TW201239004A - Method for making a polyetheramide elastomer and the polyetheramide elastomer obatined by such method - Google Patents

Abstract

This invention provides a method for making a polyetheramide elastomer which has a low specific gravity and excellent properties in melt-forming, plastic forming, toghness, antibending fatigue, rebound regilience, low temperature softness, silencing characteristics, and rubbery characteristics. It also exhibits excellent hue, stability against change in color by heat, transparency, and less change in the transparency after a heat-moisture treating, while the polymerizing promotion effect in the manufacturing process of the polyetheramide elastomer is maintained. This invention also provides the polyetheramide elastamer obtained by the above said method. The method of this invention includes the step of melt-polycondensation of a specific diamine (A), a polyamide-formed monomer (B) and dicarboxylic acid (C). In the case that a phosphorus atom-containing compound (D) is added before or during the above said process, the above said melt-polycondensation is performed under the presenee of (D); in the case that (D) is added after the above said process, the polymer obtained by the melt-polycondensation of the abovesaid prccess is melt-mixed under the presenes of (D), wherein the polyetheramide elastomer contains 0.005 to 0.3 mass part of pheeophorus atoms with respect to 100 mass part of the polyetheramide elastomer.

Description

201239004 6. DISCLOSURE OF THE INVENTION: TECHNICAL FIELD The present invention relates to a method for producing a polyether phthalamide elastomer and a polyether phthalamide elastomer produced by the method. [Prior Art] Polyether phthalamide elastomer is widely used because it has high flexibility, low specific gravity, abrasion resistance, abrasion resistance, elasticity, bending fatigue, low-temperature characteristics, moldability, and chemical resistance. A molded article such as a tube, a hose, a sporting article, a sealing material, a packing, and a muffler gear. Among the polyether amide elastomers, a polyamine-based amine elastomer or a polyether phthalamide elastomer, which is a hard segment and a polyether as a soft segment, is known. In the polyetheresteramine elastomer, a polyoxyalkylene glycol such as polyoxyethylene glycol, polyoxypropylene glycol or polyoxybutylene glycol or an α,ω-dihydroxy hydrocarbon can be used as the soft segment. Among these compounds, In terms of finance, water, low-temperature properties, elastic recovery, mechanical strength, etc., polyoxybutylene glycol is mainly used. However, polyether phthalamide elastomers of polydecylamine 12 having a polyoxybutylene glycol as a soft segment do not necessarily satisfy elastic recovery and bending fatigue resistance. Further, in the polyetheresteramine elastomer, there are problems such as water resistance and hydrolysis resistance, for example, durability in use in a high-temperature, high-humidity environment, and the use thereof is often limited. In order to solve the problems of such polyetheresteramine elastomers, Patent Documents 1 and 2 disclose a polyether phthalamide elastomer which is a polyamine unit and a polypropylene oxide. (X) and polyepoxy 4 323631 201239004 butyl (7) chemically bonded and 幵Μχ γ γ 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Patent Document 3 discloses a polyglycine amine elastomer which is formed by polyamidamine 70, polyepoxypropylene (1) and polyepoxybutylene (7) to form a χγχ type including a polyepoxide. The screaming unit and the second thief unit. In the production of such a polyether phthalamide elastomer, it has been disclosed that phosphoric acid, pyrophosphoric acid, polyphosphoric acid or the like is added as a catalyst to promote polymerization, and in order to exhibit the effects of both the catalyst and the heat-resistant agent, A compound containing an inorganic phosphorus-containing atom such as phosphorous acid, hypophosphorous acid (hyp〇ph〇sph〇r〇us acid), or an alkali metal salt or an alkaline earth metal salt may be added. In addition, the inorganic can-based metal salt and the soil-measuring metal salt compound, which are generally used in the polymerization of polydecylamine, are generally inexpensive, and have an excellent polymerization promoting effect on polyamine. It is also possible to impart a heat-resistant effect and to polymerize a catalyst of a polymer excellent in color tone. [Prior Art] [Patent Document] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A-2004-346341 (Patent Document No. JP-A-2004-346341). The problem to be solved by the invention] However, as described in the following examples, when these inorganic phosphorus-based alkali metal 5 323631 201239004 salt or alkaline earth metal salt compound is applied to a polyether phthalamide elastomer, a polyether unit is formed. The compatibility between the compound and the inorganic phosphorus-based alkali metal salt or alkaline earth metal salt compound including sodium hypophosphite monohydrate is not good, and the degree of transparency of the polyether phthalamide elastomer molded article cannot be satisfied, especially The transparency after the wet heat treatment was confirmed to be devitrified by the moisture absorption effect of the inorganic phosphorus alkali metal salt or the alkaline earth metal salt compound including sodium hypophosphite monohydrate, and the transparency was judged to be obvious. Damage. When the design and the decorative properties of the polyetheramide elastomer molded article are taken into consideration, it is of course desired to have excellent initial transparency, and it is also expected to prevent deterioration of transparency when used in various environments. An object of the present invention is to provide a method for producing a polyether phthalamide elastomer and a polyether phthalamide elastomer which can be obtained by the production method, which can solve the aforementioned problems, and has melt formability and shape processing. Excellent in properties, strong tensile strength, bending fatigue, rebound elasticity, low temperature flexibility, sound absorbing properties, and rubber properties, and at the same time, low specific gravity, and promotes polymerization when maintaining polyether amide elastomers In the meantime, it is excellent in color tone, heat discoloration property, and transparency, and the change in transparency after wet heat treatment is small. [Method for Solving the Problem] The content of the present invention is as follows. (1) A method for producing a polyether phthalamide elastomer, comprising the steps of melt-condensing a diamine compound (component A), a polyamine-forming monomer (component B), and a dicarboxylic acid compound (component C) Wherein, before, during or after the foregoing step, a compound containing a filling atom (ingredient D) is added; 323631 201239004 When the aforementioned component D is added before or during the aforementioned step, the aforementioned melting is carried out in the presence of the aforementioned component D When the component D is added after the above step, the polymer obtained by melt-condensing and melting the above step is subjected to the above-described melt-kneading in the presence of the component D; and the component A contains the following formula (1). Triblock polyether diamine compound (ingredient A1):

CH^HO ch3 ch3 ch3 hch2o (1)

CHjCHaCHjCHjO y (in the formula (1), x represents an integer of 1 to 20, y represents an integer of 4 to 50, and z represents an integer of 1 to 20); the aforementioned component B is an aminocarboxylic acid represented by the following formula (2) The compound (component B1) and/or the indoleamine compound (component B2) represented by the following formula (3): H2N - R1 - COOH (2) (in the formula (2), R1 represents a linking group containing a hydrocarbon group)

(3) In the formula (3), R2 represents a linking group containing a hydrocarbon group; and the component C is a compound represented by the following formula (4): HOOC-4 R3h-COOH (4) m (in the formula (4), R3 And a compound represented by the following formula (5), a compound represented by the following formula (6), or a compound represented by the following formula (7). The component D is a compound represented by the following formula (5). At least one compound of the compound represented by the following formula (8), the compound represented by the following formula (9), and the group represented by the following formula (10): 7 323631 201239004: 〇

