JPH11116789A - Flame-retardant polyester elastomer resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester-type block copolymer composition excellent in flame retardancy, weathering resistance, thermal aging resistance and residence stability in molding. SOLUTION: There is provided a flame-retardant polyester elastomer resin composition containing a thermoplastic polyester-type block copolymer formed from a low-melting-point polymer segment made from an acid component based on an aromatic dicarboxylic acid and a glycol component based on aliphatic and/or alicyclic dihydroxy compounds and having a molecular weight of 400-6,000 and a phosphorus compound copolymerized in an amount to give a phosphorus content of 500-10,000 ppm and a triazine compound and/or its derivative and satisfying the following formulas (1) to (3): 40<=Hs (surface hardness Shore D) <=70 (1), 20 <= critical oxygen index <=27 (2), and TGA (5% weight loss) >=350 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to flame retardancy, heat resistance,
The present invention relates to an elastomer resin composition having excellent coloring properties, weather resistance, and flexibility. Examples of the use thereof include an extrusion molded product, a blow molded product, and an injection molded product which require the above performance.

[0002]

2. Description of the Related Art In general, a thermoplastic polyester type block copolymer is a material excellent in flexibility, heat resistance and oil resistance, but is known to be poor in flame retardancy, weather resistance and heat aging resistance. . In order to impart flame retardancy to a thermoplastic polyester type block copolymer, an organic halogen compound such as hexabromobenzene or decabromophenyl ether and an inorganic compound such as antimony trioxide as a flame retardant aid can be used in combination. Are known. However, in such a method,
Poor appearance of the bleed due to the flame retardant, the flame retardant effect is lost due to heat or light deterioration, there is a possibility that it becomes flammable, the flexibility characteristic of the thermoplastic polyester type block copolymer composition is impaired, etc. There was a problem. Therefore, as a method of solving such problems of flame retardancy and molding retention stability,
A method of adding a high molecular weight halogenated bisphenol A type phenoxy resin and an inorganic flame retardant aid (Japanese Patent Publication No. 4-1413)
No. 2) and a method of adding a brominated epoxy resin (Japanese Patent Publication No. 53-18068). However, even in these cases, when imparting flame retardancy, it is necessary to add a large amount of the above-described flame retardant, molding failure due to gelation at the time of high-temperature molding, reduction in mechanical properties due to light, In particular, there is a problem of lack of flexibility. Further, for the purpose of improving the above-mentioned problems, there is a method of adding a substance imparting flame retardancy at the time of producing a polymer and copolymerizing the same. Proposed. However, in these cases, there are problems such as insufficient flame retardancy and flexibility.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a flexible flame-retardant thermoplastic polyester elastomer resin composition which has excellent flame retardancy, retention stability, weather resistance and heat aging resistance. To provide.

[0004]

[Means for Solving the Problems]

(A) An aromatic dicarboxylic acid as a main acid component, an aliphatic and / or alicyclic dihydroxy compound as a main glycol component, a low melting polymer segment having a molecular weight of 400 to 6000, and a phosphorus atom content of 500 to 10000 ppm. A thermoplastic polyester type block copolymer obtained by copolymerizing a phosphorus compound, and (b) a triazine compound and / or a derivative thereof, and satisfying the following formulas (1) to (3). Flame-retardant polyester elastomer resin composition. Equation (1) 40 ≦ Hs (Surface hardness Shore D) ≦ 70 (2) 20 ≦ Limited oxygen index ≦ 27 (3) TGA (5% weight loss) ≧ 350 ° C.

According to the present invention, (a) a flame-retardant flame retardant having a phosphorus atom content of 500 to 10,000 ppm when a specific phosphorus compound of a thermoplastic polyester elastomer composition obtained by copolymerizing a phosphorus compound having a specific structure is added. A thermoplastic elastomer composition containing the thermoplastic thermoplastic elastomer composition and (b) a triazine-based compound and / or a derivative thereof, and satisfying the above formula, particularly, retention stability, mechanical properties, and flame retardancy during molding. It is possible to provide a thermoplastic polyester elastomer resin composition having extremely excellent durability and the like.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polyester elastomer in the present invention is a copolymer composed of a high melting point hard polyester segment and a low melting point polymer segment having a molecular weight of 400 to 6000. The melting point when a high polymer is formed is 1
It is a thermoplastic polyester type block copolymer composed of components having a melting point or softening point of not higher than 50 ° C and not higher than 80 ° C when measured only with the low melting polymer segment component.

