200415283 玫、發明說明： 【發明所屬之技術領域】 本發明係關於一具有拒水性及拒油性之有機纖維，關於 一種包含該纖維之織物產品，及關於一種製備該纖維及該 織物產品之方法。 【先前技術】 吾人期望織物產品不僅可防止親水性沾污，亦可防止親 油性沾污。可藉由拒水性防止親水性沾污，且藉由拒油性 防止親油性沾污。因此，已研究出若干賦予纖維或織物產 品拒水性及拒油性之技術且此等技術已在某些應用中投入 實際使用。若干方法已用於賦予纖維或織物產品因（例如）拒 水及拒油特性而產生防污能力。舉例而言，可使用油劑或 塗覆劑。換之，該纖維或織物產品浸沒於一矽酮聚合 物、氟代烴聚合物、聚胺基甲酸酿聚合物、乙晞基聚合物 或上述任一之共聚物之乳液或溶液中，或將一包含上述聚 合物成分之噴霧施予該纖維或該織物產品，然後對其實施 乾燥以在該纖維表面形成—薄膜。目前使用的另—方法包 含使作為前驅物之單體或寡聚物在纖維表面上聚合成該等 聚合物因而形成一薄膜。 然而’即使採用任-該等方法將上述薄膜覆蓋於織物產 口口之正個表面可賦了纖維防污性能，但此一方法卻導致纖 維顯著喪失其固有手感。上述類型之塗層尤其難以滿足透 ，性及透濕性之需求。儘管亦可單獨塗覆構成織物產品之 每、戴，，隹或，戴維束’但卻無法形成厚度小於分散液中顆粒 87552 200415283 尺寸 < 薄膜。在多數情況下，該薄膜厚度至少為數十微 米，但仍缺乏足夠之強度。 因此，當使用此一塗布劑單獨塗覆纖維時，塗層具有一 足厚度’其會損害纖維及織物產品之手感。亦存在一薄膜 成型法，其使用一液態塗料，並使纖維表面上的聚合物前 驅體聚合並固化。令人遗憾的是，此方法難以獲得一具有 足夠耐久性之薄膜。 此外，在預期高強度、高阻抗性有機纖維可耐受之高溫 下，用於以此方法塗覆之聚合物熔融或分解，且某些時候 甚至燃燒。因此，其缺乏耐熱性及阻燃性，並因此不適合 要求耐熱性及阻燃性之應用，例如，消防服。因而，吾人 期望具有優良耐熱性、财久性且不喪失手感並具有優良防 污性能之纖維及由該纖維織造之織物產品。 該等織物產品可為編織產品、針織產品或不織物織物。 較佳應用包括消防服、手套及用於防護服之編織織物。 【發明内容】 •本發月&供種包含有機纖維之組合物，該有機纖維包 含一含氟代烴碎燒之薄膜。 本發明亦提供一種包含有機纖維之織物產品，該有機纖 維包含一含氟代烴矽烷之薄膜。 、本發明進一步提供一種可用於製造一高強度、耐熱纖維 或織物產品之方法’其包括：使用—包含或藉由組合⑴乳代 烴矽烷或其水解物及⑺視情況之表面活性劑、烷氧基矽烷 化合物、觸媒或其兩種或多種之組合製備而成的水性乳液 87552 200415283 接觸一纖維或織物產品，以製備一含纖維或含織物之混合 物並視情況加熱該混合物。 【實施方式】 可使用任一高強度、耐熱之有機纖維。較佳使用一包含 氟代烴矽烷之薄膜或一包含氟代烴矽烷與烷氧基矽烷之共 縮聚物之薄膜塗覆該纖維。較佳地，一適宜之纖維強度介 於約10 g/D至約50 g/D之間，較佳介於約15 g/D至約50 g/D 之間；及高溫分解溫度至少約為300°C，且較佳至少為350 t：。較佳之高強度、耐熱有機纖維之實例包括全芳族聚醯 胺纖維、全芳族聚酯纖維及雜環芳烴纖維及兩種或多種纖 維之混合物。 適宜之全芳族聚醯胺纖維可為任何已知之芳族聚醯胺纖 維。全芳族聚醯胺纖維亦稱為芳族聚醯胺纖維，其可廣義 上分類為對位芳族聚醯胺纖維及間位芳族聚醯胺纖維。可 藉由熟諳此項技藝者習知之任何方法製造及使用此類芳族 聚醯胺纖維。對位芳族聚醯胺纖維可為任何習知之對位芳 族聚醯胺纖維。此類對位芳族聚醯胺纖維之例示性實例包 括（但不限於）市售產品，例如，聚（對苯二甲醯對苯二胺）纖 維（商品名稱 KEVLAR®，由 E.I. du Pont de Nemours and Company and Du Pont-Tor ay Co·，Ltd.製造）、對苯二甲 Si 對 苯二胺/對伸苯基-3，4’-二伸苯基醚苯二甲醯胺共聚物纖維 (商品名稱TECHNORA，由Teijin Ltd·製造）或其兩種或多種 之組合。此類間位芳族聚醯胺纖維之例示性實例包括（但不 限於）市售產品，例如，聚（對苯二甲醯間苯二胺）纖維（商品 87552 200415283 名稱NOMEX⑧，由 Ε·Ι· du Pont de Nemours and Company製 造）。 適宜之全芳族聚酯纖維可為任何習知之芳族聚酯纖維。 此類全芳族聚酯纖維之例示性實例包括（但不限於）對羥基苯 甲酸自縮合聚合物、包含衍生自對苯二甲酸及乙二醇之重 複單元之聚酯、包含衍生自對苯二甲酸及對苯二酚之重複 單元之聚醚、包含衍生自對羥基苯甲酸及6-羥基-2-萘甲酸 之重複單元之聚酯纖維或其兩種或多種之組合物。可藉由 熟諳此項技藝者習知之任何方法製造及使用此類全芳族聚 酯纖維。舉例而言，適宜之全芳族聚酯纖維包括該等由 Kuraray Co·，Ltd.製造的商品名稱為VECTRAN之商品。 用於本發明之雜環芳烴纖維可為熟諳此藝者熟知之任何 纖維。此類雜環芳烴纖維之例示性實例包括（但不限於）聚 (伸苯基苯并雙嘧唑）纖維、聚（對伸苯基苯并雙嘮唑）纖維 (PBO)、聚苯并咪唑纖維或其兩種或多種之組合。可藉熟諳 此藝者熟知之任何方法製造及使用此類雜環芳烴纖維。舉 例而言，雜環芳烴纖維包括市售PBO纖維，例如，彼等由 Toyobo Co·，Ltd製造的商品名稱為ZYLON的纖維。 較佳之高強度耐熱有機纖維係由對位均聚物製造之芳族 聚醯胺纖維，其商品名稱為KEVLAR®或TWARON(由Teijin Ltd·，製備）；此類纖維因其高溫下之尺寸變化穩定性（例如， 該薄膜之剝離）、耐熱性及其相對較低之成本和良好通用性 而為熟諳此項技藝者所熟知。較佳地，該薄膜之厚度為約 1，000奈米或更低並且其強度介於10 g/D至50 g/D之間。較 87552 200415283 或夕種、自由全芳族聚醯胺纖維、全芳族聚酯纖 、雜環芳烴纖維及其兩種或多種之組合組成之群之織 、准。對苯二甲醯對苯二胺纖維尤其較佳。 織物產品包含纖維’該纖維包含或其上塗覆有—薄膜， 孩薄膜包含或係由-氟代烴魏或其水解物或氟代煙錢 與燒氧基嫩共聚物所製成。適宜之織物產品之例示性 實例包括(但不限於)藉由纖維加工獲得之產品，例如:紗、 棉絮、編織產物、针織物、各種不織物織物(包括氈及紙， 及粗紗和線繩)及其兩種或多種之組合。該織物產品亦可包 括製成品，其係藉由該等產品自>、其組合或與其他材料 之組合（例如，樹脂或金屬）獲得之產品。織物產品較佳為編 織織物、針織品或不織物織造物。消防服、手套及用作保 護服之編織織物尤其較佳。 孩包含或其上塗覆（亦即，其表面上形成有一薄膜）氟代烴 矽烷與烷氧基之共縮聚物薄膜之高強度耐熱有機纖維或織 物產品可藉由使用一水性乳液處理有機纖維或織物產品而 製成’該乳液包含（1)氟代烴矽烷或其水解物、（2)水、及視 情況之（3)表面活性劑 '烷氧基矽烷化合物、觸媒，以製備 含纖維或含織物之混合物並隨後視情況加熱該混合物。 該水性乳液可使用氟代烴矽烷及視情況之表面活性劑、 觸媒及烷氧基矽烷製備。較佳藉由下列方式製備該水性乳 液：將氟代烴矽烷及以重量計相當於0.01至10份（較佳0.1至 1份）之量之表面活性劑（每重量份氟代烴矽烷計）分散於水 中，以使該氟代烴矽烷之含量以該乳液之總重量計介於約 87552 -10- 200415283 〇·1至20 wt%之間，且較佳介於1至1〇 wt%之間。可加入一 催化量（即，約1至約1000 ppmi乳液最終濃度）之酸或鹼性 觸媒至該所得水性分散液中，隨後加入以氟代烴矽烷計相 當於0·1至10(且較佳為0·4至〇·6)莫耳份數之烷氧基矽烷以製 備一混合物。可溫和混合該多成份之混合物。為獲得厚度 為1，000奈米或更小（較佳為500奈米或更小，更佳為1〇〇奈米 或更小’且尤佳為5 0奈米或更小）之均勻且堅固薄膜，其較 佳應盡可能抑制該等氟代烴矽烷及/或該等烷氧基矽烷之自 縮合反應。為此目的，較佳充分攪拌該混合物，並避免過 快加入該等氟代烴矽烷及該等烷氧基矽烷。 氟代烴矽燒較佳為至少一類具有式Rf_(CH2)p_Si{_(〇_ CHAHdn-OR1}3之可水解氟代烴矽烷。在式中， 全氟燒基或該等基團之混合物；該複數個R1基團可為相同 或不同並獨JL地為一或多種Ci·3燒基；p為2至4; 至 10。Rf較佳為平均具有8至12個碳原子之全氟烷基之混合 物；R1代表甲基；p為2 ;且η為2至4，較佳為2至3。更特定 言之，當η為2時，以全氟烷基乙基三（2_(2_甲氧基乙氧基） 乙氧基）矽燒尤佳。當字母η為3時，以（2-(2-(2-甲氧基乙氧 基）乙氧基）乙氧基）矽烷尤佳。該類型之氟代烴矽烷可藉由 熟讀此項技藝者習知之任何方法製成。亦可用兩種或多種 氟代烴矽烷。 例示性烷氧基矽烷包括分子中至少具有兩個烷氧基之有 機石夕化合物，及其部分縮合產物。例示性實例包括：（1)式 Si(R)4之矽酸酯，其中R係選自〇cH3、〇CH2CH3及 -11- 87552 200415283 (OCH2CH2)mOCH3(m為1至l〇)中之一或多種基團；及（2)式 R nSi(OR )4_q之有機氣氧基碎燒，其中R2係《一或多種〇1_10燒 基；該複數個R3基團可相同不同獨立地為一或多種C1-3烷 基；且q為1至3。該烷基R2可由適宜之取代基取代，舉例而 言，胺基、環氧基、乙埽基、甲基丙烯醯氧基、硫醇基、 脲基或鏡基。適宜之燒氧基之具體實例包括（但不限於）二甲 基二甲氧基矽烷、甲基三甲氧基矽烷、3-胺基丙基三乙氧 基石夕燒、N-(2-胺基乙基）-3-胺基丙基甲基二乙氧基矽烷及3- %氧丙氧基二甲氧基碎坑、及任一上述之混合物及部分縮 合產物。 任一酸或一鹼性物質皆可用作觸媒。適宜之酸之具體實 例包括（但不限於）磷酸、硼酸、鹽酸、硫酸、硝酸、醋酸、 甲酸及其兩種或多種之混合物。適宜之鹼之具體實例包括 (但不限於）氨、吡啶、氫氧化鈉、氫氧化鉀及其兩種或多種 之混合物。使用鹽酸或磷酸作為觸媒實施本發明尤佳。