TWI322838B - Spandex fibers containing partially dehydroxylated hydrotalcite - Google Patents
Spandex fibers containing partially dehydroxylated hydrotalcite Download PDFInfo
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- TWI322838B TWI322838B TW96105515A TW96105515A TWI322838B TW I322838 B TWI322838 B TW I322838B TW 96105515 A TW96105515 A TW 96105515A TW 96105515 A TW96105515 A TW 96105515A TW I322838 B TWI322838 B TW I322838B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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Description
九、發明說明: 【發明所屬气技術領域】 發明領域 本發明是關於一種具有極好的抗褪色性和耐氯性的含 有部分去羥化之水滑石的斯潘德克斯纖維,以及該等斯潘 德克斯纖維固有的性質。 發明背景 斯潘德克斯纖維具有高的類似橡膠的彈性和極好的物 理性質,諸如高的張力和回復力,適合用於例如内衣、襪 子和運動衣。斯潘德克斯纖維主要由聚胺酯構成,當對氣 化水暴露時,它們的物理性質會變差,舉例來說,如果一 件由經編的斯潘德克斯和聚醯胺製造的游泳衣暴露於含有 從0.5ppm至3ppm活性氣的游泳池水。 因此’透過添加一添加劑至斯潘德克斯纖維内,很多 嘗試被進行來改進其耐氯性。例如,美國專利第4,340,527 號提出使用氧化鋅;美國專利第5,626,960號提出使用一種 碳鈣鎂礦和水菱鎂礦之混合物;韓國專利公開案第92-3250 號提出使用一碳酸ί弓和碳酸鋇之組合;日本申請案早期第 Η6-81215號提出使用一MgO/ZnO固溶體;日本申請案早期 第S59-133248號提出使用氧化鎂、氫氧化鎂或水滑石;以 及曰本申請案早期第H59-292346號提出使用經一較高脂肪 酸和一矽烷偶合劑處理的水滑石。 特別是,美國專利第5447,969號揭露了使用具有結晶 水和經-c關脂肪酸塗覆的水滑石來改進該水滑石的可分 散性並且因此防止在製備斯潘德克斯的過程中該水滑石的 黏聚,因此降低排放壓力的上升並降低當紡紗時紗線破損 的頻率,減少在韓酸溶液處理時的褪色,以及減少當被浸 入氣化水中的膨脹性。更特別地是,在這樣的專利中,一 聚胺酯溶液的乾紡製程是在一 330t的高溫條件下***作 而得到斯潘德克斯紗線。可是’在__等於或w25(rc的溫 度下操作該乾紡製程,使用具有結晶水和經一脂肪酸 塗覆的水滑石會引起斯潘德克斯紗線褪色為棕黃色。 美國專利第6,692,828號揭露了使用塗覆有具有好的耐 熱性的由一以三聚氰胺為主之化合物的水滑石作為一添加 劑,來改進斯潘德克斯纖維的耐氣性。可是,在等於或高 於250 C下操作乾紡時,該斯潘德克斯紗線仍受到褪色。IX. DESCRIPTION OF THE INVENTION: FIELD OF THE INVENTION The present invention relates to a spandex fiber containing partially dehydroxylated hydrotalcite having excellent fading resistance and chlorine resistance, and such spandex The inherent properties of the fiber. BACKGROUND OF THE INVENTION Spandex fibers have high rubber-like elasticity and excellent physical properties, such as high tension and restoring force, and are suitable for use in, for example, underwear, socks, and sportswear. Spandex fibers are mainly composed of polyurethanes, and their physical properties are deteriorated when exposed to vaporized water. For example, if a swimsuit made of warp-made spandex and polyamide is exposed to contain Swimming pool water from 0.5 ppm to 3 ppm active gas. Therefore, by adding an additive to the spandex fiber, many attempts have been made to improve its chlorine resistance. For example, U.S. Patent No. 4,340,527 discloses the use of zinc oxide; U.S. Patent No. 5,626,960 teaches the use of a mixture of a calcium-calcium-magnesium ore and hydromagnesite; and Korean Patent Publication No. 92-3250 proposes the use of a carbonated and cesium carbonate. a combination of Japanese Patent Application No. 6-81215, the use of a MgO/ZnO solid solution; Japanese Patent Application No. S59-133248, the use of magnesium oxide, magnesium hydroxide or hydrotalcite; and the early application of this application H59-292346 proposes the use of hydrotalcite treated with a higher fatty acid and a decane coupling agent. In particular, U.S. Patent No. 5,447,969 discloses the use of hydrotalcite coated with water of crystallization and trans- fatty acid to improve the dispersibility of the hydrotalcite and thus prevent the hydrotalcite during the preparation of the spandex. The cohesiveness thus lowers the discharge pressure and reduces the frequency of yarn breakage during spinning, reduces fading in the treatment of the acid solution, and reduces the swelling when immersed in the vaporized water. More specifically, in such a patent, the dry spinning process of a polyurethane solution is operated at a high temperature of 330 t to obtain a spandex yarn. However, 'the dry spinning process is operated at a temperature of __ or w25 (rc), and the use of hydrated water and a fatty acid coated hydrotalcite causes the spandex yarn to fade to a brownish color. U.S. Patent No. 6,692,828 discloses The use of hydrotalcite coated with a melamine-based compound having good heat resistance as an additive improves the gas resistance of the spandex fiber. However, the dry spinning is operated at or above 250 C. At the time, the spandex yarn was still faded.
Ept請案公開案第1 262 499 A1號揭露了使用被研磨 為一平均顆粒大小等於或小於丨μηι的部分去碳酸之水滑 石,來改進聚胺酯斯潘德克斯的耐氯性。該部分去碳酸之 水滑石是透過使水滑石的一部分碳酸離子分解成二氧化碳 和氧氣而得到的。水滑石的碳酸離子對於使一斯潘德克斯 纖維產生耐氯性是很重要的。因此,該所產生的斯潘德克 斯具有含有一低碳酸離子含量的水滑石,因此具有不令人 滿意的耐氯性。 韓國專利申請案公開案第2〇〇6_5814號揭露了 一種用 於製備具有好的抗褪色性和耐氣性的一斯潘德克斯纖維的 方法’該方法使用塗覆有由一以三聚氣胺為主之化合物並 1322838 且不含結晶水的水滑石,且沒有去羥化或去碳酸處理。可 是,在斯潘德克斯生產中製造該僅被脫水的水滑石的漿體 和該漿體與一聚合物的混合物時,因為該僅被脫水的水滑 石的高吸濕性並且它趨向轉變為具有結晶水的原始形式, 5 因此它應被仔細處理。同樣,在等於或高於250°C的乾紡 時,這樣的一種高吸濕性還會導致斯潘德克斯紗線的褪色。 儘管具有好的耐氯性,這樣一種被褪色的斯潘德克斯 使一產品的品質下降並且它不可能使斯潘德克斯染成白 色。因此,有必要既改進一斯潘德克斯纖維的抗褪色性又 10 要改進一斯潘德克斯纖維的耐氣性。 【發明内容3 發明概要 本發明的一主要目的是:當在一等於或高於200°C的溫 度下紡紗時,提供一具有極好的耐氣性而無褪色的斯潘德 15 克斯纖維。 根據本發明的一方面,提供一種斯潘德克斯纖維,它 包含一0.1 wt%至10 wt%的量的部分去經化之水滑石。 圖式簡單說明 本發明的上面和其他目的和特徵會由本發明的下面的 20 描述連同該等附圖會變得更明顯,這些附圖分別顯示: 第1圖是一顯示該水滑石結構的圖; 第2圖是一在製備例2中使用的水滑石 (Mg8Al4(0H)24(C03)2-6H20)的27A1魔角自旋核磁共振(MAS NMR)光譜; 7 第3圖是在製備例2得到的部分去羥化之水滑石 (Mg8Al4(0H)1604(C03)2)的27A1 MAS NMR光譜; 第4圖是一在實施例2中得到的斯潘德克斯纺紗的27ai MAS NMR光譜; 第5圖是一從實施例2的斯潘德克斯紡紗中提取的水% 石的27A1 MAS NMR光譜; 第6圖是一在製備例2中使用的該水滑石 (Mg8Al4(OH)24(C〇3)2,6H2〇)的红外線(IR)吸收光譜; 第7圖是一在製備例2中得到的部分去羥化之水滑石 (Mg8Al4(OH)i6〇4(C03)2)的IR吸收光譜;及 第8圖是從實施例2的斯潘德克斯紡紗中提取的水滑石 的IR吸收光譜。The use of partially decarbonated hydrotalcites which have been ground to a mean particle size equal to or less than 丨μηι to improve the chlorine resistance of the polyurethane spandex is disclosed in U.S. Patent Application Publication No. 1 262 499 A1. The partially decarbonated hydrotalcite is obtained by decomposing a part of carbonate ions of hydrotalcite into carbon dioxide and oxygen. The carbonate ions of hydrotalcite are important for making a spandex fiber resistant to chlorine. Therefore, the resulting spandex has a hydrotalcite containing a low carbonate ion content and thus has an unsatisfactory chlorine resistance. Korean Patent Application Publication No. 2-68114 discloses a method for preparing a spandex fiber having good fading resistance and gas resistance. The method is coated with a trisamine gas. The main compound is 1322838 and does not contain hydrotalcite, and is not dehydroxylated or decarbonated. However, when the slurry of the dehydrated hydrotalcite and the mixture of the slurry and a polymer are produced in the production of spandex, because of the high hygroscopicity of the dehydrated hydrotalcite only, it tends to be converted to have The original form of crystal water, 5 therefore it should be handled carefully. Also, such a high hygroscopicity results in fading of the spandex yarn at the time of dry spinning at or above 250 °C. Despite its good chlorine resistance, such a faded spandex degrades the quality of a product and it is impossible to dye the spandex white. Therefore, it is necessary to improve both the fading resistance of a spandex fiber and the gas resistance of a spandex fiber. SUMMARY OF THE INVENTION Summary of the Invention A main object of the present invention is to provide a Spand 15 yarn which has excellent gas resistance without fading when spun at a temperature equal to or higher than 200 ° C. fiber. According to an aspect of the invention, there is provided a spandex fiber comprising a partially de-saturated hydrotalcite in an amount of from 0.1 wt% to 10 wt%. BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects and features of the present invention will become more apparent from the following description of the <RTIgt; Fig. 2 is a 27A1 magic angle spin nuclear magnetic resonance (MAS NMR) spectrum of hydrotalcite (Mg8Al4(0H)24(C03)2-6H20) used in Preparation Example 2; 7 Fig. 3 is a preparation example 2 obtained 27A1 MAS NMR spectrum of partially dehydroxylated hydrotalcite (Mg8Al4(0H)1604(C03)2); Fig. 4 is a 27ai MAS NMR spectrum of a spandex obtained in Example 2; Figure 5 is a 27A1 MAS NMR spectrum of water % stone extracted from the spandex spinning of Example 2; Figure 6 is a hydrotalcite (Mg8Al4(OH)24(C) used in Preparation Example 2.红外线3) 2,6H2〇) infrared (IR) absorption spectrum; Figure 7 is an IR of partially dehydroxylated hydrotalcite (Mg8Al4(OH)i6〇4(C03)2) obtained in Preparation Example 2. The absorption spectrum; and Fig. 8 is the IR absorption spectrum of the hydrotalcite extracted from the spandex spinning of Example 2.