The polyester type block copolymer will be described in more detail. For example, terephthalic acid, isophthalic acid,
Aromatic dicarboxylic acids such as 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, bis (4-carboxyphenyl) methane, bis (4-carboxyphenyl) sulfone, and the like Esters and ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, 2,2-dimethyltrimethylene glycol, hexamethylene glycol, decamethylene glycol, p
-Polyesters prepared from diols such as xylylene glycol and cyclohexane dimethanol, or oxyacids such as co-polyester p- (β-hydroxyethoxy) benzoic acid using two or more of these dicarboxylic acids or two or more diols And polyesters derived from their esters, polylactones such as polypivalolactone, aromatic ether dicarboxylic acids such as 1,2-bis (4,4'-dicarboxyphenoxy) ethane and the above-mentioned diols. Examples thereof include polyether esters, and copolyesters obtained by combining the above dicarboxylic acids, oxy acids, and diols.

The low melting point polymer segment having a molecular weight of 400 to 6000 includes polyalkylene ether glycols such as poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, and mixtures thereof. Further, copolymerized polyether glycols obtained by copolymerizing these polyether glycol constituents can be shown. Polyesters prepared from aliphatic dicarboxylic acids having 2 to 12 carbon atoms and aliphatic glycols having 2 to 10 carbon atoms, for example, polyethylene nadipate, polytetramethylene adipate, polyethylene sebacate, polyneopentyl sebacate, polytetraethylene Examples include methylene dodecanoate, polytetramethylene azelate, polyhexamethylene azelate, poly-ε-caprolactone, and the like. Further, a polyester polyether copolymer obtained by combining the above polyester and polyether can also be shown. The ratio of the low-melting-point polymer segment component in the polyester-type block copolymer is 5 to 5.
80% by weight is preferred.

When the phosphorus atom content in the above polyester is 50,
The following general formula (A) so as to be 0 to 50,000 ppm
And adding a phosphorus compound represented by the formula:

Embedded image (Wherein, R ₁ is a monovalent ester-forming functional group;
₂ and R ₃ are the same or different groups, and each is a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, R ₁
A represents a divalent or trivalent organic residue.
N ₁ represents 1 or 2, and n ₂ and n ₃ each represent an integer of 0 to 4. )

In the present invention, the phosphorus compound used for producing the flame-retardant thermoplastic elastomer is represented by the above-mentioned general formula (A). In the formula, R ₁ represents a carboxyl group, An alkyl ester having 1 to 6 carbon atoms of a carboxyl group, a cycloalkyl ester,
Annealed ester, hydroxyl group, 2-7 carbon atoms
A hydroxylalkoxycarbonyl group of the formula
Is a group represented by

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R ₂ and R ₃ are halogen atoms such as a chlorine atom and a bromine atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an annealing group and the above-mentioned monovalent group of R _1. Are preferred. On the other hand, preferred as A are lower alkylene groups such as methylene, ethylene, 1,2-propylene and 1,3 propylene,
Arylene groups such as 1,3-phenylene and 1,4-phenylene; 1,3-xylylene; 1,4-xylylene;
A divalent group such as 4-benzylene; a trivalent group represented by Formula 7 (R ₄ represents a hydrogen atom or a lower alkyl group such as methyl or ethyl; n ₄ represents 0 or 1); And the like. The above hydrocarbon group may be substituted by a halogen group such as a chlorine atom and a bromine atom.

