraperm SFC(Archroma)、Powersoft FE 55或Wacker Finish WR 210(皆德國Wacker Chemie)。
組份(E)(任意的)
根據本發明，組成物可任意地含有三聚氰胺樹脂。
適當的三聚氰胺樹脂係例如三聚氰胺部分中的胺基的氫原子經CH2O-烷基或CH2O2C-烷基部分或完全取代之樹脂。此產品自例如US 3 480 579得知。
其他適當的三聚氰胺樹脂係三聚氰胺部分的胺基的氫原子經飽和或不飽和的直鏈、支鏈和/或環狀烴部分或完全取代之樹脂。此產品自例如DE 10 2013 209 170得知。
組份(D)存在量可由0至40重量%，以此組成 物總量(=100重量%)計。
含此適當的三聚氰胺樹脂之調合物可為市售品，例如Cerol EX(Archroma)或Freepel 1225(Emerald Performance Materials)或Phobotex JVA(Huntsmsn)。此三聚氰胺樹脂可包括例如組份(B)之烷烴蠟。
水和/或有機溶劑
根據本發明，組成物係基於水和/或有機溶劑。
“基於水和/或有機溶劑”涵蓋組成物中所含固體和/或液體化合物在水和/或有機溶劑中之溶液、乳液和分散液。“溶液”、“乳液”和“分散液”可交替使用。
“水”涵蓋蒸餾水和自來水。
“有機溶劑”較佳地涵蓋與水互溶或與部分溶於水的溶劑。較佳之與水互溶的有機溶劑係C1-2醇、二醇(例如乙二醇和丙二醇、二丙二醇或聚乙二醇)、醯胺(例如N-甲基甲醯胺和N,N-二甲基甲醯胺)。
部分水溶性溶劑亦適用。較佳的有機溶劑係二丙二醇二甲醚、乙酸甲氧基丙酯(methoxy propyl acetate)、乙酸甲氧基丁酯(丁氧基)(methoxy butyl acetate(butoxyl))、和乙酸甲氧基甲基丁酯(methoxy methyl butyl acetate)。
較佳地，根據本發明之組成物主要基於水。所謂“主要”是指有機溶劑量低於50重量%，此以水和有機 溶劑總重(=100重量%)計。較佳實施態樣中，有機溶劑量低於40重量%；更佳地低於30重量%，又更佳地低於20重量%；又更佳地低於10重量%。一個實施態樣中，組成物不含有機溶劑。
根據本發明之組成物含有0.1至90重量%水和/或有機溶劑，此分別以組成物總量(=100重量%)計。
一個實施態樣中，組成物包含5至90重量%(A)；5至90重量%(B)；0至40重量%(C)；0至40重量%(D)；0至40重量%(E)；和0.1至90重量%水和/或有機溶劑，此係基於組成物總量(=100重量%)。
一個實施態樣中，根據本發明之含水組成物的固體含量係在10至50重量%，較佳地20至40重量%且更佳地25至35重量%的範圍內，此以組成物總重(=100重量%)計。
不含氟
“不含氟”是指組成物製自不含氟的組份。
此外，一個實施態樣中，欲儘可能提供對環境無害的組成物，根據本發明之組成物不含有常用以賦予基材拒水性的以下化合物中之一或多者：N-羥甲基化合物，如N-羥甲基丙烯醯胺或帶有N-羥甲基的三聚氰胺樹脂，此由於N-羥甲基化合物具有會在常壓(特別是於提高的溫度)中釋出所不欲量的甲醛的缺點之故；常用以製備拒水組成物的含氯產物，特別是自單體(如氯乙烯或偏二 氯乙烯)衍生者。
據此，較佳的實施態樣中，根據本發明之組成物不含有具N-羥甲基或氯基的化合物。
組份(A)至(E)為此技術已知者或可根據已知方法製得。
第二態樣：根據本發明之組成物之製備
根據本發明之組成物可藉由在水和/或有機溶劑中聚合單體(M1)和(M2)和任意的(M3)並摻混組份(B)而製得。該聚合反應亦可在組份(B)存在時進行。必要時，可添加已知作為織品處理組成物中之組份的其他組份(C)至(E)中之一或多者，此較佳地於聚合反應終了之後進行。
較佳實施態樣中，根據本發明之組成物可藉由使單體(M1)和(M2)及任意的(M3)在組份(B)存在下在水和/或有機溶劑中聚合而製得。必要時，可添加一或多種已知作為織品處理組成物之組份的其他組份(C)至(E)，此較佳地於聚合反應終了之後進行。