200415283 Description of the invention: [Technical field to which the invention belongs] The present invention relates to an organic fiber having water and oil repellency, a fabric product including the fiber, and a method for preparing the fiber and the fabric product. [Previous technology] We expect that fabric products can prevent not only hydrophilic stains but also lipophilic stains. Hydrophilic staining can be prevented by water repellency, and lipophilic staining can be prevented by oil repellency. Therefore, several technologies for imparting water and oil repellency to fiber or fabric products have been researched and these technologies have been put into practical use in some applications. Several methods have been used to impart antifouling properties to fiber or fabric products due to, for example, water and oil repellency properties. For example, an oil agent or a coating agent may be used. In other words, the fiber or fabric product is immersed in an emulsion or solution of a silicone polymer, a fluorinated hydrocarbon polymer, a polyurethane polymer, an acetic acid polymer, or a copolymer of any of the above, or A spray comprising the above-mentioned polymer component is applied to the fiber or the fabric product and then dried to form a film on the surface of the fiber. Another method currently used involves polymerizing monomers or oligomers as precursors on the fiber surface to form these polymers, thereby forming a film. However, even if the above-mentioned method is used to cover the front surface of the fabric opening with the above-mentioned film to impart antifouling properties to the fiber, this method causes the fiber to lose its inherent feel significantly. The above types of coatings are particularly difficult to meet the needs for permeability, permeability and moisture permeability. Although it is also possible to separately coat each of the textile products constituting the textile product, or a David bundle ', it cannot form a film having a thickness smaller than the particles in the dispersion 87552 200415283. In most cases, the film is at least tens of micrometers thick, but still lacks sufficient strength. Therefore, when the fibers are coated by using this coating agent alone, the coating has a sufficient thickness ' which may impair the feel of the fibers and fabric products. There is also a film forming method that uses a liquid coating and polymerizes and cures the polymer precursor on the fiber surface. Unfortunately, this method makes it difficult to obtain a film having sufficient durability. In addition, the polymers used for coating in this way melt or decompose at high temperatures expected to withstand high-strength, high-resistance organic fibers, and sometimes even burn. Therefore, it lacks heat resistance and flame retardancy, and is therefore unsuitable for applications requiring heat resistance and flame retardancy, such as fire protection clothing. Therefore, I expect a fiber having excellent heat resistance, longevity, without losing the feel, and an excellent antifouling property, and a textile product woven from the fiber. The fabric products may be woven products, knitted products or non-woven fabrics. Preferred applications include fire protection clothing, gloves and woven fabrics for protective clothing. [Summary of the Invention] • The present invention provides a composition containing an organic fiber, the organic fiber containing a fluorinated hydrocarbon crushed film. The present invention also provides a fabric product comprising an organic fiber, the organic fiber comprising a film containing a fluorohydrocarbon silane. 2. The present invention further provides a method that can be used to manufacture a high-strength, heat-resistant fiber or fabric product, which includes: using-containing or by combining a fluorinated hydrocarbon silane or a hydrolyzate thereof and a surfactant, a An aqueous emulsion prepared from an oxysilane compound, a catalyst, or a combination of two or more thereof 87552 200415283 is contacted with a fiber or fabric product to prepare a fiber- or fabric-containing mixture and the mixture is heated as appropriate. [Embodiment] Any high-strength, heat-resistant organic fiber can be used. The fibers are preferably coated with a film comprising a fluorohydrocarbon silane or a film comprising a co-condensate of a fluorohydrocarbon silane and an alkoxysilane. Preferably, a suitable fiber strength is between about 10 g / D and about 50 g / D, preferably between about 15 g / D and about 50 g / D; and the pyrolysis temperature is at least about 300 ° C, and preferably at least 350 t :. Examples of preferred