TWI304450B - Aqueous dispersion of water-and oil-repelling agent - Google Patents
Aqueous dispersion of water-and oil-repelling agent Download PDFInfo
- Publication number
- TWI304450B TWI304450B TW093134063A TW93134063A TWI304450B TW I304450 B TWI304450 B TW I304450B TW 093134063 A TW093134063 A TW 093134063A TW 93134063 A TW93134063 A TW 93134063A TW I304450 B TWI304450 B TW I304450B
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- TW
- Taiwan
- Prior art keywords
- oil
- aqueous dispersion
- water
- compound
- repellent agent
- Prior art date
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- 150000007522 mineralic acids Chemical class 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- PFMBRNMAXCVTIV-UHFFFAOYSA-K trisodium hydrogen carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.OC([O-])=O.OC([O-])=O PFMBRNMAXCVTIV-UHFFFAOYSA-K 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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 a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/182—Monomers containing fluorine not covered by the groups C08F214/20 - C08F214/28
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/2243—Mono-, di-, or triglycerides
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
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- D06M2200/10—Repellency against liquids
- D06M2200/11—Oleophobic properties
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
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Description
1304450 九、發明說明: 【發明所屬之技術領域】 本發明係有關撥水撥油劑水性分散液,更詳而言之 係有關含有捕捉氯之化合物。 【先前技術】 已知具有全氟烷基或全氟烯基及丙烯酸基或曱基丙烯 酸基之聚合性化合物之聚合物可使用作為纖維織物等之撥 水撥油劑,尤其,將該聚合物經界面活性劑分散在水性介 質中之水性分散液在工業上已被廣泛使用。 而且,藉由使上述之含說聚合性化合物與所謂氣乙稀 或偏氣乙稀或α-氣丙稀酸基之含氣聚合性化合物共聚,便 可賦予其優異之耐久性者亦為眾所皆知。 然而,該等共聚物於長期保存時,則乳液呈不安定法 態,進而亦認定會引發處理時之性能減低。 ’ 為了解決此問題,便分別在曰本 ,以及曰本專利特開平4娜號公報中提:2: f反應之氯乙料體或偏氯乙烯單體 卿 以下,或將氣離子濃度調整在2〇m侧以下。在 然而,在常溫下的貯藏安定性不充分,、 貯藏時幾乎沒有貯藏伞… 在回溫1 性劑時更為明顯。疋’’尤其在使用非離子性界面3 【發明内容】 [發明所欲解決之課題] 本發明之目自纟0 g 係鍉ί、一種具有優異之保存安定性 316475 5 1304450 可賦予基材優異撥水撥油性之撥水撥油劑分散液。 [解決課題之手法] 本發明係有關一種撥水撥油劑水性分散液,其係包含: ⑴具有全IU完基或全氟烯基及丙晞酸基或曱基丙烤 酸基或α-取代丙烯酸基之聚合性化合物、含氯聚合性化合 物、以及視情況而存在之可與該等化合物共聚之其它聚: 性化合物之共聚物、以及、 ^。 (II)捕捉鹽酸之化合物 而成者。 [發明之效果] 將由乳乙烯或偏氯乙烯或α _氯丙烤酸醋之含氯聚合 性化合物經時所產生的鹽酸加以捕捉,(例如,以環氧化口合 ,或㈣基)便可得到即使長期貯藏亦不引起安定性及性 月&低落之撥水撥油劑分散液。 尤其,亦已知有抑制質地黃變的效杲。 【實施方式】 [聚合物(I)] 物(I)iT、纟具有全氟垸基或全11稀基以及丙稀 g :丙烯酸基或α-取代丙稀酸基之聚合性化合物( 即,含氟聚合性化合物)、含梟取人 虱I5性化合物、以及視情 而存在,其它聚合性化合物」所成之共聚物。 含氟聚合性化合物之例可舉如· 由式: 316475 1304450 R1
I
Rf-S02-NR20C0CR3 = CH2 ⑴
Rf-(CH2)nOCOCR3-CH2 (2) R1
I
Rf*-CONR2OCOCR3 = CH2 (3)
OH
I
Rf-CH2CHCH2OCOCR3 = CH2 ⑷ OCORa
I
Rf-CII2CHCH2OCOCR3 = CH2 (5)
Rf—〇—Ar—CH2OCOCR3 = CH2 ⑹
[式中,
Rf表示碳數1至21之全氟烷基或全氟烯基、 R1表示氫原子或碳數1至1 〇之烷基、 R2表示碳數1至1 〇之伸烷基、 R表不氫原子、甲基、氟原子、氣原子、漠原子、却 原子、CFX,r基(惟χ1以及X2係氫原子、氟原子、氯原子 漠原子或換原子。)、氰基、碳數mi之直鏈狀或μ
狀之氟烷基、取代或非取代之苄基、取代或非取代之苯基 ΑΓ表示可具有取代基之芳基、 土 η表示1至1〇之整數。1 所示之(甲基)丙烯酸酯。 在上式中,Rf基以全氟烷基為佳。 21為且,尤以2至2〇為佳,以4至i 14。哎老,Rf苴—4土 ’例如[ 次者Μ基之妷數可為1至6,尤其亦可 R f基之例有: 為1至4 316475 1304450 - CF3、—Cf2cf3、—Cf2cf2cf3、一 cf(cf3)2、一 cf2 cf2cf2cf3, ~cf2cf(cf3)2, ~c(cf3)3, -(cf2)4cf3, -(C f2)2cf(cf3)2、-cf2c(cf3)3、-cf(cf3)cf2cf2cf3、-(cf 2)5CF3n ~(CF2)3CF(CF3)2, ~(CF2)4CF(CF3)2, -(CF2)7CF3n -(cf2)5cf(cf3)2、-(cf2)6cf(cf3)2、-(cf2)9cf3 等0 含有丙烯酸基或甲基丙烯酸基之含氟聚合性化合物之 具體例可列舉如:
cf3 (CF2)7 (ch2)ococh=ch2> cf3 (cf2)6 (ch2)〇c〇c(ch3) = ch2、 (CF3)2CF(CF2)6(CH2)2OCOCH-CH2n cf3 (cf2)7 (ch2)2〇c〇c(ch3) = ch2、 cf3 (cf2)7 (CH2)2OCOCH=CH2n cf3 cf2 (CH2)2OCOCH=CH2n cf3(cf2)3 (CH2)2OCOCH-CH2n cf3 (cf2)7 so2n(ch3) (CH2)2OCOCH-CH2n