較佳實施態樣中，聚合反應之前，使(M1)和(M2)及任意的(M3)和組份(B)之混合物在水和/或有機溶劑中均質化。下文中，以實例解釋此方法：蠟(組份(B))及單體(M1)和(M2)及任意的單體(M3)熔化，較佳地在分散劑(組份(F))存在下進行。所得混合物藉攪拌(例如使用Turrax)而分散於熱水(例如85℃的熱水)中。之後藉高壓均質化，例如於400巴和80至85℃ 的溫度。此處，所得經加熱的混合物通過均化器的噴觜或孔。適當裝置為此技術已知者。均質化之後，分散液經冷卻並添加聚合反應觸媒，較佳地分散或溶於水中：分散液亦可於提高溫度(例如80℃)聚合。於例如50℃至80℃的數小時反應時間之後，中止聚合反應。
適當的分散劑(組份(F))為已知者且可選自市售品(例如非離子性界面活性劑)、乙氧化的產品(例如乙氧化的醇或乙氧化的羧酸)。市售陽離子性活性產品可為四級銨鹽或與此陽離子性活性產品和非離子性產品(例如單-或二丙二醇)之混合物。其他適當的分散劑係具兩性結構(例如具甜菜鹼和/或胺N-氧化物官能性)之化合物。
根據本發明之組成物較佳地含有0.1至3重量%，較佳由0.5至3重量%的分散劑或分散劑混合物，此以組成物總量(=100重量%)計。
通常，共聚反應係藉由使用聚合反應觸媒以自由基共聚反應進行。使用一般已知的市售品作為自由基聚合反應的觸媒，其作為自由基引發劑。本發明中，尤其，使用偶氮化合物作為觸媒。適當觸媒係例如2,2’-偶氮基雙(2-脒基丙烷)二氯化氫。
聚合反應觸媒用量可在0.1至5重量%的範圍內，此以單體(M1)和(M2)及任意的(M3)之混合物(=100重量%)計，較佳地為2.5至5重量%。
據此，本發明係關於製造第一態樣中定義之組成物之方法，其包含： (C1)令至少包含單體(M1)和(M2)和任意的(M3)、和組份(B)、及水和/或有機溶劑之混合物均質化；(C2)聚合步驟(C1)中得到的混合物。
較佳地，均質化處理係在100至1,000巴的壓力範圍內和50至100℃的溫度範圍內，較佳地藉由令混合物通過噴嘴或孔的方式進行。
較佳地，均質化處理係在200至600巴的壓力範圍內和60至90℃的溫度範圍內進行。
適當的均質化器為此技術中已知者。
第三態樣：根據本發明之組成物之用途
根據本發明之組成物特別可用於賦予基材拒水性。
“拒水性”定義纖維、絲或織品的耐潤濕特性，此如AATCC Test Method 11-2010中之定義。
據此，本發明係關於一種處理基材之方法，其至少包含步驟(S1)：(S1)令基材與第一態樣中定義之組成物接觸，或令基材與第二態樣中定義之方法製得的組成物接觸。
所謂“處理基材”涵蓋例如“修整基材”、“賦予基材疏水性”、“使得基材拒水”、“使得基材耐髒污”或“塗覆基材”。
基材之接觸可藉一般慣用的方法進行，例如 將基材浸泡或浸漬於根據本發明之組成物中，或將根據本發明之組成物噴在基材上，或藉刷施用或以海綿施用或經由強制施用或藉萃出法。接觸之後，已接觸的基材可經乾燥，及，適當時，在140℃至190℃的溫度範圍內固化。於低或甚至常態固化條件下，意謂於低於100℃或甚至於低至50℃的溫度，可達到極佳效能。
較佳地，此基材係紡織品、纖維、織品、紙、非梭織品、皮革、或其中的二或更多者之組合。
此紡織品較佳地製自棉、聚酯、或棉/聚酯混紡物、聚醯胺、聚醯亞胺、聚苯硫醚、芳醯胺、聚氯乙烯、聚丙烯腈、聚乙酸乙烯酯、聚四氟乙烯、聚乙烯、聚丙烯、聚胺甲酸酯、彈性紗、碳纖維、矽酸鹽纖維、玻璃纖維、玄武岩纖維、金屬纖維、或其中的二或更多者之混合物。此紡織品通常為梭織品、針織品或非梭織品。
據此，通常，根據本發明之組成物可作為基材(例如紡織品)的修整劑或修整劑。較佳地，此基材以線性形成形式、平面形成形式、或立體形成形式提供。
所謂“修整物”或“修整劑”涵蓋可賦予基材拒水性之組成物。修整劑可以在清洗基材之前或之後施用於基材。
一個實施態樣中，根據本發明之組成物可用於任何紡織品(=基材)或作為用於任何紡織品(=基材)之修整劑。此紡織品可為線性形成形式(例如細線和絲)、平面形成形式(例如織物、針織品、網羅織物、非梭織物、毛 氈)、或立體形成形式(例如軟管及供女性、男性和孩童用的外衣)。
一個實施態樣中，本發明係關於一種包含75至95重量%之正烷烴和5至25重量%之異烷烴和/或環烷烴和/或芳族化合物或由其組成的蠟之用途，其係以蠟的總重計，其中該正烷烴具20至60個碳原子，較佳地，其中該正烷烴具有300至600的分子量，該蠟係用於或作為任何紡織品的修整劑。較佳地，此基材以線性形成形式、平面形成形式、或立體形成形式提供。
