TW200523293A - Polyesterdiol, polyurethane obtained by this method, spandexfilament, acryl group polymer containing novel dialkylamino group, polyurethane composition and spandex - Google Patents

Abstract

The first to third phases of this invention provide an excellent spandexfilament with elastic recovery, high tension and hydrate-tolerance, a polyurethane containing spandexfilament thereof, and a polyesterdiol obtained by specific diol of spandexfilament thereof. Moreover, the forth phase of this invention provides a polyesterpolyol which contains at least a polyol including UV-receiving group or a polyol with denatured lactone and constituted ingredient units of polyol formed by other polyols and adipic acid, a washing-tolerance polyurethane obtained by this method, and a spandexfilement formed by polyurethane thereof. Besides, the fifth phase of this invention provides a spandexpolymer with high solubility in DMAc solution and protecting degeneration and color-change, additives of spandexpolymer used in by improved forever-streching character including high molecular weight of tert-amino group, and forever-stretching character improved polyurathane composition and spandex composition. Furthermore, the sixth phase of this invention provides an excellent polyurethane with soft touch, excellent hydrated-tolerance, wrinkle-tolerance and viscosity, especially used in artificial leathers.

Description

200523293 m * IX. Description of the invention: [Technical field to which the invention belongs] The first and second series of the present invention relate to a spandex fiber (polyurethane) having excellent elastic restoring force, high tension, and excellent hydrolysis resistance. Elastic fiber), a polyurethane having the same, and a polyester diol obtained from a specific diol having the same. The third series of the present invention relates to a Spandex fiber having excellent hydrolytic resistance and a novel polyurethane having the same. The fourth system of the present invention relates to a polyurethane having excellent weather resistance. In more detail, even if it has another (washing-resistant) property which is hardly reduced in weather resistance when it is washed, it is a spandex fiber made of the polyurethane. The fifth series of the present invention relates to a dialkylamino group-containing acrylonitrile-based copolymer useful as a polymer-like amine stabilizer for polyurethane. More specifically, the present invention relates in particular to the improvement of polyurethane / spandex fibers and the amine stabilizer used as a film. In the fifth, "Spandex" is used to refer to a composition containing a long-chain elastomer composed of at least 85% by weight of a segmented polyurethane. The sixth system of the present invention provides an excellent polyurethane which has a soft texture and excellent hydrolysis resistance, wrinkle resistance, and adhesion, and is particularly useful as an artificial leather. [Prior art] Polyurethanes having a linear structure according to the first and second aspects of the present invention are relatively low in long-chain diols with hydroxyl groups, organic isocyanates, and chain extenders known as chain extension 200523293. It is obtained by the reaction of diol or diamine with a molecular weight and two active hydrogens. Various proposals have been made for improving the elastic restoring power and hydrolytic resistance of the polyurethane thus obtained. It is described in Japanese Patent Laid-Open No. 5 8-5 92 1 2 that a polyurethane using polyethylene glycol adipate polyester has excellent elastic restoring power, but has poor hydrolytic resistance. . Furthermore, although 1,4-butanediol adipate polyester has a certain degree of resistance to hydrolysis, the polyurethane lacks elastic restoring power. In addition, a polyurethane formed from a polycaprolactone polyol is excellent in hydrolytic resistance, weather resistance, and heat resistance, but has poor elastic restoring power. The above-mentioned Japanese Patent Application Laid-Open No. 5 8-5 9 2 1 2 describes that a method for solving the shortcomings of polycaprolactone-based polyurethane is synthesized by dehydration esterification reaction using neopentyl alcohol and adipic acid. Of polyesterpolyol with ε-caprolactone through transesterification. In addition, Japanese Patent Application Laid-Open No. 1 1-1 822 discloses the use of 2-n-2-ethyl-1,3-propanediol and 2,2-diethyl-1,3-as a polyester polyol. Polyurethane elastic fibers, such as propylene glycol, which are excellent in alkali hydrolysis resistance. The second aspect of the present invention is described in Japanese Patent Application Laid-Open No. 6 3-9 7 6 1 7 and is made of poly (2,2-dimethyl-1,3-propanedodecanediol ester). Creates Spendex fibers with increased resistance to tapeworms. However, the elastic restoring power and hydrolytic resistance of the polyurethane described in the above-mentioned Japanese Patent Application Laid-Open No. 6 3-9 7 6 1 7 are not sufficient, and there is a demand to further improve these polyurethanes. ester. In addition, the polyurethane elastic fibers disclosed in Japanese Patent Application Laid-Open Nos. 1 1 to 8 2 2 are those having excellent hydrolytic resistance, but the aim is to further improve elastic restoring power and strength. In addition, the Spandex fibers described in JP-A-Sho 6 3-97 6 1 7 200523293 are intended to further increase the strength. The polyurethane having a linear structure according to the third aspect of the present invention is a long-chain diol having a hydroxyl group at both ends, an organic isocyanate, and a low-molecular-weight two-chain active chain called a chain extender Alcohol or diamine. Various proposals have been made for improving the properties of the polyurethane thus obtained. For example, Japanese Patent Application Laid-Open No. 1 1-1 822 discloses the use of 2-n-butyl-2-ethyl-1,3-propanediol and 2,2-diethyl- Polyurethane elastic fibers, such as 1,3-propylene glycol, which are excellent in alkali hydrolysis resistance. In addition, Japanese Unexamined Patent Publication No. 6 3-9 76 17 discloses that poly (2,2-dimethyl-1,3-propanedodecanediol) has enhanced resistance to tapeworms. Spandex fibers and so on. However, the polyurethane elastic fibers disclosed in Japanese Unexamined Patent Publication No. 1 1-1 822 are excellent in additional hydrodegradability to a certain degree, but they are desired to be further improved. The same applies to the Spandex fibers described in JP-A-Sho 6 3-9 7 6 1 7. The polyurethane having a linear structure according to the fourth aspect of the present invention is a long-chain diol having hydroxyl groups at both ends, an organic isocyanate, and a low-molecular-weight two-chain active agent called a chain extender. Diol or diamine. The polyurethane thus obtained can be used in various applications, such as thermoplastic elastomers, hard or soft urethane foams, adhesives' artificial leather, synthetic leather, coatings, and elastic fibers. (Spandex fibers) and so on. Polyamine 200523293% Body formate has the original weather resistance (including light resistance) and better durability. However, when it has another weather resistance, it can use conventional UV absorbers such as 2-(2 '-hydroxyl-5 Benzotriazoles such as, -methylphenyl) benzotriazole, 5-chloro-2- (2, hydroxy-3 ·, 5'-di-third-butylphenyl) benzotriazole, etc. Or benzophenol such as 2,4-hydroxybenzophenol and 2-hydroxy-4-octyloxybenzophenol. However, since these conventional ultraviolet absorbers are low boiling point compounds, the addition of these to polyurethanes causes various problems. For example, adding a large amount of UV absorber will cause phase separation and reduce the whiteness or mechanical strength of polyurethane B. On the other hand, when the amount of the ultraviolet absorber added is extremely small, the light resistance of the polyurethane cannot be improved to a satisfactory level. In addition, the ultraviolet absorbent is volatilized or thermally decomposed during the processing and molding of the polyurethane, or penetrates out of the surface of the molded product, so that it does not have stable light resistance after a long period of time. In addition, when the spandex fiber product is repeatedly washed, the ultraviolet absorbent may be detached from the product, resulting in a decrease in its effect. The object here is not limited to polyurethane. In order to solve the above-mentioned shortcomings, try to use the above-mentioned ultraviolet absorber with a polymerizable double bond base such as vinyl group to polymerize and quantify the substance, and improve the resin with various resins. It is compatible with UV light absorbent, and prevents the volatilization, thermal decomposition, and exudation of ultraviolet absorbers (Japanese Patent Application Laid-Open No. 6 0-3841, Japanese Patent Application Laid-Open No. 62-1 8 1 3 60, Japanese Patent Application Laid-open No. 3-28 1 6 8 5). However, these ultraviolet absorbent polymers have the following disadvantages, and there is a need for improvement. In other words, the heat of thermoplastic polyurethane resin is -9- 200523293

