TW457258B - Thermoplastic polyetherester block copolymer with enhanced light stability - Google Patents

Abstract

A thermoplastic polyetherester block copolymer having elastomer properties is composed of short chain polyester hard segments, which are comprised with dicarboxylic acid and diol, and long chain polyetherester soft segments, which are comprised with dicarboxylic acid and poly(alkylene oxide) glycol. By adding a specific mixed stabilizers, which comprising (A) hindered phenol compounds, (B) organo phosphite compounds, (C) benzotriazoles or benzotriazines or benzophenones compounds, (D) hindered amine compounds, (E) titanium dioxide, into the copolymer can get a great improvement of light stability.

Description

4 5 725 8 Printing policy A7 B7 of the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (I) The technical domain to which the invention belongs The invention relates to thermoplastic block copolyetheresters with improved light resistance, especially for Products with a large specific surface area, such as fibers or films, have excellent light resistance in the environment of light irradiation.习 知 # 术 For a long time, the materials of elastic yarns are rubber or Spandex 'rubber, which has been eliminated in recent years because it cannot be spun and is easy to relax. Spandex is not suitable for dyeing with common polyester fibers below 130 ° C due to poor humidity and heat resistance, and has poor chlorine resistance. It is prone to elasticity when used in swimming pools and other high-chlorine environments. Problems such as performance and strength reduction, therefore, the application of thermoplastic block copolyetherester elastomers in fibers has gradually received attention. The manufacturing method of thermoplastic block copolyetherester elastomer is a well-known technology, such as US Patent No. 3023192 of Joseph Clois Shivers, Jr., US Patent Nos. 3651014, 3763109 and 3766146 of William K. Witsiepe, Guenther Kurt Hoeschele et al., U.S. Patent No. 4,013,624, and Hok et al., U.S. Patent No. 3,932,326. Thermoplastic block copolyetherester elastomer has excellent physical and mechanical properties in the range of elastomers, such as toughness, fatigue resistance, financial wear resistance, impact resistance, financial resistance, thermal resistance and financial chlorine. Therefore, the amount of plastic used in plastics has been increasing in recent years. However, the use of copolyetherester elastomers is not completely unlimited. Because it is easily degraded by light, ^ paper ^ degree is generally China National Standard (CNS) T4 specification (2 丨 0 × 297 public; 5 __rt It- -I—. I--5κ ____ I (T _ n. ------- Good • _ X /.---(Please read the notes on the back first # Fill this page)-Δ 5 7 2 5 8 A7 B7 Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Bei Gong Xiao F, Cooperative, Co., Ltd. 5. Description of the invention (2) In the case of long-term outdoor exposure, especially for products with a large specific surface area such as fibers or films, in a short time The internal properties of the product may be reduced. In order to overcome the disadvantage of poor weather resistance, many technologies have been proposed. For example, Japanese Patent Publication Gazette No. 52-22744, which states that a hindered phenol compound is added to the copolyetherester elastomer. Or hindered amine compounds. Japanese Patent Laid-Open Publication No. Sho 62-192450 by Ishii Hiromitsu et al. States that a hindered amine compound and titanium dioxide are added to the copolyether S elastomer, and the two cooperate with each other. Stabilized copolymerization with the above compounds Ether ester elastomers still show weather resistance Insufficient, especially when the product has a fiber form. If only the hindered amine compound is added or the hindered amine compound is combined with titanium dioxide, the product has poor thermal oxidation resistance, and the surface layer of the elastic yarn silk cake will be severe after being left in the air for several months. Inferior solution and break. If only hindered hope compound is added, the product will not have sufficient light resistance, which will cause yellowing and surface cracking of the product in a short time under sunlight. Guan Ben Yazhang et al. Japanese Patent Publication Gazette No. 3-185133 and Sannomiya et al. Japanese Patent Publication No. 61-49433 provide a different method to improve the light resistance and chlorine resistance of copolyetherester elastic yarns. The method will include copolyetherester elasticity When the stretchable fabric of the yarn is dyed, in addition to the dye, a benzotriazene-based compound and a hindered phenol-based compound are simultaneously added to the dyeing solution, and the two stabilizers are added to the elastic yarn at the same time by the diffusion effect. The efficiency of this method is not good, and the dyeing solution will cause (please read the precautions on the back before filling in this page) -pack 1 ______ T 1.! -Lb 'Guangxian --- this paper size is suitable Using the Chinese National Standard (CMS) Α4 ^ Grid (210X 297 cm) y 457258 A7 B7 V. Description of the Invention (3) The most serious environmental pollution problem is that its stabilization effect on the copolyetherester elastic yarn is still important In addition, Yuda Yamada and others said that Japanese Patent Laid-Open Publication No. 2-272055 and Japanese Patent Laid-Open Publication No. 3-231959 proposed adding stabilizers mixed with four additives at the same time to improve the copolyetherester elasticity. The light resistance and heat resistance of the body. These four additives are respectively in JP-A-2-272055: 1). Hindered amine compounds, 2). Hindered phenol compounds, 3). Contains: thioxanthate compounds, 4). Titanium compounds and JP 3-231959: 1). Benzotriazene compounds, 2). Hindered amine compounds' 3). Hindered hope compounds, 4). Sulfur i intended compounds. The combination of the above two groups of stabilizers has greatly improved the heat resistance and light resistance of the product, and details the consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs. The inventors printed the above problems, and found out after research and review. A new stabilizer combination, if it can add the following five additives to the thermoplastic block copolyetherester: 0.1-2.0wt ° / 〇0.1-4.0wt% 0.1-5.0wt% 0.1-5.0wt% 0—— 3.0wt% (Please read the notes on the back to complete this page) (A). Hindered phenol compound (B). Organic phosphite compound (C). Benzotriazene compound or benzotriazine Compound or stupid ketone compound (D). Hindered amine compound (E). Titanium dioxide paper size is applicable to China National Standards (CNS) A4 wash (210 × 2? 7 male thin) ^ 457258 A7 B7 Composition of the stabilizer, and the addition of each component within the scope of the patent application, can be stabilized, excellent light fastness of the thermoplastic please read first, the back of the ~ ~ matters needing attention. Ύ write sex 肷丨 Yield copolyetherester elastomer In particular, it is used for fiber-dimensional or film with a large specific surface area. This new stabilizer combination is obviously similar to the date of the aforementioned Yamada Yuken et al.-Japanese Patent Laid-Open No. 2-272055 and Japanese Patent Laid-Open Publication Japanese Patent Application Laid-Open No. 3-231959. The mixed stabilizer of the present invention is composed of: (A): a hindered phenol compound, (B) an organic phosphite compound, (c) a benzotriazine compound or benzene Benzotriazine compound or benzene _ grain, (D). Hindered amine compound, (E). Titanium dioxide, and the addition amount of each component within the scope of the patent application of each other, can make mixed stabilizer The stabilizing capabilities of the ingredients are multiplied. The Ministry of Economic Affairs, the Ministry of Economic Affairs, the Bureau of Work and Consumer Cooperation, and the mixed stabilizer composed of five additives used in the present invention, and its applicable thermoplastic block The copolyetherester elastomer contains a poly / intentional hard segment of a repeating short-chain ester unit and a polyether-softening segment of a repeating long-chain Korean unit. The short-chain ester unit can be represented by the following general formula (1): 〇〇