high-strength, heat-resistant organic fibers include wholly aromatic polyamide fibers, wholly aromatic polyester fibers and heteroaromatic fibers, and mixtures of two or more fibers. Suitable wholly aromatic polyamide fibers may be any known aromatic polyamide fibers. Fully aromatic polyamide fibers are also called aromatic polyamide fibers, which can be broadly classified into para-aramid fibers and meta-aramid fibers. Such aromatic polyamide fibers can be made and used by any method familiar to those skilled in the art. The para-aramid fiber may be any conventional para-aramid fiber. Illustrative examples of such para-aramid fibers include, but are not limited to, commercially available products, for example, poly (paraphenylene terephthalamide) fibers (trade name KEVLAR®, manufactured by EI du Pont de Nemours and Company and Du Pont-Tor ay Co., Ltd.), p-xylylene Si p-phenylenediamine / p-phenylene-3,4'-diphenylene ether xylylenediamine copolymer fiber (Trade name TECHNORA, manufactured by Teijin Ltd.) or a combination of two or more thereof. Illustrative examples of such meta-aromatic polyfluorene fibers include, but are not limited to, commercially available products, such as poly (p-xylylenediisophthalamide) fibers (commercial 87552 200415283 under the name NOMEX®, manufactured by E · I · Du Pont de Nemours and Company). Suitable wholly aromatic polyester fibers can be any conventionally known aromatic polyester fibers. Illustrative examples of such wholly aromatic polyester fibers include, but are not limited to, para-hydroxybenzoic acid self-condensing polymers, polyesters containing repeat units derived from terephthalic acid and ethylene glycol, Polyethers of repeat units of dicarboxylic acid and hydroquinone, polyester fibers comprising repeat units derived from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, or a combination of two or more thereof. Such wholly aromatic polyester fibers can be made and used by any method known to those skilled in the art. By way of example, suitable wholly aromatic polyester fibers include those manufactured by Kuraray Co., Ltd. under the trade name VECTRAN. The heteroaromatic fiber used in the present invention may be any fiber known to those skilled in the art. Illustrative examples of such heterocyclic aromatic hydrocarbon fibers include, but are not limited to, poly (phenylenebenzobispyrazole) fibers, poly (p-phenylenebenzobispyrazole) fibers (PBO), polybenzimidazole Fiber or a combination of two or more of them. Such heteroaromatic fibers can be made and used by any method familiar to the artisan. For example, heteroaromatic fibers include commercially available PBO fibers, for example, fibers manufactured by Toyobo Co., Ltd. under the trade name ZYLON. Preferred high-strength, heat-resistant organic fibers are aromatic polyamide fibers made from para-homopolymers under the trade name KEVLAR® or TWARON (manufactured by Teijin Ltd.); such fibers vary in size due to their high temperature Stability (eg, peeling of the film), heat resistance, and its relatively low cost and good versatility are well known to those skilled in the art. Preferably, the film has a thickness of about 1,000 nanometers or less and its strength is between 10 g / D and 50 g / D. Compared with 87552 200415283 or evening species, free fully aromatic polyamide fiber, fully aromatic polyester fiber, heteroaromatic fiber and a combination of two or more types of group weaving. P-xylylenediamine p-phenylenediamine fibers are particularly preferred. The fabric product contains fibers' which contains or is coated with a film, and the film contains or is made of a fluorohydrocarbon or its hydrolyzate or a fluorinated nicotinic acid and a burnt oxygen tender copolymer. Illustrative examples of suitable fabric products include, but are not limited to, products obtained through fiber processing, such as: yarns, cotton batts, knitted products, knitted fabrics, various non-woven fabrics (including felt and paper, and rovings and cords) And a combination of two or more of them. The fabric product may also include a manufactured product obtained by using these products from>, a combination thereof, or a combination with other materials (for example, resin or metal). The fabric product is preferably a woven fabric, a knitwear or a nonwoven fabric. Fire protection clothing, gloves and woven fabrics used as protective clothing are particularly preferred. A high-strength, heat-resistant organic fiber or fabric product containing or coated with (ie, a film formed on its surface) a copolycondensate film of a fluorohydrocarbon silane and an alkoxy group can be treated by using an aqueous emulsion or Made of a fabric product, the emulsion contains (1) a fluorohydrocarbon silane or a hydrolyzate thereof, (2) water, and optionally (3) a surfactant, an alkoxysilane compound, and a catalyst to prepare a fiber-containing product. Or a fabric-containing mixture and then optionally heating the mixture. The aqueous emulsion can be prepared using a fluorohydrocarbon silane and optionally a surfactant, a catalyst, and an alkoxysilane. The aqueous emulsion is preferably prepared by: fluorinated hydrocarbon silane and a surfactant equivalent to 0.01 to 10 parts (preferably 0.1 to 1 part) by weight (per fluorinated hydrocarbon silane) Dispersed in water so that the content of the fluorohydrocarbon silane is between about 87552 -10- 200415283 0.1 to 20 wt%, and preferably between 1 to 10 wt%, based on the total weight of the emulsion . A catalytic amount (ie, a final concentration of about 1 to about 1000 ppmi of the emulsion) of an acid or basic catalyst may be added to the resulting aqueous dispersion, followed by the equivalent of 0.1 to 10 (and It is preferably from 0.4 to 0.6) moles of alkoxysilane to prepare a mixture. The multi-component mixture can be mixed gently. To obtain a thickness of 1,000 nm or less (preferably 500 nm or less, more preferably 100 nm or less' and even more preferably 50 nm or less), A strong film, which should preferably suppress the self-condensation reaction of the fluorohydrocarbon silanes and / or the alkoxysilanes as much as possible. For this purpose, it is preferable to stir the mixture sufficiently and avoid excessively adding the fluorohydrocarbon silanes and the alkoxysilanes. The fluorohydrocarbon sinter is preferably at least one type of hydrolyzable fluorohydrocarbon silane having the formula Rf_ (CH2) p_Si {_ (〇_ CHAHdn-OR1} 3. In the formula, perfluorocarbon or a mixture of these groups The plurality of R1 groups may be the same or different and independently JL is one or more Ci · 3 alkyl groups; p is 2 to 4; to 10. Rf is preferably a perfluoro having 8 to 12 carbon atoms on average A mixture of alkyl groups; R1 represents methyl; p is 2; and η is 2 to 4, preferably 2 to 3. More specifically, when η is 2, a perfluoroalkylethyltri (2_ ( 2_methoxyethoxy) ethoxy) is particularly preferred. When the letter η is 3, (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) Silane is particularly preferred. This type of fluorohydrocarbon silane can be made by any method familiar to those skilled in the art. Two or more fluorocarbon silanes can also be used. Exemplary alkoxysilanes include at least two in the molecule Organolithic compounds of alkoxy groups, and partial condensation products thereof. Illustrative examples include: (1) a silicate of formula Si (R) 4, wherein R is selected from the group consisting of 0cH3, 0CH2CH3, and -11- 87552. 200415283 (OCH2CH2) mOCH3 (m is 1 to 10) One or more types of groups; and (2) organic oxygen radical crushing of the formula R nSi (OR) 4_q, wherein R2 is one or more 0-10 atom groups; the plurality of R3 groups may be the same, different, and independently One or more C1-3 alkyl groups; and q is 1 to 3. The alkyl group R2 may be substituted with a suitable substituent, for example, amine, epoxy, ethenyl, methacryloxy, sulfur Alcohol group, urea group or mirror group. Specific examples of suitable alkoxy groups include, but are not limited to, dimethyldimethoxysilane, methyltrimethoxysilane, 3-aminopropyltriethoxylate N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane and 3-% oxypropoxydimethoxy pits, and any of the above mixtures and partial condensation Products. Either an acid or a basic substance can be used as a catalyst. Specific examples of suitable acids include, but are not limited to, phosphoric acid, boric acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, and mixtures of two or more thereof. Specific examples of suitable bases include, but are not limited to, ammonia, pyridine, sodium hydroxide, potassium hydroxide, and mixtures of two or more thereof. Use of hydrochloric acid It is particularly preferred to implement the invention with phosphoric acid as a catalyst.
了使用任何可穩定上述乳液之表面活性劑。該表面活性 劑通常為具有夠高之HLB值藉以抑制該氟代烴矽烷水解產 物自縮合之表面活性劑。術語r HLB」係指HLB系統（由ICIThe use of any surfactant that stabilizes the above emulsions. The surfactant is usually a surfactant having an HLB value high enough to inhibit the self-condensation of the hydrofluorinated silane hydrolysate. The term r HLB "means the HLB system (by ICI
America’s，Inc.，Wilmington，Delaware出版；Adamson，A.W.， 「表面物理化學」（“Physicai Chemistry of Surfaces，，），4th edition，John Wily & Sons，New York，1982)。該表面活性劑 可為陰離子、陽離子、非離子性、兩性或其組合。較佳之 表面活性劑係彼等HLB大於5者，較佳大於12者，且尤佳大 於1 6者。非離子表面活性劑之實例包括（但不限於）Rfi_ 87552 -12- 200415283 ch2ch2.〇.(ch2ch2〇)11-h ^ C9H19-C6H4-〇.(CH2CH2O)50-H > 其他非離子表面活性劑及其組合。陽離子表面活性劑之實 例包括（但不限於）RfLCH2CH2SCH2CH(〇H)CH2N(CH3)3 + cr 其他％離子表面活性劑及其組合。陰離子表面活性劑之 貫例包括（但不限於）Cl2H25(OCH2CH2)4〇SCVNH4+、Ci2Hn_ c0H4-so’Na+、其他陰離子表面活性劑及其兩種或多種表 面活性劑之組合。每一式中，Rfl係通常具有約3 _丨8個碳原 子之王氟燒基。該表面活性劑較佳為分子鏈中具有聚乙二 醇之非離子表面活性劑。較佳使用非離子表面活性劑，例 如 ，其中 Rfi 為 c3.18 全氟烷 基。 了單獨或組合使用各種添加劑，包括無機填料及有機填 料、抗氧化劑、熱穩定劑、紫外線吸收劑、潤滑劑、壤、 著色劑及結晶促進劑。 該乳液可就此使用或若需要經稀釋或另外改良至期望濃 度後使用’其方法為：藉由使用熟諳此項技藝者習知且最適 宜每一狀況下所實施之處理作業之任何方法（例如，浸潰、 蘸塗、塗布或噴塗）將該乳液塗覆至本發明之纖維或織物產 品。該經乳液處理之纖維或織物產品可在約i 5(rc至約5〇〇 °C(較佳在200°C至450°c，且最佳至少25CTC至400。〇下熱處 理約1分鐘至約1 〇小時，藉此不僅促使完成該氟代烴碎垸之 水解或該氟代烴;5夕燒之水解及該燒氧基秒燒水解，且亦促 使完成該水解產物之共縮聚。可形成包含氟代烴矽燒之共 縮聚物或其水解物及烷氧基矽烷之薄膜。考慮目標纖維或 -13· 87552 200415283 織物產品之耐熱性及處理之成本效率等因素後，較佳將處 理溫度及時間周期設定至最佳值。該較佳熱處理溫度及時 間周期設定至最佳值。該較佳熱處理溫度及時間依據該本 發明之纖維及織物產品之不同而不同。倘使為聚（二苯甲酸 胺對苯二胺）纖維，其經該乳液塗布後在約。“它之溫度下 熱處理約3 0分鐘尤其較佳。相對於高強度、耐熱有機纖維 之重T ’塗布於高強度纖維表面上之共縮聚物之重量比係 以熱處理後之乾燥狀態表示並在本文中稱其為「薄膜成形 劑吸收率」。該數值通常約為〇1 %至1〇%。通常，水構成 該乳液的其他部分。 薄膜之厚度係依據薄膜成形劑吸收率並基於纖維之剖面 (其通常近似圓形）為一真正圓之假設而計算出的計算值。舉 例而言，若薄膜成形劑吸收率（基於纖維重量）為2%且織物 重量為16·7克，則塗層之重量為16·7χ〇 〇2=〇·334克。若本 發明中使用的KEVLAR紗線之密度為每纖維167分特 (decitex)，長度為100,〇〇〇米，並且紗線中之纖維具有一圓 形剖面及一 12微米之剖面直徑，則整個表面積約為3.768〇 平万米（37,680平方釐米）。假設將一乾燥後比重約2克/立方 釐米之上述共縮合物之薄膜均勻覆蓋於該整個表面部分， 則該薄膜之厚度為44.3奈米。 在對纖維或織物產品實施上述乳化處理前，若需要或期 望，可藉由洗滌或溶劑洗滌作業清除纖維表面上外來雜質 (例如油劍）。此夕卜，薄膜熱處理完成後，可藉由熟讀此项技 藝者習知之任何方法(例如，水或溶劑萃取)實施一清除殘留 87552 -14- 200415283 觸：：：：活性劑之作業(例如，清洗作業) 加入上述各種添加劑。 了迺两 在本發明之貫施中，除 ! _太央… 望布一厚度較佳最多為 心/、《薄扠(其主要包含氟代烴矽烷或其水解物、及/ 或鼠代烴錢錢氧基錢之共縮聚物）之高料耐熱有機 誠料，本發明亦可處理上述共縮聚織物產品，例如，由 上述高強度耐熱有機纖維構成之機織物、由該等機織物製 成=護服或直接自該㈣維製成之賴手套），藉此在製 成孩寺織物產品之纖維表面上形成__薄膜。既使在該纖唯 表面或該織物產品表面上形成上述薄膜僅包括在該纖維之 邵分表面或該織物產品之部分表面上形成該薄膜，此等纖 維或織物產品亦將被認為歸屬於本發明之範轉。 實例 下文以舉例闡述方式給出若干貫例，雖然本發明不限於 該等實例。 所用之氟代煙石夕燒為具有式Rf_(CH2)2-Si{-(〇-CH2CH2)2-OCH3}3(其中心為p(CF2)k)之全氟燒基碎燒化合物之混合 物。其中字母k為6之化合物占混合物之1至2 wt%，其中字 母k為8之化合物占混合物之62至6 4 wt %，其中字母k為1 0 之化合物占混合物之23至30 wt%，且其中字母k為12至1 8之 化合物占混合物之2至6 wt%。 該表面活性劑係式Rf’-CH2CH2_0-(CH2CH20)n-H(其中Rf， 為3至1 8個碳原子之全氣坑基）之非離子型表面活性劑。 該有機烷氧基矽烷為甲基三甲氧基矽烷（CH3)Si(OCH3)3。 87552 -15- 200415283 實例1.氟代烴矽烷/烷氧基矽烷乳液之製備。 將以重量計100份氟代烴梦垸及以重量計30份表面活性劑 溶於水中。在藉由傳統攪拌技術攪拌下，將以乳液之總重 量計2.5 wt%之氟代烴矽烷緩慢加入所產生之水性乳液，藉 以抑制氟代烴矽烷之自縮合並將其保持在水解狀態。然 後，在使用pH计量測該乳液之pH的同時，添加磷酸並當pH 變為3時結束添加。同樣，添加甲基三甲氧基梦燒 (CH3)Si(OCH3)3以使該有機烷氧基矽烷相對於該氟代烴矽烷 之莫耳份數為0.45並攪拌4小時，從而生產氟代烴矽烷/烷氧 基石夕燒乳液。 織物產品之製備 將三股295 dtex(每一纖維密度為167 dechex)由聚（對苯 一甲醯對苯二胺）短纖維（由Du p〇nt-T〇ray c〇，Ltd，τ。^。 製造’商品名稱KEVLAR®)紡成之2〇s/l雙股紗線平行供給至 sFG_l〇標準型手套織機（由犯猶以旧Mfg·，Ltd·， Wakayama Prefecture生產）並織成1〇#手套。使用市售中性 洗滌劑正常洗滌並乾燥織成之手套。然後，將手套浸沒於 製備好的氟代烴矽烷/烷氧基矽烷乳液中，然後用手輕微扭 紋以將乳液非揮發物之吸收率調節至1 % (以該手套之重量 計）。假設纖維之剖面為圓形，該依據薄膜成形劑吸收率計 异知出的薄膜厚度為22奈米。將手套放置在25〇1烘箱中3〇 分鐘以實施熱處理及烘焙。然後，自烘箱中取出手套並冷 钟土至溫’隨後在溫水中清洗手套並乾燥。與處理前相 匕I處理之手套在手感及外觀上未顯示出變化。然而， 87552 -16- 200415283 當用水噴淋經處理之手套時，水滴散開。與未經處理之手 套相比’經處理之手套在拒水性上顯示出明顯差別。 ^-^2 ·_編織產品之製備 使用每一長絲密度為L67 decitex並由2,000長絲組成之 KEVLAR29 紗線（由 Du Pont-Toray Co·，Ltd·，Tokyo製造）製 造經紗密度為17·5經紗/25毫米、緯紗密度為16·8緯紗/25毫 米及織物單位重量為444克/平方米之平紋織物。將織成之5 X 5平方公分方形織物浸沒於製備好的氟代烴矽烷/烷氧基石夕 k乳液中5分鐘，隨後將其抽出並扭絞除去多餘液體以將乳 液非揮發物之吸收率調節至1 % (以該方形織物之重量計）。 將該機織物放置在250它烘箱中3〇分鐘以實施熱處理及烘 °如同實例1，由此獲得之薄膜厚度約為22奈米。 測試實例 Π)拒7i〇Hk $和崎忤 將純水滴及十六烷分別以2微升之量沈積於實例2獲得之 已烘焙織物之表面上，並用接觸角測定儀（由κ㈧職 Interface Science c〇·，Ltd，卩㈣⑽则製造）量測每 一液體之接觸角。測試結果顯示於下表1中。 此外，實施比較例，其中純水滴及十六烷分別以2微升之 量沈積於藉由實例2闡述之方法製成但未經氟代烴碎燒/燒 氧基碎燒乳液處理之已烘焙織物表面上。量測每一液體之 接觸角。測試結果顯示於下表i。 87552 -17- 200415283 表1.拒永性及拒油性 實例2 比較例 水 124° _因水之滲透無測 十六烷 109° 因十六烷之滲透电竺量測 貫例2中獲得之編織織物結果與比較例中獲得之編織織物 結果之比較顯示水及十六烷浸透未經處理之織物，致使無 法量測接觸角。相反，在實例2中在經氟代烴矽烷/烷氧基 矽烷乳液處理之織物上實施測試，該織物展現出高拒水性 及拒油性。 (2 ) 耐押 將經處理之機織物放置於25(rc烘箱中並在表2所示時間 消逝後量測接觸角。該測試結果顯示於表2。Published by America's, Inc., Wilmington, Delaware; Adamson, AW, "Physicai Chemistry of Surfaces," 4th edition, John Wily & Sons, New York, 1982. The surfactant can be Anionic, cationic, nonionic, amphoteric or a combination thereof. Preferred surfactants are those whose HLB is greater than 5, preferably greater than 12, and particularly preferably greater than 16. Examples of nonionic surfactants include (but Not limited to) Rfi_ 87552 -12- 200415283 ch2ch2.〇. (Ch2ch2〇) 11-h ^ C9H19-C6H4-〇. (CH2CH2O) 50-H > Other non-ionic surfactants and combinations thereof. Of the cationic surfactants Examples include (but are not limited to) RfLCH2CH2SCH2CH (〇H) CH2N (CH3) 3 + cr Other% ionic surfactants and combinations thereof. Examples of anionic surfactants include (but are not limited to) Cl2H25 (OCH2CH2) 4〇SCVNH4 +, Ci2Hn_ c0H4-so'Na +, other anionic surfactants, and a combination of two or more surfactants. In each formula, Rfl is usually a king fluorenyl group with about 3 _8 carbon atoms. The surfactant Preferably Non-ionic surfactants with polyethylene glycol in the sub-chain. Non-ionic surfactants are preferred, for example, where Rfi is c3.18 perfluoroalkyl. Various additives are used alone or in combination, including inorganic fillers and organics. Fillers, antioxidants, heat stabilizers, UV absorbers, lubricants, soils, colorants, and crystallization accelerators. The emulsion can be used as such or used after dilution or otherwise modified to the desired concentration. The method is: by This emulsion is applied to the fiber or fabric product of the present invention using any method (for example, dipping, dipping, coating, or spraying) that is well known to those skilled in the art and that is most suitable for the treatment performed in each situation. The emulsion-treated fiber or fabric product may be heat treated at about 5 ° C to about 500 ° C (preferably at 200 ° C to 450 ° C, and preferably at least 25CTC to 400 ° C) for about 1 minute to In about 10 hours, this not only promotes the completion of the hydrolysis of the fluorinated hydrocarbons or the fluorinated hydrocarbons; the hydrolysis of the yoke and the oxyhydrogenation of the sintered oxygen, but also promotes the completion of the copolycondensation of the hydrolyzed product. Form contains Hydrogenated silicon sintered copolycondensate or its hydrolyzate and alkoxysilane film. Considering the target fiber or -13 87552 200415283 fabric product's heat resistance and cost-effectiveness, the processing temperature and time are preferred. The cycle is set to the optimal value. The preferred heat treatment temperature and time period are set to the optimal value. The preferred heat treatment temperature and time vary depending on the fiber and fabric product of the present invention. In the case of poly (diphenylamine-p-phenylenediamine) fiber, it is about 1500 Å after coating with the emulsion. "It is particularly preferred to heat-treat for about 30 minutes at a temperature. The weight ratio T 'to the weight of the high-strength, heat-resistant organic fiber T'copolymerized on the surface of the high-strength fiber is expressed in the dried state after heat treatment and It is referred to herein as "thin film forming agent absorption rate". This value is usually about 0.01% to 10%. Usually, water forms the rest of the emulsion. The thickness of the film is a calculated value based on the film forming agent absorption rate and based on the assumption that the cross section of the fiber (which is generally approximately circular) is a true circle. For example, if the film-forming agent absorption rate (based on fiber weight) is 2% and the fabric weight is 16.7 grams, the coating weight is 16.7 x 〇2 = 0.334 grams. If the density of the KEVLAR yarn used in the present invention is 167 decitex per fiber, the length is 100,000 meters, and the fiber in the yarn has a circular cross section and a cross section diameter of 12 microns, then The total surface area is approximately 37,680 square meters (37,680 square centimeters). Assuming that a film of the above co-condensate having a specific gravity of about 2 g / cm 3 after drying is uniformly covered on the entire surface portion, the thickness of the film is 44.3 nm. Before the fiber or fabric product is subjected to the above emulsification treatment, if necessary or desired, foreign matter (such as oil sword) on the surface of the fiber can be removed by washing or solvent washing operation. In addition, after the heat treatment of the film is completed, any method known to those skilled in the art (for example, water or solvent extraction) can be used to carry out the removal of residual 87552 -14- 200415283. Touch: ::: Active agent operation (for example , Cleaning operations) adding the above-mentioned various additives. In the implementation of the present invention, in addition to! _ Taiyang ... Wangbu a thickness is preferably at most heart, "thin fork (which mainly contains fluorohydrocarbon silane or its hydrolyzate, and / or rat hydrocarbon (Co-polycondensate) is a high-grade heat-resistant organic material. The present invention can also process the above-mentioned co-condensation fabric products, for example, woven fabrics composed of the above-mentioned high-strength heat-resistant organic fibers, = Protective clothing or gloves made directly from this product), so as to form a __ film on the surface of the fiber made into the fabric of children's temple. Even if forming the film on the surface of the fiber or the surface of the fabric product only includes forming the film on the surface of the fiber or part of the surface of the fabric product, such fibers or fabric products will also be considered to belong to this Paradigm of invention. Examples Several examples are given below by way of example, although the invention is not limited to these examples. The fluorinated arsenite used is a mixture of perfluorocarbon-based calcined compounds having the formula Rf_ (CH2) 2-Si {-(〇-CH2CH2) 2-OCH3} 3 (the center of which is p (CF2) k). . Wherein the compound with the letter k is 6 to 1 to 2 wt%, the compound with the letter k is 8 to 62 to 64 wt%, and the compound with the letter k to 10 is 23 to 30 wt%, And the compound in which the letter k is 12 to 18 accounts for 2 to 6 wt% of the mixture. The surfactant is a non-ionic surfactant of the formula Rf'-CH2CH2_0- (CH2CH20) n-H (where Rf is a total air-pit group of 3 to 18 carbon atoms). The organic alkoxysilane is methyltrimethoxysilane (CH3) Si (OCH3) 3. 87552 -15- 200415283 Example 1. Preparation of fluorohydrocarbon silane / alkoxy silane emulsion. 100 parts by weight of the fluorohydrocarbon nightmare and 30 parts by weight of a surfactant were dissolved in water. With stirring by traditional stirring technology, 2.5 wt% of the fluorohydrocarbon silane based on the total weight of the emulsion was slowly added to the resulting aqueous emulsion, thereby suppressing the self-shrinking of the fluorocarbon silane and keeping it in a hydrolyzed state. Then, while measuring the pH of the emulsion using a pH meter, phosphoric acid was added and the addition was terminated when the pH became 3. Similarly, methyltrimethoxy dream fired (CH3) Si (OCH3) 3 was added so that the mole fraction of the organic alkoxysilane to the fluorohydrocarbon silane was 0.45 and stirred for 4 hours to produce a fluorocarbon Silane / alkoxy stone fired emulsion. Fabric products were prepared from three strands of 295 dtex (density of 167 dechex each) made of poly (p-phenylene terephthalamide-p-phenylenediamine) short fibers (from Du Pont-Toray Co., Ltd, τ. ^ Manufactured the “trade name KEVLAR®” spun 20 s / l double-ply yarn in parallel and supplied it to the sFG_10 standard glove loom (manufactured by Mfg ·, Ltd., Wakayama Prefecture) and woven into 10 #gloves. The knitted gloves were washed and dried normally using a commercially available neutral detergent. Then, the glove was immersed in the prepared fluorohydrocarbon silane / alkoxysilane emulsion, and then slightly twisted by hand to adjust the absorption rate of the nonvolatile matter of the emulsion to 1% (based on the weight of the glove). Assuming that the cross section of the fiber is circular, the thickness of the film, which is unknown based on the film-forming agent absorptivity, is 22 nm. The gloves were placed in a 2501 oven for 30 minutes for heat treatment and baking. The gloves were then removed from the oven and allowed to cool to temperature 'followed by washing the gloves in warm water and drying. The gloves treated with the same as before treatment showed no change in the feel and appearance. However, 87552 -16- 200415283 When the treated gloves were sprayed with water, water droplets spread out. Compared to untreated gloves, the 'treated gloves showed a significant difference in water repellency. ^-^ 2 · _ Weaving products are prepared using KEVLAR29 yarn (made by Du Pont-Toray Co., Ltd., Tokyo) with a density of L67 decitex and 2,000 filaments per filament. The warp density is 17 · Plain weave fabric with 5 warp yarns / 25 mm, weft yarn density of 16.8 weft yarns / 25 mm, and a fabric unit weight of 444 g / m2. The woven 5 X 5 cm square fabric was immersed in the prepared fluorohydrocarbon silane / alkoxylite emulsion for 5 minutes, then it was drawn out