«I Plastic resins have extremely high mechanical strength and are widely used in various molding materials. However, plastic polyurethane resins decompose due to alkali components and have the disadvantage of reducing their mechanical strength. Therefore, they are seeking to improve alkali resistance. Chemical resistance and solvent resistance. Furthermore, Japanese Unexamined Patent Publication No. 10-2 6 5 5 5 7 describes a lactone-modified polyol using a polyol having an ultraviolet absorber as a raw material. However, there is no description about the constituents of polyester polyols made from the polyurethane raw materials. The fifth segmented polyurethane of the present invention is known, which is a reaction of a high molecular weight diol (up to polyether alcohol or polyester alcohol) with an organic isocyanate to form an isocyanate-terminated polymer such that It is produced by reacting with a diamine or a diol by chain extension. The term "fiber" includes short fibers or continuous fibers. Hunt's US Patent No. 3,428,711 discloses that in order to stabilize segmented polyurethanes, high molecular weight tertiary amine alkyl acrylates and methacrylates are used, and spandex fibers are found It has great commercial use. Hande reveals many of these additives. The preferred stabilizers disclosed by Hand are sterically hindered isopropylaminoethyl methacrylate (hereinafter referred to as " DIPAM ") and n-decyl methacrylate (hereinafter referred to as " dm ") Of copolymers. This copolymer (hereinafter referred to as "DIPAM / DM" ") is a Spandex polymer that provides better resistance to deterioration from exposure to chlorine than amines that do not resemble steric hindrance. It is known that additives containing high molecular weight 3rd-order amine-based amines are extremely useful in preventing the deterioration and discoloration of Spandex polymers. However, these additives-10- 200523293 may cause manufacturing problems and / or cause Spandek The nature of the fibers produced by styrenic polymers poses a problem. For example, by using a poly (DIP AM / DM) additive, fibers can be dry-spun from a Spindex polymer solution, which causes various problems. Dimethylvinylamine (hereinafter referred to as " DMAc ") is the best solvent used in the production of Spandex polymer solutions. Poly (DIPAM / DM), antioxidants, and other additives such as pigments are often used in conjunction with DM Ac forms a slurry together, and then mixes it with the Spindex polymer solution before spinning. However, the slurry usually made at room temperature will suffer from the lack of solubility of the polymer amine in the DM A c solvent. There is a case of phase separation. Phase separation may be caused by agglomeration of additives, spinning problems and / or spinning solutions, and uneven distribution of additives in spinning fibers. In other words, poly (MPAM / DM) -containing or (DI PAM) additive of the Spendex polymer, because the solubility of the solvent will deteriorate during the spinning period, which will adversely affect the manufacturing process, and the elasticity of the fibers made from the new Pendex fiber will have some disadvantages, that is, Causes undesired reduction in elasticity of dry-spinned Spindex fibers (ie, permanent set). Most high molecular weight grade 3 amine alkyl (meth) acrylate additives are unavoidable. One or two disadvantages. In addition, in Rhoden JP-A No. 2-86 6 55, in order to avoid the above-mentioned problems, or to significantly reduce the above-mentioned problems, the high molecular weight content used to provide the spandex polymer is provided. Additives for sterically hindered tertiary amines' provide DIPAM and hydroxybutyl acrylate or ethacrylate-based copolymers. However, the copolymers described in JP-A No. 2-8 8 6 5 5 have deterioration in protection factors and -11-200523293 ι · The color-changing Spandex polymer, and the use of conventional additives with high molecular weight stereo-barrier grade 3 amine groups can inhibit the related reduction in elasticity (ie, permanent set (set)), but it must have sufficient resistance to DM A c solvent solubility, otherwise there may be a reduction in elasticity. The sixth series of the present invention is related to the production of artificial leather with ultra-fine fibers as the main body processed and applied to various polymer compounds, It is known that the polymer compounds used in this case are polyamines that are mostly used to obtain the properties of soft, elastic texture, durability, and dimensional stability as artificial leather. Carbon-based polymer compounds such as esters. However, these elastic polymer compounds are solutions dissolved in organic solvents, and can be applied to non-woven sheets and plates, and most of them are wet-set. In addition, the organic solvents used at this time are Very pyrophoric, and most of them are highly toxic substances. It is necessary to pay great attention when recovering solvents to prevent fire or toxic hazards. In addition, the solvents are also very expensive, and it takes a lot of cost to recover them from thin water. These various shortcomings have led to various reviews to change the elastic polymer compound applied to the non-woven sheet from an organic solvent type to an aqueous emulsion. However, when the aqueous emulsion is currently used, a satisfactory texture cannot be obtained. Artificial leather with physical properties. Generally speaking, the "urethane system with the current structure" can make long-chain diols and organic isocyanates with hydroxyl groups at both ends and diols or diamines called chain extenders with lower active molecular weights and 2 active hydrogens. The technical background of the polyurethane is as described in the technical background of the first and second aspects of the present invention. • 12-200523293 [Summary of the Invention] Therefore, 'the first and second objects of the present invention are to provide a spandex fiber which is more excellent in elastic restoring force, strength, and hydrolytic resistance, and a polyurethane having the same, and With this polyester polyol. The inventors have found that the above-mentioned problems can be solved by using a polyester polyol obtained from a specific branched chain aliphatic diol, ε-caprolactone, and adipic acid, and the first aspect of the present invention has been completed. Furthermore, the present inventors have discovered that polyester polyols obtained by using branched chain aliphatic diols, ε-caprolactone, and aliphatic dicarboxylic acids with carbon numbers of 10 to 12 are used as polyurethanes. The raw materials can solve the above-mentioned problems and complete the second aspect of the present invention. In other words, the first system (1) of the present invention provides at least one selected from the group consisting of 2-n-butyl-2-ethyl-1,3-propanediol and 2,2-diethyl-1,3- Polyester diols consisting of propylene glycol and 2,4-diethyl-1,5-pentanediol, and ε-caprolactone and adipic acid as constituent units. In addition, '(2) is a polyester diol as described in (1) above, in which the average molecular weight is 500 to 5,000. In addition, '(3) is a polyester diol provided by (1) or (2) above, wherein at least one kind is selected from 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-di Ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol diol and adipic acid polyester content unit content / ε-caprolactone content unit content ( The weight ratio is 5/95 to 80/20. In addition, (4) provides a polyurethane obtained from any one of the polyester polyols (1) to (3) and an organic diisocyanate. In addition, (5) provides a spandex-13-13200523293 fiber made of (4) polyurethane. The second system (1) of the present invention provides a polyester diol containing a branched chain aliphatic diol, ε-caprolactone, and an aliphatic dicarboxylic acid having a carbon number of 10 to 12 as a constituent unit. Furthermore, (2) provides a polyester diol in which the average molecular weight is 500 to 5,000. In addition, (3) is a polyester diol as described in (1) or (2) above, in which a polyester composed of a branched diol and an aliphatic dicarboxylic acid having a carbon number of 10 to 12 constitutes a single® Site content / ε-caprolactone's constituent unit content (weight ratio) is 5/95 to 80/20 ° In addition, (4) provides a polyester composed of any one of (1) to (3) above Polyurethanes obtained from diols and organic isocyanates. In addition, (5) provides a spandex fiber made of the polyurethane of (4). A third object of the present invention is to provide a Span φ Dex fiber which is more excellent in hydrolytic resistance, and to provide the polyurethane. The present inventors have found that the use of a polyester polyol containing a specific diol as a raw material for the polyurethane can solve the above-mentioned third problem of the present invention and complete the invention. In other words, the third system (1) of the present invention provides a polyamine obtained by reacting a polyester diol containing 2,4-diethyl-1,5-pentanediol as a constituent and an organic diisocyanate. Acid ester. Furthermore, '(2) provides a polyurethane according to (1) above, wherein the average molecular weight of the polyester-14-200523293 diol is 500 to 5,000. In addition, (3) provides a spandex fiber made of the polyurethane of (1) or (2) above. A fourth object of the present invention is to provide a spandex fiber having improved wash resistance with respect to weather resistance, and a polyurethane to be used therefor. The inventors have found that by using (A) a polyol component composed of (A 1) a UV-absorbing group-containing polyol or (A 2) a lactone-modified polyol and (A 3) other polyols As a constituent of the polyester polyol as a raw material of polyurethane, the above-mentioned problem can be solved by solution B, and then the present invention is completed. In other words, the fourth system of the present invention provides (1) (A) a polyalcohol formed by at least (A1) a polyalcohol containing an ultraviolet absorbing group or (A2) a lactone-modified polyalcohol and (A3) other polyalcohols. An alcohol component and (B) adipic acid are polyurethanes obtained by (X) polyester polyol and (γ) organic diisocyanate as constituent units. Further, the '(2) is a polyurethane as described in the above (1), wherein the polyol (A1) containing an ultraviolet absorbing group is a compound represented by the formula (1).