II II (I) -〇—DOCR—C- The standard of this paper is applicable to China National Standards (C.NS) Α4 grid (2 〖οχ2.97 公 *) ^ Yes. Member of the Central Standards Bureau of the Ministry of Economic Affairs has eliminated cooperation. Du Yinzhuang 4 725 8 A7 B7 V. Description of the invention (V) The long-chain ester unit can be represented by the following general formula (π): 0 0 〇—G_〇—C—R—C— (II) where: D is Since the molecular weight is less than 250 divalent radicals; R is the divalent radical having a molecular weight less than 300; G is the divalent radical remaining after removing the dihydrogen radical from the polyweilyl ether dihydrate, the number average molecular weight is in the machine -6_, preferably between 600-3000. In this copolymer marriage, the polyester hard segment composed of the short bond unit of the above-mentioned general formula (i) accounts for 20-50% of the total weight of the copolyetherester, and the remaining portion is given by the above-normal formula If the long-chain poly _ target segment structure ^ short-bond poly I target hard segment has a financial ratio of 2Gwt% M., The melting point of the total self-defined elastomer will become very low, making the The performance of the elastic yarn after wet heat treatment and dry reduction is large. The duck decreases. If the proportion of the short-bond polymer hard segments is greater than 50% by weight, the elastic performance of the elastic yarn is insufficient. Residue of dihydric alcohol after removal of dioxo: Residue of dicarboxylic acid after removal of dicarboxylic acid. Bensinol General Tu National Standard (CNS) 8 4 Wei_ (21G) < 2.97 Gong Ling) ( Please fill in the notes on the back of the ¾ ^ ¾ first) -Packing ·-: 1ρ · k :: 5 4 725 8 V. Description of the invention A7 B7 (Six) _ ^ Note the short chain ester unit of the general formula ⑴ means A reaction product of a diol having a molecular weight of less than 250 and a dicarboxylic acid having a molecular weight of less than 300. Low molecular weight: Among the alcohols, 4-butanediol must account for more than 70%, and the remaining less than 30%, which contains aliphatic, cycloaliphatic, and aliphatic groups that can react to form short-chain ester units. ,, Adihydrogen compound 'wherein the C2-C15 glycol is, for example, ethylene glycol, 1,3-propanediol, 1,3-isobutanediol, 1,5-pentane, 2,2- Dimethyl propylene glycol, 1,6-hexanediol, 1,10-decanediol, dioxocyclohexane, 1,4-cyclohexanedimethanol, etc., the best is C8 aliphatic Glycol. Methanol 1,4-C2 (please fill in this page with the precautions on the back of the cabinet) -pack. The long-chain ester unit of the above formula ~ (II) refers to the polyalkylene ether glycol and the A reaction product of a dicarboxylic acid in an amount of less than 300. The polyalkylene ether glycol can be selected from the group consisting of polyethylene glycol, polypropylene glycol and polytetramethylene glycol, or a copolymer of the above three. Here, the number average molecular weight of the polyalkylene ether glycol must be between 400 and 6000, and if the number average molecular weight is less than 400, the copolyetherester formed thereby easily forms a homopolymer instead of a fluorene copolymer. Elastomers have poor elastic properties, and low melting points have poor durability against wet and dry heat treatments. If the number of Hirazaki molecules 1 is greater than 6000, phase separation will occur during the polymerization reaction, and it will be difficult to form a block copolymer, resulting in poor elastic properties of the elastomer. Reacting with the above low molecular weight diols and polyalkylene ether glycols to form the second slow acid of the copolyetherester elastomer of the present invention may be an aromatic, aliphatic or cycloaliphatic dibasic acid. Diguanic acid also contains diacids that can form vinegar bonds. The paper size is based on Chinese Standards (CNS) A4 (210X 297 mm) wading --- ^ ^ JI Jizhong Printed by the Bureau Lugong Consumer Cooperative 45 45 725 8 A7 B7 Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, V. Invention Description (7) Derivatives. At least 80 mol% of the dicarboxylic acid and its derivative must be aromatic compounds. Useful aromatic compounds include: terephthalic acid, isophthalic acid, phthalic acid, 2,6-dicarboxylic acid, 2,7-dicarboxylic acid, and the like. Among them, terephthalic acid and isophthalic acid are the best. Non-aromatic compounds below 20 mol% in the dicarboxylic acid may be oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, 1,3-cyclohexanedicarboxylic acid , 1,4-cyclohexanedicarboxylic acid, diethylmonomalonic acid, etc. Among them, cyclohexanedicarboxylic acid and adipic acid are preferred. The best polyether ester in the present invention is made of dimethyl terephthalate, 1,4-butanediol and polytetramethylene ether glycol with a molecular weight of 2000. = dicarboxylic acid in the final product The molar ratio of the polyalkylene ether glycol or its derivative and the polyalkylene ether glycol is the same as the molar ratio of the two in the reactant. The actual content of the low molecular weight diol is the dicarboxylic acid or its derivative in the reactant. And the molar number of polyalkylene ether glycol. The copolyetherester elastomer of the present invention can be prepared by a conventional transesterification reaction. The preferred method is to disulfophthalate, poly The fluorenyl ether diol and excess 1,4-butanediol are heated to 150-250 ° C in the presence of a catalyst for four times, and the methanol produced by the reaction is distilled off, thereby obtaining the prepolymer of the reaction. After the prepolymer obtained is further distilled to remove excess J, 4-butanediol, the molecular weight of the prepolymer produced can be gradually increased. During this distillation process, further S-swap reactions will occur to increase the molecular weight. And cause random arrangement of various copolyester units of the molecule: •-. · __ This paper is not easy to use 8 National Standards (CNS) A4 Washing (210X2.97 mm '(please read the precautions on the back before filling out this page) Binding _ Order — 457258 A7 Employee Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs, India_B7_ 5 Explanation of the invention (8) In order to avoid the polymer staying in the high temperature environment for a long time, irreversible thermal degradation may occur, and appropriate catalysts should be carefully selected in this reaction. Although the types of catalysts available are very wide, but among them Organic titanates are best used alone or in combination with alkali gold or alkaline earth acetate compounds. Complex titanates derived from alkali gold or alkaline earth alkoxides and titanates are also extremely effective. Other suitable catalysts include mixtures of inorganic titanates, calcium acetate and antimony trioxide, and lithium alkoxides, magnesium alkoxides, etc. In order to make the block copolyetherester elastomers described in the present invention for specific applications In particular, it can be used for occasions where the specific surface area of fibers or films is extremely large to exert its excellent physical properties. It is necessary to add the aforementioned five additives to the block copolyetherester elastomer: (A). Obstructed expectations Compounds, (B). Organic .. Phosphite compound, (C). Benzotriazene compound or benzotriazabenzene compound or benzophenone compound, (D) · Hindered amine compound, (E). Titanium dioxide The composition of the mixed stabilizer and its composition must meet the aforementioned requirements. The hindered phenol compound used in the mixed stabilizer of the present invention has the following structure: t-Bu _ Η Η 0 ^ (〇 ^-(III) R: Hydrogen or alkyl-(Please read the notes on the back before filling out this page}

