1237079 五、發明說明（1) 【技術領域】 本發明係關於不含鹵素、優越之難燃性且適用於室內 設計領域，特別是需具備難燃性的交通工具座椅等用途 ，由聚酯類細纖維及高分子彈性體組成，具有柔軟的觸 感、觀感之難燃性皮革樣片基體。 【背景技術】 自古以來，合成纖維特別是聚酯纖維和聚醯胺纖維等 ，因其優越的外型安定性、耐天候性、機械性特性、耐 久性等，爲衣料、室內設計等材料不可或缺的成分。但 期望能依用途使其具有更特殊的功能。例如在室內設計 領域特別是火車座椅和汽車座椅、飛機座椅等的表層材 料使用的人造皮革之領域中，具有難燃性能是非常重要 的。 以前，使用在極細纖維不織布的纒繞空間含有由高分 子彈性體組成的黏合劑之基材作爲人造皮革的基體層， 在此基材的表面其具有樹脂層，即成爲所謂的塗銀風格 的人造皮革，又在此基材的表面使具有絨毛，即成爲所 謂的絨面風格的人造皮革。使這類人造皮革基體層具有 難燃性的方法，例如利用後加工等的方法使難燃劑黏付 在纖維及黏合劑的表面之方法、將難燃性片層疊在內部 之方法、在攪拌混合有難燃性微粒之熱塑性聚合物中使 用已紡絲的纖維之方法等。 這些方法中，若採用後加工的方法，除了破壞人造皮 革的觸感、觀感之外，而且此人造皮革的表面若爲有絨 1237079 五、發明說明（2) 毛的絨面風格時，因難燃處理使表面的細緻的絨毛狀態 發生聚集使外觀變差。又，若採用將難燃性片層疊在內 部之方法，除了表面和裡面的難燃性會產生差異之外， 亦會破壞人造皮革的觸感、觀感。 使難燃劑攪拌混合在熱塑性聚合物時一般常用的添加 方法有，將以磷類或鹵素類化合物爲有效成份的難燃劑 攪拌混合在聚乙烯、聚丙烯、聚乙烯聚丙烯共聚物、聚 苯乙烯等成型材料中，使其具有難燃效果之方法。另一 方面，將此難燃劑攪拌混合在尼龍6、尼龍66、尼龍 6 1 0等聚醞胺類聚合物、聚對苯二甲酸乙二醇酯、聚對 苯二甲酸三亞甲基酯、聚對苯二甲酸丁二醇酯等聚酯類 聚合物時，從熔融紡絲溫度中難燃劑和聚合物的安定性 之觀點，紡絲溫度的設定、聚合物及難燃劑的選擇等受 限制，在生產性方面發生問題。 又採用將上述的難燃劑攪拌混合在纖維的方法時，上述 難燃性纖維若爲大於普通dtex亦即0.5 dtex的纖維即可使 用’過細的纖維不適用。例如纖維的細度對絨面風格的人 造皮革很重要，使用纖度爲小於05 dtex的纖維時可具有 細緻高級感的纖維絨毛，又從觸、觀感的觀點，可具有天 然皮革般的充實感，惟在這類的極細纖維中攪拌混合難燃 性微粒後，因難燃性微粒的粒徑和纖維切面積的關係，使 纖維物性變得極差且不耐用。 即使在纖維物性不低落並使難燃性的有機物質等分散 時，濕式處理中形成微多孔性基體去除溶劑凝固時，或 1237079 五、 發明說明 ( 3) 由 極 細 纖 維 發 生 型 纖 維 特 別 是 海 島 結 構 纖 維 組 成 薄 片 時 極 細 化 時 在 一 般 採 用 的 去 除 海 成 份 的 步 驟 中 ? 因 難 燃 性 的 有 機 物 質 會 脫 落 因 此 不 易 達 到 預 期 的 難 燃 程 度 〇 又 5 直 接 糸方 絲 等 製 造 直 接 極 細 纖 維 時 > 使 用 有 機 類 難 燃 劑 時 難 燃 劑 會 移 至 纖 維 的 表 面 可 能 發 生 使 用 製 品 時 難 燃 劑 移 至 表 面 (滲出） ，或使, 用； 於 交： 通. X 具 座: 椅 時 因: 揮 發 使 窗 戶 玻 璃 模 糊 (成霧）等 問； 題 〇 另 一 方 面 製 造 難 燃 性 皮 革 樣 片 基 體 時 使 分 散 在 局 分 子 弓早 性 體 的 難 燃 劑 可 使 用 通 常 用 於 樹 脂 的 眾 知 難 燃 劑 例如 鹵 素 類 或 磷 類 Λ 氮 類 等 有 機 難 燃 劑 金 屬 氫 氧 化 物 和 紅 磷 、 矽 類 的 Μ 機 化 合 物 等 惟 必 須 不 促 進 局 分 子 彈 性 體 及 極 細 纖 維 的 惡 化 5 又 ， 皮 革 樣 片 的 製 造 步 驟 中 進 行 凝 固 浴 和 極 細 纖 維 發 生 步 驟 時 不 被 處 理 液 溶 解 分 解 0 在 含 有 鹵 素 類 物 質 的 情 況 下 燃 燒 皮 革 樣 片 時 ， 因 會 釋 放 戴 奧 辛 類 等 有 害 物 質 ， 造 成 環 境 問 題 的 負 擔 〇 本 發 明 的 巨 的 係 單 纖 度 小 於 0 • 5 dt < 5 X 的 極 細 纖 維 較 理 想 爲 2 成 份 以 上 的 熱 可 塑 性 聚 合 物 組 成 的 合 成 或 混 合 紡 絲 纖 維 中 的 1 成 份 以 上 被 去 除 後 所 得 的 極 細 纖 維 使 此 纖 維 具 有 難 燃 性 能 但 不 使 其 纖 維 物 性 大 幅 下 降 同 時 不 促 進 局 分 子 彈 性 體 的 分 解 並 使 其 具 有 難 燃 性 具 有 柔 軟 的 觸 感 、 觀 感 而 且 不 含 鹵 素 、 耐 久 性佳 的 難 燃 性 皮 革 樣 片 〇 [ 發 明 的 揭 示 ] 本 發 明 的 作 者 們 硏 究 有 關 不 5 - 含 鹵 素 的 難 燃 性 皮 革 樣 片 1237079 五、發明說明（4) 而完成本發明。 亦即，本發明的難燃性皮革樣片基體之特徵，係小於 0 · 5 d t e X的極細纖維（A)三維纏繞形成的不織布和充塡 在其中的高分子彈性體（B )組成的皮革樣片基體中，極 細纖維（A)是由有機磷成份共聚合聚酯形成，且高分子 彈性體（B)必須滿足下列（1)或（2)中任一項。 (1)高分子彈性體（B)含有金屬氫氧化物； (2 )局分子彈性體（B )係由有機磷成份共聚而成。 又，本發明的難燃性皮革樣片基體之製法，其特徵係 製造由小於0.5 dtex的極細纖維（A)三維纏繞形成的不 織布和充塡在其中的高分子彈性體（B)組成的皮革樣片 基體時，下列①〜③的步驟， ① 以含有有機磷成份的聚酯爲極細纖維，製造由極細 纖維發生型纖維組成的纖維纏繞不織布之步驟， ② 使此不織布中含有包含金屬氫氧化物或由有機磷成 份共聚形成的高分子彈性體（B)之步驟， ③ 將此極細纖維發生型纖維轉換成單纖維纖度小於 〇· 5 dtex的極細纖維（A)束之步驟， 以①②③的順序或①③②的順序進行。 【進行發明的最佳型態】 此製法中，可利用眾知的方法製造單纖維纖度小於 〇· 5 dtex的極細纖維束。例如由相溶性小的2種類以上 的聚合物組成，切面中含有至少1種類的聚合物以此爲 島成份，除此之外尙有至少1種類的聚合物爲海成份所 1237079 五、發明說明（5 ) 組成的極細纖維發生型纖維，溶解或分解去除極細纖維 發生型纖維中的至少1成份（通常爲海成份聚合物）可製 得極細纖維束，或相溶性小的2種類以上的聚合物，以 機械性或化學性處理具有已接合切面形狀的黏合型極細 纖維發生型纖維使2成份的界面脫離，藉由分解或去除 其中至少I成份可製得極細纖維束。 爲了使組成極細纖維束之極細纖維的單纖維纖度小於 0·5 dtex特別是小於0.2 dtex，在步驟上使用纖維切面由 海島結構組成的極細纖維發生型纖維比使用黏合型的極細 纖維發生型纖維更有助益。又，若單纖維纖度大於 0.0 5 dtex且具有充分的外觀、品質之皮革樣片基體，不需 進行纖維成份抽提處理或界面脫離處理等極細化步驟，亦 可利用直接紡絲法等直接製造極細纖維或由極細纖維組成 的不織布，而不需使用抽提步驟。 上述1 -3的步驟，只記載本發明的皮革樣片基體中使 用極細纖維發生型纖維時所須之步驟，亦可添加此1 -3 之外的步驟，例如1的步驟後可添加不織布的熱加壓步 驟，或將代表性的糊材料加入聚乙烯醇中，使暫行固定 之步驟等。 本發明中，從海島結構纖維取得極細纖維時，可將2 種類以上相溶性小的熱塑性聚合物經過合成紡絲或混合 紡絲而製得。因此，爲了使從海島結構纖維去除海成份 所得的極細纖維束具有難燃性，必需使島成份中使用的 樹脂難燃化。 1237079 五、發明說明（6) 纖維本身的難燃化（非爲後加工）通常採用在紡絲時攪 拌混入無機化合物、有機鹵化物、含鹵素之有機磷化合 物、有機磷化合物等難燃劑之方法，惟會發生難燃劑的 反應惡化、纖維物性低落等問題，以極細纖維爲對象時 ，去除海成份聚合物時會發生難燃劑脫落等問題。又， 使用含鹵素化合物雖可提供優越的難燃性能，惟會有燃 燒時產生對人體有害的物質例如戴奧辛等問題。因此， 爲了使交通工具的座椅片中使用的人造皮革具有難燃性 ，使用含鹵素化合物之方法並不理想。 了解全部的這些問題，爲使極細纖維具有難燃性的方 法，在本發明中採用海島結構纖維時使用有機磷成份共 聚樹脂作爲島成份。有機磷成份共聚樹脂例如有纖維素 、聚酯、苯酚等的共聚樹脂，考量可用於熔融紡絲及滿 足合人造皮革的必要物性等，本發明中使用有機磷成份 共聚合聚酯。例如可使用特開昭5 1 - 8 2 3 9 2號公報、特 開昭5 5 - 7 8 8 8號公報、特公昭55-41610號公報中記載 的眾知的有機磷成份共聚合聚酯。在此無特別規定有機 磷成份共聚合聚酯的製法，例如可採用二羧酸二酯和二 醇的酯交換法時，進行酯交換反應時添加有機磷化合物 之方法、縮聚反應前或反應初期階段中添加有機磷化合 物之方法，當利用二羧酸和二醇的酯化法時，亦可採用 在任意的酯化反應階段中添加有機磷化合物之方法。 反應中使用的有機磷化合物例如前述的公報中所舉 例的噚磷酸、膦酸衍生物、磷菲衍生物等，其中以下述 1237079 五、發明說明（7) 化學式I表示的磷菲衍生物爲最理想的含磷原子化合物。1237079 V. Description of the invention (1) [Technical Field] The present invention relates to halogen-free, superior flame retardancy, and is suitable for interior design fields, especially for uses such as vehicle seats that require flame retardance. Composed of fine fibers and polymer elastomers, it has a soft flame-resistant leather-like film base with a soft touch and appearance. [Background Art] Since ancient times, synthetic fibers, especially polyester fibers and polyamide fibers, have been unsuitable for materials such as clothing and interior design due to their superior appearance stability, weather resistance, mechanical properties, and durability. Or missing ingredients. However, it is expected to have more special functions depending on the application. For example, in the field of interior design, particularly in the field of artificial leather used as the surface material of train seats, car seats, aircraft seats, etc., it is very important to have flame retardancy. In the past, a base material containing an adhesive composed of a polymer elastomer in the winding space of an ultra-fine fiber nonwoven fabric was used as a base layer of artificial leather. A resin layer was formed on the surface of the base material, which became a so-called silver-coated style. The artificial leather has a fluff on the surface of the substrate, which is a so-called suede-like artificial leather. Methods for making such artificial leather substrates flame-resistant, for example, methods such as post-processing to adhere flame-retardants to the surfaces of fibers and adhesives, methods to laminate flame-resistant sheets inside, and stirring A method of using a spun fiber in a thermoplastic polymer mixed with flame-resistant fine particles, and the like. Among these methods, if the post-processing method is used, in addition to destroying the feel and look of the artificial leather, and if the surface of the artificial leather is velvet 1237079 V. Description of the invention (2) The suede style of wool is difficult. Combustion treatment aggregates the fine fluff on the surface and deteriorates the appearance. In addition, if a method of laminating a flame-resistant sheet inside is used, in addition to the difference in flame resistance between the surface and the inside, the touch and look of artificial leather are also destroyed. Commonly used addition methods for mixing and mixing flame retardants in thermoplastic polymers include mixing and mixing flame retardants containing phosphorus or halogen compounds as effective ingredients in polyethylene, polypropylene, polyethylene polypropylene copolymer, and polymer. It is a method for making flame retardant effects in molding materials such as styrene. On the other hand, this flame retardant is stirred and mixed in polyamine polymers such as nylon 6, nylon 66, and nylon 6 10, polyethylene terephthalate, polytrimethylene terephthalate, For polyester polymers such as polybutylene terephthalate, from the viewpoint of the stability of the flame retardant and the polymer at the melt spinning temperature, the setting of the spinning temperature, the selection of the polymer and the flame retardant, etc. Restricted and problems in productivity. When the method of mixing and mixing the above-mentioned flame retardant with the fiber is used, if the flame retardant fiber is a fiber larger than ordinary dtex, that is, 0.5 dtex, the fiber which is too thin is not suitable. For example, the fineness of the fiber is very important for suede-like artificial leather. When using a fiber with a fineness of less than 05 dtex, it can have a fine and high-quality fiber fluff, and from the perspective of touch and appearance, it can have a natural leather-like fullness. However, after the flame retardant fine particles are stirred and mixed in such ultrafine fibers, the physical properties of the fibers are extremely poor and not durable due to the relationship between the particle size of the flame retardant fine particles and the fiber cut area. Even when the fiber's physical properties are not degraded and the flame-resistant organic substances are dispersed, a microporous substrate is formed in the wet process to remove the solvent and solidify, or 1237079 V. Description of the invention (3) Ultrafine fiber-generating fibers, especially islands In the process of thinning the structure fiber to form a thin sheet, in the general step of removing the sea component? Because the flame-retardant organic material will fall off, it is difficult to achieve the desired flame-retardant level. When using organic flame retardant, flame retardant will move to the surface of the fiber. It may happen that the flame retardant moves to the surface (bleeding out) when using the product, or use, use; Interchange: Pass. X Seat: Chair when: The volatility makes the window glass fuzzy (fog), etc .; On the other hand, when manufacturing a flame-resistant leather-like matrix, the flame retardant dispersed in the local molecular bow premature body can be used. Well-known flame retardants such as halogen-based or phosphorus-based Λ-nitrogen-based organic flame retardants such as metal hydroxides, red phosphorus, and silicon-based organic compounds, but must not promote the deterioration of local molecular elastomers and ultrafine fibers. In the manufacturing step of the leather sample, the coagulation bath and the ultrafine fiber generation step are not dissolved and decomposed by the treatment solution. 