JP2002060596A - Flame-retardant polyester elastomer resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyester elastomer resin composition excellent in flame retardance and flexibility, and capable of providing a molded product having a uniform thickness containing no foreign particles. SOLUTION: This flame-retardant polyester elastomer resin composition is obtained by compounding (A) 100 pts.wt. of a polyetherester block copolymer comprising (a) a high-melting crystalline polymer segment mainly composed of a crystalline aromatic polyester unit and (b) a low-melting polymer segment mainly composed of an aliphatic polyether unit with (B) 1-50 pts.wt. of a phosphorus compound and (C) 0.01-10 pts.wt. of a fatty acid amide compound. The flame retardant polyester elastomer resin composition is prepared by, as desired, further compounding (D) 0.1-30 pts.wt. of a nitrogen containing compound, (E) 0.01-10 pts.wt. of a fluorine resin and (F) 0.01-10 pts.wt. of a monocarbodiimide compound and/or (G) 0.01-10 pts.wt. of a polycarbodiimide compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester elastomer resin composition which is excellent in flame retardancy and flexibility, has good appearance without foreign matters, and provides a molded article having a uniform thickness.

[0002]

2. Description of the Related Art Polyester elastomers having a hard segment of a crystalline aromatic polyester unit such as a polybutylene terephthalate unit and a soft segment of an aliphatic polyether unit such as a poly (alkylene oxide) glycol unit are extrudable. Excellent in injection moldability, high mechanical strength, rubber properties such as impact resistance, elastic recovery, flexibility, low and high temperature properties, water resistance, etc. Because
Its applications are expanding to automotive parts, electric / electronic parts, textiles, films, etc.

[0003] In order to improve the flame retardancy of polyester elastomers, many studies have been made on the addition of various flame retardants. Recently, from the viewpoints of safety and environmental considerations, techniques using non-halogen flame retardants have been studied. There are suggestions. For example, JP-A-8-259787 discloses a flame-retardant elastomer composition obtained by blending a phosphorus-based compound and a nitrogen-containing compound with a thermoplastic polyester elastomer. JP-A-11-48428 discloses a flame-retardant elastomer laminated sheet in which a phosphoric compound such as an ammonium phosphate is added to a polyester block copolymer. JP-A-9-143346 discloses a flame-retardant polyester block copolymer composition obtained by adding ammonium sulfate and a melamine compound to a polyester block copolymer.

However, when a phosphorus-based compound is blended with the polyester elastomer, foreign matters are easily formed by thermal decomposition during melting. If this foreign substance is colored black,
Even when it appears as black dots on the surface of the molded product and is not colored, bumps are formed on the surface of the molded product when processed by extrusion or the like, and the appearance of the molded product is poor. In addition, when a phosphorus-based compound is blended with the polyester elastomer, pulsation is likely to occur during molding, which causes uneven thickness particularly during extrusion molding, so that it is difficult to obtain a molded product having a uniform thickness. For this reason, a polyester elastomer resin composition having a good appearance without a foreign substance and the like, giving a molded article having a uniform thickness, and also having high flame retardancy and excellent mechanical properties represented by flexibility. It is the present situation that appearance is expected.

Further, Japanese Patent Publication No. 47-49174 discloses a polyester composition in which a fatty acid amide is blended with an elastic polyester to improve the anti-blocking property and anti-adhesion property, and Japanese Patent Application Laid-Open No. 9-364977. Discloses a technique for blending a carboxylic acid amide-based wax with a polyester block copolymer to provide a thermoplastic polyester elastomer having excellent mold release properties from a molding die and low mold depositability during continuous molding. Have been.

[0006]

SUMMARY OF THE INVENTION The present invention has been made as a result of studying to solve the problems in the prior art described above.

[0007] Accordingly, an object of the present invention is to provide a polyester elastomer resin having a good appearance and a uniform thickness without the presence of foreign substances, and having excellent flame retardancy, flexibility, and viscosity stability during melt retention. It is to provide a composition.