XlO—P—OX3 (5) OX2 ο R4 — Ρ—ΟΧ5 (6) ΟΧ4 ο R5 ——一ΟΧ6 (7) I6 3Χ9 (8) χ7ο ——Ρ— οχ8 οχ11 (9) R7 —-Ρ—ΟΧ10 乂9 (10) R8 - Ρ - ΟΧ12 (In the formulae (5) to (10), R4 to R9 may be the same or different and represent a hydrogen atom, or an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, X 至 005 003 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 005 0质量份。 To 0.3 parts by mass. (2) A polyether amide elastomer which is produced by the production method described in the above (1). [Effects of the Invention] According to the present invention, a method for producing a polyether phthalamide elastomer and a polyether phthalamide elastomer obtained by the method, and a melt formability and molding of the polyether phthalamide elastomer can be provided. Excellent processability, excellent strength, bending fatigue resistance, rebound elasticity, low temperature flexibility, sound absorbing properties, and rubber properties, and low specific gravity, and promotes polymerization when maintaining polyether amide elastomers In the meantime, it is excellent in color tone, heat discoloration property, and transparency, and the change in transparency after wet heat treatment is small. [Embodiment] The method for producing a polyether phthalamide elastomer of the present invention (hereinafter also referred to as the production method of the present invention) has a diamine compound (component A) and a polyamine forming monomer (component B). a method for producing a polyether amide elastomer which is a step of melt-condensing a dicarboxylic acid compound (component C); wherein a compound containing a phosphorus atom (component D) is added before or during the above step (form 1), Or adding the aforementioned component D (form 2) after the foregoing step; when the form 1 of the component D described above is added before or during the foregoing step, the aforementioned melt-condensation is carried out in the presence of the aforementioned component D; When Form 2 of the component D is added, the polymer obtained by melt-condensing the above-mentioned step is melt-kneaded in the presence of the component D. 9 323631 201239004 Specifically, in the form 2, after the components A, B, and C are melt-condensed and polymerized to obtain a polymer, the polymer is directly melt-kneaded, the component D is added thereto, and the polymerization is carried out in the presence of the component D. When the material is melt-kneaded; the polymer obtained by melt-polymerizing the components A, B, and C is formed into a pellet. When the pellet is subjected to a forming process, the component D is added in the stage of performing the melt-kneading, and the component D is added. In the presence of the poly person, the poly person is melted and kneaded. The production method of the present invention of the first aspect is preferably a method for producing a polyanthracene elastomer which comprises (A) a bicyclal compound containing the (A1) triblock polyether diamine compound, and is selected from the group consisting of (B1) an amino-based antacid compound and (B2) an indoleamine compound (B) a polyamine-forming monomer and a component of the (C) dicarboxylic acid compound, which are selected from the group consisting of (D1) structuring compounds, D2) phosphonic acid compound, (D3) phosphinic acid compound, (D4) phosphorous acid compound, (D5) phosphonous acid compound and (D6) phosphinous acid The melt polycondensation is carried out in the presence of at least one (D) phosphorus atom-containing compound in the group of the compounds. The polymycetamine elastomer obtained by the production method of the present invention of Form 1 is obtained by containing (A) a diamine compound containing a (A1) triblock polyether diamine compound, selected from (B1) The (B) polyamine-forming monomer of the aminocarboxylic acid compound and the (B2) indoleamine compound and the component of the (C) dicarboxylic acid compound are selected from the group consisting of (D1) phosphate compound and (D2) phosphonic acid. At least one of the group consisting of a compound, a (D3) phosphinic acid compound, a (D4) phosphorous acid compound, a (D5) phosphinic acid compound, and a (D6) phosphinic acid compound (D) a phosphorus atom-containing compound There is a polyether phthalamide elastomer prepared by melt polycondensation under 10 323631 201239004. One of the desirable forms of the polyether phthalamide elastomer obtained by the production method of the present invention of the first aspect is that the XYX-type triple-embedded polycondensation diamine compound (A1) represented by the formula (1) is mixed with the diamine ( A branched type saturated diamine having 6 to 22 carbon atoms, a branched alicyclic diamine having 6 to 16 carbon atoms, or at least one of norbornane diamine (A2) other than A1) (A) a diamine compound of the diamine compound, which is selected from the group consisting of the (B1) aminocarboxylic acid compound represented by the formula (3) and the (B2) indoleamine compound represented by the formula (4). A polyether phthalamide elastomer obtained by polymerizing a monomer and a (C) dicarboxylic acid compound represented by the formula (2). [Component A] Component A contains a triblock polyether diamine represented by the following formula (1) (ingredient A1):

(l) rT3 1 [ ch3 ch3

H2N--€HCH20 - CHjCHjCI^CHjO- - CI^CHO -C "xl· jyL Jz (in the formula (1), x represents an integer from 1 to 20, y represents an integer from 4 to 50, and z represents from 1 to 20 Integer). The component Al represented by the formula (1) (hereinafter also referred to as χγχ-type triblock polyether diamine compound) may, for example, be a propylene oxide added to both ends of poly(oxytetramethylene) glycol or the like ( After propylene oxide is formed into a polypropylene glycol, a polyfluorinated diamine obtained by reacting a gas with a terminal of the polypropylene glycol is prepared. In the XYX-type triblock polyether diamine compound, the rubber-elastic stability property of the polyether phthalamide elastomer (also referred to as polyether amide elastomer) obtained by the production method of the present invention is ensured. Further, in the method of the present invention, the manufacturer's method of 323631 11 201239004, the compatibility with the amine component is improved. (4) From the viewpoint of (4) (iv) poly-amine elastomer, X and Z are usually from 1 to 20, and preferably from 1 to 18, and Preferably, it is preferably from 1 to 14, and more preferably from 1 to ;2; y is usually from 4 to 50, and preferably from 5 to 45, and preferably from 6 to 4, and 7 Better to 35, and 8 to 3 is especially good. Specific examples of the XYX-type diblock polysquameric diamine compound include XTJ_533 manufactured by HUNTSMAN Co., Ltd. (in the formula (1), χ is about 12, y is about 11, z is about 11), and XTJ- 536C In the formula (1), x is about 8 5, y is about 17, z is about 7 5), XTJ-542 (in the formula (1), χ is about 3, y is about 9, z is about 2 In XTJ-559C (1), x is about 3, y is about 14, and z is about 2) In addition, XYX-1 can also be used (in equation (1), χ is about 5, y is about 14, z is about 2), XYX-2C (1) where 'x is about 3, y is about 19, and Z is about 2) as an XYX-type triblock poly-diamine compound. From the viewpoint of ensuring the stability of the stability of the polyether phthalamide elastomer composition produced by the production method of the present invention, the component A preferably contains a component selected from the group consisting of carbon atoms of 6 to 22 in addition to the component M. At least one diamine compound (ingredient A2) in a group of a branched saturated diamine, a branched alicyclic diamine having a stone counter atom number of 6 to 16, and a norborne diamine. Further, the branched-type saturated diamine having 6 to 22 carbon atoms of the (human 2) diamine compound used in the ideal form can be, for example, 2, 2, 4_trimethyl-hydrazine, 6_323631 12 201239004 2 Aminohexane, 2,4,4-trimethyl-1,6-diaminohexane, 2-methyl-1,5-diaminopentane, 2-mercapto-1,8-di Amino octane and the like. These may be used alone or in combination of two or more. The branched alicyclic diamine having 6 to 16 carbon atoms of the component A2 used in the desired form may, for example, be 5-amino-2,2,4-trimethyl-1-cyclopentyl decylamine. 5-Amino-1,3,3-trif-cyclocyclohexanemethylamine (also known as "isophorone diamine") and the like. Further, these diamines may be either cis or trans, or a mixture of such isomers. These may be used alone or in combination of two or more. The norbornadiene diamine of the component A2 used in the preferred embodiment may, for example, be 2, 5-norbornane dimethylamine or 2,6-norbornane dimethylamine. These may be used alone or in combination of two or more. Further, the diamine compound (ingredient A) may contain other diamine components (component A3) other than the component A1 and the component A2. The component A3 may, for example, be 1,2-diaminoethane, hydrazine, 3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, hydrazine, 6-diamine. Hexane, hydrazine, 'diamino heptane, 1,8-diaminooctane, anthracene, 9-diaminodecane, M〇_diamine hydrazine 13, 1, U-diamine One hospital, aliphatic diamine such as 112-diaminodidecyl pentoxide; bis(4-aminocyclohexyl)methane, bis(4-aminocyclohexyl)propane, bis(3-methyl-4-amino group Cyclohexyl)decane, bis(3-indolyl-4-isocyclohexyl)propane, 1,3-/1,4-diaminomethylcyclohexan, bis(aminopropyl)piperidine An aromatic diamine such as an alicyclic diamine such as bis(aminoethyl)piperidine or tricyclodecane dimethylamine or m-/p-xylenediamine. These may be used alone or in combination of two or more. 323631 13 201239004 [Component B] Component B is an aminocarboxylic acid compound (component B1) represented by the following formula (2) and/or an indoleamine compound (component B1) represented by the following formula (3): H2N - R1 — COOH (2) (In the formula (2), R1 represents a linking group containing a hydrocarbon chain)