C資施方式:J 較佳實施例之詳細說明 本發明的斯潘德克斯纖維具有極好的耐氣性並且不會 在等於或高於200°C下操作的紡紗製程時褪色,該斯潘德克 斯纖維可透過在一200°C至39(TC的溫度下熱處理一具有結 晶水的水滑石而引起脫水和部分去經化,並且然後向一聚 胺酯溶液中加入因此得到的部分去經化之水滑石來製備。 因此’根據本發明,水滑石是透過在一高溫下歷時一 長時間段操作的熱處理而被部分去羥化的,該時間段超過 那些在韓國專利申請案第2006-5814號揭露的時間段,並且 它沒有被脫碳酸而產生充足的耐氣性,不同於在EP申請案 公開案第1 262 499 A1號中所使用的。 儘官美國專利第5,447,969號揭露了使用具有結晶水的 水滑石此有效的防止在鞣酸溶液處理時的褪色問題和當被 ίχ入在氯化水時的膨脹問題,這些問題被發現可透過使用 根據本發月的無結晶水的部分去經化之水滑石而被克服。 根據本發明的斯潘德克斯纖維如下被詳細地描述。 應被理解的是用於本文中的術語是考慮本發明的功能 而被定義的’並且該含義會根據該技術領域中技術的目的 而被更改’且沒有限制本發明的結構。 用於本文中的術語,,纺紗,,或,,纺紗製程,,不是指熔紡就 是指乾紡。用於本文中的術語”紡紗溫度,,是指在一紡紗製 程時一斯潘德克斯聚合物所受到的最大溫度,舉例來說, 在一熔紡製程中一聚合物切粒的熔融溫度,或一乾紡製程 的紡絲通道溫度。該術語,,褪色,,是指一白色纖維變色為黃 色或棕色。 在本發明中使用的水滑石是一種金屬氫氧化物,,它 的結構是由兩個呈一雙層形式的八面體單元、陰離子(Αη-) 和ΗζΟ分子構成,該等八面體單元具有被六個氫氧根離子 (0Η·)圍繞的二價或三價(Μ+2或Μ+3)金屬陽離子,而陰離子 (Αη_)和Ηβ分子是用來均衡在該等雙層之間的荷電容量 (charged capacity),如第1圖中所顯示的。這樣一種水滑石 可在一高的溫度下被熱處理而除去來自該等雙層之間的 H2〇分子’並且更進一步在一較高溫度下被熱處理以引起去 羥化。如果該水滑石在一高於去羥化溫度的較高溫度下被 熱處理,可引起脫碳酸作用(見Stanimirova等,Clay 1322838C. Application: J. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The spandex fiber of the present invention has excellent gas resistance and does not discolor at a spinning process operating at or above 200 ° C, the spandex The fiber can be dehydrated and partially de-hydrogenated by heat-treating a hydrotalcite having crystal water at a temperature of 200 ° C to 39 ° C, and then adding the thus obtained partially dehydrogenated water to a polyurethane solution. The talc is prepared. Thus, according to the present invention, the hydrotalcite is partially dehydroxylated by heat treatment which is operated at a high temperature for a long period of time, which is disclosed in the Korean Patent Application No. 2006-5814. The time period, and it is not decarbonated to produce sufficient gas resistance, as used in the EP application No. 1 262 499 A1. The use of crystal water is disclosed in U.S. Patent No. 5,447,969. This hydrotalcite is effective in preventing the problem of fading in the treatment of tannic acid solution and the problem of swelling when it is poured into chlorinated water. These problems are found to be achievable through the use of this month. The partially dehydrated hydrotalcite of the crystal water is overcome. The spandex fiber according to the present invention is described in detail as follows. It should be understood that the term used herein is defined in consideration of the function of the present invention. And the meaning is changed according to the purpose of the technology in the technical field 'and does not limit the structure of the invention. The term used herein, spinning, or,, spinning process, does not mean melt spinning means Dry spinning. The term "spinning temperature" as used herein refers to the maximum temperature to which a spandex polymer is subjected during a spinning process, for example, a polymer pellet in a melt spinning process. The melting temperature, or the spinning channel temperature of a dry spinning process. The term, fading, means that a white fiber is discolored to yellow or brown. The hydrotalcite used in the present invention is a metal hydroxide, and its The structure consists of two octahedral units, an anion (Αη-) and a ruthenium molecule in the form of a bilayer, which has a divalent or trivalent ring surrounded by six hydroxide ions (0Η·). Price (Μ+2 Or Μ+3) a metal cation, and the anion (Αη_) and Ηβ molecules are used to balance the charged capacity between the two layers, as shown in Figure 1. Such a hydrotalcite can be Heat treated at a high temperature to remove H2 〇 molecules from between the two layers' and further heat treated at a higher temperature to cause dehydroxylation. If the hydrotalcite is above a dehydroxylation temperature Heat treated at higher temperatures can cause decarbonation (see Stanimirova et al., Clay 1322838)
Minerals,39: 177-191,2004)。 被用於本文中的術語”部分去羥化之水滑石”是指一透 過在一高的溫度下熱處理一具有結晶水的水滑石來引起脫 水和去羥化而得到的水滑石,可由20H· — H20 + 02來表 5 示。該部分去羥化之水滑石既具有八面體位點又具有四面 體位點,後者在該雙層結構内含有一被四個羥基圍繞的金 屬陽離子(見Stanimirova等,Clay Materials,39 : 177-191, 2004)。 在本發明中,該部分去羥化之水滑石可由化學式⑴表 10 示: M2+,2.yAly(OH)24-2z〇z(C〇3)y/2mH20 (I) 其中,Μ是Mg、Ca或Zn,y是一在2.4<y$4範圍内的數 值,z是一在0<zS8範圍内的數值,以及m是0或一正整數。 較佳的是該部分去羥化之水滑石是選自由下列化合物 15 構成之群組:Mg8Al4(OH)丨604(C〇3)2、Mg8Al4(0H)808(C03)2、 Mg9Al3(OH)18〇3(C〇3)i 5 、 Mg9Al3(0H)1206(C03)15 、Minerals, 39: 177-191, 2004). The term "partially dehydroxylated hydrotalcite" as used herein means a hydrotalcite obtained by heat-treating a hydrotalcite having crystal water at a high temperature to cause dehydration and dehydroxylation, which may be 20H· – H20 + 02 is shown in Table 5. The partially dehydroxylated hydrotalcite has both an octahedral and a tetrahedral site, the latter containing a metal cation surrounded by four hydroxyl groups in the bilayer structure (see Stanimirova et al, Clay Materials, 39: 177-191). , 2004). In the present invention, the partially dehydroxylated hydrotalcite can be represented by the chemical formula (1): Table 10: M2+, 2.yAly(OH)24-2z〇z(C〇3)y/2mH20 (I) wherein Μ is Mg, Ca or Zn, y is a value in the range of 2.4 < y$4, z is a value in the range of 0 < zS8, and m is 0 or a positive integer. Preferably, the partially dehydroxylated hydrotalcite is selected from the group consisting of Mg8Al4(OH)丨604(C〇3)2, Mg8Al4(0H)808(C03)2, Mg9Al3(OH) 18〇3(C〇3)i 5 , Mg9Al3(0H)1206(C03)15 ,
Mg9.6Al2.4(〇H)19.2〇2.4(C〇3)l.2 ' Mg9.6Al2.4(OH)14.4〇4.8(C03)i.2 'Mg9.6Al2.4(〇H)19.2〇2.4(C〇3)l.2 'Mg9.6Al2.4(OH)14.4〇4.8(C03)i.2 '