In addition, '(3) provides a polyurethane as described in (丨) or (2) above, wherein the lactone is £ -caprolactone. In addition, (4) provides the polyurethanes as described in (丨) to (3) above, wherein the average molecular weight of the poly-15-200523293 ester polyol is 500 to 5,000. Furthermore, (5) provides the polyurethane as described in (1) to (4) above, wherein the content of the unit of the polyester composed of the (A) polyol component and adipic acid / the content of the unit of the lactone is provided. (Weight ratio) is 5/95 ~ 80/20. In addition, (6) provides the polyurethane as described in (1) to (5) above, in which the molar ratio of the constituent unit content of the polyol is {(A 1) + (A2)} / {(A1) + (A2) + (A3)} is 0.01 to 10. In addition, (7) of the present invention provides a spandex fiber made of a polyurethane as described in any one of (1) to (6) above. The fifth object of the present invention is to provide a Spandex polymer which has high solubility in DMAc solvents, protection from deterioration and discoloration, and can further improve and use a conventional high molecular weight steric obstacle containing a tertiary amine. Additive-reduced elasticity (permanent stretch (set)), high molecular weight tertiary amine-containing additives used in real-world Spandex polymers, polyurethane compositions containing the additives, and polyurethanes Pentex composition. φ In order to solve the above-mentioned problems, the inventors have made intensive investigations and found that a novel compound formed by using diaminoamino ethyl (meth) acrylate and a reactive monomer having a specific structure as an essential copolymer component The tertiary amine acrylonitrile copolymer has high solubility in DMA c solvent, and its effect is determined to overcome the above problems, and the fifth aspect of the present invention is completed. In other words, the fifth aspect of the present invention (1) is to provide a dialkylamino group-containing acrylonitrile-based copolymer, which is characterized by (meth) propionate dialkylamine represented by the following general formula (1): Ethyl ester and the reactive monomer represented by the general formula (2) are -16-200523293 * ί must be formed by copolymer components. CH2 = CRC00CH2CH2NR ° R ° (1) (where 'R represents hydrogen or methyl; R◦ represents alkyl having 1 to 4 carbon atoms) CH2 = CRCOOCH2CH2〇 [-c (= 0) (CR1R2) x- 〇-] η · Η (2) (where R represents hydrogen or methyl; X ... and ... each represents independent hydrogen or an alkyl group having 1 to 12 carbon atoms; η ring-opening lactone chains It can be the same or different; X is an integer of 4 to 7; the average 値 of η is 1 to 5) and '(2) provides a dialkylamino group-containing acrylonitrile as described in (1) above. Polyurethane based copolymer. In addition, (3) provides the polyurethane composition as described in (2) above, wherein the content of the dialkylamino group-containing acrylonitrile-based copolymer is 0.5 to 10% by weight. In addition, (4) A Spandex composition is provided, which is characterized by containing a dialkylamino group-containing acrylonitrile copolymer according to the invention (1) above. • '(5) provides the spandex composition as described in (4) above, wherein the content of the dialkylamino group-containing acrylonitrile copolymer is 0.5 to 10% by weight. A sixth object of the present invention is to provide an artificial body having more excellent elastic restoring force, strength, and hydrolytic resistance, that is, artificial characteristics having excellent hydrolytic resistance, wrinkle resistance, and adhesiveness, and a satisfactory texture. Polyurethane for leather. In order to solve the above-mentioned sixth problem of the present invention, the present inventors have repeatedly researched -17-200523293 ^ 9 as a result of research, and thus completed the present invention. In other words, the sixth aspect (1) of the present invention provides a polyester diol, which is characterized by containing an aliphatic diresidual acid having at least 9 to 12 carbon atoms, an aliphatic diol, and ε-caprolactone. Is a constituent unit. Furthermore, '(2) provides a polyester diol as described in (1) above, wherein the average molecular weight is 500 to 5,000. In addition, ((3)) provides a polyester diol as described in (1) or (2) above, in which the polyester diol is composed of an aliphatic diol and an aliphatic dicarboxylic acid having 9 to 12 carbon atoms. Unit content / ε-caprolactone's constituent unit content (weight ratio) is 5/95 ~ 80/20 ° In addition, '(4) is to provide a polyester diol as described in any one of (1) to (3) above Polyurethane obtained with organic diisocyanate. Furthermore, (5) provides a polyurethane for artificial leather as described in (4) above. The best mode for carrying out the invention φ The following describes the embodiment of the first invention and the second invention in the following order. The first invention will be described. The diol used in the present invention is a specific diol, that is, at least one kind selected from 2-n-butyl-2-ethyl-1,3-propanediol and 2,2-diethyl-1,3-propanediol And 2,4-diethyl-1,5-pentanediol group of diols. These can be used alone or in combination of two or more. Further, as long as the effects of the present invention are not impaired, glycol compounds other than these may be used. Examples of this diol compound-18-200523293 > * such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl alcohol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,8-nonanediol, diethylene glycol, dipropylene glycol, cyclohexanedimethanol, and the like. The acid component of the polyester polyol of the present invention uses adipic acid, but other acid components such as glutaric acid, suberic acid, azelaic acid, sebacic acid, Aliphatic or aromatic dicarboxylic acids such as dodecanedioic acid, 1,11-undecane dicarboxylic acid, p-benzoic acid, isobenzoic acid, and 5-sulfosodium isobenzoic acid. These other acid ingredients can be used alone or as a mixture of 2 or more ® with adipic acid. Moreover, the acid component of the raw material may be used in the form of an ester derivative or an acid anhydride. The other component constituting the polyester polyol in the present invention is ε-caprolactone, but other lactones such as monomethyl-ε-caprolactone and trimethyl can be used within a range that does not impair the effect of the present invention. -ε-Caprolactone and other methylated ε-caprolactone, r-butyrolactone, 5-valerolactone and other auxiliary components of ε-caprolactone. The method for producing the polyester polyol of the present invention is not particularly limited, and a conventional method φ can be used. For example, it is manufactured based on the method described in Japanese Patent Application Laid-Open No. 5 8-5 9 2 12. In other words, it can be produced by mixing and heating the diol, ε-caprolactone, and adipic acid, and performing a dehydration esterification reaction, a ring-opening reaction, and a transesterification reaction (one-time heating method), or by using a diol The polyester polyol obtained by dehydration and esterification reaction with adipic acid is a polycaprolactone polyol synthesized by ring-opening reaction with ε-caprolactone in a polyhydric alcohol, usually mixed with polycaprolactone diol Manufactured by transesterification of the two. In addition, it can be produced by ring-opening polymerization of ε-caprolactone in a polyester polyol having a small molecular weight -19-200523293 a >. Among these, the one-time heating method is relatively simple and desirable. These reactions are preferably performed at 130 to 240 ° C, and more preferably 140 to 230 V, in terms of preventing coloring and preventing the depolymerization reaction of ε-caprolactone. For these reactions, the catalyst is usually used in an amount of 0.05 to 1000 ppm by weight, preferably 0.1 to 100 ppm by weight, for all the monomers. The catalyst can use organic titanated compounds such as tetrabutyl titanate, tetrapropyl titanate, dibutyl tin laurate, tin octoate, dibutyl tin oxide, tin chloride, tin bromide, Tin compounds such as tin iodide. The reaction is carried out by flowing an inert gas such as nitrogen, and it is desirable to prevent the color of the obtained target substance. The content of the constituent unit of the polyester polyol of the present invention is determined by using at least one member selected from the group consisting of 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, and Polyester constituent unit content of diols grouped by 2, 4-diethyl-1,5-pentanediol and adipic acid / ε-caprolactone constituent unit content (weight ratio) is φ 5 / 95 ~ 80/20, that is, the use of each raw material in the ratio in this range. The same applies when polyε-caprolactone is used. The polyester diol thus obtained has an average molecular weight of 500 to 5,000, preferably 1,500 to 4,000. When the molecular weight is 5,000 or more, the soft segment crystallinity is increased, and it is difficult to obtain a Spandex fiber having satisfactory physical properties. The average molecular weight can be measured by the hydroxyl value (j I S KK 1 5 5 7). A polyurethane formed from the polyester diol obtained above and an organic isocyanate is produced. The method for producing polyurethane is a known method, for example, the methods described in Japanese Patent Application Laid-Open No. 58-20-20-200523293 5 92 1 2 and Japanese Patent Application Laid-Open No. 1-1 822, and the like may be used as a reference. In other words, there is a primary reaction method in which a polyester diol, a low molecular weight diol or diamine as a chain extender, and an organic diisocyanate are reacted together with or without a solvent, or a polyester diol and organic A prepolymer method in which a diisocyanate is reacted in advance to obtain a prepolymer, and then a low-molecular-weight diol is reacted with or without a solvent. In terms of cost, a melt polymerization method produced without a solvent is preferred. At this time, the blending ratio of the raw materials is all the OH groups of the NC0 group of the organic isocyanate / polyester diol and the low molecular weight diol = 0.5 to 1.5, and preferably 0.8 to 1.2. Examples of the solvent include toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, dimethyl formase amine, and tetrahydrofuran. Examples of the organic diisocyanate used in the present invention include 2,4-diisocyanotoluene, 2,6-diisocyanotoluene, p-diisocyanophenylene, 4,4, -diisocyanate Acid diphenylmethane, m-diphenylene cyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, 2, naphthalene diisocyanate, 4,4, _ Monophenylene diisocyanate, xylylene diisocyanate, xylylene diisocyanate, dicyclohexane diisocyanate, 4,4,2-diisocyanate Dicyclohexylmethane isocyanate, isophorone diisocyanate, etc. These can be used alone or in combination of two or more. As the above-mentioned low-molecular-weight diol as a chain extender, the diol used in the present invention or the above-mentioned diol compound usable therewith can be used. As the diamine of the chain extender, ethylenediamine, hydrazine, isophoronediamine, methylphenylenediamine, 4,4'-diaminodiphenylmethane, and diaminodiphenyl can be used. Code, 3,3, _di-21-200523293 ^ m Chloro-4,4 ^ diaminophenylmethane, etc. The polyurethane obtained by the above method can be used in various applications where polyurethane is generally used, such as thermoplastic elastomers, hard or soft urethane foams, adhesives, artificial leather, synthetic leather , Coatings, etc., especially for Spandex fibers. The spinning method for producing the spandex fiber from the polyurethane of the present invention is a known method, that is, a dry spinning method, a wet spinning method, a melt spinning method, and the like. Among these, melt spinning is preferable in terms of cost. In addition, after spinning B, the elastic fibers are heat-treated to obtain those having higher physical properties. To the Spandex fiber of the present invention, an antioxidant such as a phenol derivative, a UV absorber such as a substituted benzotriazole, an anti-adhesive such as a higher fatty acid metal salt or a polysiloxane compound may be added as necessary. . The Spandex fiber provided by the present invention has excellent elastic restoring power, strength, and resistance to water decomposition. Therefore, the Spandex fiber can be used in a general use form, that is, in the form of interlacing and interweaving of nylon, cotton and the like. _ Especially when using cotton as the target raw material, the process of scouring, bleaching, mercerizing, etc., which are processed after cross-knitting or interlacing, that is, high-temperature processing in an acidic or aerobic atmosphere, can still exert good resistance to hydrolysis. . An embodiment of the second invention will be described below. The branched chain aliphatic diols used in the present invention include, for example, 1,2-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, neopentyl alcohol, and 3-methyl-1, 5-pentanediol, 2-n-butyl-2-ethyl-1,3-butanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1, 3-propanediol, 2,4-diethyl-1,5-pentane-22- 3 9 2 32. 5 00 2 · Alcohol hexanol is not present, and it is divided into two parts. The alcohol is used to mix dioxin for mixed use so that the chain branch of the aliphatic fat is not compounded. 一一 一一 2cohol bis, dipropyl should be in the range of CO. 1. Use the substance and make it mellow. The single effect alcohol. The single-effect alcohol B can be used. This is the case of this example. As a consequence, iso-alcohols such as alcohols can also be alcohols 0-di-1, nonyl 8-carbon 1, and 6-alcohols 1,2-diesters, di-di-butyl amines 4-benzyl 1, which are ester alcohols. It is used as a glycol diol difatty acid such as carboxylic acid, such as sebacic acid, dodecanedioic acid, 1,11-undecanedicarboxylic acid, and the like. Among them, sebacic acid and dodecanedioic acid are preferred. Further, as long as the effect of the present invention is not impaired, other acid components can be used. For example, glutaric acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,1 1-11 can be used. Aliphatic or aromatic dicarboxylic acids such as alkane dicarboxylic acid, p-benzoic acid, isobenzoic acid, and 5-sulfosodium isobenzoic acid. These other acid components can be used alone or as a mixture of two or more kinds with aliphatic dicarboxylic acids having 10 to 12 carbon atoms. The acid component of the raw material may be used in the form of an ester derivative or an acid anhydride. The other components constituting the polyester diol of the present invention are the same ε-caprolactone as in the first invention, but other lactones similar to the first invention of the present invention may be used as auxiliary components. The polyester diol of the present invention can be produced by the same method as described in the first aspect of the present invention. The content of the constituent unit of the polyester diol of the present invention is the content of the constituent unit of the polyester formed from the branched diol and the aliphatic dicarboxylic acid having a carbon number of 10 to 12 / ε-the content of the constituent unit of caprolactone (weight Ratio) is 5/95 ~ 80/20, preferably 20/80 ~ 80/20 -23- 200523293 km, that is, each raw material in this range ratio is used. The same applies when poly? -Caprolactone is used. The average molecular weight of the polyester diol thus obtained is 5,000 to 5,000, and more preferably 1,500 to 4,000. When the molecular weight is 5,000 or more, the crystallinity of the 'soft segment increases, and it is difficult to obtain a spandex fiber having satisfactory physical properties. The average molecular weight can be measured by the valence of hydroxyl (I S KK 1 5 5 7). The method for producing a polyurethane formed from the polyester diol and the organic isocyanate obtained above, and the organic isocyanate used are as described in the first aspect of the present invention. As the low-molecular-weight diol used as a chain extender, a branched aliphatic diol used in the present invention or the above-mentioned unbranched diol compound used therefor can be used. The diamine system as the chain extender is the same as the first exemplifier of the present invention. The application of the first polyurethane of the present invention and the description of the spandex fiber are also the same in the second aspect of the present invention. An embodiment of the third invention will be described below. • The diol used in the present invention is 2,4-diethyl-1,5-pentanediol. However, this diol and other diols may use, for example, one or more kinds of ethylene glycol, propylene glycol, 2-n-butyl-1,3-propanediol, and 2,2-diethyl-1,3- Propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,8- Nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, and the like. At this time, in terms of the effect of the present invention, it is preferable to use 2,4-diethyl-1,5-pentanediol at 5 mol% or more, and more preferably 10 mol% or more. In terms of performance, the preferred range is 80 mol% to 24, 205,293,293% or less, and the more preferred range is 70 mol% or less. The acid component of the polyester diol of the present invention is not particularly limited, such as glutaric acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1, n-undecanedicarboxylic acid, Aliphatic or aromatic dicarboxylic acids such as p-benzoic acid, isobenzoic acid, and 5-sulfosodium isobenzoic acid. These acid components can be used alone or in combination of two or more. The acid component of the raw material can be used in the form of an ester derivative or an acid anhydride. Among these, adipic acid is preferred. The production method of the polyester diol of the present invention is not particularly limited, and a conventional ® method can be used. The reaction usually uses a catalyst of 0.05 to 1,000 ppm by weight, preferably 0.1 to 100 ppm by weight for all the monomers. As the catalyst, organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and the like, dibutyltin laurate, tin octoate, dibutyltin oxide, tin chloride, tin bromide, and tin iodide can be used. Tin compounds. The reaction is carried out by circulating an inert gas such as nitrogen, and it is desirable to prevent the coloration of the obtained target substance. The above-mentioned polyester diol has an average molecular weight of 500 to 5,000, preferably φ 1,500 to 4,000. When the molecular weight is 5,000 or more, the crystallinity of the soft segment increases, and it is difficult to obtain a spandex fiber having satisfactory physical properties. The average molecular weight can be measured by a hydroxyl value (J I S K 1 5 5 7). The method for producing a polyurethane formed from the polyester diol and the organic isocyanate obtained above, and the organic isocyanate used are as described in the first aspect of the present invention. As the low-molecular-weight diol system as a chain extender, a branched aliphatic diol used in the present invention or the above-mentioned unbranched diol compound used therefor can be used. -25- 200523293 As the bond elongating agent, ^ fe is the same as the first exemplifier of the present invention. The use of the first polyurethane of the present invention and the description of the spandex fiber are also the same in the third aspect of the present invention. An embodiment of the fourth invention will be described below. The polyol (A 1) containing an ultraviolet absorbing group used in the present invention is not particularly limited, and examples thereof include a diol having two alcoholic warp groups represented by the following formula (1). This system is bis (3- (2H-benzotriazol-2-yl) -4-hydroxy-phenylethanol) methane. The diol may be a synthetic product or a commercially available product.