The addition amount of this hindered hope compound must be between 0.1-2.0 wt%. The size of this paper is based on the national standard (CNS) A4 (210X297 mm) of the country t. 45 725 8 A7 B7 Printed by the Central Government Standards Bureau of the Ministry of Economic Affairs and other consumer cooperatives. 5. Description of the invention (9) The right side is less than 0.1 wt. % 'The product is susceptible to oxidation when it is heated, and even after being left for a period of time in the atmospheric environment at room temperature, the surface reacts with oxygen and is inferior. Conversely, if the added amount is more than 2.0wt%, the elastic properties of the product will decrease; Typical examples of the hindered compounds having the structure of the above formula (II) and which can be used in the mixed stabilizer of the present invention are as follows: U, 3-tris (2-methyl-4-hydroxy-5-phenylbutyl) Butane 4,4'-butylene-bis (6-tert-butyl-m-cresol) tetramethyl-3 (3 ', 5'-ditert-butyl-hydrophenyl) methylpropionate 1 '3,5-trimethyl-2,4,6-tri (3,5-ditert-butyl_4-hydrofluorenyl-benzyl) benzene 4,4'-bis (2,6-ditert Butyl-phenol) stearyl-3 (3,5_-tert-butyl-4-nitrooxyphenyl) propionic acid g-tert-butyl-6- (3-tert-butyl-5-methyl 2-Hydroxy-2-phenyloxyphenyl) -4_tolyl-propionic acid S4,4, butylene-bis (3-fluorenyl-6-tert-butyl-phenol) triethylene glycol-bis -3- (3-tert-butyl-4-hydroxo-5-benzyl) propionate tris (4-tert-butyl-3 · hydroxyl-2,6-dimethyl_benzylmethyl p-L-triazabenzyl-2,4,6-trione is used in the mixed stabilizer of the present invention. The organic linoleate compound has the following structure: < Please read the notes on the back first (Fill in this page again) f *-°

T

45 725 8 A7 B7 V. Description of the invention (ten)