[0008]

In order to achieve the above object, the flame-retardant polyester elastomer resin composition of the present invention comprises: (1) a high-melting crystalline polymer mainly composed of crystalline aromatic polyester units; With respect to 100 parts by weight of a polyetherester block copolymer (A) having a segment (a) and a low-melting point polymer segment (b) mainly composed of an aliphatic polyether unit as a main component, a phosphorus compound ( B) 1 to 50 parts by weight, and 0.01 to 10 parts by weight of a fatty acid amide compound (C).

(2) The composition (1) is further characterized in that 0.1 to 30 parts by weight of a nitrogen-containing compound (D) is blended with the composition (1).

(3) The composition (2) is further characterized in that the composition is mixed with 0.01 to 10 parts by weight of a fluororesin (E).

(4) The composition (1) is further characterized in that the composition (1) is mixed with 0.01 to 10 parts by weight of a monocarbodiimide compound (F) and / or a polycarbodiimide compound (G).

(5) The composition (2) is further characterized in that the monocarbodiimide compound (F) and / or the polycarbodiimide compound (G) are mixed in an amount of 0.01 to 10 parts by weight.

(6) Further, the composition (3) is characterized in that 0.01 to 10 parts by weight of a monocarbodiimide compound (F) and / or a polycarbodiimide compound (G) is blended.

(7) In the flame-retardant polyester elastomer resin composition of the present invention, the high-melting crystalline polymer segment (a) which is a component of the polyetherester block copolymer (A) is used. (8) a low-melting polymer segment (b) which is a component of the polyetherester block copolymer (A)
Is composed of a poly (tetramethylene oxide) glycol unit and / or an ethylene oxide addition polymer unit of poly (propylene oxide) glycol. (9) The low-melting polymer segment in the polyetherester block copolymer (A). (B) the copolymerization amount is 10 to 80% by weight; (10) the phosphorus compound (B) is an organic phosphate and / or an inorganic phosphorus compound; and (11) the fatty acid amide compound. Compound (C) has 1 carbon atom
A monoamide compound of two or more higher fatty acids, (12) the fatty acid amide compound (C) has 1 carbon atom
(13) The fatty acid amide-based compound (C) is a bisamide compound of two or more higher fatty acids,
A fatty acid amide-based wax obtained by reacting a mixture of two or more higher aliphatic monocarboxylic acids and polybasic acids with a diamine compound; (14) the nitrogen-containing compound (D) is a triazine-based compound (15) the fluorine-based resin (E) is a polytetrafluoroethylene-based polymer; (16) the monocarbodiimide compound (F) is bis (2,6-diisopropylphenyl) carbodiimide; 17) The polycarbodiimide compound (G) is a polymer of triisopropylphenylene-1,3-diisocyanate, and (18) an electric wire coating or an optical fiber coating. When these conditions are applied, it is possible to expect to obtain a better effect.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The present invention provides a polyether having a high melting point crystalline polymer segment (a) mainly composed of a crystalline aromatic polyester unit and a low melting point polymer segment (b) mainly composed of an aliphatic polyether unit as main components. The ester block copolymer (A) is used.

The high-melting crystalline polymer segment (a) of the polyetherester block copolymer (A) is mainly composed of a crystalline aromatic aromatic carboxylic acid or its ester-forming derivative and an aliphatic diol. "Predominantly" means a unit containing about 70 mol% or more of these units, preferably terephthalic acid and / or polybutylene derived from dimethyl terephthalate and 1,4-butanediol. It is a terephthalate unit. In addition, terephthalic acid, isophthalic acid, phthalic acid, and naphthalene-2,6-
A dicarboxylic acid component such as dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sulfoisophthalic acid, or an ester-forming derivative thereof; and a molecular weight of 300 The following diols, for example, aliphatic diols such as 1,4-butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, 1,4-cyclohexanedimethanol, tricyclo Alicyclic diols such as decane dimethylol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane , Bis [4- (2-hydroxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,
Polyester units derived from aromatic diols such as 4'-dihydroxy-p-terphenyl and 4,4'-dihydroxy-p-quarterphenyl, or a copolymer of two or more of these dicarboxylic acid components and diol components. It may be a polymerized polyester unit. It is also possible to copolymerize a trifunctional or higher polyfunctional carboxylic acid component, a polyfunctional oxyacid component, a polyfunctional hydroxy component and the like in a range of 5 mol% or less.