(In the formula (3), R2 represents a linking group containing a hydrocarbon group chain). The R1 in the component B1 is preferably an aliphatic having 2 to 20 carbon atoms from the viewpoint of ensuring the stability of the polyether amide elastomer composition obtained by the production method of the present invention, and the mechanical properties such as the modulus of elasticity. And an alicyclic or aromatic hydrocarbon group, and preferably an alkylene group having 2 to 20 carbon atoms, preferably a hydrocarbon group having 3 to 18 carbon atoms, and having an alkyl group having 3 to 18 carbon atoms. Preferably, it is preferably the above hydrocarbon group having 4 to 15 carbon atoms, and preferably a hydrocarbon group having 4 to 15 carbon atoms, preferably a hydrocarbon group having 10 to 15 carbon atoms, and having 10 to 15 carbon atoms. The stretch base is preferred. The R2 in the component B2 is preferably an aliphatic having 3 to 20 carbon atoms from the viewpoint of ensuring the stability of the polyether amide elastomer composition obtained by the production method of the present invention, and the mechanical properties such as the modulus of elasticity. And an alicyclic or aromatic hydrocarbon group, and preferably an alkyl group having 3 to 20 carbon atoms, preferably a hydrocarbon group having 3 to 18 carbon atoms, and having a carbon number of 3 to 18 Preferably, 14 323631 201239004 is preferably a hydrocarbon group having 4 to 15 carbon atoms and preferably a hydrocarbon group having 4 to 15 carbon atoms, preferably a hydrocarbon group having 10 to 15 carbon atoms and having 10 carbon atoms. The alkylene group of '15 is preferred. 'Component B1 may, for example, be 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminohexanoic acid, 10-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecadin An aliphatic aminocarboxylic acid having 5 to 20 carbon atoms such as an acid. These may be used alone or in combination of two or more. The component B2 may, for example, be an aliphatic group having 5 to 20 carbon atoms such as caprolactam, heptanoin, eleven internal amine, dodecylamine, 2-pyrrolidone or the like. Amidoxime and the like. These may be used alone or in combination of two or more. [Component C] Component C is a dicarboxylic acid compound represented by the following formula (4): HOOC-f R3) - COOH (4) m (In the formula (4), R3 represents a linking group containing a hydrocarbon group bond, and m represents 0. Or 1). From the viewpoint of ensuring the rubber elasticity or flexibility of the stability of the polyether phthalamide elastomer composition produced by the production method of the present invention, R3 in the component C is preferably an aliphatic or alicyclic ring having 1 to 20 carbon atoms. a hydrocarbon group of a group or an aromatic group or an alkylene group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 15 carbon atoms, and preferably an alkyl group having 1 to 15 carbon atoms, preferably a carbon atom The above hydrocarbon group of 2 to 12 is preferably an alkyl group having 2 to 12 carbon atoms. 15 323631 201239004 The above hydrocarbon group having 4 to 10 carbon atoms is preferred, and a stretching group having 4 to 10 carbon atoms is preferred. Further, m represents 0 or 1. The component C may, for example, be at least one dicarboxylic acid selected from the group consisting of aliphatic, alicyclic and aromatic dicarboxylic acids or such derivatives. Specific examples of the component C include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanedioic acid, and the like. a linear aliphatic dicarboxylic acid having 2 to 25 carbon atoms or a dimerized aliphatic dicarboxylic acid having 14 to 48 carbon atoms obtained by dimerizing an unsaturated fatty acid obtained by fractionating triglyceride ( Dimer acid) and an aliphatic dicarboxylic acid such as a hydride of such a dicarboxylic acid (hydrogenated dimer acid); 1,3-/1,4-cyclohexanedicarboxylic acid, dicyclohexane decane -4, 4'-dicarboxylic acid, norbornane dicarboxylic acid such as norbornane dicarboxylic acid, and phthalic acid, isophthalic acid, 1,4- An aromatic dicarboxylic acid such as /2, 6-/ 2,7-naphthalenedicarboxylic acid. These may be used alone or in combination of two or more. Component C is preferably the above aliphatic dicarboxylic acid or alicyclic dicarboxylic acid. For the component C, the dimer acid and the hydrogenated dimer acid can be used under the trade names "Pripol 1004", "Pripol 1006", "Pripol 1009", "Pripol 1013" manufactured by Unichema Co., Ltd., and the like. [Component D] The component D is a compound represented by the following formula (5), a compound represented by the following formula (6), a compound represented by the following formula (7), a compound represented by the following formula (8), At least one compound of the group represented by the following formula (9) and the compound represented by the following formula (10): 16 323631 201239004 ο X1 R4 R5 ο X7 R7 R8 9 ox 3 (5) 2 X ο ο&quot ; χ5 (6) Γ 6 X ο 6 οχ9. (8) ροχ1· οχ8 (9) ρ R9. ρ οχ1 οχ1 (In the formulas (5) to (10), R4 to R9 may be the same or different, and represent a hydrogen atom or an alkyl group. A cycloalkyl group, an aryl group, or an aralkyl group, and X1 to X12 represent a hydrogen atom, or a group, a cycloalkyl group, an aryl group, an aralkyl group, except for a metal element). [Compound containing a base atom] The components A, B, and C are melted in the presence of a compound containing a filler atom. 133631 201239004 Melt polymerization (morphology 丨), or a polymer obtained by melt polymerization of components A, B, and C The polyether phthalamide elastomer obtained by melt-kneading (Form 2) in the presence of a compound containing a phosphorus atom is excellent in color tone, heat-resistant discoloration/transparency, and has little change in transparency after wet heat treatment. In the straight formula (10), the alkyl group of R4 to R9 and X1 to p is a linear or branched alkyl group having 1 to 24 carbon atoms, and examples thereof include methyl group, ethyl group, and positive group. Propyl, isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, n-pentyl, isodecyl, second fluorenyl, neopentyl, hexyl, second hexyl, g Base, second heptyl, octyl, second octyl, 2-ethylhexyl, decyl, second fluorenyl, fluorenyl, second fluorenyl, ^-alkyl, dodecanyl, tridecane Base, isotridecyl, tetradecyl, hexadecyl, octadecyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2 - Octyl fluorenyl, 2-hexyldodecyl, and the like. In the formula (5) to the formula (1), the cycloalkyl group of R4 to R9 and X1 to X12 is a cycloalkyl group having 3 to 20 carbon atoms, and examples thereof include a cyclopentyl group, a nonylcyclopentyl group, and a cyclopenta group. Base group, 2-cyclopentylethyl, cyclohexyl, methylcyclohexyl, dinonylcyclohexyl, cyclohexyldecyl, 2-cyclohexylethyl, ethylcyclohexyl, propylcyclohexyl, cycloheptane Base, indenylcycloheptyl, cyclooctyl, cyclooctyldecyl, 2-cyclooctylethyl, and the like. In the formulae (5) to (10), the aryl group of the ruthenaries 4 to R9 and X1 to X12 is an aryl group having 6 to 24 carbon atoms (including all of the substituted isomers), and examples thereof include a phenyl group and a fluorene group. Phenyl, diphenylphenyl, cumylmethylphenyl (2,4,6-trimethylphenyl), ethylphenyl, ethylmethylphenyl, diethylphenyl , ethyl decyl phenyl, triethyl phenyl, propyl phenyl, propyl 18 323631 201239004 nonylphenyl, propyl ethyl phenyl, dipropyl phenyl, tripropyl phenyl, butyl Phenylphenyl, dibutylphenyl, tributylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, nonylphenyl, undecylbenzene , dodecylphenyl, 1-naphthyl, 2-naphthyl, nonylnaphthyl, anthracenyl, benzylphenyl, cumylphenyl, biphenyl, 2, 4, 6- Triphenylphenyl and the like. In the formulae (5) to (10), the aralkyl group of R4 to R9 and χι to χΐ2 is an aralkyl group having 7 to 24 carbon atoms (including all substituted isomers), and examples thereof include benzyl group ( Benzyl), phenethyl, benzhydryl, fluorenylphenyl, phenylpropyl, phenylbutyl, naphthylmethyl, nonylphenyl fluorenyl, nonylphenylethyl, decylnaphthyl Methyl, phenyl, methyl and the like. The phosphorous acid compound represented by the formula (8) may be tautomerized with a phosphonic acid compound represented by the general formula (6) by the influence of a hydrogen ion concentration or the like, and the phosphonic acid represented by the general formula (6) The compound may also be tautomeric with a telluric acid compound represented by the formula (8) due to the influence of temperature or the like. The phosphinic acid