Ri——0 'Ρ —ο

〇R4 (IV) R2— 〇 R5 where R1 and R2 can be the same or different, and can represent substituted or unsubstituted Cl-C6 alkyl, C3-C6 cycloalkyl, C6-C12 aromatic, C7- C15 aralkyl or alkaryl. R3, R4, R5 may be the same as or different from each other, and may represent substituted or unsubstituted hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C7-C16 aralkyl or alkaryl, but R3 And at least one of R5 is a three-dimensional hindered substituent, such as tert-butyl. The amount of the organic linolenic acid vinegar compound must be between 0.1 and 4.0% by weight, and the ratio of the amount of the hindered hydrazone compound (A) between 1/1 and 4/1 is optimal. If the addition amount of the organic phosphite compound is less than 0.1% by weight, the product is easy to be oxidized and discolored during thermal processing, and the heat resistance is poor. If the added amount exceeds 4.0% by weight, the elastic properties of the product will be reduced to 0 (please read the precautions on the back before filling this page)-The typical consumer sub-cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, which is printed in accordance with the above formula (IV) Examples of phosphate compounds are as follows: tris (2,4-di-tert-butyl-phenyl) phosphite tris (2,6-di-tert-butyl-phenyl) phosphite tris (2-tert-butyl-p- Tolyl) phosphite tris (2-tert-butyl-m-tolyl) phosphite tris (6: tert-butyl-p-phenylene) phosphite This paper is scaled to China National Standards (CMS) A4 Specifications (210X297 mm) 45 725 8 A7 B7 V. Description of the invention (ten) Di-n-butyl (2-tert-butyl-p-tolyl) phosphite di-n-butyl (2,4-di-t-butyl- Phenyl) phosphite di-n-butyl (2,6-di-tert-butyl-p-fluorenyl) phosphite 'di-n-hexyl (2-tert-butyl-m-phenyl) phosphite di-n-hexyl (2-tert-butyl-p-phenylene) phosphite di-n-octyl (2-tert-butyl-p-phenylene) phosphite diphenyl (2-tert-butyl-p-tolyl) phosphite Esters used in the mixed stabilizers of the present invention The benzotriazene compound or benzotriazene compound or benzophenone compound functions as a UV absorber and its structure is as follows:

, R3 (V) ----- ^ --- outfit 丨 —— 1 -I-.-(Please read the precautions on the back before filling out this page) Printed by the staff of the Central Standards Bureau of the Ministry of Economic Affairs for consumer cooperation

Rio

(VI) N-

(VII) The size of this paper is applicable to the national car (CNS) A4 of this country (210X297 mm) ^ 45 725 8 Employees of the Central Bureau of the Ministry of Economic Affairs of the People's Republic of China Cooperative Cooperative Seal A7 B7 V. Description of Invention (Judge) X: Hydrogen or chlorine R6, R7, R8, R9, RIO, Rm, Rn: a group consisting of carbon, hydrogen, oxygen, and nitrogen 'm, n = 1-5, (V), (VI), (VII) The three ultraviolet light absorbers can be a single compound or a mixture. (V), (VI), (VII) must be added in an amount of 0.1-5.0wt%. If the added amount is less than Q.lwt%, the light resistance of the product is insufficient, and it is in outdoor environment. After a period of use, it will cause a cracking reaction due to ultraviolet light, which will reduce the elastic properties of the product, reduce its strength, and weaken it. Conversely, if the added amount exceeds 5.0 wt%, the physical properties of the product will be reduced, and the price of such compounds is high. The high added amount will also significantly increase the raw material cost of the product. A practical example conforming to the above three formulas (V), (VI), (VII) is as follows: 2- [2'-Hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrooxy O-phenylenediimide-methyl) -5'-pyrene.yl] benzotriazene 2- (2, nitrooxy-3 ', 5'-di-tert-butyl-phenyl) benzene Hexamidine. 2- (2'-Hydroxy-5'-Texyl-phenyl) benzotriazene. 2- [2, -Hydroxy-3 ', 5'-di (1,1-Difluorenyl-phenylfluorenyl) -phenyl] benzotriazepine., Bis [2-nitrogen-5-tetyl-3- (epiaminopenta-2-) Radical) benzyl] pyridine 2- (2'-hydroxyl-3 ', 5'-di-t-pentyl-phenyl) benzotriazine (Please read the precautions on the back before filling in this page ) 'Bi' This paper uses China National Standard (CNS) A4 size (2I0X 297 mm) | ^ 45 725 8 A7 B7 V. Description of the invention (Shi) '~ — 2,4-Double (2,4 -Dimethylphenyl) _6, (2hydroxyl * n-octyloxyphenyl) _1,3,5, benzotriazabenzene 2- (2_benzodioxapentyl), 4_ _Methyl Hope The compound in the mixed stabilizer of the present invention acts as a light stabilizer and has the following structure:

Rll R12

N Y- / V Rl4 Rl3 Y · Nitrogen or carbon atom (VHI) Rll—Ri4: Burning groups with 1 to 6 carbon atoms, which may be the same or different (please read the precautions on the back before filling out this page) The direct addition must be between 0.1 and 5.0 wt%. The ratio of the (C) component in the mixed elixir of the present invention is usually, and at this time there will be a multiplied light stabilization effect. A practical example conforming to the above (vm) formula is as follows: Bis- (2,2,6,6-tetrafluorenyl-4-p-diazahexyl) adipate. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Bis- (2,2,6,6-.tetramethyl-4-p-diazahexyl) suberate bis- (1,2,2,6,6-pentafluorenyl-4-pair Diazahexyl) _n-butyl (3 5_di_4-hydrooxyphenylfluorenyl) malonate bis- (1,2,2,6,6-pentafluorenyl, 4-p-diphenyl N-hexyl-phenylphenyl) malonate 4-Hydroxy-2 ·, 2,6,6-tetramethyl_1-azacyclohexane-ethanol and dimethylsuccinate Polymer 4-Benzyloxy-2,2,6,6-tetramethyl-p-diazacyclohexane This paper is sized for China National Standards (CNS) A4 (2 丨 0X297 mm) 45 725 8 A7 B7 made by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (IV) The titanium difluoride (E) component used in the mixed stabilizer of the present invention acts as a sunscreen. Adding titanium dihalide to the copolyetherester elastomer can block part of the ultraviolet light, I1 and stop it from causing the elastomer to crack. However, the addition of titanium dioxide will affect the transparency of the product, and the addition of excessive amounts will deteriorate the processability of the elastomer and reduce the physical properties. Therefore, the added amount of titanium dioxide must be controlled below 3.0 wt%, and the actual added amount depends on the use of the copolymer 'ether ester elastomer. If it is used for products requiring transparency, it may be added without titanium dioxide. In the mixed stabilizer of the present invention, the addition amounts of the five components (A), (B), (C), (D), and (E) to the copolyether vinegar elastomer must meet the aforementioned requirements for the range of paint addition and Cooperate with each other to obtain a copolyetherester elastomer with excellent light resistance and heat resistance. (A) (b) (c) (d) (e) The ratio of the hindered phenol compound (A) component and the organic phosphite (B) component to the copolyetherester elastomer is preferably U1- Between 1/4. The ratio of the component (c) and the hindered amine compound (D) of the benzotriazene compound or benzotriazine compound or benzophenone compound to the copolyetherester elastomer is preferably 1: 1. ° In the present invention, the additive range of the component (E) is between 0-3. Controlling (A) component '(JB) component, (C) component' (D) component and (E) component are added within this range 'can achieve a multiplicative effect among the additives, thereby copolyetherester The elastic fiber or film made of the elastomer can have excellent weather resistance, especially the light resistance can be greatly improved. ~ (A) component, (B) component '(C) component' (D) component and (E) component in the above-mentioned mixed stabilizer are added to the copolyetherester elastomer. The method is not changed. The scale is applicable to China National Standards (CNS) Agut (210X297 mm) 丨 g. (Please read the notes on the back to fill out this page first)-Packing. Order the cooperation of the Ministry of Economic Affairs and the Central Standards Bureau. Press ¾ T25 8 A7 — —— — B7 _— V. Description of the invention ~:-Fixed. It can be added when the copolyetherester elastomer is synthesized, or it can be added in the molten state after the polyetherester elastomer is synthesized. For example, single screw extruder, twin screw extruder, roller mixer, ten thousand horsepower mixer and other equipment are used. Alternatively, the mixed stabilizer is first made into a mixed stabilizer masterbatch having a high concentration of about 20% to 40% by weight. When used, the high concentration mixed stabilizer masterbatch is added to a pure copolyetherester elastomer for dilution. It is also possible to disperse the mixed stabilizer directly into the copolyetherester elastomer with a static stirrer during spinning. The preferred method is to add the copolyetherester elastomer in different ways according to the characteristics of the components in the mixed stabilizer. Examples The following examples are specific illustrations of the present invention. However, the scope of the present invention is still subject to the scope of patent application. The amounts of the reactants, additives, etc. used in the examples are all by weight. The components used in the examples and comparative examples are shown in Table (I). The copolyetherester elastomers in the examples are The characteristics are analyzed by the following methods: 1. Strength, 70% sample length, initial load 0.04g / d, and elongation rate 600mm / min. The samples were analyzed on a tensile tester ~ STATIMAT Μ manufactured by the German TEXTECHNO company. The strength and elongation were analyzed 10 times and the average value was taken. .. · ·. * · · This paper is suitable for China National Rubbing (CNS) Α4 Washing (2 丨 0X297mm i ~~ ^ '(Please read the precautions on the back before filling this page). Loading. Order

45 725 B Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ¾ A7 B7 V. Description of the invention (soil) y \ 2. Simultaneous samples are placed in QUV TESTER manufactured by Q-PANEL Company in the United States to control the temperature in QUVTESTER to be maintained at The sample was irradiated at 60 ° C for 4 hours with an ultraviolet lamp with a length of 3l3rim. Analyze the intensity of the sample before and after UV irradiation, and divide the intensity of the sample after QUVTESTER by the intensity of the sample without QUV TESTER to obtain the strength retention rate. The light resistance of the sample is expressed by this characteristic value. '··· 1-2 Take 141.1 parts of dimethyl terephthalate, 98.2 parts of 1,4-butanediol, 240 parts of polytetramethylene ether glycol with a number average molecular weight of 2000, and dissolve in 1, 3.2 parts of 4-butanediol tetra-n-butyl titanate five percent solution. The above reactants were placed in a stainless steel reactor equipped with a stirring mechanism, a distillation tube, a heater, a nitrogen pipeline and a vacuum device. After the above reactants were placed in the reactor, the air in the reactor was driven out with nitrogen, followed by stirring and heating. The speed of the stirrer was set to 50 rpm, and the heater was set to 190 ° C. At the same time, a trace amount of nitrogen was continuously fed to take out the methanol produced by the reaction. When the temperature gradually increased to 160-170 ° C, the transesterification reaction started, and methanol began to distill. The temperature of the heater was maintained at 190 ° C. When the distillate amount of methanol reached 85% of the theoretical value, the transesterification reaction stopped. Add the components (A) and (B) listed in Table (II) separately (adjust the slurry with 1,4-butanediol to 10%), and gradually apply the vacuum to reduce the pressure in the tank within one hour. Below ImmHg, the heater gradually heats up to 250 ° C. The scale of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210X 2.97). "客 1ι ·« ^ ί 丨 til d ^ l —ii-r — ^^ 1 «--I tn—» — -I — · 丨 Deaf, -... (please note the back of sf before filling this page)

--Quan. TT d5 725 8 Printed by A7 ____B7, the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs. 5. Description of the invention (ten) Seven in 250t :, the vacuum state below ImmHg continues to react, waiting for the limit of copolyetherester elastomer When the viscosity reaches about 1.70, the reaction is stopped, the product is vented with water under nitrogen pressure to cool, and then cut into small pieces for use. The copolyetherester elastomer cut into small pieces in the previous step was dried in a vacuum oven at 80 ° C for 4 hours. The dried copolyetherester elastomer pieces were placed in a stainless steel heating and stirring tank. This heating and stirring tank is equipped with a variable speed stirring mechanism, an electric heater, a vacuum pump and a nitrogen line. The bottom of this heating and stirring tank is provided with a cylindrical discharge hole with a hole diameter of 3mm and a hole length of 3mm. The copolyetherester elastomer melted by heating and uniformly mixed with additives can be discharged through this hole. After the vacuum dried copolyetherester elastomer was put into this stainless steel heating and stirring tank, a vacuum was applied for 5 minutes to remove the air in the tank, followed by nitrogen, and when the pressure in the tank returned to normal pressure, nitrogen gas was added. The flow rate is adjusted to a minimum, and the electric heating heater is turned on at the same time. The heater temperature is set to 250 ° C. When the material temperature in the tank reaches 160 ° C, start the agitator and set the speed to 50 rpm. At this time, it can be seen that the torque value of the agitator rises with the temperature of the material. High and gradually decreased. After 40 minutes from the beginning of heating, the torque value of the agitator dropped to a stable value, showing that the contents of the tank had been mixed into a uniform state. At this time, nitrogen was passed into the tank to make the gauge pressure in the tank reach 0.6 Kg / cm 2. The melted copolyetherester elastomer in the tank is discharged through a drain hole at the bottom of the tank into a cooling water tank for cooling, and then it is wound on a drum at a roll speed of 140m / min. The rolled copolyetherester fibrous material was then non-contacted with a hot plate, and then extended 2.5 times to make a fibrous sample with a thickness of about 85 denier, and the sample was analyzed by the aforementioned analysis method. Fortune. From the data in Table (II), it can be known that if the copolyetherester elastomer is only applicable to the standard of the polymerization reaction, the Chinese national standard (CNS) A4 (2 丨 0X2.97mm) ~ Γ〇 'n alkflp 0 (Please read the precautions on the back before filling in this page) ------------ -11 ----- i .. 45 725 8 A7 ---________ B7_ V. Description of the invention (ten) Eight o'clock Adding a hindered phenol compound or both a hindered phenol compound and an organic phosphorous acid ester compound, the processed fiber products have very poor light resistance. _ ^ (I) Code name: A-1 Tetramethyl-3- (3 ', 5, -di-tert-butyl, methoxy-phenyl) methylpropionate A-2 Tris (4 ~ Tert-butyl-3-hydroxoxy: -2,6-dimethyl-benzyl) -L-triazaphenyl-2,4,6-triazayl A-3 4,4'-butylene Bis- (3-fluorenyl-6-tert-butyl-pentanyl) B-1 bis (2,4-ditert-butyl-phenyl) phosphinic acid g purpose B-2 tris (2,6-ditert Butyl-benzyl) phosphite-B-3 bis (2-tert-butyl-p-tolyl) phosphite-C-1 2- (2oxy-3 ', 5'-di-t-pentyl- Phenyl) -benzyltrione heterofluorene C-2 2- [2-Hydroxy Ayl-3 ', 5'-bis (U-dimethyl-phenylfluorenyl) -phenyl] benzotriazene C-3 Deaf [2-Hydroxy-5-tetractyl-3- (benzotriazacenyl-2-yl) benzyl 1 methyl alcohol C-4 2- (2-benzodiazepine )-(Methylphenol ... D-1 4-benzyloxy-2,2,6,6-tetramethyl-p-diazacyclohexyl D-2 4-ratyl-2,2,6, 6-tetramethyl-l-air heterocyclohexanoyl, polymer of ethanol and succinate, Example 1 Example 2 The experimental procedure is the same as Comparative Example 1, except that the copolyetherester elastomer is small The pieces were supplied at 80 ° C for two hours, and dried for 4 hours. 