The low-melting-point polymer segment (b) of the polyester block copolymer (A) used in the present invention mainly comprises units containing aliphatic polyether as a constituent. It contains about 70 mol% or more of units. Specific examples of the aliphatic polyether include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, poly ( Examples include an ethylene oxide addition polymer of (propylene oxide) glycol and a copolymer of ethylene oxide and tetrahydrofuran. Among these aliphatic polyethers, it is preferable to use poly (tetramethylene oxide) glycol and an ethylene oxide adduct of poly (propylene oxide) glycol because the resulting polyester block copolymer has excellent elastic properties. Further, the number average molecular weight of these low melting point polymer segments is preferably about 300 to 6000 in a copolymerized state.

The polyetherester block copolymer (A) of the present invention comprises the above-mentioned crystalline polymer segment (a) having a melting point.
And the above-mentioned low-melting polymer segment (b) as a main constituent requirement, and “main” means that these (a) and (b) are contained in about 70% or more.

The copolymerization amount of the low melting point polymer segment (b) in the polyetherester block copolymer (A) used in the present invention is preferably 10 to 80% by weight,
More preferably, the content is 15 to 75% by weight.

The polyetherester block copolymer (A) used in the present invention can be produced by a known method. For example, a method of subjecting a lower alcohol diester of a dicarboxylic acid, an excessive amount of a low-molecular-weight glycol, and a low-melting polymer segment component to a transesterification reaction in the presence of a catalyst, and polycondensing the obtained reaction product, or an excess method with a dicarboxylic acid A method of subjecting an amount of glycol and a low-melting polymer segment component to an esterification reaction in the presence of a catalyst to polycondensate the resulting reaction product. Any method may be used, such as a method in which the compound is added and randomized by a transesterification reaction.

Specific examples of the phosphorus compound (B) as one of the components used in the present invention include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, octyl diphenyl phosphate, Zyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, trixylenyl phosphate, diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate, bis (1,3-phenylenediphenyl) phosphate, resorcinol-bis- (di- 2,6-dimethylphenyl phosphate), hydroquinone-bis- (di-2,6-dimethylphenyl phosphate), 4,4'-biphenylene-bis- (di-2,6-dimethylphenyl) Phenyl phosphate), organic phosphates such as resorcinol-bis- (di-4-methylphenyl phosphate), hydroquinone-bis- (di-4-methylphenyl phosphate), resorcinol-bis- (dimethylphenyl phosphate) and / or Inorganic phosphorus compounds such as ammonium polyphosphate and melamine phosphate are exemplified. Among these, triphenyl phosphate, resorcinol-bis- (di-
Use of 2,6-dimethylphenyl phosphate), hydroquinone-bis- (di-2,6-dimethylphenyl phosphate) and ammonium polyphosphate is preferred. Ammonium polyphosphate whose surface is coated can also be used. The compounding amount of the phosphorus compound (B) is determined based on the polyetherester block copolymer (A) 10
1 to 50 parts by weight, preferably 3 to 45 parts by weight with respect to 0 parts by weight.
Parts by weight, more preferably 5 to 40 parts by weight.