compound represented by the formula (9) may be tautomeric with the phosphinic acid compound represented by the formula (7) by the influence of hydrogen ion concentration or the like, and the phosphinic acid represented by the formula (7) The compound may also undergo tautomerization with a phosphinic acid compound represented by the general formula (9) due to the influence of temperature or the like. The phosphorus atom-containing compound represented by the formula (5) is a (D1) phosphoric acid compound, and examples thereof include phosphoric acid, a phosphate ester, and an acid phosphate. The phosphate ester may, for example, be tridecyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triamyl phosphate, trihexyl phosphate, triheptyl phosphate, 19 323631 201239004 trioctyl phosphate, phosphoric acid tri (2-ethylhexyl ester), tridecyl phosphate, tridecyl phosphate, tris(undecyl) phosphate, tris(dodecyl) phosphate, tris(tetradecyl) phosphate, tris(10) Pentadecyl ester), tris(hexadecyl ester) phosphate, tris(heptadecane) phosphate, tris (eighteen burned vinegar), acid-filled triolein, dibutyl acetate, tricyclohexyl phosphate Ester, triphenyl vinegar, tribasic acid (formyl vinegar), tris (xylylene vinegar), tris(phenylphenyl vinegar), ethyl phthalate, benzyl phosphate Diphenyl ester, ethyl diphenyl phosphate, diphenyl phthalate, diphenyl phosphate diphenyl phosphate, diterpene phenolic vinegar, acid (ethyl phenyl ester) diphenyl ester , di(ethylphenyl) benzene vinegar, diphenyl phenyl phosphate, di(propyl phenyl) phenyl phosphate, butyl phenyl phosphate Phenyl phosphate, di (butylphenyl) phenyl phosphate, tris (ethylphenyl) phosphate, tris (propylphenyl) phosphate, tris (butylphenyl) and the like. These may be used alone or in combination of two or more. Examples of the acid acid ester include, for example, an acid-type acid mono- or di-acetic acid vinegar, an acid succinic acid mono- or di-ethyl ester, an acid mono- or di-n-propyl phosphate, an acid acid mono- or di-isopropyl ester, and an acid type. Mono or dibutyl phosphate, mono or diamyl phosphate, mono or dihexyl acid phosphate, mono or diheptyl acid acid, mono or dioctyl acid acid, acid phosphate or Bis(2-ethylhexyl ester), mono or dinonyl acid phosphate, mono or dinonyl acid phosphate, mono or di (undecyl) acid phosphate, mono or diacid acid Alkane ester), acid mono or di(tridecyl ester), mono or di(tetradecyl) acid phosphate, mono or di (pentadecane), acid mono or di Cetyl ester), acid phosphate mono or di (seventeen burnt), acid phosphate mono or di (eighteen burned vinegar), acid Weidan or one or two oil 323631 20 201239004 ester, acid phosphate Or diphenyl ester, mono or dicyclopentyl acid phosphate, mono or dicyclohexyl acid phosphate, mono or dicyclooctyl acid phosphate, acid mono or diphenyl phosphate g. ‘One or two or more of these can be used. The compound containing a phosphorus atom represented by the formula (6) is a (D2) phosphonic acid compound, and examples thereof include a phosphonic acid, a mercaptophosphonic acid, an ethylphosphonic acid, a propylphosphonic acid, a butylphosphonic acid, and an octylphosphonic acid. , 2-ethylhexylphosphonic acid, decylphosphonic acid, decylphosphonic acid, dodecylphosphonic acid, tridecylphosphonic acid, octadecylphosphonic acid, oleylphosphonic acid, phenylphosphonic acid,曱Phenylphosphonic acid, decylphosphonium decylate, ethyl decylphosphonate, dodecyl decylphosphonate, phenyl decylphosphonate, decyl phenylphosphonate, ethyl phenylphosphonate, Dodecyl phenylphosphonate, phenyl phenylphosphonate, dinonyl methylphosphonate, diphenyl decylphosphonate, dinonyl phenylphosphonate, nonylphenyl phenylphosphonate, benzene Diethyl phosphinate, diphenyl phenylphosphonate, dimethyl phenylphosphonic acid, diethyl phenylphosphonate, dipropyl phenylphosphonic acid, and the like. These may be used alone or in combination of two or more. The phosphorus atom-containing compound (D3) represented by the formula (7) is a phosphinic acid compound, and examples thereof include a phosphinic acid (hypophosphorous acid), a tris-phosphinic acid, and a dihydrazino group. Ethylphosphonate, propyl diphosphoryl phosphinate, butyl bisphosphonate, amyl quinhophosphinate, hexyl phosphinate, heptyl dimethylphosphinate, Octyl bisphosphonate, phenyl dimethylphosphinate, decyl bisphosphonate, naphthyl dimethylphosphinate, decyl methylphenylphosphinate, nonylphenyl Ethyl phosphinate, decyl diethylphosphinate, triethylphosphinic acid, propyl diethylphosphinate, butyl diethylphosphinate, amyl diethylphosphinate, two Ethyl 21 323631 201239004 hexyl phosphinate, heptyl diethylphosphinate, octyl diethylphosphinate, phenyl diethylphosphinate, decyl diethyl phosphinate, diethyl Naphthyl phosphinate, decyl ethylphosphonium phosphinate, ethyl ethyl decylphosphinate, propyl ethyl decylphosphinate, decyl ethyl propyl phosphinate, ethyl propyl Ethyl phosphinate, ethyl propyl phosphinic acid Esters, ethyl phenyl phosphinate, ethyl ethyl phenylphosphinate, methyl dipropyl phosphinate, ethyl propyl phosphinate, tripropyl phosphinic acid, dipropyl Butyl phosphinate, amyl propyl phosphinate, hexyl propyl phosphinate, heptyl dipropyl phosphinate, octyl dipropyl phosphinate, phenyl dipropyl phosphinate, P-phenyl phenyl phosphinate, naphthyl dipropyl phosphinate, tributylphosphinic acid, trioctylphosphinic acid, triphenylphosphinic acid, decyl diphenylphosphinate, two Phenylphosphonate cyclohexyl ester, triterpene phenylphosphinic acid, tricyclohexylphosphinic acid, dicyclohexylphosphinic acid phenyl ester, trityl phosphinic acid, dimercaptophosphinic acid!, A Ethyl phosphinate, ethyl decylphosphinate, dodecyl decylphosphinate, phenyl decylphosphinate, diphenylphosphinic acid, decyl phenylphosphinate, phenyl Ethyl phosphinate, lauryl phenylphosphinate, phenyl phenylphosphinate, decylphosphinic acid, ethylphosphinic acid, hexylphosphinic acid, octylphosphinic acid, dodecane Phosphine, cetylphosphinic acid, octadecylphosphinic acid, cyclohexyl Acid, phenyl phosphinic acid, phenyl phosphinic acid Yue, Yue phenyl phosphinic acid group, phosphinic acid phenethyl and the like. These may be used alone or in combination of two or more. The phosphorus atom-containing compound (D4) represented by the formula (8) is a phosphorous acid compound, and examples thereof include phosphorous acid, phosphite, and acid phosphite mono- or diester. The phosphite may, for example, be tridecyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, triamyl phosphite, trihexyl 22 323631 201239004 ester, triheptyl phosphite , trioctyl phosphite, triisooctyl phosphite, tris(2-ethylhexyl phosphite), tridecyl phosphite, tridecyl phosphite, sub-packaged tris (11 vinegar), sub Filled with acid three (12 burns S), sub-acid three (threeteen burned vinegar), phthalic acid three (sixteen burned vinegar), acetylated acid three (eighteen burned vinegar), trioleyl phosphite, Tricyclohexyl phosphite, triphenyl phosphite, tris(nonylphenolate) phosphite, tris(ethylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite Ester), tris(nonylphenyl) phosphite, isooctyl diphenyl phosphite, diisooctyl phosphite, diethylhexyl phosphite diphenyl ester, phenyl phosphite di 2-ethylhexyl ester), phenyl phthalate didecyl ester, decyl phosphite diphenyl ester, decyl phosphite phenyl ester, phenyl phosphite di(dodecyl ester), dodecyl phosphite II Ester, tridecyl phthalate diphenyl ester, decyl phosphite dioctyl ester, dodecyl phosphite dioctyl ester, bis(2,4-di-tert-butylphenyl) phosphite Dialkyl ester, bis(2,4-di-tert-butylphenyl) octyl phosphite, (2,4-di-t-butylphenyl ester) diisooctyl ester, phosphorous acid (nonylphenyl ester) decyl ester, (2,4-di-tert-butylphenyl ester) dicyclohexyl phosphite, diisononyl phosphite nonyl phenyl ester, and the like. These may be used alone or in combination of two or more. The acidic phosphite may, for example, be mono or dinonyl hydrogen phosphite, mono or diethyl hydrogen hydride, mono or dipropyl hydrogen phosphite, mono or dibutyl hydrogen phosphite, mono or diammonium hydrogen phosphite. Ester, mono or dihexyl hydrogen phosphite, mono or diheptahydro hydrogen phosphite, mono or dioctyl hydride of hydrogen hydrazine, mono or di(2-ethylhexyl) hydro hydrazine, hydrogen phosphite single Or diterpene ester, mono or dinonyl hydrogen phosphite, mono or di (undecyl) hydrogen phosphite, mono or di (dodecane 23 323631 201239004 sulphur), hydrogen linalic acid mono or Two (sixteen vinegar), hydrogen phosphite mono or di (octadecane vinegar), hydrogen sulphate mono or dioleic vinegar, nitrogen squaraine mono or dicyclohexanoic vinegar, chlorine, phosphoric acid mono or diphenyl g The purpose is hydrogen sulphate mono or dimethyl vinegar, hydrogen sulfite acid or xylene vinegar, hydrogen sulfite mono or diphenyl hydrazine vinegar, hydrogen sulfite mono or diphenyl ethyl ester. These may be used alone or in combination of two or more. The phosphorus atom-containing compound represented by the formula (9) is a (D5) phosphinic acid compound, and examples thereof include a phosphinic acid, a methylphosphinic