In addition, the lactone-modified polyol is not particularly limited, and examples thereof include a diol compound represented by the formula (2). In the production of the polyester polyol described below, the (A2) lactone-modified polyol may be used alone or in combination with the (A1) polyol. -26- 200523293

(R1 to R2 represent fluorene and a carbon number of 1 to 10; η and η 'represent integers of 4 to 8; m and m' represent 1 to 20) The ultraviolet-absorbing compound represented by formula (2) The production method is obtained by subjecting a lactone represented by the following formula (3) to ring-opening addition polymerization in a diol represented by the above formula (1). R1

φ ^ (3) (R1 to R2 represent fluorene and an alkyl group having 1 to 10 carbon atoms; N represents an integer of 4 to 8) The lactones represented by the above formula (3) include ε-caprolactone, Trimethyl-ε-caprolactone, monomethyl-ε-caprolactone, 7-butyrolactone, (5-valerolactone, etc. Among them, ε-caprolactone is preferred. In the above formula (1) Among the diols shown, the catalyst used in the ring-opening addition polymerization of the lactones represented by the above formula (3) includes, for example, tetrabutyl titanate, -27- 200523293 m * tetrapropyl titanium Organic titanium compounds such as acid esters, tin compounds such as dibutyltin laurate, tin octoate, dibutyltin oxide, tin chloride, tin bromide, tin iodide, etc. The amount of catalyst used is for the raw materials added 0.1 to 1000 ppm, preferably 1 to 5000 ppm. If the amount of catalyst used is less than 0.1 ppm, the ring-opening reaction of internal vinegar is significantly slower, which is uneconomical. On the other hand, if it is greater than 1,000 ppm, the ring-opening reaction is not economical. The time is early, and the synthetic resin using the obtained compound has poor physical properties such as durability and water resistance, so it is not desirable. ® The reaction temperature is 90 ~ 240 ° C, preferably 100 ~ 220 ° C. When the temperature is less than 90 ° C, the ring-opening reaction of lactones becomes significantly slower, which is uneconomical. On the other hand, if it is above 240 ° C, the depolymerization reaction due to the ring-opening addition polymerization of polylactone is not effective. In addition, in the reaction, synthesis under the atmosphere of an inert gas such as nitrogen gas can make the color of the product equal and have good results. The ultraviolet absorbent of the present invention is thus synthesized. The detailed description of these is as in JP-A-10 -2 6 5 5 5 7. φ Other (A3) polyglycols include ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, and 2-methyl-1,3-propanediol , Neopentyl alcohol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,8-nonane Diethylene glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, 2-n-butyl-2-ethyl-1,3-butanediol, 2,2-dimethyl-1 , 3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,2-octanediol, etc. These can be used alone or in combination of two or more. Mixed use. The acid component of the polyester polyol of the present invention is adipic acid. Other acid components-28- 200523293 can be used in the same manner as described in the first invention, and in the form described. The method for producing the polyester polyol of the present invention is not particularly limited, and conventional methods can be used. For monomers, 0.05 to 100 ppm (weight) catalyst is used, preferably 0.1 to 100 ppm. The catalyst can be organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, etc. , Dibutyltin laurate, tin octoate, dibutyltin oxide, tin chloride, tin bromide, tin iodide and other tin compounds. For the purpose of preventing the coloration of the obtained object, the reaction is preferably carried out by flowing an inert gas such as nitrogen. ® The average molecular weight of the above-mentioned polyester polyols is 500 to 5,000, preferably 1,500 to 4,000. When the molecular weight is 5,000 or more, the soft segment has increased crystallinity and it is not easy to obtain a spandex fiber having satisfactory physical properties. The average molecular weight is measured by a hydroxyl value (J IS K 1 557). The content of the constituent unit of the polyester polyol of the present invention refers to the content of the polyester constituent unit formed by the (A) polyol component and adipic acid / the content of the constituent unit of the lactone (weight ratio) is 5/95 to 80/20 That is, each raw material is used at a ratio in this range. φ In the method for producing a polyurethane from a polyester diol and an organic isocyanate obtained as described above, the organic isocyanate used is the one described in the first aspect of the present invention. As the low-molecular-weight diol of the chain extender, the above-mentioned diol compounds of other polyols used in the present invention can be used. The diamine as the chain extender is the same as the first example of the present invention. The use of the polyurethane obtained by the above method is the use described in the first aspect of the present invention. In particular, in terms of washing resistance, it is preferable to use -29-200523293 for Spandex fibers. In the fourth method of the present invention, a spinning method for producing a spandex fiber from polyurethane is directly used in the first method of the present invention. The Spandex fiber provided by the present invention has excellent weather resistance and washing resistance. The general use form of the Spandex fiber, that is, the form of interlacing and interweaving of nylon and cotton is used. In particular, when cotton is used as the raw material, it is processed after cross-knitting or interlacing, that is, in an acidic or alkaline atmosphere, it has good weather resistance even if it is subjected to high-temperature scouring, bleaching, and mercerizing processes, and When it is used as a product, the weather resistance is hardly reduced even if it is repeatedly washed. An embodiment of the fifth invention will be described below. The polymer-like tertiary amine compound used in the present invention is a copolymer of a dialkylaminoethyl (meth) acrylate. More specifically, a dialkylethyl (meth) acrylate represented by the following general formula (1) is used as a copolymer. φ CH2 = CRCOOCH2CH2NR ° R ° (1) (where R represents hydrogen or methyl; R. represents alkyl having 1 to 4 carbon atoms) The specific type of monomer is diisopropylaminoethyl methacrylic acid Esters (DIPANM), dimethylaminoethyl methacrylate (DMAM), diethylaminoethyl methacrylate (DEAM), dimethylaminoethyl acrylate (DEAA), and the like. The most suitable monomer among these monomers is DIPAM. The amount of the monomer used is usually 60 to 90% by weight of the copolymer. It is preferably 70 to 80% by weight. -30- 200523293 • »In addition, the co-monomer that forms a copolymer with the dialkylaminoethyl (meth) acrylate used in the present invention has a reactivity represented by the following general formula (2) monomer. CH2 = CRC〇CH2CH2〇 [-c (= 0) (CRiR2) 〆. -] nH (2) (wherein R is hydrogen or methyl; x number! ^ 1 and R2 are each hydrogen or alkyl group having 1 to 12 carbon atoms; n ring-opening lactone chains may be the same as each other or Different. X is an integer of 4 ~ 7; the average 値 of η is 丨 ~ 5) _ If the average 値 of η is greater than 5, the solvent solubility of the obtained copolymer, the polyurethane resin, and the spandex composition The compatibility and other problems can cause problems. This reactive monomer is produced by reacting a lactone represented by the following general formula (3) with a monoacrylate or a monomethacrylate of ethylene glycol. r ~ Cc (=: 〇) (cR1R2) ___ (3) (where 'X R1 and R2 are independent hydrogen or an alkyl group having 1 to 12 carbon atoms; X is 4 to 7) The above formula (3) The lactones shown are ε-caprolactone, dimethyl-ε-caprolactone, monomethyl caprolactone, butyrolactone, (5-valerolactone, etc., among which £ _caprolactone , 4-methyl-ε-caprolactone and 3-methyl-ε-caprolactone are more preferred. A more specific manufacturing method is a catalyst having a content of about 200 ppm or less (preferably 100 ppm -31-200523293 or less). In the presence, the lactone is reacted with the monoacrylate or monomethacrylate of ethylene glycol. The catalyst used in the present invention is one or two kinds of organometallic compounds and other metal compounds such as chlorinated Tin compounds such as tin, tin bromide, tin iodide, dibutyltin oxide, or iron chloride, and other Lewis acids and protonic acids, etc. The preferred catalysts are tin chloride, tin titanate, and dibutyltin di Laurate, and other tin compounds; tetraisopropyl titanate and titanate of tetrabutyl titanate, etc. ® The reaction is at about 100 to 140 ° C (preferably about 1 1 0 ~ 1 3 0 ° C). The reaction can be carried out at atmospheric pressure, or under high or low pressure. The reaction is performed in an atmosphere where the oxygen concentration is adjusted to 4% to 8%. The polymerization of alcohol monoacrylate or monomethacrylate is preferred. The reaction time is about 2 to 30 hours, more preferably about 3 to 20 hours. This reaction is based on monoacrylate to prevent ethylene glycol. Or a suitable inhibitor of the polymerization of the double bond of the monomethacrylate is carried out. Such inhibitors are, for example, monomethyl ether of hydroquinone, benzoquinone, methylhydroquinone, 2,5-di-third-butane Quinone, hydroquinone, and other general free radical inhibitors known in the industry. The amount of inhibitor used is 1,000 ppm or less, preferably 800 ppm or less, and more preferably 600 ppm or less. The preferred specific examples are In the method of the present invention, the lactone is dispersed in an inert gas of nitrogen and the lactone is added to the reactor, and then the lactone is heated to a reaction temperature (about 100 to 140 ° C) to be performed. The lactone used is first added to the reaction The container is dried, for example, using a conventional agent such as a molecular sieve. DA-32-200523293 When or after the temperature is changed, the dispersion of the inert gas is changed to an atmosphere mixture whose oxygen concentration is adjusted to 4% to 8%. Other various methods can also be used. For example, the oxygen concentration in the system is adjusted to 4 % ~ 8% of the atmosphere mixture is dispersed within a short period of time, that is, within about 5 to 10 minutes, and then the dispersion is interrupted, and the gas phase space of the reactor is still full after the entire reaction. Dispersion of the inert gas is stopped, so that the entire reaction mixture is still filled in the system. Alternatively, the gas mixture is dispersed through the system, and an inert gas is used between the reactions to fill the gas phase space. These methods can also be combined as needed. The monoacrylate or monomethacrylate of ethylene glycol mixes the catalyst with the inhibitor, and the mixture is added to the heated lactone. Other methods can also be heated before the inhibitor is added to the lactone. In addition, after heating, a monoacrylate or a monomethacrylate of ethylene glycol is added, or all of the reactants are initially charged into the reactor and then reacted. Various methods can be used for adding lactone, acrylate or methacrylate, catalyst and inhibitor. φ The final reaction mixture is kept at the reaction temperature for about 2 to 30 hours. Further, the method is performed, for example, in the presence of a suitable solvent containing no active hydrogen or a polymerizable ethylenically unsaturated group. Such solvents include, for example, ketones, esters, ethers, aromatic and aliphatic hydrocarbons, and the like, or mixtures thereof. Preferred solvents are sol acetate esters. The method described in this specification is preferred. For 1 to 12 moles of lactone, ε · caprolactone and 4-methyl-ε-are used at a ratio of 1 mole acrylate or methacrylate. Caprolactone or 3-methyl-ε-caprolactone and mixtures thereof -33-200523293 react with the monoacrylate or methacrylate of ethylene glycol. These compositions may be solid or liquid, with the most preferred composition being a liquid. The most preferred composition is 1 to 5 moles of ε-caprolactone, 4-methyl-ε-caprolactone or 3-methyl-ε-caprolactone and mixtures thereof The ratio of monoacrylate or monomethacrylate of erythrylene glycol is such that ε-caprolactone, 4-methyl-ε-caprolactone or 3-methyl-ε-caprolactone and these mixtures with Monoethylene glycol or methacrylic acid ester of ethylene glycol is produced by reaction. The reaction mixture was recovered and used without purification. If desired, the reaction mixture can be refined by conventional methods such as vacuum stripping. The above-mentioned method for producing the copolymer of the present invention is described in Japanese Patent Application Laid-Open No. 2-86 6 55 of Rhoden, and is produced by a general radical solvent polymerization. The specific detailed production methods of these copolymers are described in the examples of the present invention. The copolymer of the present invention has an average molecular weight of 2,000 to 2,000,000, preferably 5,000 to 500,000, and a weight average molecular weight of 4,000 to 5,000 in terms of solubility in solvents and compatibility with polyurethane or φ spandex. 4000000, preferably 10000 ~ 1 000000. The copolymers of the present invention are most useful in polyurethane / spandex fibers. The present invention provides an improved polyurethane composition and a spandex composition containing an acrylonitrile copolymer containing a dialkylamino group. The additive-containing polyurethane and spandex composition not only has good resistance to deterioration and discoloration, but also is the same polymer as the conventionally known high molecular weight tertiary amine additive-34-200523293 additive. In comparison, it exhibits excellent processability and permanent stretching. The improved Spendex polymer composition of the present invention is based on segmented polyurethanes such as polyether, polyester, polyester polyether, etc. Make it. This Spandex polymer is known, and the methods disclosed in U.S. Patent Nos. 2,929,804, 3,097,192, 3,428,711, 3,533,290, and 3,555,115 are disclosed. Manufacturing. The composition of the present invention is the polyurethane composition and the spandex composition of the present invention, which is the most widely used spandex based on polyether. It is a polyol having hydroxyl groups at both ends and / or Polyester, organic isocyanate, and lower molecular weight chain extender with two active hydrogen diols, diamines, etc., are obtained in the presence of the required catalyst. Polyols such as ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, neopentyl alcohol, 1,4-butanediol, 1,6-hexanediethylene glycol Alcohol, 3-methyl-1,5-pentanediol, 1,8-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, 2-n-butyl-2- Ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol and 2,4 · diethyl-1,5-pentanediol, 1,2-hexanediol, 1,2 -Alcohol, Polyols such as ethylene oxide, propylene oxide, butylene oxide, and the like, and modified products thereof. These can be used singly or in combination of two or more kinds. The acid component of the polyester polyol is adipic acid. Other acid components such as glutaric acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, and 1,11-35 can also be used. -200523293 • »~ 1--Industrial di-residual acid, p-benzoic acid, isobenzoic acid, 5-sulfo sodium isobenzoic acid and other aliphatic or aromatic dicarboxylic acids. These other acid components may be used alone or as a mixture of two or more. The acid component of the raw material may be used in the form of an ester derivative or an acid anhydride. The organic diisocyanate is as described in the first aspect of the present invention. As the low-molecular-weight diol system as the chain extender, the diol compound described above can be used. The diamine system as a chain extender is the same as the first example of the present invention. The amount of useful additives for protecting the Spendex polymer in the present invention can generally be used in a wide range of 0.5% to 10% by weight of the Spendex polymer. Preferably, the concentration of the additive is 2 to 6% by weight. If it is less than 0.5% by weight, the effect is insufficient, and if it is more than 10% by weight, it does not have the characteristics of Spandex fibers, so it is not desirable. In the present invention, a method for adding a dialkylamino (meth) acrylate copolymer additive to a Spandex polymer can be a general method. For example, the solvent of the additive is prepared in the same solvent as that used when preparing the spinning solvent for Spindex. The solvent is added to the solution before the polymer is formed into a product such as a fiber or a film. The addition of the copolymer of the present invention is a general form of the addition method disclosed by Hande (US Patent No. 3,428,711), and can refer to the disclosure. The spandex polymer composition of the present invention may contain various additives depending on the purpose. Among these additives, pigments or delustering agents (such as titanium dioxide), anti-blocking agents or smoothing agents (such as magnesium stearate and stearic acid-36-200523293 »Μ brocade), white enhancers ( Such as ultramarine), tinctures (such as talc). In addition to the useful uses of fibers and films, the polyurethanes containing the dialkylamino (methyl) propionate copolymers of the present invention can also be used in applications such as artificial leather. An embodiment of the sixth invention will be described below. In addition to the branched aliphatic diols exemplified in the second aspect of the present invention, the aliphatic diols used in the present invention include, for example, non-branched aliphatic diols exemplified as secondary components of the second diol of the present invention . These can be used alone or in combination of two or more. In the present invention, the acid component of the polyester polyol is an aliphatic dicarboxylic acid having a carbon number of 9 to 12, such as azelaic acid, sebacic acid, dodecanedioic acid, and 1, η · 丨 monocarboxylic acid. Wait. Among them, azelaic acid, sebacic acid and dodecanedioic acid are preferred. In addition, as long as the effect of the present invention is not impaired, glutaric acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, φ undecanedicarboxylic acid, and p-benzene can be used as other acid components. Aliphatic or aromatic dicarboxylic acids such as formic acid, isobenzoic acid and 5-sulfo sodium isobenzoic acid. These other acid components may be used singly or in a mixture of two or more kinds with an aliphatic dicarboxylic acid having 9 to 2 carbon atoms. The acid component of the raw material may be used in the form of an ester derivative or an acid anhydride. The other components constituting the polyester polyol of the present invention are the same ε-caprolactone as in the first aspect of the present invention, and other lactones similar to the first aspect of the present invention may be used as auxiliary components. -37- 200523293 The method for producing the polyester polyol of the present invention may be the same as that described in the first aspect of the present invention. The content of the polyester polyol constituting unit of the present invention is a content of a polyester constituting unit using an aliphatic diol and an aliphatic dicarboxylic acid having a carbon number of 9 to 12 / ε-caprolactone constituting unit content ( The weight ratio is 5/95 to 80/20 (preferably 20/80 to 80/20), that is, each raw material is used in a proportion within this range. The same applies when poly? -Caprolactone is used. The polyester diol thus obtained has an average molecular weight of 500 to 5,000, preferably 1,500 to 4,000. When the molecular weight is 5,000 or more, the soft segment crystallinity is increased, and it is difficult to obtain a spandex fiber having satisfactory physical properties. The average molecular weight can be measured by a hydroxyl value (J IS KK 1 5 5 7). The production method of the polyurethane obtained from the polyester diol and the organic isocyanate obtained above and the organic isocyanate used are as described in the first aspect of the present invention. As the above-mentioned low-molecular-weight diol as a chain extender, the branched aliphatic diol of the present invention or the above-mentioned unbranched diol compound which can be used therewith can be used. The diamine as the chain extender is the same as the first example of the present invention. The polyurethane obtained by the above method can be used in various applications for general polyurethanes, such as thermoplastic elastomers, hard or soft urethane foams, adhesives, spandex fibers, Synthetic leather, paint, etc., but used in artificial leather is preferred. In addition, in the form of the polyurethane used in the present invention for the artificial leather, a solvent-based urethane or a water-based urethane can be used, and both of them will be described below. -38- 200523293 The solvent-based polyurethane used in the present invention is preferably a compound with a coefficient of 15% to 150cm2 when stretched to 00%, and more preferably 15 to 70kg / cm2 . If the coefficient at 100% stretching is less than i5kg / cm2, the durability of the obtained sheet is not good and the vertical stretching is intense during the extraction and removal process of the sea ingredients, making industrial production difficult. On the other hand, if the coefficient at 1000% is greater than 150 kg / cm2, it is difficult to obtain an artificial leather with high density, low reflectivity, and good texture, which is the object of the present invention. Since the polyurethane used in the present invention is impregnated in the fabric, it can be used as a solution. Preferred solvents at this time include, for example, dimethylformamide, dimethylacetamide, dioxane, and tetrahydrofuran. The polyurethane impregnated in the present invention is coagulated with a non-solvent, that is, a wet coagulation method must be used. In the case of non-solvent coagulation, a method of impregnation and drying to remove the solvent is used. In other words, the dry coagulation method has a very hard texture and cannot obtain a low anti-hair feeling, so it is not desirable. A typical example is a liquid in a coagulation bath when the polyurethane is wet-set, such as water or a mixed solution of water and the above-mentioned solvent. In addition, the solvent used for extracting and removing the matrix component of the ultrafine fiber-generating fibers includes, for example, aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as trichloroethylene, tetrachloroethylene, and carbon tetrachloride. Wait. Various additives used in conventional polyurethanes can be added to the polyurethane used in the present invention, such as flame retardants such as phosphorus compounds, halogen-containing compounds, antioxidants, ultraviolet absorbers, and pigments. , Dyes, plasticizers, etc. However, in the process of extracting the resin component of the matrix, it will be extracted at the same time. '-39- 200523293 Even if it is added, its effect cannot be exhibited. The cloth used in the present invention is not particularly limited, and a non-woven cloth or a woven cloth can be used. Among them, a three-dimensionally complexed non-woven fabric is preferred. The fibers constituting the fabric are ultrafine fiber-generating fibers having an island structure using a thermoplastic resin that can be removed by solvent extraction as a matrix resin component and a fiber-forming thermoplastic resin as an island component. The resin used for the island component is, for example, polyamide resin or polyester resin, and the thermoplastic resin used for the solvent-extractable base component is, for example, polyolefin, polystyrene, or modified polyethylene.