0 When the leather sample is burned with a halogen-containing substance, it may release dioxin and other harmful substances, causing a burden on environmental problems. 〇 The ultra-fine fibers of the present invention having a single fineness of less than 0 • 5 dt < 5 X are more preferably obtained by removing more than 1 component from synthetic or mixed spinning fibers composed of a thermoplastic polymer having 2 or more components. The ultrafine fiber makes this fiber have flame retardant properties but does not greatly reduce its fiber physical properties and does not promote the Decompose and make it non-flammable, have a soft touch, look and feel, and contain halogen-free, durable flame-resistant leather samples. [Disclosure of the Invention] The authors of the present invention have investigated Flammable leather sample 1237079 V. Description of the invention (4) The present invention has been completed. That is, the characteristics of the base of the flame-resistant leather-like sheet of the present invention are a leather-like sheet composed of a non-woven fabric formed by three-dimensional winding of extremely fine fibers (A) less than 0.5 dte X and a polymer elastomer (B) filled therein. In the matrix, the ultrafine fibers (A) are formed by copolymerizing polyesters with an organic phosphorus component, and the polymer elastomer (B) must satisfy any of the following (1) or (2). (1) High molecular elastomer (B) contains metal hydroxide; (2) Local molecular elastomer (B) is made by copolymerizing organic phosphorus components. In addition, the method for producing a flame-resistant leather sample matrix of the present invention is characterized by manufacturing a leather sample composed of a non-woven fabric formed by three-dimensionally winding ultrafine fibers (A) of less than 0.5 dtex and a polymer elastomer (B) filled therein. In the case of the substrate, the following steps ① to ③, ① use polyester containing an organic phosphorus component as an ultrafine fiber to produce a fiber-wound nonwoven fabric composed of ultrafine fiber-generating fibers, ② make the nonwoven fabric contain a metal hydroxide or The step of polymer elastomer (B) formed by the copolymerization of organic phosphorus components. ③ The step of converting this ultrafine fiber-generating fiber into an ultrafine fiber (A) bundle with a single fiber fineness of less than 0.5 dtex, in the order of ①②③ or ①③②Sequence. [Best Mode for Inventing] In this production method, a superfine fiber bundle having a single fiber fineness of less than 0.5 dtex can be produced by a known method. For example, it is composed of two or more types of polymers with low compatibility, and at least one type of polymer is included in the cut surface as an island component. In addition, at least one type of polymer is the sea component. 1237079 5. Description of the invention (5) The ultra-fine fiber-generating fibers of the composition are dissolved or decomposed to remove at least one component (usually a sea-component polymer) of the ultra-fine fiber-generating fibers to obtain ultra-fine fiber bundles or two or more types of polymers with low compatibility. The superfine fiber-generating fiber having a bonded cut surface shape is mechanically or chemically treated to separate the two-component interface, and an ultra-fine fiber bundle can be obtained by decomposing or removing at least one of the components. In order to make the single fiber fineness of the ultrafine fibers constituting the ultrafine fiber bundle less than 0.5 dtex, especially less than 0.2 dtex, in the step, the ultrafine fiber-generating fiber composed of the sea-island structure with the fiber cut surface is used more than the ultrafine fiber-generating fiber of the bonding type. More helpful. In addition, if the single fiber fineness is greater than 0.0 5 dtex and the leather-like sample substrate has sufficient appearance and quality, it does not need to perform ultra-fine steps such as fiber component extraction treatment or interface detachment treatment, and it can also directly produce ultra-fine fibers by direct spinning method. Fibers or non-woven fabrics consisting of very fine fibers without the need for an extraction step. The above steps 1-3 only describe the steps required when using the ultrafine fiber-generating fibers in the leather-like sheet substrate of the present invention. Steps other than this 1-3 can also be added. For example, the heat of a non-woven fabric can be added after step 1. The pressing step, or the step of adding a representative paste material to polyvinyl alcohol to temporarily fix it. In the present invention, when ultrafine fibers are obtained from sea-island structure fibers, two or more types of thermoplastic polymers with low compatibility can be obtained by synthetic spinning or mixed spinning. Therefore, in order to make the ultrafine fiber bundle obtained by removing the sea component from the sea-island structure fiber flame-resistant, it is necessary to make the resin used in the island component flame-resistant. 1237079 V. Description of the invention (6) The flame retardant (not post-processing) of the fiber itself is usually mixed with inorganic compounds, organic halides, halogen-containing organic phosphorus compounds, organic phosphorus compounds and other flame retardants during spinning. In this method, problems such as deterioration of the reaction of the flame retardant and low physical properties of the fiber may occur. When the ultrafine fiber is used as a target, the problem of the flame retardant falling off may occur when the polymer of the sea component is removed. In addition, although the use of halogen-containing compounds can provide superior flame resistance, there is a problem that substances that are harmful to the human body such as dioxin are generated during combustion. Therefore, in order to make the artificial leather used in a seat sheet of a vehicle flame-resistant, a method using a halogen-containing compound is not ideal. In view of all of these problems, in order to make the ultrafine fiber flame-resistant, the organic phosphorus component copolymer resin is used as the island component when the sea-island structure fiber is used in the present invention. The organic phosphorus component copolymer resin includes, for example, copolymer resins of cellulose, polyester, and phenol. In consideration of the physical properties necessary for melt spinning and meeting artificial leather, the organic phosphorus component copolymerized polyester is used in the present invention. For example, a well-known organophosphorus copolymer copolymer polyester described in JP 5 1-8 2 3 92, JP 5 5-7 8 8 8 and JP 55-41610 can be used. . There are no special regulations for the production method of copolymerized polyesters with organophosphorus components. For example, when the transesterification method of a dicarboxylic acid diester and a diol is used, a method of adding an organophosphorus compound during the transesterification reaction, before the polycondensation reaction, or at the initial stage In the method of adding an organic phosphorus compound in the stage, when an esterification method of a dicarboxylic acid and a diol is used, a method of adding an organic phosphorus compound in an arbitrary esterification reaction stage may also be adopted. The organic phosphorus compounds used in the reaction are, for example, phosphonium phosphoric acid, phosphonic acid derivatives, and phenanthrene derivatives as exemplified in the aforementioned publication. Among them, the following 1237079 V. Description of the invention (7) The phenanthrene derivative represented by the chemical formula I is the most Ideal compound containing phosphorus atom.
Η h2c—c—cooch2ch2oh h2c—CO〇CH2CH2OH [I ] 又，基體的聚酯可使用例如聚對苯二甲酸乙二醇酯、 聚對苯二甲酸三亞甲基酯、聚對苯二甲酸丁二醇酯等眾 知的聚酯及其變性聚合物、混合聚合物、共聚聚合物等。 使用本發明的有機磷成份共聚合聚對苯二甲酸乙二醇 酯類聚酯時，可製得具有來自有機磷成份的難燃性及來 自聚對苯二甲酸乙二醇酯類聚酯的優越的機械物性和良 好的染色性之皮革樣片，較理想。 又，製造本發明有機磷成份共聚合對苯二甲酸乙二醇 酯類及聚對本二甲酸三亞甲基酯類聚酯時，主要的酸成 份用對苯二甲酸，以聚對苯二甲酸乙二醇酯類的聚酯爲 乙二醇成份時使用乙二醇，若以聚對苯二甲三亞甲基酯 類的聚酯爲乙二醇成份時則使用三亞甲基二醇，亦可依 需求含有共聚單位例如其他的二竣酸成份、羥基殘酸成 份’其他1種或2種以上的乙二醇成份。此時，其他的 一殘酸成份例如二苯二竣酸、萘二羧酸等芳香族二殘酸或 這些的酯形成性衍生物；5 -硫代對苯二甲酸二甲酯鈉、5 _硫 1237079 五、發明說明（8) 代對苯二甲酸二（2-羥乙基）酯鈉等含金屬磺酯基芳香族 羧酸或其衍生物；草酸、己二酸、葵二酸、十二烷二酸 等^肪族二羧酸或其酯形成性衍生物等。又，羥基殘酸 成份例如對羥基苯甲酸、對_ ^ _羥基乙氧基苯甲酸或其 醋形成性衍生物等。乙二醇成份例如二乙二醇、〗，1丁 二醇、1，6-己二醇、新戊二醇等脂肪族二醇；丨〆-二 (万-趁基乙氧基）苯、聚乙二醇、聚丁二酵等。 此處所謂「主要酸成分爲對苯二甲酸」係指酸成分中 ，對苯二甲酸佔的比例爲的5 〇莫耳％以上、1 〇 〇莫耳％ 以下’又以80莫耳％以上、100莫耳的以下較理想，所 謂「主要乙二醇成份爲三亞甲基二醇」係指在乙二醇成 份中’三亞甲基二醇佔的比例爲5 〇莫耳。以上、1 〇 〇莫 耳％以下，又以80莫耳％以上、100莫耳％以下較理想 又，使用這些的有機磷成份共聚合聚酯時，因碟成份 藉由共聚亦即共價鍵和聚合物鏈結，紡絲時以及之後製 造人造皮革時的各步驟中不會發生難燃劑脫落等問題。 又，現今的環境重視不含鹵素，因此可避免使用含鹵 素化合物。此時，較理想的有機磷成份共聚合聚酯係充 分發揮強度等纖維物性之樹脂且紡絲條件下熔融黏度比 海島結構纖維中的海成份聚合物大，而且表面張力小的 樹脂，能進行熔融紡絲之樹脂較適用。例如篩孔口徑直 徑：2 m m、 載重：3 2 5 g的條件下，在測定的紡絲溫度中熔 融流動溫度爲5〜5〇g/10分，纖維強度爲1.〇〜5.〇g/dtex -10- 1237079 五、 發明說明 ( 9) 之 樹 脂 較 理 想 0 又 有 機 磷 成 份 共 聚 合 聚 酯 中 的 磷 原 子 濃度 在 3 0 0 Opp 111 以 上 2 0 0 0 Opp] η以下i 替^ 咬3 哩' 想 ，特別」 以 5 0 0 Ορρ m 以 上 1 5 0 0 Opp] 以下者更佳 。若小於 3 0 0 Oppm 5 作 爲 皮 革 樣 片 基 體 時 不 易 具 有 充 分 的 難 燃性 能 0 若超 過 20000ρρ] Q1 會發生因樹月i 旨的黏度減少使製得的纖維 之 物 性 低 落 和 紡 絲 性 等 生 產 性 惡 化 等 問 題 ，不 易 使 用。 