TWI688601B - 含氟的斥水性組成物 - Google Patents

含氟的斥水性組成物 Download PDF

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TWI688601B
TWI688601B TW104121332A TW104121332A TWI688601B TW I688601 B TWI688601 B TW I688601B TW 104121332 A TW104121332 A TW 104121332A TW 104121332 A TW104121332 A TW 104121332A TW I688601 B TWI688601 B TW I688601B
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isomers
weight
composition
monomer
substrate
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TW201627383A (zh
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沃夫根 克內普
華彩 加薩芬馬丁
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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，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)由下列單體之聚合反應所得到的聚丙烯酸酯(M1)CH2=CR3COO-R1，與(M2)CH2=CR3COO-R2，(M3)CH2=CR6COO-Y-RF，和任意地(M4)CH2=CR3-X-R4；(B)蠟；(C)封端的異氰酸酯；(D)有機聚矽氧烷；(E)三聚氰胺樹脂；其中R1 是(甲基)丙烯酸酯單體(M1)中之含1至8個碳原子的醇部分；R2 是(甲基)丙烯酸酯單體(M2)中之含9至40個碳 原子的醇部分；R3 是H、CH3、或C2H5；RF-Y 是(甲基)丙烯酸酯單體(M3)中的醇部分，其中Y 是-(CH2)m-，其中m是1至10的整數；RF是CxF2x+1，其中x是1至12，較佳地1至6，更佳地4至6，的整數；R6 是H、CH3、Cl或F；X 是COO或CONH；R4 是環氧丙基或CH2(CH2)n-OR5，其中n 是1-10的整數，R5 是H或含1至6個碳原子的殘基；且其中該組成物係基於水和/或有機溶劑。

Description

含氟的斥水性組成物
本發明係關於一種含氟組成物，其含有自至少三種不同的(甲基)丙烯酸酯(其中的一者係含氟的(甲基)丙烯酸酯)形成的聚丙烯酸酯、和烷烴蠟、及任意之選自封端的異氰酸酯、聚矽氧烷和三聚氰胺樹脂或其混合物的其他成份，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)以賦予拒水、拒油和拒髒污性之方法，及該經處理的基材。該組成物係基於水和/或有機溶劑。
已經知道以適當的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。為使織品得到拒水性，已經知道使用含氟產物的含水分散液。
EP 1 899 391係關於藉由混合稀釋組成物與氟化分散液而製得的含水分散液以賦予拒油、拒髒污和拒水性及其他表面效果。
EP 1 485 533 B1係關於基於水和/或有機溶劑 之製劑及其作為紡織品上的塗料之用途。此製劑可含有含三氟甲基的反應產物。
EP 1 424 433係關於自高碳乙烯酯之共聚物衍生的水載疏水性阻擋塗料。此塗料含有含氟的界面活性劑。
US 2007/0009663係關於聚合物延展組成物，其可與氟聚合物摻混以提供經處理的基材表面效果。
[發明目的]
在工業中，對於提供賦予基材(例如織品)持久的拒水性之組成物一直有需求存在。
[發明總論]
以一種組成物達到此目的，該組成物至少包含組份(A)和(B)，其中組份(A)係使至少三種不同的(甲基)丙烯酸酯(其中之一係含氟的(甲基)丙烯酸酯)聚合所得的聚丙烯酸酯，組份(B)係蠟，和水和/或有機溶劑。
據此，第一特點中，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)由下列單體之聚合反應所得到的聚丙烯酸酯(M1)CH2=CR3COO-R1，與(M2)CH2=CR3COO-R2，和 (M3)CH2=CR6COO-Y-RF，和任意地(M4)CH2=CR3-X-R4；(B)蠟；(C)封端的異氰酸酯；(D)有機聚矽氧烷；(E)三聚氰胺樹脂；其中R1 是(甲基)丙烯酸酯單體(M1)中之含1至8個碳原子的醇部分；R2 是(甲基)丙烯酸酯單體(M2)中之含9至40個碳原子的醇部分；RF-Y 是(甲基)丙烯酸酯單體(M3)中的醇部分，其中Y 是-(CH2)m-，其中m是1至10的整數；和RF 是CxF2x+1，其中x是1至12，較佳地1至6，更佳地4至6，的整數；R6 選自H、CH3、Cl或F；單體(M1)、(M2)和(M4)中的R3係獨立地選自H、CH3、或C2H5；單體(M4)中的X是COO或CONH；單體(M4)中的R4是環氧丙基或CH2(CH2)n-OR5，其中n 是1-10的整數，R5 是H或含1至6個碳原子的殘基；且其中該組成物係基於水和/或有機溶劑。