'In. Put the non-recording steel heating and smashing trough before mixing it with (B)' (C) '(D), (，) listed in Table (II), (玢 The ingredients are mixed step by step, and each subsequent step is It is the same as Comparative Example 1. The size of this paper is universal. CNS A4 scale (210X 2. dmm) Λ5 725 8 A 7 Β7 5. Description of the invention (ten) Nine f Note on the back, please fill in this again. 1} From the light resistance numbers listed in Table (π), we know that the fiber stabilizer of the copolyetherester elastomer can be lightfastened by adding the mixed stabilizer of the present invention to the copolyetherester elastomer. The performance has been greatly improved. Comparative Examples 3-6 'Example 17 The experimental procedures are the same as in Example 1. From the light resistance figures listed in Table (Π), it is known that if the copolyether disintegrating elastomer does not comply with the application of the present invention The scope of the patents (A), (B), (C), (D), and (E) added to the stabilizers of the present invention has insufficient light resistance, which results in insufficient results. Application of the invention. May patent scope added to the mixture. (A) '(B)' (C) '(D)' (E) each component, the light resistance of the product are all Significant improvement can be obtained.-Paste Example 8-12 The printing procedures of the Central Laboratories of the Ministry of Economic Affairs and the Consumers' Cooperatives in India are the same as in Example 1, except that the hindered phenol compounds in Table (II) are added after the transesterification reaction ( Α) At the same time, add the (it) ingredients listed in the table. Dioxin Dioxin Dioxin is adjusted to 1,5% butanediol to 25%, and then added to the reaction tank, and gradually apply a vacuum. The pressure in the tank was reduced to less than 1 mmHg within one hour, and the remaining steps were the same as in Example 1. According to the lightfastness numbers listed in Table (Π), it is known that ‘copolyether’ aims at elasticity. If an appropriate amount of Ti02 is added, it will have a light-shielding effect, which can improve the lightfastness of high products. '.', .. The paper scale is based on the Chinese National Standard (^ That) 8 4 squares (210 father 2.97 mm) ~ " '----- Duo Yin, Staff Consumption Cooperation, Central Bureau of the Ministry of Economic Affairs System 725 8 A7 __B7 V. Description of the invention (Table (II) Test No. A component B component c component D component E component Lightfastness Comparative Example 1 A-1 l.Owt%-— — — 3% Comparative Example 2 A- 1 l.Owt% Bl l.Owt% — — — 7% Example 1 A-1 0.8wt% Bl l.Owt% Cl 2.0wt% Dl 2.0wt% —._ 61% Example 2 A-2 0.6wt % B-2 0.6wt% C-2 2.5wt% D-2 2.5wt% — 63% Comparative Example 3 A-1 0.8wt% — Cl 2.0wt% Dl 2.0wt% — 43% Comparative Example 4 A-1 0.8 wt% — — Dl 2.0wt% — 20% Comparative Example 5 A-1 0.8wt% — Cl 2.0wt% — — 22% Comparative Example 6 — Bl l.Owt% Cl 2.0wt% Dl 2.0wt% — 36% Example 3 A-1 0.5wt%-Bl l.Owt% C-2 l.Owt% Dl l.Owt%-53% Example 4 .A-1 0.5wt% B-2 l.Owt% C-2 3.0wt% Dl 3.0wt%-67% Example 5 A-2 1.5wt% B-2 3.0wt% C-3 0.5wt% D-2 0.5wt%-47% Example 6 A-3 1.5wt% B -2 1.5wt% C-4 1.2wt% D-2 1.2wt% 56% Example 7 A-2 l, 5wt% B-2 1. 5wt% C-3 0.7wt% D-2 0.7wt% ---- 51% Example 8 A-2 0.4wt% B-3 0.4wt% Cl l.Owt% D-2 i l.Owt% Ti02 0.3wt% 49% Example 9 A-2 0.4wt% B-3 0.4wt% C-2 l.Owt% D-2 ^ l.Owt% 'Ti02 0.3wt% 46% Example 10 A-2 1.5wt% B- 2 1.5wt% C-3 0.7wt% D-2 0.7wt%, Ti02 0.5wt% 54% Example 11 A-2. 1.5wt% B-2 1.5wt% C-3 .0.7wt% D-2 0.7 wt% Ti02 l.Owt% 62% Example 12 A-2 1.5wt% B-2 [1.5wt% C-3 0.7wt% D-2 0.7wt% Ti02 2.0wt% 67% (Please read the Please fill in this page again for attention) p vi ^^ i f-tj · 1 ^ ρί τ ^ ι «— ^ ϋ \ uy rJ» -ϋ », this paper size is applicable to China National Standards (CNS) A4 washing grid (210X2 .97 mm>

Claims (1)

45 725 8 Wei 871103 Welcome--Yue Ri Zheng 90 · 3 · ％ [1 τα ° Supplement of stomach_ί3Good fortune light thermoplastic block copolyetherester elastomer, the scope of application is specifically based on dicarboxylic acid and A short-chain polyester hard segment composed of two 7G alcohols and a long-chain polyether ester soft segment composed of a dicarboxylic acid and a polyalkylene ether glycol poly_ are added to the following five compounds and mixed.合 定 定 剂 'and each composition in this mixed stabilizer must meet the following ranges: i 0. 1-2. 〇wt〇 / 〇0. 1-4. 〇wt〇 / o 0. 1-5.〇 wt% 0. 1-5. 0 wt% 0-3. 0 wt% (A). Hindered phenol compound (B). Organic linolenate compound (C) _benzotriazene compound or benzodiazepine Benzene compound or benzene compound (D). Hindered amine compound (E-oxin 2. As a thermoplastic block type copolyetherester elastomer having improved light resistance, as described in the first item of the scope of patent application, wherein the block formula The copolyetherester elastomer contains 20-50% by weight of the total weight of the co-ether ether polyester repeating short-chain ester units of the polyester hard, segment and the remaining repeating long-chain ester units of the polyester soft segments, the short Chain ester units can The following general formula (I) represents: " 〇 〇 C R-C-(I) Page 6 45 725 8 Case number 87110300 First amendment 6. Scope of patent application: The long-chain ester unit can be expressed by the following general formula ([丨) represents 0 丨 丨 0 丨 丨 -0-G-0-CRC Π) ( I) and the formula (II), 'D is the divalent group remaining after the removal of the dihydroxyl group with a molecular weight of less than 25. R is a small molecular weight since the molecular weight is small. G is a divalent fluorene: group remaining from 400 to 60,000 after the dihydroxyl group is removed from the ether glycol long chain polyether of = 300. 1 Becky molecular weight 3. As shown in item 2 of the patent application scope, a copolyetherester elastomer with the formula in the right is a thermoplastic block (II) with a light-emitting property. It represents: The following general formula is used: 〇〇0-G 〇C ~ P〜 II Formula (II), where R is the divalent group remaining after the molecular weight is small; G is the dialkyl group remaining after the dicarboxylic acid dihydroxyl group is removed from the self-polymerized dibasic acid. The ether is removed and the molecular weight is between 600-3000. 4. > f plastic material range of the first and the ancient & ------------------------------ thermoplastic thermoplastic segment 457258 _ Case No. 87110300_ Year Month__ VI. Patent application scope Copolyetherester elastomer, the added stabilizer can be added during the synthesis of copolyetherester elastomer, and can also be used in copolyetherester elastomer After synthesis, it is added in a molten state, and the ingredients in the mixed stabilizer can be added at the same time or in batches. Page 8 Years and Months Revised-_m Revised Zhongyancang TV, f Case No .: 871i0300 n 0 誧 Greed-1, Category) Π'πΐ τΟ1 Μ (Noted by J / Fine by the Bureau)-Invention patent specifications 7253 Chinese name Thermoplastic Polyetherester Block Copolymer with Enhanced Light Stability. Name (Chinese) 1. Jian Richun, Second Inventor's Name (English) 1. ZO-CHUN , JEN. Nationality 1. Republic of China residence, residence 1. Taipei 201, No. 201, Dunhua North Road Name (Name) (Chinese) 1. Name (Name) (English) of Nan Ya Plastic Industry Co., Ltd. l. NAN YA PLASTICS CORPORATION Nationality 1. Chinese People's Letter, Second Applicant's Residence and Residence (Office) 1. Name of Representative (Chinese), No. 201, Dunhua North Road, 105, Taipei City 1. Name of Representative of Wang Yongqing (English) 1. YCWANG 45 725 8 Case No. 87110300 Modified Chinese Abstract of Invention (Name of the invention: Thermoplastic block copolyether Jt ester elastomer with improved light resistance) mz Thermoplastic block copolyether ester with elastomeric properties, which contains It consists of a short-chain polyester hard segment composed of a dicarboxylic acid and a diol, and a long-chain polyether ester soft segment composed of a dicarboxylic acid and a polyether ether glycol. The body is added by: (A). Hindered phenol compound, (B). Organic phosphite compound, (C). Benzotriazine compound or benzotriazine compound or benzophenone compound, (D) Hindered amine compound, (E). Mixed stabilizer composed of titanium dioxide, can significantly improve the light resistance of the elastomer. English Abstract (Name of the invention: Thermoplastic Polyetiierester Block Copolymef with Enhanced Light Stability.) A thermoplastic po1yetherester block copolymer having elastomer properties is composed of short chain polyester hard segments, which are contained with di carboxy 1 ic acid and diol, and long chain po1yetherester soft segments, which are contained with dicarboxylic acid and poly (alkylene oxide) glycol. By adding a specific mixed stabilizers, which includes (A). Hindered phenol compounds (B). Organo phosphite compounds (C). Benzotriazoles or Benzotr i az i nes or Benzophenones compounds (D). Page 2 457258 #M 87110300 Rev. je, 9 Four Chinese Abstracts of Invention (Name of Invention: Thermoplastic Block Copolymers with Improved Lightfastness: Stupid %% Green) Supplementary Abstract of English Inventions $ Name of Invention: Thermoplastic Polyettierester Block Copolymer with Enhanced Light Stability.) Hindered amine compounds (E). Titanium dioxide, into the copolymer can get a great improvement of light stability. Page 3 45 725 8 Wei 871103 Welcome--Yue Ri Zheng 90 · 3 · ％ [1 τα ° Supplement stomach_ί3 Good fortune light thermoplastic block copolyetherester elastomer, the application scope is specifically The short-chain polyester hard segment composed of carboxylic acid and di-7G alcohol and the long-chain polyether ester soft segment composed of dicarboxylic acid and polyalkylene ether glycol poly- are added to the following five compounds The blended stabilizers' and the components in this mixed stabilizer must meet the ranges shown below: i 0. 1-2. 〇wt〇 / 〇0. 1-4. 〇wt〇 / o 0. 1- 〇wt% 〇.1-5.〇wt% 0-3.00wt% (A). Hindered phenol compound (B). Organic linolenate compound (C) _benzotriazene compound or Benzodigas heterobenzene compound or benzene compound (D). Hindered amine compound (E-oxin 2. As a thermoplastic block type copolyetherester elastomer with improved light resistance as described in the first patent application scope, wherein the The block type copolyetherester elastomer contains 20-50% by weight of the total weight of the co-ether ether polyester repeating short-chain ester units of the polyester hard, segment and the remaining repeating long-chain ester units of the polyester soft segments , The short-chain ester mono Yuan can be represented by the general formula (I) below: " 〇 〇 C R-C-(I) Page 6