More specifically, specific examples of the island component resins used in the present invention include 6-Nylon, 6,6-Nylon, 6,1 0-Nylon, 1 2 -Nylon, and other aromatic groups. Spinnable polyamide, poly (p-phenylene benzoate), poly (butylene terephthalate), sulfoisobenzoic acid-modified poly (p-phenylene benzoate), sulfoisobenzoic acid-modified poly (p-phenylene) Resin such as butene benzoate. In addition, the polymer constituting the number of components of the matrix is a resin that has a different solubility from the island component in the solvent and has less affinity with the island component, and has a lower melt viscosity than the island component resin under spinning conditions. Ethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ethylene-α-olefin copolymer, polystyrene, styrene-isoprene copolymer, styrene- Hydrogenates of isoprene copolymers, styrene-butadiene copolymers, hydrogenations of styrene-butadiene copolymers, modified polyethylene glycols, modified polyesters, etc. A method for producing a fiber made of an island component and a matrix component resin is, for example, mixing -40-200523293 island component resin and a matrix component resin at a predetermined mixing ratio and dissolving them in the same gluten solution system to form a mixed system for spinning. Method, or a method of dissolving each with a different dissolving system and joining two polymers in the same direction with a spinner needle head, splitting, and repeating several times to form a mixed system for spinning, or dissolving with a different dissolving system and using The spinning machine mold part specifies the shape of the fiber so that the two polymers are combined into one to spin. The proportion of the island component resin in the fiber is preferably 40 to 80% by weight, and the number of ultrafine fiber components in the cross section of the fiber is 5 or more, and more preferably 50 to 10,000. The ultra-fine fiber-generating fibers spun in this way can be subjected to general fiber treatment processes such as drawing and heat-fixing as required, and the fiber fineness is 2 to 15 denier, and the average fineness of the ultrafine fiber component is 0.2 denier. Fibers having a density of less than or equal to 0.1 denier and more preferably 0.001 or more denier. The ultrafine fiber-forming fibers obtained in this manner are cut and defibered, and then passed through a net to form random waves or intersecting filaments, and the resulting fiber waves are laminated to a desired weight and thickness. Then, the fiber wave is subjected to a complexing treatment of φ with a pinhole, water spray, air spray, or the like by a conventional method to form a fiber-entangled nonwoven fabric. Of course, it is also possible to use ultra-fine fiber-generating fibers to form spin yarns by a general method, and to form multi-filament yarns as knitted fabrics. Alternatively, it may be a laminated non-woven fabric or a woven fabric. When the fibrous substrate has excellent fullness and good texture, it is better to have a density of 0.2 to 0.5 g / cm3 before the polyurethane impregnation, and the more preferable is 0.25 to 0.40 g / cm3. . If the density of the fibrous substrate is less than 0.2 g / cm3, the surface smoothness of the obtained sheet is not good. If the density is greater than 0.5 g / cm3, the obtained -41-200523293 ginseng can not obtain a full feeling and good texture due to the high density of the object of the present invention. The sheet of the artificial leather of the present invention is made of a cloth made of bundles of ultrafine fibers and a polyurethane is present in its internal space, but the polyurethane is present in the bundle of ultrafine fibers and extremely fine It is preferable that the fiber bundles are not substantially present between the ultrafine fiber bundles. When there is substantially no polyurethane in the ultrafine fiber bundle, since the ultrafine fibers are not fixed by the polyurethane, the obtained sheet is rich in solidity, and the obtained sheet has a fiber B dimension. It fully releases from polyurethane, so it does not have a rubber-like anti-hairy feeling, and a soft texture can be obtained. In the sheet of the present invention, the ratio of polyurethane in the sheet is preferably 15 to 60% by weight, and more preferably 25 to 50% by weight. When the proportion of polyurethane is less than 15% by weight, the change in physical properties such as surface strength over time becomes large, and there is a feeling of cracking and paper-like feeling when touched by hand. When the polyurethane ratio is more than 60% by weight, the surface of the obtained sheet is not smooth enough and the texture becomes hard. p The polyurethane-impregnated cloth obtained by the above method is coated with a resin by spraying or gravure coating to form a surface layer, or the resin layer formed on the release paper is integrated with the cloth. Methods, etc., to obtain a natural leather panel with silver surface. Furthermore, the surface of the cloth is impregnated with polyurethane, and the mat is treated with sandpaper or the like to obtain a suede sheet. In addition, when a polyurethane emulsion produced using the specific polyester polyol of the present invention is applied to artificial leather, it is applied with a polyurethane produced by a polyester polyol obtained by a condensation reaction of a dibasic acid and an alcohol. Compared with artificial leather of ester emulsion, it has improved hydrolytic resistance when compared to -42- 200523293 fistula. It is made with polyether polyols using polyalkylene oxide glycols or oxyalkylene adducts. Compared with the artificial leather of polyurethane emulsion, it has excellent hydrolytic resistance and heat resistance. Furthermore, the artificial leather having a polyurethane emulsion produced using the specific polyester diol of the present invention has a soft texture. In short, when using the specific polyester diol of the present invention, it is possible to obtain a very excellent artificial leather with satisfactory physical properties. [Embodiment] ® In the following, examples 1 to 5 of the present invention will be described more specifically by examples and the like, but the present invention is not limited by these. In addition, the "part" of an Example and a comparative example means "weight part." The following is a first embodiment of the present invention. The compounds used in the examples and comparative examples are abbreviated. The relationship between the abbreviation and the compound is shown in Table 1-1. In the following examples, the strength retention rate, 200% stress, and 200% stress retention rate were measured by the following methods. φ (1) Strength retention rate: {breaking stress after alkali treatment ("treatment strength" in the table) / breaking stress ("strength" in the table)} X100 (2) 200% stress: stress at 200% elongation (3) 200% stress retention rate: (200% stress / 200% stress after alkali treatment) X100 -43- 200523293