一個具體實施例中，R1含1至6個碳原子， 而R2含12至40個碳原子。
其他具體實施例中，R1是支鏈或非支鏈或環狀C1-C6烷基，R2是支鏈或非支鏈或環狀C12-C40烷基。
其他具體實施例中，R1是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是選自由下列組成的群組中之一或多者：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。
一個具體實施例中，(A)係得自下列的聚合反應：5至40重量%單體(M1)；30至85重量%單體(M2)；和1至50重量%單體(M3)；和任意地0.1至20重量%單體(M4)； 以(A)總重(=100重量%)計。
另一具體實施例中，(A)係得自下列的聚合反應：5至30重量%單體(M1)；30至70重量%單體(M2)；5至40重量%單體(M3)；和任意地0.1至10重量%單體(M4)；以(A)總重(=100重量%)計。
其他具體實施例中，蠟(B)具有在50至130℃，較佳地60至90℃範圍內的熔點。
其他具體實施例中，蠟(B)係烷烴蠟。
其他具體實施例中，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)；0.1至90重量%水和/或有機溶劑；此係基於組成物總重(=100重量%)。
其他具體實施例中，組成物另外包括包含兩性結構的組份(例如甜菜鹼和/或胺N-氧化物)[組份(F)]。
一個具體實施例中，該組成物包含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)；0.1至87重量%水和/或有機溶劑；0.1至3重量%包含兩性結構之組份[組份(F)]；此係基於組成物總重(=100重量%)。
第二特點中，本發明係關於一種製造如前述申請專利範圍中任一項定義之組成物的方法，其至少包含步驟(C1)至(C2)：(C1)令至少包含單體(M1)、(M2)、(M3)和蠟(B)、及水和/或有機溶劑之混合物均質化；(C2)使步驟(C1)中得到的混合物聚合。
第三特點中，本發明係關於一種處理基材之方法，其至少包含步驟(S1)：(S1)令基材與第一特點或文中揭示的任何具體實施例定義之組成物接觸，或令基材與根據第二特點中定義之方法製得的組成物接觸。
一個具體實施例中，所述基材係紡織品、纖維、織品、紙、非梭織品、皮革、或其中二或更多者之組合。
一個具體實施例中，本發明係關於第一特點中定義之組成物用於或作為任何紡織品的修整劑之用途，其中該紡織品是為線性形成形式(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)。
第四特點中，本發明係關於一種基材，其至少包含第一方面中定義之組份(A)和(B)。
一個具體實施例中，所述基材是經或者已經經第三特點中定義之方法處理。
一個具體實施例中，該基材為線性形成形式(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)；或其中該基材係紡織品、纖維、織品、紙、非梭織品、皮革、或其中二或更多者之組合。
本發明進一步係關於一種蠟(B)的用途，而該蠟包含以蠟的總重計75至95重量%之正烷烴和5至25重量%之異烷烴、環烷烴或芳族化合物中的一或多者或由其組成，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，而該紡織品是為線性形成形式(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)。
以下所有以引號標示的詞彙之定義係在本發 明中之意義內。
第一特點：根據本發明之組成物
第一特點中，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)由下列單體之聚合反應所得到的聚丙烯酸酯(M1)CH2=CR3COO-R1，與(M2)CH2=CR3COO-R2，和(M3)CH2=CR6COO-Y-RF；和任意地(M4)CH2=CR3-X-R4；(B)蠟；(C)封端的異氰酸酯；(D)有機聚矽氧烷；(E)三聚氰胺樹脂；其中R1 是(甲基)丙烯酸酯單體(M1)中之含1至8個碳原子的醇部分；R2 是(甲基)丙烯酸酯單體(M2)中之含9至40個碳原子的醇部分；RF-Y 是(甲基)丙烯酸酯單體(M3)中的醇部分，其中Y 是-(CH2)m-，其中m是1至10的整數；和RF 是CxF2x+1，其中x是1至12，較佳地1至6，更佳地4至6，的整數； R6 選自H、CH3、Cl或F；單體(M1)、(M2)和(M4)中的R3係獨立地選自H、CH3、或C2H5；單體(M4)中的X是COO或CONH；R4 是環氧丙基或CH2(CH2)n-OR5，其中n是1-10的整數，R5是H或含1至6個碳原子的殘基；且其中該組成物係基於水和/或有機溶劑。
用語“聚丙烯酸酯(A)係在單體(M1)與(M2)和(M3)及任意的(M4)之聚合反應中得到”是指聚丙烯酸酯(A)包含由單體(M1)、(M2)和(M3)及任意的(M4)衍生的部分或由彼所組成。
組份(A)
組份(A)係單體(M1)與單體(M2)和(M3)之聚合反應所得的反應產物。任意地，單體(M4)可額外地施用至單體(M1)、(M2)和(M3)。
單體(M1)和(M2)係彼此不同的丙烯酸酯。用語“彼此不同”是指(M1)和(M2)至少在單體的酯部分之組成不相同。