cf3 (cf2)7 s〇2n(c2h5) (ch2)2〇coc(ch3) = ch2、 (CF3)2 CF (CF2)6CH〇CH(OCOCH3)CH2OCOC(CH3)-CH2n (cf3)2 cf (cf2)6ch2ch(〇h) ch2〇c〇ch二 ch2、 ch2o-coch=ch2 C5F】 r0^^CH20-C0C(CH3)=CH2 C8Fn-0-^^C00CH2CHCH20C0C(CH3)=CH2
OH 316475 1304450 CH20-C0CH=CH2 C6F] ]-0-^^>-CH20-C0C(CH3)=CH2 如^取代㈣酸基中,t取代基之例為:鹵素原子(例 气厂二=、乳原子 '漠原子、峨原子)、以鹵素原子取代 風=如:碳數1至21)之燒基(例如:單氣甲基以及 一既甲基)、减、芳族基(例如:取代或非取代之〒基、 取代或非取代之苯基)。 具有α取代丙_基之含氣聚合性化合物之具體例 如下: 0 p
Rf — ch2ch2- Rf*
Rf-f Ό—C-C~CH〇 Ο ρ -o—C~C=:CH2 O f
II I 0~c-c—ch9
RfO~0~ 0 p ^ II I Ό—C—c=ch2 〇 ci r£-CH2CH2-
^ ii I
…mH 316475 9 1304450
Rf—CH2CH厂ο
Rf—CH2CH2—< Rf—CH2CH2——〇
Rf—CH2CH 厂丨
Rf-CH2CH2——( Rf—CH2CH2—o-
Rf-CH2CH2—C 〇Br II I -0-0==0¾ 0 I II I )—c—c=ch2 〇cf3 II l_ 丨一C—C~CH2 0—C—C~CH2 II Ψ 3-0-0==0¾ 0 ch2-c6h5 -c—C^CHa X^ch2 10 316475 1304450 丁酯、第三_丁酯、丙酯、2-乙基己酯、己酯、癸酯、月桂 酯、硬脂酯、異冰片酯、点-羥乙酯、縮水甘油酯,苯酯、 苄酯、4-氰基苯酯類、 (2) 乙酸、丙酸、辛酸、月桂酸 '硬脂酸等脂肪酸之乙烯酯 類、 (3) 苯乙烯、曱基苯乙烯、對—曱基苯乙烯等苯乙烯系化 合物、 (4) 氟乙烯、溴乙烯、偏氟乙烯等(氯化物除外)鹵化乙烯或 亞乙炸化合物類、 (5) 庚酸烯丙酯、辛酸烯丙酯、己酸烯丙酯等脂肪族烯丙酯 類。 (6 )乙烯基曱酮、乙烯基乙酮等乙烯基烷酮類、 (7) Ν-甲基丙烯醯胺、Ν一羥曱基曱基丙烯醯胺等丙烯醯胺 類、以及、 (8) 2, 3-二氯-1,3-丁二烯、異戊二烯等二烯類等。 在聚合物(I)中,含氟聚合性化合物之量係3〇至 重量%,例如可為50至80重量% ;含氣聚合性化合物之量 係1至50重量%,例如可為5至3〇重量% ;其它聚合性化 合物之量係0至5〇重量%,例如可為5至3〇重量%^ 聚合物(I)之重量平均分子量係以凝膠滲透層析法 (GPC · Gel Permeation Chromatography)測定(以聚苯乙烯 換算),一般為5,〇00至2,000,000,尤其亦可為1〇,〇〇〇 至 500, 〇〇〇 。 [捕捉鹽酸之化合物(11)] 316475 12 1304450 捕捉鹽酸之化合物(u)之例 ,彳钻裱氧化合物以及弱鹼性 化合物。捕捉鹽酸之化合物Πη 人 糸以環氧化合物以及弱鹼 性化合物併用為佳。 # 4 環氧化合物之例有··環氧化植 _ ^ ^ 值物油、環氧化脂肪酸酯。 壤乳化植物油之例有:環5 一 油 _ „ ^ 、礼化大豆油、環氧化亞麻籽 锿虱化棉籽油、環氧化紅花油。 環氧化大豆油為例如下列式一 j八所不之化合物: /°\ H2C-0-C0-(CH2)7CH-CH-(CH2)rCH3
、 A H-C-0-C0-(CH2)7CH-CH-(CH2)7-CH3 /°\ 八 H2C-0-C0-(CH2)7CH-CH-CH2-CH-CH-(CH2)4-CH3 環氧化亞麻籽油為例如下列式所示之化合物: /°\ H2C-0-C0-(CH2)7-CH-CH-(CH2)rCH3 /°\ /°\ H-C-0-C0-(CH2)7-CH-CH-CH2-CH-CH-(CH2)4-CH3 /°\ /°\ /〇\ H2C-0-C〇.(CH2)rCH.CH-CH2-CH^CH-CH2«CH.CH.CH2-CH3 弱驗性化合物係呈弱驗性之化合物。弱㈣Μ. 例有··酸之金屬鹽。在酸之金屬鹽中,酸可為無機酸或有 機酸、金屬可為驗金屬或鹼土金屬。弱鹼性化合物之例有· 石反酸氫鈉、碳酸鈉、氨、氫氧化鎂、氫氧化銅、氫氧化鋁、 氫氧化鐵。使用水性分散液於基體時,處理浴之Μ〗一妒 3至8,特別是4至7。 &… 3]6475 13 1304450 捕捉氯之化合物⑴)之量,對於含氣聚合物⑽重量 :係〇· 5至5。重量份。尤其可為i至2。重量份。在併用 艰乳化合物與弱驗性化合物時,環氧化合物與弱驗性化人 5物之重量比為m·1至1:9,尤其可為9.5:〇.5至5口:
[界面活性劑J 本發明中,為了使含氟聚合物良好地分散在水性分 =中…般使用界面活性劑。界面活性劑可為非離 =隹子性(例如:陽離子性、陰離子性、兩性)。界面活性 =以使用陰離子性界面活性劑及/或陽離子性界面活性巧 為佳。界面活性劑可為單由非離子性界面活性劑所㈣, =非離子性界面活性劑與陽離子性界面活性劑之組合者 非料界㈣性劑之财:聚氧化 =稀十三_、聚氧化乙軸驗、聚心 嫩壤驗、聚氧化乙烯硬脂鱗、聚氧化乙稀棒J 月桂酸酯、聚氧化乙烯單硬脂酸酯、聚氧 :編曰、山梨糖醇軒單月桂酸酯、山梨糖醇酐 :、山梨糖醇酐單棕櫚酸醋、山梨糖醇酐刹 糖醇肝倍半油酸醋、山梨糖醇軒三嶋 二: 糖醇酐單月桂酸酯、取匕却山木 r • 减山梨糖軸單棕摘酸醋、 一飞化乙烯山梨糖醇酐單硬脂酸酿、聚氧 酐單油酸酯、聚氧化乙、梳取气# 平山木糖西子 月m匕/乳化丙稀礙段聚合物、聚甘油 日、㈣改性㈣油(商品名:SH3746、SH3748、 316475 14 1304450 = 3749 ' SH3771 (東麗•道康寧·矽酮油股份公司製造))、. 全齓烷基乙烯氧化物加成物(商品名:Umdyne DS-401、 DS 403(泰金工業股份有限公司製造)、氣烧基乙稀氧化物· ::物(商品名:Unidyne DS_4〇6(泰金工業股份有限公司-衣D王氟*兀基低聚物(商品名:Unidyne DS-451、(泰金 工業股份有限公司製造)等。 非綠子性界面活性劑之市售品之例有:聚氧化乙稀油 醚(商品名:EMULGEN 340、花王股份有限公司製造)、聚氧 化乙稀月桂I迷(商品名:贿〇LBL_2卜日光化學股份有;艮% 公司製造)。 陽離子性界面活性劑之例包括:十二烧基三甲基錢乙 一甲基十四烷基銨氯化物、十六烷基三曱基銨溴化 物、二甲基十八烷基銨氯化物、山蕞基三甲銨氯化物、(十 文元基甲基一卞基)二曱基銨氯化物、二(十二烧基)二甲基 叙氣化物、二(十八烷基)二甲基銨氯化物、苄基十二烷基 一甲基錄氣化物、▼基十四烷基二甲基銨氯化物、节基十· 八烷基一甲基銨氯化物、甲基十二烷基二(氫聚氧化乙烯) 銨氯化物、苄基十二烷基二(氫聚氧化乙烯)銨氯化物、 N- [ 2-( 一乙胺基)乙基]油酿胺鹽酸鹽。 本發明中,尤其以使用3種非離子性界面活性劑為 佳。3種非離子性界面活性劑係以 · (a) HLB(Hydrophile- Lipophile-Balance:親水親油平衡 值)未滿1 2之非離子性界面活性劑、 (b) HLB在12以上、1 7以下之非離子性界面活性劑、 316475 1304450 (c)HLB在1 7以上之非離子性界面活性劑 之3種界面活性劑為佳。hlb值有目錄值時係採用其HLB 值’若無則採用計算值(參考文獻:w. G. Grifiin,j· s〇c·
Cosmetic Chemists,1,3UU949)以及 w. G· Griffin,j· S〇c· Cosmetis Chemists, 5, 249(1954))。 界面活性劑(a)、(b)、(c)之例係如下述: (a) ··日本油脂製造之非離子pp-4〇R(HLB值:β·7) (b) ··日本油脂製造之非離子pT-221(HLB值·· ι5· 6) (c) ··日本油脂製造之非離子s —4〇(hlb值·· ΐ8· 2) 界面活性劑之量,對含氟聚合物(1)100重量份,係1
本發明之撥水撥油劑水性分散液可含或 1。有機溶劑之例係可使用 為 20 至 40 : 50 至 7〇 : 1〇 至 2〇 [有機溶劑]