Table 1-1 Abbreviated compound BEPD 2-n-butyl-2-ethyl-1,3-propanediol DEPD 2,2-diethyl-13-propanediol DBND 2,4-diethyl-1,5-pentyl Di_ AA Adipic acid CL £ -caprolactone NPG neopentyl alcohol BD 1, 4-butanediol HD 1,6 ~ adipic acid ·? M PD 3 -methyl-1,5-pentanediol. The evaluation of the alkali hydrolysis resistance of the obtained polyurethane elastic fibers was performed in the following alkaline atmosphere. (Alkali Hydrolysis Resistance of Polyurethane Elastic Fibers) Polyurethane fibers were immersed in a 60 g / L sodium hydroxide aqueous solution at 98 ° C for a fixed length for 30 minutes to evaluate the polyamine The strength retention rate of formate fiber and 200% stress retention rate. -44-200523293 (Examples 1 -1 to 1 -10) 101 parts of polyester polyol having an average molecular weight of 2 0 0 with a composition shown in Table 1-2 heated and melted at 80 ° C, 39 parts of warp The molten MDI (4, 4, diphenylmethane diisocyanate) and 9.5 parts of BD heated at 45 ° C were continuously supplied to the biaxial extruder by a dosing pump, and were continuously performed at 24 ° C. The polymer was melt-polymerized, and the produced polyurethane was extruded into a monofilament form and then cut into pellets. The pellets were dried under a nitrogen gas flow of 80 t for 24 hours. The pellets were spun on a spinning machine with a uniaxial extruder at a spinning temperature of 2 17 ° C and a spinning speed of 600 m / min to obtain a polyurethane elasticity of 40 denier and monofilament. fiber. Using this polyurethane fiber, various physical properties and alkali hydrolytic resistance were evaluated. The results are shown in Tables 1-3. At all times, it has good silk properties and alkali hydrolysis resistance. (Comparative Examples 1-1 to 1-7) Except using at least one member selected from the group consisting of 2-n-butyl-2-ethyl-1,3-propanediol and 2,2-diethylene as shown in Table 1-3. Of -1,3-propanediol and 2,4-diethyl-φ 1,3-pentanediol and the composition of the polyester constituting adipic acid and the content of the polyester / ε-caprolactone Polyurethane elastic fibers were prepared in the same manner as in Examples except for polyester polyols having a unit content (weight ratio) of 5/95 to 80/20, and silk properties and alkali hydrolytic resistance were evaluated. The results are shown in Table 3. -45- 200523293 Composition ratio of diol (mol%) PE (wt ° / 〇) CL (wt ° / 〇) BEPD DEPD DEND NPG ED BD HD glycol / AA CL Example 1-1 100 40 60 Example 1 · 2 100 40 60 Example i-3 100 40 60 Example 14 100 20 80 Example 5 100 60 4Γ Example 1-6 100 80 20 Example 1-7 50 50 40 60 Example 1-8 50 50 40 60 Example 9-50 50 40 60 Example 1050 50 40 60 Comparative Example M 30 70 100 0 Comparative Example 1-2 50 50 100 0 Comparative Example 1-3 100 40 60 Comparative Example M 100 100 0 Comparative Example 1-5 100 100 0 Comparative Example K 0 100 Comparative Example 7 100 95 5 In the table, PE (wt%) represents a polyester unit obtained from various diol components and a dicarboxylic acid, and CL represents e- The weight ratio of the caprolactone constituent units. -46- 200523293 Table 1-3 Strength m Elongation (%) 200% Stress (g / d) Alkali treatment strength f (g / d) Retention rate (%) 200% Stress and force (g / d) Retention rate ( %) Example 1 1.56 510 036 1.45 93 0.33 92 Example 1.54 514 036] · 46 95 0.34 94 Example 3 3, 58 518 036 L50 95 0.34 94 Example L65 504 039 135 82 032 82 Example 1- 5 1.50 528. 034 138 92 0.31 90 Example κ 1.40 547 0.32 1.37 98 031 96 Example 1-7 1.41 513 033 1 · 27 — 90 0,29 89 Example 1-8 L48 521 0.32 1.30 88 .0.28 86 Implementation Example 1-9 1.52 '' 524 0-34 1.35 89 0,29 86 Example M0 1.58 512 0.36 1.45 92 032 88 Comparative Example 1_1 L28 460 0.32 L10 86 0.26 82 Comparative Example 1-2 L19 512 0.28 0.98 82 0.23 82 Comparative Example W L52 518 0,35 0,99 65 65,22 63 Comparative example 14 0.75 320 0,12 0 · 56 75 0,09 72 Comparative example 1_5 1.76 405 0.44 0.97 55 0.23 53 Comparative example P6 1.79 1 402 0.47 0.98 55 0.25 53 Comparative Example 1 "7 L29 458 0.33 1.10 85 0.27 81 As can be seen from Table 1-3, at least one selected from 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl -1,3-propanediol and 2,4-diethyl The content of the polyester constituting a group of diols formed from a group of 1,5-pentanediol and adipic acid / the content of the constituting unit (weight ratio) of ε-caprolactone is 5/95 to 80/20 Polyurethane elastic fibers of Examples 1-1 to 1-10 of polyester polyols, compared with the comparative examples, have significant strength after alkaline hydrolysis and no stress reduction at 200% elongation. Satisfactory silk properties. The second embodiment of the present invention will be specifically described in the following examples. In addition, the compounds used in the examples and comparative examples are abbreviated. Jan-47-200523293 0 · 1 household catty The strength retention rate and 200% stress N. 7 are the same as the first of the present invention. Table 2-1 Abbreviations ^^ Compound BEPD ^ __ 2-n-butyl ~ 2 ▽. &Amp; ~ 1, 3 ~ propylene glycol MPD 3-methyl ~ 1, 5 '! Gediol DEND 2, 4 ~ — Acetyl-r 1, pentadiol AA Adipic acid DA ----- Sebacic acid DD A ---------- Dodecanedioic acid CL ε -caprolactone BD 1,4- Butanediol HD 1 > 6-hexane