所謂“線性形成”、“平面形成”和“立體形成”為紡織工業已知者。
根據本發明之組成物亦可施用作為待清洗的外衣的修整劑。
第四態樣中，本發明係關於一種基材，其至少包含第一態樣中定義之組份(A)和(B)。
一個實施態樣中，該基材係經或已經第三態樣中定義之方法處理。
實例 實例#1至#9：根據本發明之組成物之製備
5g甲基丙烯酸三級丁酯和15g丙烯酸硬脂酯加至4.8g Genapol ID 100(脂肪醇乙氧化物(Clariant))和0.4g鯨蠟基三甲基氯化銨於10g二丙二醇和120g水之 約80℃的熱混合物中並藉攪拌分散。在獨立槽中，40g烷烴蠟(熔化範圍68至74℃)熔化。上述單體分散液加至熔融的烷烴蠟中。進一步分散2分鐘之後，混合物藉Manton-Gaulin均質化設備(於400巴，85℃)二度均質化，直到得到安定的乳液。溫度維持介於75至80℃，添加稀釋於1.8g水中的0.2g 2,2’-偶氮基雙(2-甲基丙脒)二氯化氫引發劑(Wako V-50)，此混合物於75℃在N2下以有護套的回流冷凝管處理6小時。此得到約200g產物，其固體含量約33重量%(藉由於120℃/2小時乾燥測得)。
類似於實例#1中描述的方法，其他單體組合和烷烴蠟類型用以製造安定分散液。細節示於表1：
Figure 104121331-A0202-12-0026-1
 (t-BuMA=甲基丙烯酸三級丁酯；i-BuMA=甲基丙烯酸異丁酯；MMA=甲基丙烯酸甲酯；HexAC=丙烯酸己酯；SA=丙烯酸硬脂酯；BeMA=丙烯酸山萮酯；LA=丙烯酸月桂酯；HEMA=甲基丙烯酸羥乙酯；GMA=甲基丙烯酸環氧丙酯；HBAC=丙烯酸羥丁酯；烷烴蠟：Sasolwax 8775)
實例#10：此實例描述紡織品以實例#1至#9製得之分散液進行之處理
梭織100%聚酯織品(100g/m2)和梭織100%棉織品(200g/m2)經處理。棉織品在軋雜機(pad-mangle)中以含1g/l醋酸、20g/l纖維素交聯劑及50g/l和70g/l實例#1至#9之分散液之液體處理。液體的典型重量攝入(pick-up)為80%。聚酯織品以含有1g/l醋酸、1g/l潤濕劑、及40g/l和60g/l實例#1至#9的分散液之液體軋染。典型重量攝入為60%。軋染之後，織品於160℃乾燥3分鐘。
實例#10之經修整的織品進行AATCC 22-2010,ISO 4920(EN 24920)的噴水試驗，此於原始(初始)和於40℃的10次清洗循環之後(DIN ISO 6330)進行。清洗循環之後，織品在噴霧試驗之前經顛動乾燥。典型顛動乾燥溫度60-65℃達30分鐘。根據噴灑試驗分級表，等級100是指織品面不發黏或沒有被潤濕，等級90是指織品面輕微隨機發黏或潤濕，等級80是指織品面於噴灑點被潤濕，等級70是指噴灑點上方處的織品面被部分潤濕，而等級50是指織品面完全被潤濕。
聚酯
Figure 104121331-A0202-12-0027-2
棉
Figure 104121331-A0202-12-0028-3
實例顯示，在聚酯上，即使於低添加量，甚至於清洗後亦有極佳的拒水和拒油效果。用於棉，達到極佳的初始效果。
藉由添加額外的交聯劑(如Cassurit FF)，在聚酯上、但特別是在棉織品上的拒水效果之耐久性，獲進一步改良。
棉
Figure 104121331-A0202-12-0028-4
聚酯
Figure 104121331-A0202-12-0029-5
在施用浸液中添加20g/l三聚氰胺樹脂調合物(例如Cerol EX或Freepel 1225)，拒水效果的耐久性獲得類似的改良。
儘管經實例#1至#9的調合物處理的織品已提供良好手感，有時仍希望賦予經處理的織品特別佳的柔軟手感。藉由在施用浸液中另外添加基於有機聚矽氧烷的柔軟劑調合物(例如Ceraperm SFC)，可達到此目的。
聚酯
Figure 104121331-A0202-12-0029-7
除了極柔軟的舒適手感以外，達到極佳的初始和耐久拒水性。

Claims (15)