在製造本發明之分散液時, 係在界面活性劑之存在 316475 !304450 下,使聚合性化合物於視需要添加有機溶劑 化聚合而得聚合物之乳濁液。並 ,土扎 加水及/或界面活性劑而得撥水撥油劑水要;八在 =液中添 :合使用本發明之分散液之適當基體為膜=、 職以及由天”合物物質或改性之天缺T入 物物質或合成聚合物物質所得之單絲纺紗 :^ 作成之製品。基體係以纖維H %5叫所 佳。 /次可之形悲的纖維製品為 使用本發明之分散液於基體時,以塗佈、浸潰
:τ輕塗或組合上述之方法者為佳。例如,使浴之固V 請作為浸崎 基脰在该冷中次軋,接著,以—般絞輪去除多 =吸γ基f上之錢聚合物之重量)成為基體^ 〇·οι至1重I%。接著,以將處 熱為宜。 子處理基-在⑽至20(TC中加 [實施例] =下呈示實施例及比較例以更詳細說明本發明。 貫施例及比較例中,進行如下之評估。 盘油性之耐洗滌性 將水性分散液以自來水稀釋成固形物濃度為工〇重量 %’將綿布浸泡在處理液中,以碼壓機礙絞,使濕塗層量(wet Pd叩)為60% ’在1〇(rc下乾燥2分鐘,於16代下鼽處 理1分鐘。依AAKC(美國紡織化學家及染色家協會:The 316475 17 1304450
American Association 〇f Textile Chemists and C〇l〇ur1Sts)-135法進行3次之反覆洗滌,之後,評估農 撥水撥油性(HL-3)。 ° 撥水性:AATCC-22法 撥油性:AATCC-118法 貯存安定性 將水性分散液(固形物30重量%)之初期及於5〇t 1個月後之平均粒徑(散射強度),分別以大塚電子製造 FPAR-1 000測定,依下列基準評估。 〇:變化率為10%以下 △ ··變化率為1 〇%至2〇% X :變化率為20%以上 質地之音變、 將水性分散液以自來水稀釋成固形物濃度丨· 〇重量 %,將綿布浸泡在處理液中,以碾壓機碾絞 以吴此達(Mmolta)製造之CR_3⑽色差計測定與未經處理 布之b值的差異,依下列基準評估。 〇·· △ b = 0· 1以下 △ ·· △ b二0· 1 至 〇· 5 X : △ b=0· 5 以上 實施例1 在1公升之高壓釜中加入150g之CnF2n+]CH2CH2〇COCH= (η 6 8 10、12、14 (η之平均為8)之化合物的混合物) 336475 1304450 (FA)(含氟單體) 烯萨胗· ’bg之丙,布酸硬脂酯、3g之N-羥f基丙 烯鯭、300g之純水、8 烯月桂醚、l〇g之产、孚、25§之聚氧化乙 波乳化分散30分;乳 油,在授掉中於机以超音 接著,將·之氯二=添加1"之正—十二刪, 六 、布(3氯聚合性化合物)壓入充填。再 :而V-ll偶氮二異丁脒―2鹽酸鹽’於6rc下反應5小 率約為ϋΓ水性錢。聚合物之組成係氯乙烯之反應 該水性其它單體之反應率約為100%之組成。在 7\ 外加〇,7g之碳酸氫鈉、得到ΡΗ值經調整至 7之拖水撥油劑水性分散液。 ★對於撥水撥油劑水性分散液,分別評估初期及5 01下 貝丁存1個月後之耐洗滌性與初期之質地黃變。 其結果示於表1。 實施例2至5 除了使用表1所示相同重量之化合物作為含 化合物以及環氧化合物以外,其餘依實施例J相同之^序 5覆操作。實施例4係以相同重量(1〇5·α'氣兩烯酸硬 脂酯取代氯乙烯以及丙烯酸硬脂酯。 另外,隨著pH設定值的變化,碳酸氫鈉之添加旦 下所述。 、里糸如 實施例2 : 0. 7g 實施例3 : 0. 5g 實施例4 ·· 0· 4g 實施例5 : 1. 5g 316475 ]9 1304450 其結果不於表1。 實施例6至7 除了使用表1中所示相同重量之化合物作為含氣聚合, 性化合物以及環氧化合物,並追加十八烷基三曱基銨氯化 物(實施例6為3g,實施例7為2§)於25§之聚氧化乙烯月‘ 桂喊中以外’如同實施例丄之順序反覆操作。其結果示於 表1 〇 實施例8 除了以相同重量⑽g)之C細2ch2〇coch=char ·