The relationship between the compound and the compound is shown in Table 2 and the measurement of the 200% stress retention rate. The evaluation of the alkali hydrolytic resistance of the obtained polyurethane elastic fiber is the same as that of the first invention. (Example 2-1 to 2-10) 101 parts of the composition shown in Table 2-2 were melted by heating at 80 ° C. The average molecular weight was -48- 200523293 polyester polyol with an amount of 2000 and 39 parts at 45 ° C. The melted MDI (4, 4, diphenylmethane diisocyanate) and 9.5 parts of BD were each continuously supplied to a biaxial extruder by a dosing pump, and continuous melt polymerization was performed at 240 ° C, so that The produced polyurethane was extruded into water in a monofilament shape and cut into pellets. The pellets were dried at 80 ° C under a stream of nitrogen for 24 hours. The pellets were spun on a spinning machine of a uniaxial extruder at a spinning temperature of 2 17 t and a spinning speed of 600 m / min to obtain 40 denier, monofilament polyurethane elastic fibers. Using this polyurethane fiber, various physical properties and resistance to alkali hydrolysis were evaluated. The results are shown in Table 2-3. At all times, it exhibits good silk properties and alkali hydrolysis resistance. (Comparative Examples 2-1 to 2-7) Except the use of a polyester constituting unit content of a branched diol and an aliphatic dicarboxylic acid having a carbon number of 10 to 12 as shown in Table 2-2 / ε -Polyurethane elastic fibers were prepared in the same manner as in the examples except for polyester polyols with a content (weight ratio) of caprolactone of 5/95 to 80/20, and silk properties and alkali resistance were evaluated. Water-decomposable. The results are shown in Table 2-3. -49- 200523293 Table 2-2 Acid component PE (wt%) CL (wt%) BEPD MPD DEND BD HD Diol MH CL Example 2-1 100 DA 40 60 Example 2-2 100 DA 40 60 Example 2 -3 100 DA 40 60 Example 100 DA 20 80 Example 2-5 100 DA 60 40 Example 2-6 100 DA 80 20 Example 7 7 100 * DDA 40 60 Example 2-8 50 50 DA 40 60 Implementation Example 9 9 50 50 DA 40 60 Example 2-10 50 50 DDA 40 60 Comparative Example 2-1 30 70 ΑΑ 100 0 Comparative Example 2-2 50 50 ΑΑ 100 0 Comparative Example 2-3 100 100 ΑΑ 40 60 Comparative Example 24 100 ΑΑ 100 0 Comparative Example 2.5 5 ΑΑ 100 0 Comparative Example 6 ΑΑ 0 100 Comparative Example 2-7 100 ΑΑ 95 * 5 In the table, PE (wt%) indicates that it is obtained from various diol components and dicarboxylic acids. The polyester constituting unit, CL represents the weight ratio of the constituent unit of caprolactone. -50- 200523293 Table 2-3 Strength _ Elongation (%) 200% Stress m Alkali treatment strength m Retention rate (%) 200% Rattan force (g / d) Retention rate (%) Example 2-1 L55 508 036 1.43 92 0.33 91 Example 2 1.52 513 036 1. ^ 11 93 0.33 92 Example 2-3 1.51 516 036 1,4--0 93 0.33 92 Example 24 L61 502 039 1,43 89 0.34 87 Example 2- 5 1.48 519 0.34 135 91 0.30 89 Example 2-6 1.42 526 0.32 132 93 030 93 Example 2-7 1.48 527 0.33 1.36 92 030 91 Example 8 1A2 530 0.32 1.26 89 01 88 Example 9 9 1.52 516 034 1 · 32 87 0.30 88 — Example 2-10 1.48 508 0.36 1.35 91 0.31 85 Comparative Example 2-1 1,28 460 0.32 1.10 86 0.26 82 Comparative Example 2-2 L19 512 0.28 0.98 82 0.23 82 Comparative Example 2-3 1.52 518 0.35 0 · 99 65 0.22 63 Comparative Example 24 0.75 320 0.12 0,56 75 0.09 72 Comparative Example 2-5 1.76. 405 0.44 0.97 55 0,23 53. Comparative Example 2-6 L79 402 0.47 0,98 55 0.25 53 Compare Example 2-7 1.29 458 0.33 1,10 85 0.27 81 As can be seen from Table 2-3, the content of the unit constituting the polyester using a branched chain diol and an aliphatic dicarboxylic acid having a carbon number of 10 to 12 is ε Of caprolactone The polyurethane elastic fibers of Examples 2-1 to 2-10 of the polyester polyols having a unit content (weight ratio) of 5/95 to 80/20 were compared with the comparative examples. With significant strength and no stress reduction at 200% elongation, satisfactory silk properties can be obtained. The third embodiment of the present invention will be specifically described in the following examples. The compounds used in the examples and comparative examples are abbreviated. The relationship between the abbreviation and the compound is shown in Table 3. The method of measuring the strength retention rate, 200% -51-200523293 stress and 200% stress protection ratio is the same as the first method of the present invention. Table 3-1

Abbreviation ---- ^^ BEPD 21-butyl-2-ethyl ~ 13_propanediol DEPD ~ ---- 2,2-diethyl-1,3 ~ propane_DEND 2,4- Diethyl-1,5-glutarylene, AA, adipic acid, CL, caprolactone, NPG, neopentyl alcohol, BD, 1,4-butanediol, HD, 1,6-hexanediol, M PD 3-methyl- 1,5-Glutaric acid Further, the evaluation of alkali hydrolysis resistance of the obtained polyurethane elastic fiber was the same as that of the first aspect of the present invention. (Examples 3-1 to 3-7) The average molecular weight of the composition shown in Table 3-2, which was melted at 80 ° C, was 101 parts -52- 200523293, and the polyester polyol having the amount of 2 0 0, 3 Nine parts of MD I (4,4, -diphenylmethane diisocyanate) and 95 parts of BD heated and melted at 45 ° C were continuously supplied to the biaxial extruder by a dosing pump, and the temperature was 2 4 0 Continuous melt polymerization was performed at ° C, and the generated polyurethane was extruded into water in a monofilament shape, and cut into pellets. The pellets were dried at 80 ° C under a stream of nitrogen for 24 hours. The pellets were spun on a spinning machine of a uniaxial extruder, with a spinning temperature of 21 ° C and a spinning speed of 60 0 m / min, to obtain a polyurethane elasticity of 40 denier and monofilament. fiber. Using this polyurethane fiber, various physical properties and resistance to alkali hydrolysis were evaluated. The results are shown in Table 3-3. At all times, it has good silk properties and alkali hydrolysis resistance. (Comparative Examples 3-1 to 3-7) The same as the Example except that the polyester polyols without 2,4-diethyl · 1,5-pentanediol as shown in Table 3-2 were used. The polyurethane elastic fibers were prepared by the method described above, and the silk physical properties and alkali hydrolytic resistance were evaluated. The results are shown in Table 3-3.

-53- 200523293 Table 3-2

Composition ratio of diol (mol%) BEPD DEM) DBND NPG ED BD HD Examples 3-1 10 90 Examples 3-2 3 0 70 Examples 3-3 50 50 Examples 3-4 7 0 30 Examples 3-5 3 0 4 0 30 Example 3-6 30 4 0 30 Example 3-7 50 30 40 3 0 Comparative Example 3-1 30 70 Comparative Example 3-2 50 50 Comparative Example 3-3 100 Comparative Example 3-4 10 0 Comparative Example 3-S 1 0 0 Comparative Example 3-6 100 Comparative Example 3-? 100 -54- 200523293

w I Table 3-3 Strength (g / d) Elongation (%) 200% Stress _ Alkali _ — Treatment strength (g / d) Retention rate (%) 200% Stress _ Retention rate (%) One Example 3- 1 1.65 504 039 L35 82 0.32 82 one example 3-2 1.50 528 0.34 1.38 92 _ 0 · 31 90 one example 3_3 1.40 547 0.32 1.37 98 0.31 96 one example 34 1 Λ1 513 033 1.27 90 0.29 89 example 3-5 1,56 510 0.36 1.45 93 033 92 one example 3-6 1.54 514 0.36 1,46 95 034 94 _ example 3-7 1.58 513 0.36 1.50 96 034 94 one comparative example 3-1 1.28 460 0.32 UO 86 0 * 26 82 A comparative example 3-2 L19 512 0.28 0.98 82 0,23 82 Comparative example 3-3 1.52 518 0.35 0.99 65 0.22 63 A comparative example 34 0.75 320 0.12 0.56 75 0.09 72 A comparative example 3-5 1 , 76 405 0.44 0.97 55 0.23 53 Comparative Example 3-6 1.79 402 0.47 0.98 55 0-25 53 Comparative Example 3-7 L29 468 0.33 L10 85 0.27 81 As can be seen from Table 3-3, the polyester is used to form the polyester. For the diol component of the diol, the polyurethane elastic fibers of Examples 3-1 to 3-7 containing 10 to 70 mol% of the polyester diol were compared with the comparative example. With significant strength And there is no stress reduction at 200% elongation, and satisfactory silk properties can be obtained. The fourth embodiment of the present invention will be specifically described in the following examples. (Synthesis Example 4-1) A glass flask equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer was charged with 129 · 39 bis (3-(2H-benzotriazol-2-yl) -4 · hydroxyl -Phenylethanol) A Institute (trade name "MBEP", manufactured by Otsuka Chemical Co., Ltd.), 170.3g ε -55- 200523293 -caprolactone, 50ppm mono-n-butyltin fatty acid salt (trade name "SCAT_24", Sankyo Mechanical synthesis (stock) system). The reaction temperature was maintained at 15 ° C (6 hours after rc), and the reaction was terminated when the ε-caprolactone concentration in the reaction solution was determined to be 0.43% by gas chromatography. The acid value of the reactant was obtained (1112) ^ 〇11 / 2) is 丨 .8, the viscosity is 2 645CP / 60 ° C, the number average molecular weight (MN) by GPC analysis is 1391, the weight average molecular weight (_) is 1688, mw / MN = 1.213 room temperature (Synthesis Example 4-2) ® Using the same apparatus as in Synthesis Example 4-1, and adding 93.79 bis (3- (2H-benzotriazol-2-yl) -4-hydroxy-phenylethanol) Methane (trade name "MBEp", manufactured by Otsuka Chemical Co., Ltd.), 206.3 g ε-caprolactone, 50 ppm mono-n-butyltin fatty acid salt (trade name "SCAT-24", manufactured by Sankyo Organic Synthesis Co., Ltd.) After the reaction temperature was maintained at 150 ° C for 6 hours, the reaction was terminated when the ε-caprolactone concentration in the reaction solution was determined to be 0.55% by gas chromatography. The acid value (mgKOH) of the reactant was obtained / g) A room temperature solid compound with a viscosity of 2.5, a viscosity of 987CP / 60 I ° C, a GPC analysis of a number average molecular weight (MN) of 2017, and a weight average molecular weight (MW) of 2465 'MW / MN = 1.222. Example 4-1) ε-caprolactone-modified polyol and adipic acid obtained from Synthesis Example 4-1 or 4-2, or MBEP and adipic acid used in Synthesis Example, each producing a polyester Polyol, and the polyester polyester and the melted MD I (4,4 · -diphenylmethane diisocyanate) and BD (1,4-butanediol) are continuously supplied by quantitative pumps. The biaxial extruder was continuously melted and polymerized, and the generated polyurethane was mono-56- 200523293. The filament was extruded into water and cut into pellets. The pellets were allowed to stand at 80 ° C under a stream of nitrogen. The pellets were dried for 24 hours. The pellets were spun with a spinning machine of a uniaxial extruder, a spinning temperature of 217 ° C, and a spinning speed of 600 m / min to obtain 40 denier and monofilament polyurethane. Ester elastic fiber. Since the polyurethane fiber has an ultraviolet absorbing group in the constituent molecule, the polyurethane fiber has superior weather resistance and washing resistance as compared to a spandex fiber with an ultraviolet absorber. The following examples are based on this. Detailed description of the fifth invention. Test Method ® The following methods are used to determine various properties and parameters of the copolymer of the present invention. (1) Evaluation of Solvent Solubility The polymer solutions shown in Examples 5-1 to 5-6 and Comparative Examples 5-1 to 5-2 were produced, and the solution was cooled to room temperature (2 5 °) by observation. C) Appearance at the time of white turbidity is poor, transparent solution is better. (2) Production of test sample To evaluate the suitability of the polymer additive for Spandex, a thin film sample of polymer containing the additive was prepared. When a thin film sample was prepared, a polymer solution was prepared by substantially the method described in Example 5-1. Then, the polymer solution was completely mixed with 20 g of a N, N-dimethylvinylamine solvent containing a desired amount of a test additive. The polymer solution containing the additive was allowed to stand for 30 minutes. Then, using a spatula with a lid having a width of 0.5 cm, the film was cast on a "Mylar" polyester sheet. A ν, N-dimethylvinylamine solution was cast into a mold ' to obtain a test sample having a size of about 20.3 cm / 8.9 cm. After the film of this • 57-200523293 mold was air-dried for 24 hours, the test sample was peeled from the "buy and pull" sheet. After the thin film sample was produced, the sample was immersed in a water bath. To make an aqueous bath, the sample was immersed in 80 to 8 5 t of 8 g "Duponol (Duponol)" anionic surfactant (diethanolamine laurel manufactured by DuPont Co., Ltd. Salicylic acid ester), 5 g of pyrrolyl 3 · sodium tetrauric acid and 1.5 g of ethylenediaminetetraacetic acid in a 2 liter 80-85 ° C water bath for 1 hour. After the sample was taken out of the bath, the bath additive was washed to remove trace amounts, and the washing was repeated until it could not be detected from the water and became clean water. Example 5-1 Production of a copolymer (copolymer) of a dialkylaminoethyl (meth) acrylate and a monomethylpropionate of ethylene glycol of ε-caprolactone A 300cc four-necked double flask with a thermometer, a dropping funnel, and a nitrogen supply device. First, the flask was sufficiently replaced with nitrogen, and 259 dimethyl vinylamidine (DM A c) was added to increase the temperature in the flask. It is heated at a temperature of 8-5. Then, the following weight components were dropped into the flask at a uniform rate over 4 hours. 2,2-Aromatic bis-2-methylbutane (six 31 ^^): 0.6752 diisopropylaminoethyl methacrylate (DIPAM): 45g black cell FM2D (monomethyl glycol Ε-caprolactone adduct of methacrylic acid ester: manufactured by Laixilu Chemical Co., Ltd.): 15 g of dimethylvinylamine (DMAC): 15.4 g. The dropwise reaction was stopped for 4 hours, and then After the ripening reaction was performed at 85t for 1 h-58-200523293 hours, 0.65 g of ABN-E was added to the flask. Then, the reaction was carried out at 85 ° C for 3 hours. When the solid content concentration (N.V.) of the content is 57.1%, the molecular weight of the polymer is measured by gel permeation chromatography (GPC), and the following results can be obtained. Furthermore, in order to evaluate the solubility of DMAc, when the appearance was observed at room temperature (25 ° C), it was found that the resulting solution was transparent and had good solubility. Average molecular weight Mη: 13700 Weight average molecular weight Mw: 46100 ^ Molecular weight dispersion Mw / Mn: 3.36 Example 5-2 ~ 5-6 Ethylene glycol of dialkylaminoethyl (meth) acrylate and ε-caprolactone The production of the monomethacrylate copolymer (copolymers 2 to 6) was performed in the same manner as in Example 5-1 except that the dropping solution composition shown in Table 5-1 was used, to obtain copolymer 2 to 6. In addition, the solid content concentration of the obtained solution, the results of GPC analysis (for those who cannot be measured are because the tortuosity is too close to the solvent, so it cannot be detected), and the solubility in DMAC is shown in Table 5-1. Comparative Examples 5-1 to 5-2 Dialkylaminoethyl (meth) acrylate copolymers (comparative copolymers 1 to 1) without mono-methacrylate of ethylene glycol without ε-caprolactone 2) Manufacturing. Except having used the dripping solution composition shown in Table 5-1, the same operation as Example 5-1 was performed, and the comparative copolymers 1-2 were obtained. The solid content concentration of the obtained solution, the results of GPC analysis, and the solubility in DMAc are shown in Tables 5-1-5-200523293. Examples 5-7 to 5-12, Comparative Examples 5-3 to 5-4 Copolymerization of Dimethyaminoethyl (meth) acrylate and Ethyl-caprolactone-containing ethylene glycol monomethacrylate Evaluation of the heating and curing efficiency of the Spendex film as an additive (copolymers 1 to 6), making the segmented polyurethane N, N-dimethylvinylamine solution according to US Patent No. 3,428, 71 The general method described in No. 1 (for example, the first text of the embodiment II and the description of the embodiment) is manufactured. # Make ρ, ρ'-methylene diphenyl diisocyanate and polytetramethylene ether alcohol (molecular weight of about 1 800) sufficiently mix at a molar ratio of 1. 63 to prepare a mixture at about 80 to 90 ° C. Maintain 90 to 100 minutes at temperature to produce isocyanate-terminated polyethers (ie, end-treated alcohols with an NCO content of 2.4%), cool to 60 ° C, and mix with N, N-dimethylvinylamine to form solid About 45% solution. Then, mix vigorously and bring the end-treated alcohol to about 75. (: At a temperature of 2 to 3 minutes, react diethylamine and ethylenediamine with a molar ratio of 90/10 and 1,3-cyclohexanediamine 0 chain extender. Diamine chain extender and diethylamine The molar ratio is 6.3. The unreacted segmented polyurethane solution of the diamine chain extender and the end-treated alcohol contains about 36% solids and has a viscosity of about 2100 poise at 40 ° C. Disperse various additives in dimethylvinylamine solvent, and then completely mix with the polymer solution to prepare the final film with the solid content of the copolymers 1 to 6 obtained in Examples 5-1 to 5-6 to 2%, 3% zinc oxide, sterically hindered phenolic antioxidant (2, 4, 6-ginseng (2, 6-dimethyl-4- 3rd-butyl-) 3-Hydroxybenzyl) isocyanate) 5%. Polysilicon-60- 200523293 Oxane oil 0 · 0 1% concentration solution, all concentrations here are based on the weight of the Spendex polymer The film mold of the solution prepared in this way was washed with a known aqueous solvent before the test. The heating and curing efficiency was measured. The results are shown in Table 5-1.