and twisted to remove excess liquid to absorb the non-volatile content of the emulsion Adjust to 1% (based on the weight of the square fabric). The woven fabric was placed in a 250-degree oven for 30 minutes to perform heat treatment and baking, as in Example 1, and the thickness of the film thus obtained was about 22 nm. Test Example ii) Rejection 7 Hk $ and ruggedly deposit pure water droplets and hexadecane in an amount of 2 microliters respectively on the surface of the baked fabric obtained in Example 2, and use a contact angle tester (by κ㈧Interface Science c (, Ltd., Ltd.) Measure the contact angle of each liquid. The test results are shown in Table 1 below. In addition, a comparative example was implemented in which pure water droplets and hexadecane were deposited in an amount of 2 microliters each on a baked product prepared by the method described in Example 2 but not treated with a fluorinated hydrocarbon calcined / oxygen calcined emulsion. On the fabric surface. Measure the contact angle of each liquid. The test results are shown in Table i below. 87552 -17- 200415283 Table 1. Permanent and oil-repellent properties Example 2 Comparative example Water 124 ° _Not measured due to water penetration hexadecane 109 ° Weaving obtained in Example 2 due to penetration of cetane The comparison of the fabric results with the results of the woven fabric obtained in the comparative example showed that water and hexadecane penetrated the untreated fabric, making it impossible to measure the contact angle. In contrast, the test was carried out in Example 2 on a fabric treated with a fluorohydrocarbon silane / alkoxy silane emulsion, which exhibited high water and oil repellency. (2) Resistance to taring The treated woven fabric was placed in a 25 ° C oven and the contact angle was measured after the elapsed time shown in Table 2. The test results are shown in Table 2.
使用吸管將—滴汽車發動機油（在汽車内已實際使用約 1，〇〇〇么里的發動機油）沈積在—經處理之編織織物及一未經 處理之編織織物上三個位置之每一位置處，隨後使該等織 物放置1小時。將洗滌劑(由曰本東京花王公司製造，商品 87552 -18 - 200415283 名稱attack)溶於自爽 帶有發動機、標準使用濃度0-083wt%。將 八 A放置於合成洗滌劑溶液中並攪拌5 刀叙，然後用自來水、、西、生，' 現.t + 示洗1分鐘。比較兩個樣品之外觀發 、 <、扁、織織物之油污未消失但經處理之編Using a straw, deposit a drop of automotive engine oil (engine oil that has actually been used in the car at about 1,000 mils) on each of the three locations on the treated woven fabric and an untreated woven fabric Position, the fabrics were then allowed to stand for 1 hour. The detergent (manufactured by Tokyo Kao Co., Ltd., product 87552 -18-200415283, named attack) is dissolved in a self-refrigerating machine with a standard concentration of 0-083wt%. Put eight A in the synthetic detergent solution and stir for 5 knives, then wash with tap water, water, and raw water, and then wash for 1 minute. Compare the appearance of the two samples. The oil stains of the <
、、哉、我物 < 油污已完V 嘀失。此外，經洗滌之織物中仍保持 足夠又拒水性。 上述結果顯示本發明、 可&供具有優良耐熱性和耐久性及 優良防污性能且不損失 (、天子感 < 咼強度耐熱有機纖維。使用 本發明之此等纖維 λ于諸如消防服或手套之織物產品， 其除具有優良之耐切刻把L Ώ . 町刀。!1性外，斫具有阻燃性及高溫下之尺 寸穩定性，且其纖維表 、 叫玉復拒水及拒油薄膜。該等織 物產ρρ耐站/了並易於清洗。此外，由於薄膜厚度極小，因 此可獲得極少損失或基本上不損失構成纖維之时特性（例 如手感）之織物產品。另一女品 士〜Ώ , 另万面，本發明提供一能夠生產上 述纖維及織物產品之方法，由於此拒水性及拒油性之存 在’孩方法易於賦予織物產品—高防污性能且不損失高強 度对熱有機纖維之固有特性（例如手感）。 87552 19-、、 哉 、 我 物 < Oil pollution is over V lost. In addition, the washed fabric remained adequate and water repellent. The above results show that the present invention can be & provided with excellent heat resistance and durability and excellent antifouling properties without loss (, tianzigan < 咼 strength heat-resistant organic fibers. Use of the fibers of the present invention λ in such as fire protection clothing or Glove fabric products, in addition to having excellent resistance to cutting L Ώ. Machi.! 1, 斫 has flame resistance and dimensional stability at high temperatures, and its fiber surface, called Yufu water and oil repellent Films. These fabrics are durable and easy to clean. In addition, because the film thickness is very small, it is possible to obtain fabric products with little or no loss of characteristics (such as hand feel) of the constituent fibers. Another lady On the other hand, the present invention provides a method capable of producing the above-mentioned fibers and fabric products. Due to the existence of water and oil repellency, the method can easily impart fabric products with high antifouling performance without losing high strength to thermal organic materials. Intrinsic properties of fibers (such as hand feel) 87552 19-