Mg8Al4(0H)1604(C03)26H20、Mg8Al4(0H)808(C03)2.7H20、 Mg9Al3(0H)1803(C03)L5.7.5H20、Mg9Al3(OH)1206(C03)15 8H20 20 和此等之一混合物。 根據本發明’該具有結晶水的起始水滑石較佳地是在 一氮、氦、氧、氫或二氧化碳的無水氛圍中在一200°C至 390°C的溫度下被熱處理,更佳地是在250°C至300°C。 如果該具有結晶水的水滑石在一小於2〇〇。〇的溫度下 10 被熱處理,該水滑石可能不被去羥化。如 的水滑石在一高於39〇°C的溫度下被熱處理,該水滑石$能 經過去羥化和更進一步的去碳酸作用,導致變差的耐氟 性。因此,在約25(TC至3〇〇t:的熱處理得到的該部分去經 化之水滑石對於耐氯性的改進是有用的。 本發明的部分去羥化之水滑石可吸收空氣中的水份’ 但是大部分被吸收的水份在約100。(:下被蒸發,並且因此這 種被吸收的水份是不同於在熱處理之前出現在該水滑石中 並且在約17(TC至22(TC下蒸發的結晶水。因此,該部分去 羥化之水滑石據信在一等於或高於2 0 0。(3的紡紗製程時對 該斯潘德克斯紗線的褪色不產生影響,因為在其内被吸收 的水份在約1〇〇。(:下已被除去,而當具有結晶水的該水滑石 中的初始結晶水在一等於或高於20〇。〇下的紡紗製程中蒸 發時’可引起該斯潘德克斯紗線的褪色。 同樣,透過加入該部分去羥化之水滑石的本發明斯潘 ^克斯纖維比透過加入具有結晶水的水滑石而製備的斯潘 义、克斯纖維具有較好㈣氣性,這被料是該部分去經化 ,水滑石的雙層氫氧化㈣統被改變而增加了它對水吸收 和離子交換的容量的一個結果。 =據本發明的斯潘德克斯纖維的製備中使用的聚胺 由技術中已知的-傳統妓來製備,舉 使一有機二異氰㈣與-二料合物反 心透過 驅物,枯# 應產生—聚胺酯前 盘〜使遠前驅物溶解於-有機溶劑並且允 /、〜二胺和單胺反應^可料本發 |的溶液 啊機一異氰酸酯包 括二苯甲烷-4,4’-二異氰酸酯、六亞甲基二異氰酸酯、甲苯 —異氰酸酯、伸丁基二異氰酸酯(butylenediscocyanate)和氫 化的二苯甲烷-4,4’-二異氰酸酯。同樣,可用於本發明的二 醇聚合物的例子包括聚丁醚二元酵、聚丙二醇、聚碳酸二 5醇等等。使用二胺作為一鏈伸長劑並且它的例子是乙二 胺、丙二胺和肼。使用單胺作為一鏈終止劑,並且該單胺 可是二乙二胺(diethyldiamine)、乙醇胺或二甲胺。 在本發明中,用於製備該斯潘德克斯纖維的聚胺酯還 可包含有機添加劑,該有機添加劑包括以受阻酚為主之化 10合物、苯并呋喃酮(benz〇furanons)、胺基脲、苯並三唾、以 雙阻胺為主之化合物,以及包含聚合性三級胺安定劑,諸 如一含有三級氮原子的聚胺酯和聚二烷基胺基烷基甲基丙 稀酸 S旨(polydialkyl aminoalkyl methacrylate),以致防止該斯 潘德克斯纖維褪色和物理性質的變差。 15 此外,本發明的斯潘德克斯纖維還可包含無機添加 劑,諸如一氧化鈦和硬脂酸鎮。根據所欲的斯潘德克斯纖 維的白度’該一氧化欽可以一 〇.lwt%至5wt%的量被使用。 為增加該斯潘德克斯纖維的退繞性質,該硬脂酸鎂可以— O.lwt%至2wt°/〇的量被使用。 2〇 根據本發明,以被使用的聚胺酯的重量計,該部分去 經化之水滑石可以一 0Jwt%至l〇wt%的量被使用。當該量 小於O.lwt%時,該斯潘德克斯纖維的耐氣性是不充足的, 並且當該量大於l〇wt%時,該斯潘德克斯纖維的強度、伸 長率和模數變差。 12 在根據本發明的斯潘德克斯纖維的製備中,該部分去 羥化之水滑石可在任何方便的時間被加入該聚胺酯中,舉 例來說,在與一添加劑混合接著是一磨砂或研磨製程之 後或在缺少一添加劑的·一磨砂或研磨製程之後。 5 在本發明中,該部分去羥化之水滑石可被更進步由 —技術中傳統使用的塗覆劑塗覆或不塗覆,這不影響斯潘 德克斯紡紗的耐氣性和褪色。塗覆劑的例子包括脂肪族 醇、脂肪酸、脂肪酸鹽、脂肪酸酯、填酸酯、苯乙烤/順丁 烯二酸酸酐共聚物和此等之衍生物、以矽烷為主之偶合 10 劑、以鈦酸鹽為主之偶合劑、聚有機石夕氧炫 '聚有機氫砂 氧烷和以三聚氰胺為主之化合物。在這些例子之中,脂肪 酸、脂肪酸鹽及/或以三聚氰胺為主之化合物是較佳的,因 為在透過熱處理的水滑石的去羥化之時,該前二者顯示出 極好的塗覆效率並且最後一個可以使褪色最小化。 15 水滑石的塗覆製程可透過將一塗覆劑添加至(以水滑 石的重量計,該塗覆劑是以一O.lwt%至10wt%的量被加入) 一諸如水、醇、醚或二噚烷的溶劑而得到一塗覆劑溶液, 向其中加入水滑石並且在一50°C至170°C的升高溫度下(如 果必要,使用一高壓反應器)攪拌所產生的溶液歷時10分鐘 2〇 至2小時,然後過濾並且乾燥而***作。選擇性地,該塗覆 製程也可透過熱熔一不含溶劑的塗覆劑並且在一高速混合 器中混合該熔融的塗覆劑與水滑石而操作。 特別地,使用在水中以三聚氰胺為主之化合物的塗覆 製程應在大氣壓力下於一高於或等於15(TC的溫度下*** 13 1322838 作,這是由於以三聚氰胺為主之化合物的一高熔點。 使用在水中的該等脂肪酸或該等脂肪酸鹽的塗覆製程 較佳地是在一等於或高於100°c的溫度下被進行。當該塗覆 溫度小於l〇〇°C時,很難達到均勻的塗層和非褪色,並且所 5 需要的塗覆劑的量是增加的。例如,在小於100°C下以塗覆 製程中的水滑石計,使用的該等脂肪酸或脂肪酸鹽的量是 約3wt%,而在等於或高於100°C下以塗覆製程中的水滑石 計,使用的量可被減少至1.5wt%。在該水滑石的熱處理中, 這樣一減少的塗覆劑的量可減少其褪色作用。 10 在本發明中被用作一塗覆劑的該等脂肪酸較佳地是選 自單羥基脂肪酸或聚羥基脂肪酸,單羥基脂肪酸或聚羥基 脂肪酸是具有3至40個碳原子的線型或支鏈型烴鏈,舉例來 說月桂酸、己酸、十六酸或硬脂酸。 在本發明中被用作一塗覆劑的該等脂肪酸鹽是由具有 15 6至30個碳原子的單官能或雙官能並且飽和或不飽和的脂 肪酸,以及一選自元素週期表的族I至族III的金屬和鋅而形 成的。該等脂肪酸鹽的例子包括油酸、十六酸或硬脂酸的 鋰鹽、鎂鹽、鈣鹽或鋅鹽,較佳地是硬脂酸鎂、硬脂酸鈣 和硬脂酸,更佳地是硬脂酸鎂。 20 在本發明中被用作一塗覆劑的該等以三聚氰胺為主之 化合物包括三聚氰胺化合物、含有磷的三聚氰胺化合物以 及氰尿酸三聚氰胺化合物,選擇性地是由一具有羧基的有 機化合物所取代,它可單獨被使用或組合被使用。 三聚氰胺化合物的例子包括亞甲基二三聚氰胺、伸乙 14 基二三聚氰胺、三亞甲基二三聚亂胺、四亞甲基二三聚氛 胺、六亞甲基二三聚氰胺、十亞甲基二三聚氰胺、十二亞 甲基二三聚氰胺、1,3-亞環己基二三聚氰胺、對伸苯基二三 聚氰胺、對二甲苯二三聚氰胺、二伸乙基三三聚氰胺、三 5 伸乙基四三聚氰胺、四伸乙基五三聚氰胺、六伸乙基七三 聚氰胺和三聚氰胺甲醛。 含有填的三聚氰胺化合物的例子包括任何上面提到的 三聚氰胺化合物與磷酸或一磷酸鹽連接,舉例來說,二三 聚氰胺焦磷酸鹽、三聚氰胺一級磷酸鹽、三聚氰胺二級磷 10 酸鹽、三聚氰胺聚磷酸鹽和雙-(新戊四醇磷酸酯)碟酸的三 聚氰胺鹽等等。 該等氰尿酸三聚氰胺化合物的例子包括由至少一選自 甲基、苯基、羧曱基、2-羧乙基、氰曱基或2_氰乙基的取代 基所取代的氰尿酸三聚氰胺化合物。 15 20 較佳的是該等上面的以三聚氰胺為主之化合物與一具 有-竣基时機化合物反應。具有—縣的㈣化合物的 例子包括脂肪族單叛酸(舉例來說,辛酸、十-酸、月桂酸、 十一酸+四酸、十五酸、十六酸、十七酸'硬脂酸、十 九&L 一十S夂、—十二酸)、脂肪族二敌酸(舉例來說,丙二 酸、丁二酸、戊二酸、己二酸 '庚二酸、辛二酸、壬二酸、 —,·十一烷二酸吵⑺癸二酸⑶十一烷二 甲酸、1,12-十二烷二甲酸、113_十三烷二甲酸和w十四 院二甲酸)、芳香族單紐(舉例來說,苯甲酸、苯乙酸、& 萘甲酸' β_#甲酸、eynnamie _、對胺馬尿酸和4 (2·嗟 15 唑胺磺醯基)-phthalaninoic acid)、芳香族二羧酸(舉例來 說,對苯二曱酸、間苯二甲酸和鄰苯二甲酸)、芳香族三羧 酸(舉例來說’偏苯三甲酸、l53,5_苯三甲酸和順(2-羧乙基) 二聚異氰酸酯)、芳香族四幾酸(舉例來說,苯四甲酸和聯笨 5四甲酸)、脂肪族環狀單羧酸(舉例來說,環己烷羧酸)和脂 肪族環狀二羧酸(舉例來說’丨,2_環己烷二羧酸)。 塗覆劑增加了在一斯潘德克斯聚合物溶液中該水滑 石的分散性並且保持該斯潘德克斯的可紡性。 可是’儘管該水滑石沒有被塗覆,它可以表現出極好 10的可纺性’實質上地相當於當被磨砂或研磨時該被塗覆的 水滑石的可紡性。 15 20 該磨砂或研磨製程可透過使用一傳統的珠粒研磨機研 磨—種該水滑石、少量聚胺自旨和-溶綱混合物或漿體而 ***作。使用的少量聚胺酯能增加該水滑石的可分散性。 可破用於該磨砂或研磨製程的溶劑的例子包 一 τ丞乙職 胺、二甲基甲醯胺 '二甲基亞砜和此等之—混合物。 备该水滑石被磨砂或被研磨而具有一小、 等於15吨平均大小的次級粒子時,在製備該斯潘楝: 維時,它可顯示出的功能本質上相當於被塗覆並且被纖 或研磨的水滑石的功能。 破磨砂 同樣’在本發明中,用於該水滑石趣化的熱 使用各種類型的乾燥劑以產生約2〇(rc至39〇 可 作,舉例來咋如 的…、而*** 例來心在_對流、傳導、輻射、微 製程中操作那些。 ^具二加熱 16 本發明將參考實施例而更進一步被詳細描述。可是, 應被理解的時本發明不被該等特定的實施例所限制。 實施例 分去羥化之光滑石的製備 5 製備例1 硬脂酸和具有化學式Mg8Al4(OH)24(C〇3)2.6H2〇之水滑 石被接連地加入到水中。以該水滑石的重量計,硬脂酸的 量是2wt°/w所產生的混合物在15〇。(:下被攪拌20分鐘,被過 濾並且被乾燥’以得到經硬脂酸塗覆的水滑石。該經塗覆 10 的水滑石在250°C下被熱處理4小時,以得到經硬脂酸塗覆 的具有化學式Mg8Al4(0H)1604(C03)2之水滑石。 製備例2 硬脂酸、三聚氰胺聚磷酸鹽和具有化學式 Mg8Al4(OH)24(C〇3)2*6H2〇之水滑石被接連地加入到水中。 15 以該水滑石的重量計,硬脂酸和三聚氰胺聚磷酸鹽的量分 別是2wt%和1 wt%。所產生的混合物在160°C下被授拌30分 鐘、被過濾並且被乾燥,以得到經硬脂酸和三聚氰胺聚磷 酸鹽塗覆的水滑石。該經塗覆的水滑石在250°C下被熱處理 4小時,以得到經硬脂酸和三聚氰胺聚鱗酸鹽塗覆的具有化 20 學式 Mg8Al4(0H)1604(C03)2 之水滑石。 製備例3 除了用3wt%的三聚氰胺聚磷酸鹽塗覆具有化學式 Mg8Al4(0H)24(C03)2.6H20之水滑石外,重複製備例2中的程 序,以得到經三聚氰胺聚磷酸鹽塗覆的具有化學式 17 .' Mg8Al4(〇H)i6〇4(C〇3)2之水滑石。然後,該產物在濕空氣下 . 被暴露7天,以得到經三聚氰胺塗覆的具有化學式Mg8Al4(0H)1604(C03)26H20, Mg8Al4(0H)808(C03)2.7H20, Mg9Al3(0H)1803(C03)L5.7.5H20, Mg9Al3(OH)1206(C03)15 8H20 20 and one of these mixture. According to the invention, the starting hydrotalcite having water of crystallization is preferably heat treated at a temperature of from 200 ° C to 390 ° C in an anhydrous atmosphere of nitrogen, helium, oxygen, hydrogen or carbon dioxide, more preferably It is between 250 ° C and 300 ° C. If the hydrotalcite with crystal water is less than 2 Torr. At a temperature of 10, it is heat treated and the hydrotalcite may not be dehydroxylated. If the hydrotalcite is heat treated at a temperature above 39 ° C, the hydrotalcite can undergo dehydroxylation and further decarbonation, resulting in poor fluorine resistance. Therefore, the partially de-saturated hydrotalcite obtained by heat treatment at about 25 (TC to 3 〇〇t: is useful for improvement of chlorine resistance. The partially dehydroxylated hydrotalcite of the present invention can absorb air. Moisture's but most of the absorbed water is at about 100. (: is evaporated, and therefore this absorbed water is different from that in the hydrotalcite before heat treatment and at about 17 (TC to 22) (The crystal water evaporated under TC. Therefore, the partially dehydroxylated hydrotalcite is believed to have an effect on the fading of the spandex yarn at a ratio equal to or higher than 200. Because the water absorbed therein is about 1 〇〇. (: has been removed, and when the initial crystallization water in the hydrotalcite with crystal water is equal to or higher than 20 〇. The evaporation of the spandex during the process can cause fading of the spandex yarn. Similarly, the spandex fiber of the present invention obtained by adding the partially dehydroxylated hydrotalcite is prepared by adding hydrotalcite having crystal water. Pan Yi, Kesi fiber has better (four) gas, which is expected to be this part De-chemicalization, the double-layered hydroxide (tetra) of the hydrotalcite is altered to increase its effect on the capacity of water absorption and ion exchange. = Polyamines used in the preparation of spandex fibers according to the present invention are Known - conventional