TW299364B - - Google Patents

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TW299364B
TW299364B TW84103988A TW84103988A TW299364B TW 299364 B TW299364 B TW 299364B TW 84103988 A TW84103988 A TW 84103988A TW 84103988 A TW84103988 A TW 84103988A TW 299364 B TW299364 B TW 299364B
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Taiwan
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diamine
polyhexamethylene
weight
fiber
cns
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TW84103988A
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Chinese (zh)
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Asahi Chemical Ind
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Priority claimed from JP26684693A external-priority patent/JP3272834B2/en
Priority claimed from JP11301994A external-priority patent/JP3281177B2/en
Priority claimed from JP14331394A external-priority patent/JP3375419B2/en
Application filed by Asahi Chemical Ind filed Critical Asahi Chemical Ind
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Publication of TW299364B publication Critical patent/TW299364B/zh

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A7 A7 經濟部中央橾準局員工消費合作社印製 B7 五、發明説明（1 ) 本發明係有關對於纖維加工時所受到之熱具有極優異 抗熱變黃性的聚己二醯己二胺纖維，組成物及可以極有利 地製造此種纖維之方法者。本發明係除具有極優異之抗熱 變黃性，還可以染色爲鮮艷，深色之適於衣料用途之聚己 二醯己二胺繊維及其商業上極有利之製造方法。 一般之聚醯胺（尼龍）係力學特性及耐久性優者，所 以大量地被使用於輪胎帘線等產業資材用織維，或地毯用 纖維等纖維，以及成形品上用途。另一方面，由於具有優 異之柔軟性或染色性，所以，做爲衣料用纖維，尤其內衣 用纖維亦同樣被大量使用》 聚己二醯己二胺織維（尼龍6 6 )係聚醯胺之一代表 性種類者，亦普遍地被使用於產業資材用纖維、地毯用纖 維、衣料用纖維，以及各種成形品等。惟與同一聚醯胺代 表性的聚-e -己醯胺（尼龍6 )相比有加熱會顯著變黃 ，做爲衣料用纖維具有極大缺點。不論在纖維、成形品上 ，此缺點對於被要求外觀需要白色之用途成爲極重大問題 。尤其衣料用纖維係單絲徑小（比表面積大），所以原來 即易受到熱氧化，更由於布帛製造過程中，二次加工時熱 固定（熱處理）係必須經過之步驟，使上述變黃之問題更 爲嚴重。爲此聚己二醯己二胺繊維被使用於衣料用纖維乃 受到極大之限制。 例如睡衣或內衣等係對於具有柔軟性或適度吸濕性之 聚醯胺纖維爲極適宜之用途。惟聚己二醯己二胺纖維卻因 如上述熱固定時會極顯著地變黃，破壞製品之白色度，染 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 、-βA7 A7 B7 printed by the Employees ’Consumer Cooperative of the Central Department of Economic Affairs of the Ministry of Economic Affairs 5. Description of the invention (1) The present invention relates to polyhexamethylene diamine hexamethylene diamine fiber with excellent heat yellowing resistance to the heat received during fiber processing , Compositions and methods that can be used to manufacture such fibers very advantageously. In addition to having excellent resistance to heat yellowing, the present invention can also be dyed into bright, dark colored polyhexamethylene diamine diamines suitable for clothing and its commercially advantageous manufacturing method. Generally, polyamide (nylon) is excellent in mechanical properties and durability, so it is widely used in textile fabrics for tire cords and other industrial materials, fibers for carpets, and molded articles. On the other hand, because of its excellent softness or dyeability, it is also used in a large amount as fiber for clothing, especially for underwear. "Polyhexamethylene diamine hexamethylene diamine (nylon 6 6) polyamide One of the representative types is also commonly used in industrial materials fiber, carpet fiber, clothing fiber, and various molded products. However, compared with the poly-e-hexamide (nylon 6), which is the representative of the same polyamide, it will turn yellow significantly when heated, and it has great disadvantages as a fabric fiber. Regardless of the fiber or molded product, this shortcoming becomes a major problem for applications that require white appearance. In particular, the fibers used for clothing have a small monofilament diameter (large specific surface area), so they are initially susceptible to thermal oxidation. Furthermore, in the fabric manufacturing process, the heat fixation (heat treatment) is a step that must be passed during the secondary processing to make the above yellow. The problem is more serious. For this reason, the use of polyhexamethylene diamine diamine as a fiber for clothing is greatly restricted. For example, pajamas or underwear are extremely suitable for polyamide fibers with softness or moderate hygroscopicity. However, the polyhexamethylene diamine fiber will yellow significantly when it is heat-fixed as described above, destroying the whiteness of the product, and the standard of the dyed paper is the Chinese National Standard (CNS) A4 (210X297mm) (please first Read the notes on the back and fill out this page), -β

T -4 - ^^9S〇4 a7 B7 五、發明説明（2 ) 色後呈現於製品之顔色不鮮明（混濁顏色），爲此事實上 幾乎不被使用於上述內衣用途。內衣用途上現今仍以使用 聚一 e -己醯胺纖維及聚酯繊維爲最多。 聚_ ε —己醯胺纖維係與聚己二醯己二胺纖維相比， 其抗熱變黃性顯著優異，熱固定後極少變黃，使用做爲上 述內衣用途幾乎沒有問題。另外，聚酯纖維之抗熱變黃性 比聚一 e -己醯胺更優，熱固定後幾乎完全不會變黃（即 ，可維持纖維之白色）。 因此製造聚己二醯己二胺繊維之業者通常係以改良該 纖維之抗熱變黃性達到可以與聚_ e _己醯胺繊維比肩之 地步爲其初步目標，而以改良至可以與聚酯纖維比肩之水 準爲最後目標。惟可達成此等目標之技術迄今仍未被開發 〇 經濟部中央標準局貝工消費合作杜印製 (請先閱讀背面之注意事項再填寫本頁) 通常熔融成形、熔融紡絲熱塑性有機聚合物時係在聚 合物原料中配合防熱氧化劑等熱安定劑、抑制或減輕聚合 物之熱劣化、變色等熱變質。視聚合物種類之不同而選擇 適當之添加劑，惟現今被廣泛採用可通用於聚合物之熱安 定劑係包含受阻砑類之酚系抗氧化劑。配合對象之聚合物 成形品用途上要求，聚合物之抗變質水準亦顯著不同。爲 此乃有人嚐試除酚系抗氧化劑以外，併用其他化學物質， 例如有機銻化合物、磷化合物、硫醚系抗氧化劑的各種配 合系" 特開昭4 6 _ 7 4 5 5號公報中係記載藉由配合有機 銻化合物與酚系氧化劑，可以防止以聚烯烴爲主之各種聚 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 5 A7 B7 五、發明説明（3 ) 合物的氧化劣化。該公報說明書中曾例示包含2，4 -雙 (烷硫基）—6 — (3，5 -二烷基一 4 —羥苯胺基）_ 1 ’ 3，5-三氮阱之多數酚系抗氧化劑，記載適用上述 三氮阱衍生物之抗氧化劑於聚丙烯的具體例。此先行技術 係以對聚合物之抗氧化效果評估氧吸收量，完全未提及對 聚合物之防熱變黃效果。 經濟部中央標準局員工消費合作社印裝 (請先閲讀背面之注意事項再填寫本頁) 特開平6 _ 1 6 9 2 9號公報中係記載聚醯胺中配合 受阻酚系抗氧化劑、磷系抗氧化劑及硫醚系抗氧化劑之三 種，藉此可抑制聚醯胺射出成形品之氧化劣化所引起之變 色。惟該公報上並無有關抑制變色之效果上的定量性記載 。根據本發明人等檢討之結果，即使添加該公報上所列化 合物於聚己二醯己二胺纖維亦無法得到充分之抗熱變黃性 。例如爲使用於睡衣居家服而染爲粉紅色或淺藍色時，由 於會因熱固定而變黃，無法得所希望之顏色，只能得混濁 之顏色而已。即，以該公報之技術無法得到爲促進擴大聚 己二醯己二胺纖維使用於內衣應具備之抗熱變黃性。又， 該公報所記載抗氧化劑中亦未記載有關2，4 -雙（烷硫 基）—6 — (3，5 —二烷基—4 一羥苯胺基）一1 ，3 ，5 —三氣哄。 特開昭5 1 - 1 5 5 7號公報說明書中係記載配合完 全與本發明化合物完全不同之具特定構造的酚系抗氧化劑 ，視其需要的磷化合物，以抑制聚醯胺之熱變黃》惟公報 上亦未記載防熱變黃效果上有關之定量上記載。根據本發 明人等檢討之結果，即使添加該公報說明書上所列化合物 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） A7 B7 五、發明説明（4 ) 於聚己二醯己二胺繊維亦無法得到充分之抗熱變黃性。例 如爲使用於睡衣居家服而染爲粉紅色或淺藍色時，由於會 因熱固定而變黃，無法得所希望之顏色，只能得混濁之顔 色而已。即，以該公報之技術無法得到爲促進擴大聚己二 醯己二胺纖維用途之抗熱變黃性。 另外，該公報說明書中被具體地記載的化合物係耐熱 低，所以熔融混練具有2 6 0 °C以上髙熔點之聚己二醯己 二胺時，還會發生使該化合物本身發生變質之弊害。 美國專利第3 5 9 4 4 4 8號說明書中曾記述改善聚 醯胺與聚酯之摻合物纖維的白色度，許多種類之受阻酚化 合物爲有效。其中還包含上述之三氮阱化合物〔I〕。惟 該美國專利說明書所記載之發明係爲抑制聚醯胺與聚酯之 摻合物料特有現象之兩成份界面上劣化反應，結果可以改 善因摻合物料所引起之變黃者。 經濟部中央榡準局貝工消費合作杜印製 (請先閲讀背面之注意事項再填寫本頁) 特公昭5 5 - 2 0 4 9 8中係敘述對於主鏈中具有環 構造之聚醯胺，配合硼酸系金屬鹽，有機磷化合物，位阻 (steric hindrance)性酚之三種，藉此抑制該聚醯胺之 著色黃化》惟該公報之發明僅爲解決具有環構造之聚醯胺 特有的問題者。即，抑制該聚合物之胺基末端基所引起之 分子鏈熱分解反應，防止分子量降低，凝膠化，黃化爲目 的者。 特開昭54 — 82496公報說明書中係記載2，4 —雙（烷硫基）—6— (3，5 —二烷基—4 一羥苯胺基 )一 1 ，3 ’ 5 —三氮阱在提高橡膠等含雙鍵結合之聚合 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） A7 B7 五、發明説明（5 ) 物的熱安定性有效。此公知說明書中並沒有對於抑制聚醯 胺，尤其對於抑制聚己二醯己二胺纖維之變黃性有任何之 表？K、暗不。 以往爲抑制聚醯胺之熱劣化，通常係配合Ν，Ν / — 伸己基雙（3，5 —二第三丁基—4 —羥基一氫化肉桂醯 胺〔例如日本汽巴凱基公司「近年來對聚醯胺系樹脂之用 途開發所示安定化配方」〕，惟該化合物雖可以提高聚己 二醯己二胺之力學上耐熱安定性，但仍不足抑制該聚合物 特有之極強烈熱變黃顯示其效果。 聚醯胺纖維中之胺基末端基濃度係與可以深色染色之 纖維與聚醯胺聚合物的可紡性有極密切之關係。設定爲高 濃度之胺基末端基，可以用酸性染料深染之聚醢胺纖維係 商業上爲公知者。 經濟部中央榡準局貝工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 美國專利第3 0 7 8 2 4 8號說明書中記載，若提高 聚己二醯己二胺之胺基末端基濃度時熔融紡絲中常會發生 料滴（dripping紡絲被切斷之一種現象），很難順利地紡 絲。胺基末端基濃度增加時，斯業界人士均知常會發生料 滴或斷絲，眾所知其原因在於胺基末端基會促進聚合物之 熱分解或支鏈生成反應所引起。 爲此工業上紡絲聚己二醯己二胺纖維時常使用胺基末 端基濃度低，即富含羧基末端基之聚合物，以達成正常之 紡絲水準（例如特公平3 — 57966號公報）。 通常爲抑制熔融紡絲時發生料滴或斷絲，做爲安定劑 (熱分解抑制劑、支鏈生成抑制劑）揭示使用具有特定構 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -8 - 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（6 ) 造之有機磷化合物（美國專利第3 0 7 5 2 4 8號說明書 )，二羧酸或胺基羧酸之鹸金屬鹽（特開平 1-104654號公報）。 爲此，本發明之最大目的係欲提高聚己二醯己二胺纖 維之使用上特質，尤其衣料用纖維特性譜達到可以與聚己 醯胺及聚酯纖維之該等特性比肩之水準。 本發明之具體目的係在於提供至少具有可以與聚己醯 胺纖維比肩之抗熱變黃性的聚己二醯己二胺纖維。 本發明之其他具體目的係在提供適於衣料用纖維特性 被改良之高含胺基末端基的聚己二醯己二胺纖維及其被改 良之製造方法。 本發明又以提供兼具有高水準之抗熱變黃性及濃染性 之聚己二醯己二胺纖維爲一目的。 本發明還以提供可以製得抗熱變黃性之聚己二酿己二 胺纖維等成形物的有用組成物爲其目的。 本發明之第一形態係依據含有（A) 2，4 一雙（院 硫基）—6 — (3，5 -二院基一 4 —羥苯胺基）—1， 3，5 —三氮阱，與（B) —種或複數種選自亞磷酸、亞 磷酸衍生物、次磷酸、次磷酸衍生物群的含磷化合物所成 己二醯己二胺具有高度抗熱變黃性的性質者。即，本發明 之第一形態係分子鏈中含有1 0 0〜7 0重量％己二醯己 二胺重覆單位 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝. ^39364 A7 B7 五、發明説明（T -4-^^ 9S〇4 a7 B7 V. Description of the invention (2) The color that appears on the product after the color is not clear (turbid color), for this reason it is practically not used for the above underwear. The use of poly-e-hexamide fiber and polyester fiber is still the most used in underwear today. Poly_ε-hexamethylene amide fiber system has significantly better heat yellowing resistance than polyhexamethylene hexamethylene diamine fiber, and rarely yellows after heat fixation. It is almost no problem to use it as the above-mentioned underwear. In addition, the thermal yellowing resistance of polyester fiber is better than poly-e-hexamethylene amide, and almost no yellowing after heat fixation (ie, can maintain the white color of the fiber). Therefore, the manufacturer of polyhexamethylene diamine hexamethylene diamine is usually to improve the fiber's resistance to heat yellowing to reach the point where it can be comparable to poly _ e _ hexamethylene diamine dimensional, and to improve it to be compatible with poly The level of ester fiber is the final goal. However, the technology that can achieve these goals has not yet been developed. The printing is produced by Beigong Consumer Cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back and then fill out this page). In this case, thermal stabilizers such as heat-resistant oxidants are added to the polymer raw materials to suppress or reduce thermal deterioration and discoloration of the polymer. The appropriate additives are selected according to the type of polymer, but nowadays, widely used heat stabilizers that can be applied to polymers include hindered phenolic antioxidants. In accordance with the application requirements of the polymer molded products, the polymer's resistance to deterioration is also significantly different. For this reason, there have been attempts to use various chemical substances in addition to phenol-based antioxidants, such as organic antimony compounds, phosphorus compounds, and sulfide-based antioxidants. Various systems of " Japanese Patent Publication No. 4 6 _ 7 4 5 5 It is stated that by combining organic antimony compounds and phenolic oxidants, it is possible to prevent the application of Chinese national standards (CNS) A4 specifications (210X 297 mm) for various polyolefin-based paper standards. 5 A7 B7 5. Description of the invention (3) Oxidative deterioration of the compound. In the specification of this gazette, many phenol-based anti-oxidants containing 2,4-bis (alkylthio) -6- (3,5-dialkyl-4-hydroxyanilinyl) _ 1 '3,5-trinitrogen trap were exemplified The oxidizing agent describes specific examples of applying the antioxidant of the above-described trinitrogen trap derivative to polypropylene. This advanced technique is based on the evaluation of the oxygen absorption of the antioxidant effect of the polymer, and there is no mention of the anti-heat yellowing effect on the polymer. Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page) JP 6_ 1 6 9 2 9 describes that the compounded hindered phenolic antioxidant and phosphorus compound are incorporated in the polyamide There are three types of antioxidants and thioether-based antioxidants, which can suppress the discoloration caused by the oxidative deterioration of the polyamide injection molded products. However, there is no quantitative record on the effect of suppressing discoloration in the bulletin. According to the results of the review by the inventors, even if the compounds listed in the publication are added to the polyhexamethylene diamine diamine fiber, sufficient heat yellowing resistance cannot be obtained. For example, when it is dyed pink or light blue for use in pajamas and home wear, it will turn yellow due to heat fixation, and the desired color cannot be obtained, only a turbid color. That is, the technology of the publication does not provide the heat yellowing resistance that is necessary for promoting the expansion of the polyhexamethylene diamine fiber used in underwear. In addition, the antioxidant described in this bulletin also does not describe 2,4-bis (alkylthio) -6- (3,5-dialkyl-4-hydroxyanilinyl) -1,3,5-trigas coax. Japanese Patent Application Laid-Open No. 5 1-1 5 5 7 describes the blending of a phenolic antioxidant with a specific structure that is completely different from the compound of the present invention, and a phosphorus compound as needed to suppress the thermal yellowing of polyamide "However, there are no quantitative records on the effect of preventing heat yellowing in the communique. According to the results of the review by the inventors, even if the compounds listed in the specification of the bulletin are added, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) A7 B7 V. Description of the invention (4) Yujujidi Hexanediamine can also not obtain sufficient resistance to heat yellowing. For example, when it is dyed in pink or light blue for use in pajamas and home clothes, it will turn yellow due to heat fixation, and the desired color cannot be obtained, only a turbid color. That is, with the technique of this publication, the heat yellowing resistance for promoting the expansion of the application of polyhexamethylene diamine fiber cannot be obtained. In addition, the compound specifically described in the specification of this publication has a low heat resistance, so when melt-kneading polyhexamethylenediamine having a high melting point of 260 ° C or higher, the compound itself may be deteriorated. U.S. Patent No. 3 5 9 4 4 4 8 describes that improving the whiteness of blend fibers of polyamide and polyester, many kinds of hindered phenol compounds are effective. It also contains the above-mentioned trinitrogen trap compound [I]. However, the invention described in the US patent specification is to suppress the degradation reaction at the interface of the two components which is a unique phenomenon of the blending material of polyamide and polyester. As a result, the yellowing caused by the blending material can be improved. Printed by the Ministry of Economic Affairs, Central Bureau of Customs, Shellfish Consumer Cooperation (please read the precautions on the back and then fill out this page) 特 公 昭 5 5-2 0 4 9 8 The system describes the polyamide with a ring structure in the main chain , With boric acid-based metal salts, organic phosphorus compounds, steric hinderance (steric hindrance) three kinds of phenols, thereby inhibiting the coloring yellowing of the polyamide "but the invention of the bulletin is only to solve the ring structure of polyamide unique Questioner. That is, it is intended to suppress the thermal decomposition reaction of the molecular chain caused by the amine end group of the polymer and prevent the molecular weight from lowering, gelation, and yellowing. Japanese Unexamined Patent Publication No. 54-82496 describes 2,4-bis (alkylthio) -6- (3,5-dialkyl-4-hydroxyanilinyl) -1,3'5-trinitrogen trap in To improve the size of the polymer paper containing double bonds, such as rubber, the standard of China National Standard (CNS) A4 (210X 297mm) is applicable. A7 B7 5. Invention description (5) The thermal stability of the material is effective. This well-known specification does not have any list on the suppression of polyamide, especially on the yellowing of polyhexamethylene diamine diamine fibers? K, secretly. In the past, in order to suppress the thermal degradation of polyamide, it is usually combined with Ν, Ν /-extended hexyl bis (3,5-di-tert-butyl-4-hydroxymonohydrocinnamamide amide (for example, Japan Ciba Key Group "in recent years To develop the stabilized formulation shown for the use of polyamidoamine resins "], but the compound can improve the mechanical heat stability of polyhexamethylenediamine diamine, but it is still insufficient to suppress the extremely strong heat unique to the polymer It turns yellow to show its effect. The concentration of amine end groups in polyamide fibers is very closely related to the spinnability of fibers that can be dyed in dark colors and the polyamide polymer. It is set to a high concentration of amine end groups , Polyamide fibers that can be deeply dyed with acid dyes are commercially known. Printed by the Beigong Consumer Cooperative of the Central Bureau of Economics of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) US Patent No. 3 0 7 8 2 4 No. 8 describes that if the concentration of amine end groups of polyhexamethylene diamine is increased, droplets (a phenomenon of dripping spinning being cut) often occur in melt spinning, which makes it difficult to spin smoothly Silk. Concentrated amine end groups When increasing, Sri Lankan people all know that dripping or filament breakage often occurs. The reason for this is known to be that the amine terminal group will promote the thermal decomposition of the polymer or the branching reaction. For this reason, spinning polyhexamethylene Acetyl diamine fibers often use polymers with a low concentration of amine end groups, that is, rich in carboxyl end groups, to achieve a normal spinning level (for example, Japanese Patent Publication No. 3-57966). It is usually used to suppress the occurrence of melt spinning Gob or broken wire, as a stabilizer (thermolysis inhibitor, branched chain generation inhibitor) reveals the use of paper with a specific constitutive scale and applies the Chinese National Standard (CNS) A4 specification (210X297mm) -8-Central Ministry of Economic Affairs A7 B7 printed by the Bureau of Standards and Staff ’s Consumer Cooperative V. Description of invention (6) Organic phosphorus compound (US Patent No. 3 0 7 5 2 4 8), metal salt of dicarboxylic acid or aminocarboxylic acid (special) Kai Ping 1-104654). Therefore, the biggest object of the present invention is to improve the use characteristics of polyhexamethylene diamine fiber, especially the fiber characteristic spectrum for clothing can reach the polyhexamethylene and polyester fiber. Equivalent characteristics. The specific object of the present invention is to provide polyhexamethylenediamine diamine fibers having at least a thermal yellowing resistance comparable to polyhexamethylene fibers. Other specific objects of the present invention are to provide suitable High amine group-containing polyhexamethylenediamine diamine fiber with improved fiber characteristics for clothing and its improved manufacturing method. The present invention also provides high-level thermal yellowing resistance and concentrated dyeing The purpose of this invention is to provide a useful composition that can produce shaped articles such as polyhexamethylene diamine fibers that resist heat yellowing. The first of the invention The morphology is based on containing (A) 2,4 a double (homosulfuryl group)-6-(3,5 -dihomoyl group-4-hydroxyaniline group)-1, 3,5-trinitrogen trap, and (B) -A kind or a plurality of kinds of phosphorous compounds selected from phosphorous acid, phosphorous acid derivatives, hypophosphorous acid, hypophosphorous acid derivative group, and the hexamethylene diamine hexamethylene diamine has the property of being highly resistant to heat yellowing. That is, the first form of the present invention is that the molecular chain contains 100 0 to 70% by weight of hexamethylene diamine hexamethylene diamine repeating unit. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) Read the precautions on the back and then fill out this page) Pack. ^ 39364 A7 B7 5. Description of the invention (

I I C(CH2)4CN(CH2)6N II II 的聚己二醯己二胺纖維’或含有1 〇 〇〜7 〇重量％之聚 己二醯己二胺纖維與0〜3 0重量％其他聚醯胺之摻混纖 維，其特徵爲 (A)含有0·01〜10重量％以下式〔I〕所示2 ，4 —雙（院硫基）—6 —( 胺基）一 1，3，5 —三氮阱 5 —二院基一 4 —經苯IIC (CH2) 4CN (CH2) 6N II II of the polyhexamethylene diamide hexamethylene diamine fiber 'or containing 100 to 70 percent by weight of polyhexamethylene diammonium diamine fiber and 0 to 30 percent by weight of other polyamide Amine blended fiber, characterized in that (A) contains 0.01 ~ 10% by weight as shown in the following formula [I] 2,4-bis (homosulfuryl group) -6- (amino group) -1,3,5 —Trinitrogen trap 5 —Secondary base one 4 —Benzene

⑴ (請先閲讀背面之注意事項再填寫本頁) 装· 訂 經濟部中央標準局員工消費合作社印製 (式中Rt表示第三丁基或碳數1〜4之烴基，R2 ，R3表示碳數5〜10烴基），以及 (B)含有0.005〜1.0重量％—種或複數種 選自亞磷酸、亞磷酸衍生物、次磷酸、次磷酸衍生物， 所成的抗熱變黃性聚己二醣己二胺嫌維。 如上述被特定之聚己二醃己二胺織維係即使末端基濃 度在任何範圍，可以做爲內衣及其他極嚴格地要求白色度 之衣料用纖維，具有可媲美聚- e -己醯胺之抗熱變黃性 ，即使經過包含加熱在內之加工亦實質上不會降低白色度 本發明之第二形態係在特定可以用酸性染料予以濃色 染色之抗熱變黃性聚己二醯己二胺纖維者。即，胺基末端 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ~ 10 - A7 B7_ 五、發明説明（8 ) 基濃度（〔_NH2〕）與羧基末端濃度（〔一 COOH 〕）之和在於70〜200meq/kg範圍，分子鏈中含 有7 0〜1 〇 〇重量％己二醢己二胺重覆單位 Η Η —C(CH2)4 CN(CH 2)6 Ν —⑴ (Please read the precautions on the back before filling out this page) Binding · Bookmarked by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (where Rt represents the third butyl group or a hydrocarbon group with 1 to 4 carbon atoms, R2 and R3 represent carbon Number 5 to 10 hydrocarbon groups), and (B) contains 0.005 to 1.0% by weight-one or more kinds selected from phosphorous acid, phosphorous acid derivatives, hypophosphorous acid, hypophosphorous acid derivatives, the resulting heat-resistant yellowing polyhexadiose Hexanediamine is too heavy. As mentioned above, it is maintained by the specific polyhexamethylene diamine hexamethylenediamine, even if the terminal group concentration is in any range, it can be used as underwear and other clothing fibers with strict whiteness requirements, which is comparable to poly-e-hexaneamide The thermal yellowing resistance does not substantially reduce the whiteness even after processing including heating. The second form of the present invention is to specifically heat-resistant yellowing resistant polyhexamethylene diacetyl, which can be dyed with acid dyes. Amine fiber. That is, the paper size of the amine terminal is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ~ 10-A7 B7_ V. Description of the invention (8) Base concentration ([_NH2]) and carboxyl terminal concentration ([-COOH]] ) The sum is in the range of 70 ~ 200meq / kg, and the molecular chain contains 70 ~ 100% by weight of hexamethylene diamine hexamethylene diamine repeating unit Η Η -C (CH2) 4 CN (CH 2) 6 Ν-

II II ο ο 之聚己二醯己二胺組成物，可以滿足 (a) C-COOH] ^60 (meq/kg)，以及 (b) 含有0 . 005〜0 . 5重量％鹼金屬化合物 之條件爲特徵之聚己二醯己二胺織維。 值得矚目的是此等被特定之聚己二醯己二胺織維係在 1 0 o°c以上高溫、髙壓熱水處理（摺痕加工、高溫高壓 染色等）中，與以往之聚己二醢己二胺繊維相比其降低之 強度顯然更小。 本發明之第三形態係組合第一及第二形態所得具有高 度抗熱變黃性之濃染性聚己二醯己二胺纖維。即胺基末端 基濃度（〔一 NH2〕）與羧基末端基濃度（ 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 〔―COOH〕）之和在於7 5〜1 7 5me q/kg範圍 ，分子鏈中含有1 0 0〜7 0重量％己二醯己二胺重覆單 位 Η ΗII II ο ο polyhexamethylene hexamethylene diamine composition, which can satisfy (a) C-COOH] ^ 60 (meq / kg), and (b) contains 0.005 ~ 0.5 wt% of alkali metal compounds The condition is characterized by polyhexamethylene diamine diamine weave. It is worth noting that these special polyhexamethylene diamine diamine woven fabrics are maintained in high temperature, high pressure and hot water treatment (crease processing, high temperature and high pressure dyeing, etc.) above 10 o ° C, and they are the same as the previous ones. The divinyl diamine is obviously smaller than its reduced strength. The third aspect of the present invention is a concentrated dyed polyhexamethylene diamine fiber having high heat yellowing resistance obtained by combining the first and second aspects. That is, the sum of the concentration of the amine terminal group ([one NH2]) and the concentration of the carboxyl terminal group (printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page) [―COOH]) is 7 5 ~ 1 7 5me q / kg, the molecular chain contains 1 0 0 ~ 7 0% by weight of hexamethylene diamide hexamethylene diamine repeat unit Η Η

I I -C(CH2)4CN(CH2)eN —I I -C (CH2) 4CN (CH2) eN —

II II 0 0 之聚己二醯己二胺之繊維，可以同時滿足 本紙張尺度適用中國國家標準（CNS ) A4規格（2I〇X297公釐）~ -11 - 經濟部中央標準局員工消費合作社印製 A7 --^_B7_ ______ 五、發明説明（9 ) (a) C-COOH] ^60 (meq/kg)， (c) [-NH2] ^55 (meq/kg)，且含有 (A) 0 · 01〜1 . 〇重量％以下式〔I〕所示2 ’ 4 -雙（烷硫基）一6_ (3，5 —二烷基—4 一羥苯 胺基）一 1，3，5 —三氮阱，II II 0 0 The dimensions of polyhexamethylene diamine and diamine can also meet the paper standard and apply the Chinese National Standard (CNS) A4 specification (2I〇X297 mm) ~ -11-Printed by the Employees Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs System A7-^ _ B7_ ______ V. Description of the invention (9) (a) C-COOH] ^ 60 (meq / kg), (c) [-NH2] ^ 55 (meq / kg), and contains (A) 0 01 ~ 1. 〇% by weight represented by the following formula [I] 2 '4-bis (alkylthio) 6_ (3, 5-dialkyl-4-hydroxyanilinyl)-1, 3, 5--three Nitrogen trap,

(式中Ri表示第三丁基或碳數1〜4之烴基，R2 ’尺3表示碳數5〜10烴基），以及含有 (B) 0 . 〇〇5〜1 . 0重置％—種或複數種選自 亞磷酸、亞磷酸衍生物、次磷酸、次磷酸衍生物所成群’ 所成的抗熱變黃性濃染性聚己二醯己二胺嫌維。 本發明之第四形態係一種聚己二醯己二胺纖維之製& 方法的發明，具有以下特定之特徵者，即，藉由熔融結絲、 法製造胺基末端基濃度（〔一 NH2〕）與羧基 度（〔 — COOH〕）之和在於 75 〜ΐ75Ηΐεα/& 範圍，分子鏈中含有1 0 0〜7 0重量％己二酿B — 覆單位 Η Η(In the formula, Ri represents a third butyl group or a hydrocarbon group with a carbon number of 1 to 4, R2 'ruler 3 represents a hydrocarbon group with a carbon number of 5 to 10), and contains (B) 0. 〇〇5 ~ 1. 0 reset%-species Or a plurality of groups selected from the group consisting of phosphorous acid, phosphorous acid derivatives, hypophosphorous acid, and hypophosphorous acid derivatives. The fourth aspect of the present invention is an invention of a method for making & polyhexamethylene diamine fiber, which has the following specific characteristics, namely, the concentration of amine end groups ([-NH2 〕) The sum of the carboxyl group degree (〔— COOH〕) is in the range of 75 ~ 175ΗΙεα / &, the molecular chain contains 1 0 0 ~ 7 0% by weight adipic acid B — coating unit Η Η

I I -C(CH2)4CN(CH2)6N —I I -C (CH2) 4CN (CH2) 6N —

II II (請先閱讀背面之注意事項再填寫本頁) 裝· 訂 之聚己二醯己二胺之纖維，可以同時滿足II II (Please read the precautions on the back before filling in this page) The fiber of polyhexamethylene diamine can be satisfied at the same time

經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（10 ) (c) C-NH2] ^55 (meq/kg)，且該聚 合物爲含有 (A) 0 · 〇1〜1 _ 〇重量％以下式〔I〕所示2 ，4 一雙（院硫基）—6 — (3，5 —二院基—4—羥苯 胺基）—1 ’ 3，5 —三氮阱，A7 B7 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (10) (c) C-NH2] ^ 55 (meq / kg), and the polymer contains (A) 0 · 〇1 ~ 1 _ 〇% by weight represented by the following formula [I] 2, 4 a bis (Yuan thio group)-6-(3, 5-Diyuan group-4-hydroxyaniline group)-1 '3, 5-trinitrogen trap,

(式中Ri表示第三丁基或碳數1〜4之烴基，R2 ，R3表示碳數5〜10烴基），以及含有 (B) 0 · 005〜1 . 0重量％—種或複數種選自 亞磷酸、亞磷酸衍生物、次磷酸、次磷酸衍生物所成群， 並且又含有 (C) 〇.005〜0.5重量％鹸金靥化合物 爲特徵之耐變黃性濃染性聚己二醢己二胺纖維的製造方法 者》 本發明中所稱聚己二醯己二胺係指分子鏈中含有7 〇 〜1 0 0重量％較佳係8 5〜1 0 0重量％己二醯己二胺 之重覆單位的聚合物或該聚合物與其他聚醢胺聚合物之慘 混物而言者。己二醯己二胺重覆單位爲7 0重量％以下的 聚合物會失去聚己二醯己二胺織維之特徴的高度染色堅牢 性 '髙度尺寸安定性等。上述摻混物中若其他聚醯胺爲 3 0重量％以上時亦同樣會失去聚己二醯己二胺纖維之上 述特徵優點。本發明中所用聚合物或摻混物之例，除爲 本紙張尺度適用中國國家標準（CNS > A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁} 4° Γ -13 - 經濟部中央標準局員工消费合作社印製 A7 B7 五、發明説明（11 ) 1 0 0重量％聚己二醯己二胺繊維所成者以外，可爲與例 如尼龍6、尼龍12、尼龍610，尼龍612，尼龍 46，尼龍6 T等之共聚物或摻墀物。 本發明之第二形態有關之聚己二醯己二胺織維中，胺 基末端基濃度（〔―NH2〕）與羧基末端基濃度（ 〔一COOH〕之和必須在70〜200meq/kg，較 佳係7 5〜1 7 5m e q/kg之範圍。以此二個末端基濃 度之和即可被特定聚合物之數平均分子量，進而可特定聚 合物之粘度，惟末端基濃度之和爲7 0m e q/kg以下時 聚合物粘度會過髙，很難紡絲。相反若爲2 0 Om e d/ kg以上時，聚合物粘度過低，破壞其牽絲性或降低纖維之 機械性強度等，無法得到具有實用性之纖維。實用上最佳 之範圍係7 5〜1 7 5me q/kg。 如本發明第二形態之藉由控制末端基濃度顯著提髙抗 熱變黃性之聚己二醯己二胺纖維必須爲可滿足： (a) 〔― C〇OH〕S60(meq/kg) 之條件。無法滿足此等條件時除非含有2，4 -雙（烷硫 基）—6 — (3 ’ 5 —二烷基—4 —羥苯胺基）一 1，3 ’ 5 —三氮阱，否則無法達成本發明之目的，羧基末端基 濃度之最佳範圍係〔一 COOH〕$5 5 (me q/kg) ο 本發明中組合含有特定化合物之方法與控制末端基濃 度之方法二者’以相乘地更提髙聚己二醯己二胺纖維之抗 熱變黃性’並且使其具有濃染性時，必須使羧基末端基濃 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝. 訂 經濟部中央標準局貝工消费合作社印製 A7 ____B7___ 五、發明説明（12 ) 度與胺基末端基濃度同時滿足以下（a )與（c )不可。 (a) C-COOH] ^60 (meq/kg) (c) [― NH2) ^5 5 (meq/kg) 無法滿足上述（a )條件時，聚合物本身之抗熱熱變 黃性低，所以即使配合本發明化合物亦無法得到超過聚一 ε —己醯胺纖維，可媲美聚酯纖維之極顯著性之耐變黃性 質。羧基末端基濃度之最佳範圍係〔_COOH〕$5 5 (m e q / kg )。另一方面無法滿足上述（c)條件時酸 性染料之染色性不佳，無法得到本發明目標之具高染料吸 附率（依本發明之測定方法爲5 〇以上）的濃染性纖維。 並且還無法顯現可在1 0 〇°c以上高溫加壓熱水處理很意 外地抑制強度降低之本發明特徵效果。胺基末端基濃度之 最佳範圍係〔一NH2〕26 0 (meq/kg)。 本發明中所用式〔I〕所示2，4 一雙（烷硫基）一 6 — (3，5 —二烷基—4 —羥苯胺基）—1 ，3，5 — 三氮阱可爲2，4-雙（正辛硫基）—6— (4 —羥基一 3，5-二第三丁苯胺基）—1 ，3，5 —三氮阱。此例 示之化合物可以自汽巴凱其公司製造之商品Iluganoxe 5 6 5取得。 式〔I〕所示三氮阱化合物係不但與聚己二醯己二胺 有極佳之互溶性，其本身之耐熱性亦極佳。因此與具有 2 6 0 °C以上高熔點之聚己二醯己二胺與熔融混練時亦不 會降低抗氧化性。又，除酚系抗氧化劑之構造以外，還具 有硫醚構造或芳香族胺構造等，所以可以發揮抑制構成聚 本紙張尺度逋用中國國家標準（CNS ) A4規格（210X297公釐> ' -15 - (請先閲讀背面之注意事項再填寫本頁) 裝·(In the formula, Ri represents a third butyl group or a hydrocarbon group with a carbon number of 1 to 4, R2, R3 represents a hydrocarbon group with a carbon number of 5 to 10), and contains (B) 0. 005 ~ 1. Grouped from phosphorous acid, phosphorous acid derivatives, hypophosphorous acid, hypophosphorous acid derivatives, and containing (C) 0.005 ~ 0.5% by weight of emeraldium compound, which is characterized by yellowing resistance and concentrated dye The manufacturer of the hexamethylene diamine fiber "The polyhexamethylene diamine diamine referred to in the present invention means that the molecular chain contains 70 to 100% by weight, preferably 8 5 to 100% by weight of hexamethylene diamide. For repeating units of hexamethylene diamine or a miscible blend of this polymer with other polyamine polymers. Polymers with a repeating unit of hexamethylenediamine and hexamethylenediamine of 70% by weight or less will lose the high dyeing fastness of polyhexamethylenediamine diamine and its high-quality dyeing stability and stability. In the above blend, if the other polyamide is more than 30% by weight, the above-mentioned characteristic advantages of the polyhexamethylene diamide fiber will also be lost. The examples of polymers or blends used in the present invention, except for the paper size, are applicable to the Chinese National Standard (CNS > A4 specification (210X297mm) (please read the precautions on the back before filling this page) 4 ° Γ- 13-A7 B7 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (11) 100% by weight of polyhexamethylene diamide, diamine and diamine, other than nylon 6, nylon 12, nylon 610, Nylon 612, Nylon 46, Nylon 6 T, etc. copolymers or admixtures. In the polyhexamethylene diamine diamine texture of the second form of the present invention, the concentration of the terminal amino groups (〔―NH2〕) The sum of the concentration of carboxyl end groups ([one COOH] must be in the range of 70 ~ 200meq / kg, preferably in the range of 7 5 ~ 1 7 5m eq / kg. The sum of the concentration of the two end groups can be used for specific polymers The average molecular weight can be used to determine the viscosity of the polymer, but when the sum of the terminal group concentrations is below 70 m eq / kg, the polymer viscosity will be too high and it is difficult to spin. On the contrary, if it is above 20 Om ed / kg , The viscosity of the polymer is too low, destroying its stringiness or reducing the mechanical strength of the fiber, etc. It is impossible to obtain a fiber with practicality. The practically optimal range is 7 5 ~ 1 7 5me q / kg. As in the second form of the present invention, by controlling the concentration of terminal groups, the polyhexamethylene compound that significantly improves the resistance to thermal yellowing can be obtained The hexamethylenediamine fiber must meet the following conditions: (a) 〔― 〇OH〕 S60 (meq / kg). If these conditions cannot be met, unless it contains 2,4-bis (alkylthio) -6 — (3 '5 —dialkyl-4-hydroxyanilino) -1,3' 5 —trinitrogen trap, otherwise it cannot achieve the purpose of the invention, the optimal range of carboxyl terminal group concentration is [one COOH] $ 5 5 (me q / kg) ο The method of combining specific compounds and the method of controlling the concentration of terminal groups in the present invention 'in order to multiply improve the heat yellowing resistance of polyhexamethylene dihexamethylene diamine fiber' and make it concentrated When dyeing, the carboxyl end-group concentrated paper size must be in accordance with Chinese National Standard (CNS) Α4 specification (210Χ297mm) (please read the precautions on the back before filling this page). Printed by consumer cooperatives A7 ____B7___ V. Description of invention (12) Degree and amine terminal When the concentration satisfies the following (a) and (c) at the same time: (a) C-COOH] ^ 60 (meq / kg) (c) [― NH2) ^ 5 5 (meq / kg) When the condition (a) above cannot be met The polymer itself has low resistance to thermal yellowing, so even with the compound of the present invention, it is not possible to obtain poly-ε-hexamide fibers, which are comparable to the extremely significant yellowing resistance of polyester fibers. Carboxyl end groups The optimal range of concentration is [_COOH] $ 5 5 (meq / kg). On the other hand, when the above condition (c) cannot be satisfied, the dyeability of the acid dye is not good, and the highly dyeable fiber having a high dye absorption rate (50 or more according to the measuring method of the present invention) targeted by the present invention cannot be obtained. Moreover, the characteristic effect of the present invention that can unexpectedly suppress the strength reduction at a high-temperature pressurized hot water treatment at 100 ° C or higher cannot be exhibited. The optimal range of amine terminal group concentration is [one NH2] 26 0 (meq / kg). The 2,4-bis (alkylthio) -6- (3,5-dialkyl-4-hydroxyanilinyl) -1,3,5-triazine trap used in the present invention represented by formula [I] may be 2,4-Bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilinyl) -1,3,5-trinitrogen trap. The compound exemplified in this example can be obtained from the product Iluganoxe 5 6 5 manufactured by Ciba Keqi. The trinitrogen trap compound represented by formula [I] not only has excellent miscibility with polyhexamethylene diamine hexamethylene diamine, but also has excellent heat resistance. Therefore, when mixed with polyhexamethylene diamine having a high melting point of more than 260 ° C and melted, it will not reduce the oxidation resistance. In addition to the structure of phenolic antioxidants, it also has a thioether structure or aromatic amine structure, etc., so it can be used to inhibit the formation of poly-papers. It uses the Chinese National Standard (CNS) A4 standard (210X297mm> '- 15-(Please read the precautions on the back before filling out this page)

、1T at B7 五、發明説明（13 ) 己二醯己二胺熱變黃反應之各種反應的效果。式〔I〕所 示三氮阱衍生物對聚己二醯己二胺而言之含量必須爲 0 · 01〜1 . 0重量％。0 · 01重量％以下時除非可 滿足本發明之末端基濃度的條，否則無法得到本發明目的 之優異抗變黃性》另一方面1.0重量％以上時，則會破 壞聚己二醯己二胺纖維之紡絲安定性。最佳之含量範圍係 0 · 01〜0 , 2重量％。 經濟部中央標準局員工消费合作社印製 (請先閲讀背面之注意事項再填寫本頁} 本發明之第一、三、四之發明形態中係除式〔I〕所 示三氮阱衍生物以外，還必須含有0.005〜1.0重 量％範圍一種或複數種選自亞磷酸、亞磷酸衍生物、次_ 酸、次磷酸衍生物之群者。0 . 005重量％以下時，除 非可以滿足本發明之末端基濃度的條件，否則無法得傻異 之抗熱變黃性。另一方面1.0重量％以上時，聚己二酶 己二胺會顯著地增加粘度，或發生紡絲濾網之堵塞等，破 壞紡絲安定性。最佳含量範圍係0 . 005〜0 . 2重量 %。上述群中亞磷酸衍生物係以例如以下式〔Π〕所示雙 (2，6—二第三丁基_甲苯基）亞磷酸酯，以下式〔m 〕所示亞磷酸三（2，4 —二第三丁苯基）酯等最爲適宜 本紙張尺度適用中國國家標準（CNS ) A4規格（210x297公釐） 16 A7 B7 五、發明説明（14 h3c lBu普。一 'Bu /〇H3C.< > \〇h2〆 ch2〇. ch2o、 1T at B7 V. Description of the invention (13) The effects of various reactions of hexamethylene diamine hexamethylene diamine thermal yellowing reaction. The content of the trinitrogen trap derivative represented by the formula [I] to the polyhexamethylene diamide hexamethylene diamine must be 0.01 ~ 1.0% by weight. 0. 01% by weight or less Unless the bar of the terminal group concentration of the present invention can be satisfied, the excellent yellowing resistance of the object of the present invention cannot be obtained. On the other hand, when the content is 1.0% by weight or more, polyhexamethylene diacetate will be destroyed Stability of amine fiber spinning. The optimum content range is 0.01 ~ 0, 2% by weight. Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page) The first, third, and fourth invention forms of the present invention are in addition to the trinitrogen derivative shown in formula [I] , Must also contain 0.005 ~ 1.0% by weight of one or more kinds selected from the group of phosphorous acid, phosphorous acid derivatives, hypo-acid, hypophosphorous acid derivatives. When 0.005% by weight or less, unless it can meet the present invention Under the condition of terminal group concentration, otherwise it is impossible to obtain stupid resistance to heat yellowing. On the other hand, when the content is more than 1.0% by weight, the hexamethylenediamine polyadipase will significantly increase the viscosity, or clogging of the spinning filter, etc. Damage to spinning stability. The optimal content range is 0.005 ~ 0.2% by weight. The phosphorous acid derivative in the above group is bis (2,6-di-tert-butyl_ as shown in the following formula [Π] Tolyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite as shown in the following formula [m] is most suitable for this paper size. It is applicable to the Chinese National Standard (CNS) A4 specification (210x297 mm ) 16 A7 B7 V. Description of the invention (14 h3c lBu. One 'Bu /〇H3C.< > \ 〇h2〆 ch2〇. Ch2o

*Bu P ~ 0 ~)—CH3 W 〔I〕* Bu P ~ 0 ~) —CH3 W 〔I〕

'Bu /S cm) 另一方面，次磷酸衍生物係例如以下式（IV)所示苯 基次磷酸鉀，以下式（V)所示二次磷酸四（2，4 一二 第三丁苯基）一4，4>一伸聯苯酯 (9)~'Bu / S cm) On the other hand, hypophosphorous acid derivatives are, for example, potassium phenyl hypophosphite represented by the following formula (IV), tetraphosphoric acid tetrakis (2,4 one-two third butylbenzene represented by the following formula (V) Group)-4,4> monobiphenyl (9) ~

I P-0K II 〔IV〕 (請先閲讀背面之注意事項再填寫本頁) -§ Γ lBu dU \I P-0K II 〔IV〕 (Please read the precautions on the back before filling this page) -§ Γ lBu dU \

〔V〕 經濟部中央標準局員工消費合作社印製 本發明之藉由末端基濃度控制聚己二醣己二胺繊維以 更提髙抗熱變黃性的步驟中必須含有鹼金屬化合物•若不 含該化合物時會使聚合物顯著地熱分解或發生支鏈生成反 應，常發生料滴或斷絲。鹸金靥化合物之含量必須爲 0 . 005〜0 . 5重量％。0 . 005重量％以下時， 無法充分抑制熱分解或生成支鏈。另一方面〇.5重量％ 以上時則會發生聚合阻礙或紡絲濾材驟然堵塞等問題。所 以最佳之範圍係0.01〜0.2重量％。 鹼金屬化合物係使用氫氧化鈉或氫氧化鉀等鹼金靥氫 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 17 經濟部中央標準局貝工消費合作社印製 A7 B7 五、發明説明（15 ) 氧化物、硫酸鈉或硝酸鉀等無機酸之鹸金靥鹽、己二酸鈉 或乙酸鉀等有機酸之鹼金屬鹽較爲有效。其中以己二酸鈉 及己二酸鉀爲最有效。 本發明之第三、四形態中使其含有（A)以式（I ) 所示2，4_雙（烷硫基）_6-（3，5 —二烷基—4 一羥苯胺基）_1 ，3，5_三氮阱及（B) —種或複數 種選自亞磷酸、亞磷酸衍生物、次磷酸、次磷酸衍生物群 之化合物的步驟並不特別限制，可以自配合上述（A )及 (B )添加劑予聚合物時常採用之一般手法中適當地選擇 。例如在該聚合物之聚合階段配合之方法，或使用雙軸擠 製機等熔融混練機予以配合之方法等。 使聚己二醯己二胺纖維之羧基末端基濃度與胺基末端 基濃度滿足（a )及（c )條件進行調製聚合物之方法並 不特別限定，惟例如可對於己二酸伸己基二銨（AH鹽） 之水溶液添加相對應於所欲末端基濃度之伸己基二胺後， 依常法予以聚合之方法較簡便。惟聚合時常會引起伸己基 二胺成份之逸散，所以抑制其量，並配合其量予以決定該 胺的添加量。又，含尼龍6 6之聚合物爲由複數之聚醯胺 所成摻混物時，調整末端基濃度係可以配合其摻混比率調 整複數之聚醯胺片的各末端基濃度。 本發明中藉由末端基濃度的控制以大幅度提高聚己二 醯己二胺纖維之抗熱變黃性的手法中，含有鹸金靥化合物 之方法並無特別限制，以對於原料單體之水溶液添加該化 合物’依常法聚合之方法爲宜。 本紙張尺度適用中國國家標牟（CNS ) A4規格（21〇Χ297公釐） (請先閱讀背面之注意事項再填寫本頁) 衮· 、1Τ _ 18 _ 經濟部中央標準局貝工消費合作社印製 A7 B7 五、發明説明（16 ) 本發明之纖維可以藉由公知之熔融紡絲裝置輕易地製 造。例如可採用將一種或複數之聚醯胺片與本發明化合物 之混合物直接供予一般用之熔融紡絲機予以紡絲之方法， 或將該混合物供給予二軸混練機，以製造摻混物，然後再 將其供給予一般用之熔融紡絲機予以紡絲之方法》紡絲之 速度係配合製品用途在1 0 0〜8 0 0 Om /分鐘之範圍 適當地選擇即可，精加工劑亦可適當地用配合其用途之組 成者》 本發明還可以應用於功能性製品。將使用於本發明纖 維的聚合物供予射出成形機或擠製成形機，即可以安定地 製造顯著提高抗熱變黃性之樹脂製品。 本發明之纖維還可以視其用途含有本發明必須要件之 化合物以外的添加劑，例如氧化鈦等消光劑、乳酸錳等耐 候劑、受阻胺系等光安定劑、苯並***系等紫外線吸收劑 以外，還可含有螢光增白劑。又，爲使其具有耐熱性、可 以使其含有一般所用之乙酸銅等銅鹽，碘化鉀或溴化鉀等 鹼金靥鹵化物。亦可視其需要配合硬脂酸鈣、伸乙基雙（ 硬脂醯胺）等公知之添加物。 以下藉由實施例詳述本發明。 又，以下各例中使用之化合物示於表1、表2。又， 以下各例中各種測定值係依以下方法實施者。 (1)羧基末端基濃度：將4 . Og試料於170°C 下溶於5 Omi苯甲醇中，以酚酞做爲指示藥，在 1/1 ON氫氧化鈉溶液（乙二醇溶液）予以中和滴定求 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） ：----.--.--f 装-- (請先閲讀背面之注意事項再填寫本頁) ,11 A 7 B7 五、發明説明（17 ) 得。 (2) 胺基末端基濃度：於50 °C溶解4 . 〇g試料 於50m$ 90%酚中，使用pH值測儀，以 1 / 2 0 N鹽酸予以中和滴定求得。 (3) 相對粘度：溶解5.試料於50m5 90%甲酸，於25 °C測定。 (4 )黃色度：用日本電色工業製Σ90 COLOR MESURING SYSTEM, SZ-OPTICAL SENSOR (光源 C / 2 )， 測定編織布之Yellow Index (YI)、及白色度（W) 〔Hunter 方式〕。 (5 )染料吸附率：用 Diacid Alizarine Light Blue 4GL (C. I.Acid Blue 23; Cl 61125) ( 3 % 〇 w f )，以浴比1 : 100，90 °C下染色45分鐘時之染料 吸附率，係由染液之吸光度算出。 (6 )高溫加壓熱水處理時之強度保持率：於1 3 0 °C加壓狀態下熱水處理3 0分鐘》測定處理前後之纖維強 度，算出對處理前強度的處理後強度保持率。 (請先閱讀背面之注意事項再填寫本頁) -6 Γ 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家橾準（CNS ) A4规格（210X 297公釐） -20 - A7 B7 五、發明説明（18) 表1 化合物群（A ) 化合物號碼 化 合 物 A - 1 ιΒυ Η0-^〇 'Βύ" ΝΗ-<^〇^〔V〕 The step of controlling the polyhexamethylene dihexamethylenediamine by controlling the concentration of terminal groups of the present invention by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs to improve the resistance to heat yellowing must contain an alkali metal compound. If not When the compound is contained, the polymer will be decomposed significantly thermally or branching reaction may occur, and droplets or broken filaments often occur. 5wt%。 The content of the emerald gold compound must be 0.005 ~ 0.5% by weight. When the content is 0.005% by weight or less, thermal decomposition or branching cannot be sufficiently suppressed. On the other hand, at 0.5% by weight or more, problems such as inhibition of polymerization and sudden clogging of the spinning filter material may occur. Therefore, the optimal range is 0.01 to 0.2% by weight. The alkali metal compound uses alkali gold or hydrogen hydroxide such as sodium hydroxide or potassium hydroxide. The paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm). Description of the invention (15) Alkali metal salts of organic acids such as oxides, sodium sulfate, potassium nitrate and other inorganic acids, and alkali metal salts of organic acids such as sodium adipate or potassium acetate are more effective. Among them, sodium adipate and potassium adipate are the most effective. In the third and fourth forms of the present invention, it contains (A) 2,4_bis (alkylthio) -6- (3,5-dialkyl-4 monohydroxyanilinyl) represented by formula (I) _1 , 3,5_ trinitrogen trap and (B)-one or more kinds of compounds selected from the group of phosphorous acid, phosphorous acid derivatives, hypophosphorous acid, hypophosphorous acid derivatives are not particularly limited, you can mix the above (A ) And (B) are appropriately selected from the general methods commonly used for additives to polymers. For example, a method of blending at the polymerization stage of the polymer, or a method of blending using a melt-kneading machine such as a twin-screw extruder. The method for preparing the polymer so that the concentration of the carboxyl terminal group and the concentration of the amine terminal group of the polyhexamethylene diamine fiber satisfy the conditions (a) and (c) is not particularly limited, but for example, hexyl diadipate After adding the hexyl diamine corresponding to the desired terminal group concentration in the aqueous solution of ammonium (AH salt), the method of polymerization according to the usual method is relatively simple. However, polymerization often causes the hexyl diamine component to escape, so the amount is suppressed and the amount of the amine added is determined in accordance with the amount. In addition, when the polymer containing nylon 66 is a blend of a plurality of polyamides, the terminal group concentration can be adjusted according to the blending ratio to adjust the terminal group concentration of the plurality of polyamide tablets. In the method of controlling the concentration of terminal groups in the present invention to greatly improve the heat yellowing resistance of the polyhexamethylenediamine diamine fiber, the method of containing the emeraldium compound is not particularly limited. The method of adding the compound in aqueous solution according to the usual method is suitable. This paper scale is applicable to China National Standards (CNS) A4 (21〇297mm) (Please read the precautions on the back before filling out this page) 衮 ·, 1Τ _ 18 _ Printed by Beigong Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Preparation A7 B7 5. Description of the invention (16) The fiber of the present invention can be easily manufactured by a well-known melt spinning device. For example, a method of directly supplying a mixture of one or more polyamide tablets and the compound of the present invention to a general-purpose melt spinning machine for spinning, or supplying the mixture to a two-axis kneading machine to produce a blend , And then supply it to a general-purpose melt spinning machine for spinning method. "The spinning speed is selected according to the use of the product in the range of 100 0 ~ 800 Om / min. The finishing agent The composition suitable for its use can also be appropriately used. The present invention can also be applied to functional products. By supplying the polymer used in the fiber of the present invention to an injection molding machine or an extrusion molding machine, it is possible to stably manufacture a resin product having significantly improved resistance to heat yellowing. The fiber of the present invention may also contain additives other than the compounds essential to the present invention, such as matting agents such as titanium oxide, weathering agents such as manganese lactate, light stabilizers such as hindered amines, and ultraviolet absorbers such as benzotriazole. In addition, it can also contain fluorescent brighteners. In addition, in order to make it heat resistant, it may contain copper salts such as generally used copper acetate and alkali halide such as potassium iodide or potassium bromide. It can also be blended with well-known additives such as calcium stearate and ethyl bis (stearate) depending on its needs. The present invention will be described in detail in the following examples. The compounds used in the following examples are shown in Table 1 and Table 2. In addition, the various measured values in the following examples are implemented by the following method. (1) Concentration of carboxyl end groups: 4.0 g of the sample is dissolved in 5 Omi benzyl alcohol at 170 ° C, and phenolphthalein is used as an indicator in 1/1 ON sodium hydroxide solution (ethylene glycol solution). For titration, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm): ----.--.-- f Pack-- (please read the precautions on the back before filling this page), 11 A 7 B7 V. Description of the invention (17). (2) Amino terminal concentration: Dissolve 4.0 g sample at 50 ° C in 50m $ 90% phenol, use pH meter to neutralize and titrate with 1/20 N hydrochloric acid. (3) Relative viscosity: Dissolve 5. Sample in 50m5 90% formic acid, measured at 25 ° C. (4) Yellowness: Use Σ90 COLOR MESURING SYSTEM, SZ-OPTICAL SENSOR (light source C / 2) manufactured by Nippon Denshoku Industries to measure the Yellow Index (YI) and whiteness (W) of the woven fabric [Hunter method]. (5) Dye adsorption rate: using Diacid Alizarine Light Blue 4GL (CIAcid Blue 23; Cl 61125) (3% 〇wf), with a bath ratio of 1: 100, the dye adsorption rate when dyeing at 90 ° C for 45 minutes, is Calculated from the absorbance of the dye liquor. (6) Strength retention rate during high-temperature pressurized hot water treatment: hot water treatment at 130 ° C under pressure for 30 minutes》 Measure the fiber strength before and after treatment and calculate the post-treatment strength retention rate for the pre-treatment strength . (Please read the precautions on the back before filling out this page) -6 Γ The paper standard printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is applicable to the Chinese National Standard (CNS) A4 (210X 297 mm) -20-A7 B7 V. Description of the invention (18) Table 1 Compound group (A) Compound number Compound A-1 ιΒυ Η0- ^ 〇'Βύ " ΝΗ- < ^ 〇 ^

SCsH SC8Hi 2，4 —雙（正辛硫基）_6— (4-羥基—3，5 —二第三丁苯胺基）_1 ，3，5 —三氮阱 -----.--.--(裝—— (請先閲讀背面之注意事項再填寫本頁)SCsH SC8Hi 2,4-—bis (n-octylthio) _6— (4-hydroxy-3,5-di-third butylanilinyl) _1, 3,5 —trinitrogen trap -----.--.- -(Install—— (please read the notes on the back before filling this page)

lBu lBu A - 2 — 1 ，6 —雙（3，5 —二第三丁基 _4 —羥苯氧基）_己烷 經濟部中央標準局員工消費合作社印製lBu lBu A-2 — 1, 6 — bis (3, 5 — di-third butyl _4 — hydroxyphenoxy) _ Hexane Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

3 I A3 I A

lBu H0-^〇>-CH2CH2CNHCH2CH2CH1厂 0 1^，1^/—伸己基雙（3，5—二第三 丁基）一4 一羥基—氫化肉桂醯胺lBu H0- ^ 〇 > -CH2CH2CNHCH2CH2CH1 plant 0 1 ^, 1 ^ /-hexanyl bis (3, 5-di-third butyl)-4 monohydroxy-cinnamyl hydride

本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -21 - A7 B7 五、發明説明（19 ) 表1 化合物群（A )(續） 經 部 中 央 標 準 局 員 工 消 費 合 作 杜 印 製 化合物號碼 化合物 A — 4 a \ ho-\〇^ch2ch2coch2—l·- c \ 'Bu^ 0 /4 季戊四醇基—四〔3— (3，5 —二第三丁 基一 4 _羥苯基）丙酸酯 A — 5 *Bu CHa /CHa \ H0-^〇^CHCH2Ch4-^〇^0H I 、CH3 \ lBu 12 三（2_甲基_4_羥基一 5 —第三丁苯基 )丁烷 A - 6 / *Bu \ (HO-^>-CH2CH2JjOCH2CH2—j— S \ lBii 0 /2 2，2_硫代—二伸乙基雙〔3 — (3，5 一二第三丁基—4 一羥苯基）丙酸酯〕 A - 7 4Bu H0^〇)-CH2P(0C2H5)2 lBu^ 0 3，5_二第三丁基一 4 —羥基一苯甲基磷 酸二乙酯 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 請 先 閱 面 意 事 項 再 填 寫 本 頁 裝 訂 -22 - 4- 6 σο P QV 9^This paper scale applies the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) -21-A7 B7 V. Description of the invention (19) Table 1 Compound group (A) (continued) Printed by the Ministry of Central Standards Bureau staff consumption cooperation Compound number Compound A — 4 a \ ho- \ 〇 ^ ch2ch2coch2-l · -c \ 'Bu ^ 0/4 pentaerythritol group — tetra [3— (3,5-didibutyl-4_hydroxyphenyl) Propionate A — 5 * Bu CHa / CHa \ H0- ^ 〇 ^ CHCH2Ch4- ^ 〇 ^ 0H I, CH3 \ lBu 12 tris (2_methyl_4_hydroxyl 5 —third butylphenyl) butane A-6 / * Bu \ (HO-^ > -CH2CH2JjOCH2CH2—j— S \ lBii 0/2 2,2_thio-diethylidenebis [3 — (3,5 one-two third butyl- 4 monohydroxyphenyl) propionate] A-7 4Bu H0 ^ 〇) -CH2P (0C2H5) 2 lBu ^ 0 3,5-di-tert-butyl-4-hydroxy-benzyl diethyl phosphate on this paper The standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm). Please read the notice before filling in this page. -22-4- 6 σο P QV 9 ^

7 B 五、發明説明（20 ) 經濟部中央標準局員工消費合作社印製 表2 化合物群（B ) 化合物號碼 化合物 Β - 1 'Bu 'Bu /-< /0H2Cx /CH20v 厂乂 H3 C—\〇/— 0 — P v . C v . P — 0—\〇/— CH3 ^ \〇H2C〆 \CH2〇〆 lBu 'Bu 亞磷酸雙（2，6_二第三丁基_4_甲苯 基）酯 Β - 2 i ^u.-^O^-O A-P V *Bu /3 亞磷酸三（2，4_二第三丁苯基）酯 Β - 3 Η (oV-p-ok w II 0 苯基次磷酸鉀 Β ~~ 4 / ；Βυ\ ^ _ /tBUv \ (t 0 少大1 Buj 二次磷酸四（2，4一二第三丁苯基）一 4，4 > —伸聯苯酯 Β — 5 N a Η 2 P 0 2 次磷酸鈉 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁) ,τ Γ -23 - A7 B7 五、發明説明（21 ) 實施例1〜6、比較例1〜8 將表3所示組成之各種化合物混合於相對粘度4 8， 胺基末端基濃度4 8m e q/kg，羧基末端基濃度爲7 8 m e q/kg之聚己二醯己二胺後使用一般之熔融紡絲機， 以2 9 0 °C紡絲溫度，4 5 0 Om/m i η紡絲速度紡絲 ’製造1 0 d/5 f之繊維。以所得纖維作成編織布，除 去精加工劑後，以上述測色機測定於1 9 0°C加熱5分鐘 時之黃色度（Y I )。結果示於表3。 實施例1〜6係含有式〔I〕所示三氮阱衍生物之化 合物A_ 1所成的聚己二醯己二胺繊維，顯著地被抑制其 熱變黃。 與之相比，完全不含任何化合物之織維〔比較例1〕 及含有以往之化合物的纖維（比較例2〜7)係顯然的熱 變黃。又不含化合物A- 1，僅含有亞磷酸衍生物時（比 較例8)亦極顯著地熱變黃。 m· ftm nn —^ϋ nn nn TJ . . 一浲 i (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS) M規格（210X297公釐） 一 24 -7 B V. Description of the invention (20) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 2 Compound Group (B) Compound Number Compound B-1 'Bu' Bu /-< / 0H2Cx / CH20v Factory H3 C— \ 〇 / — 0 — P v. C v. P — 0— \ 〇 / — CH3 ^ \ 〇H2C〆 \ CH2〇〆lBu 'Bu Phosphite bis (2,6_dithirdbutyl_4_tolyl ) Ester Β-2 i ^ u .- ^ O ^ -O AP V * Bu / 3 phosphite tris (2,4-di-third-butylphenyl) ester Β-3 Η (oV-p-ok w II 0 Potassium phenyl hypophosphite Β ~~ 4 /; Βυ \ ^ _ / tBUv \ (t 0 less than 1 Buj tetraphosphoric acid tetrakis (2,4—two tertiary butylphenyl) —4,4 >-extension Phenyl ester B — 5 N a Η 2 P 0 2 Sodium hypophosphite This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) (please read the precautions on the back before filling this page), τ Γ- 23-A7 B7 5. Description of the invention (21) Examples 1 to 6, Comparative Examples 1 to 8 Various compounds of the composition shown in Table 3 were mixed with a relative viscosity of 48, the concentration of terminal amino groups was 48 m eq / kg, carboxyl After the concentration of the end group is 7 8 meq / kg, the polyhexamethylene diamine hexamethylene diamine is used after the general melting Melt spinning machine, spinning at a spinning temperature of 2 9 0 ° C and a spinning speed of 4 5 0 Om / mi η to produce 10 d / 5 f dimensions. The resulting fiber is used as a woven cloth, after removing the finishing agent The yellowness (YI) when heated at 190 ° C for 5 minutes was measured by the above colorimeter. The results are shown in Table 3. Examples 1 to 6 are compounds containing a trinitrogen derivative represented by formula [I] The dimensions of the polyhexamethylene diamine diamine formed by A_1 are significantly inhibited from thermal yellowing. Compared to this, weaves that do not contain any compounds [Comparative Example 1] and fibers containing conventional compounds (comparison Example 2 ~ 7) is obviously heat yellowing. It does not contain compound A-1, and only contains a phosphorous acid derivative (Comparative Example 8) is also very significant heat yellowing. M · ftm nn — ^ ϋ nn nn TJ. . Yi Hani (please read the precautions on the back before filling in this page) This paper printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) M specifications (210X297 mm).

AA

7 B 五、發明説明（22 ) 表3 經濟部中央標準局員工消費合作社印製 化合物 群（Α) (重量％) 化合物 群(B) (重量％) 纖度 (但尼爾） 強度 (g/d) 伸度 (%) 沸水 收縮率 (%) 黃色度 (Y I ) (190。。 X 5min) 1 A— 1 (0.15) B — 1 (0.15) 10 4.36 67.1 3.1 3 實 2 A- 1 (0.10) B- 1 (0.05) 10 4. 25 68.1 2.9 5 施 3 A- 1 (0.10) B-2 (0. 05) 10 4.33 66.2 3.0 6 4 A— 1 (0.10) B-3 (0.10) 10 4.36 67.0 3.1 6 例 5 A- 1 (0.10) B — 4 (0. 05) 10 4.28 67.2 3.0 5 6 A- 1 (0.10) B- 5 (0.02) 10 4.37 67.5 3.0 6 1 — — 10 4.30 67.9 3.0 32 2 Α-2 (0.20) B-3 (0.10) 10 4.35 67.6 3.1 24 比 3 Α-3 (0.10) B-2 (0.05) 10 4. 28 67.8 3.0 22 較 4 A — 4 (0.10) B-2 (0.05) 10 4.26 67.5 2.9 20 5 A- 5 (0.10) B — 5 (0.02) 10 4.33 66.5 3.0 24 例 6 A-6 (0.10) B-4 (0.05) 10 4. 35 66.8 3.1 26 7 A-7 (0.10) B- 1 (0. 05) 10 4. 36 66.9 3.1 27 8 — B— 1 (0.05) 10 4. 33 66.4 3.0 24 本紙張尺度逋用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 、τ Γ -25 - 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（23 ) 實施例7及8、比較例9及10 將9 〇重量％己二酸伸己基二銨（AH鹽）與1 〇重 量％ ε —己內醯胺之混合物水溶液放入以氮取代之不銹鋼 製熱壓鍋中，使內壓爲1 7 . 6kg/cni ’同時餾去水， 繼續加熱。當內溫達到2 4 0°C時開始放壓’經9 0分鐘 使其慢慢恢復至常壓，然後維持常壓3 0分鐘進行常壓聚 合（內溫2 6 8 °C)。藉由氮壓將上述所得聚合物擠壓至 冷水中，藉由切割機使之成爲片狀。所得聚合物之相對粘 度係54，胺基末端基濃度係44meq/kg，羧基末端 基濃度係6 4m e q/kg » 在該片狀物中混合表4所示組成之各種化合物，使用 一般用之熔融紡絲裝置，在2 9 0 °C紡絲溫度，5 5 0 〇 m/mi η紡絲速度紡絲，製造爲50d/20 f纖維。 以所得纖維編織布料，除去精加工劑後，以上述測定方法 測定於19 0°C加熱5分鐘時之黃色度（YI)。結果示 於表4。實施例7及8之含有化合物A- 1之聚己二醯己 二胺纖維係與比較例9及1 0相比係具有極顯著抗熱變黃 性之纖維。 實施例9及1 0、比較例1 1及1 2 除使用8 0重量％己二酸伸己基二銨（ah鹽）與 2 0重量％ ε —己內醯胺之混合物水溶液以外，其他均與 實施例7 —樣之方法聚合得聚合物》所得聚合物之相對粘 度係5 2，胺基末端基濃度係4 3m e q/kg，羧基末端 (請先閱讀背面之注意事項再填寫本頁) 裝. 訂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -26 - 26 A 7 B7 五、發明説明（24 ) 基濃度係6 4meq/kg。 在該片狀物中混合表4所示組成之各種化合物，使用 —般用之熔融紡絲裝置’在2 7 0。(：紡絲溫度，5 5 0 0 m/m i η紡絲速度紡絲’製造爲5 〇 d/2 0 f纖維。 以所得纖維編織布料’除去精加工劑後，以上述測定方法 測定於1 9 0°C加熱5分鐘時之黃色度（γ I )。結果示 於表4。實施例9及1 0係含有式（I )所示三氮阱衍生 物之化合物A_ 1所成聚己二醯己二胺纖維，與添加化合 物A— 3 ’ A — 4，A— 5及A — 6之纖維相比更能抑制 熱變黃。 (請先閱讀背面之注意事項再填寫本頁) -07 B V. Description of Invention (22) Table 3 Compound Group (Α) (wt%) Compound Group (B) (wt%) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Compound (B) (wt%) Denier (Denier) Strength (g / d ) Elongation (%) Boiling water shrinkage (%) Yellowness (YI) (190 ... X 5min) 1 A— 1 (0.15) B — 1 (0.15) 10 4.36 67.1 3.1 3 Actual 2 A-1 (0.10) B- 1 (0.05) 10 4. 25 68.1 2.9 5 Shi 3 A- 1 (0.10) B-2 (0.05) 10 4.33 66.2 3.0 6 4 A— 1 (0.10) B-3 (0.10) 10 4.36 67.0 3.1 6 Example 5 A- 1 (0.10) B — 4 (0.05) 10 4.28 67.2 3.0 5 6 A- 1 (0.10) B- 5 (0.02) 10 4.37 67.5 3.0 6 1 — — 10 4.30 67.9 3.0 32 2 Α-2 (0.20) B-3 (0.10) 10 4.35 67.6 3.1 24 to 3 Α-3 (0.10) B-2 (0.05) 10 4. 28 67.8 3.0 22 vs 4 A — 4 (0.10) B-2 ( 0.05) 10 4.26 67.5 2.9 20 5 A- 5 (0.10) B — 5 (0.02) 10 4.33 66.5 3.0 24 Example 6 A-6 (0.10) B-4 (0.05) 10 4. 35 66.8 3.1 26 7 A-7 (0.10) B- 1 (0.05) 10 4. 36 66.9 3.1 27 8 — B— 1 (0.05) 10 4. 33 66.4 3.0 24 This paper scale uses the Chinese National Standard (CNS) A4 specification (210X 297 (Please read the precautions on the back before filling in this page), τ Γ -25-Printed by the Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperative A7 B7 5. Description of the invention (23) Examples 7 and 8, Examples 9 and 9 10 Put a mixture aqueous solution of 90% by weight adenyl diammonium adipate (AH salt) and 10% by weight ε-caprolactam into a stainless steel hot autoclave replaced with nitrogen to make the internal pressure 1 7 . 6kg / cni 'at the same time distill off the water, continue to heat. When the internal temperature reached 240 ° C, the pressure was released. After 90 minutes, the pressure was slowly returned to normal pressure, and then the normal pressure was maintained for 30 minutes to perform atmospheric pressure polymerization (internal temperature 2 6 8 ° C). The polymer obtained above was extruded into cold water by nitrogen pressure, and made into a sheet shape by a cutter. The relative viscosity of the obtained polymer is 54, the concentration of amine end groups is 44meq / kg, and the concentration of carboxyl end groups is 6 4m eq / kg »Various compounds of the composition shown in Table 4 are mixed in the sheet, and the general ones are used. The melt spinning device was spun at a spinning temperature of 290 ° C and a spinning speed of 5 500 m / mi η to produce 50d / 20 f fibers. After weaving the fabric with the obtained fiber and removing the finishing agent, the yellowness (YI) when heated at 190 ° C for 5 minutes was measured by the above-mentioned measurement method. The results are shown in Table 4. The polyhexamethylenediamine diamine fiber containing the compound A-1 in Examples 7 and 8 is a fiber having extremely significant heat yellowing resistance as compared with Comparative Examples 9 and 10. Examples 9 and 10, Comparative Examples 1 1 and 1 2 except for the use of a mixture aqueous solution of 80% by weight adenyl adipate (ah salt) and 20% by weight ε-caprolactam Example 7-Polymer obtained by the same method "The relative viscosity of the obtained polymer is 52, the concentration of the amine terminal group is 4 3m eq / kg, the carboxyl terminal (please read the precautions on the back before filling this page) . The size of the paper for the specification is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -26-26 A 7 B7 5. Description of invention (24) The base concentration is 6 4meq / kg. Various compounds of the composition shown in Table 4 were mixed with the sheet-like material, and the melt spinning apparatus used in the conventional method was used at 270. (: Spinning temperature, 5 5 0 0 m / mi η spinning speed spinning 'manufactured as 5 〇d / 2 0 f fiber. After the finishing agent is removed from the resulting fiber woven cloth', measured by the above measurement method at 1 9 Yellowness (γ I) when heated at 0 ° C. for 5 minutes. The results are shown in Table 4. Examples 9 and 10 are polyhexane composed of compound A_1 containing a trinitrogen trap derivative represented by formula (I) Acetylenediamine fiber, compared with the fiber with compound A-3'A-4, A-5 and A-6, can inhibit thermal yellowing more. (Please read the precautions on the back before filling this page) -0

T 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 一 27 -T Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. This paper scale applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 1 27-

A B 經濟部中央標準局員工消費合作社印装 五、發明説明（25 ) 表4 聚合物組成 化雜群 沸水 (A) (B) 嫌 度 強 度 伸度 輸率 黄触(丫 I ) ΑΗ鹽 e-己內麵 (ΜΑ%/ (mm%/ (但尼爾） (g/d) (96) (96) (190°CX5min) (SM%) (ΜΛ%) 聚合物） 聚合物） 7 90 10 A—1 B —1 50 5.74 39.2 11.5 6 實 (0.10) (0.05) 8 90 10 A-l B —2 50 5.72 39.4 11.3 7 施 (0.10) (0.05) 9 80 20 A-l B-l 50 5.59 34.9 21.4 6 例 (0.10) (0.05) 1 0 80 20 A-l B-4 50 5.57 35.1 20.8 6 (0.10) (0.05) 9 go 10 A-3 B-l 50 5.74 39.5 11.3 26 比 (0.10) (0.05) 1 0 90 10 A — 4 B-2 50 5.59 39.1 11.5 25 較 (0.10) (0.05) 1 1 80 20 A-5 B-l 50 5.60 34.8 21.2 25 例 (0.10) (0.05) 1 2 80 20 A-6 B — 4 50 5.74 34.6 21.4 27 (0.10) (0.05) (請先閱讀背面之注意事項再填寫本頁) 、τ 本紙張尺度適用中國國家標準（CNS〉A4規格（210X 297公釐） _ 28 - 經濟部中央標準局員工消費合作社印製 A 7 B7 五、發明説明（26 ) 由表可知配合式〔I〕所示三氮阱衍生物以外之化合 物的比較例9〜1 2聚己二醯己二胺纖維係抗熱變黃性極 差。 實施例1 1及1 2、比較例1 3及1 4 在9 0重量％之相對黏度爲4 5，胺基末端基濃度 4 8，羧基末端基濃度7 8之聚己二醯己二胺片狀物，與 1 0重量％相對黏度8 7，胺基末端基濃度4 3，羧基末 端基濃度3 9之聚一 e _己醯胺片狀物的混合物中，添加 〇 · 2重量％伸乙基雙硬脂醯胺，用以表5所示組成添加 各種化合物，使用一般用熔融紡絲機，以5 0 0 Om/ mi η紡絲速度紡絲，製造爲l〇d/2〇f纖維。以所 得纖維作成編織布，除去精加工劑後，以上述測定方法測 定於19 0°C加熱5分鐘時之黃色度（YI)。結果示於 表5。與比較例13及14相比，含有式〔I〕所示三氮 阱化合物之實施例11及12的熱變黃被顯著地抑制。 實施例1 3及1 4、比較例1 5及1 6 在8 0重量％之相對黏度爲4 5，胺基末端基濃度 4 8，羧基末端基濃度7 8之聚己二醯己二胺片狀物，與 2 0重量％相對黏度8 7，胺基末端基濃度4 3，羧基末 端基濃度3 9之聚己醯胺片狀物的混合物中，添加0 . 2 重量％伸乙基雙硬脂醯胺，用以表5所示組成添加各種化 合物，使用一般用熔融紡絲機，以5 0 0 Om/m i η紡 本紙張尺度適用中國國家標準（CNS ) Α4規格（2丨Ο X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 、-口 Τ -29 - A 7 B7 五、發明説明（27 ) 絲速度紡絲’製造爲1 〇 d/2 0 f纖維。以所得纖維編 織布料’除去精加工劑後，以上述測定方法測定於1 9 0 °C加熱5分鐘時之黃色度（Y I )。結果示於表5。 實施例1 3〜1 4係含有三氮阱衍生物（I )，所以 熱變黃性被顯著地抑制，含有其化合物之聚己二酿己二胺 纖維係抗熱變黃性差，可由比較例15〜16獲知。 (請先閱讀背面之注意事項再填寫本頁) 裝- 丁 經濟部中央標準局員工消費合作社印製 本紙張尺度通用中國國家標準（CNS ) A4規格（210X297公釐） 30AB Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (25) Table 4 Polymer-complexed boiling water (A) (B) Suspect strength elongation rate Yellow touch (amma I) ΑΗ 盐 e- Internal surface (ΜΑ% / (mm% / (denier) (g / d) (96) (96) (190 ° CX5min) (SM%) (ΜΛ%) polymer) polymer) 7 90 10 A —1 B —1 50 5.74 39.2 11.5 6 Actual (0.10) (0.05) 8 90 10 Al B —2 50 5.72 39.4 11.3 7 Application (0.10) (0.05) 9 80 20 Al Bl 50 5.59 34.9 21.4 6 cases (0.10) (0.05) 1 0 80 20 Al B-4 50 5.57 35.1 20.8 6 (0.10) (0.05) 9 go 10 A-3 Bl 50 5.74 39.5 11.3 26 ratio (0.10) (0.05) 1 0 90 10 A — 4 B- 2 50 5.59 39.1 11.5 25 vs. (0.10) (0.05) 1 1 80 20 A-5 Bl 50 5.60 34.8 21.2 25 cases (0.10) (0.05) 1 2 80 20 A-6 B — 4 50 5.74 34.6 21.4 27 (0.10 ) (0.05) (please read the precautions on the back before filling in this page), τ This paper size is applicable to China National Standard (CNS> A4 specification (210X 297 Mm) _ 28-A 7 B7 printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (26) From the table, it can be seen that the compound 9-9 is a compound other than the trinitrogen derivative represented by formula [I]. 2 Polyhexamethylene diamine hexamethylenediamine fiber system is extremely poor in resistance to heat yellowing. Examples 1 1 and 1 2. Comparative Examples 1 3 and 1 4 The relative viscosity at 90% by weight is 45, and the concentration of amine end groups 4 8, polyhexamethylene diamine diamine sheet with a carboxyl end group concentration of 7 8 and a relative viscosity of 10% by weight of 8 7, an amine end group concentration of 4 3, and a carboxyl end group concentration of 3 9 poly-e _ To the mixture of the hexamethylene amide sheet, 0.2% by weight of ethyl bis-stearyl amide is added, and various compounds are added with the composition shown in Table 5, using a general-purpose melt spinning machine at 50,000 Om / It is spun at a mi η spinning speed and produced as a lod / 2of fiber. The resulting fiber was used as a woven cloth, and after removing the finishing agent, the yellowness (YI) when heated at 190 ° C for 5 minutes was measured by the above measurement method. The results are shown in Table 5. Compared with Comparative Examples 13 and 14, Examples 11 and 12 containing the trinitrogen trap compound represented by formula [I] were significantly inhibited from thermal yellowing. Examples 1 3 and 1 4 and Comparative Examples 1 5 and 1 6 Polyhexamethylene diamine diamine tablets with a relative viscosity of 4 5 at 80% by weight, an amine terminal group concentration of 4 8 and a carboxyl terminal group concentration of 7 8 2% by weight of ethyl bis-bearing compound, with a relative viscosity of 8% by weight of 20% by weight, 7, an amine terminal group concentration of 4 3, and a carboxyl terminal group concentration of 3 to a mixture of polyhexamide tablets. Aliphatic amine, add various compounds with the composition shown in Table 5, use a general-purpose melt spinning machine, and spin the paper at 500 Om / mi η. The paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (2 丨 Ο X 297 Mm) (please read the precautions on the back before filling in this page),-口 Τ-29-A 7 B7 Fifth, the invention description (27) Silk speed spinning 'is made of 1 〇d / 2 0 f fiber. After removing the finishing agent from the obtained fiber knitted fabric ', the yellowness (Y I) when heated at 190 ° C for 5 minutes was measured by the above-mentioned measurement method. The results are shown in Table 5. Example 1 The 3 ~ 14 series contains the trinitrogen derivative (I), so the thermal yellowing is significantly suppressed, and the polyhexamethylene dihexamethylene diamine fiber system containing the compound has poor thermal yellowing resistance, which can be compared with the comparative example 15 ~ 16 learned. (Please read the precautions on the back before filling this page) Outfit-D Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. This paper is based on the Chinese National Standard (CNS) A4 (210X297mm) 30

A B 經濟部中央標準局員工消費合作社印製 五、發明説明（28 ) 表5 聚合物組成 化飾群 化雜群 沸水 (A) (B) 嫌 度 強 度 伸度 輸率 黄色度(Y I ) 尼龍6 6 尼龍6 (.ΜΛ%/ cmm%/ 麵爾） (g/d) (%) (96) (190°CX5rain) (重ft%) (重：&%) 聚合物） 聚合物） 11 90 10 A-1 B-1 10 5.62 33.5 9.2 5 實 (0.10) (0.05) 12 90 10 A-1 B —2 10 5.60 33.4 9.1 6 施 (0.10) (0.05) 13 80 20 A-1 B-1 10 5.56 33.0 10.8 5 例 (0.10) (0.05) 14 80 20 A-1 B — 4 10 5.53 33.2 10.5 5 (0.10) (0.05) 13 90 10 A-3 B-1 10 5.61 33.2 9.2 24 比 (0.10) (0.05) 14 90 10 A-4 B-2 10 5.58 33.5 9.0 23 較 (0.10) (0.05) 15 80 20 A-5 B—1 10 5.52 33.5 10.7 25 例 (0.10) (0.05) 16 80 20 A-6 B — 4 10 5.55 33.4 10.5 26 (0.10) (0.05) (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X2.97公釐） 31 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（29 ) 實施例1 5 依以下比率將原料投入容量4 0 0公升之熱壓器中進 行分批式聚合。 使用2 8 0公升AH鹽之5 0重量％水溶液 4 · 4公升伸己基二胺之1 4重量％水溶液 0 . 4公升氧化鈦之8重量％水溶液 0 · 104kg己二酸二鈉 首先使原料水溶液在濃縮槽中，於1 5 0°C，加熱4 小時濃縮至8 0重量％。其次送至聚合槽，繼續加熱一邊 控制內壓爲1 7 . 5kg/crrf，一邊除去縮合水，昇溫至 250 °C，進行1 · 5小時聚合。其次將內溫昇至280 °C，以1小時之時間慢慢恢復至常壓，再保持3 0分鐘， 其後以氮氣加壓聚合物以排出，經水冷，得1 3 0kg片狀 物。 將此聚合物片狀物之甲酸相對黏度示於表6。使用該 片狀物，以300 °C紡絲溫度，5000m/mi η紡絲 速度製造7 0 d/2 4 f之纖維時的紡絲噴嘴清除周期， 對所得纖維之胺基及羧基末端基濃度，編織布之加熱處理 (1 9 0°C 5分鐘之變黃性質。結果示於表6。實施例 1 5係羧基末端基濃度可滿足6 0m e q/kg以下之條件 ，所以得到顯著抑制熱變黃之纖維。而且聚合物中係含有 本發明之鹼金屬化合物，所以很少因聚合物之熱分解引起 生成劣化物，清掃紡絲噴嘴之時間可以隔較長期間、可長 期間穩定地生產。 本紙張尺度適用中國國家標準（CNS )八4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝· 、?τ -32 - 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（30 ) 實施例1 6 如下設定所放入原料之比率，與實施例1 5 —樣之聚 合方法作成聚合物片狀物。 使用2 8 0公升AH鹽之5 0重量％水溶液 2 · 4公升伸己基二胺之1 4重量％水溶液 〇 . 4公升氧化鈦之8重量％水溶液 0 . 065kg己二酸二鈉 將此聚合物片狀物之甲酸相對粘度，或用該片狀物，與實 施例1 5 —樣之方法紡絲時之紡絲噴嘴的清除周期，更對 所得絲評估胺基及羧基末端基濃度，編織布之加熱處理（ 1 9 0°C 5分鐘之變黃性質。結果示於表6。實施例1 6 係羧基末端基濃度可滿足6 Om e q/kg以下之條件，所 以得到顯著抑制熱變黃之纖維》而且該實施例係含有本發 明之鹼金屬化合物，所以很少因聚合物之熱分解引起生成 劣化物，清掃紡絲噴嘴之時間可以隔較長期間、可長期間 穩定地生產。 比較例1 7 如下設定所放入原料之比率，與實施例1 5 —樣之聚 合方法作成聚合物片狀物。 使用2 8 0公升AH鹽之5 0重量％水溶液 4 · 5公升伸己基二胺之1 4重量％水溶液 0 . 4公升氧化鈦之8重量％水溶液 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝· 訂 -33 - 經濟部中央標準局貝工消費合作社印製 A7 B7 五、發明説明（31 ) 將此聚合物片狀物之甲酸相對粘度，或用該片狀物，與實 施例1 5 —樣之方法紡絲時之紡絲噴嘴的清除周期，更對 所得絲評估胺基及羧基末端基濃度，編織布之加熱處理（ 1 9 0°C 5分鐘之變黃性質。結果示於表6。 比較例1 7中胺基末端基濃度雖較高，但不含鹼金屬 化合物所以常會因聚合物之熱分解而生成劣化物，必須常 常清除紡絲噴嘴，相隔時間較短，亦極顯著地熱變黃。 比較例1 8 如下設定所放入原料之比率，與實施例1 5 —樣之聚 合方法作成聚合物片狀物》 使用2 8 0公升AH鹽之5 0重量％水溶液 2 . 5公升伸己基二胺之14重量％水溶液 0 . 4公升氧化鈦之8重量％水溶液 將此聚合物片狀物之甲酸相對粘度，或用該片狀物，與實 施例1 5 —樣之方法紡絲時之紡絲噴嘴的清除周期，更對 所得絲評估胺基及羧基末端基濃度，編織布之加熱處理（ 1 9 0°C 5分鐘之變黃性質》結果示於表6。 比較例1 8中胺基末端基濃度雖較高，但不含鹼金屬 化合物所以常會因聚合物之熱分解而生成劣化物，必須常 常清除紡絲噴嘴，相隔時間較短，亦極顯著地熱變黃。 比較例1 9 如下設定所放入原料之比率，與實施例1 5 —樣之聚 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝· 訂 -34 - 經濟部中央標準局貝工消费合作社印製 ^g^S64 at B7 五、發明説明（32 ) 合方法作成聚合物片狀物。 使用2 8 0公升AH鹽之5 0重量％水溶液 0 . 4公升氧化鈦之8重量％水溶液 將此聚合物片狀物之甲酸相對粘度，或用該片狀物，與實 施例1 5 —樣之方法紡絲時之紡絲噴嘴的清除周期，更對 所得絲評估胺基及羧基末端基濃度，編織布之加熱處理（ 1 9 0°C 5分鐘之變黃性質。結果示於表6。比較例1 9 係未滿足羧基末端基濃度爲6 Om e q/kg以下之條件， 所以遇熱顯著地變黃。 比較例2 0 如下設定所放入原料之比率，與實施例1 5 —樣之聚 合方法作成聚合物片狀物。 使用2 8 0公升AH盥之5 0重量％水溶液 1 1 . 7公升伸己基二胺之1 4重量％水溶液 0.4公升氧化鈦之8重量％水溶液 將此聚合物片狀物之甲酸相對粘度，或用該片狀物，與實 施例1 5 —樣之方法紡絲時之紡絲噴嘴的清除周期，更對 所得絲評估胺基及羧基末端基濃度，編織布之加熱處理（ 1 90 °C 5分鐘之變黃性質。結果示於表6。比較例20 係羧基末端基濃度未能滿足6 Ome q/kg條件，所以熱 變黃極爲顯著。 實施例1 7 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閱讀背面之注意事項再填寫本頁) -βAB Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (28) Table 5 Polymer composition decoration clustered clustered boiling water (A) (B) Suspect strength elongation rate yellowness (YI) Nylon 6 6 Nylon 6 (.ΜΛ% / cmm% / surface) (g / d) (%) (96) (190 ° CX5rain) (weight ft%) (weight: &%) polymer) polymer) 11 90 10 A-1 B-1 10 5.62 33.5 9.2 5 Actual (0.10) (0.05) 12 90 10 A-1 B -2 10 5.60 33.4 9.1 6 Application (0.10) (0.05) 13 80 20 A-1 B-1 10 5.56 33.0 10.8 5 cases (0.10) (0.05) 14 80 20 A-1 B — 4 10 5.53 33.2 10.5 5 (0.10) (0.05) 13 90 10 A-3 B-1 10 5.61 33.2 9.2 24 ratio (0.10) ( 0.05) 14 90 10 A-4 B-2 10 5.58 33.5 9.0 23 Comparison (0.10) (0.05) 15 80 20 A-5 B—1 10 5.52 33.5 10.7 25 cases (0.10) (0.05) 16 80 20 A-6 B — 4 10 5.55 33.4 10.5 26 (0.10) (0.05) (Please read the precautions on the back before filling in this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X2.97mm) 31 Central Bureau of Standards Department of Economic Co-op employees five printed A7 B7, the raw material input capacity of 400-liter batch autoclave to carry out polymerization in Example 15 by the following described invention, a ratio of (29) embodiment. Use 2 80 liters of 50% by weight aqueous solution of AH salt 4.4 liters of 14% by weight aqueous solution of hexyl diamine 0.4 liters of 8% by weight aqueous solution of titanium oxide 0. 104kg disodium adipate first In a concentration tank, heat at 150 ° C for 4 hours and concentrate to 80% by weight. Next, it was sent to the polymerization tank, and heating was continued while the internal pressure was controlled to 17.5 kg / crrf, while the condensation water was removed, the temperature was raised to 250 ° C, and polymerization was carried out for 1.5 hours. Next, the internal temperature was raised to 280 ° C, and the pressure was slowly returned to normal pressure for 1 hour, and then maintained for 30 minutes. After that, the polymer was pressurized with nitrogen to discharge, and after water cooling, 130 kg of flakes were obtained. The relative viscosity of formic acid of this polymer sheet is shown in Table 6. Using this sheet-like material, the spinning nozzle cleaning cycle when producing a fiber with a spinning temperature of 300 ° C and a spinning speed of 5000 m / mi η at 70 d / 2 4 f, the concentration of amine groups and carboxyl end groups of the resulting fiber , Heat treatment of woven cloth (1 0 0 ° C 5 minutes yellowing properties. The results are shown in Table 6. Example 1 5 series carboxyl terminal group concentration can meet the conditions of 60 m eq / kg or less, so significantly inhibited heat The fiber turns yellow. And the polymer contains the alkali metal compound of the present invention, so the degradation of the polymer is rarely caused by the thermal decomposition of the polymer, and the time to clean the spinning nozzle can be stably produced over a long period of time This paper scale is applicable to the Chinese National Standard (CNS) 84 specifications (210X297mm) (please read the notes on the back before filling this page) Installed,? Τ -32-Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 5. Description of the invention (30) Example 1 6 The ratio of the raw materials put in is set as follows, and the same polymerization method as in Example 1 5 is used to make polymer flakes. The weight of 2 8 0 liters of AH salt is used. % Aqueous solution 2 · 4 liters 14 wt% aqueous solution of diamine based 0.4 liter of 8 wt% aqueous solution of titanium oxide 0.065 kg disodium adipic acid The relative viscosity of the formic acid of this polymer flake, or use the flake, and the examples 1 5 The same method as the removal period of the spinning nozzle during spinning, and the concentration of amine groups and carboxyl end groups was evaluated on the resulting silk, and the heat treatment of the woven cloth (190 ° C 5 minutes yellowing property. The results show In Table 6. Example 1 The concentration of the 6-carboxyl carboxyl terminal group can satisfy the condition of 6 Om eq / kg or less, so a fiber that significantly inhibits thermal yellowing is obtained. Moreover, this example contains the alkali metal compound of the present invention, so few Degradation is generated due to thermal decomposition of the polymer, and the time for cleaning the spinning nozzle can be stably produced over a long period of time. Comparative Example 1 7 Set the ratio of the raw materials charged as follows, as in Example 15 Polymerization method is used to make polymer flakes. 2 8 0 liters of 50% by weight aqueous solution of AH salt 4 5 liters of 14% by weight aqueous solution of hexyl diamine 0.4 4 liters of 8% by weight aqueous solution of titanium oxide The paper Scale applies to China Home Standard (CNS) A4 Specification (210X297mm) (Please read the precautions on the back before filling in this page) Binding · Order-33-A7 B7 printed by Beigong Consumer Cooperative of Central Bureau of Standards, Ministry of Economy V. Description of invention (31 ) The relative viscosity of the formic acid of this polymer sheet, or using this sheet, the spinning cycle of the spinning nozzle during spinning in the same manner as in Example 15 is evaluated for the amino groups and carboxyl end of the resulting silk Base concentration, heat treatment of woven cloth (190 ° C for 5 minutes yellowing property) The results are shown in Table 6. Although the concentration of amine end groups in Comparative Example 17 is high, it does not contain alkali metal compounds, so it often generates degradation products due to the thermal decomposition of the polymer. The spinning nozzle must be removed frequently, the interval between them is short, and the heat change is extremely significant yellow. Comparative Example 18 The ratio of the raw materials put in is set as follows, and the same polymerization method as in Example 1 5 is used to make a polymer flake. "2 8 0 liters of AH salt in 50% by weight aqueous solution 2.5 liters of hexyl two 14% by weight aqueous solution of amine 0.4 liters of 8% by weight aqueous solution of titanium oxide The relative viscosity of the formic acid of this polymer sheet, or using this sheet, spinning when spinning in the same manner as in Example 15 The cleaning cycle of the silk nozzle, the concentration of amine groups and carboxyl end groups of the obtained silk was further evaluated, and the heat treatment of the woven fabric (190 ° C 5 minutes yellowing property) results are shown in Table 6. Amino groups in Comparative Example 18 Although the end group concentration is high, it does not contain alkali metal compounds, so it often generates degradation products due to the thermal decomposition of the polymer. The spinning nozzle must be cleaned frequently, the interval between them is short, and the heat turns extremely yellow. Comparative Example 1 9 is as follows Set the ratio of the raw materials to be put in, and the size of the same paper as in Example 1 5 is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling in this page) -34-Central Standard of the Ministry of Economic Affairs Printed by Beigong Consumer Cooperative ^ g ^ S64 at B7 5. Description of the invention (32) Synthetic method to make polymer flakes. Use 2 8 0 liters of 50% by weight aqueous solution of AH salt 0. 4 liters of 8 weight of titanium oxide The relative viscosity of the formic acid of this polymer sheet in a% aqueous solution, or using the sheet, the spinning cycle of the spinning nozzle during spinning in the same way as in Example 15 is evaluated for amine groups and carboxyl groups on the resulting silk End group concentration, heat treatment of the woven cloth (190 ° C for 5 minutes yellowing property. The results are shown in Table 6. Comparative Example 1 9 does not satisfy the condition that the carboxyl end group concentration is 6 Om eq / kg or less, so It turns yellow significantly when it is heated. Comparative Example 2 0 The ratio of the raw materials put in is set as follows, and a polymer sheet is formed by the same polymerization method as in Example 15. The use of 2 8 0 liters of 50% by weight aqueous solution of AH toilet 1 1. 7 liters of 14% by weight aqueous solution of hexyl diamine 0.4 liters of 8% by weight aqueous solution of titanium oxide The relative viscosity of the formic acid of this polymer sheet, or use the sheet, as in Example 15 The method of removing the spinning nozzle during spinning is more important The concentration of amine groups and carboxyl end groups was evaluated by silk, and the heat treatment of the woven cloth (the yellowing property at 1 90 ° C for 5 minutes. The results are shown in Table 6. Comparative Example 20 The concentration of carboxyl end groups failed to meet the 6 Ome q / kg condition Therefore, heat yellowing is extremely significant. Example 1 7 This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) (please read the precautions on the back before filling this page) -β

X 35 經濟部中央標準局貝工消費合作社印製 A7 ___B7_ 五、發明説明（33 ) 如下設定所放入原料之比率，與實施例1 5 —樣之聚 合方法作成聚合物片狀物。 使用2 8 0公升AH鹽之5 0重量％水溶液 4 . 4公升伸己基二胺之1 4重量％水溶液 0 . 4公升氧化鈦之8重量％水溶液 0 . 6 5kg己二酸二鈉 所得聚合物片狀物放入4 0 0公升容量之轉鼓型固相 聚合器中，一邊通入氮氣一邊於1 8 0°C溫度加熱2 0小 時，進行固相聚合以提高其聚合度。 將此聚合物之甲酸相對粘度，或用該片狀物，與實施例 1 5 —樣之方法紡絲時之紡絲噴嘴的清除周期，更對所得 絲評估胺基及羧基末端基濃度，編織布之加熱處理（ 1 9 0°C 5分鐘之變黃性質。結果示於表6。實施例1 7 係羧基末端基濃度可滿足6 Om e q/kg以下之條件，所 以得到顯著抑制熱變黃之纖維。而且實施例係含有本發明 之鹼金屬化合物，所以很少因聚合物之熱分解引起生成劣 化物’清掃紡絲噴嘴之時間可以隔較長期間、可長期間穩 定地生產。 實施例1 8 如下設定所放入原料之比率，與實施例1 7 —樣之聚 合方法作成聚合物片狀物。 使用2 8 0公升AH鹽之5 0重量％水溶液 2 · 4公升伸己基二胺之1 4重量％水溶液 本上張尺度適用中國國家榡準（CNS ) A4規格（21〇Χ297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝- 訂 -36 - 經濟部中央標準局員工消费合作社印製 A7 B7 五、發明説明（34 ) 0 . 4公升氧化鈦之8重量％水溶液 0 . 039kg己二酸二鈉 將此聚合物之甲酸相對粘度，或用該片狀物，與實施例 1 5 —樣之方法紡絲時之紡絲噴嘴的清除周期’更對所得 絲評估胺基及羧基末端基濃度’編織布之加熱處理（ 1 9 0°C 5分鐘之變黃性質。結果示於表6。實施例1 8 係羧基末端基濃度可滿足6 〇m e q/kg以下之條件，所 以得到顯著抑制熱變黃之纖維。而且該實施例係含有本發 明之鹸金屬化合物，所以很少因聚合物之熱分解引起生成 劣化物，清掃紡絲噴嘴之時間可以隔較長期間、可長期間 穩定地生產。 比較例2 1 如下設定所放入原料之比率，與實施例1 7 —樣之聚 合方法作成聚合物片狀物。 使用2 8 0公升AH鹽之5 0重量％水溶液 1 1 · 7公升己二酸之4重量％水溶液 0 . 4公升氧化鈦之8重量％水溶液 將此聚合物之甲酸相對粘度，或用該片狀物，與實施例 1 5 —樣之方法紡絲時之紡絲噴嘴的清除周期，更對所得 絲評估胺基及羧基末端基濃度，編織布之加熱處理（ 1 9 0°C 5分鐘之變黃性質。結果示於表6。 比較例2 1係無法滿足羧基末端基濃度必須在6 0 m e q/kg以下條件者，所以熱時極顯著變黃。 本紙張尺度適用中國國家標隼（CNS > A4規格（210X297公釐) (請先閱讀背面之注意事項再填寫本頁) 裝· 訂 -37 - A7X 35 Printed by Beigong Consumer Cooperative of Central Bureau of Standards of the Ministry of Economic Affairs A7 ___B7_ V. Description of the invention (33) Set the ratio of the raw materials put in as follows, and make a polymer sheet by the same polymerization method as in Example 15. A polymer obtained by using 280 liters of a 50% by weight aqueous solution of AH salt 4.4 liters of a 14% by weight aqueous solution of hexyldiamine 0.4 liter of an 8% by weight aqueous solution of titanium oxide 0.65 kg of disodium adipic acid polymer The flakes were put in a drum-type solid-phase polymerizer with a capacity of 400 liters and heated at 180 ° C for 20 hours while passing nitrogen gas through to perform solid-phase polymerization to increase the degree of polymerization. The relative viscosity of the formic acid of this polymer, or using this sheet, the spinning cycle of the spinning nozzle during spinning in the same manner as in Example 15 and evaluating the concentration of amine groups and carboxyl end groups on the resulting silk, weaving The heat treatment of cloth (1 9 0 ° C 5 minutes yellowing property. The results are shown in Table 6. Example 1 7 The concentration of carboxyl terminal groups can meet the conditions of 6 Om eq / kg or less, so the heat yellowing is significantly suppressed And the examples contain the alkali metal compound of the present invention, so the degradation of the polymer is rarely caused by thermal decomposition of the polymer '. The time for cleaning the spinning nozzle can be stably produced over a long period of time and over a long period of time. 1 8 Set the ratio of the raw materials put in as follows, and make a polymer sheet by the same polymerization method as in Example 17. Use 2 8 0 liter of AH salt in 50% by weight aqueous solution 2.4 liter of hexyl diamine 1 The 4% by weight aqueous solution is based on the Chinese National Standard (CNS) A4 specification (21〇Χ297 mm) (please read the precautions on the back before filling out this page) Binding-Order-36-Central Bureau of Standards, Ministry of Economic Affairs Employee Consumer Cooperative Printed A7 B7 5. Description of the invention (34) 0.4 liter of 8% by weight aqueous solution of titanium oxide 0.039 kg disodium adipate relative viscosity of this polymer, or use the flake, and Example 1 5 The same method. The cleaning cycle of the spinning nozzle during spinning. The concentration of amine groups and carboxyl end groups of the resulting silk is evaluated. The heat treatment of the woven fabric (190 ° C for 5 minutes. Yellowing properties. The results are shown in Table 6. Example 18 The concentration of the carboxyl terminal group of the 8-series can satisfy the condition of 6 〇meq / kg or less, so the fiber that significantly inhibits thermal yellowing is obtained. Moreover, this example contains the emu metal compound of the present invention, so there are few The thermal decomposition of the polymer causes the formation of degraded products, and the time for cleaning the spinning nozzle can be stably produced over a longer period of time. Comparative Example 2 1 Set the ratio of the raw materials charged as follows, as in Example 17 Polymerization method is used to make polymer flakes. The polymer is prepared by using 280 liter of 50% by weight aqueous solution of AH salt 1 1.7 liter of 4% by weight aqueous solution of adipic acid 0.4 liter of 8% by weight aqueous solution of titanium oxide The relative viscosity of formic acid, Using this sheet, the cleaning cycle of the spinning nozzle during spinning in the same manner as in Example 15 was evaluated for the concentration of amine groups and carboxyl end groups on the resulting silk, and the heat treatment of the woven cloth (190 ° C The yellowing property after 5 minutes. The results are shown in Table 6. Comparative Example 2 The 1 series cannot meet the conditions of the carboxyl terminal group concentration must be below 60 meq / kg, so it turns extremely yellow when it is hot. This paper scale is applicable to the Chinese national standard Falcon (CNS > A4 size (210X297mm) (please read the precautions on the back before filling out this page) 装 · 定 -37-A7

7 B 經濟部中央標準局員工消費合作社印製 五、發明説明（35 ) 表6 聚合物片 [麗2] [COOH] [NH2] + [COOH] 鹸金靥鹽 紡絲噴嘴 之甲酸相 毫米當量/ 毫米當量/ 毫米當置/ -bH A*. nV 黃色度 一次清潔 對粘度 kg聚合物 kg聚合物 kg聚合物 添加量/聚雜 相隔時間 實施例 43.3 85 44 129 己二酸二納 10 24小時 15 0. 08重量％ 實施例 46.5 67 55 122 己二酸二鈉 13 24小時 16 0. 比較例 44.0 86 44 130 Ant. m 20 5小時 17 比較例 46.7 68 54 122 frrf m 23 7小時 18 比較例 41.4 52 82 134 <fnf- m 27 24小時 19 比較例 41.1 33 102 135 Jhrt m 37 24小時 20 實施例 80.7 69 29 98 己二酸二鈉 8 24小時 17 0. 實施例 82.4 51 41 92 己二酸二鈉 10 24小時 18 0.03¾¾¾ 比較例 78.3 18 87 105 Ant. m 30 24小時 21 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -38 - 經濟部中央標準局員工消費合作社印裂 A7 ^------ B7 五、發明説明（36 ) 實施例1 9〜2 3 在5 0重量％之己二酸伸己基二銨水溶液中添加 〇 . 40重量％ (對聚合物重量）己烯二胺，〇 . 〇5重 量％ (對聚合物重量）己二酸二鉀及5 2重量％p pm ( 對聚合物重量），得原料水溶液。 將該水溶液放入以氮取代之不銹鋼製熱壓鍋中，使內 壓爲1 7 . 6kg/cirf，同時餾去水，繼續加熱在內溫達 到220 °C時，以10。(：水溶液之狀態添加0 . 05重量 % T i 〇 2 ，再繼績加熱◊ 當內溫達到2 5 3 °C時開始放壓，經9 0分鐘使其慢 慢恢復至常壓，然後維持常壓3 0分鐘進行常壓聚合（內 溫2 7 3 °C)。藉由氮壓將上述所得聚合物擠壓至冷水中 ’藉由切割機使之成爲片狀。所得聚合物之相對粘度係 4 8，胺基末端基濃度係7 7m e q/kg，羧基末端基濃 度係 4 9meq/kg。 在該片狀物中混合表7所示組成之各種化合物，使用 —般用之熔融紡絲裝置，在290 °C紡絲溫度，5500 m/mi η紡絲速度紡絲，製造爲50d/20 f纖維。 將所得纖維之各種測定結果示於表8。 實施例1 9〜2 3係含有式〔I〕所示化合物之化合 物A — 1，並且羧基末端基濃度6 Ome q/kg以下，胺 基末端基濃度5 5m e q/kg以上之聚己二醯己二胺纖維 例。所得纖維係可提高抗熱變黃性達到極高水準之纖維。 抗熱變黃性可以更超出聚己醯胺繊維，而且還可以媲美聚 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝. 訂 -39 - A 7 B7 五、發明説明（37 ) 酯纖維之水準。另外，該實施例所得纖維係兼有染料吸附 率高（濃染性），髙溫加熱壓水處理時強度保持率高之實 用上極有用特徵者》 比較例2 2〜2 6 實施例1 9中代替己烯二胺添加0 . 3 0重量比（對 聚合物比）以外，其他均與其一樣之條件製造聚合物。 所得聚合物之相對粘度係4 5，胺基末端基濃度係2 4 me q/kg，羧基末端基濃度係9 9me q/kg。 在該片狀物中混合表7所示組成之各種化合物，以實 施例1 9 一樣之條件紡絲，製造5 0 d/1 7 f纖維。所 得纖維之各種測定結果示於表8。 比較例2 2〜2 6均爲無法滿足本發明要件，所以熱 變黃極爲顯著。又，染料吸附率與高溫加壓熱水處理時之 強度保持率均極低》 (請先閱讀背面之注意事項再填寫本頁) 裝. 訂 經濟部中央標準局貝工消費合作社印裝 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -40 -7 B Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (35) Table 6 Polymer sheet [丽 2] [COOH] [NH2] + [COOH] Millimeter equivalent of formic acid phase in the spinning nozzle of the ember gold salt / Mm equivalent / mm when placed / -bH A *. NV yellowness one-time cleaning on viscosity kg polymer kg polymer kg polymer addition amount / poly-interval time Example 43.3 85 44 129 dioxin adipic acid 10 24 hours 15 0.08% by weight Example 46.5 67 55 122 Disodium adipate 13 24 hours 16 0. Comparative example 44.0 86 44 130 Ant. M 20 5 hours 17 Comparative example 46.7 68 54 122 frrf m 23 7 hours 18 Comparative example 41.4 52 82 134 < fnf-m 27 24 hours 19 Comparative Example 41.1 33 102 135 Jhrt m 37 24 hours 20 Example 80.7 69 29 98 Disodium adipate 8 24 hours 17 0. Example 82.4 51 41 92 Hexane Disodium acid 10 24 hours 18 0.03¾¾¾ Comparative Example 78.3 18 87 105 Ant.m 30 24 hours 21 (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specifications (21 0X297mm) -38-A7 ^ ------ B7 printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (36) Example 1 9 ~ 2 3 at 50% by weight of adipic acid To an aqueous solution of hexyldiammonium was added 0.40% by weight (by weight of polymer) hexylenediamine, 0.05% by weight (by weight of polymer) dipotassium adipate and 52% by weight p pm (for polymer Weight), get raw material aqueous solution. The aqueous solution was placed in a stainless steel hot autoclave replaced with nitrogen so that the internal pressure was 17.6 kg / cirf. At the same time, water was distilled off, and heating was continued at an internal temperature of 220 ° C to 10. (: Add 0.05 wt% T i 〇2 in the state of the aqueous solution, and then continue heating ◊ When the internal temperature reaches 2 5 3 ° C, the pressure is released, and after 90 minutes, it is slowly returned to normal pressure, and then maintained Normal pressure polymerization was carried out at normal pressure for 30 minutes (internal temperature 2 7 3 ° C). The polymer obtained above was squeezed into cold water by nitrogen pressure and made into a sheet by a cutter. The relative viscosity of the obtained polymer It is 4-8, the concentration of amine end groups is 7 7 m eq / kg, and the concentration of carboxyl end groups is 4 9 meq / kg. Various compounds of the composition shown in Table 7 are mixed in this sheet, and the usual melt spinning is used The device was spun at a spinning temperature of 290 ° C and a spinning speed of 5500 m / mi η to produce 50d / 20 f fibers. Various measurement results of the obtained fibers are shown in Table 8. Example 1 9 ~ 2 3 series contains An example of the compound A-1 of the compound represented by the formula [I], and the carboxyl terminal group concentration of 6 Ome q / kg or less, and the amine terminal group concentration of 5 5 eq / kg or more of polyhexamethylene dihexamethylene diamine fiber. The resulting fiber system Fibers that can improve the heat yellowing resistance to a very high level. The heat yellowing resistance can exceed the dimension of polyhexanamide, and Comparable to the size of poly-paper. Applicable to China National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling out this page). Binding-39-A 7 B7 5. Description of the invention (37) Ester The level of the fiber. In addition, the fiber system obtained in this example has both a high dye adsorption rate (deep dyeing property) and a practically extremely useful feature that has a high strength retention rate during heating and pressurized water treatment. Comparative Example 2 2 ~ 2 6 In Example 19, the polymer was produced under the same conditions as in addition to 0.30 weight ratio (to polymer ratio) in place of hexenediamine. The relative viscosity of the obtained polymer was 45, and the concentration of amine terminal groups It is 2 4 me q / kg, and the carboxyl terminal group concentration is 9 9 me q / kg. Various compounds of the composition shown in Table 7 were mixed with this sheet, and spun under the same conditions as in Example 1 9 to produce 50 d / 1 7 f fiber. Various measurement results of the obtained fiber are shown in Table 8. Comparative Examples 2 2 to 2 6 are unable to meet the requirements of the present invention, so the heat yellowing is extremely significant. In addition, the dye adsorption rate and high temperature pressurized hot water The intensity retention rate during treatment is extremely low "(please read first Note the surface to fill out this page) stapling Ministry of Economic Affairs Bureau of Standards HIGHLAND consumer cooperatives India with this paper scale applicable Chinese National Standard (CNS) A4 size (210X297 mm) -40 -

A B 五、發明説明（38 ) 表 7 經濟部中央標準局員工消費合作社印製 相 對 粘 度 〔-NH2] (meq/kg) [-C00H] (meq/kg) 鹸金屬化合物 (重量％) 化合物 群 (A) (重量％) 化合物 群 (B ) (重量％) 實 19 48 77 49 己二酸二鉀 (0.05) A- 1 (0. 10) B - 1 (0. 05) 20 48 77 49 同 上 A- 1 (0. 15) B - 1 (0.15) 施 21 48 77 49 同 上 A- 1 (0. 10) B — 2 (0.05) 例 22 48 77 49 同 上 A- 1 (0. 10) B - 3 (0.10) 23 48 77 49 同 上 A- 1 (0. 10) B — 4 (0.05) 比 22 45 24 99 同 上 — — 23 45 24 99 同 上 — B — 1 (0. 10) 較 24 45 24 99 同 上 A- 3 (0.20) B - 1 (0. 10) 例 25 45 24 99 同 上 A - 4 (0. 10) B - 1 (0. 05) 26 45 24 99 同 上 A - 5 (0.10) B - 1 (0.05) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁) -41 - 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（39 ) 表8 纖度 (但尼爾） 強度 (g/d) 伸度 (%) 沸水 麵率 (%) 紡絲 絲切斷率 (次/噸） 染料 吸附率 (%) 高溫加壓 熱水處理時 強度赌率 (96) 黃色度 (Y I) (190。。 X5min) 白色度 (W) (190。。 X5min) 實 19 50 4.63 65.2 3.6 3 75 78 <1 95 20 50 4.61 65.4 3.6 4 74 82 <1 95 施 21 50 4. 60 65,2 3.6 5 75 80 <1 94 例 22 50 4.58 66.3 3.5 3 76 78 1 93 23 50 4.64 65.0 3.6 3 74 81 <1 95 比 22 50 4. 62 65.0 3.6 3 22 18 36 67 23 50 4. 66 65.2 3.6 5 23 17 27 71 較 24 50 4.63 65.4 3.5 3 22 19 26 71 25 50 4.62 65.3 3.6 3 22 18 25 72 T7U 26 50 4.62 65.4 3,5 4 21 18 27 70 I---Γ--:--{^-- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -42 - A7 B7 五、發明説明（40 ) 實施例24〜28、比較例27〜3 1 實施例1 9中改變己烯二胺之添加量爲如表9所示（ 或添加己二酸），將常壓聚合時間變更如表所示以外，以 同樣條件製造聚合物後，以同表所示條件固相聚合。 (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -43 -AB V. Description of Invention (38) Table 7 Relative Viscosity [-NH2] (meq / kg) [-C00H] (meq / kg) Printed by Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs [-C00H] (meq / kg) A) (wt%) Compound group (B) (wt%) Actual 19 48 77 49 Dipotassium adipate (0.05) A- 1 (0.10) B-1 (0.05) 20 48 77 49 Ibid. A -1 (0. 15) B-1 (0.15) Shi 21 48 77 49 Ibid. A- 1 (0. 10) B — 2 (0.05) Example 22 48 77 49 Ibid. A- 1 (0. 10) B-3 (0.10) 23 48 77 49 Ibid. A-1 (0. 10) B — 4 (0.05) than 22 45 24 99 Ibid. — 23 45 24 99 Ibid. — B — 1 (0. 10) Ibid. 24 45 24 99 Ibid. A- 3 (0.20) B-1 (0. 10) Example 25 45 24 99 Ibid. A-4 (0. 10) B-1 (0. 05) 26 45 24 99 Ibid. A-5 (0.10) B-1 (0.05) This paper scale is applicable to China National Standard (CNS) A4 (210X 297mm) (please read the precautions on the back before filling in this page) -41-A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 3. Description of the invention (39) Table 8 Fineness (denier) Strength (g / d) Elongation (%) Boiling water Area ratio (%) Spinning yarn cutting rate (times / ton) Dye adsorption rate (%) Strength bet rate during high-temperature pressurized hot water treatment (96) Yellowness (YI) (190 ... X5min) Whiteness (W ) (190. X5min) 19 50 4.63 65.2 3.6 3 75 78 < 1 95 20 50 4.61 65.4 3.6 4 74 82 < 1 95 Shi 21 50 4. 60 65, 2 3.6 5 75 80 < 1 94 cases 22 50 4.58 66.3 3.5 3 76 78 1 93 23 50 4.64 65.0 3.6 3 74 81 < 1 95 to 22 50 4. 62 65.0 3.6 3 22 18 36 67 23 50 4. 66 65.2 3.6 5 23 17 27 71 vs 24 50 4.63 65.4 3.5 3 22 19 26 71 25 50 4.62 65.3 3.6 3 22 18 25 72 T7U 26 50 4.62 65.4 3,5 4 21 18 27 70 I --- Γ-:-(^-(Please read the back first Please pay attention to this page and then fill out this page) This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm) -42-A7 B7 5. Description of the invention (40) Examples 24 ~ 28, Comparative Examples 27 ~ 3 1 In Example 19, the amount of added hexene diamine was changed as shown in Table 9 (or the addition of adipic acid), and the normal pressure polymerization time was changed as shown in the table. After producing the polymer under the same conditions, the same table was used. Solid-state polymerization under the conditions shown. (Please read the precautions on the back before filling out this page) Binding · Order Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) -43-

A7 7 B 經濟部中央標準局員工消費合作社印製 五、發明説明（41 ) 表 9 己嫌二胺 添加量 (對聚合物 重量％ ) 己二酸 添加量 (對聚合物 重量％ ) 常壓聚合 時間 (273〇C ' min) 固相聚合 時間 (180°C ' hr) 24 0. 62 0 30 23 實 25 0. 40 0 30 0 施 26 0. 55 0 15 0 例 27 0. 61 0 35 0 28 0. 97 0 20 0 27 0. 21 0 15 0 比 28 0. 10 0 10 0 較 29 0 0 30 0 例 30 0 0. 27 35 0 31 0 0. 15 30 22 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS〉A4規格（210X 297公釐） -44 — ^^9364 A7 _______B7 五、發明説明（42 ) 所得聚合物之特性示於表1 〇。對此聚合物混合該表 所示組成之化合物，以實施例1 9 一樣之條件紡絲，製造 5 0 d/1 7 f之纖維。所得繊維之各種測定結果示於表 1 1 〇 實施例2 4〜2 8係含有式〔I〕所示化合物之化合 物A—1 ’並且羧基末端基濃度6 0meq/kg以下，胺 基末端基濃度5 5m e q/kg以上之聚己二醯己二胺纖維 例。所得纖維係可提高抗熱變黃性達到極髙水準之纖維。 抗熱變黃性可以更超出聚己醯胺纖維，而且還可以媲美聚 酯纖維之水準。另外，該實施例所得纖維係兼有染料吸附 率高（濃染性），高溫加壓熱水處理時強度保持率高之實 用上極有用特徵者。比較例27〜31之纖維係含本發明 範圍外之熱安定劑，末端基濃度之聚己二醯己二胺纖維的 例，熱變黃極爲顯著。 (請先閱讀背面之注意事項再填寫本頁) 裝· 訂 經濟部中央標準局貝工消费合作社印製 本紙張尺度適用中國囷家標準（CNS ) A4規格（210X297公釐） -45 -A7 7 B Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (41) Table 9 Addition amount of hexamethylene diamine (% by weight to polymer) Addition amount of adipic acid (% by weight to polymer) Atmospheric pressure polymerization Time (273〇C'min) Solid phase polymerization time (180 ° C'hr) 24 0. 62 0 30 23 Actual 25 0. 40 0 30 0 Application 26 0. 55 0 15 0 Example 27 0. 61 0 35 0 28 0. 97 0 20 0 27 0. 21 0 15 0 than 28 0. 10 0 10 0 compared with 29 0 0 30 0 Example 30 0 0. 27 35 0 31 0 0. 15 30 22 (please read the notes on the back first Please fill in this page for details.) This paper scale is applicable to the Chinese National Standard (CNS> A4 specification (210X 297mm) -44 — ^^ 9364 A7 _______B7 V. Description of the invention (42) The characteristics of the resulting polymer are shown in Table 10. This polymer was mixed with a compound having the composition shown in the table, and spun under the same conditions as in Example 19 to produce a fiber of 50 d / 1 7 f. The various measurement results of the obtained dimensions are shown in Table 1 1 Example 2 4 ~ 28 is compound A-1 'containing the compound represented by formula [I], and the carboxyl terminal group concentration is 60 meq / kg or less, and the amine terminal group concentration is 5 5m eq Examples of polyhexamethylenediamine diamine fibers of more than / kg. The resulting fibers can improve the heat yellowing resistance to a very high level. The heat yellowing resistance can exceed the polyhexamethylene fiber and can be comparable to poly The level of ester fiber. In addition, the fiber obtained in this example also has a practically useful feature that has a high dye adsorption rate (dense dyeing property) and a high strength retention rate during high-temperature pressurized hot water treatment. Comparative Examples 27 to 31 The fiber contains a heat stabilizer outside the scope of the present invention, and the example of polyhexamethylene diamine fiber with a terminal group concentration, the heat yellowing is extremely significant. (Please read the precautions on the back before filling out this page) The size of the paper printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Standards is applicable to the Chinese standard (CNS) A4 specification (210X297 mm) -45-

A7 7 B 五、發明説明（43 ) 表 10 經濟部中央標準局員工消費合作社印製 相 對 粘 度 C-ΝΗ2] (meq/kg) [-C00H] (meq/kg) 鹸金屬化合物 (重量％) 化合物 群 (A ) (重量％) 化合物 群 (B ) (重量％) 實 24 81 76 16 己二酸二鉀 (0.05) A - 1 (0. 10) B - 1 (0.05) 施 25 48 77 49 同 上 同上 同上 26 34 102 51 同 上 同.上 同上 例 27 48 92 34 同 上 同上 同上 28 35 131 19 同 上 同上 同上 比 27 34 76 76 同 上 — — 28 29 77 88 同 上 — — 較 29 46 48 78 同 上 — — 例 30 46 24 99 同 上 — — 31 80 21 71 同 上 — — 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁)A7 7 B V. Description of Invention (43) Table 10 Relative Viscosity C-ΝΗ2] (meq / kg) [-C00H] (meq / kg) printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Group (A) (wt%) Compound group (B) (wt%) Actual 24 81 76 16 Dipotassium adipate (0.05) A-1 (0.10) B-1 (0.05) 25 25 77 77 Ibid Ibid. Ibid. 26 34 102 51 Ibid. Ibid. Ibid. Example 27 48 92 34 Ibid. Ibid. 28 35 131 19 Ibid. Ibid. Ibid. 27 34 76 76 Ibid. — 28 29 77 88 Ibid. — Compared to 29 46 48 78 Ibid. — Example 30 46 24 99 Ibid. — 31 80 21 71 Ibid. — This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) (please read the precautions on the back before filling this page)

bL 、τ Γ -46 -bL, τ Γ -46-

A B 經濟部中央標準局員工消費合作社印製 五、發明説明（44 ) 表11 纖度 (但尼爾） 強度 (g/d) 伸度 (%) 沸水 輸率 (%) 結絲 絲切斷率 (次/噸） 染料 吸附率 (%) 髙口壓 熱水處理時 強度勝率 (%) 黃色度 (Y I) (190。。 X5min) 白色度 (W) (190。。 X5min) 實 24 50 4.12 71.6 4.2 4 74 74 81 <1 25 50 4.63 65.2 3.6 3 76 76 78 <1 施 26 50 4.81 65.5 3.3 3 99 99 82 <1 例 27 50 4. 60 65.3 3.5 4 89 89 82 <1 28 50 4. 83 65· 2 3.3 3 100 100 84 <1 比 27 50 4. 79 65.4 3.3 3 74 74 65 30 28 50 4.88 65· 3 3.2 3 76 76 60 34 較 29 50 4,60 65.2 3.6 3 45 45 21 32 例 30 50 4. 59 66.0 3.5 4 21 21 18 36 31 50 4.11 71.5 4.2 3 18 18 20 30 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -47 - 經濟部中央標準局員工消費合作杜印製 A7 B7 五、發明説明（45 ) 實施例2 9 實施例2 5中’代替己二酸二鉀做爲鹼金靥化合物， 使用0 · 0 5重量％ (對聚合物比重量而言）己二酸二鈉 以外，其他均以同樣組成、條件製造聚合物，所得聚合物 物性示於表1 2。使用該聚合物，混合該表所示組成之化 合物，與實施例2 5 —樣之紡絲條件製造5 0 d/1 7 f 之纖維。所得纖維之各種測定結果示於表1 3。 實施例3 0 實施例2 7中，代替己二酸二鉀做爲鹼金靥化合物， 使用0.10重量％(對聚合物比重量而言）己二酸二鈉 以外’其他均以同樣組成、條件製造聚合物，所得聚合物 物性示於表1 2。使用該聚合物，混合該表所示組成之化 合物’與實施例2 7 —樣之紡絲條件製造5 0 d/1 7 f 之纖維。所得纖維之各種測定結果示於表1 3。 比較例3 2，3 3 實施例2 5及2 7中，除不添加鹼金靥化合物以外， 其他均以同樣組成、條件製造聚合物。將所得聚合物之物 性示於表1 2。使用該聚合物，混合該表所示組成之化合 物’與實施例2 5及2 7 —樣之紡絲條件製造5 0 d/ 1 7 f之纖維。所得纖維之各種測定結果示於表1 3。 實施例25，27，29，30係含有本發明之製造 方法中必須要件的鹸化合物，所以即使成爲胺基末端基濃 ------------------ 本紙强"从逋用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 -48 - A7 ^^9364 B7 五、發明説明（46 ) 度較高之聚合物，亦可得安定之紡絲水準。 另一方面，比較例3 2及3 3因不含任何鹼金屬化合 物，所以紡絲時常發生料滴、斷絲極多，很難安定生產爲 如本發明之纖維。 ^^^1' ^^^^1 ^^^^1 In i^i^i —B^^i ^ n^i Bm nn -i , ·--¾ i (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -49 -AB Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of Invention (44) Table 11 Fineness (Denier) Strength (g / d) Elongation (%) Boiling Water Transmission Rate (%) Knotted Wire Cut Rate ( Times / ton) Dye adsorption rate (%) High-pressure strength hot water treatment rate (%) Yellowness (YI) (190 ... X5min) Whiteness (W) (190 ... X5min) Actual 24 50 4.12 71.6 4.2 4 74 74 81 < 1 25 50 4.63 65.2 3.6 3 76 76 78 < 1 Shi 26 50 4.81 65.5 3.3 3 99 99 82 < 1 Example 27 50 4. 60 65.3 3.5 4 89 89 82 < 1 28 50 4 .83 65 · 2 3.3 3 100 100 84 < 1 to 27 50 4. 79 65.4 3.3 3 74 74 65 30 28 50 4.88 65 · 3 3.2 3 76 76 60 34 compared to 29 50 4,60 65.2 3.6 3 45 45 21 32 cases 30 50 4. 59 66.0 3.5 4 21 21 18 36 31 50 4.11 71.5 4.2 3 18 18 20 30 (please read the precautions on the back before filling in this page) This paper size is applicable to China National Standard (CNS) A4 specifications ( 210X297mm) -47-A7 B7 printed by the consumer cooperation of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (45) Example 2 9 Example 2 5 'In place of dipotassium adipate as alkali metal , By using 05 wt% 0.5 (ratio of the weight of polymer) other than disodium adipate, other compositions are the same, conditions of production of the polymer, the resulting polymer characteristics are shown in Table 12. Using this polymer, the compounds of the composition shown in the table were mixed, and the spinning conditions were the same as in Example 25 to produce fibers of 50 d / 1 7 f. Various measurement results of the obtained fibers are shown in Table 13. Example 3 0 In Example 2 7, instead of dipotassium adipate as an alkali gold compound, 0.10% by weight (in terms of specific polymer weight) other than disodium adipate are used, all of which have the same composition and conditions The polymer was produced, and the physical properties of the obtained polymer are shown in Table 12. Using this polymer, the compound of the composition shown in the table was mixed with the same spinning conditions as in Example 2 7 to produce a 50 d / 1 7 f fiber. Various measurement results of the obtained fibers are shown in Table 13. Comparative Example 3 2, 3 3 In Examples 25 and 27, a polymer was produced with the same composition and conditions except for the addition of an alkali gold compound. Table 12 shows the physical properties of the obtained polymer. Using this polymer, the compound of the composition shown in the table was mixed with the spinning conditions similar to those in Examples 25 and 27 to produce fibers of 50 d / 1 7 f. Various measurement results of the obtained fibers are shown in Table 13. Examples 25, 27, 29, and 30 are emulsified compounds containing essential elements in the production method of the present invention, so even if they become concentrated with amine end groups ------------------ this paper Strong " From the use of Chinese National Standard (CNS) A4 specifications (210X297mm) (please read the precautions on the back before filling in this page) 装 · 定 -48-A7 ^^ 9364 B7 V. Description of the invention (46) Higher degree of polymer can also get stable spinning level. On the other hand, Comparative Examples 3 2 and 3 3 do not contain any alkali metal compounds, and therefore, there are many droplets and broken filaments during spinning, which makes it difficult to produce the fibers of the present invention in a stable manner. ^^^ 1 '^^^^ 1 ^^^^ 1 In i ^ i ^ i —B ^^ i ^ n ^ i Bm nn -i, · --¾ i (Please read the notes on the back before filling in This page) The paper standard printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (210X297mm) -49-

A7 7 B 經濟部中央標準局員工消費合作社印製 五、發明説明（47 ) 表 12 相 化合物 化合物 對 〔-nh2] [-COOH] 鹼金屬化合物 群 群 粘 (A) (B ) 度 (meq/kg) (meq/kg) (重量％) (重量％) (重量％) 25 48 77 49 己二酸二鉀 A- 1 B - 1 實 (0.05) (0.10) (0.05) 29 48 77 49 己二酸二鈉 同上 同上 施 (0. 05) 27 48 92 34 己二酸二鉀 同上 同上 例 (0.05) 30 48 92 34 己二酸二鈉 同上 同上 (0.10) 比 較 32 48 77 49 — — — 例 33 48 92 34 — — — (請先閲讀背面之注意事項再填寫本頁) Γ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -50 - A7A7 7 B Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (47) Table 12 Phase compound compound pair [-nh2] [-COOH] Alkali metal compound group adhesion (A) (B) Degree (meq / kg) (meq / kg) (wt%) (wt%) (wt%) 25 48 77 49 Dipotassium adipate A- 1 B-1 Actual (0.05) (0.10) (0.05) 29 48 77 49 Hexane Disodium acid Same as above (0. 05) 27 48 92 34 Dipotassium adipate Same as above (0.05) 30 48 92 34 Disodium adipate Same as above (0.10) Comparison 32 48 77 49 — — — Example 33 48 92 34 — — — (Please read the precautions on the back before filling out this page) Γ This paper size is applicable to China National Standard (CNS) A4 specification (210X 297mm) -50-A7

7 B 經濟部中央標準局員工消費合作社印製 五、發明説明（48 ) 表13 沸水 紡 絲 染料 髙溫加壓 黃色度 纖度 強度 伸度 率 絲切斷率 吸附率 熱水處理時 (Y I ) 強度保持率 (190°C (但尼爾） Cg/d) (%) (%) (次/噸） (%) (%) X5min) 實 25 50 4.63 65.2 3.6 3 76 78 <1 29 50 4.64 65.1 3.6 3 78 78 <1 施 27 50 4.60 65.3 3.5 4 89 82 <1 例 30 50 4.58 66.2 3.5 3 88 80 <1 比 較 32 50 4.55 64.0 3.6 36 78 43 23 例 33 50 4. 52 64.3 3.5 61 88 48 20 (請先閱讀背面之注意事項再填寫本頁) 、τ Γ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -51 - A7 B7 五、發明説明（49 ) 實施例3 1〜34、比較例34〜37 對於依表15之比率混合己二酸伸己基二銨（AH鹽 )與ε -己內醯胺之水溶液，添加表1 4所示比率之己醯 二胺，並且添加0 . 0 5重量％ (對聚合物之重量）己二 酸二鉀，得原料水溶液。 m- m tn^i ml nn I nn ^ ml ml I 1 1 • · ^ i (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Μ規格（210X297公釐） -52 - 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（50 ) 表 14 己烯二胺添加量 (對聚合物重量％ ) 己二酸添加量 (對聚合物重量％ ) 實 施 例 3 1 0.32 0 3 2 0.20 0 比 較 例 3 4 0 0.07 3 5 0 0 實 施 例 3 3 0.28 0 3 4 0.20 0 比 較 例 3 6 0 0 3 7 0 0.06 m· imt ϋ n^i n ^tn ^ ^m· ^^^1· —^n HBBi TJ . . (洚 i (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -53 - 經濟部中央標準局員工消費合作社印裝 A 7 B7 五、發明説明（51 ) 將該水溶液放入以氮取代之不銹鋼製熱壓鍋中，使內 壓爲1 7 . 6kg/cma，同時餾去水，繼績加熱。當內溫 達到2 4 0°C時開始放壓，經9 0分鐘使其恢復至常壓， 然後維持常壓3 0分鐘進行常壓聚合（內溫2 6 8 °C)。 藉由氮壓將上述所得聚合物擠壓至冷水中，藉由切割機使 之成爲片狀。將所得聚合物之相對粘度及末端基濃度示於 表1 5。 在該片狀物中混合表1 5所示組成之各種化合物，使 用一般用之熔融紡絲裝置，在2 9 0 °C紡絲溫度， 5 5 0 Om/m i η紡絲速度紡絲，製造爲5 0 d/ 2 0 f纖維。將所得纖維之各種測定結果示於表1 6。 實施例3 1〜34係含有式〔I〕所示化合物之化合 物A—1 ，並且羧基末端基濃度60meq/kg以下，胺 基末端基濃度5 5m e q/kg以上之聚己二醯己二胺纖維 例。所得纖維係可提高抗熱變黃性達到極髙水準之纖維。 抗熱變黃性可以更超出聚己醯胺纖維，而且還可以媲美聚 酯纖維之水準。另外，該實施例所得纖維係兼有染料吸附 率高（濃染性），高溫加壓熱水處理時強度保持率高之實 用上極有用特徵者。 另一方面，比較例3 4〜3 7之組成係極顯著地熱變 黃又，染料吸附率與高溫加壓熱水處理時之強度保持率均 極低。 本紙張尺度適用中國國家揉準（CNS ) A4规格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) -β Γ -54 - A7 經濟部中央標準局員工消費合作社印製 五、發明説明（52 ) 表15 聚合物誠 鹼金雇 化飾群 相對 [-ΝΗζ] [-COOH] 化雜 (A) (B) AH鹽 ε —己內醯胺 粘度 (meq/kg) (meq/kg) (SM96X (重量 (ΜΛ96Χ (聿最％) (軍最96) 聚合物） 聚合物） 聚潍） 實 31 90 10 54 72 39 己二酸二鉀 A-1 B-1 施 (0. 05) (0.10) (0. 05) 32 90 10 55 61 49 同上 A-1 B-4 例 (0.10) (0. 05) 比 34 90 10 54 38 72 同上 A-3 B-1 較 (0.10) (0. 05) 35 90 10 54 45 65 同上 A-4 B — 4 例 (0.10) (0. 05) 實 33 80 20 52 67 40 同上 A-1 B-1 (0.10) (0. 05) 倫 34 80 20 52 60 47 同上 A-1 B —4 例 (0.10) (0. 05) 比 36 80 20 53 42 65 同上 A-3 B-1 較 (0.10) (0.05) 37 80 20 52 38 69 同上 A-4 B-4 例 (0.10) (0.05) (請先閱讀背面之注意事項再填寫本頁) -* 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -55 -7 B Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (48) Table 13 Boiling water spinning dye High temperature Pressurized yellowness Fineness elongation rate Silk cut rate Adsorption rate Hot water treatment (YI) Intensity Retention rate (190 ° C (denier) Cg / d) (%) (%) (times / ton) (%) (%) X5min) Actual 25 50 4.63 65.2 3.6 3 76 78 < 1 29 50 4.64 65.1 3.6 3 78 78 < 1 Shi 27 50 4.60 65.3 3.5 4 89 82 < 1 case 30 50 4.58 66.2 3.5 3 88 80 < 1 comparison 32 50 4.55 64.0 3.6 36 78 43 23 case 33 50 4. 52 64.3 3.5 61 88 48 20 (Please read the precautions on the back before filling in this page), τ Γ This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm) -51-A7 B7 V. Description of the invention (49) Implementation Example 3 1 ~ 34, Comparative Examples 34 ~ 37 To the aqueous solution of hexadecyl diammonium adipate (AH salt) and ε-caprolactam mixed in the ratio of Table 15, add the ratio of Hexamethylene II in Table 14 Amine, and added 0.05 wt% (to the weight of the polymer) dipotassium adipate to obtain the raw material aqueous solution. m- m tn ^ i ml nn I nn ^ ml ml I 1 1 • · ^ i (please read the precautions on the back before filling in this page) The paper standard printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs is applicable to Chinese national standards (CNS) Μ specification (210X297mm) -52-A7 B7 printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (50) Table 14 Addition amount of hexenediamine (weight% to polymer) Adipic acid Addition amount (% by weight of polymer) Example 3 1 0.32 0 3 2 0.20 0 Comparative example 3 4 0 0.07 3 5 0 0 Example 3 3 0.28 0 3 4 0.20 0 Comparative example 3 6 0 0 3 7 0 0.06 m · Imt ϋ n ^ in ^ tn ^ ^ m · ^^^ 1 · — ^ n HBBi TJ.. (洚 i (please read the precautions on the back before filling in this page) This paper size is applicable to China National Standards (CNS) A4 specification (210X297mm) -53-Printed by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A 7 B7 V. Description of the invention (51) Put the aqueous solution into a stainless steel autoclave replaced by nitrogen, so that the internal pressure is 17.6kg / cma, at the same time distilling off the water, and then heating. When the internal temperature reaches 2 4 0 ° C began to release pressure, after 9 Return to normal pressure in 0 minutes, and then maintain normal pressure for 30 minutes to perform atmospheric pressure polymerization (internal temperature 2 6 8 ° C). The above-obtained polymer is extruded into cold water by nitrogen pressure, and the It is in the form of a sheet. The relative viscosity and end group concentration of the resulting polymer are shown in Table 15. Various compounds of the composition shown in Table 15 are mixed in this sheet, and a general-purpose melt spinning device is used in 2 Spinning temperature of 9 0 ° C, spinning at 5 5 0 Om / mi η spinning speed, produced as 50 d / 2 0 f fiber. Various measurement results of the obtained fiber are shown in Table 16. Example 3 1 ~ 34 is an example of compound A-1 containing the compound represented by formula [I] and having a carboxyl terminal group concentration of 60 meq / kg or less and an amine terminal group concentration of 55 m eq / kg or more. It can improve the heat yellowing resistance to a very high level of fiber. The heat yellowing resistance can be more than polyhexamethylene fiber, and it can also be comparable to the level of polyester fiber. In addition, the fiber obtained in this example also has a dye High adsorption rate (dense dyeing), high strength retention rate during high temperature and pressure hot water treatment Who spend a very useful feature. On the other hand, the composition of the train 3 7 Comparative Example 4~3 very significant yellowing and geothermal, dye adsorption rate and the high temperature strength of the pressurized hot water treatment rate remains low. This paper scale is applicable to the Chinese National Standard (CNS) A4 (210X297mm) (please read the notes on the back before filling this page) -β Γ -54-A7 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Description of the invention (52) Table 15 Polymer-alkali gold base chemical decoration group relative [-ΝΗζ] [-COOH] hybrid (A) (B) AH salt ε-caprolactam viscosity (meq / kg) (meq / kg) (SM96X (weight (MΛ96Χ (避 最%) (jun 96) polymer) polymer) poly Wei) solid 31 90 10 54 72 39 dipotassium adipate A-1 B-1 Shi (0.05 ) (0.10) (0.05) 32 90 10 55 61 49 Same as A-1 B-4 Example (0.10) (0.05) than 34 90 10 54 38 72 Same as A-3 B-1 (0.10) ( 0. 05) 35 90 10 54 45 65 Ibid. A-4 B — 4 cases (0.10) (0. 05) Actual 33 80 20 52 67 40 Ibid. A-1 B-1 (0.10) (0. 05) Lun 34 80 20 52 60 47 Ibid A-1 B — 4 cases (0.10) (0.05) than 36 80 20 53 42 65 Ibid A-3 B-1 compared (0.10) (0.05) 37 80 20 52 38 69 Ibid A -4 B-4 cases (0. 10) (0.05) (Please read the precautions on the back before filling in this page)-* This paper size is applicable to China National Standard (CNS) A4 specification (210X 297mm) -55-

A B 經濟部中央標準局員工消費合作社印製 五、發明説明（53 ) 表1 6 纖度 (但尼爾） 強度 (g/d) 伸度 (%) 沸水 棚率 (%) 紡 絲 絲切斷率 (次/噸） 染料 吸附率 (%) 高溫加壓 熱水處理時 強度保持率 (%) 黃色度 (Y I ) (190°C X5rain) 實 施 例 31 50 5.72 39.3 11.4 4 70 80 <1 32 50 5.75 39.0 11.5 3 59 77 <1 比 較 例 34 50 5.70 39.5 11.2 3 36 18 25 35 50 5.72 39.3 11.3 3 44 21 24 實 施 例 33 50 5.58 34.8 20.9 3 65 75 <1 34 50 5.60 35.0 21.0 3 58 76 <1 比 較 例 36 50 5.59 34.7 20.8 4 40 20 26 37 50 5. 57 35.1 20.8 3 37 18 25 (請先閲讀背面之注意事項再填寫本頁) 、τ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -56 - A7 B7 五、發明説明（54 ) 產業上可利用性 本發明有關之聚己二醯己二胺纖維係極顯著改良抗熱 變黃性者，可以含較廣範圍之胺基末端基濃度（量）之纖 維提供此高水準之抗熱變黃性聚己二醯己二胺繊維是本發 明最有利之優點。本發明纖維中含相對性高濃度胺基末端 基的聚己二醯己二胺繊維係具有上述高抗熱變黃性，使用 酸性染料亦可深色染色之纖維，受到高溫加壓熱水處理亦 很少會脆化而降低強度具有此極髙經濟效益之處，可期待 應用於二次加工製品。例如以往無法付諸實行之摺痕加工 (百摺裙）或高溫加壓染色，在本發明之聚己二醯己二胺 纖維與聚酯纖維交絡編織製品可得實現。 由以上可知，本發明係具有以往聚己二醯己二胺纖維 中無法具有之廣範圍衣料用纖維特性譜，可提供媲美聚一 e —己醯胺纖維，聚酯纖維之聚己二醯己二胺纖維，以及 其商業上之製造方法者。 n i 1^1 l i ^ an· ^^^1 ^^^1 一J « , ^ u^. i (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 本紙張尺度適用中國國家標準（CNS >A4規格（210x297公着） -57 -AB Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (53) Table 1 6 Denier (denier) Strength (g / d) Elongation (%) Boiling water shed rate (%) Spinning yarn cut rate (Times / ton) Dye adsorption rate (%) Strength retention rate during high-temperature pressurized hot water treatment (%) Yellowness (YI) (190 ° C X5rain) Example 31 50 5.72 39.3 11.4 4 70 80 < 1 32 50 5.75 39.0 11.5 3 59 77 < 1 Comparative Example 34 50 5.70 39.5 11.2 3 36 18 25 35 50 5.72 39.3 11.3 3 44 21 24 Example 33 50 5.58 34.8 20.9 3 65 75 < 1 34 50 5.60 35.0 21.0 3 58 76 < 1 Comparative Example 36 50 5.59 34.7 20.8 4 40 20 26 37 50 5. 57 35.1 20.8 3 37 18 25 (please read the precautions on the back before filling in this page), τ This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -56-A7 B7 V. Description of the invention (54) Industrial applicability The polyhexamethylene diamine diamine fiber system related to the present invention significantly improves the resistance to heat yellowing and may contain Fibers with a wide range of amine end group concentrations (amounts) provide this high level of resistance to heat yellowing Acyl hexanediamine Xian dimension is most advantageous in the present invention advantages. The fiber of the invention contains relatively high concentration of amine terminal groups, and the polyhexamethylene diamine diamine has the above-mentioned high heat yellowing resistance, and the fiber can also be dyed in dark colors using acid dyes, and subjected to high temperature and hot water treatment It also rarely embrittles and reduces strength, which has such extremely high economic benefits and can be expected to be used in secondary processed products. For example, crease processing (a hundred-fold skirt) or high-temperature pressure dyeing, which could not be carried out in the past, can be realized by interweaving knitted fabrics of polyhexamethylene diamine fiber and polyester fiber of the present invention. As can be seen from the above, the present invention has a wide range of fiber characteristics spectrum for clothing that cannot be possessed by conventional polyhexamethylene diamine fibers, and can provide polyhexamethylene diamide fibers comparable to poly-e-hexyamide fibers and polyester fibers. Diamine fibers, and their commercial manufacturing methods. ni 1 ^ 1 li ^ an · ^^^ 1 ^^^ 1 一 J «, ^ u ^. i (please read the notes on the back before filling out this page) Printed copy of Beigong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs The paper standard is applicable to Chinese national standard (CNS > A4 specification (210x297 publication) -57-

Claims (1)

A 經濟部中央櫺準局属工消費合作社印袈 申請專利範固 AS B8 C8 D8A Printed by the Industrial and Consumer Cooperatives of the Central Bureau of Trade and Industry of the Ministry of Economic Affairs, applying for patent Fan Gu AS B8 C8 D8 7 χί7 ^ 第84103988號專利申請案 中文申請專利範圍修正本 民國85年松月修正 1 . 一種聚己二醯己二胺纖維，其特徵爲該聚己二釀 己二胺織維爲分子鏈中含有10 〇〜7 0重量％己二醯己 二胺重覆單位 -C(CH2)&lt;CN(CHi)«N-II II 或由7 0重置％以上聚己二醯己二胺與3 0重量％以下其 他聚醯胺所成摻混物之纖維，並且可滿足以（A)及（B )之條件 (A)含有〇·〇1〜1.〇重置％以下式〔I〕所示2 ’ 4 一雙（烷硫基）一6 -（3，5 —二烷基一 4 一羥苯 胺基）一1 ，3，5 —三氮阱， RI ^ ^ SRί HO ~〈〇〉— NH— 'Bu SR j C I) 4之烴基，R 2 (式中Rx表示第三丁基或碳數1 ，R3表示碳數5〜10烴基）•以及 (B)含有〇.〇〇5〜1.0重置％—種或複數種 選自亞磷酸、亞磷酸衍生物、次磷酸、次磷酸衍生物· 2 .—種聚己二醢己二胺繊維，其特徼爲該聚己二醯 本紙張尺度逋用t國國家揉準（CNS &gt;八4此格（210X297公釐） --------二------订 (请先聞讀背面之注意事項再填寫本筲) 、申請專利範圍 己二胺織維爲由胺基末端基澳度（〔一 NH2〕）與羧基 末端基濃度（〔一 COOH〕）之和在於70〜200 me q/kg範圍、分子鏈中含有70〜1 〇〇重置％己二 醯己二胺重覆單位 Η Η I I -C(CH2)&lt;CN(CHi),N-I! II ； 0 0 i 或7 0重置％以上聚己二醯己二胺與3 0重量％以下其他 聚醯所成摻混物之嫌維，且可以滿足以下（a )及（b ) 者， (a) 〔-COOH〕S6〇(meq/kg) · (b) 含有〇·005〜0.5重置％鹼金靥化合物 3 .如申請專利範圍第2項之織維，其中鹼金靥化合 物爲己二酸二鈉或己二酸二鉀· 經濟部中央標筚局属工消費合作社印装 (請先閲讀背面之注意事項再填寫本頁) 4 . 一種聚己二醯己二胺嫌維，其特徴爲該聚己二醯 己二胺織維爲由胺基末端基澳度（〔一 NH2〕）與羧基 末端基溴度（〔一 COOH〕）之和在於75〜175 m e q/kg範圍，分子鏈中含有1 〇 〇〜7 0重置％己二 醯己二胺重覆單位 I I -C(CHi),CN(CHt),N II II 0 0 之聚己二醣己二胺之繊維，可以同時滿足 本紙伕尺度遴州中阃國家樣準（CNS ) A4此格（2丨〇X297公釐） 六、申請專利範圍 A3 B8 C8 D8 ( a ) C — C 0 0 Η〕 ^ 6 0 (me q / kg )， ( c ) C — Ν Η 2〕 5 5 (m e q / kg ) 1該織維 且 可 以 滿足 以 下 '( A ) 及（ B ) 之 條件者， ( A ) 含 有 0 • 0 1〜 1 . 0 重置％以下式 〔I〕所 示 2 1 4 - 雙 ( 燒 硫 基 )- 6 — ( 3，5 -二烷 基-4 - 羥 苯 胺 基） 一 1 9 3 9 5 - 三氮 哄 &gt; R, 、 U一 SR* 1 H0 &gt;- •NH· Ν 一 »N …⑴ ( Bu 〈SR, (請先《讀背面之注意事項再填疼本頁) 經濟部中夬#準局貝工消费合作社印裝 (式中Ri表示第三丁基或碳數1〜4之烴基，R 2 ，R3表示碳數5〜10烴基），以及含有 (B)含有〇.〇〇5〜1.0重置％—種或複數種 選自亞磷酸 '亞磷酸衍生物、次磷酸、次磷酸衍生物所成 群。 5 ·如申請專利範圍第1或第4項之聚己二醯己二胺 織維，其中2，，4 一雙（烷硫基）_6-（3，5 —二烷 基一 4 一羥苯胺基）一 1，3，5 —三氮阱爲2，4_雙 (正辛硫基）—6 -（4 一羥基一 3，5-二第三丁苯胺 基）一1，3，5-三氮阱* 6 .如申請專利範圈第1或第4項之聚己二醢己二胺 嫌維•其中亞磷酸衍生物、次磷酸衍生物爲二磷酸四（2 ,4_二第三丁苯基）—4 · 4 ^ 一伸聯苯基酯、亞磷酸 雙（2 . 6 -二第三丁基一 4 一甲苯基）酯及苯基次磷酸 鉀* 訂 ^紙法尺度遘用t «國家«準(CNS) A4^(2l〇X297^t ) 、申請專利範圍 7 ,如申請專利範園第5項之聚.己二醯己二胺嫌維， 其中2，4 一雙（烷硫基）一6 -（3 ，5-二烷基一 4 —羥苯胺基）一‘1 ，3，5 -三氮阱爲2，4 一雙（正辛 硫基）一 6_ (4 -羥基_3，5 —二第三丁苯胺基）一 1 ’ 3，5 -三氮阱，亞磷酸衍生物、次磷酸衍生物爲二 磷酸四（2 , 酯、亞磷酸雙 苯基次磷酸鉀 8 .—種 使用胺基末端 C - c ο ο η ，分子鍵中含 位 4 —二第三丁苯基）一 4，4，一伸聯苯基 (2 · 6 —二第三丁基一 4 一甲苯基）酯及 • 聚己二醯己二胺織維的製造方法，其特徽爲 基濃度（〔一 ΝΗ2〕）與羧基末端澳度（ 〕）之和在於75〜175meq/kg範園 有1 0 0〜7 0重置％己二醯己二胺重覆單 I I -C(CH2)&lt;CNCCH2),N- •II II (請先閲讀背面之注意事項再填寫本頁) 經濟部中央揉牵局属工消费合作社印装 之聚己二醯己二胺做爲原料，藉由熔融紡絲法予以製造嫌 維時’以可以滿足以下（a )及（b )之聚己二醯己二胺 做爲原料· (a) 〔― COOH〕彡 60(meq/kg) (c) C- NH2J ^5 5 (meq/kg) 在該原料中使其含有分別爲〇 . 〇 1〜1 . 〇重量％， 0·005〜1.0重置％及〇.〇〇5〜0.5重量％ 以下之（Α) · (Β)及（C)所特定之化合物者， 本纸浪尺度適用中國國家梯率（CNS ) Α4礼格 ( 210X297公釐） A8 B8 C8 D8 穴'申旖專利範固 A)以下式〔I〕所示2，4 一雙（烷硫基）一 6 ’ 5 —二烷基一 4 一羥苯胺基）一 1 ，3，5 —三 氮阱 SR. c η (請先Η讀背面之注意事項再填寫本頁) ^u. SRj (式中Rx表示第三丁基或碳數1〜4之烴基，R2 ，R3表示碳數5〜10烴基）， (B) 〇 . 005〜1 . 0重量％ —種或複數種選自 亞磷酸、亞磷酸衍生物、次磷酸、次磷酸衍生物所成群， 並且又含有. (C) 〇 · 005〜0 . 5重置％鹼金屬化合物· 9 ·如申請專利範園第8項之聚己二Μ己二胺纖維的 製造方法，其中2，4 一雙（烷硫基）一 6- (3 ，5 — 二烷基—4 一羥苯胺基）一 1，3，5 —三氮阱爲2，4 一雙（正辛硫基）一 6 -（4 一羥基一 3 ，5 -二第三丁 苯胺基）一 1，3，5 -三氮阱· 經濟部中央揉準扃貞工消费合作社印策 1 0 .如申請專利範團第8或第9項之聚己二醣己二 胺嫌維的製造方法，其中亞磷酸衍生物、次磷酸衍生物爲 二磷酸四（2，4 一二第三丁苯基）一 4，4 伸聯苯 基酯、亞磷酸雙（2，6 —二第三丁基一 4 一甲苯基）酯 及苯基次磷酸鉀· 1 1 .如申請專利範围第8項之聚己二醯己二胺嫌維 的製造方法，其中驗金饜化合物爲己二酸二鈉或己二酸二 本紙法尺度遑用中國«家揲準（CNS ) Α4此格（210Χ297公釐&gt; 經濟部中央標準局一®：工消費合作社印製 ^9364 A8 B8 C8 D8六、+請專利範圍 鉀。 1 2 .如申請專利範圍第8項之聚己二醯己二胺織維 之製造方法’其中2 ’ 4 一雙（院硫基）一 6 -（3，5 —二烷基一 4 —羥苯胺基）一 1 ’ 3，5 -三氮阱爲2， 4 一雙（正辛硫基）—6 -（4 —經基一 3，5—二第三 丁苯胺基）一 1，3，5 —三氮阱，亞磷酸衍生物、次磷 酸衍生物爲二磷酸四（2，4 一二第三丁苯基）一 4， 4 --伸聯苯基酯、亞磷酸雙（2，6-二第三丁基-4 一甲苯基）酯及苯基次磷酸鉀，鹼金靥化合物爲己二酸二 鈉或己二酸二鉀。 1 3 . —種聚己二醯己二胺纖維組成物，其特徵爲胺 基末端基濃度（〔一 NH2〕）與羧基末端基濃度（〔 一 COOH〕）之和在於70〜200meci/kg範圍， 分子鏈中含有7 0〜1 0 0重量％己二醯己二胺重覆單位 Η Η ； I I ~C(CHI)&lt;CNCCH1),N-•II II 0 0 之聚己二醯己二胺的纖維組成物，且可以滿足， (a) 〔一 COOH〕S60(meq/kg)，並且 含有 (b) 〇.005〜0·5重量％鹼金屬化合物者。 I裝------訂-----Π線 (請先閲讀背面之注$項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）7 χί7 ^ Patent Application No. 84103988 Amendment of the Chinese application patent scope Amendment of the Song Dynasty in 1985. 1. A polyhexamethylene dihexamethylene diamine fiber, characterized in that the polyhexamethylene dihexamethylene diamine fiber is contained in the molecular chain 10 〇 ~ 70% by weight of hexamethylene diamide hexamethylene diamine repeating unit-C (CH2) &lt; CN (CHi) «N-II II or reset by 70% or more polyhexamethylene diammonium diamine with 3 0 Fibers of blends made of other polyamides below 1% by weight and satisfying the conditions (A) and (B) of (A) containing 〇.〇1 ~ 1.0 reset% as shown in the following formula [I] 2 '4-bis (alkylthio)-6-(3,5-dialkyl-4-hydroxyanilinyl)-1,3,5-trinitrogen trap, RI ^ ^ SRί HO ~ <〇>-NH — 'Bu SR j CI) 4 hydrocarbon group, R 2 (where Rx represents a third butyl or carbon number 1, R3 represents a carbon number 5 ~ 10 hydrocarbon group) • and (B) contains 〇〇〇5 ~ 1.0 weight Set%-one or more species selected from phosphorous acid, phosphorous acid derivatives, hypophosphorous acid, hypophosphorous acid derivatives · 2.-A kind of polyhexamethylene diamine hexamethylene diamine, the characteristics of which are the size of the polyhexamethylene dichloride paper Use the country of the country t (CNS &gt; 4 this grid (210X297mm) -------- two ----- order (please read the precautions on the back and then fill out this book), the scope of patent application Hexanediamine woven dimension is the amine The sum of the base end group degree ([one NH2]) and the concentration of the carboxyl end group ([one COOH]) is in the range of 70 ~ 200 me q / kg, and the molecular chain contains 70 ~ 100% reset% Diamine repeating unit Η Η II -C (CH2) &lt; CN (CHi), NI! II; 0 0 i or 7 0 reset% or more polyhexamethylene diamide hexamethylene diamine and 30% by weight or less other polyamide The resulting blend has a suspected dimension, and can satisfy the following (a) and (b), (a) [-COOH] S6〇 (meq / kg) · (b) contains 0.005 ~ 0.5 reset% alkali Gold compound 3. For example, the woven dimension of the second patent application, in which the alkali gold compound is disodium adipate or dipotassium adipate. Printed by the Industrial and Consumer Cooperative Cooperative of the Central Standardization Bureau of the Ministry of Economic Affairs (please read first (Notes on the back and then fill out this page) 4. A kind of polyhexamethylene diamine hexamethylene diamine suspected dimension, the special feature is that the polyhexamethylene diamide hexamethylene diamine dimension is composed of amine end groups ([NH2]) and Carboxyl terminal bromide (〔 -COOH]) The sum is in the range of 75 ~ 175 meq / kg, and the molecular chain contains 100 ~ 70% reset% hexamethylene diamide hexamethylene diamine repeating unit II -C (CHi), CN (CHt), N II II 0 0 The dimensions of the polyhexamethylene dihexamethylene diamine can meet the paper standard at the same time Linzhou Zhonglang National Sample Standard (CNS) A4 (2 丨 X297mm) VI. Patent application scope A3 B8 C8 D8 (a) C — C 0 0 Η] ^ 6 0 (me q / kg), (c) C — Ν Η 2] 5 5 (meq / kg) 1 The weave dimension can satisfy the following '(A) and (B) The condition, (A) contains 0 • 0 1 ~ 1.0 reset% shown in the following formula [I] 2 1 4-bis (burned thio)-6-(3,5-dialkyl -4-hydroxyaniline)-1 9 3 9 5-trinitrogen &gt; R,, U-SR * 1 H0 &gt;-• NH · Ν 一 »N… ⑴ (Bu <SR, (please first read Note on the back and fill in this page again) Printed by the Ministry of Economic Affairs # 結局 Beigong Consumer Cooperative (where Ri represents the third butyl group or a hydrocarbon group with a carbon number of 1 ~ 4, R 2 and R3 represent the carbon number 5 ~ 10 hydrocarbon groups), and containing (B) containing There are 〇〇〇5 ~ 1.0 reset%-species or plural species selected from the group of phosphorous acid 'phosphite derivatives, hypophosphorous acid, hypophosphorous acid derivatives. 5 · For example, the polyhexamethylenediaminediamine woven fabric of item 1 or 4 of the patent application scope, in which 2,4-bis (alkylthio) _6- (3,5-dialkyl-4-monohydroxyaniline Radical) a 1,3,5-trinitrogen trap is 2,4-bis (n-octylthio) -6- (4-monohydroxy-3,5-di-third butylanilinyl) -1,3,5- Trinitrogen trap * 6. If the patent application circle item 1 or 4 of polyhexamethylene diamine hexamethylene diamine is suspected • Among them, the phosphorous acid derivative and hypophosphorous acid derivative are diphosphoric acid tetra (2,4_dithird Butylphenyl) — 4 · 4 ^ Bisbiphenyl ester, bis (2.6-di-tert-butyl-4-tolyl) phosphite and phenyl potassium hypophosphite * Order ^ Paper method scale for t «National« Quasi (CNS) A4 ^ (2l〇X297 ^ t), patent application scope 7, such as the application of patent Fan Garden item 5 poly. Hexanediamide hexamethylenediamine suspected dimension, of which 2,4 a double (alkane Thio)-6- (3,5-dialkyl-4-hydroxyanilinyl)-'1,3,5-trinitrogen trap is 2,4 a double (n-octylthio)-6_ (4-hydroxyl _3,5 —di-third butylanilinyl group) 1 1 3,5-trinitrogen trap, phosphorous acid derivatives, hypophosphorous acid derivatives are diphosphorus Tetrakis (2, ester, bisphosphite potassium phosphite 8.-using amine terminal C-c ο ο η, molecular bond contains position 4-two third butyl phenyl)-4, 4, one extended Phenyl (2 · 6-di-tert-butyl-4-methyl-tolyl) ester and the production method of polyhexamethylene diamine hexamethylene diamine, its special emblem is the base concentration ([一 ΝΗ2]) and the carboxyl terminal o The sum of degrees ()) lies in 75 ~ 175meq / kg Fanyuan has 1 0 0 ~ 7 0 reset% hexamethylene diamide hexamethylene diamine repeating form II -C (CH2) &lt; CNCCH2), N- • II II ( Please read the precautions on the back and then fill out this page) The polyhexamethylene diamine printed by the Industrial and Consumer Cooperative of the Central Ministry of Economic Affairs of the Ministry of Economic Affairs is used as the raw material, and it is manufactured by the melt spinning method. Polyhexamethylene diamine that meets the following (a) and (b) as raw materials · (a) 〔― COOH〕 彡 60 (meq / kg) (c) C- NH2J ^ 5 5 (meq / kg) in This raw material is made to contain (A), (B) and (C) of 0.001 to 1.0% by weight, 0.005% to 1.0% by replacement, and 0.005% to 0.5% by weight or less. For specific compounds, this paper wave scale is applicable National Gradient (CNS) Α4 Lige (210X297mm) A8 B8 C8 D8 Cave 'Shen Yi Patent Fan Gu A) as shown in the following formula [I] 2, 4 a double (alkylthio) 6 6 5-two Alkyl-4 4-hydroxyaniline) -1 1,3,5-trinitrogen trap SR. C η (please read the precautions on the back before filling this page) ^ u. SRj (where Rx represents the third butyl group Or a hydrocarbon group with a carbon number of 1 to 4, R2, R3 represents a hydrocarbon group with a carbon number of 5 to 10), (B) 005 to 1.0% by weight-one or more kinds are selected from phosphorous acid, phosphorous acid derivatives, hypophosphorous acid , Grouped by hypophosphorous acid derivatives, and also contains. (C) 005 ~ 0.5 reset% alkali metal compounds · 9 · such as the application of patent Fan Yuan 8 polyhexamethylene hexamethylenediamine fiber Manufacturing method, in which 2,4-bis (alkylthio) -6- (3,5-dialkyl-4-hydroxyanilinyl) -1,3,5-trinitrogen trap is 2,4-bis (positive Octylthio) -6- (4-monohydroxy-3,5-di-tributylanilinyl) -1,3,5-trinitrogen trap Apply for the 8th or 9th party The manufacturing method of sugar hexamethylene diamine, wherein the phosphorous acid derivative and hypophosphorous acid derivative are tetraphosphoric acid tetrakis (2,4-di-tributylphenyl) -4,4-biphenylene diphosphite and bisphosphite 2,6-Di-tert-butyl-4-methyl-tolyl) ester and potassium phenyl hypophosphite · 1 1. For the manufacturing method of polyhexamethylene diamine hexamethylene diamine, such as item 8 of the patent application scope, the verification The gold compound is disodium adipic acid or adipic acid. The standard method is Chinese «Home Press (CNS) Α4 (210Χ297mm)> Central Bureau of Standards of the Ministry of Economy®: Printed by the Industrial and Consumer Cooperative ^ 9364 A8 B8 C8 D8 Six, + please patent the scope of potassium. 1 2. The manufacturing method of polyhexamethylene diamine diamine woven fabric as the 8th item of patent scope 'where 2' 4 a double (homosulfuryl group) a 6- (3,5-dialkyl-4-hydroxyl Aniline group) a 1 '3,5-trinitrogen trap is 2, 4 a double (n-octylthio)-6-(4-through the base a 3, 5-didibutylanilinyl) a 1, 3, 5—Trinitrogen trap, phosphorous acid derivatives and hypophosphorous acid derivatives are tetrakis (2,4-di-tributylphenyl) diphosphate, 4,4-biphenylene, bisphosphite (2,6 -Di-tert-butyl-4 (tolyl) ester and phenyl potassium hypophosphite, and the basic alkalium compound is disodium adipate or dipotassium adipate. 1 3. A kind of polyhexamethylene diamine hexamethylene diamine fiber composition, characterized by the sum of the concentration of amine end groups ([-NH2]) and the concentration of carboxyl end groups ([-COOH]) in the range of 70 ~ 200meci / kg , The molecular chain contains 7 0 ~ 100% by weight of hexamethylene diamine hexamethylene diamine repeat unit Η Η; II ~ C (CHI) &lt; CNCCH1), N- • II II 0 0 of polyhexamethylene diacetyl An amine fiber composition that satisfies (a) [-COOH] S60 (meq / kg) and contains (b) 0.005% to 0.5% by weight of an alkali metal compound. I installed ------ ordered ----- Π line (please read the $ item on the back and then fill in this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm)
TW84103988A 1993-10-26 1995-04-22 TW299364B (en)

Applications Claiming Priority (3)

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JP26684693A JP3272834B2 (en) 1993-10-26 1993-10-26 Yellow-resistant polyhexamethylene adipamide fiber
JP11301994A JP3281177B2 (en) 1994-05-26 1994-05-26 Yellowing-resistant deep-dyeing polyhexamethylene adipamide fiber and method for producing the same
JP14331394A JP3375419B2 (en) 1994-06-24 1994-06-24 Polyamide composition with improved thermal yellowing

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