有 關 海 成 分 聚 合 物 其 溶 解 性 或 分 解 性 異於 島 成 份 聚 合 物 對 溶 劑 或 分 解 劑 之 溶 解 性 或 分 解 性 (比島成份聚 合 物 的 溶 解 性 或 分 解 性 大 )， 係- -種和島成份相溶性小 的 樹 脂 例 如 至 少 一 種 之Β巳 m 白 聚 乙 Μ 、 聚 苯 乙烯 Λ 聚 乙烯 丙 烯 共 聚 物 硫 代 間 苯 二 甲 酸 蘇 打 等 共 聚 的變 性 聚 酯等 之 聚 合 物 〇 例 如 聚 苯 乙 烯 和 聚 乙 烯 比 甲 苯 和三 氯 乙 烯更 容 易 抽 提 > 又 可 利 用 驗 分 解 去 除 硫 代 間 苯二 甲 酸 蘇打 共 聚 聚 對 苯 二 甲 酸 乙 二 醇 酯 等 變 性 聚 酯 〇 因此 從 海島 結 構 纖 維 中 抽 提 或 分 解 去 除 海 成 份 可 使 海 島結 構 纖 維轉 變 爲 極 細 纖 維 束 〇 本 發 明 的 海 島 結 構 纖 維 的 橫 切 面 中 亦 可將 海 成 份分 割 成 比 島 成 份 更 多 個 例 如 海 成 份 和 島 成 份分 別 形 成層 亦 可 形 成 多 層 黏 合狀 態 的 纖 維 〇 又 5 島 成 份 可 爲 在 纖 維 長 方 向 Μ J \ ΛΝ 切 □ 連 續的 狀 態 ，亦 可 爲 不 連 續 的 狀 態 〇 並 j\w 特 別 規 定 海 島 結 構 纖 維 的 纖 維 橫 切 面 中鳥 的 個 數， 惟 轉 換 成 極 細 纖 維 束 後 5 必 須 11 _ an 5又 定 單 纖 維 纖維 度 小 於 1237079 五、發明說明（1〇) 0 · 5 dtex。本發明中使用的海島纖維結構的製法例如各 種ί谷融紡絲法（碎片摻合（c h i p b 1 e n d)方式、針管（n e e d 1 e Pipe)方式、黏合方式等）。 組成使用於本發明的海島結構纖維的海成份和島成份 之比率’從製得的皮革樣片基體的物性和良好觸、觀感 的平衡點考量，其重量比爲8 : 2〜2 : 8之範圍較理想。 本發明中從海島結構纖維去除海成份聚合物後形成的 極細纖維束’其中組成份的極細纖維之平均粗度，如前 所述必須小於0.5 dtex，其下限値爲0.001 dtex較理想. 。特別是考量皮革樣片基體的物性和良好觸、觀感的平 衡，以0.0 1〜0.3 dtex的範圍較適當。又，亦可在纖維 的島成份中添加染料和顏料等著色劑和各種穩定劑。 本發明中’亦必須使黏合劑的高分子彈性體具有難燃 性。具體的方法，必須在下列2種方法中至少使用1種。 (1 )高分子彈性體含有金屬氫氧化物； (2)高分子彈性體係和有機磷成份共聚而成； 因此，使用上述（1 )的金屬氫氧化物時，較理想的金 屬氫氧化物例如至少1種選自鋁、鎂等金屬的氫氧化物 ，具體而言例如氫氧化鋁、氫氧化鎂等，其中以氫氧化 鋁更理想。 在纖維纏繞不織布中塡充高分子彈性體時可使用眾知 的方法，例如將此不織布浸漬在含有高分子彈性體的液 狀組成物浴中，之後將此不織布浸漬在凝固浴使高分子 彈性體凝固，即所謂的濕式凝固法，或使不織布含有高 -12- 1237079 五、 發明說明 ( 11) 分 子 彈 性 體丨 乳液後再使加熱膠化即所謂的乾式凝固法等。 要 使 局 分 子 彈性 體 含 有 難燃劑，可將難燃劑分散在 浸 漬 不 織 布 的 液狀 組 成 物 中。相對於高分子彈性體100 重 量 單 位 ， 金 屬氫 氧 化 物 的含量爲10〜200重量單位較 佳 ， 又 以 30〜 100 重 量 單 位更理想。金屬氫氧化物若少 於 1 〕重量單位，當作皮革樣片基體時不易具有充分的 難 燃 性 9 若 超 過200 重 量 單位，高分子彈性體不易充分 保 持 金 屬 氫 氧 化物 ， 同 時 高分子彈性體的柔軟性等性能 易 受 破 壞 〇 金 屬 氫 氧 化 物的 粒 徑 越 小（每重量單位的表面積越大 者 )其難燃效果越佳， 但考慮在浸漬液中的分散安定性 本 發 明 使 用 的金 屬 氫 氧 化物的粒徑平均爲0.1〜20· m 較 理 想 又 以 0.5 - 、3 .0 β m範圍的微粒更佳。又，可依 需 求 使 用 經 過 各種 處 理 之 金屬氫氧化物顆粒，可增強其 耐 溼 > 耐 熱 Λ 耐水 、 耐 酸 等性能。 含 有 金 屬 氫 氧化 物 之 局 分子彈性體，例如至少1種 聚 合 物 二 醇 選 自平 均 分 子 量爲500〜3000的聚酯二醇、 聚 醚 二 醇 、 聚 碳酸 酯 二 醇 等二醇或聚酯聚醚等複合二醇 5 和 至 少 1 種 選自 4: ，4丨-二 .甲苯二異氰酸酯、佛爾酮二 異 氰 酸 酯 、 亞甲 基 二 異 氰酸酯等芳香族類、脂環族類 N 脂 肪 族 類 的 二異 氰 酸 酯 ，和至少I種類的乙二醇、佛 爾 酮 胺 等 含 有 2個 以 上 活 性氫原子之低分子化合物，和 以 規 定 的 莫 耳 比使 反 應 後 所得之聚脲烷及其變性物，其 他 如 聚 酯 彈 性 體、 苯 乙 烯 -異戊二烯塊共聚物的氫化物 -13- 1237079 五、發明說明（12 ) 等高分子彈性體及丙烯酸類樹脂等，及眾知的高分子彈 性體。亦可將這些混合成聚合物組成物。惟考量其柔軟 性、彈性復原性、多孔質高分子彈性體形成性、耐久性 等，使用上述的聚脲烷較理想。 又’上述（2)的方法亦即使有機磷成份在高分子彈性 體中進行共聚時，高分子彈性體中的磷原子濃度在 3000ppm-20000ppm 的範圍較佳，以 5000ppm_20000ppm 的範圍更理想。若磷原子濃度小於3 000ppm，作爲皮革 樣片基體時不易具有充分的難燃性能。若超過20000ΡΡηι ’則不易滿足皮革樣片基體所需的物性。 在高分子彈性體中進行共聚的有機磷成份可使用眾知 的磷酸酯類、有機膦化合物等，考量因高分子彈性體的 加水分解所引發對劣化的影響，以使用有機磷化合物較 理想。有機磷化合物中的三官能型在反應時不易發生膠 化，因此較二官能型化合物更適用。 如前所述，和有機磷成份共聚的高分子彈性體可使用 眾知者，其中聚脲烷因其柔軟性、彈性復原性、多孔質 高分子彈性體形成性、耐久性等優越較適用。可使用前 述眾知的聚脲烷，考量對加水分解的安定性以其中的聚 醚類、聚碳酸酯類聚脲烷較理想，又以聚碳酸酯類更佳。 使用聚醚類和聚酯類的聚脲烷時，製作皮革樣片基 體後隨即具有難燃性，惟因對熱水的穩定性不佳，較聚 碳酸酯類聚脲烷更易失去難燃性，例如染色處理和淸洗 處理中可能隨加水分解使難燃性低落。因此使用在不太 -14- 1237079 五、發明說明（13) 重視耐久性的部位不會形成困擾。使用聚碳酸酯類的聚 脲烷時，因可明顯地抑制劣化的進行速度，較適用於重 視耐久性的部位用之皮革樣片基體。 所謂「聚碳酸酯類聚脲烷」係指在組成聚脲烷的高分 子二醇中，聚碳酸酯二醇所佔的比例在5 0〜1 0 0 %的範 圍較佳，以7 0〜1 0 0 %的範圍更理想。因此，本發明的 高分子彈性體，若使用較理想的聚碳酸酯類聚脲烷時， 可以只使用聚碳酸酯類聚脲烷，亦可使用和其他高分子 彈性體的混合物，惟高分子彈性體的5 0〜1 0 0 %爲聚碳 酸酯類聚脲烷較理想。其他的高分子彈性體例如聚碳酸 酯類聚脲烷之外的聚脲烷、聚酯彈性體、苯乙烯-異戊 二烯塊共聚物的氫化物等高分子彈性體及丙烯酸類樹脂 等。 本發明中較適用的有機磷成份共聚合聚碳酸酯類聚脲 烷，例如下列的聚脲烷的調製過程； (1) :以聚六亞甲基碳酸酯等眾知的碳酸酯爲主成份， 藉由至少1種類的聚合物二醇和至少1種類選自4，4，-二甲苯二異氰酸酯、異佛爾酮二異氰酸酯、六亞甲基二 異氰酸酯等芳香族類、脂環族類、脂肪族類的二異氰酸 酯之反應得到中間二醇的反應， (2) :在（1)中所得的中間二醇添加至少1種如乙二醇、 異氟爾酮二胺等含有2個以上的活性氫原子之低分子化 合物和至少1種類選自4，4 ’ -二甲苯二異氰酸酯、異佛 爾酮二異氰酸酯、六亞甲基二異氰酸酯等芳香族類、脂 -1 5 - 1237079 五、發明說明（14) 環族類、脂肪族類的二異氰酸酯，藉由鏈延長反應使聚 合物伸長之反應， 在其中添加部分（1)的聚合物二醇、或部分（2)的含有活 性氫原子之低分子化合物、或（1)(2)二反應中正丁基-二 (3 -羥丙基）膦氧化物、正丁基-(2-羥基-1 -甲基乙基）-3-羥丙基膦氧化物、正丁基-二（2-羥基-1-甲基乙基）膦 氧化物等含磷二醇，藉此可製得有機磷成份共聚合聚碳 酸酯類聚脲烷。 含磷二醇可在任何階段導入，只要最後聚脲烷中的 磷原子濃度在3000ppm以上即所謂理想的範圍內，無 論含磷二醇在任何階段導入都可製得用於難燃性皮革樣 片基體之理想的聚脲烷。又，採用眾知的一步發泡法和 預聚體法時，只要不明顯破壞反應和製得的聚脲烷之物 性，有機磷成份共聚合聚脲烷的原料亦可使用其他含磷 化合物，此時的磷原子濃度係有機成份共聚合聚脲烷和 含磷化合物的合計濃度，其理想的濃度範圍同樣爲 3 OOOppm 以上。 其次，說明有關本發明中採用理想的海島結構纖維時 難燃性皮革樣片基體的製法。 詳述本發明的製法前，首先如前所述般，以眾知的方 法在島成份中製造已使用有機磷成份共聚合聚酯的極細 纖維發生型海島結構纖維短纖維。纖維的纖度爲1.0〜 1 0 · 0 dt ex時，因其具有良好的梳棉機通過性故較理想 ，又以上3.0〜6.0dtex更佳。 -16- 1237079 五、發明說明（15) 其次以梳棉機開鬆此海島結構纖維短纖維，通過纖維 網機形成纖維網’將所得的纖維網層疊成期望的重量及 厚度’接著以眾知的方法例如針穿孔機方法和高壓水流 纏繞處理方法等進行纏繞處理形成不織布或將此短纖維 分散在水中作爲製造用的生料，將此生料、製成的不織 片層疊在編織布後，利用水流等使重疊的編織布纏繞形 成複合不織布。考慮以此不織布當作皮革樣片時的厚度 ，必須作成因應其目的之型態，以在步驟中處理之簡便 性的觀點考量，網目爲2 0 0〜1 5 0 0 g/m2，厚度爲1〜 1 0 m m的範圍較理想。 又’依需求利用上述方法製成的不織布中，使具有聚 乙烯醇類的膠料或在組成纖維的表面進行熔融，黏著不 織布的組成纖維，亦可將不織布進行暫行固定的處理。 藉者此處理可預防在之後進行的高分子彈性體溶液的浸 漬等步驟中，因張力等使不織布的結構被破壞，又，組 成高分子彈性體和不織布的極細纖維不需實際地黏合即 可具有皮革樣的柔軟觸感、觀感。將上述的高分子彈性 體熔融或溶解或分散在分散劑形成浸漬液，使不織布浸 漬在此浸漬液中，以樹脂的非溶劑處理使進行濕式凝固 ，形成多孔質狀或非孔質狀的高分子彈性體相，或直接 加熱乾燥使形成膠化多孔質狀的高分子彈性體相等方法 ，可製得由海島結構纖維和高分子彈性體組成的難燃性 皮革樣片基體。亦可依需求在此浸瀆液中添加著色劑、 凝固調節劑、抗氧化劑、分散劑等添加劑。 -1 7- 1237079 五、發明說明（16) 其次，將由海島結構纖維和高分子彈性體組成的片經 過藥劑處理，此藥劑係島成份聚合物及高分子彈性體的 非溶劑且爲海成份聚合物的溶劑或分解劑，之後可使海 島結構纖維轉換成極細纖維。若以添加低分子量的難燃 劑使極細纖維或高分子彈性體含有難燃成份時，在步驟 中有容易流失之虞，聚酯極細纖維中及高分子彈性體中 的有機磷成份係藉由共聚作用存在於各個聚合物中，因 此完全不會脫落。又，高分子彈性體中含有金屬氫氧化 物時，其中的大部分不易脫落在高分子彈性體，高分子 彈性體中有有機磷成份共聚時和極細纖維相同的原因完 全不脫落。去除海成份後的難燃性皮革樣片基體中，高 分子彈性體所佔的比率以固形分的重量比而言在5%〜 7 0%較佳，又以10%〜50%的範圍更理想。彈性體比率 少於5 %時不形成細緻的多孔質高分子彈性體，極細纖 維發生後容易使金屬氫氧化顆粒脫落。又，若超過70% ，所得的難燃性皮革樣片基體容易具有橡膠般的觸感、 觀感。 如此製成的難燃性皮革樣片基體會形成下列2種情況 :(1)有機磷成份共聚合聚酯的極細纖維和保持金屬氫氧 化物之多孔質或非孔質高分子彈性體的組合，或（2)有 機磷成份共聚合聚酯的極細纖維和有有機磷成份共聚之 多孔質或非孔質高分子彈性體的組合。 這些的組合不易理論性地實證其最適當者，不含難燃 成份的聚酯纖維和保持金屬氫氧化物的高分子彈性體之 -18- 1237079 五、發明說明（17) 組合，或有機磷成份共聚合聚酯的極細纖維和不含金屬 氫氧化物的高分子彈性體之組合，即使盡可能地提高其 中一種的難燃成份的濃度，仍無法使全體皮革樣片基體 難燃化。又，不含難燃成份的聚酯纖維和含有有機磷成 份的高分子彈性體之組合，或有機磷成份共聚合聚酯的 極細纖維和不含難燃成份的高分子彈性體之組合，即使 盡可能地提高其中一種的難燃成份的濃度，仍無法使全 體皮革樣片基體難燃化。 如本發明的皮革樣片基體般的複合材料中，使難燃成 份存在各個組成物中是有效的方式，惟無法確認其詳細 情形但可推論下列情形，特別是上述（1)的組合，藉由 形成有機磷化合物的碳化皮膜而來的抑制燃燒機制，和 經由金屬氫氧化物特別是由氫氧化鋁的效果爲明顯吸熱 ，藉此而來的抑制燃燒機制，在燃燒過程的多數個步驟 因抑制燃燒而發揮相乘效果。又，若採用上述（2)的組 合’因全體的片均爲相同難燃機制，不需要難燃機制不 同時所需的平衡調節，只要藉由改變難燃劑的濃度即可 控制難燃性，此點有利於工業上的應用。 使纖維片含有難燃劑之方法，例如將此纖維片浸漬在 含難燃劑液中，以一般的方法乾燥，此法中當纖維爲極 細纖維束而難燃劑爲微粒時，難燃劑幾乎不進入至極細 纖維束的內部，大部分的難燃劑停留在纖維束的外部和 高分子彈性體的外部表面。在此狀態時，難燃劑容易脫 落，不易獲得具有耐久性的難燃效果。爲要防止難燃劑 - 19- 1237079 五、發明說明（18) 脫落，將難燃劑攪拌混合在黏合劑樹脂中，再將片浸漬 在此黏合劑樹脂液的方法，即使採用這方法仍無法浸透 至極細纖維束的內部，又，因尙有樹脂充塡在纖維片中 ，會破壞纖維片的柔軟性且無法製得良好的絨毛狀態等 缺點，而本發明無這類的缺點。 使本發明的難燃性皮革樣片基體的表面具有絨毛，藉 此可製得絨面風格的人造皮革，藉由在纖維片的表面熔 融並平滑化或在表面塗抹樹脂更可使表面具有如天然皮 革樣的表面凹凸，製得塗銀風格的人造皮革。 這樣的人造皮革除了可應用在鞋類、皮包、小袋子等 ，亦可用於沙發等室內設計用品、衣料等用途。本發明 的難燃性皮革樣片基體適用於特別是汽車用座椅、火車 用座椅、飛機用座椅、船用座椅等要求難燃性的交通工 具用座椅等用途，且需要強度的用途等。爲要增強作用 ，亦可在本發明的皮革樣片基體上層疊其他的編織物和 不織布，這些的增強用布料以具難燃性者較理想。 其次以實例具體地說明本發明，惟本發明不受限於這 些實例。又，實例中的單位及。/〇均指與重量相關者。又 ，利用下列的方法求出本發明中纖維粗度及金屬氫氧化 物的平均粒徑。又，根據下列的方法評估實例中的難燃 性。 [纖維的組度]:在電子顯微鏡下以5 0 0〜20 0 0倍的倍率 觀察，從纖維徑的實測値換算求得 [金屬氫氧化物的平均粒徑]:以電子顯微鏡觀察測得 -20 - 1237079 五、發明說明（彳9) [難燃性試驗方法1 :根據Π S D 1 2 0 1汽車室內用有機資材 的難燃性試驗方法的燃燒試驗，可區分出下列幾種 易燃性：燃燒速度超過l〇〇mm/min者 遲然性：燃燒速度小於l〇〇mm/min者 自熄性：從標線開始50mm內且60秒內熄火者。 又，使用甲雷亞修公司製的ICP發光分析裝置IRIS AP，測定實例中纖維片中的磷原予濃度。 實例1〜2 採用眾知的聚酯聚合法，在聚合中添加磷類難燃劑 M-Ester(三光（股）製，分子量434，磷含量7wt%)，可 得磷原子濃度分別爲5 000ppm及12000ppm的2種磷類 難燃劑共聚合聚對苯二甲酸乙二醇酯類聚酯。 利用熔融紡絲可製得海島型複合紡絲纖維（海成份/島 成份=3 5/65，島數16)，其中的島成份爲此磷類難燃劑 共聚合聚酯，海成份爲高流動性低密度聚乙烯，將此纖 維在7 0 °C的溫水中展延成2.5倍，添加纖維油劑，進 行機械捲縮並乾燥後裁剪成51mm作爲5·0 dtex的短纖 維，以交叉重疊法形成網目爲65 〇g/m2的纖維網，接著 從二面交互地同時進行約25 00p/m2的的針穿孔’並加 熱，在冷卻滾輪間進行冷卻的同時亦進行加壓，可製得 表面平滑的纏繞不織布。此纏繞不織布的網目爲 1 2 0 0 g/m2，密度爲〇·48 g/cm3。相對於以聚碳酸酯類 脲烷爲主體而固型分1 4 %的聚脲烷的二甲基甲醯胺 (D M F)溶液1 0 0單位，在D M F中將平均粒徑1 V㈤的氫 -21 - 1237079 五、發明說明（2〇) 氧化鋁分散成40 %分散液，添加此分散液17.5單位經 調節後的浸漬液（聚脲烷：氫氧化鋁=1 0 0 : 5 0)，將此纏繞 不織布浸漬在此浸漬液，其次將浸漬後的不織布再浸於 D M F/水混合液中進行濕式凝固後，在熱甲苯中將海島 型複合纖維中的海成份溶出去除後即爲極細纖維，製得 具難燃性能厚度爲1 . 3 mm的皮革樣片基體。 極細纖維的平均纖度爲0.2 dtex。皮革樣片基體中的 纖維的重量和聚脲烷的重量比率約爲8 : 2。在顯微鏡下 觀察製得的皮革樣片基體的纖維切面時，證實氫氧化鋁 顆粒多數存在於多孔質高分子彈性體的內部。製得的各 皮革樣片基體的難燃性、磷原子濃度之評估結果如表i 所示。使纖維片的表面具有絨毛，以分散染料染色製作 絨面風格的人造皮革，其爲一種難燃性優越，適用於室 內設計領域特別是交通工具用座椅等需要難燃性等用途 ，具有柔軟的觸、觀感的絨面風格之人造皮革。 除了使表面具有絨毛之外，亦可使表面具有厚度爲 6 0微米的聚脲烷層，使具有天然皮革風的壓紋模樣， 進行揉搓處理後同樣地爲一種難燃性優越，適用於室內 設計領域特別是交通工具用座椅等需要難燃性等用途， 具有柔軟的觸、觀感的具銀面層之人造皮革。又，這些 製品完成處理後，此人造皮革經過：Π S D 1 2 0 1燃燒試驗 評定爲自熄性。 使用製得的絨面風格或塗銀風格的人造皮革製作汽車 用座椅時，不會發生因強度等引起的加工上的問題，製 -22- 1237079 五、發明說明（21) 成的座椅具有和使用天然皮革時相近的觸感、外觀且具 有汽車座椅需要的難燃性。 實例3〜4 除了使用1 3 0單位的平均粒徑卜m的氫氧化鎂取代 氫氧化鋁爲添加在高分子彈性體的難燃劑之外，以和實 例1、2相同的條件製作皮革樣片基體，及絨面風格或 具銀面塗層的人造皮革。使用製得的絨面風格或具銀面 塗層的人造皮革製作汽車座椅時，不會發生因強度等引 起的加工上的問題，製成的座椅具有和使用天然皮革時 相近的觸感、外觀且具有汽車座椅需要的難燃性。評估 皮革樣片基體的難燃性、磷原子濃度的結果如表1所示。 實例5〜6 除了使用三亞甲基二醇爲主要乙二醇成份之外，以和 實例1、2相同的條件製作皮革樣片基體。使用製得的 絨面風格或具銀面塗層的人造皮革製作汽車座椅時，不 會發生因強度等引起的加工上的問題，製成的座椅具有 和使用天然皮革時相近的觸感、外觀且具有汽車座椅需 要的難燃性。評估皮革樣片基體的難燃性、磷原子濃度 的結果如表2所示。 比較例1 除了島成份中使用無聚合的聚對苯二甲酸乙二醇酯類 聚酯爲磷類難燃成份之外，以和實例1相同的條件製作 皮革樣片基體。評估製得的皮革樣片基體的難燃性、磷 原子濃度的結果如表1所示。 -23- 1237079 五、發明說明（22 ) 比較例2〜3 除了局分子彈性體中不添加氫氧化銘之外，以和實例 1相同的條件製作皮革樣片基體。評估製得的皮革樣片 基體的難燃性、磷原子濃度的結果如表1所示。 比較例4 除了使用在島成份中攪拌混合低分子量的磷類難燃劑 所製成的海島纖維之外，和實例1相同的條件製作皮革 樣片基體。評估製得的皮革樣片基體的難燃性、磷原子 濃度的結果如表1所示。 實例7〜8 採用眾知的聚酯聚合法，在聚合中添加磷類難燃劑 M-Ester(三光（股）製，分子量434，磷含量7wt%)，可 得磷原子濃度分別爲5000ppm及12000ppm的2種磷類 難燃劑共聚合聚對苯二甲酸乙二醇酯類聚酯。 利用熔融紡絲可製得海島型複合紡絲纖維（海成份/島 成份=3 5/65，島數16)，其中的島成份爲此磷類難燃劑 共聚合聚酯，海成份爲高流動性低密度聚乙烯，將此纖 維在7 0 °C的溫水中展延成2 · 5倍，添加纖維油劑，進 行機械捲縮並乾燥後裁剪成5 1 m m作爲5.0 d t e X的短纖 維，以交叉重疊法形成網目爲65 Og/m2的纖維網，接著 從二面交互地同時進行約2 5 00P/cm2的針穿孔，並加熱 ’在冷卻滾輪間進行冷卻的同時亦進行加壓，可製得表面 平滑的纏繞不織布。此纏繞不織布的網目爲200g/m2=，密 度爲 〇.48g/cm3。 -24- 1237079 五、發明說明（23 ) 利用下列的方法調製用於浸漬此不織布的高分子彈性 體溶液。 使用N-甲基二乙醇胺8.2重量單位作爲含三級胺基 二醇，以數平均分子量2000的聚己二醇碳酸酯236.1 重量單位、數平均分子量2000的聚丁二烯己二酸酯 4〇·3重量單位、及數平均分子量2000的聚四亞甲基二 醇4 4.0重量單位作爲聚合物二醇，以己基二異氰酸酯 28.9重量單位作爲有機二異氰酸酯，及DMF 105.9重 量單位放入反應器，在氮氣氣流下以規定的溫度在規定 的時間內進行反應可得中間體。確認不含異氰酸酯基後 ，使用GPC測定此中間體的重量平均分子量爲4萬。 在上述所得的中間體二醇的DMF溶液中，添加乙二 醇18.2重量單位作爲低分子二醇、比矽可磷ρ〇_4500 (曰本化學工業（股）製，分子量222.26，磷含量13.9 wt % )21.8重量單位及二苯基甲烷-4，4’-二異氰酸酯 1 1 2 · 6重量單位使進行反應，可得濃度2 5 %、重量平均 分子量32萬的聚脲烷溶液。在製得的聚脲烷溶液100 重量單位中添加DMF 7 8重量單位，作爲固型分14%的 浸漬液。 將上述的纏繞不織布浸漬在此浸漬液後，其次將浸漬 後的不織布再浸於DMF/水混合液中進行濕式凝固後， 在熱甲苯中將海島型複合纖維中的海成份溶出去除後即 爲極細纖維，製得具難燃性能厚度爲1 .3mm的皮革樣 片基體。極細纖維的平均纖度爲〇 . 2 d t e X。皮革樣片基 -25 - 1237079 五、發明說明（24 ) 體中的纖維的重量和聚脲烷的重量比率約爲8 : 2。評估 製得的各皮革樣片基體的難燃性、磷原子濃度的結果如 表2所示。使纖維片的表面具有絨毛、染色，製成聚絨 面風格的人造皮革，其爲一種染色性佳且難燃性優越， 適用於室內設計領域特別是交通工具用座椅等需要難燃 性等用途，具有柔軟的觸、觀感的絨面風格之人造皮革 〇 除了使表面具有絨毛之外，亦可使表面具有厚度爲 60微米的聚脲烷層，使具有天然皮革風格的壓紋模樣 ，進行揉搓處理後同樣地爲一種難燃性優越，適用於室 內設計領域特別是交通工具用座椅等需要難燃性等用途 ，具有柔軟的觸、觀感的具銀面層之人造皮革。又，這 些製品完成處理後，此人造皮革經過Π S D 1 2 0 1燃燒試 驗評定爲自熄性。