hydrazine preparation, such that an organic diisocyanate (tetra) and - two compound anti-heart drive through the product, dry # should produce - polyurethane front disk ~ make the far precursor dissolved in - organic solvent and allow / , ~Diamine and monoamine reaction ^ The solution of the present invention - the isocyanate includes diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, toluene-isocyanate, butyl diisocyanate ( Butylenediscocyanate) and hydrogenated diphenylmethane-4,4'-diisocyanate. Likewise, examples of the diol polymer which can be used in the present invention include polybutylene glycol, polypropylene glycol, polydicarbonate, and the like. The diamine serves as a chain extender and examples thereof are ethylenediamine, propylenediamine and hydrazine. A monoamine is used as a chain terminator, and the monoamine may be diethyldiamine, ethanolamine or dimethylamine. In the present invention, The polyurethane for preparing the spandex fiber may further comprise an organic additive comprising a hindered phenol-based compound 10, benz furanone, an amine urea, a benzotrisene, a double a hindered amine-based compound, and a polymeric tertiary amine stabilizer, such as a polyamine having a tertiary nitrogen atom and a polydialkyl aminoalkyl methacrylate, so as to prevent The spandex fiber is discolored and deteriorates in physical properties. Further, the spandex fiber of the present invention may further comprise an inorganic additive such as titanium oxide and stearic acid. The whiteness of the spandex fiber is desired. 'The one oxidation can be used in an amount of from 1 wt% to 5 wt%. To increase the unwinding properties of the spandex fibers, the magnesium stearate can be used in an amount of from 0.1% by weight to 2% by weight. 2〇 According to the present invention, the partially de-hydrophobized hydrotalcite may be used in an amount of from 0 Jwt% to 100% by weight based on the weight of the polyurethane to be used. When the amount is less than 0.1% by weight, the gas resistance of the spandex fiber is insufficient, and when the amount is more than 10% by weight, the strength, elongation and modulus of the spandex fiber are deteriorated. . In the preparation of spandex fibers according to the invention, the partially dehydroxylated hydrotalcite can be added to the polyurethane at any convenient time, for example, by mixing with an additive followed by a sanding or grinding process. Thereafter or after a matte or grinding process that lacks an additive. 5 In the present invention, the partially dehydroxylated hydrotalcite can be more advanced coated or uncoated by the coating agent conventionally used in the art, which does not affect the gas resistance and fading of the spandex. Examples of the coating agent include aliphatic alcohols, fatty acids, fatty acid salts, fatty acid esters, carboxylic acid esters, styrene-bake/maleic anhydride copolymers, and derivatives thereof, and decane-based couplings 10 , a titanate-based coupling agent, a polyorganisms, a polyoxo-polyorganohydrogen oxane, and a melamine-based compound. Among these examples, fatty acids, fatty acid salts and/or melamine-based compounds are preferred because the first two exhibit excellent coating efficiency when dehydrogenated by heat-treated hydrotalcite. And the last one can minimize fading. 15 The hydrotalcite coating process can be carried out by adding a coating agent (the coating agent is added in an amount of 0.1% by weight to 10% by weight based on the weight of the hydrotalcite), such as water, alcohol, ether Or a solvent of dioxane to obtain a coating agent solution, adding hydrotalcite thereto and stirring the resulting solution for a period of time at an elevated temperature of 50 ° C to 170 ° C (if necessary, using a high pressure reactor) It was operated for 2 minutes to 2 hours, then filtered and dried. Alternatively, the coating process can also be operated by hot melt a solvent free coating agent and mixing the molten coating agent with hydrotalcite in a high speed mixer. In particular, the coating process using a melamine-based compound in water should be carried out at atmospheric pressure at a temperature higher than or equal to 15 (TC 13 1322838) due to the melamine-based compound. High melting point. The coating process using the fatty acids or the fatty acid salts in water is preferably carried out at a temperature equal to or higher than 100 ° C. When the coating temperature is less than 10 ° C It is difficult to achieve a uniform coating and non-fading, and the amount of coating agent required is increased by, for example, at less than 100 ° C in terms of hydrotalcite in the coating process, or The amount of the fatty acid salt is about 3% by weight, and the amount used can be reduced to 1.5% by weight based on the hydrotalcite in the coating process at 100 ° C or higher. In the heat treatment of the hydrotalcite, such a The reduced amount of coating agent can reduce its fading effect. 10 The fatty acids used as a coating agent in the present invention are preferably selected from monohydroxy fatty acids or polyhydroxy fatty acids, monohydroxy fatty acids or polyhydroxy fatty acids. Is 3 to 40 carbon atoms a branched or branched hydrocarbon chain, for example, lauric acid, caproic acid, palmitic acid or stearic acid. The fatty acid salts used as a coating agent in the present invention are composed of 15 6 to 30 carbons. a monofunctional or difunctional and saturated or unsaturated fatty acid of an atom, and a metal selected from the group consisting of metals of Group I to Group III of the Periodic Table of the Elements and zinc. Examples of such fatty acid salts include oleic acid, palmitic acid or The lithium, magnesium, calcium or zinc salt of stearic acid is preferably magnesium stearate, calcium stearate and stearic acid, more preferably magnesium stearate. 