單體(M3)係全氟烷基丙烯酸酯。
用語“丙烯酸”涵蓋用語“甲基丙烯酸”。因此，用語“(甲基)丙烯酸”涵蓋丙烯酸或甲基丙烯酸二者。
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)定義中所用的用語“殘基”是指酯或單體(M1)的醇部分。
一個具體實施例中，R1係飽和或非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。
亦可以使用具有不同的單體(M1)之混合物。
與R1相關之用語“異構物”涵蓋位置異構物。
一個具體實施例中，R1代表含1至6個碳原子之殘基，即，酯的醇部分。
一個具體實施例中，R1係支鏈或非支鏈或環狀C1至C6烷基，其係飽和或未飽和。
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、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代表含有9至40個碳原子之殘基，即，酯的醇部分。R3選自由下列組成的群組：H、CH3或C2H5。
單體(M2)定義中所用的用語“殘基”是指酯或單體(M2)的醇部分。
一個具體實施例中，R2是支鏈或非支鏈或環狀C9至C40烷基，其係飽和或未飽和。
較佳地，R2選自由下列組成的群組：正壬基和其異構物、正癸基和其異構物、正十一烷基和其異構物、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。
亦可施用具有不同的單體(M2)之混合物。
與R2相關之用語“異構物”涵蓋位置異構物。
一個具體實施例中，R2代表含12至40個碳原子之殘基，即，酯的醇部分。
一個具體實施例中，R2是飽和或未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。
一個具體實施例中，單體(M1)中的R1係支鏈或非支鏈或環狀C1至C6烷基，單體(M2)中的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、環己基中之一或多者；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。
一個具體實施例中，單體(M1)中的R1係支鏈或非支鏈或環狀C1至C5烷基，單體(M2)中的R2係飽和或未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。
單體(M3)
根據本發明，單體(M3)係丙烯酸酯CH2=CR6COO-Y-RF，其中RF-Y代表殘基，即，酯的醇部分。此處，Y是-(CH2)m-，其中m是1至10的整數。RF是CxF2x+1，其中x是1至12，較佳地1至6，更佳地4至6，的整數。因此，RF-Y代表全氟烷基。
一個具體實施例中，CxF2x+1係支鏈。
另一具體實施例中，CxF2x+1非支鏈。
一個具體實施例中，x的範圍由1至12。
較佳具體實施例中，x的範圍由1至6。
更佳的具體實施例中，x是4、5或6。
更佳的具體實施例中，x=6。
R6選自H、CH3、Cl或F。
一個具體實施例中，可施用超過一種單體(M3)，即，二或更多種單體(M3)之混合物。
單體(M4)
根據本發明，組成物可在單體(M4)(其為單體CH2=CR3-X-R4)存在下製得。
一個具體實施例中，單體(M4)是丙烯酸的環氧丙酯(X=COO，R4=環氧丙基)。
另一具體實施例中，單體(M4)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是由 1至4，且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。
一個較佳的具體實施例中，若R4=CH2(CH2)n-OR5，則n是1至4的整數，且R5是H或正丁基或異丁基。
一個具體實施例中，單體(M4)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。
另一具體實施例中，單體(M4)是丙烯醯胺的環氧丙酯(X=CONH，R4=環氧丙基)。
另一具體實施例中，單體(M4)是丙烯醯胺的酯，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是由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。
亦可施用具有不同的單體(M4)之混合物。
在單體(M4)之丙烯酸酯或丙烯醯胺的較佳具體實施例中，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(M4)可賦予帶有能夠與該環氧丙基反應之基團(例如羥基或胺基)的基材提高的黏著性。
一個具體實施例中，(A)係得自下列的反應： 5至40重量%單體(M1)；30至85重量%單體(M2)；和1至50重量%單體(M3)；和任意地0.1至20重量%單體(M4)；以(A)總重(=100重量%)計。
另一具體實施例中，(A)係得自下列的反應：5至30重量%單體(M1)；30至70重量%單體(M2)；5至40重量%單體(M3)；和任意地0.1至10重量%單體(M4)；以(A)總重(=100重量%)計。
組份(B)
根據本發明，(B)是蠟，較佳地，具疏水性(例如拒水性)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。