此人造皮革在製作後3 0天以9 0 °C的 熱水浸漬處理後仍維持其難燃性。 使用製得的絨面風格或塗銀風格的人造皮革製作汽車 用座椅時，不會發生因強度等引起的加工上的問題，製 成的座椅具有和使用天然皮革時相近的觸感、外觀且具 有汽車座椅需要的難燃性。 實例9〜1 〇 除了使用聚醚二醇取代聚己烯碳酸酯作爲聚合物二醇 之外，以和實例7，8相同的條件製作皮革樣片基體。使 用製得的絨面風格或塗銀風格的人造皮革製作汽車用座 椅時，不會發生因強度等引起的加工上的問題，製成的 -26- 1237079 五、發明說明（25 ) 座椅具有和使用天然皮革時相近的觸感、外觀且具 車座椅需要的難燃性。評估製得的皮革樣片基體的 性、磷原子濃度的結果如表2所示。 實例1 1〜12 除了使用聚酯二醇取代聚己烯碳酸酯作爲聚合物 之外，以和實例7，8相同的條件製作皮革樣片基體 用製得的絨面風格或塗銀風格的人造皮革製作汽車 椅時’不會發生因強度等引起的加工上的問題，製 座椅具有和使用天然皮革時相近的觸感、外觀且具 車座椅需要的難燃性。評估製得的皮革樣片基體的 性、磷原子濃度的結果如表2所示。 實例1 3〜1 4 除了使用三亞甲基二醇作爲主要乙二醇成份之外 以和實例7，8相同的條件製作皮革樣片基體。使用 的絨面風格或塗銀風格的人造皮革製作汽車用座椅 不會發生因強度等引起的加工上的問題，製成的座 有和使用天然皮革時相近的觸感、外觀且具有汽車 需要的難燃性。評估製得的皮革樣片基體的難燃性 原子濃度的結果如表2所示。 比較例5 除了島成份中使用無聚合的聚對苯二甲酸乙一酉享 聚酯爲磷類難燃成份之外’以和實例7相同的條件 皮革樣片基體。評估製得的皮革樣片基體的難燃性 原子濃度的結果如表2所示。 有汽 難燃 二醇 〇使 用座 成的 有汽 難燃 製得 時， 椅具 座椅 、磷 酯類 製作 、磷 1237079 五、發明說明（％) 比較例6〜7 除了合成高分子彈性體時不添加有機磷類難燃成份之 外’以和實例7，8相同的條件製作皮革樣片基體。評估 製得的皮革樣片基體的難燃性、磷原子濃度的結果如表 2所示。 【應用在產業上的可能性】 本發明的皮革樣片基體，不含鹵素、難燃性優越且此 難燃性的耐久性亦相當優越。又，本發明的皮革樣片基 體具有皮革般柔軟的觸、觀感，作爲絨面風格或塗銀風 格的人造皮革的基體層非常理想，適用於汽車座椅、火 車座椅、飛機座椅、柔軟的表層材料等需具備難燃性等 用途。本發明的皮革樣片基體，除了使用在常用人造皮 革之外，亦可使用於例如壁紙、絨毯等一般用途。 -28- 1237079 —-—__ 五、發明說明（27) 表1 島成分•島成分 中的磷原子濃度 (紡絲後原綿中） [ppm] —~一 — ____-—1 島成分中的 磷原子濃度 (片基體中） [ppm] 金屬氫氧化物 添加量 (對高分子彈性 體） [phr] 燃燒試驗 JIS D1201 實施例1 聚對苯二甲酸乙 二醇酯5 X 103 5 X 103 氫氧化銘5 0 自.熄性 實施例2 聚對苯二甲酸乙 二醇酯 12 X 1〇3 12 X 103 氫氧化鋁5 0 自熄性 實施例3 聚對苯二甲酸乙 二醇酯5xl03 5 X 103 氫氧化鎂1 3 0 遲燃性 實施例4 聚對苯二甲酸乙 二醇酯 12xl 03 12 X 103 氫氧化鎂130 自熄性 實施例5 聚對苯二甲酸三 亞甲基酯5x1 03 5 X 103 氫氧化鋁5 0 自熄性 實施例6 聚對苯二甲酸三 亞甲基酯12x1 03 12 X 103 氫氧化鋁5 0 自熄性 比較例1 聚對苯二甲酸乙 二醇酯0 0 氫氧化鋁5 0 易燃性 比較例2 聚對苯二甲酸乙 二醇酯5X 1〇3 5 X 103 0 易燃性 比較例3 聚對苯二甲酸乙 二醇酯 1 2 X 1 03 12 X 103 0 易燃性 比較例4 聚對苯二甲酸乙 二醇酯5 X 103 1 X 103 氫氧化鋁5 0 易燃性 -29· 诼正 1237079 —1-二'一麥丨— ------------------- < . 1 申請曰期 91.2.22 '------------- 案 號 91103126 類 別 Vc^^/ίψ (以上各攔由本局填註） (94年1月5曰修正） 霧I專利說明 書 中 文 難燃性皮革樣片基體 發明 新型 名稱 英 文Η h2c—c—cooch2ch2oh h2c—CO〇CH2CH2OH [I] The polyester of the matrix can be, for example, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate Well-known polyesters such as alcohol esters, and denatured polymers, mixed polymers, copolymers, and the like thereof. When the polyethylene terephthalate-based polyester is copolymerized with the organic phosphorus component of the present invention, it is possible to obtain a flame retardant derived from the organic phosphorus component and a polyethylene terephthalate-based polyester. Leather samples with excellent mechanical properties and good dyeability are ideal. In the production of the copolymerized polyethylene terephthalate and polytrimethylene terephthalate polyesters of the present invention, the main acid component is terephthalic acid and polyethylene terephthalate is used. Ethylene glycol is used when the glycol ester polyester is an ethylene glycol component. If poly (terephthalylene) is used as the ethylene glycol ingredient, trimethylene glycol is used. It is required to contain copolymerized units such as other dibasic acid components, hydroxy residual acid components, and other 1 or 2 or more kinds of ethylene glycol components. At this time, other mono-residual acid components such as dibenzoic acid, naphthalenedicarboxylic acid, and other aromatic di-residual acids or ester-forming derivatives of these; 5-dimethyl thioterephthalate, 5 _ Sulfur 1237079 V. Description of the invention (8) Metal sulfoester-containing aromatic carboxylic acids or derivatives thereof such as sodium di (2-hydroxyethyl) terephthalate; oxalic acid, adipic acid, succinic acid, ten Aliphatic dicarboxylic acids, such as aliphatic dicarboxylic acids or their ester-forming derivatives. Further, the hydroxy residual acid component is, for example, p-hydroxybenzoic acid, p-^-hydroxyethoxybenzoic acid or an vinegar-forming derivative thereof. Ethylene glycol components such as diethylene glycol, aliphatic diols such as 1-butanediol, 1,6-hexanediol, neopentyl glycol, etc .; 〆-bis (10,000-thenylethoxy) benzene, Polyethylene glycol, polybutadiene, etc. The term "main acid component is terephthalic acid" means that the proportion of terephthalic acid in the acid component is 50 mol% or more, 100 mol% or less, and 80 mol% or more. Below 100 mol, the so-called "main ethylene glycol component is trimethylene glycol" means that the proportion of 'trimethylene glycol' in the ethylene glycol component is 50 mol. Above, 100 mol% or less, and preferably 80 mol% or more and 100 mol% or less are preferred. When using these organic phosphorus components to copolymerize polyester, the dish components are covalently bonded, that is, covalent bonds. With the polymer chain, the flame retardant does not fall off during the spinning and subsequent steps of manufacturing artificial leather. Also, today's environment places emphasis on the absence of halogens, so the use of halogen-containing compounds can be avoided. At this time, a more ideal organic phosphorus copolymer polyester resin is a resin that fully exhibits fiber properties such as strength, and has a melt viscosity greater than that of a sea component polymer in a sea-island structure fiber under spinning conditions, and a resin having a small surface tension. Melt spinning resins are more suitable. For example, under the conditions of the diameter of the sieve opening: 2 mm, and the load: 3 2 5 g, the melt flow temperature at the measured spinning temperature is 5 to 50 g / 10 minutes, and the fiber strength is 1. 〇 ~ 5. 〇g / dtex -10- 1237079 V. The description of the invention (9) is ideal. The phosphorus atom concentration in the copolymerized polyester with organophosphorus component is 3 0 0 Opp 111 or more and 2 0 0 0 Opp. ^ Bite for 3 miles, think, "specially" with 5 0 0 Ορρ m or more and 1 50 0 Opp] or better. If it is less than 3 0 0 Oppm 5 It is not easy to have sufficient flame retardancy when used as a leather sample substrate. 0 If it exceeds 20000ρρ] Q1, the viscosity of the tree will decrease due to the reduction of the physical properties of the fibers and spinnability. Deterioration and other issues are not easy to use. The solubility or decomposability of the sea component polymer is different from the solubility or decomposability of the island component polymer to the solvent or the decomposer (greater than the solubility or decomposability of the island component polymer). Low-solubility resins such as at least one type of polymer such as B 巳 m white polyethylene, polystyrene Λ polyethylene propylene copolymer thioisophthalic acid soda copolymerized modified polyester, etc. such as polystyrene and polyethylene Easier extraction than toluene and trichloroethylene > It can also be used to remove denatured polyesters such as thioisophthalic acid soda copolymerized polyethylene terephthalate. Therefore it can be extracted or decomposed from sea-island structural fibers Removal of the sea component can transform the sea-island structure fiber into an ultra-fine fiber bundle. The cross-section of the sea-island structure fiber of the present invention can also divide the sea component into more than the island component. For example, the sea component and the island component form a layer of fibers that can form a multi-layer bonding state. 5 The island component can be in a continuous state in the fiber length direction M J \ ΛN □ continuous or discontinuous state 0 and j \ w The number of birds in the cross section of the sea-island structure fiber is specifically specified, but after conversion to a very fine fiber bundle, 5 must be 11 _ an 5 and the single fiber fiber degree is less than 1237079. 5. Description of the invention (1〇) 0 · 5 dtex. The manufacturing method of the sea-island fiber structure used in the present invention is, for example, various gluten-spinning methods (c h i p b 1 e n d method, needle tube (n e e d 1 e Pipe) method, bonding method, etc.). The ratio of the sea component and the island component constituting the sea-island structure fiber used in the present invention is considered from the balance between the physical properties of the leather sample substrate and the good touch and look and feel, and its weight ratio is in the range of 8: 2 ~ 2: 8 More ideal. In the present invention, the ultrafine fiber bundle formed after removing the sea component polymer from the sea-island structure fiber has an average thickness of the ultrafine fibers in the composition, as described above, which must be less than 0. 5 dtex, with a lower limit of 0. 001 dtex is ideal. . In particular, considering the balance between the physical properties of the leather sample substrate and the good touch and look and feel, it is 0. 0 1 ~ 0. A range of 3 dtex is more appropriate. In addition, colorants such as dyes and pigments, and various stabilizers may be added to the island component of the fiber. In the present invention, it is also necessary that the polymer elastomer of the adhesive has flame retardancy. Specific methods must use at least one of the following two methods. (1) The polymer elastomer contains a metal hydroxide; (2) The polymer elastic system is copolymerized with an organic phosphorus component; therefore, when the metal hydroxide of the above (1) is used, a preferable metal hydroxide such as At least one kind of hydroxide selected from metals such as aluminum and magnesium, and specifically, for example, aluminum hydroxide and magnesium hydroxide, among which aluminum hydroxide is more preferable. A known method may be used for filling the polymer-elastomer into the fiber-wound nonwoven fabric. For example, the nonwoven fabric is immersed in a liquid composition bath containing the polymer elastomer, and then the nonwoven fabric is immersed in a coagulation bath to make the polymer elastic. Body coagulation, the so-called wet coagulation method, or the non-woven fabric containing high -12-1237079 V. Description of the invention (11) Molecular elastomers 丨 emulsion and then heat gelation is called the so-called dry coagulation method. To make the local molecular elastomer contain a flame retardant, the flame retardant can be dispersed in a liquid composition impregnated with a non-woven fabric. Compared with 100 weight units of polymer elastomer, the content of metal hydroxide is preferably 10 ~ 200 weight units, and more preferably 30 ~ 100 weight units. If the metal hydroxide is less than 1] weight unit, it is not easy to have sufficient flame resistance when used as a leather sample substrate. 