20 Used in the present invention The melamine-based compound as a coating agent includes a melamine compound, a phosphorus-containing melamine compound, and a melamine cyanurate compound, optionally substituted by an organic compound having a carboxyl group, which may be used alone or in combination. Used. Examples of melamine compounds include methylene dimelamine, ethylene-14 bismelamine, trimethylene diglycolamine, tetramethylene diglycolamine, hexamethylene dimelamine, and tenth Base two three Cyanamide, dodecamethylene dimelamine, 1,3-cyclohexylidene dimelamine, p-phenylene dimelamine, p-xylene dimelamine, di-extension ethyl tri-melamine, tri- 5 ex-ethyl tetramelamine, four Ethyl pentamine, hexaethyl melamine and melamine formaldehyde. Examples of melamine-containing compounds include any of the above-mentioned melamine compounds linked to phosphoric acid or monophosphate, for example, melamine pyrophosphate, melamine a primary phosphate, a melamine secondary phosphorus 10-acid salt, a melamine polyphosphate, a bis-(neopentitol phosphate) melamine salt, etc. Examples of the cyanuric acid melamine compound include at least one selected from the group consisting of A melamine cyanurate compound substituted with a substituent of a phenyl group, a phenyl group, a carboxymethyl group, a 2-carboxyethyl group, a cyanoguanidinyl group or a 2-cyanoethyl group. Preferably, the above melamine-based compound is reacted with a compound having a fluorenyl group. Examples of the compound of the (four) having - county include aliphatic monoretinic acid (for example, caprylic acid, deca-acid, lauric acid, undecanoic acid + tetraacid, pentadecanoic acid, palmitic acid, heptadecanoic acid stearic acid) , 19 &L -10 S夂, -dodecanoic acid), aliphatic diacyl acid (for example, malonic acid, succinic acid, glutaric acid, adipic acid 'pimelic acid, suberic acid , azelaic acid, —,·undecanedioic acid (7) azelaic acid (3) undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 113-tridecanedicarboxylic acid, and w-fourth dicarboxylic acid) , aromatic mononuclear (for example, benzoic acid, phenylacetic acid, & naphthoic acid 'β_# formic acid, eynnamie _, p-amino hippuric acid and 4 (2·嗟15 oxazolidine)-phthalaninoic acid), Aromatic dicarboxylic acids (for example, terephthalic acid, isophthalic acid, and phthalic acid), aromatic tricarboxylic acids (for example, 'trimellitic acid, l53, 5-benzenetricarboxylic acid, and Cis(2-carboxyethyl)dimeric isocyanate), aromatic tetraacids (for example, pyromellitic acid and biphenyltetracarboxylic acid), aliphatic cyclic monocarboxylic acids (for example, cyclohexane carboxylate) Acid) and aliphatic Like dicarboxylic acids (for example 'Shu, cyclohexanedicarboxylic acid 2_). The coating agent increases the dispersibility of the hydrotalcite in a spandex polymer solution and maintains the spinnability of the spandex. However, 'although the hydrotalcite is not coated, it can exhibit an excellent spinnability of 10' which is substantially equivalent to the spinnability of the coated hydrotalcite when it is sanded or ground. 15 20 The sanding or grinding process can be operated by grinding with a conventional bead mill, the hydrotalcite, a small amount of polyamine, and a mixture or slurry. The small amount of polyurethane used increases the dispersibility of the hydrotalcite. Examples of solvents which can be used in the sanding or grinding process include a mixture of oxime, dimethylformamide, dimethyl sulfoxide and the like. When the hydrotalcite is ground or ground to have a small secondary particle equal to an average size of 15 tons, in the preparation of the Span: dimension, it can exhibit a function equivalent to being coated and The function of fiber or ground hydrotalcite. Broken sand is also 'in the present invention, the heat used for the hydrotalcite is used to produce various types of desiccant to produce about 2 〇 (rc to 39 〇 can be made, for example, for example, and is handled by the heart Those operating in convection, conduction, radiation, microfabrication. The invention will be further described in detail with reference to the embodiments. However, it should be understood that the invention is not Limitations. Preparation of the smoothed stone which was dehydroxylated in the examples. 5 Preparation Example 1 Stearic acid and hydrotalcite having the chemical formula Mg8Al4(OH)24(C〇3)2.6H2〇 were successively added to water. The amount of stearic acid was 2 wt/w produced by the mixture at 15 Torr. (: stirred for 20 minutes, filtered and dried) to obtain stearic acid coated hydrotalcite. The hydrotalcite coated with 10 was heat-treated at 250 ° C for 4 hours to obtain a stearic acid-coated hydrotalcite having the chemical formula Mg8Al4(0H)1604(C03) 2. Preparation Example 2 Stearic acid, melamine polyphosphoric acid Salt and hydrotalcite with the chemical formula Mg8Al4(OH)24(C〇3)2*6H2〇 are successively added Into the water. 15 The amounts of stearic acid and melamine polyphosphate were 2 wt% and 1 wt%, respectively, based on the weight of the hydrotalcite. The resulting mixture was mixed at 160 ° C for 30 minutes, filtered and It is dried to obtain hydrotalcite coated with stearic acid and melamine polyphosphate. The coated hydrotalcite is heat treated at 250 ° C for 4 hours to obtain a coating of stearic acid and melamine polysulphate. Covered hydrotalcite having a chemical formula of Mg8Al4(0H)1604(C03)2. Preparation Example 3 Except that hydrotalcite having the chemical formula Mg8Al4(0H)24(C03)2.6H20 was coated with 3 wt% of melamine polyphosphate The procedure in Preparation 2 was repeated to obtain a hydrotalcite coated with melamine polyphosphate having the formula 17 ''Mg8Al4(〇H)i6〇4(C〇3) 2. Then, the product was under humid air . exposed for 7 days to obtain melamine coated chemical formula
Mg8Al4(〇H)1604(C〇3)2.6H20 之水滑石。 I備例4 具有化學式Mg8Al4(OH)24(C03)2.6H2〇之水滑石在 25〇°C下被熱處理4小時,以得到具有化學式 Mg8Al4(0H)1604(C03)2之水滑石。該產物在室溫下被浸入水 • 中5小時並且在6(TC下被乾燥48小時,以得到具有化學式Mg8Al4(〇H) 1604(C〇3) 2.6H20 hydrotalcite. I. Preparation 4 Hydrotalcite having the chemical formula Mg8Al4(OH)24(C03)2.6H2〇 was heat-treated at 25 ° C for 4 hours to obtain hydrotalcite having the chemical formula Mg8Al4(0H)1604(C03)2. The product was immersed in water for 5 hours at room temperature and dried at 6 (TC for 48 hours to obtain a chemical formula).
Mg8Al4(〇H)16〇4(C03)2.7H20 之水滑石。 1〇 I備例5 除了用1.5wt%的硬脂酸塗覆具有化學式Mg9Al3(〇H)24 (e〇3)i.5’7.5H20之水滑石外,重複製備例1中的程序,以得 到經硬脂酸塗覆的具有化學式Mg9Al3(〇H)18〇3(c〇3)15之水 滑石。 * !備例6 ® 除了用1.5wt%的硬脂酸和lwt%的三聚氰胺聚磷酸鹽 塗覆具有化學式Mg9Al3(0H)24(C03)15.7.5H20之水滑石 外’重複製備例2中的程序,以得到由硬脂酸和三聚氰胺聚 鹽塗覆的具有化學式Mg9Ai3(〇H)i8〇3(C〇3)i.5之水滑 20石。 製備侧7 除了用3wt%的三聚氰胺聚璃酸鹽塗覆具有化學式 Mg9Al3(〇H)24(c〇3)15_7.5H20之水滑石外,重複製備例2中 的程序’以得到經三聚氰胺聚磷酸鹽塗覆的具有化學式 18 1322838Water talc of Mg8Al4(〇H)16〇4(C03)2.7H20. 1〇I Preparation Example 5 The procedure in Preparation Example 1 was repeated except that hydrotalcite having the chemical formula Mg9Al3(〇H)24(e〇3)i.5'7.5H20 was coated with 1.5 wt% of stearic acid. A hydrotalcite having a chemical formula of Mg9Al3(〇H)18〇3(c〇3)15 coated with stearic acid is obtained. *Reference 6 ® except the procedure of coating the hydrotalcite having the chemical formula Mg9Al3(0H)24(C03)15.7.5H20 with 1.5 wt% of stearic acid and 1 wt% of melamine polyphosphate. To obtain a water-slip 20 stone having the chemical formula Mg9Ai3(〇H)i8〇3(C〇3)i.5 coated with stearic acid and melamine polysalt. Preparation Side 7 The procedure in Preparation 2 was repeated except that a talc of the chemical formula Mg9Al3(〇H)24(c〇3)15_7.5H20 was coated with 3 wt% of melamine polyphosphate, to obtain melamine polyphosphate. Salt coated with the chemical formula 18 1322838
MggAldOHkCMCOA.s之水滑石。然後,該產物在濕空氣 下被暴露7天,以得到經三聚氰胺聚磷酸鹽塗覆的具有化學 式 Mg9Al3(OH)1803(C03)15.7.5H20 之水滑石。 製備例8 5 具有化學式之水滑石在 250°C下被熱處理4小時,以得到具有化學式 Mg9Al3(0H)1803(C〇3)15之水滑石。該產物在室溫下被浸入 水中5小時並且在60°C乾燥48小時,以得到具有化學式 Mg9Al3(〇H)i8〇3(C〇3)i.5.8H2〇之水滑石。 10 比較製備例1 除了用3wt%的經硬脂酸取代的三聚氰胺聚磷酸鹽塗 覆具有化學式Mg6Al2(0H)i6C03.5H20之水滑石外,重複製 備例2的塗覆程序。該產物在180°C下被熱處理4小時,以得 到經經三聚氰胺聚磷酸鹽取代的硬脂酸塗覆的具有化學式 15 Mg6Al2(〇H)i6C〇3之水滑石。 比較製備例2 除了用3wt%的經硬脂酸取代的三聚氰胺聚填酸鹽塗 覆具有化學式Mg^XOHhCCVSHsO之水滑石外,重複製 備例2的塗覆程序。該產物在l〇〇°C下被熱處理丨小時,以得 20 到經經三聚氰胺聚磷酸鹽取代的硬脂酸塗覆的具有化學式 Mg6Al2(0H)16C03.5H20 之水滑石。 比較製備例3 除了用3wt%的三聚氰胺聚磷酸鹽塗覆具有化學式 MguAl/OH^COd.SH2。之水滑石外’重複製備例2的塗 19 1322838 覆程序。然後,該產物在100 C下被乾燥1小時,以得到用 三聚氰胺聚磷酸鹽塗覆的具有化學式 Mg4.5Al2(〇H)nC〇3_3 ·5Η2〇之水滑石。 比較盤備例4 5 硬脂酸和具有化學式Mg6Al2(〇H)i6C〇3.5H2〇之水滑石 被接連地加入到水中》以該水滑石的重量計,硬脂酸的量 是3wt% ’並且所產生的混合物在95°C下被攪拌3〇分鐘、被 過濾並且被乾燥,以得到經硬脂酸塗覆的水滑石。該經塗 覆的水滑石在180°C下被熱處理4小時,以得到經硬脂酸塗 1〇 覆的具有化學式Mg6Al2(0H)16C03之水滑石。 比較Μ備例5 具有化學式Mg6Al2(OH)i6CCV5H2〇之水滑石在18〇。〇 下被熱處理4小時,以得到具有化學式Mg6Al2(〇H)16C03之 水滑石。 15 實驗實施例1 :水滑石的27A1魔角自旋核磁$艇丨ΜΑς NMR)分妍 該得到的水滑石是由27Α1魔角自旋核磁共振(MAS NMR)分析來檢查其中的部分去經化。 明確地,27A1 MAS NMR分析是使用一400MHz固態 2〇 NMR光譜儀(Varian,USA)在如下條件下***作的:Al2〇3 標準品,104·21ΜΗζ發射頻率,15kHz轉速,掃描次數: 512(水滑石粉末)或8192(含有水滑石的紗線)和一具有2.3gs 脈波長的脈衝。 該得到的27A1 MAS NMR結果可被用來確定在該水滑 20 1322838 石内A13周圍的結構。例如,來自製備例2中使用的具有化 學式 Mg8Al4(OH)24(C〇3)2.6H2〇之初始水滑石的 27Ai j^AS NMR資料顯示出一有關於八面體配位的a13+的峰,如第2圖 中所顯示’而在製備例2中得到的Mg8Al4(〇H)1604(C03)2之 5水滑石的資料既顯示八面體配位的Al3+的峰又顯示作為部 分去經化的結果的四面體配位的Al3+的峰,如第3圖所顯示。 因此,在製備例2中得到的水滑石被發現部分去羥化, 可由四面體的峰的存在而被證實。 實驗實施例2 :水滑石的紅外線(iw今析 10 在製備例2中得到的水滑石也由IR光譜分析來檢查其 中的部分去羥化。如果該水滑石被部分去羥化,一IR吸收 光譜在約1500cm-1至1600cm-1的波數處顯示一明顯的峰。 明確地,IR分析是根據ATR(減弱全反射法)使用IFS 88(Bruker,德國)在如下條件下***作: 15的波數區域’ ^m·1解析度,以及掃描次數:16。 在製備例2中使用的具有化學式 Mg8Al4(OH)24(C〇3)2’6H2〇之初始水滑石的ir吸收光譜顯示 出在約1300cm1至1400cm-1波數處的一足夠大的吸收峰,如 第6圖所顯示,而在製備例2中得到的具有化學式 20 MgsAl4(OH)i6〇4(C〇3)2之水滑石的光譜顯示在約13〇〇cm-i 至1400cm·1和約1500cm1至1600cm·1的波數處的相當大的 吸收峰’如第7圖所顯示的。 因此,只有在製備例2中得到的水滑石被發現是部分去 羥化的,是由在約1500cm·1至1600cm·1處一明顯的峰的存在 21 1322838 而被證實。 實施例1 -8和比鲂f施例1 -5 518g二苯甲烷-4,4,-二異氰酸酯和2,328g聚丁醚二元醇 (Mw 1,800)在一氮氣氛圍内80°C下攪拌反應9〇分鐘’產生一 5 在兩個端基具有異氰酸酯基的聚胺酯預聚合物。在使該預 聚合物冷卻至室溫後,加入4,269g二甲基乙醯胺,得到一 聚胺酯預聚合物溶液。接下來,在l,117g二甲基乙醯胺中溶 解34.4g乙二胺、l〇.6g丙二胺和9.1g二乙胺。該產物溶液在 等於或低於l〇°C下被加入該預聚合物溶液中,以得到一聚 10 胺酯溶液。 以該聚胺酯溶液固體部分的全部重量計,lwt%的亞乙 基-雙(氧亞乙基)雙-(3-(5-第三丁基-4-羥基-間-甲苯基)-丙 酸酯)、lwt%的雙(N,N-二甲基醯肼氨基-4-苯基)甲烷、lwt〇/0 的聚(N,N-二乙基-2-胺乙基甲基丙烯酸酯)、〇.5wt%的二氧 15 化鈦、0.5wt%的硬脂酸錢、4wt%的由製備例1-8和比較製備 1-5得到的每一個水滑石(透過使用Advantis V3(Drais Mahnheim,德國)在二曱基乙醯胺中分散和研磨)與該聚胺 酯溶液混合,以得到一聚胺酯的紡絲溶液。 該聚胺酯的紡絲溶液然後在一 250°C的紡紗溫度下繼 2〇 而被去泡沬並且被乾紡,得到一4-絲40-丹尼的斯潘德克斯 纖維。 測量該等得到的斯潘德克斯纖維的下列性質,並且該 等結果在表1中顯示: (1)耐氣性 22 1322838 受到50%拉伸的斯潘德克斯紡紗用水(pH 4.2,97-981) 處理2小時並且被冷卻至室溫。該斯潘德克斯紡紗被浸在45 公升含有3.5ppm活性氣的氣化水(pH 7.5)中24小時,並且其 強度是在300mm/min的衝頭移動速率下,用Instron 5 4301(Instron Co·,USA)透過將 lkg的小室(cell)施加至一5cm 長的樣件上來測量,如下計算強度保存率: 強度保存率(%)=(S/SG)xl〇〇 (其中,S〇是處理之前的強度,以及S是處理之後的強度) (2)抗褪色性 10 單獨使用一斯潘德克斯在一管針針織機(KT-400,直徑 是4英吋,400針,Nagata Seiki Company,日本)上製備圓形 針織物,並且在90°C下使用一洗滌劑、2g/L的UNITOL CT-81 (Shinyong Chemical,韓國)、3g/L的 UNITOL-SMS(ShinyongWater talc of MggAldOHkCMCOA.s. Then, the product was exposed to moisture for 7 days to obtain a hydrotalcite having a chemical formula of Mg9Al3(OH)1803(C03)15.7.5H20 coated with melamine polyphosphate. Production Example 8 5 Hydrotalcite having a chemical formula was heat-treated at 250 ° C for 4 hours to obtain a hydrotalcite having a chemical formula of Mg9Al3(0H)1803(C〇3)15. The product was immersed in water at room temperature for 5 hours and dried at 60 ° C for 48 hours to obtain hydrotalcite having the chemical formula Mg9Al3(〇H)i8〇3(C〇3)i.5.8H2〇. 10 Comparative Preparation Example 1 The coating procedure of Preparation Example 2 was repeated except that the hydrotalcite having the chemical formula Mg6Al2(0H)i6C03.5H20 was coated with 3 wt% of the stearic acid-substituted melamine polyphosphate. The product was heat-treated at 180 ° C for 4 hours to obtain a stearic acid-coated hydrotalcite having a chemical formula of 15 Mg6Al2(〇H)i6C〇3, which was substituted with melamine polyphosphate. Comparative Preparation Example 2 The coating procedure of Preparation 2 was repeated except that the hydrotalcite having the chemical formula Mg^XOHhCCVSHsO was coated with 3 wt% of the stearic acid-substituted melamine poly-salt. The product was heat treated at 1 ° C for a few hours to obtain a hydrotalcite of the formula Mg6Al2(0H)16C03.5H20 coated with stearic acid substituted with melamine polyphosphate. Comparative Preparation Example 3 except that the chemical formula MguAl/OH^COd.SH2 was coated with 3% by weight of melamine polyphosphate. Outside the hydrotalcite' repeat the preparation procedure of the preparation of Example 2, 13 1322838. Then, the product was dried at 100 C for 1 hour to obtain a hydrotalcite having a chemical formula of Mg4.5Al2(〇H)nC〇3_3 ·5Η2〇 coated with melamine polyphosphate. Comparative tray preparation example 4 5 stearic acid and hydrotalcite having the chemical formula Mg6Al2(〇H)i6C〇3.5H2〇 are successively added to water. The amount of stearic acid is 3 wt% 'by weight of the hydrotalcite and The resulting mixture was stirred at 95 ° C for 3 minutes, filtered and dried to obtain a stearic acid coated hydrotalcite. The coated hydrotalcite was heat-treated at 180 ° C for 4 hours to obtain a stearic acid-coated hydrotalcite having the chemical formula Mg6Al2(0H)16C03. Comparative Preparation Example 5 Hydrotalcite having the chemical formula Mg6Al2(OH)i6CCV5H2 is at 18 Torr. The crucible was heat treated for 4 hours to obtain a hydrotalcite having the chemical formula Mg6Al2(〇H)16C03. 15 Experimental Example 1: 27A1 Magic Angle Spin Nuclear Magnetic Reel of Hydrotalcite NMR) The hydrotalcite obtained by this method was examined by 27 Α 1 magic angle spin nuclear magnetic resonance (MAS NMR) analysis to examine partial de-chemicalization. . Specifically, 27A1 MAS NMR analysis was performed using a 400 MHz solid state 2 NMR spectrometer (Varian, USA) under the following conditions: Al2〇3 standard, 104·21 ΜΗζ emission frequency, 15 kHz rotation, number of scans: 512 (water) Talc powder) or 8192 (hydrotalcite-containing yarn) and a pulse having a wavelength of 2.3 gs. The resulting 27A1 MAS NMR results can be used to determine the structure around the A13 in the water slide 20 1322838. For example, the 27Ai j^AS NMR data from the initial hydrotalcite having the chemical formula Mg8Al4(OH)24(C〇3)2.6H2〇 used in Preparation Example 2 shows a peak of a13+ with respect to octahedral coordination, The data of the 5 hydrotalcite of Mg8Al4(〇H)1604(C03)2 obtained in Preparation Example 2 as shown in Fig. 2 shows both the octahedral coordinated Al3+ peak and the partial de-chemicalization. The result of the tetrahedral coordination of the Al3+ peak is shown in Figure 3. Therefore, the hydrotalcite obtained in Preparation Example 2 was found to be partially dehydroxylated, which was confirmed by the presence of a tetrahedral peak. Experimental Example 2: Infrared rays of hydrotalcite (iw) 10 The hydrotalcite obtained in Preparation Example 2 was also examined for partial dehydroxylation by IR spectroscopy. If the hydrotalcite is partially dehydroxylated, an IR absorption The spectrum shows a distinct peak at a wavenumber of about 1500 cm-1 to 1600 cm-1. Specifically, the IR analysis is operated according to ATR (attenuated total reflection method) using IFS 88 (Bruker, Germany) under the following conditions: Wavenumber region ' ^m·1 resolution, and number of scans: 16. The ir absorption spectrum of the initial hydrotalcite having the chemical formula Mg8Al4(OH)24(C〇3)2'6H2〇 used in Preparation Example 2 A sufficiently large absorption peak at a wavenumber of about 1300 cm1 to 1400 cm-1, as shown in Fig. 6, and having the chemical formula 20 MgsAl4(OH)i6〇4(C〇3)2 obtained in Preparation Example 2 The spectrum of the hydrotalcite shows a considerable absorption peak at a wave number of about 13 〇〇cm-i to 1400 cm·1 and about 1500 cm1 to 1600 cm·1 as shown in Fig. 7. Therefore, only in the preparation example The hydrotalcite obtained in 2 was found to be partially dehydroxylated and was a distinct peak at about 1500 cm·1 to 1600 cm·1. It was confirmed that there was 21 1322838. Example 1 -8 and specific 鲂 f Example 1-5 518 g of diphenylmethane-4,4,-diisocyanate and 2,328 g of polybutylene glycol (Mw 1,800) in a nitrogen atmosphere The reaction was stirred at 80 ° C for 9 minutes to produce a 5 polyurethane prepolymer having an isocyanate group at both end groups. After cooling the prepolymer to room temperature, 4,269 g of dimethylacetamide was added. A polyurethane prepolymer solution was obtained. Next, 34.4 g of ethylenediamine, 1.06 g of propylenediamine and 9.1 g of diethylamine were dissolved in 1,117 g of dimethylacetamide. The product solution was equal to or low. Adding to the prepolymer solution at 10 ° C to obtain a poly 10 amine ester solution. 1 wt% of ethylene-bis(oxyethylene) double based on the total weight of the solid portion of the polyurethane solution -(3-(5-t-butyl-4-hydroxy-m-tolyl)-propionate), 1 wt% of bis(N,N-dimethylindenyl-4-phenyl)methane, Poly (N,N-diethyl-2-amine ethyl methacrylate) of lwt 〇 /0, 5 5 wt% of titanium dioxygen pentoxide, 0.5 wt% of stearic acid money, 4 wt% of Preparation Examples 1-8 and Comparative Preparations 1-5 each obtained The hydrotalcite (dispersed and ground by dispersing and grinding in dimercaptoacetamide using Advantis V3 (Drais Mahnheim, Germany)) is mixed with the polyurethane solution to obtain a spinning solution of a polyurethane. The spinning solution of the polyurethane is then The spinning temperature of 250 ° C was defoamed and dried by spinning to obtain a 4-wire 40-denier spandex fiber. The following properties of the obtained spandex fibers were measured, and the results are shown in Table 1: (1) Gas resistance 22 1322838 Spandex spinning water subjected to 50% stretching (pH 4.2, 97-981 ) treated for 2 hours and cooled to room temperature. The spandex spinning was immersed in 45 liters of vaporized water (pH 7.5) containing 3.5 ppm of active gas for 24 hours, and its strength was at a punch moving rate of 300 mm/min using Instron 5 4301 (Instron Co) ·, USA) By applying a lkg cell to a 5 cm long sample, the intensity retention rate is calculated as follows: Strength retention rate (%) = (S/SG) xl 〇〇 (where S〇 is The strength before treatment, and S is the strength after treatment) (2) Foil resistance 10 Separately used a spandex in a needle knitting machine (KT-400, diameter 4 inches, 400 needles, Nagata Seiki Company, A circular knitted fabric was prepared on Japan, and a detergent, 2 g/L of UNITOL CT-81 (Shinyong Chemical, Korea), 3 g/L of UNITOL-SMS (Shinyong) was used at 90 °C.
Chemical ’韓國)和0.5g/L的NaOH之混合物在水中被洗滌歷 15 時30分鐘,水的重量是該織物重量的40倍。在如下條件下, 使用一色彩觀察(color-view)分光光度計(BKY-Gardener, USA)測量該被洗務的織物的黃化值”b” :儀器幾何形狀 (instrument geometrypAS'O。,發光物/觀測者= D65/10〇, 11 mm的樣品槔孔徑(port aperture) ’以及3次重複測量。較 2〇 低的b值是指較少的褪色。 23 C β ) 1322838 表1 塗覆劑(量a) 實施例1 實施例2 硬脂酸(2wt%) + S 聚氱胺聚磷酸鹽 nwt%) 實施例3 實施例4 實施例5 實施例6 三聚氰胺聚磷酸鹽 _(3wt%)_ 硬脂酸(.5wt%) + S 聚氰胺聚磷酸鹽 (lwt%)A mixture of Chemical 'Korea) and 0.5 g/L of NaOH was washed in water for 15:30 minutes, and the weight of water was 40 times the weight of the fabric. The yellowing value "b" of the fabric being washed was measured using a color-view spectrophotometer (BKY-Gardener, USA) under the following conditions: instrument geometry (AS) geometry (instrument geometry pAS'O., luminescence Object/observer = D65/10〇, 11 mm sample port aperture ' and 3 repeated measurements. Lower b value than 2〇 means less fading. 23 C β ) 1322838 Table 1 Coating Agent (Amount a) Example 1 Example 2 Stearic acid (2 wt%) + S polyamine polyphosphate nwt%) Example 3 Example 4 Example 5 Example 6 Melamine polyphosphate _ (3 wt%) _ Stearic acid (.5wt%) + S melamine polyphosphate (lwt%)
實施例7 實施例8 比較實施例1 比較實施例2 比較實施例3 比較實施例4 比較實施例5 三聚氰胺聚磷酸鹽 _(3wt%)_ 經硬脂酸取代的三 聚氰胺聚磷酸鹽 _(3wt°/〇)_ 經硬脂酸取代的三 聚氰胺聚磷酸鹽 (3wt°/〇) 氰尿酸三聚氰胺 (3wt°/〇) 硬脂酸(3wt%) :以水滑石重量計,該塗覆劑的量 水滑石 Mg8Al4(〇H)|6〇4(C〇3)2 Mg8Al4(〇H)16〇4(C03)2 Mg8Al4(0H)1604(C03)2.6H20 Mg8Al4(0H)1604(CO3)2.7H20 Mg9Al3(OH)1803(C03)15 Mg9Al3(OH)l803(C03)15 Mg9Al3(OH)18〇3(C〇3)i.5-7.5H20 Mg9Al3(0H)1803(C03)i.s-8H20 Mg6Al2(0H)16C03 Mg6Al2(0H)16C03.5H20 Mg4.5Al2(0H)13C03-3_5H20 MgeAl2(0H)16C03 Mg6Al2(OH)i6CO^Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Melamine Polyphosphate_(3wt%)_ Stearic acid-substituted melamine polyphosphate_(3wt° /〇)_ melamine polyphosphate substituted by stearic acid (3wt ° / 〇) melamine cyanurate (3wt ° / 〇) stearic acid (3wt%): the amount of water of the coating agent based on the weight of hydrotalcite Talc Mg8Al4(〇H)|6〇4(C〇3)2 Mg8Al4(〇H)16〇4(C03)2 Mg8Al4(0H)1604(C03)2.6H20 Mg8Al4(0H)1604(CO3)2.7H20 Mg9Al3( OH)1803(C03)15 Mg9Al3(OH)l803(C03)15 Mg9Al3(OH)18〇3(C〇3)i.5-7.5H20 Mg9Al3(0H)1803(C03)is-8H20 Mg6Al2(0H)16C03 Mg6Al2(0H)16C03.5H20 Mg4.5Al2(0H)13C03-3_5H20 MgeAl2(0H)16C03 Mg6Al2(OH)i6CO^
如表1所顯示,實施例1至實施例8的該等斯潘德克斯 維含有部分去羥化之水滑石,並且因此在一等於或高於 5 200°C的溫度下紡紗時它們不會褪色以及有好的耐氣性。相 反地’含有結晶水的斯潘德克斯纖維(比較實施例2和3)既顯 示出對在一高溫下紡紗時較差的抗褪色性又顯示出較差的 耐氣性。同樣,該等含有未部分去羥化並且缺少結晶水之 水滑石(比較實施例1、4和5)的斯潘德克斯纖維比含有結晶 10水的水滑石的斯潘德克斯纖維更抗褪色,可是,與該等發 明的斯潘德克斯纖維相比,它們較不抗褪色並且也不耐氯。 24 1322838 實驗實施例3 :在斯_轉 MAS NMR分妍 在實施例2中得到的該斯潘德克斯紗線θ SAw ., 例1的程序中的27A1MASNMR分析,並且辞从e ^ D果在第4圖中 -如第4圖中所顯示,實施例的斯潘德克斯纖維的 顯不八面體配位的ai3+的峰又顯示四面體配位的匐3+、As shown in Table 1, the spandex of Examples 1 to 8 contains partially dehydroxylated hydrotalcite, and therefore they do not spun at a temperature equal to or higher than 5 200 ° C. Fading and good gas resistance. In contrast, spandex fibers containing water of crystallization (Comparative Examples 2 and 3) showed both poor fading resistance at the time of spinning at a high temperature and poor gas resistance. Similarly, these spandex fibers containing hydrotalcite which is not partially dehydroxylated and lacking water of crystallization (Comparative Examples 1, 4 and 5) are more resistant to fading than spandex fibers containing hydrotalcite which crystallizes 10 water, but They are less resistant to fading and are also resistant to chlorine than the spandex fibers of these inventions. 24 1322838 Experimental Example 3: The spandex yarn θ SAw . obtained in Example 2 in the _ _ MAS NMR analysis, the 27A1 MAS NMR analysis in the procedure of Example 1, and the resignation from the e ^ D fruit in the first 4 - as shown in Fig. 4, the peak of the ai3+ of the octahedral coordination of the spandex of the embodiment shows the tetrahedral coordination of 匐3+,
MAS NMR今析 10 評估在實施例2中得到的部分去羥化之水滑石存在的 斯潘德克斯紗線。MAS NMR analysis 10 The spandex yarn present in the partially dehydroxylated hydrotalcite obtained in Example 2 was evaluated.
5 顯示 明確地’實施例2的斯潘德克斯紗線是透過石油醚處理 而被去油的,該無油的紗線被溶解在甲基乙醯胺中至一小 於或等於1.3%的濃度,該曱基乙酿胺含有小於或等於 15 i〇〇ppm的水分,並且該溶液是受到兩次離心分離而提取水 滑石。該被提取的水滑石在60。(:下被乾燥並且透過根據實 驗實施例1的程序中的27A1MASNMR而被分析的。 該总果證實該被提取的水滑石既具有八面體結構又具 有四面體結構,如第5圖中所顯示的。5 shows that the spandex yarn of Example 2 was degreased by treatment with petroleum ether, which was dissolved in methyl acetamide to a concentration of less than or equal to 1.3%. The mercaptoamine contains less than or equal to 15 i〇〇ppm of water, and the solution is subjected to two centrifugation to extract hydrotalcite. The extracted hydrotalcite is at 60. (The lower layer was dried and analyzed by 27A1 MAS NMR in the procedure according to Experimental Example 1. The total fruit confirmed that the extracted hydrotalcite had both an octahedral structure and a tetrahedral structure, as shown in Fig. 5. to show.
由實施例2得到的斯潘德克斯纖維提取的水滑石也是 根據實驗實施例2的程序中的IR光譜分析。 結果,該被提取的水滑石的IR吸收光譜顯示出在約 1500〇!1-1至1600(:111-1的波數處的一相當大的吸收峰如在第 25 1322838 8圖中所顯示的。 如上所描述的’本發明的斯潘德克斯纖維在紡紗時在 一等於或高於200°C的溫度下既具有高的耐氣性又具有高 的抗褪色性,並且因此對於内衣、襪子並且尤其是諸如游 5 泳衣的運動衣是有用的。The spandex extracted from the spandex obtained in Example 2 was also analyzed by IR spectroscopy in the procedure of Experimental Example 2. As a result, the IR absorption spectrum of the extracted hydrotalcite shows a considerable absorption peak at a wavenumber of about 1500 Å! 1-1 to 1600 (: 111-1 as shown in the figure of No. 25 1322838 8 As described above, the spandex fiber of the present invention has both high gas resistance and high fading resistance at a temperature equal to or higher than 200 ° C during spinning, and thus for underwear, Socks and especially sportswear such as swimwear 5 are useful.
當本發明是由該專特定的具體例所描述時,應被認可 的是由熟悉技術之人士進行的對本發明的修改和改變也被 歸入到本發明的範圍内,如該等附加的申請專利範圍所定 義的。While the invention has been described with respect to the specific embodiments, it is to be understood that modifications and variations of the invention are intended to be included within the scope of the invention As defined in the scope of patents.
10 【圖式簡單說明:J 第1圖是一顯示該水滑石結構的圖; 第2圖是一在製備例2中使用的水滑石 (Mg8Al4(OH)24(C〇3)2.6H2〇)的27Ai魔角自旋核磁共振 NMR)光譜; 15 第3圖是在製備例2得到的部分去叙儿 刀云羡化之水滑石 (Mg8Al4(OH)16〇4(C03)2)的 27A1 MAS NMR光令嚴. 第4圖是一在實施例2中得到的斯潘德克斯纺紗的〜 MAS NMR光譜; 第5圖是一從實施例2的斯潘德克斯紡紗中提取 a 20 石的27A1 MAS NMR光譜; '月 第6圖是一在製備例2中使用认 τ 1更用的該水滑石 (Mg8Al4(OH)24(C03)2.6H2〇)的紅外線(ir)吸收光^並 第7圖是一在製備例2中得到的部分去羥化之水滑石 (Mg8Al4(〇H)i6〇4(C03)2)的IR吸收光譜;及 26 1322838 第8圖是從實施例2的斯潘德克斯紡紗中提取的水滑石 的IR吸收光譜。 【主要元件符號說明】 (無)10 [Simple description of the drawings: J Figure 1 is a diagram showing the structure of the hydrotalcite; Figure 2 is a hydrotalcite (Mg8Al4(OH)24(C〇3)2.6H2〇) used in Preparation Example 2 27Ai Magic Angle Spin NMR NMR Spectroscopy; 15 Figure 3 is the 27A1 MAS of the hydrotalcite (Mg8Al4(OH)16〇4(C03)2) obtained in Preparation Example 2 NMR light is strict. Fig. 4 is a ~MAS NMR spectrum of a spandex obtained in Example 2; Fig. 5 is a 27A1 of a 20 stone extracted from the spandex of Example 2. MAS NMR spectrum; 'month 6 is an infrared (ir) absorption light of the hydrotalcite (Mg8Al4(OH)24(C03)2.6H2〇) which is used in the preparation example 2, and the seventh The figure is an IR absorption spectrum of a partially dehydroxylated hydrotalcite (Mg8Al4(〇H)i6〇4(C03)2) obtained in Preparation Example 2; and 26 1322838. FIG. 8 is a Spandec from Example 2. IR absorption spectrum of hydrotalcite extracted from Sifang. [Main component symbol description] (none)
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KR101130282B1 (en) * | 2009-10-26 | 2012-03-26 | 이화여자대학교 산학협력단 | Sepiocite Compound derived from Layered Double Hydroxide and Method for Preparing the Same |
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KR101186818B1 (en) | 2012-02-17 | 2012-09-28 | (주)우진고분자 | A surface-treated hydrotalcite and a composition comprising the same |
KR102412143B1 (en) | 2022-01-17 | 2022-06-22 | ㈜쿨베어스 | Anti-chlorine spandex containing echinoderms-derived porous material and method for manufacturing the same |
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