acid, an ethylphosphinic acid, a dodecylphosphonic acid, and a phenylene group. Phosphonic acid, methyl phosphinate monomethyl ester, methyl phosphinic acid. Monoethyl ester, methyl phosphinate monododecyl ester, decylphosphonic acid monophenyl ester, ethyl phosphinate monomethyl ester , ethyl phosphinate monoethyl ester, ethyl phosphinate monododecyl ester, ethyl phosphinate monophenyl ester, phenyl phosphinate monomethyl ester, phenyl phosphinate monoethyl ester, phenyl Phosphonic acid monododecyl ester, phenylphosphinic acid monophenyl ester, trimethylphosphinic acid, decylphosphonic acid methyl ethyl ester, decylphosphonic acid diethyl ester, decylphosphonic acid Propyl ester, dibutyl decylphosphonate, diphenyl methyl phosphinate, didecyl ethyl phosphinate, triethyl phosphinate, dipropyl ethyl phosphinate, ethyl phosphine Dibutyl acrylate, diphenyl ethyl phosphinate, dinonyl propyl phosphinate, diethyl propyl phosphinate, tripropyl phosphinate, dibutyl propyl phosphinate, propyl Diphenyl phosphinate, dinonyl butyl phosphinate, diethyl butyl phosphinate, Dipropyl butylphosphinate, tributylphosphinic acid, diphenyl butylphosphinate, dinonyl phenylphosphinate, methyl ethyl phenylphosphinate, phenylphosphinic acid Ethyl ester, dipropyl phenyl phosphinate, dibutyl phenyl phosphinate, trisuccinylphosphonic acid, and the like. These may be used alone or in combination of two or more. 24 323631 201239004 The phosphorus atom-containing compound represented by the formula (10) is a (D6) subphosphinic acid compound, and examples thereof include a hypophosphinic acid, a mercaptophosphinic acid, an ethyl phosphinic acid, and a butyl sub-time. Phosphonic acid, phenylphosphinic acid, decyl phosphinic acid, ethyl decyl phosphinate, butyl decyl phosphinate, phenyl decyl phosphinate, ethyl sub- Ethyl phosphonate, ethyl ethyl phosphinate, butyl ethyl phosphinate, phenyl ethyl phosphinate, butyl phosphinate, ethyl butyl phosphinate, Butyl phosphinate, butyl phosphinate, phenyl phosphinate, ethyl phenyl phosphinate, butyl phenyl phosphinate, phenylphosphinium Phenyl phenyl ester, dimethyl phosphinic acid, methyl ethyl phosphinic acid, diethyl phosphinic acid, dibutyl phosphinic acid, diphenyl phosphinic acid, tridecyl sub- Phosphonic acid, triethyl phosphinic acid, tributyl phosphinic acid, triphenyl phosphinic acid, ethyl dimercaptophosphinate, butyl dimethyl phosphinate, dimercapto Phenylphosphinate, decyl diethylphosphinate, diethyl Butyl phosphinate, phenyl diethylphosphinate, methyl dibutyl phosphinate, ethyl dibutyl phosphinate, phenyl dibutyl phosphinate, diphenyl phenyl Ethyl phosphinate, ethyl diphenyl phosphinate, butyl diphenyl phosphinate, and the like. These may be used alone or in combination of two or more. Among the components D, since the component D has high catalytic activity and low coloring property, it is preferably selected from the (D1) phosphate compound represented by the formula (5) and the (D3) phosphinic acid compound represented by the formula (7). At least one compound selected from the group consisting of the (D4) phosphorous acid compounds represented by the formula (8) is preferably at least one compound selected from the group consisting of phosphoric acid, phosphorous acid and hypophosphorous acid. Further, the component D is excluded from the following: a metal salt formed from phosphoric acid, phosphorous acid or hypophosphorous acid and a metal of the periodic table 1 25 323631 201239004, which is generally used as a polymerization catalyst for polyamine. Metal ruthenium phosphate metal salts, metal phosphites [Components A, B, Γ n ^ 本--::: Polyetheramide elastomers obtained by the polymerization of polyamines The strength and elasticity are extremely high, and the elastic properties of the obtained polyether phthalamide elastomer are ensured, and the rubber elasticity or the soft-fit ratio phase appears in a stable manner. The measurement of 100 mass knives of Β and C, that is, the composition of Λ, Β and C relative to the composition Β, Β and C is preferably from 1 〇 to 95 皙 and is in the mass of ～85 mass/summer (preferably from 15 to 90% by mass, component A) And component 2: just 15 to 8 ° is better; 85 皙 5 is preferably 5 to 90% by mass, 10 to Zeng 曰 ^ 〇 'good, and 15 to 85% by mass, and 20 to 85, 1% and more preferably. When component A and component C are added, the amine group of component a (including other amines) The carboxyl group of C is almost equimolar; the molar ratio of the amine group of component A (including the amine group of other diamine compound) and the component c of the component c is preferably 45/55 to 55/45. More preferably, it is 47/53 to 53/47, and more preferably 49/51 to 51//49, more preferably 50/50. In the production method of the present invention, among the obtained polyetheramide elastomers, It is preferred that the carboxylic acid or sulfhydryl group at the end of the components A, β and c (i.e., from the components a and C) and the amine group at the terminal become almost equal to 323631 26 201239004 = The components A and B and the acid or the ester group and the terminal amine group are charged in a ratio of almost equimolar. (4) The manufacturing method of the (4) manufacturing method is performed. (4) Lai _ Sexual body composition (4) Gel elasticity or recorded 34 traits The ratio of the component A1 in the nr smelting polymerization of the ship and the performance is preferably 50 to 10% by mass in 100 mass, and is 80 to the mass/better, and 90 to 1 〇〇 mass%. (4) If the component A2 is contained in a timely manner, the total amount of transparency relative to the components A and UC determined by the composition of the polylysine elastomer composition of the present invention is ensured. The mass fraction is better than that of G.5 to 10, and the polycondensation system of the polylysine elastomer and the mixed elastomer = component D in the m mass% of the training system=1, or Adding the amount of component D in the polyether amide blending system in the form 2, (4) coloring the initial color of the phthalamide in the polymerization, improving the polymerization promoting effect, calming the color tone or heat discoloration, and suppressing the additive 詈, system J A Shi. The production of polyether amides and the cost of the law

The h should be made, and the stability of the product which may be caused by the component D is suppressed, the yield of the plaque which is blocked by the reducer during molding is suppressed, and the stability of the molded article is ensured and transparent, and the transparent and transparent after the heat treatment is ensured. From the viewpoint of the property, 100 parts by mass of the total amount of the component Α and β κ, or the mass of the elastomer, and the mass of the elastomer are 323631 27 201239004 0. 005 to 0·3 The mass part is preferably from 0.1 to 〇. 2 parts by mass, and preferably from 〇〇3 to 〇. 15 parts by mass. In addition, from the same viewpoint, the total amount of the component a, b & c is 100 parts by mass or the amount of the component D is preferably 〇. 005 to 4. 5 parts by mass, more preferably 〇1 to 3.0 parts by mass, and more preferably 〇·03 to 1.5 parts by mass. [Other Manufacturing Conditions of Polyether Amidyl Elastomer] The production method of the present invention is a method for producing a polyether amine elastomer, which comprises (A) an amine compound containing a (A1) three-stage polyether diamine compound, (B) a polyamine-forming monomer selected from the group consisting of (B1) an amino-based oxo-acid compound and (B2) an indoleamine compound, and a component of the (C) dicarboxylic acid compound, selected from the group consisting of (D1) acid-filling compound At least one of the group of (D2) phosphonic acid compound, (D3) phosphinic acid compound, (D4) phosphorous acid compound, (D5) phosphinic acid compound, and (j) 6) phosphinic acid compound. (D) Hyun fusion condensation in the presence of a compound containing a filler atom. When the component D is added to the reaction system (form 丨) or the kneading system (form 2), the addition time may be before the start of the polycondensation reaction and during the reaction, or before the start of the kneading and at any time during the kneading. D is less scattered to the reaction system or the mixing system, and the polymerization time or the mixing time is shortened. The addition time of the component D is preferably from the beginning of the polycondensation reaction until the polymerization reaction is carried out to bring the relative viscosity of the reactants to 1.2. , or from the beginning of the mixing until the relative viscosity of the kneading secrets reaches 1.2. The component D may be added to the reaction system or the kneading system in the form of a slurry or a dissolved solution which is dispersed in a liquid such as water. 28 323631 201239004 For example, the ingredients may be simultaneously pressurized and/or include the components A, B, C, and D, and under the decompression (4) melt a 2 (four) melt polymerization, Method of component B and component C of °2 #. In addition, it is also possible to use D-starting and component A polymerization (four) method; after the enthalpy polymerization, and then in the manufacturing method of the present invention, thermal decomposition is carried out to obtain a stable "good polymerization reaction, and the temperature is preferably suppressed. From the viewpoint of (10) to the polymer of (10) to 3 = ^, it is preferably 180 to 25 Å. It is preferably 160 to 280 C, and is used as a component or an atmospheric pressure melt polymerization and is used in combination. When the method of the step of condensing and melting the polycondensation polymerization is carried out, on the one hand, when the MU is used as the component B, the water may be coexisted with the water of the appropriate one, which is generally under the pressure of Q. In the production method of the present invention, the desired property of the polyether decylamine is stably obtained by ensuring the coloring stability and suppressing the coloring due to the heat 77 solution. From the viewpoint of the elastomer, it can be usually produced in a period of from 5 to 2 hours. ^ In the production method of the present invention, it may be carried out in batch form or in a continuous manner. Further, it may be used alone or in appropriate combination. Use batch-type reaction dad, early trough or multi-tank continuous A device, a tubular continuous reaction device, etc. The mechanical properties of the polyether phthalamide elastomer which is obtained by the production method of the present invention are ensured, and it is not necessary to obtain a polymerization for a long time in the production method of the present invention. From the viewpoint of the ether amide elastomer, it is preferred to make the relative viscosity (77 r) of the polyether amide elastomer produced by the production method of the present invention (0.5 mass/volume% between metacresol solutions, 25 °C) is from 1. 2 to 3.5. [Polyether amide elastomer produced by the production method of the present invention] The polyether phthalamide elastomer obtained by the production method of the present invention is produced in the present invention. In the method, the added component D is mixed. Hereinafter, the polyether phthalamide elastomer obtained by the production method of the present invention refers to a state in which the component D is mixed, and may also be referred to as the production method of the present invention. a polyether phthalamide elastomer mixture or a polyether amide amine elastomer mixture. The polyether phthalamide elastomer obtained by the production method of the present invention contains a unit derived from the component A and a component derived from the component B. The unit from component C The compound is preferably from 10 to 95% by mass, and preferably from 15 to 90% by mass, based on 100% by mass of the total of the unit derived from the component A, the unit derived from the component B, and the unit derived from the component C. More preferably, it is 15 to 85% by mass, and more preferably 15 to 80% by mass; and the total of the unit derived from the component A and the unit derived from the component C is preferably 5 to 90% by mass, and 10 to 85% by mass. Preferably, it is preferably 15 to 85% by mass, more preferably 20 to 85% by mass; and the unit derived from the component A and the unit derived from the component C are preferably an amine residue derived from the component A (containing other The diamine compound also contains an amine group thereof and the carboxylic acid residue derived from the component C becomes almost equimolar. Further, in the polyether phthalamide elastomer, 100 parts by mass of the unit 30 from the component A, the unit derived from the component B, and the single s component from the component c, in the polymer of the present hairpin The component D to be mixed is preferably from 2 to 2 parts by mass, more preferably from 3 to 0.15 parts by mass. 〇1 The composition and composition of the material from the component A and the unit from the component C: in the polylysine elastomer can be determined by using liquid chromatography or gas phase after & B The chromatograph ir, ^ is generally determined by the method for evaluating the polymer. The MR and other ethers, the material from the component eight in the elastomer, the singularity and the quantification of the unit derived from the component C and the component C can be used after the hydrolysis of the monomer, using a liquid chromatograph or a gas phase. The chromatograph IR, ^ is generally used to evaluate the polymer (4) ^ illustrates an example of a method for analyzing the composition by hydrolysis. Hydrogen, hydrochloric acid or the like which selectively hydrolyzes the polyamine can be used as the hydrazine. The amount of hydrazine relative to the polyamide elastomer mixture is up to 100 ml.里 4 50 In order to promote hydrolysis more quickly, the polyamine amine elastomer mixture is pulverized and pulverized in the form of 'saki-like shape. , ,,. The temperature at the time of hydrolysis is from 1 Torr to 13 (TC. After the hydrolysis, the insoluble matter is separated from the acid solution by filtration or centrifugation, and high-speed liquid chromatography (HpLC) or gas chromatography/mass analysis (GC/) can be used. For example, if it is GC/MS, the analytical instrument can be used as the GCMS-QP5050A model manufactured by Shimadzu Corporation 31 323631 201239004, and the column system is Ultra all〇y + _(ms / ΗΤ) (0. 25 Φχ15ιη, 0·15#m), with a column temperature of 120 to 390 ° C (maintaining i2 ° C / min), at the inlet temperature 34 (rc, interface temperature 340 ° After introducing a carrier gas He at 2.0 ml/min in C, the ionization method (Ei method 70 eV), the measurement range 2 〇 to 9 〇〇, and the main entry method are cut (sp 1 it) method 1 8. The amount of injection 1 is measured by 1. The polyether phthalamide elastomer obtained by the production method of the present invention may be added with a heat-resistant agent, an ultraviolet absorber, a light stabilizer, or an antioxidant, without impeding the properties thereof. , antistatic agent, slip agent, slipagent, crystal nucleating agent, adhesive agent, sealing modification a polyether phthalamide elastomer composition prepared by the production method of the present invention, an anti-fogging agent, a release agent, a plasticizer, a pigment, a dye, a fragrance, a flame retardant, a reinforcing material, or the like. Elastomer, compatibility with thermoplastic resins other than polyether amide elastomers such as polyamide, polyethylene, polyurethane resin, acrylonitrile/butadiene/styrene copolymer (ABS) A polyether phthalamide elastomer composition which is excellent in moldability, impact resistance, elasticity, flexibility, and the like of the resin can be produced by mixing with such a thermoplastic resin. The polyether amide elastomer can maintain the color tone, the thermochromic property, and the transparency under the property originally possessed by the polyether phthalamide elastomer, and the change in transparency after the wet heat treatment is small. A polymerization-promoting effect in the production of a polyether phthalamide elastomer, and a polymer having a desired degree of polymerization is obtained with good productivity. The polyether phthalamide elastomer obtained by the production method of the present invention can be used by 323631 32 201239004A known molding method such as molding, extrusion molding, blow molding, vacuum molding, or pressure forming is used to obtain a molded article. The obtained molded article is applied to, for example, automobile parts, electrical and electronic parts, industrial parts, sporting goods, medical treatment. 'Pharmaceutical supplies, etc. Car parts can be listed, for example, joint boots, rack and pinion boots, suspension boots, suspension boots, etc. Ball joint seal, seat belt parts, bumper fascia, emblem, decorative, instfiiinent panel, center panel ), center console box, door trim, pillar, assist grip, steering wheel, airbag cover, etc. Examples of electrical and electronic components include wire covering materials, fiber covering materials, gears, rubber switches, membrane switches, tact switches, switch cases, watch bands, and vacuum cleaners. Bumper, remote control switch, keytop of office automation equipment, silencer gear, etc. Examples of industrial parts include hydraulic hoses, coil tubes, seals, gears, cams, bearings, bearing packing, gaskets, and packing. ), 0-ring (ring-ring), conveyor belt, V-belt, roll, shock-proof material, shock absorber, coupling (C0Upiing), diaphragm (diaphragm) , fasteners, valves, joints, grips, caster rollers, clips (cnp), etc. Sports items such as golf balls, 323631 33 201239004 baseball, soccer, land sports and other sports shoes soles; ski boot ball games and so on. Designing or decorative parts are required, for example, sunglasses, eyeglasses, and the like. Examples of medical articles include medical tubes, blood transfusion bags, and catheters. Further, examples thereof include elastic fibers, elastic sheets, small tubes, hoses, pipes, rods, films, sheets, brushes, and the like. Fish nets, nets, composite plates, hot melt adhesives, alloy materials made with other resins, etc. [Examples] Hereinafter, the present invention will be described by way of Examples and Comparative Examples, but the present invention is not limited to the scope of the Examples. [Metal Property Measurement, Forming, and Evaluation Method] Physical property measurement, molding, and evaluation were carried out as follows. 1) Relative viscosity (77 r) Using a meta-cresol of a reagent grade as a solvent, the concentration was measured at 25 ° C using an Oswald viscometer (〇stwald viSC0Simeter) at a concentration of 5 g/dm 3 . 2) The terminal carboxyl group concentration is added to 4 〇mL of phenylhydrin in a polymer of about lg, and after heating and dissolving in a nitrogen atmosphere, phenolphthalein as an indicator is added to the obtained sample solution to N/20 hydrogen. Potassium oxide-ethanol solution titration. 3) The terminal amine group concentration is such that about lg of the polymer is dissolved in 4 〇mL of the phenol/methanol mixed solvent (capacity ratio: 9/1), and the phenol ugly as an indicator is added to the obtained sample solution to N/ 20 hydrochloric acid titration. 323631 34 201239004 4) Analysis of the atomic concentration of the atom is carried out by dry ashing in the coexistence of sodium carbonate or after wet decomposition in ♦ H-sulfuric acid or sulfur/peroxidic acid aqueous solution. Phosphorus as orthophosphoric acid Next, the molybdate is reacted in an lm〇1/L sulfuric acid solution to prepare phosphomolybdic acid, which is reduced by hydrazine sulfate to produce a hemoglobin blue heteropoly acid. The absorbance at 83 〇 nm of the cerium molybdenum blue heteropoly acid was measured by (U-3000, manufactured by Hitachi, Ltd.), and colorimetric quantification was performed. 5) Analysis of sodium atom concentration After the sample was ash-decomposed in a white gold crucible, 6 m〇l/L hydrochloric acid was added to evaporate and dry. After dissolving in 1.2 m〇i/L hydrochloric acid, the solution was quantified by an atomic absorption spectrophotometer (AA_66〇, manufactured by Shimadzu Corporation). 6) Mechanical properties The determinations of (1) to (3) indicated below are After the injection molding was carried out into the following test piece, it was measured using it. (1) Tensile yield strength and tensile fracture strain: A test piece having a thickness of 4 mm was used in accordance with ISO 527-1, 2, and measured in 23.0. (2) Bending test (bending strength and flexural modulus): A test piece having a thickness of 4 mm was used, and it was measured at 23 ° C according to iso 178. (3) Charpy impact strength (notched (n〇tch)): using a notched 4 mm thick test piece according to ISO 179-leA (edge impact test) at 23 ° C and -40 ° C The measurement was carried out. 35 323631 « 201239004 7) Haze Use a 25 mm x 60 mm x 2 mm thin sheet formed by injection molding, and use a direct reading haze computer (Suga Tester Co., Ltd., HGM-2DP) in accordance with JIS K-7105. The measurement was carried out. 8) Transparency after hot water treatment A sheet of 25 mm x 60 mm x 2 mm thick formed by injection molding was immersed in hot water at 80 ° C for 24 hours. Then, the sample is taken out, and the haze of the sample after the hot water treatment is measured in the same manner as the above 7) haze, and the change in haze is obtained by the difference between the initial haze and the initial haze, and the hot water treatment is evaluated. Transparency. When the change value of the haze is 12% or less, it is judged that the transparency after the hot water treatment is excellent. 9) Hue using a chromaticity computer (made by Suga Tester Co., Ltd.), the yellowness of the resulting pellet is Yi. 10) Heat discoloration The resulting granules are placed in a TC oven. Then, the particulate matter is taken out, and the yellowness Y1 of the particulate matter after the heat treatment is measured in the same manner as the above 9), and the change in the yellowness Y1 (ΔΥ1) is obtained by the shame of the initial yellowness γ1. The discoloration of the heat treatment was evaluated. When ΔΥ1 is 10.0 or less, it is determined that the heat discoloration property after heat treatment is excellent. [Materials used] (Machine D) Compounds containing Dish atoms (D-1) Phosphorous acid (made by Taiping Chemical Industry Co., Ltd.) 36 323631 201239004 (D-2) Hypophosphorous acid (Taiping Chemical Industry Co., Ltd.) (D_3) Phosphoric acid (made by Taiping Chemical Industry Co., Ltd.) (D-4) Sodium hypophosphite (made by Taiping Chemical Industry Co., Ltd.) * (D-5) Sodium phosphite (made by Taiping Chemical Industry Co., Ltd.) Example 1] Loading 12-aminododecane in a 70-liter pressure vessel equipped with a mixer, a thermometer, a torque meter, a pressure gauge, a nitrogen inlet, a pressure regulator, and a polymer outlet. Acid (Ube Industries, Ltd.) 9. 000kg, adipic acid (Asahi Kasei Co., Ltd.) 〇. 747kg, XYX type triblock polyether diamine (manufactured by HUNTSMAN: m-542, amine price: 1. 96 meq / g) 3. 564 kg, isophorone diamine (Evonik company: VESTAMIN IPD) 274 274 kg, (D-1) phosphorous acid 20.4 g and heat-resistant agent (Jifu Pharmaceutical Co., Ltd., Tominox 917 ) 40.8g. After the inside of the vessel was sufficiently replaced with nitrogen, the pressure in the vessel was adjusted to 〇. 〇 5 MPa while supplying nitrogen gas at 186 liters/hour, while taking 3.5 hours to raise the temperature from room temperature to 23 (TC, and the inside of the vessel was The pressure was adjusted to 0. 〇 5 MPa, and the polymerization was carried out at 23 (TC). The ampere value of the mixing power was recorded by the time S, and the time point at which the ampere value of the mixing power reached 4.75 A was used as the polymerization end point. Thereafter, the mixing was stopped, and the colorless transparent polymer in a molten state was taken out from the polymer outlet, and after being water-cooled, pelletized to obtain pellets. [Example 2] 12-aminododecanoic acid (manufactured by Ubetsu 323631 37 201239004) 9. 510kg, adipic acid (made by Asahi Kasei Co., Ltd.) 0. 511kg, XYX type triblock polyether diamine (HUNTSMAN) A polyether phthalamide elastomer was obtained in the same manner as in Example 1 except that m-542, an amine price: 1.96 meq/g) of 3.565 kg, and no isophorone diamine was used. Examples 3 to 4] In addition to the addition amount of (D-1) in Example 1 The polyether phthalamide elastomer was obtained in the same manner as in Example 1 except for the ratios shown in Table 1. [Example 5] (D-1) was changed to (D) in Example 1. -2) The polyether phthalamide elastomer was obtained in the same manner as in Example 1 except that the ratio shown in Table 1 was changed. [Example 6] (D-1) except in Example 1. The polyether phthalamide elastomer was obtained in the same manner as in Example 1 except that (D-3) was changed to the ratio shown in Table 1. [Comparative Example 1] Except that it was not used in Example 1. A polyether phthalamide elastomer was obtained in the same manner as in Example 1 except for (D-1). [Comparative Examples 2 to 3] The addition amount of (D-1) in Example 1 was changed to The polyether phthalamide elastomer was obtained in the same manner as in Example 1 except for the ratios shown in Table 1. [Comparative Example 4] 38 323631 201239004 In addition to the modification of (D-1) in the first embodiment ( A polyether phthalamide elastomer was obtained in the same manner as in Example 1 except for D-4. [Comparative Example 5] 'In addition to Example 1, (D-1) was changed to (D-5). Outside, the rest A polyether phthalamide elastomer was obtained in the same manner as in Example 1. The time required for the polycondensation reaction (polymerization time) and the relative amount of the polymer were obtained for the polyether phthalamide elastomer obtained in each of the examples and the comparative examples. The results of analysis of viscosity, terminal carboxyl group concentration, terminal amine group concentration, phosphorus atom concentration, sodium atom concentration, and the results of the above evaluation are shown in Table 1. 39 323631 201239004 Comparative Example 5 in Λ CO ο CO CO Oi to inch 0.0428 0.0336 &gt 300 〇C<1 03 g ο 35.4 50.2 m L 〇 a comparative example 4 γ a 0.15 ο another CO σ> CO oo CO 0. 0455 0.0352 >300 = IT) g π oo c>i CO 46.9 Cjj c〇 Comparative Example 3: Λ1.94 inch CO eg 1 0.3780 <0.001 CO > 300 in CM CO g ο in i〇n 13.7 oo τ CO cJ 1 Comparative Example 2 Λ S ο ο 03 1.90 CO CO 05 CvJ 2 ο ο <0. 001 CO >300 = in CM g 2 CO IT) oo O) 0*3 Comparative Example 1 I 1 1050 1 1.89 ΙΛ CO S <0. 001 <0.001 CO >300 in g CO CsJ cd σ> CO Example 6 CO Λ CM ο ο CO CsJ L〇O) s σ> 0. 0623 <0.001 >300 CNi o CM 03 g CO ο 05 CsJ Γ3 oo an embodiment 5 CM Λ OJ ο s CM CO O) oo 呀 - 1 0.0923 < 0.001 > 300 CO 〇 CM Cs3 g CO CSJ 00 cvj 10.8 OO CO eg an embodiment 4 ό CO ο o CM Cvj 03 in oo in 03⁄4 ο <0.001 >300 C0 s eg g ΙΛ CO in CO CO σί -4.0 c- c<i Example 3 Λ ο 〇Cv3 CO 03 CO to m 0. 0382 <0.001 In >300 〇〇in g OO s ο 03 -2.8 CM CO Example 2 ό C<1 ο o in CM £ CO ΙΛ 0. 0798 <0.001 卜>300 i〇oo CM g = o CO σ> CM CM eg· Example 1 Λ 03 ο tn in eg 1.95 CO CD o 0. 0790 <0.001 >300 = L〇OO g CO CO CNJ oo OO CO LT? C^j Type of quality portion of money 1 ueq/ g I β eq/g parts by mass CQ C0 CO kJ/m! kJ/m! 1 1 formulation amount polymerization time relative viscosity terminal carboxyl group concentration terminal amine concentration phosphorus atom concentration sodium atom concentration tensile strength tensile rupture strain Flexural strength Flexural modulus 23°C -40°C Haze (Thickness 2 awake) Change in haze (thickness 2 legs) after hot water treatment Initial yellowness (YI) Change in yellowness after heat treatment (zYI ) (D ) Charpy impact strength (notched) of compound containing phosphorus atom 40 323631 201239004 It can be seen from Table 1 that Comparative Example 1 which does not use component D requires a large amount of time until the polymerization is completed, and the initial color tone or the degree of discoloration after heat treatment is large. , heat resistant discoloration is not good. In Comparative Example 2 in which the amount of the component D was not within the predetermined range, it took a lot of time until the polymerization was completed, and the initial color tone or the degree of discoloration after the heat treatment was large, and the heat discoloration resistance was poor. Further, in Comparative Example 3 in which the amount of the component D was more than the predetermined range, the balance of the terminal groups was broken, so that the polymerization time was long and the transparency after hot water treatment was poor. In Comparative Examples 4 and 5 using the component D other than the above-described regulations, the transparency after hot water treatment was poor. On the other hand, it is understood that the polyether phthalamide elastomers specified in the present invention of Examples 1 to 6 are excellent in color tone, heat discoloration resistance, and transparency while maintaining the properties originally possessed by the polyether phthalamide elastomer. The change in transparency after the wet heat treatment is small, and there is also a sufficient polymerization promoting effect. [Simple description of the diagram] None. [Main component symbol description] None. 41 323631

Claims (1)

201239004 VII 1. Patent Application Range: A method for producing a polyether amide elastomer having a diamine compound (ingredient A), a polyamine forming monomer (ingredient B), and a dicarboxylic acid compound (ingredient C) a step of performing melt polycondensation; wherein, before, during or after the foregoing step, a compound containing a male atom (ingredient D) is added; when the aforementioned component D is added before or during the aforementioned step, the component D is When the component D is added after the step, the polymer obtained by melt-condensing the melt in the above step is subjected to the melt-kneading in the presence of the component D; the component A contains the following formula; (1) A triblock polyether diamine compound (ingredient A1): ch3 ... .CH3 CH, Η, HCHp CH2CH2CH2CH2〇CHjJhO -C^HN^ (1) y (in the formula (1), x represents an integer of 1 to 20, y represents an integer of 4 to 50, and z represents an integer of 1 to 20); (2) An aminocarboxylic acid compound (component B1) and/or an indoleamine compound (component B2) represented by the following formula (3): H2N-R1 - COOH (2) (in the formula (2), R1 Represents a linker containing a hydrocarbyl chain) (3) 1 323631 201239004 (In the formula (3), R2 represents a linking group containing a hydrocarbon group); the component C is a compound represented by the following formula (4): HOOC-f R3)~-COOH (4) m 4 (formula) (4), R3 represents a linking group containing a hydrocarbon group chain, and m represents 0 or 1); 'The component D is a compound represented by the following formula (5), a compound represented by the following formula (6), and the following At least one compound of the compound represented by the formula (7), the compound represented by the following formula (8), the compound represented by the following formula (9), and the compound represented by the following formula (10): 〇ΧιΟ- Ρ—OX3 (5) ΟΧ2 ο R4 — Ρ—ΟΧ5 (6) ΟΧ4 ο R5 ——Ρ—ΟΧ6 (7) I6 ΟΧ9 (8) χ7ο — Ρ— χ8 οχ11 (9) R7——Ρ — ΟΧ10 2 323631 (10) (10 ) 201239004 ι9 R8 —-P——OX12 (In the formulae (5) to (10), R4 to R9 may be the same or different and represent a hydrogen atom, or an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, X1 To X12 represents a hydrogen atom, or a pyridyl group, a cycloalkyl group, an aryl group, an aryl group, except for a metal element;; relative to the aforementioned polyether phthalamide elastomer 100 Parts, the phosphorus atom is 0.005 to 0.3 parts by mass. 2. The method for producing a polyether amide elastomer according to the first aspect of the invention, wherein, in the step (1), the total amount of the components B, 100 and C is 100% by mass of the component B. The ratio is from 10 to 95% by mass. 3. The method for producing a polyether amide elastomer according to the first or second aspect of the invention, wherein, in the step (1), the component is 100% by mass based on the total amount of the components A, B and C. The ratio of B is from 15 to 80% by mass, and the total ratio of the above components A and C is from 20 to 85% by mass. 4. The method for producing a polyether amide elastomer according to any one of claims 1 to 3, wherein R1 of the above formula (2) contains an alkylene group having 2 to 20 carbon atoms. 5. The method for producing a polyether amide elastomer according to any one of claims 1 to 4, wherein R2 of the above formula (3) contains an alkylene group having 2 to 20 carbon atoms. 6. The method for producing a polyether amide amine 3 323631 201239004 y according to any one of claims 1 to 5, wherein x of the above formula (1) is 2 to 6 is β to 12 'And z is 1 to 5. Such as the scope of patent application! The method for producing a polyamine-containing elastomer according to any one of the above-mentioned items, wherein the above formula (1) has X of 2 to 10, y of 13 to 28' and z of 1 to 9. • For example, the 14: ^ method of the poly-salt ampoule described in the above-mentioned items of items 1 to 7 wherein the component 纟 contains a component selected from the group consisting of 6 to 22 carbon atoms. At least one diamine compound (ingestane Α 2) in the group of a branched saturated diamine, a branched alicyclic diamine having 6 to 16 carbon atoms, and a norbornane diamine. The method for producing a polyether phthalamide elastomer according to the above aspect of the invention, wherein the ratio of the component Α2 is 0.5 to 1% by mass based on the total amount of the components Α, β and C. 10% by mass. The method for producing a polyether amide elastomer according to claim 8 or claim 9, wherein the branched saturated diamine having 6 to 22 carbon atoms is selected from the group consisting of 2, 2, 4-trimethyl-1,6-diaminohexane, 2,4,4-trimethyl 6-monoaminocarb, 2-mercapto-1,5-diaminopentane, 2- Mercapto~1,8-diamino octyl or a diamine in a mixture of such. The method for producing a polyether amide elastomer according to any one of claims 8 to 1, wherein the aforementioned branched alicyclic diamine having 6 to 16 carbon atoms is selected from the group consisting of 5 -Amino-2,2,4-trimethyl-1-cyclopentandecylamine, 5-amino-1,3,3-trimethylcyclohexanedecylamine or such far-reaching compound The diamine in the. 12. The polyether phthalamide according to any one of claims 8 to 11, wherein the method for producing an elastomer is wherein the aforementioned norbornane diamine is selected from the group consisting of 2, 5-norborns. Mercaptoamine, 2,6-norbornone dimethylamine or a diamine in a mixture of such. The method for producing a polyether phthalamide elastomer according to any one of claims 1 to 12, wherein the component C is an aliphatic dicarboxylic acid or an alicyclic ditolic acid. The method for producing a polyether phthalamide elastomer according to any one of the preceding claims, wherein m of the above formula (4) is i, and R3 is a carbon number of 1 to 20. Alkyl. 15. The method for producing a polyether amide elastomer according to the above-mentioned patent application, wherein the above-mentioned is at least selected from the group consisting of phosphoric acid, squaric acid and hypophosphorous acid. - kind. 16. A polyamine elastomer which is produced by the method for producing a polylysine elastomer according to any one of the above-mentioned patents. 323631 5 201239004 IV. Designated representative map: (1) The representative representative of the case is: The case has no schema. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: The chemical formula that is not represented in this case. 3 323631