9 If it is more than 200 weight units, it is difficult for the polymer elastomer to sufficiently retain the metal hydroxide. The properties such as flexibility are easily damaged. The smaller the particle size of the metal hydroxide (the larger the surface area per weight unit), the better the flame retardancy effect. However, the stability of the metal hydrogen used in the present invention is considered in terms of dispersion stability in the impregnating solution. The particle size of the oxide is on average 0. 1 ~ 20m is more ideal and 0. 5-, 3. Particles in the 0 β m range are more preferred. In addition, metal hydroxide particles that have undergone various treatments can be used as required to enhance their resistance to moisture > heat resistance Λ water resistance, acid resistance, etc. Local molecular elastomers containing metal hydroxides, for example, at least one polymer diol is selected from diols such as polyester diols, polyether diols, polycarbonate diols, or polyester polymers having an average molecular weight of 500 to 3000. Ether and other complex diols 5 and at least one selected from 4 :, 4 丨 -di. Toluene diisocyanate, phorone diisocyanate, methylene diisocyanate and other aromatic, alicyclic N aliphatic diisocyanates, and at least one type of ethylene glycol, phorone amine, etc. contain two or more Low-molecular-weight compounds with active hydrogen atoms, and polyurenes and their denatured products obtained by reacting at a specified molar ratio, other hydrides such as polyester elastomers, styrene-isoprene block copolymers, etc. -1237079 V. Description of the invention (12) Polymer elastomers and acrylic resins, etc., and well-known polymer elastomers. These can also be mixed into a polymer composition. However, in consideration of its flexibility, elastic resilience, porous polymer elastomer formation properties, durability, etc., it is preferable to use the above-mentioned polyurea. Further, the method (2) described above also allows the phosphorus atom concentration in the polymer elastomer to be in the range of 3000 ppm to 20,000 ppm, and more preferably in the range of 5000 ppm to 20,000 ppm, even when the organic phosphorus component is copolymerized in the polymer elastomer. If the phosphorus atom concentration is less than 3,000 ppm, it is difficult to have sufficient flame retardancy when used as a leather sample substrate. If it exceeds 20,000 PPn, it is difficult to satisfy the physical properties required for the leather-like sheet substrate. As the organic phosphorus component to be copolymerized in the polymer elastomer, known phosphate esters, organic phosphine compounds, and the like can be used. Considering the effect of degradation caused by the hydrolysis of the polymer elastomer, the use of the organic phosphorus compound is preferable. The trifunctional type of the organophosphorus compound is less prone to gelation during the reaction, so it is more suitable than the difunctional type compound. As mentioned above, known polymer elastomers copolymerized with organophosphorus components can be used. Among them, polyurenes are suitable because of their flexibility, elastic resilience, porous polymer elastomer formation, and durability. The aforementioned known polyurethanes can be used. In consideration of the stability to hydrolysis, polyethers and polycarbonates are preferred, and polycarbonates are more preferred. When using polyether-based and polyester-based polyurea, it is flame-resistant immediately after making the leather-like matrix, but because of its poor stability to hot water, it is more likely to lose flame resistance than polycarbonate-based polyurea. For example, in the dyeing process and the decontamination process, the flame retardancy may be lowered with the decomposition of water. Therefore, it is not too difficult to use -14-1237079 V. Description of the invention (13) Durability is not a concern. When a polycarbonate-based polyurea is used, the progress rate of deterioration can be significantly suppressed, and therefore it is more suitable for a leather-like sheet substrate for parts where durability is important. The so-called "polycarbonate polyurethane" means that the proportion of the polycarbonate diol in the polymer diols that make up the polyurethane is preferably in the range of 50 to 100%, and 70 to A range of 100% is more desirable. Therefore, in the polymer elastomer of the present invention, if a more suitable polycarbonate-based polyurea is used, only the polycarbonate-based polyurea may be used, or a mixture with other polymer elastomers may be used. 50% to 100% of the elastomer is preferably a polycarbonate-based polyurea. Other polymer elastomers include polyurethanes other than polycarbonate-based polyurethanes, polyester elastomers, polymer elastomers such as hydrogenated styrene-isoprene block copolymers, and acrylic resins. Polycarbonate polyurethane copolymerized with an organophosphorus component suitable for use in the present invention, for example, the following polyurethane preparation process: (1): well-known carbonates such as polyhexamethylene carbonate as the main component With at least one kind of polymer diol and at least one kind selected from 4,4, -xylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and other aromatics, alicyclics, fats Reaction of a group of diisocyanates to obtain an intermediate diol, (2): Add at least one kind of intermediate diol obtained in (1), such as ethylene glycol, isoflurone diamine, etc., to contain more than two activities Low-molecular compounds of hydrogen atom and at least one kind selected from 4,4′-xylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and other aromatics, lipids 1 5-1237079 5. Description of the invention (14) Cyclocyclic and aliphatic diisocyanates are reacted to elongate the polymer by chain extension reaction, and part (1) of the polymer diol or part (2) of the active hydrogen atom is added thereto. Low molecular compounds, or (1) (2) two reactions N-butyl-bis (3-hydroxypropyl) phosphine oxide, n-butyl- (2-hydroxy-1 -methylethyl) -3-hydroxypropylphosphine oxide, n-butyl-bis (2- Phosphorus-containing diols such as hydroxy-1-methylethyl) phosphine oxide can be used to prepare polycarbonate-type polyurenes copolymerized with organic phosphorus components. Phosphorus-containing diols can be introduced at any stage, as long as the phosphorus atom concentration in the final polyureane is above 3000 ppm, which is the so-called ideal range. Regardless of the introduction of the phosphorus-containing diols at any stage, it can be used for flame-resistant leather samples. Ideal polyurethane for the substrate. In addition, when the well-known one-step foaming method and prepolymer method are used, as long as the reaction and the physical properties of the obtained polyuretane are not significantly damaged, other phosphorus-containing compounds may be used as the raw material for the polyurethane copolymerized with the organic phosphorus component. The phosphorus atom concentration at this time is the total concentration of the organic component copolymerized polyuretane and the phosphorus-containing compound, and its ideal concentration range is also 3 000 ppm or more. Next, a description will be given of a method for producing a flame-resistant leather-like sheet substrate when ideal sea-island structure fibers are used in the present invention. Before describing the production method of the present invention in detail, first, as described above, the ultrafine fiber-generating sea-island structure fiber short fiber having an organic phosphorus component copolymerized polyester is produced in an island component by a known method. The fineness of the fiber is 1. 0 ~ 1 0 · 0 dt ex, it is ideal because it has good card passing ability, more than 3. 0 ~ 6. 