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Table 5-1 Examples Comparative Examples 5-1 5 · 2 5-3 5-4 5-5 5-6 5-1 5-2 Initial stretching DMAc 25 25 25 25 25 25 25 25 Drop composition DMAc 15.4 15.4 15.4 15.4 15.4 15.4 15.4 15,4 'ABN-E 0,675 0.675 0300 0,675 0.675. 0.675 0.675 0.675 DIPAM 45 45 45 45 45 DEAM 45 DMAM 45 DMAA 45 PCI / FM2D 15 7.5 15 15 15 15 n-decyl ~ MA 15 lauryl-MA 7.5 15 After adding ABN-E 0.675 0.675 •; 0.675 0.675 0.675 '0.675 0,675 0.675 N, Y (%) 57.1 58.3 57.8 56.9 59.7 58.2 57.7 58.8 Mn 13700 12500 14000 THF-based GPC cannot be measured THF-based GPC cannot be measured 14500 12700 Mw 46100 33800 246000 32700 29800 Mw / Mn 3.36 2.70 17.6 2.26 234 Examples Comparative Examples 5-7 5-8 5-9 5-10 5-11 5-12 5-3 5-4 DMAc has good solubility Jia Jia Jia Jia Jia Poor Poor HSE (more than 70% is good) 82 80 85 78 76 75 80 81 DIPAM: Diisopropylaminoethyl methacrylate DMAc: Dimethylacetamide DEAM: Di Ethylaminoethyl methacrylate DMM: dimethylaminoethyl methacrylate DMAA : Dimethylamino ethyl acrylate HSE: Thermal curing efficiency Good results in either test. From the results of the above examples, it is known that a monomethacrylate-based copolymer additive in which the dialkylaminoethyl (meth) acrylate of the present invention and the ethylene glycol of ε-caprolactone is added to Spandex- 62-200523293, it has good solvent solubility and beneficial effects on heating and curing efficiency. According to the results of the above examples, it can be known from the results of the above embodiments that the first, second, and third inventions can be used to produce polyacrylic elastic fibers with excellent alkali hydrolytic resistance and high tension. It is extremely expensive in the industry. From the above, it can be seen that the fourth aspect of the present invention makes it possible to obtain polyurethane fibers having excellent weather resistance and excellent washing resistance. Therefore, they are extremely useful in the industry. The fifth novel acrylonitrile copolymer containing a dialkylamino group of the present invention has high solubility in DMAc solvents, and protects polyurethane and spandex polymers that are deteriorated and discolored, and contains the copolymer. Polyurethane composition and spandex composition of materials can improve the situation of reduced elasticity when using conventional additives with high molecular weight three-dimensional steric grade 3 amine groups, and have good permanent tensile properties. φ In the sixth use of the present invention, an excellent artificial leather can be obtained by using a polyurethane produced by using a specific polyester diol. [Schematic description] New button [Description of main component symbols] Μ -63-

Claims (1)

200523293 10. Scope of patent application: 1. A polyester diol characterized by being selected from 2-n-butyl-2-ethyl-1,3-propanediol and 2, 2-diethyl-1,3 · A diol of at least one of propylene glycol and 2,4-diethyl-1,5-pentanediol, and ε-caprolactone and adipic acid are constituent units, and selected from 2-n-butyl-2 Diol and adipic acid of at least one of -ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol and 2,4-diethyl-1,5-pentanediol The content of the polyester constituting unit / ε-caprolactone (weight ratio) is 5/95 to 80/20 ° ® 2. For example, the polyester diol of item 1 of the patent application scope, wherein the average molecular weight is 5 00 to 5,000. 3. A polyurethane, which is characterized by being obtained from a polyester diol and an organic diisocyanate such as those in the scope of claims 1 or 2. 4. A spandex fiber characterized by being formed from a polyurethane as described in item 3 of the patent application. 5. A polyester diol characterized by containing a branched aliphatic diol, ε-caprolactone, and an aliphatic dicarboxylic acid having 10 to 12 carbons as constituent units. 6. The polyester diol according to item 5 of the patent application, wherein the average molecular weight is 500 to 5,000. 7. The polyester diol as claimed in item 5 or 6 of the patent application scope, wherein the polyester unit composed of a branched diol and an aliphatic dicarboxylic acid having 10 to 12 carbons has a unit content of ε-caprolactone The content of the constituent unit (weight ratio) is 5/95 to 80/20 〇.-A kind of polyurethane, which is characterized by the polyester diol and the organic isocyanate obtained from the patent application No. 5 or 6. -64- 200523293 9. A spandex fiber, which is characterized by being made of polyurethane as described in item 8 of the patent application. 10. A polyurethane 'characterized in that a polyester diol containing 2,4-diethyl-1,5-pentanediol as a constituent and an organic diisocyanate are obtained by a reaction. 1 1. The polyurethane according to item 10 of the patent application range, wherein the average molecular weight of the polyester diol is 500 to 5,000. 1 2. A kind of Spandex fiber, which is characterized by being made of a polyurethane such as item 10 or 11 of the scope of patent application. 13. An acrylonitrile-based copolymer containing a dialkylamino group, which is characterized by a dialkylaminoethyl (meth) acrylate represented by the following general formula (1) and a general formula (2) The reactive monomer is formed by the necessary copolymer components. CH2 = CRCOOCH2CH2NR0R0 (1) (where R is hydrogen or methyl; R ° is alkyl with 1 to 4 carbon atoms) CH2 = CRC00CH2CH20 [- C (= 0) (CR ^ Mx-O-] nH (2) (where R represents hydrogen or methyl; x R1 and R2 each represent independent hydrogen or an alkyl group having 1 to 12 carbon atoms Η ring-opening lactone chains may be the same or different; X represents an integer of 4 to 7; the average 値 of η is 1 to 5). 1 4. A polyurethane composition characterized by containing For example, a propylene fluorene-based copolymer containing a dialkylamine group in the scope of application for item 13. 15. A polyurethane composition in the scope of the application for scope of application for item 14 in which the dialkylamine group-containing The content of the acrylonitrile-based copolymer is 0.5 to 10% by weight. -65- 200523293 1 6. A kind of Spandex composition, which is characterized by containing Acrylonitrile-based copolymers containing dialkylamino groups. 17. The Spandex composition according to item 16 of the patent application scope, wherein the content of the acrylonitrile-based copolymers containing dialkylamino groups is 0.5. ~ 10% by weight. -66- 200523293 VII. Designated Representative Map: (1) The designated representative map in this case is: (none) map. (2) Brief description of the component symbols in this representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: