TW299364B - - Google Patents

Description

A7 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 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 (

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 (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 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 —

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,

(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 —

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

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,

(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 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 / 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〕 (Please read the precautions on the back before filling this page) -§ Γ lBu dU \

〔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-—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 — 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 A

lBu H0- ^ 〇 > -CH2CH2CNHCH2CH2CH1 plant 0 1 ^, 1 ^ /-hexanyl bis (3, 5-di-third butyl)-4 monohydroxy-cinnamyl hydride

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 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).

A

7 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 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-

AB 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

AB 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 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 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 -

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 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 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-

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 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 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-

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 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 ^ 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)