0dtex is better. -16- 1237079 V. Description of the invention (15) Secondly, open the sea-island structure fiber staple fiber with a card, and form a fiber web through a fiber web machine to 'stack the resulting fiber web into a desired weight and thickness'. The method such as a needle punch method and a high-pressure water-winding treatment method is used to form a non-woven fabric by winding or dispersing the short fibers in water as a raw material for manufacturing. The raw material and the produced non-woven sheet are laminated on a woven fabric. The composite woven fabric is formed by winding overlapping woven fabrics with a water stream or the like. Considering the thickness of this non-woven fabric as a leather swatch, it is necessary to make a type according to its purpose, and consider from the viewpoint of the simplicity of processing in the steps. The mesh is 2 0 ~ 1 5 0 0 g / m2, and the thickness is 1 A range of ~ 10 mm is ideal. Moreover, in the non-woven fabric made by the above method as required, a compound having polyvinyl alcohols or a surface of the constituent fibers is melted to adhere the constituent fibers of the non-woven fabric, or the non-woven fabric may be temporarily fixed. By this treatment, the structure of the non-woven fabric can be prevented from being damaged due to tension and the like during the subsequent impregnation of the polymer elastomer solution, and the ultrafine fibers constituting the polymer elastomer and the non-woven fabric need not be physically bonded. With leather-like soft touch and look. The above-mentioned polymer elastomer is melted or dissolved or dispersed in a dispersant to form an impregnating solution, a non-woven fabric is immersed in the impregnating solution, and the resin is treated with a non-solvent to perform wet coagulation to form a porous or non-porous Polymer elastomer phase, or direct heating and drying to equalize the gelled porous polymer elastomer, can produce a flame-resistant leather-like sheet matrix composed of sea-island structure fibers and polymer elastomer. Additives such as colorants, coagulation regulators, antioxidants, and dispersants can also be added to this dope as required. -1 7- 1237079 V. Description of the invention (16) Secondly, the sheet composed of sea-island structure fiber and polymer elastomer is treated with a medicament. This medicament is a non-solvent of island-based polymer and high-molecular elastomer and is a polymer of sea-based polymer. Solvent or decomposing agent, and then the sea-island structure fiber can be converted into very fine fiber. If a low-molecular-weight flame retardant is added to make ultrafine fibers or polymer elastomers contain flame retardant components, there is a risk of easy loss in the step. The organic phosphorus components in polyester ultrafine fibers and polymer elastomers are caused by Copolymerization exists in each polymer, so it does not fall off at all. When the polymer elastomer contains metal hydroxides, most of them are not easily detached from the polymer elastomer. When the polymer elastomer contains an organic phosphorus component, it does not fall off at all for the same reasons as the ultrafine fibers. In the flame-retardant leather sample matrix after removing the sea component, the proportion of the polymer elastomer is preferably 5% to 70% in terms of the weight ratio of the solid content, and more preferably in the range of 10% to 50%. . When the elastomer ratio is less than 5%, a fine porous polymer elastomer is not formed, and the metal hydroxide particles are liable to fall off after the occurrence of extremely fine fibers. Moreover, if it exceeds 70%, the obtained flame-resistant leather-like sheet substrate tends to have a rubbery touch and look. The base of the flame-resistant leather sample thus prepared will form the following two cases: (1) a combination of ultrafine fibers of an organic phosphorus component copolymerized polyester and a porous or non-porous polymer elastomer holding a metal hydroxide, Or (2) a combination of ultrafine fibers of an organic phosphorus component copolymerized polyester and a porous or non-porous polymer elastomer copolymerized with an organic phosphorus component. The combination of these is not easy to theoretically prove the most appropriate one. Polyester fiber without flame retardant components and polymer elastomer holding metal hydroxide. -18-1237079 5. Description of the invention (17) Combination, or organic phosphorus The combination of the ultrafine fibers of the component copolymer polyester and the polymer elastomer containing no metal hydroxide, even if the concentration of one of the flame retardant components is increased as much as possible, the entire leather-like sheet substrate cannot be flame retardant. In addition, the combination of polyester fibers containing no flame retardant components and polymer elastomers containing organic phosphorus components, or the combination of ultrafine fibers of polyester copolymerized with organic phosphorus components and polymer elastomers containing no flame retardant components, even Increasing the concentration of one of the non-combustible components as much as possible still cannot make the entire leather sample matrix difficult to combust. In the composite material like the leather-like matrix of the present invention, it is effective to make flame retardant components exist in each composition, but the detailed situation cannot be confirmed, but the following situations, especially the combination of the above (1), can be inferred. The combustion suppression mechanism formed by the formation of a carbonized film of an organophosphorus compound, and the obvious endothermic effect through the effect of metal hydroxides, especially aluminum hydroxide, and the combustion suppression mechanism resulting from this are suppressed in most steps of the combustion process. Multiply by burning. In addition, if the combination of the above (2) is used, since all the tablets have the same flame retardant mechanism, the balance adjustment required at the same time is not required, and the flame retardant property can be controlled by changing the concentration of the flame retardant. This is conducive to industrial applications. The method for making the fiber sheet contain a flame retardant, for example, immersing the fiber sheet in a liquid containing a flame retardant and drying the fiber in a general method. In this method, when the fiber is an extremely fine fiber bundle and the flame retardant is a fine particle, the flame retardant is It hardly enters the inside of the ultrafine fiber bundle, and most of the flame retardant stays on the outside of the fiber bundle and on the outside surface of the polymer elastomer. In this state, the flame retardant is easily detached, and it is difficult to obtain a durable flame retardant effect. In order to prevent the flame retardant-19-1237079 V. Description of the invention (18) The method of mixing the flame retardant in the binder resin, and then immersing the sheet in the binder resin liquid, even if this method is still not used It penetrates into the inside of the ultrafine fiber bundle, and because the resin sheet is filled in the fiber sheet, the fiber sheet can be damaged and the softness of the fiber sheet cannot be obtained. However, the present invention does not have such disadvantages. The surface of the base of the flame-resistant leather-like sheet of the present invention is provided with fluff, so that a suede-like artificial leather can be obtained. By melting and smoothing the surface of the fiber sheet or applying a resin on the surface, the surface can have a natural appearance. The leather-like surface is uneven, and a silver-coated artificial leather is produced. Such artificial leather can be used not only in shoes, leather bags, pouches, etc., but also in interior design articles such as sofas, clothing and the like. The flame-resistant leather sample substrate of the present invention is suitable for applications such as automobile seats, train seats, aircraft seats, and marine seats that require flame-resistant vehicle seats and other applications that require strength. Wait. In order to enhance the effect, other knitted fabrics and non-woven fabrics may be laminated on the leather-like sheet substrate of the present invention. These reinforcing fabrics are preferably those having flame resistance. Next, the present invention will be specifically described with examples, but the present invention is not limited to these examples. In addition, the units and in the examples. / 〇 refers to those related to weight. The fiber thickness and the average particle diameter of the metal hydroxide in the present invention were determined by the following methods. The flame retardancy in the examples was evaluated according to the following methods. [Fiber group degree]: Observed under an electron microscope at a magnification of 500 to 2000, and calculated from the actual measurement of fiber diameter. [Average particle diameter of metal hydroxide]: Observed by electron microscope observation -20-1237079 V. Description of the invention (彳 9) [Flammability test method 1: According to the flammability test method of Π SD 1 2 0 1 for organic materials used in automotive interiors, the following types of flammability can be distinguished Properties: Burning speed is more than 100mm / min. Lateness: Burning speed is less than 100mm / min. Self-extinguishing property: Those who extinguish within 50mm from the marked line and within 60 seconds. In addition, the pre-phosphorus preconcentration in the fiber sheet in the example was measured using IRIS AP, an ICP emission analysis device manufactured by Carrex Corporation. Examples 1 to 2 A well-known polyester polymerization method was used, and a phosphorus-based flame retardant M-Ester (made by Sanko (strand), molecular weight 434, phosphorus content 7wt%) was added to the polymerization, and the phosphorus atom concentrations were 5 000 ppm. And 22000 ppm of two kinds of phosphorus flame retardant copolymerized polyethylene terephthalate polyester. The sea-island type composite spinning fiber can be obtained by melt spinning (sea composition / island composition = 3 5/65, island number 16), among which the island composition is a phosphorus-based flame retardant copolymer polyester, and the sea composition is high. Flowable low-density polyethylene, this fiber is stretched into 2 at 70 ° C warm water. 