此處用語“蠟”是指文獻“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。
植物蠟係例如棕櫚蠟，動物蠟係例如蜂蠟。
礦物蠟係例如地蠟。
亦可使用石化蠟，例如礦脂、烷烴蠟和微晶蠟。
經化學改質的蠟係蠟，例如褐煤酯蠟和sasol蠟。
合成蠟係基於聚伸烷和聚伸乙二醇的蠟。
較佳具體實施例中，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，根據組份(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。
一個具體實施例中，蠟包含75至95重量%之正烷烴和5至25重量%之異烷烴、環烷烴或芳族化合物中之一或多者，或由以上者所組成，此基於蠟總量(=100重量%)。
例如，具68℃至74℃之熔點範圍的烷烴蠟係市售品(CAS No.8002-74-2)。
此適當的蠟係市售品，例如Sasolwax 8775、Sasolwax 7040、Sasolwax 3971、Sasolwax 6805、或Sasolwax 2222。
一個具體實施例中，施用不同的蠟(B)之混合物。
組份(C)(選用)
根據本發明，組成物可任意地含有封端或部分封端的異氰酸酯。
用語“封端的異氰酸酯”涵蓋單-、二-和聚異氰酸酯，其中異氰酸酯基已與封端劑反應，於加熱時釋出異氰酸酯和封端劑。適當的封端劑為此技術中已知者，例如胺、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(例如適當基材(例如纖維)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 封端的異氰酸酯，特別是封端的聚異氰酸酯，會賦予帶有基團(例如可與該封端的異氰酸酯反應的胺或羥基)的基材提高的黏著性。
組份(C)存在量可由0至40重量%，以此組成物總量(=100重量%)計。
此適當之封端的異氰酸酯為市售品，例如Arkophob DAN、Arkophob SR、和Cassurit FF(皆Archroma)；Phobol XAN(Huntsman)和Ruco-Guard WEB(Rudolf)。
組份(D)(選用)
根據本發明，組成物可任意地含有有機聚矽氧烷樹脂。
用語“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。適當產品由例如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，例如Ceraperm SFC(Archroma)、Powersoft FE 55或Wacker Finish WR 210(皆得自德國Wacker Chemie)。
組份(E)(選用)
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未飽和的直鏈、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(E)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
一個具體實施例中，組成物係基於水和/或有機溶劑。
用語“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。用語“溶液”、“乳液”和“分散液”可交替使 用。
用語“水”涵蓋蒸餾水和自來水。
用語“有機溶劑”較佳地涵蓋與水互溶或與水部分互溶的溶劑。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、甲氧基乙酸丙酯、甲氧基乙酸丁酯(丁氧基)、和甲氧基甲基乙酸丁酯。
較佳地，根據本發明之組成物主要基於水。用語“主要”是指水和有機溶劑總重(=100重量%)計，有機溶劑量低於50重量%。較佳具體實施例中，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%。一個具體實施例中，組成物不含有機溶劑。
根據本發明之組成物以組成物總量(=100重量%)計可含有0.1至90重量%水和/或有機溶劑。
一個具體實施例中，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)；0.1至90重量%水和/或有機溶劑， 此係基於組成物總重(=100重量%)。
一個具體實施例中，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。
此外，一個具體實施例中，組成物可含有一或多種常用以賦予基材拒水性的以下化合物：N-羥甲基化合物，例如N-羥甲基丙烯醯胺或帶有N-羥甲基的三聚氰胺樹脂；含氯的產品，特別是自單體移除者，例如氯乙烯或偏二氯乙烯。
組份(A)至(E)為此技術已知者或可根據已知方法製造。
第二特點：根據本發明之組成物之製備
根據本發明之組成物可藉由使單體(M1)、(M2)和(M3)及任意的(M4)在水和/或有機溶劑中聚合及摻混組份(B)而製得。
該聚合反應亦可在組份(B)存在下進行。
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。
較佳具體實施例中，根據本發明之組成物可藉由使單體(M1)、(M2)和(M3)及任意的(M4)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。