  1. 一種組成物，包含至少組份(A)和(B)及任意地組份(C)至(E)中之至少一者：(A)單體之聚合反應中得到的聚丙烯酸酯(M1)CH2=CR3COO-R1和(M2)CH2=CR3COO-R2和任意地(M3)CH2=CR3-X-R4；(B)蠟；(C)嵌段的異氰酸酯；(D)有機聚矽氧烷；(E)三聚氰胺樹脂；其中R1是單體(M1)中之含1至8個碳原子的醇部分；R2是單體(M2)中之含9至40個碳原子的醇部分；R3是H、CH3、或C2H5；X是COO或CONH；R4是環氧丙基或CH2(CH2)n-OR5，其中n是範圍1-10中的整數，且R5是H或含1至6個碳原子的殘基；以及其中該組成物係基於水和/或有機溶劑且係不含氟以及不含含氯產物。
  2. 如申請專利範圍第1項之組成物，其中R1含1至6個碳原子而R2含12至40個碳原子。
  3. 如申請專利範圍第1或2項之組成物，其中R1是支鏈或非支鏈或環狀C1-C6烷基，且R2是支鏈或非支鏈或環狀C12-C40烷基。
  4. 如申請專利範圍第1或2項之組成物，其中R1選自由下列所組成的群組中之一或多者：甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊基和其異構物、正己基和其異構物、環丙基、環丁基、環戊基、環己基；且R2選自由下列所組成的群組中之一或多者：正十二基(月桂基)和其異構物、正十三基和其異構物、正十四基(肉豆蔻基)和其異構物、正十五基和其異構物、正十六基(鯨蠟基)和其異構物、正十七基和其異構物、正十八基(硬脂基)和其異構物、正十九基和其異構物、正二十基和其異構物、正二十一基和其異構物、正二十二基(山萮基)(behenyl)和其異構物、正二十三基和其異構物、正二十四基和其異構物、正二十五基和其異構物、正二十六基(蠟基)和其異構物、正二十七基和其異構物、正二十八基和其異構物、正二十九基和其異構物、正三十基(蜜蠟基)和其異構物。
  5. 如申請專利範圍第1或2項之組成物，其中(A)係基於(A)總量(=100重量%)，在5至45重量%單體(M1)與55至95重量%單體(M2)之聚合反應中得到；或基於(A)總量(=100重量%)，在5至44重量%單體(M1)與55至94重量%單體(M2)和0.1至20重量%(M3)之聚合反應中得到。
  6. 如申請專利範圍第1或2項之組成物，其中該蠟具有在50至130℃或60至90℃範圍內的熔點。
  7. 如申請專利範圍第1或2項之組成物，其中該蠟係烷烴蠟(paraffin wax)。
  8. 如申請專利範圍第1或2項之組成物，其中該組成物包含5-90重量%(A)；5-90重量%(B)；0-40重量%(C)；0-40重量%(D)；0-40重量%(E)；0.1-90重量%水和/或有機溶劑；此係基於該組成物總重(=100重量%)。
  9. 如申請專利範圍第1或2項之組成物，其中該組成物不含有包含N-羥甲基或氯基之化合物。
  10. 一種製造如申請專利範圍第1至9項中任一項之組成物之方法，其至少包含步驟(C1)至(C2)：(C1)令至少包含單體(M1)和(M2)、和組份(B)、及水和/或有機溶劑之混合物均質化；(C2)聚合步驟(C1)中得到的該混合物。
  11. 一種處理基材之方法，其至少包含步驟(S1)：(S1)令基材與如申請專利範圍第1至9項中任一項之組成物接觸，或令基材與如申請專利範圍第10項之方法製得的該組成物接觸。
  12. 一種基材，其至少包含如申請專利範圍第1項之組份(A)和(B)。
  13. 如申請專利範圍第12項之基材，其藉如申請專利範圍第11項之方法處理。
  14. 如申請專利範圍第12或13項之基材，其中該基材為絲、織物、針織品、網羅織物(knotted fabric)、非梭織物(non-woven fabric)、毛氈、紡織品、纖維、織品、紙、非梭織品、皮革、或其中的二或更多者之組合。
  15. 一種如申請專利範圍第11項之方法獲得之基材，其中該基材為絲、織物、針織品、網羅織物(knotted fabric)、非梭織物(non-woven fabric)、毛氈、紡織品、纖維、織品、紙、非梭織品、皮革、或其中的二或更多者之組合。
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