FA>並从、加〇· 9g之碳酸鈉以取代〇· 7g之碳酸氫鈉將pH 值私為8以外’如同實施例j之順序反覆操作。其結果 示於表1。 實施例9 除了以相同重量(1响)之C4F9CH2CH20C0CC1=CH2取代 FA且不使用氯乙烯,而將丙稀酸硬脂醋之量增加至 加。,之碳酸納取代"§之碳酸氯 =:8以外,> 同實施们之順序反覆操作。其結果 實施例10 FA,::: = :(15Gg)之 GF侧纖㈣ ^ 用虱乙烯,並將丙烯酸硬脂酯之量掸加至 胸,以及添加〇,之碳酸納 : P Η值調整為8以外,如n〜如〗代0 · 7 g之奴酸氣納將 果示於表丨。 〜〜例1之順序反覆操作。其結 316475 20 1304450 實施例11 除了不使用碳酸氫納以外,如同實施例1之順序反承 操作。其結果示於表1。 设 實施例12 除了不使用環氧化女δ、丄 _ 大丑油以外,如同實施例1之順居 反覆彳呆作。其結果示於表1。 比較例1 除了不使用氯乙烯、戸e / ’ 衣乳化大豆油以及石炭酸氫鋼,並 將5g之十八烷基三曱其 1 θ ^ . L T基釦鼠化物追加於25g之聚氧化乙烯 月桂醚中以外,如间每# μ, 神 於表丨。 貝&彳1之順序反覆操作。其結果示 比較例2 除了不使用環氧化、 施例1之順序反覆操並及:=納义夕卜如同 比較例3 /、、、、。果不於表1。 除了不使用環氧一 取代W之碳酸氫納將並添加㈣之氫氧化納以 1之順序反覆摔作# p ㈣為9以外’如同實施例 ” F ’其結果示於表1。 316475 21 1304450 黃變 i (初期) 1 1 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 X 50°Cx 1個月後 |安定性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 X X IIL-3 |撥油性 寸 CO 寸 CO CO CO CO 1( τ—Η HL-3 撥水性 LO LO LO 寸 LO LO LO 寸 LO 寸 寸 CN1 CO 初期 HL-3 i撥油性 1 LTD 呀 CO CO 寸 CO LO LO CO CO ^ Λ令 LO LO LO 寸 LO LO in 寸 LO LO LO LO CO LO 界面活性劑 陽離子系 1 1 1 1 1 Ο 〇 1 1 1 1 1 〇 1 1 非離手系 〇 〇 〇 〇 〇 Ο 〇 〇 〇 〇 〇 〇 〇 〇 〇 初期 pH值 設定 卜 卜 CD 卜 〇〇 卜 CO 〇〇 〇〇 〇〇 寸 〇〇 LO CO CJi J 弱鹼性 化合物 碳酸氫鈉 碳酸氫鈉 碳酸氫鈉 碳酸氫納 破酸氫納 碳酸氮納 石炭酸&納 碳酸鈉 碳酸鈉 碳酸鈉 1 破酸氫鈉 1 1 氫氧化納 環氧 化合物 環氧化大豆油 環氧化亞麻籽油 環氧化大豆油 環氧化大豆油 環氧化大豆油 環氧化亞麻籽油 環氧化大豆油 環氧化大豆油 環氧化大豆油 環氧化大豆油 環氧化大豆油 1 1 1 1 含氣 聚合性 氣乙稀 氣乙稀 偏氣乙稀 α -氣-丙稀駿硬脂酯 氣乙稀 氣乙稀 偏氯乙烯 氣乙烯 C4F9CH2CH20C0CC1-CH2 C2F5CH2CH20C0CC1=CH2 氣乙烯 氣乙烯 氣乙稀 氣乙稀 1- 氣乙稀 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 1_ 實施例8 實施例9 實施例10 實施例11 實施例12 比較例】 比較例2 比铰例3
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1304450
、申請專利範圍
一種撥水撥油劑水性分散液,其係包含: (I)具有全氟烷基或全氟烯基以及丙烯酸基或甲基丙烯 酸基或α -取代丙烯酸基之聚合性化合物、含氯聚合性 化合物,以及視情況而存在之可與該等共聚合之其他聚 合性化合物之共聚物;以及 (11)捕捉鹽酸之化合物 而成者。 2·如申請專利範圍第1項之撥水撥油劑水性分散液,其 中,捕捉鹽酸之化合物係環氧化合物或弱鹼性化合物或 併用該兩者者。 3.如申請專利範圍第2項之撥水撥油劑水性分散液,其 中’環氧化合物係環氧化植物油。 4·如申請專利範圍第3項之撥水撥油劑水性分散液,其 中,環氧化植物油係環氧化大豆油或環氧化亞麻籽油'。 5·如申請專利範圍第2項之撥水撥油劑水性分散液,其 中,弱鹼性化合物係酸之金屬鹽。 6·如申請專利範圍第2項之撥水撥油劑水性分散液,其 中,弱驗性化合物係碳酸氫納或碳酸納。 7·如申請專利範圍第1項之撥水撥油劑水性分散液,其 中,含氯聚合性化合物係氯乙烯或偏氯乙婦或α 一氯化丙 稀酸酯或甲基丙烯酸3-氯-2-經基丙酯。 8.如申請專利範圍第!至7項中任一項之撥水撥油劑水性 为散液,其中,水性分散液亦包含界面活性劑,而界面 316475(修正版) 23 1304450 活性劑係僅由非離子性界面活性劑所成者。 9·如申晴專利範圍第8項之撥水撥油劑水性分散液,其 中,非離子性界面活性劑係HLB(親水親油平衡值; Hydrophi 1 ic-Lipophi 1 ic Balance)不同之 3 種者。 1 〇· —種纖維製品,係使用申請專利範圍第丨項至9項中任 一項之水性分散液者。 11·種纖維製品之加工法,係使用申請專利範圍第1至9 項中任一項之水性分散液者。 316475(修正版) 24
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US (1) | US20070100064A1 (zh) |
EP (1) | EP1690909A4 (zh) |
JP (1) | JPWO2005047417A1 (zh) |
KR (1) | KR100751611B1 (zh) |
CN (1) | CN1878847A (zh) |
CA (1) | CA2545353A1 (zh) |
TW (1) | TWI304450B (zh) |
WO (1) | WO2005047417A1 (zh) |
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US9732464B2 (en) | 2015-01-29 | 2017-08-15 | Kwong Lung Enterprise Co., Ltd. | Method for producing water repellent down |
TWI617711B (zh) * | 2014-09-19 | 2018-03-11 | Kwong Lung Enterprise Co Ltd | Water-dropping manufacturing method |
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EP1477543A4 (en) * | 2002-01-21 | 2007-10-31 | Daikin Ind Ltd | AQUEOUS HYDRO AND OLEOPHOBY DISPERSION |
ES2564980T3 (es) * | 2007-04-27 | 2016-03-30 | Asahi Glass Company, Limited | Composición hidrófuga/oleófuga, método para la producción de la misma y artículo |
JP5572385B2 (ja) * | 2007-04-27 | 2014-08-13 | 旭硝子株式会社 | 撥水撥油剤組成物、その製造方法および物品 |
US10077327B2 (en) * | 2008-03-28 | 2018-09-18 | Daikin Industries, Ltd. | Fluorine-containing copolymer and water- and oil-repellent agent |
CN101981069B (zh) * | 2008-03-28 | 2013-03-27 | 大金工业株式会社 | 氯乙烯类聚合物 |
KR101578243B1 (ko) * | 2008-06-04 | 2015-12-16 | 아사히 가라스 가부시키가이샤 | 공중합체, 그 제조 방법 및 발수 발유제 조성물 |
WO2010030042A1 (en) * | 2008-09-15 | 2010-03-18 | Daikin Industries, Ltd. | Fluorosilicone polymers and surface treatment agent |
CN101798366B (zh) * | 2010-03-12 | 2012-02-08 | 常州光辉化工有限公司 | 水性全氟烷基氟碳乳液和含有该乳液的水性电缆防结冰涂料及其制备方法 |
CN104024292B (zh) * | 2011-12-28 | 2019-01-04 | 大金工业株式会社 | 含氟组合物及含氟聚合物 |
US9534343B2 (en) | 2012-10-18 | 2017-01-03 | The Chemours Company Fc, Llc | Partially fluorinated copolymer emulsions containing fatty acids and esters |
CN103669004A (zh) * | 2013-11-22 | 2014-03-26 | 南通市通州区川姜镇盛世王朝家用纺织品设计工作室 | 织物防水整理剂 |
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- 2004-11-04 KR KR1020067009257A patent/KR100751611B1/ko active IP Right Grant
- 2004-11-04 WO PCT/JP2004/016319 patent/WO2005047417A1/ja active Application Filing
- 2004-11-04 CN CNA2004800331795A patent/CN1878847A/zh active Pending
- 2004-11-04 CA CA002545353A patent/CA2545353A1/en not_active Abandoned
- 2004-11-04 US US10/579,216 patent/US20070100064A1/en not_active Abandoned
- 2004-11-04 EP EP04818454A patent/EP1690909A4/en not_active Withdrawn
- 2004-11-04 JP JP2005515411A patent/JPWO2005047417A1/ja active Pending
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI617711B (zh) * | 2014-09-19 | 2018-03-11 | Kwong Lung Enterprise Co Ltd | Water-dropping manufacturing method |
US9732464B2 (en) | 2015-01-29 | 2017-08-15 | Kwong Lung Enterprise Co., Ltd. | Method for producing water repellent down |
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KR100751611B1 (ko) | 2007-08-22 |
CN1878847A (zh) | 2006-12-13 |
WO2005047417A1 (ja) | 2005-05-26 |
KR20060086965A (ko) | 2006-08-01 |
EP1690909A1 (en) | 2006-08-16 |
US20070100064A1 (en) | 2007-05-03 |
TW200526842A (en) | 2005-08-16 |
EP1690909A4 (en) | 2010-12-15 |
CA2545353A1 (en) | 2005-05-26 |
JPWO2005047417A1 (ja) | 2007-05-31 |
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