較佳具體實施例中，聚合反應之前，使(M1)、(M2)和(M3)及任意的(M4)和組份(B)之混合物在水和/或有機溶劑中均質化。此方法舉例說明如下：蠟(B)和單體(M1)、(M2)和(M3)和任意的單體(M4)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400bar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)。市售陽離子性界面活性產品可為四級銨鹽或與此陽離子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以組成物總量(=100重量%)計，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。
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，以單體(M1)和(M2)和(M3)及任意的(M4)之混合物(=100重量%)計，可在0.1至5重量%的範圍內，較佳地為2.5至5重量%。
據此，一個具體實施例中，本發明係關於製造第一特點中定義之組成物之方法，其包含：(C1)令至少包含單體(M1)和(M2)及任意地(M3)和組份(B)、及水和/或有機溶劑之混合物均質化；(C2)使步驟(C1)中得到的混合物聚合。
較佳地，均質化處理係在100至1,000bar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600bar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。
第三特點：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、拒油和/或拒髒污性。
用語“拒水性”定義纖維、絲或織品的耐潤濕 特性，依據AATCC Test Method 11-2010中之定義。
用語“拒油性”定義纖維、絲或織品的耐烴特性，依據AATCC Test Method 118-2002中之定義。
用語“拒髒污性”定義纖維、絲或織品之耐髒污或釋出油的特性，依據AATCC Test Method 130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)令基材與第一特點中定義之組成物接觸，或令基材與第二特點中定義之方法製得的組成物接觸。
用語“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”等用語。
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。
用語“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。
一個具體實施例中，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)。
一個具體實施例中，本發明係關於一種蠟之用途，該蠟包含以蠟的總重計75至95重量%之正烷烴和5至25重量%之異烷烴、環烷烴或芳族化合物中的一或多者或由其組成，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。
用語“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。
第四特點中，本發明係關於一種基材，其至少包含第一特點中定義之組份(A)和(B)。
一個具體實施例中，該基材係經或已經經第三特點中定義之方法處理。
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丙烯酸硬脂酯和5g甲基丙烯酸2-全氟己基乙酯加至約80℃之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水的熱混合物中並攪拌分散。在另一槽中，將40g烷烴蠟(熔化範圍68至74℃)熔化。將上述單體分散液加至熔融烷烴蠟中。進一步分散2分鐘之後，混合物藉Manton-Gaulin均質化設備(於400bar，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)二鹽酸鹽引發劑(Wako V-50)，此混合物於75℃在N2下在有護套的回流冷凝管下處理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，使用其他單體組合和烷烴蠟類型以製造安定分散液。細節示於表1：
Figure 104121332-A0202-12-0028-1
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
處理梭織100%聚酯織品(100g/m2)和梭織100%棉織品(200g/m2)。
棉織品在軋雜機(pad-mangle)中以含1g/l醋酸、20g/l纖維素交聯劑和70g/l實例#1至#9之分散液之 液體處理。液體的典型攝入重量為80%。
聚酯織品以含有1g/l醋酸、1g/l潤濕劑、和40g/l實例#1至#9的分散液之液體軋染。典型攝入重量為60%。軋染之後，織品於160℃乾燥3分鐘。
實例#10之經修整的織品接受AATCC 22-2010,ISO 4920(EN 24920)的噴水試驗和AATCC Test Method 118-2002的拒油試驗，於原始(初始)和於40℃的10次清洗循環(DIN ISO 6330)之後進行試驗。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至65℃達30分鐘。
聚酯(噴水試驗/拒油試驗)
Figure 104121332-A0202-12-0029-2
棉(噴水試驗/拒油試驗)
Figure 104121332-A0202-12-0029-3
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。
藉由在施用浸液中添加額外的交聯劑(例如Cassurit FF)，在聚酯上，但特別是在棉織品上，拒水和拒油效果的持久性進一步獲得改良。
棉(噴水試驗/拒油試驗)
Figure 104121332-A0202-12-0030-4
聚酯(噴水試驗/拒油試驗)
Figure 104121332-A0202-12-0030-7
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)，拒水和拒油效果的持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(噴水試驗/拒油試驗)
Figure 104121332-A0202-12-0031-8
除了極柔軟的舒適手感以外，達到極佳的初始和耐久的拒水性和拒油性。

Claims (14)

  1. 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，其中該組成物包含：5至90重量%的(A)由單體之聚合反應所得到的聚丙烯酸酯，其中(A)係得自下列之聚合反應：5至40重量%的單體(M1)CH2=CR3COO-R1，30至85重量%的單體(M2)CH2=CR3COO-R2，1至50重量%的單體(M3)CH2=CR6COO-Y-RF，和任意地0.1至20重量%的單體(M4)CH2=CR3-X-R4；5至90重量%的(B)蠟，其中蠟(B)具有在50至130℃範圍內的熔點；0至40重量%的(C)封端的異氰酸酯；0至40重量%的(D)有機聚矽氧烷；0至40重量%的(E)三聚氰胺樹脂；及0.1至90重量%的水和/或有機溶劑；其中R1 是(甲基)丙烯酸酯單體(M1)中之含1至8個碳原子的醇部分；R2 是(甲基)丙烯酸酯單體(M2)中之含9至40個碳原子的醇部分；RF-Y 是(甲基)丙烯酸酯單體(M3)中的醇部分，其中Y 是-(CH2)m-，其中m是1至10的整數；和 RF 是CxF2x+1，其中x是1至12的整數；R6 選自H、CH3、Cl或F；單體(M1)、(M2)和(M4)中的R3係獨立地選自H、CH3、或C2H5；單體(M4)中的X是COO或CONH；R4 是環氧丙基或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；且其中該組成物係基於水和/或有機溶劑。
  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至C6烷基，R2是支鏈或非支鏈或環狀C12至C40烷基。
  4. 如申請專利範圍第3項之組成物，其中R1是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；及R2是選自由下列組成的群組中之一或多者：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。
  5. 如申請專利範圍第1項之組成物，其中(A)係得自下列的聚合反應：5至30重量%單體(M1)；30至70重量%單體(M2)；5至40重量%單體(M3)；和任意地0.1至10重量%單體(M4)，以(A)總重(=100重量%)計。
  6. 如申請專利範圍第1項之組成物，其中蠟(B)具有在60至90℃範圍內的熔點。
  7. 如申請專利範圍第1項之組成物，其中蠟(B)係烷烴蠟。
  8. 一種製造如申請專利範圍第1至7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)、(M2)、(M3)和蠟(B)、及水和/或有機溶劑之混合物均質化；(C2)使步驟(C1)中得到的混合物聚合。
  9. 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7項中任一項之組成物接觸，或令基材與由申請專利範圍第8項之方法製得的組成物接觸。
  10. 一種基材，其至少包含如申請專利範圍第1項中所定義之組成物中的組份(A)和(B)。
  11. 如申請專利範圍第10項之基材，其藉如申請專利範圍第9項之方法處理。
  12. 如申請專利範圍第10或11項之基材，其中該基材為線性形成形式、平面形成形式、或立體形成形式、或其中二或更多者之組合。
  13. 如申請專利範圍第9項之方法，其中該基材為線性形成形式、平面形成形式、或立體形成形式、或其中二或更多者之組合。
  14. 一種如申請專利範圍第1至7項中任一項之組成物或如申請專利範圍第8項之方法製得的組成物之用途，其用於或作為任何紡織品的修整劑，而該紡織品是為線性形成形式、平面形成形式、或立體形成形式。
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