The aliphatic amide compound (C), which is one of the components used in the present invention, is an aliphatic compound having an amide group in its chemical structure. Specific examples thereof include oleyl oleamide and stearyl olein. Aliphatic amide compounds such as acid amide and oleyl stearamide;
Methylenebisstearic acid amide, ethylenebisstearic acid amide, methylenebisoleic acid amide, ethylenebisoleic acid amide, methylenebispalmitic acid amide, ethylenebispalmitic acid amide, methyleneoleic acid stearic acid diamide, ethylene oleic acid stearic acid diamide, Reaction of aliphatic bisamide compounds such as methylene oleic acid palmitic acid diamide, ethylene oleic acid palmitic acid diamide, methylene stearic acid palmitic acid diamide, ethylene stearic acid palmitic acid diamide, and a mixture of aliphatic monocarboxylic acid and polybasic acid with diamine And the like. Such a fatty acid amide-based wax is obtained by a dehydration reaction of a mixture of an aliphatic monocarboxylic acid and a polybasic acid with a diamine. As the aliphatic monocarboxylic acid, a saturated aliphatic monocarboxylic acid and a hydroxycarboxylic acid are preferable, and examples thereof include palmitic acid, stearic acid, behenic acid, montanic acid, and 12-hydroxystearic acid. As the polybasic acid, a dibasic acid or higher carboxylic acid, for example, an aliphatic dicarboxylic acid such as malonic acid, succinic acid, adipic acid, sebacic acid, pimelic acid, and azelaic acid, and an aromatic compound such as phthalic acid and terephthalic acid Group dicarboxylic acids and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and cyclohexylsuccinic acid. As the diamine compound, for example,
Ethylenediamine, 1,3-diaminopropane, 1,4
-Diaminobutane, hexamethylenediamine, metaxylenediamine, tolylenediamine, paraxylylenediamine, phenylenediamine, isophoronediamine and the like. The fatty acids constituting these fatty acid amide compounds are preferably higher fatty acids having 12 or more carbon atoms.

When the flame-retardant polyester elastomer resin composition of the present invention contains a nitrogen-containing compound (D), the flame retardancy, mechanical properties and moldability are further improved in a well-balanced manner. Here, the nitrogen-containing compound (D) is an aliphatic amide compound defined as the above (C), (F)
Excluding the monocarbodiimide compound defined as (G) and the polycarbodiimide compound defined as (G).

Specific examples of the nitrogen-containing compound (D) which is one of the components used in the present invention include melamine, cyanuric acid, melamine cyanurate, melamine phosphate, benzoguanamine, acetoguanamine and the like. Of these, melamine cyanurate is particularly preferred. The compounding amount of the nitrogen-containing compound (D) is based on 100 parts by weight of the polyetherester block copolymer (A).
0.1 to 30 parts by weight, preferably 0.3 to 25 parts by weight,
More preferably, it is 0.5 to 20 parts by weight.

Further, when the flame-retardant polyester elastomer resin composition of the present invention contains a fluorine-based resin (E), dripping during combustion is suppressed, which is effective for improving flame retardancy. Specific examples of the fluororesin (E) which is one of the components used in the present invention include polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkylvinylether) copolymer, and (tetrafluoroethylene / ethylene) copolymer. Tetrafluoroethylene-based polymers such as a polymer and a (tetrafluoroethylene / hexafluoropropylene) copolymer are exemplified. Among these, use of polytetrafluoroethylene is particularly preferred. The blending amount of the fluororesin (E) is 0.1 to 100 parts by weight of the polyetherester block copolymer (A).
The amount is from 0.01 to 10 parts by weight, preferably from 0.05 to 7 parts by weight, more preferably from 0.1 to 5 parts by weight.

When the flame-retardant polyester elastomer resin composition of the present invention is blended with a monocarbodiimide compound (F) and / or a polycarbodiimide compound (G), the viscosity stability during melt retention is further improved. Specific examples of the monocarbodiimide compound (F) which is one of the components used in the present invention include dimethylcarbodiimide, diisopropylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, dodecylisopropylcarbodiimide, dicyclohexylcarbodiimide, diphenylcarbodiimide, diphenylcarbodiimide, and diphenylcarbodiimide. o-
Examples include tolylcarbodiimide, bis (2,6-diethylphenyl) carbodiimide, bis (2,6-diisopropylphenyl) carbodiimide, di-β-naphthylcarbodiimide, benzylisopropylcarbodiimide, and phenyl-o-tolylcarbodiimide. Among these, bis (2,6-diisopropylphenyl)
The use of carbodiimides is preferred. The polycarbodiimide compound (G), which is one of the components used in the present invention, comprises:
A compound having at least two carbodiimide groups in the molecule, usually a compound derived from an isocyanate compound. Specific examples thereof include aromatic diisocyanates such as phenylene diisocyanate, toluene diisocyanate, methylene bisphenyl diisocyanate, xylene diisocyanate, triisopropylphenylene-1,3-diisocyanate, and tetramethylxylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. And carbodiimide compounds derived from aliphatic diisocyanates. Further, urea-modified polycarbodiimide obtained by reacting an aliphatic diisocyanate with a primary or secondary organic aliphatic amine to introduce a urea bond into the aliphatic diisocyanate and then carbodiimidating the urea-modified polycarbodiimide is also included. Among them, triisopropylphenylene-
The use of polymers of 1,3-diisocyanate is preferred.
The compounding amount of the monocarbodiimide compound (F) and / or the polycarbodiimide compound (G) is based on 100 parts by weight of the polyetherester block copolymer (A).
It is 0.01 to 10 parts by weight, preferably 0.03 to 7 parts by weight, more preferably 0.05 to 5 parts by weight.

In addition to the additives (B) to (G), various additives can be added to the flame-retardant polyester elastomer resin composition of the present invention as long as the object of the present invention is not impaired. For example, molding auxiliaries such as known nucleating agents and lubricants, various antioxidants and heat-resistant agents, UV absorbers and hindered amine-based light stabilizers, hydrolysis resistance improvers,
A coloring agent such as a pigment or a dye, an antistatic agent, a conductive agent, a reinforcing agent, a filler, a plasticizer, a release agent, a silane coupling agent and the like can be optionally contained.

The method for producing the flame-retardant polyester elastomer resin composition of the present invention is not particularly limited. For example, a predetermined phosphorus compound and a fatty acid amide compound are mixed with a polyetherester block copolymer. Raw material or a raw material obtained by mixing a predetermined phosphorus compound and a fatty acid amide compound and, if necessary, a nitrogen-containing compound, a fluorine resin or a carbodiimide compound in a polyetherester block copolymer, is supplied to a screw-type extruder. Melt-kneading method, screw-type extruder, first supply and melt polyetherester block copolymer, further supply phosphorus-based compound and other additives from other supply ports, kneading method, screw-type extruder First, supply the polyetherester block copolymer and fatty acid amide compound to the extruder and melt them. And a method of further kneaded by supplying phosphorus compound and other additives than the other supply port,
It can be adopted as appropriate. It is also possible to adopt a method in which the vent port of the screw type extruder is connected to a vacuum pump or the like to forcibly discharge volatile components and the like in the extruder.

The flame-retardant polyester elastomer resin composition of the present invention obtained in this way is not only excellent in flame retardancy and flexibility, but also has good appearance without any foreign matter and uniform thickness. Which is excellent in extrusion moldability and injection moldability. Therefore, it is extremely useful in fields such as automobile parts, electric / electronic parts, fibers, films, sheets and tubes. Further, since it is flexible and can be colored freely, it is also useful for covering electric wires or covering optical fibers.

[0030]

EXAMPLES The structure and effect of the present invention will be further described below with reference to examples. All percentages and parts in the examples are on a weight basis unless otherwise specified. The physical properties shown in Reference Examples were measured as follows. [Relative viscosity] 0.5 using o-chlorophenol as a solvent
% Polymer solution was measured at 25 ° C. [Melting Point] Differential Scanning Calorimeter (Du Pont DSC-
910) was measured at the top of the melting peak when heated at a rate of 10 ° C./min in a nitrogen gas atmosphere. [Hardness (Shore D scale)] Measured according to JIS K-7215. [Flame Retardancy] Flame retardancy of a test piece for flame retardancy evaluation obtained by injection molding was evaluated in accordance with the evaluation criteria defined in UL94. [Tensile modulus] Measured according to JIS K-7113. [Reference Example] [Production of polyester block copolymer (A-1)] 322 parts of terephthalic acid, 280 parts of 1,4-butanediol and 80 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1000 were added to titanium. 0.15 part of tetrabutoxide was charged into a reaction vessel equipped with a helical ribbon type stirring blade, and heated at 190 to 225 ° C for 3 hours to carry out an esterification reaction while distilling reaction water out of the system.
0.75 parts of "Irganox" 1010 (a hindered phenolic antioxidant manufactured by Ciba Geigy) was added to the reaction mixture, the temperature was raised to 245 ° C, and the pressure in the system was reduced to 27 Pa over 50 minutes. The polymerization was carried out under the conditions for 2 hours and 45 minutes. The obtained polymer was discharged into water in the form of a strand, and cut into pellets. [Production of polyetherester block copolymer (A-2)] 294 parts of dimethyl terephthalate, 243 parts of 1,4-butanediol and 178 parts of poly (tetramethylene oxide) glycol (number average molecular weight of about 1400) were added to titanium tetraester. 0.15 parts of butoxide were charged into a reaction vessel equipped with a helical ribbon-type stirring blade, and heated at 210 ° C. for 2 hours to give 95% of the theoretical methanol.
Was distilled out of the system. After adding 0.75 parts of “Irganox” 1010 to the reaction mixture, the temperature was raised to 245 ° C., and then the pressure in the system was reduced to 27 Pa over 50 minutes, and polymerization was carried out for 2 hours and 20 minutes under the conditions. I let you. The obtained polymer was discharged into water in the form of a strand, and cut into pellets. [Production of polyetherester block copolymer (A-3)] 189 parts of dimethyl terephthalate, 160 parts of 1,4-butanediol, and poly (propylene oxide) glycol end-capped with ethylene oxide (number-average molecular weight of about 2,200, EO content 26.8%) 29
7 parts together with 0.15 part of titanium tetrabutoxide and 3 parts of trimellitic anhydride were charged into a reaction vessel equipped with a helical ribbon type stirring blade, and heated at 210 ° C. for 2 hours and 30 minutes to give 95% of the theoretical methanol amount. Was distilled out of the system. Add "Irganox" 1010 to the reaction mixture.
After adding 0.75 parts, the temperature was raised to 245 ° C., and the pressure in the system was reduced to 27 Pa over 50 minutes, and polymerization was carried out for 1 hour and 50 minutes under these conditions. The obtained polymer was discharged into water in the form of a strand, and cut into pellets.

The polymer (A-
Table 1 shows the compositions and physical properties of (1), (A-2), and (A-3).

[0032]

[Table 1] [Examples 1 to 7] The polyetherester block copolymers (A-1), (A-2), and (A-
3) dry blending a phosphorus compound, a fatty acid amide compound, a nitrogen-containing compound, a fluororesin, and a carbodiimide compound in a mixing ratio shown in Table 2;
Using a twin screw extruder having a screw of 5 mmφ, 2
After melt-kneading at 40 ° C., the mixture was pelletized. The pellets were dried at 80 ° C. for 5 hours, and injection molded at a molding temperature of 240 ° C. and a mold temperature of 60 ° C.

Using the obtained pellets and injection molded pieces, the flame retardancy and tensile modulus were measured. The dried pellets obtained here were press-molded to a thickness of 0.2
mm sheet was prepared. The length of this sheet is 1
A 0 cm square was cut out, and the number of foreign substances observed therein was counted. Table 3 shows the results.

[0034]

[Table 2]

[0035]

[Table 3] [Comparative Examples 1 to 4] The raw materials of the resin composition were dry-blended at the respective mixing ratios shown in Table 2, and pelletized as in Examples 1 to 7. From these pellets, Examples 1 to 7
A test piece was prepared by injection molding in the same manner as described above.
Press sheets were prepared in the same manner as in Examples 1 to 7, and the number of foreign substances was counted. Further, a tube was formed in the same manner as in Examples 1 to 7, and the number of bumps was measured. The results are shown in Table 3.

As is evident from the results in Table 3, the flame-retardant polyester elastomer resin composition of the present invention in which a phosphorus compound and a fatty acid amide compound are blended with the polyetherester block copolymer has a high flame retardancy. Excellent flexibility and no foreign matter. Further, the flame-retardant polyester elastomer resin composition of the present invention comprising a polyetherester block copolymer, a phosphorus compound, a fatty acid amide compound, and a nitrogen-containing compound, a fluorine-based resin, and a carbodiimide compound. Good characteristic balance. On the other hand, the resin composition of the comparative example has more foreign substances than the resin composition of the present invention. Example 8 A tube having an inner diameter of 6.5 mm and a wall thickness of 0.5 mm was formed from the dried pellets obtained in Example 2 by extrusion using a vacuum sizing method at an extrusion temperature of 240 ° C. Although the viscosity was reduced during molding, a tube having a good surface state in which bumps were not observed at all around 500 m of the tube could be obtained. Example 9 Using the dried pellets obtained in Example 6, a tube was formed in the same manner as in Example 8. The viscosity at the time of molding was stable, the workability was good, and a tube having a good surface state in which no bumps were observed at all per 500 m could be obtained. The uniformity of the thickness was also good. Comparative Example 5 A tube was formed using the dried pellets obtained in Comparative Example 2 in the same manner as in Example 8. The viscosity decreased during molding, and workability was not good. Furthermore, ten bump-like projections were observed per 500 m of the obtained tube, and the thickness was not kept uniform.

[0037]

As described above, the flame-retardant polyester elastomer resin composition of the present invention is obtained by blending a polyetherester block copolymer with a phosphorus compound and a fatty acid amide compound. By blending a phosphorus-based compound, an aliphatic amide-based compound, a nitrogen-containing compound, a fluorine-based resin, and a carbodiimide compound into the ether ester block copolymer, it exhibits excellent flame retardancy and flexibility, and further contains foreign substances By not doing so, a molded article having excellent appearance and uniform thickness can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/521 C08K 5/521 C08L 75/00 C08L 75/00 C09K 21/04 C09K 21/04 21/10 21/10 21/12 21/12 // (C08L 67/00 (C08L 67/00 27:18) 27:18) F term (reference) 4H028 AA07 AA30 AA35 AA42 BA04 BA06 4J002 BD152 CF101 CF141 CK003 DH046 DH056 EP017 EP027 ER009 EU178 EU188 EW046 FD13 GM00 GQ01 GT00

Claims (18)

[Claims] 1. A polymer comprising, as main components, a high-melting crystalline polymer segment (a) mainly composed of a crystalline aromatic polyester unit and a low-melting polymer segment (b) mainly composed of an aliphatic polyether unit. Flame retardancy obtained by mixing 1 to 50 parts by weight of a phosphorus compound (B) and 0.01 to 10 parts by weight of a fatty acid amide compound (C) with respect to 100 parts by weight of an ether ester block copolymer (A). Polyester elastomer resin composition. 2. A polymer comprising, as main components, a high-melting crystalline polymer segment (a) mainly composed of crystalline aromatic polyester units and a low-melting polymer segment (b) mainly composed of aliphatic polyether units. 1 to 50 parts by weight of phosphorus compound (B), 0.01 to 10 parts by weight of fatty acid amide compound (C), nitrogen-containing compound (D) based on 100 parts by weight of ether ester block copolymer (A)
A flame-retardant polyester elastomer resin composition containing 0.1 to 30 parts by weight. 3. A polymer comprising, as main components, a high-melting crystalline polymer segment (a) mainly composed of crystalline aromatic polyester units and a low-melting polymer segment (b) mainly composed of aliphatic polyether units. 1 to 50 parts by weight of phosphorus compound (B), 0.01 to 10 parts by weight of fatty acid amide compound (C), nitrogen-containing compound (D) based on 100 parts by weight of ether ester block copolymer (A)
0.1 to 30 parts by weight, fluorine resin (E) 0.01 to 1
A flame-retardant polyester elastomer resin composition containing 0 parts by weight. 4. A polymer comprising, as main components, a high-melting crystalline polymer segment (a) mainly composed of crystalline aromatic polyester units and a low-melting polymer segment (b) mainly composed of aliphatic polyether units. For 100 parts by weight of the ether ester block copolymer (A), 1 to 50 parts by weight of the phosphorus compound (B), 0.01 to 10 parts by weight of the fatty acid amide compound (C), the monocarbodiimide compound (F) and A flame-retardant polyester elastomer resin composition comprising 0.01 to 10 parts by weight of a polycarbodiimide compound (G). 5. A polymer comprising, as main components, a high-melting crystalline polymer segment (a) mainly composed of crystalline aromatic polyester units and a low-melting polymer segment (b) mainly composed of aliphatic polyether units. 1 to 50 parts by weight of phosphorus compound (B), 0.01 to 10 parts by weight of fatty acid amide compound (C), nitrogen-containing compound (D) based on 100 parts by weight of ether ester block copolymer (A)
0.1 to 30 parts by weight, monocarbodiimide compound (F)
And / or polycarbodiimide compound (G) 0.0
A flame-retardant polyester elastomer resin composition containing 1 to 10 parts by weight. 6. A polymer mainly comprising a high-melting crystalline polymer segment (a) mainly composed of crystalline aromatic polyester units and a low-melting polymer segment (b) mainly consisting of aliphatic polyether units. 1 to 50 parts by weight of phosphorus compound (B), 0.01 to 10 parts by weight of fatty acid amide compound (C), nitrogen-containing compound (D) based on 100 parts by weight of ether ester block copolymer (A)
0.1 to 30 parts by weight, fluorine resin (E) 0.01 to 1
A flame-retardant polyester elastomer resin composition comprising 0 parts by weight and 0.01 to 10 parts by weight of a monocarbodiimide compound (F) and / or a polycarbodiimide compound (G). 7. The high-melting crystalline polymer segment (a), which is a component of the polyetherester block copolymer (A), is composed of polybutylene terephthalate units. 3. The flame-retardant polyester elastomer resin composition according to item 1. 8. The low-melting polymer segment (b), which is a constituent component of the polyetherester block copolymer (A), comprises poly (tetramethylene oxide) glycol units and / or poly (propylene oxide) glycol with ethylene oxide. The flame-retardant polyester elastomer resin composition according to any one of claims 1 to 7, which is composed of a polymer unit. 9. The polyetherester block copolymer (A) according to claim 1, wherein the copolymerization amount of the low melting point polymer segment (b) is 10 to 80% by weight. Flame retardant polyester elastomer resin composition. 10. The phosphorous compound (B) is an organic phosphoric acid ester and / or an inorganic phosphorus compound.
10. The flame-retardant polyester elastomer resin composition according to any one of items 1 to 9. 11. The flame-retardant polyester elastomer resin composition according to claim 1, wherein the fatty acid amide compound (C) is a monoamide compound of a higher fatty acid having 12 or more carbon atoms. 12. The flame-retardant polyester elastomer resin composition according to claim 1, wherein the fatty acid amide compound (C) is a bisamide compound of a higher fatty acid having 12 or more carbon atoms. 13. The fatty acid amide wax obtained by reacting a mixture of a higher aliphatic monocarboxylic acid having 12 or more carbon atoms and a polybasic acid with a diamine compound as the fatty acid amide compound (C). Any one of 10
Item 10. The flame-retardant polyester elastomer resin composition according to item 8. 14. The flame-retardant polyester elastomer resin composition according to claim 2, wherein the nitrogen-containing compound (D) is a triazine-based compound. 15. The flame-retardant polyester elastomer resin composition according to claim 3, wherein the fluorine-based resin (E) is a polytetrafluoroethylene-based polymer. 16. The monocarbodiimide compound (F)
Is bis (2,6-diisopropylphenyl) carbodiimide, the flame-retardant polyester elastomer resin composition according to any one of claims 4 to 6. 17. The polycarbodiimide compound (G)
Is a polymer of triisopropylphenylene-1,3-diisocyanate, the flame-retardant polyester elastomer resin composition according to any one of claims 4 to 6. 18. The flame-retardant polyester elastomer resin composition according to claim 1, which is used for coating electric wires or coating optical fibers.