5 times, adding fiber oil agent, mechanically crimping and drying, cutting into 51mm short fibers of 5.0mm dtex, forming a fiber network with a mesh of 65 〇g / m2 by cross-overlap method, and then simultaneously and interactively from both sides Needle perforation of about 25 00p / m2 is performed, and heating is performed while cooling is performed between the cooling rollers and pressure is applied, so that a nonwoven fabric with a smooth surface can be obtained. The mesh of the wound nonwoven fabric was 1,200 g / m2, and the density was 0.48 g / cm3. Compared to 100 units of a dimethylformamide (DMF) solution containing 14% of polyurethan with a solid content of 14% based on a polycarbonate-based urethane, hydrogen having an average particle diameter of 1 V㈤ in DMF- 21-1237079 V. Description of the invention (20) Alumina is dispersed into a 40% dispersion, and this dispersion is added 17. 5 units of adjusted impregnating solution (polyurethane: aluminum hydroxide = 1 0 0: 5 0), immerse the wound nonwoven fabric in the impregnating solution, and then immerse the impregnated non-woven fabric in the DMF / water mixed solution After the wet coagulation, the sea component in the sea-island composite fiber is dissolved and removed in hot toluene to become an ultra-fine fiber, and the thickness of the flame retardant is 1. 3 mm leather-like substrate. The average fineness of ultrafine fibers is 0. 2 dtex. The ratio of the weight of the fibers in the leather-like matrix to the weight of the polyurea is about 8: 2. When the fiber cut surface of the obtained leather-like sheet substrate was observed under a microscope, it was confirmed that most of the aluminum hydroxide particles existed inside the porous polymer elastomer. The evaluation results of the flame retardancy and the phosphorus atom concentration of each of the prepared leather sample substrates are shown in Table i. The surface of the fiber sheet has fluff, and dyed with disperse dye to produce suede-like artificial leather, which is superior in flame retardancy, and is suitable for use in interior design fields, especially for transportation seats, where flame retardance is required. Touch and look suede-style artificial leather. In addition to making the surface fluffy, it is also possible to make the surface have a polyurea layer with a thickness of 60 micrometers, so that the embossing pattern with natural leather wind is similarly superior in flame resistance after being rubbed, and is suitable for indoor use. In the design field, particularly for vehicles such as seats for vehicles, which require flame retardancy and other applications, artificial leather with a silver surface layer having a soft touch and appearance. In addition, after these articles were treated, the artificial leather was evaluated as a self-extinguishing property through a Π S D 1 2 01 combustion test. When using the prepared suede-style or silver-coated artificial leather to make automotive seats, processing problems due to strength and other problems will not occur. Manufacturing -22-1237079 V. Description of the invention (21) It has a touch and appearance similar to that when using natural leather, and has the flame retardancy required for car seats. Examples 3 to 4 Leather samples were produced under the same conditions as in Examples 1 and 2 except that magnesium hydroxide with an average particle size of 130 units was used instead of aluminum hydroxide as a flame retardant added to the polymer elastomer. Base, and suede-style or silver-coated artificial leather. When the car seat is made of the suede-like or silver-coated artificial leather, processing problems caused by strength and the like do not occur, and the finished seat has a touch similar to that when using natural leather Appearance and flame resistance required for car seats. Table 1 shows the results of evaluating the flame retardancy and the phosphorus atom concentration of the leather sample substrate. Examples 5 to 6 A leather sample sheet substrate was produced under the same conditions as in Examples 1 and 2 except that trimethylene glycol was used as the main ethylene glycol component. When the car seat is made of the suede-like or silver-coated artificial leather, processing problems caused by strength and the like do not occur, and the finished seat has a touch similar to that when using natural leather Appearance and flame resistance required for car seats. Table 2 shows the results of evaluating the flame retardancy and the phosphorus atom concentration of the leather sample substrate. Comparative Example 1 A leather-like sheet substrate was produced under the same conditions as in Example 1 except that the non-polymerized polyethylene terephthalate-based polyester was used as the phosphorus-based flame retardant component in the island component. Table 1 shows the results of evaluating the flame retardancy and the phosphorus atom concentration of the obtained leather-like substrate. -23- 1237079 V. Description of the invention (22) Comparative Examples 2 to 3 A leather sample sheet was produced under the same conditions as in Example 1 except that no hydroxide was added to the local molecular elastomer. Table 1 shows the results of evaluating the flame retardancy and the phosphorus atom concentration of the obtained leather-like substrate. Comparative Example 4 A leather sample substrate was produced under the same conditions as in Example 1 except that the low-molecular-weight phosphorus-based flame retardant was used in the island component, and a sea-island fiber was used. Table 1 shows the results of evaluating the flame retardancy and the phosphorus atom concentration of the obtained leather-like substrate. Examples 7 to 8 A well-known polyester polymerization method was used, and a phosphorus-based flame retardant M-Ester (made by Sanko (strand), molecular weight 434, and phosphorus content 7wt%) was added to the polymerization to obtain phosphorus atom concentrations of 5000 ppm and Polyethylene terephthalate polyester was copolymerized with 12,000 ppm of two phosphorus flame retardants. The sea-island type composite spinning fiber can be obtained by melt spinning (sea composition / island composition = 3 5/65, island number 16), among which the island composition is a phosphorus-based flame retardant copolymer polyester, and the sea composition is high. Flowable low-density polyethylene. This fiber is stretched to 2.5 times in warm water at 70 ° C. The fiber oil is added, mechanically crimped and dried to cut into 5 1 mm as 5. The short fibers of 0 dte X were formed into a fiber web with a mesh size of 65 Og / m2 by the cross-overlap method, and then a needle perforation of about 2.5 00P / cm2 was performed simultaneously from the two sides and heated. At the same time, pressure is also applied to produce a wound nonwoven fabric with a smooth surface. The mesh of this wound non-woven fabric is 200g / m2 =, and the density is 〇. 48g / cm3. -24- 1237079 V. Description of the invention (23) A polymer elastomer solution for impregnating the nonwoven fabric is prepared by the following method. Use N-methyldiethanolamine 8. 2 weight units as tertiary amine-containing diols, with a number average molecular weight of 2000 polyhexylene glycol carbonate 236. 1 weight unit, polybutadiene adipate with a number average molecular weight of 2000 40.3 weight unit, and polytetramethylene glycol with a number average molecular weight of 4 4. 0 weight units as polymer diol to hexyl diisocyanate 28. 9 weight units as organic diisocyanate, and DMF 105. 9 weight units were placed in the reactor, and the reaction was carried out under a nitrogen gas flow at a predetermined temperature for a predetermined time to obtain an intermediate. After confirming that the isocyanate group was not contained, the weight average molecular weight of this intermediate was measured by GPC to be 40,000. To the DMF solution of the intermediate diol obtained above, ethylene glycol 18. 2 weight units as low-molecular-weight diols, than silicophos ρ〇_4500 (manufactured by this chemical industry (stock), molecular weight 222. 26, phosphorus content 13. 9 wt%) 21. 8 weight units and diphenylmethane-4,4'-diisocyanate 1 1 2 · 6 weight units were reacted to obtain a polyurea solution having a concentration of 25% and a weight average molecular weight of 320,000. DMF 78 was added to 100 weight units of the prepared polyuretane solution as an impregnating solution with a solid content of 14%. After the entangled nonwoven fabric is immersed in the impregnating solution, the impregnated non-woven fabric is then immersed in a DMF / water mixed solution to perform wet coagulation, and the sea component in the sea-island composite fiber is dissolved and removed in hot toluene. It is an ultra-fine fiber with a thickness of 1. 3mm leather-like substrate. The average fineness of ultrafine fibers is 0. 2 d t e X. Leather sample base -25-1237079 V. Description of the invention (24) The ratio of the weight of the fiber in the body to the weight of the polyurea is about 8: 2. Table 2 shows the results of evaluating the flame retardancy and the phosphorus atom concentration of each of the prepared leather sample substrates. The surface of the fiber sheet is fluffed, dyed, and made into a suede-like artificial leather, which is a kind of dyeable and flame retardant. It is suitable for interior design, especially for vehicles such as seats for vehicles, etc. Use, soft touch and look suede-like artificial leather. In addition to making the surface with fluff, the surface can also have a polyurea layer with a thickness of 60 microns, so that it has a natural leather-like embossed appearance. After kneading, it is also a kind of artificial leather with excellent flame resistance, suitable for interior design field, especially for transportation seats, etc., which need flame resistance, and has a soft touch and look and feel with a silver surface layer. In addition, after these products were processed, the artificial leather was evaluated as self-extinguishing through a Π S D 1 2 01 combustion test. This artificial leather maintains its flame resistance after being immersed in hot water at 90 ° C for 30 days after production. When using the manufactured suede-like or silver-coated artificial leather to make automotive seats, processing problems caused by strength and the like do not occur. The finished seat has a touch similar to that when using natural leather, Appearance and flame resistance required for car seats. Examples 9 to 10 A leather-like sheet substrate was produced under the same conditions as in Examples 7 and 8 except that polyether diol was used instead of polyhexene carbonate as the polymer diol. When using the prepared suede-style or silver-coated artificial leather to make automotive seats, processing problems caused by strength and other factors will not occur. -26-1237079 V. Description of the invention (25) It has a touch and appearance similar to that of natural leather, and has the flame retardancy required for a car seat. Table 2 shows the results of evaluating the properties and the phosphorus atom concentration of the obtained leather-like substrate. Example 1 1-12 Except using polyester diol instead of polyhexene carbonate as the polymer, a suede-like or silver-coated artificial leather was prepared under the same conditions as in Examples 7 and 8 to produce a leather sample substrate. When manufacturing a car seat, there are no processing problems due to strength and the like. The seat has a touch and appearance similar to that when using natural leather, and has the flame retardancy required for a car seat. Table 2 shows the results of evaluating the properties and the phosphorus atom concentration of the obtained leather-like substrate. Example 1 3 to 1 4 A leather sample base was produced under the same conditions as in Examples 7 and 8 except that trimethylene glycol was used as the main ethylene glycol component. The suede-style or silver-coated artificial leather made of automotive seats does not cause processing problems due to strength, etc. The finished seat has a touch and appearance similar to that when using natural leather, and has automotive needs. Flame resistance. Table 2 shows the results of evaluating the flame retardancy of the obtained leather-like substrate. Comparative Example 5 A leather-like sheet substrate was prepared under the same conditions as in Example 7 except that a non-polymerized polyethylene terephthalate polyester was used as the phosphorus-based flame retardant in the island component. Table 2 shows the results of evaluating the flame retardancy of the obtained leather-like substrate. Gas-fired flame retardants 〇 When made of gas-fired flame retardants using seats, chairs and seats, phosphoric esters, phosphorus 1237079 V. Description of the invention (%) Comparative examples 6 to 7 Except for synthetic polymer elastomers A leather sample substrate was produced under the same conditions as in Examples 7 and 8 except that no organic phosphorus-based flame retardant component was added. Table 2 shows the results of evaluating the flame retardancy and the phosphorus atom concentration of the obtained leather sample substrate. [Possibility of application in industry] The leather-like sheet substrate of the present invention is halogen-free, has excellent flame retardancy, and has excellent flame retardance durability. In addition, the leather-like sheet substrate of the present invention has a leather-like soft touch and look and feel, and is ideal as a base layer of suede-like or silver-coated artificial leather, and is suitable for car seats, train seats, aircraft seats, soft The surface material and the like must have flame retardant and other uses. The leather-like sheet substrate of the present invention can be used in general applications such as wallpaper, velvet, etc., in addition to commonly used artificial leather. -28- 1237079 —-—__ V. Description of the invention (27) Table 1 Island composition • Phosphorus concentration in the island composition (in the raw cotton after spinning) [ppm] — ~ 一 — ____-— 1 Phosphorus in the island composition Atomic concentration (in the base of the sheet) [ppm] Metal hydroxide added (for polymer elastomer) [phr] Fire test JIS D1201 Example 1 Polyethylene terephthalate 5 X 103 5 X 103 Hydroxide Inscription 5 0 to. Extinction Example 2 Polyethylene Terephthalate 12 X 1 0 3 12 X 103 Aluminum Hydroxide 5 0 Self Extinction Example 3 Polyethylene Terephthalate 5xl03 5 X 103 Magnesium Hydroxide 1 3 0 Flame retardance example 4 Polyethylene terephthalate 12xl 03 12 X 103 Magnesium hydroxide 130 Self-extinguishing example 5 Polytrimethylene terephthalate 5x1 03 5 X 103 Aluminum hydroxide 5 0 Self-extinguishing Example 6 Polytrimethylene terephthalate 12x1 03 12 X 103 Aluminum hydroxide 5 0 Self-extinguishing Comparative Example 1 Polyethylene terephthalate 0 0 Aluminum hydroxide 5 0 Flammable Comparative example 2 Polyethylene terephthalate 5X 1 03 5 X 103 0 Flammability Comparative example 3 Polyethylene terephthalate 1 2 X 1 03 12 X 103 0 Comparative example of flammability 4 Polyethylene terephthalate 5 X 103 1 X 103 Aluminum hydroxide 5 0 Flammability -29 · 诼 正 1237079 —1-di'one wheat 丨 —— ----------- -------- <. 1 Application date 91.2.22 '------------- Case No. 91103126 Type Vc ^^ / ίψ (The above blocks are to be filled by this Office) (Amended on January 5, 1994 ） Mist I Patent Specification Chinese Flame Retardant Leather Sample Base Invention New Name English
NON-FLAMMABLE LEATHER-LIKE SHEET MATERIAL 姓 名 1. 安田佳明（Yoshiaki Yasuda) 2. 武田康宏（Yasuhiro Takeda) 3. 石野修平（Ishino Shuhei) 4. 丹波善博（Yoshihiro Tanba) 發明 創作 人 三、申請人 國 住、居所 姓 名 (名稱） 國 籍 住、居所 (事務所） 代表人 姓 名 1-4皆屬曰本 1. 岡山縣倉敷市酒津1621番地株式会社夕y b內 c/o Kuraray Co., Ltd. 1621, Sakazu, Kurashiki-Ci ty, Okayama-Pref., Japan 2. 岡山縣倉敷市乙島7471番地株式会社夕y PR c/o Kuraray Co., Ltd. 7471,0toshima, Kurashiki-City, Okayama-Pref., Japan 3 - 4同1.所 可樂麗股份有限公司（株式会社夕y b) Kuraray Co ., Ltd . 曰本 岡山縣倉敷市酒津1621番地 1621, Sakazu Kurashiki-Ci ty, Okayama-Pref, 和久井康明（Yasuaki Wakui)NON-FLAMMABLE LEATHER-LIKE SHEET MATERIAL Name 1. Yoshiaki Yasuda 2. Yasuhiro Takeda 3. Ishino Shuhei 4. Inventor and creator of Yoshihiro Tanba 3. Applicant's national residence 、 Name of residence (name) Nationality residence, residence (office) Representative names 1-4 are Japanese 1. 1. C / o Kuraray Co., Ltd. 1621, Sakazu, Shibuzu 1621, Kurashiki City, Okayama Prefecture , Kurashiki-Ci ty, Okayama-Pref., Japan 2. PR c / o Kuraray Co., Ltd. 7471,0toshima, Kurashiki-City, Okayama-Pref., Japan 3 -4 Same as 1. Sokolaray Co., Ltd. (Kuraray Co., Ltd.) 1621, Shisui, Kurashiki, Okayama, 1621, Sakazu Kurashiki-Ci ty, Okayama-Pref, and Yasuaki Wakui
Japan ‘S 妗 1237079 (1 五、發明說明（28 表2 島成分•島成分 中的磷原子濃度 (紡絲後原綿中） [ppm] 聚脲烷的主 成分 聚脲烷中的磷 原子濃度 [ppm] 燃燒試驗 JIS D1201 實施例7 聚對苯二甲酸乙 二醇酯5 X 103 聚碳酸酯類 5 X 103 自熄性 實施例8 聚對苯二甲酸乙 二醇酯 12 X 103 聚碳酸酯類 5 X 103 自熄性 實施例9 聚對苯二甲酸乙 二醇酯5xl03 聚醚類 5 X 103 自熄性 實施例10 聚對苯二甲酸乙 二醇酯 12x 103 聚醚類 5 X 103 自熄性 實施例11 聚對苯二甲酸乙 二醇酯5χ103 聚酯類 5 X 103 自熄性 實施例12 聚對苯二甲酸乙 二醇酯 12x1 03 聚酯類 5 X 103 自熄性 實施例13 聚對苯二甲酸三 亞甲基酯5xl 03 聚碳酸酯類 5 X 103 自熄性 實施例14 聚對苯二甲酸三 亞甲基酯12x1 03 聚碳酸酯類 5 X 103 自熄性 比較例5 聚對苯二甲酸乙 二醇酯〇 聚碳酸酯類 5 X 103 易燃性 比較例6 聚對苯二甲酸乙 二醇酯5x1 03 聚碳酸酯類 0 易燃性 比較例7 聚對苯二甲酸乙 二醇酯 12x 103 聚碳酸酯類 0 易燃性 -30-Japan 'S 妗 1237079 (1 V. Explanation of the invention (28 Table 2 Phosphorus atom concentration in island components and island components (in raw cotton after spinning) [ppm] Phosphorus atom concentration in polyuret, the main component of polyurethane [ ppm] Flammability test JIS D1201 Example 7 Polyethylene terephthalate 5 X 103 Polycarbonate 5 X 103 Self-extinguishing Example 8 Polyethylene terephthalate 12 X 103 Polycarbonate 5 X 103 self-extinguishing example 9 polyethylene terephthalate 5x103 polyether 5 X 103 self-extinguishing example 10 polyethylene terephthalate 12x 103 polyether 5 X 103 self-extinguishing Example 11 Polyethylene terephthalate 5 × 103 Polyester 5 X 103 Self-extinguishing Example 12 Polyethylene terephthalate 12x1 03 Polyester 5 X 103 Self-extinguishing Example 13 Poly Trimethylene terephthalate 5xl 03 Polycarbonate 5 X 103 self-extinguishing Example 14 Polytrimethylene terephthalate 12x1 03 Polycarbonate 5 X 103 Self-extinguishing Comparative Example 5 Polyparaphenylene Polyethylene Dicarboxylate 0 Polycarbonate 5 X 103 Comparative Example 6 Flammability Polyethylene Terephthalate Ester 5x1 03 Polycarbonate 0 Flammability Comparative Example 7 Polyethylene terephthalate 12x 103 Polycarbonate 0 Flammability -30-