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[0012]

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In the present invention, the phosphorus compound represented by the general formula (A) is used as a phosphorus atom in a polymer in an amount of 500 to 50.
It is appropriate to use so as to contain 000 ppm,
Particularly, it is preferable to use 1000 to 10000 ppm. When the amount of the phosphorus compound used is smaller than the above range, an expected flame-retardant thermoplastic elastomer cannot be obtained. On the other hand, when the amount used is larger than the above range, the mechanical strength is unfavorably poor.

These polyester type block copolymers can be produced by a usual polycondensation method. A preferred method is to heat an aromatic dicarboxylic acid or its dimethyl ester, a low melting segment forming diol and a molecular weight diol to a temperature of about 150-260 ° C. in the presence of a catalyst, and then form by a polycondensation or transesterification reaction. A method of removing a water or methanol, heating the resulting prepolymer under vacuum to remove excess low molecular weight diol to obtain a polyester type block copolymer having a high degree of polymerization, a pre-adjusted high melting polyester. A segment-forming prepolymer and a low-melting polymer A segment-forming prepolymer is mixed with a bifunctional compound that reacts with the terminal functional group of the prepolymer, and then the system is kept at a high vacuum to remove volatile components. A method of making a polyester type block copolymer by doing
There is a method in which a high-melting-point polyester having a high degree of polymerization is mixed with a lactone monomer by heating, and the lactone is subjected to ring-opening polymerization to form an ester block copolymer.

The phosphorus compound may be added at the time of transesterification, before the polycondensation after transesterification or at a relatively early stage of the polycondensation reaction. Is not limited.

The above-mentioned triazine compound and / or a derivative thereof are contained, and general formulas (b) to (d) can be mentioned.

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[0017]

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[0018]

Embedded image (Wherein R ₁ , R ₂ , and R ₃ are a hydrogen atom, an amino group, an alkyl group, an annealing group, and a phenyl group, and R ₁ , R ₂ , and R ₃
May be the same or different. )

Further, as a derivative of the triazine compound, an isocyanate group-containing compound represented by the following general formula may also be mentioned. R1- (NCO) n (where n = 1 to 4, the structure of R1 is arbitrary.) Of these, the most common ones are MDI, TD
It is used as a raw material for urethane such as I. In these, without lowering the physical properties of the polyester type block copolymer, blooming does not occur,
Melamine cyanurate, which is an adduct of melamine and cyanuric acid, is particularly preferred. More preferably, it is melamine cyanurate in powder form, and is a scanning electron microscope (SEM).
The average particle size of the approximate powder obtained by analyzing the image of the approximate powder taken in the above with an image analyzer is 2 μm to 100 μm. The addition amount of the triazine-based compound and / or its derivative may be a thermoplastic elastomer resin composition.
0.5 to 20 parts by weight is preferable for 100 parts by weight. Particularly, 1 to 5 parts by weight is preferable from the viewpoint of flexibility and flame retardancy.

As the method for adding the phosphorus compound, the phosphorus compound may be added during the transesterification reaction, before the polycondensation after the transesterification or at a relatively early stage of the polycondensation reaction, or may be added by a heating roll or extrusion. Can be mixed using a kneader such as a kneader or a Banbury mixer, and the addition method is not particularly limited.

Further, the composition of the present invention may contain, as additives, known antioxidants such as hindered phenol, sulfur, and phosphorus, hindered amine, triazole, benzophenone, benzoate, nickel, salicyl. -Based light stabilizers, antistatic agents, lubricants, molecular regulators such as peroxides, metal deactivators, organic and inorganic nucleating agents, neutralizing agents,
One or more antacids, antibacterial agents, optical brighteners, fillers, flame retardants, flame retardant auxiliaries, and the like can be added.

Hindered phenolic antioxidants Hindered phenolic antioxidants which can be incorporated into the resin composition of the present invention include 3,5-di-t-
Butyl-4-hydroxy-toluene, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylphenyl) propionate, tetrakis [methylene-
3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6'-tris (3,5-di-t-butyl -4-hydroxyhydroxy) benzene, calcium (3,5-di-t-butyl-4-hydroxy-benzyl-monoethyl-phosphate), triethylene glycol-bis [3- (3-t-butyl-5 -Methyl-4-hydroxyphenyl) propionate], 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4)
-Hydroxy-5-methylphenyl) propionyloxydiethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis [3,3-bis (4′hydroxy-3′-t-butylphenyl) ) Butyric acid] glycol ester, tocopherol, 2,2′-ethylidenebis (4,6-di-t-butylphenol), N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyl] hydrazine, 2,2′-oxamidobis [ethyl-3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate], 1,1,3
-Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-tris (3 ', 5'
-Di-t-butyl-4'-hydroxybenzyl) -S-
Triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,
3,5-di-t-butyl-4-hydroxyhydrocinnamic acid triester with-1,3,5-tris (2-hydroxyethyl) -S-triazine-2,4
6 (1H, 3H, 5H) and the like.

Sulfur-based antioxidants Examples of the sulfur-based antioxidants which can be incorporated in the resin composition of the present invention include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiol. Dipropionate, distearyl-3,3'-thiodipropionate, laurylstearyl-3,3 '
-Thiodipropionate, dioctadecyl sulfide, pentaerythritol-tetra (β-lauryl-thiopropionate) ester and the like.

Phosphorous Antioxidants The phosphoric antioxidants that can be incorporated in the resin composition of the present invention include tris (mixed, mono and dinolylphenyl) phosphite and tris (2,3-di -T
-Butylphenyl) phosphite, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-) Tridecylphosphite-5
-T-butylphenyl) butane, bis (2,4 di-t
-Butylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenephosphanite, bis (2,6-di-t-butyl-4-) Methylphenyl) pentaerythitol-di-phosphite, 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) -2
-Ethylhexyl-phosphite, bis (2,4,6
-Di-t-butylphenyl) pentaerythritol-di-phosphite, triphenyl phosphite, diphenyldecyl phosphite, didecylphenyl phosphite, tridecyl phosphite, trioctyl phosphite, tridodecyl phosphite, trioctadecyl phosphite Phyto, trinonyl phenyl phosphite, tridodecyl trithio phosphite and the like can be mentioned.

Hindered amine light stabilizer The hindered amine light stabilizer that can be incorporated in the resin composition of the present invention includes dimethyl succinate and 1-
(2-hydroxyethyl) -4-hydroxy-2,2,
Polycondensate with 6,6-tetramethylpiperodine, poly [[6- (1,1,3,3-tetrabutyl) imino-
1,3,5-Triazine-2,4-diyl] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imyl]], bis (1,2-butylmalonic acid)
2,2,6,6-pentamethyl-4-piperidyl) ester, tetrakis (2,2,6,6-tetramethyl-4)
-Piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4)
-Piperidyl) sebacate, N, N'-bis (2,2,
Polycondensate of 6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane, poly [(N, N'-bis (2,2,6,6-tetramethyl-4- Piperidyl) hexamethylenediamine)-(4-
Monophorino-1,3,5-triazine 2,6-diyl)
-Bis (3,3,5,5-tetramitylpiperazinone), tris (2,2,6,6-tetramethyl-4-piperidyl) -dodecyl-1,2,3,4-butanetetracarboxylate , Tris (1,2,2,6,6-pentamethyl-4-piperidyl) -dodecyl-1,2,3,
4-butanetetracarboxylate, bis (1,2,2
2,6,6-pentamethyl-4-piperidyl) sebacate, 1,6,11-tris [｛4,6-bis (N-butyl-N- (1,2,2,6,6-pentamethylpiperidine- 4-yl) amino-1,3,5-triazine-2-
Il @ amino] undecane, 1- [2- [3-5-di-
t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 8
-Benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2,4-dione, 4-benzoyloxy-2,2
6,6-tetramethylpiperidine, N, N'-bis (3
-Aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,3
5-triazine condensate and the like can be mentioned.

Light stabilizers such as triazole, benzophenone, benzoate, nickel and salicylic acid which can be incorporated in the resin composition of the present invention. Triazole, benzophenone, benzoate, nickel and salicylic acid. Examples of light stabilizers include 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, pt-butylphenyl salicylate, and 2,4-di-t-butylphenyl- 3,5-di-t-butyl-4-hydroxybenzoate, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-
5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2,
5-bis- [5'-t-butylbenzoxazolyl-
(2)]-thiophene, [bis (3,5-di-t-butyl-4-hydroxybenzylphosphoric acid monoethyl ester)]
Nickel salt, 2-ethoxy-5-t-butyl-2'-ethyloxalic acid-bis-anilide 85-90
% And 2-ethoxy-5-t-butyl-2'-ethyl-
4'-t-butyloxalic acid-bis-anilide 10-15% mixture, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole,
-[2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2
-Ethoxy-2'-ethyloxalic acid bisanilide, 2- [2'hydroxy-5'-methyl-3'-
(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimido-methyl) phenyl] benzotriazole, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2- (2′- Hydroxy-5'-t-
(Octylphenyl) benzotriazole, 2-hydroxy-4-i-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, and the like.

Antistatic agent Antistatic agent that can be incorporated in the resin composition of the present invention.
Glycerin fatty acid (C₈ ~ C_{twenty two}) Esthetic
Sorbitan fatty acid (C₈ ~ C_{twenty two}) Ester, propyl
Ren glycol fatty acid (C₈ ~ C_{twenty two}) Ester, sucrose
Acid fatty acid (C₈ ~ C_{twenty two}) Ester, citric acid mono
Is tri) stearyl ester, pentaerythritol fat
Fatty acid (C₈ ~ C₁₈) Ester, trimethylolpropane
Fatty acids (C ₈ ~ C₁₈) S, polyglycerin fatty acid
(C₈ ~ C_{twenty two}) Ester, polyoxyethylene (20
Le) glycerin fatty acid (C₁₂~ C₁₈) Ester, oily
Oxyethylene (20 mol) sorbitan fatty acid (C₁₂~
C₁₈) Esters, polyethylene glycol fatty acids (C₈ 
~ C_{twenty two}) Ester, polyoxyethylene fatty alcohol
(C₁₂~ C₂₀) Ether, polyoxyethylene (4-5
0 mol) alkyl (C _Four Phenyl ether, N,
N-bis (2-hydroxyethyl) fat (C₈~ C₁₈)
Condensation of amines and fatty acids with diethanolamine
Material, polyoxypropylene polyoxyethylene block
Polymer, polyethylene glycol, polypropylene
Nonionic surfactants such as recall; alkyl (C_Ten
~ C₂₀) Sulfonate (Na, K, NH_Four ), Alkyl
Naphthalene sulfonate (Na), sodium dialkyl
(C_Four ~ C₁₆) Sulfone succinate, alkyl (C₈ 
~ C ₂₀) Sulfate (Na, K, NH)_Four ),fatty acid
(C₈ ~ C_{twenty two}) Anionic such as salt (Na, K, NH4)
Surfactant; N-acyl (C₈ ~ C₁₈) Sarcosinate
Zwitterionic surfactants such as polyacrylic acid and its
Other auxiliaries such as thorium salts can be used.

Lubricants Lubricants that can be incorporated into the resin composition of the present invention include hexylamide, octylamide, stearylamide, oleylamide, ercylamidoethylenebisstearylamide, laurylamide, behenylamide, methylenebisstearyl C3-30 saturated or unsaturated aliphatic amides such as amide and ricinolamide and derivatives thereof; C3-30 saturated or unsaturated aliphatic esters such as butyl stearate and isobutyl stearate and derivatives thereof Commercially available silicone release agents; silicone compounds such as silicone oil and silicone gum; commercially available fluorine-based release agents; and fluorine-based compounds such as ethylene tetrafluoride.

Metal Deactivator The metal deactivator which can be incorporated in the resin composition of the present invention includes 3-N'-salicyloylamino-1,
2,4-triazole, salicylaldehyde, salicylhydrazine, N, N'-bis- [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionyl] hydrazine, oxalyl-bis [benzylidene hydrazide], 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 3,4,5,6
-Dibenzo-1,2-oxaphosphan-2-oxide, tris [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5-t-butyl) phenyl-5
-Methyl] phenylphosphite, 2,2′-oxamido-bis- [ethyl-3 (3,5-di-t-butyl-
4-hydroxyphenyl) propionate].

Nucleating agent Examples of the nucleating agent that can be incorporated in the resin composition of the present invention include 1,3,2,4-di-benzylidene-sorbitol, 1,3,2,4-di-di- ( (p-methyl-benzylidene) sorbitol, 1,3,2,4-di- (p-ethyl-benzylidene) sorbitol, 1,3,2,4-di- (2 ′, 4′-di-methyl-benzylidene) Sorbitol, 1,3-p-chloro-benzylidene-2,4-p
-Methyl-benzylidene-sorbitol, 1,3,2
4-di- (p-propyl-benzylidene) sorbitol, aluminum-mono-hydroxy-di-pt-butylbenzoate, sodium-bis (4-t-butylphenyl) phosphate, sodium-2,2'-methylene -Bis- (4,6-di-t-butyl-phenyl) phosphate, talc, sodium benzoate, lithium-
2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate and the like can be mentioned.

Neutralizers and antacids The neutralizers and antacids that can be incorporated in the resin composition of the present invention include lithium stearate, 1,2-hydroxylithium stearate, sodium stearoyl lactate, Sodium stearate, potassium stearate,
Lithium behenate, lithium montan, sodium behenate, sodium montanate, calcium stearyl lactate, calcium behenate, calcium montanate, cadmium stearate, cadmium laurate, cadmium ricinoleate, barium naphthenate, barium 2-ethylhexoate, stearin Barium acid, barium 2-ethylhexoate, calcium stearate, calcium laurate, calcium ricinoleate, strontium stearate, zinc stearate, zinc laurate, zinc ricinoleate, zinc 2-ethylhexoate,
Higher fatty acids such as zinc stearate, dibasic lead stearate, lead naphthenate, tin stearate, aluminum stearate, and magnesium stearate; alkali or alkaline earth metal salts of alkyl lactic acid; basic magnesium aluminum hydroxide Carbonate hydrate (hydrotalcite), basic zeolite,
Examples thereof include epichlorohydrin and bisphenol A polymers, epoxidized soybean oils, epoxidized fatty monoesters, epoxidized alicyclic fatty acid esters, polycarbodiimides, and isocyanate compounds.

Fillers Fillers that can be incorporated into the resin composition of the present invention include magnesium oxide, aluminum oxide, silicon oxide, calcium oxide, titanium oxide, chromium oxide (3
Value), iron oxide, zinc oxide, silica, diatomaceous earth, alumina fiber, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon and other oxides, magnesium hydroxide, aluminum hydroxide,
Basic substances or hydroxides such as basic magnesium carbonate; carbonates such as magnesium carbonate, calcium carbonate, barium sulfate, ammonium sulfate, calcium sulfite, dolomite, dawsonite; calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, basic sulfuric acid (Sulfite) such as magnesium; silicic acid such as sodium silicate, magnesium silicate, aluminum silicate, potassium silicate, calcium silicate, talc, clay, mica, asbestos, glass fiber, montmorillolite, glass balloon, glass beads, pentonite, etc. Salt; kaolin (porcelain), pearlite, iron powder, copper powder, lead powder, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, brass fiber, potassium titanate, lead zirconate titanate, zinc borate, aluminum borate, Metabo It can be barium, calcium borate, sodium borate and the like.

[0033]

Next, the present invention will be described with reference to the following examples.
Physical properties were evaluated by the following methods. Surface hardness ASTM-D-2240 method Tensile test JIS K6251 method Stress at 50% elongation JIS K6251 method Melt viscosity: Melt flow index (MFI) ASTM-D-1238 method Combustion test UL-94V test method Sample thickness 1/16 inch The burning time was the sum of the burning time after two flames in each of the five samples. Limiting oxygen index (LOI) method JIS K7201 (A-1) method TGA 5% weight loss temperature Heating rate 20 ° C / min

Example 1 Polymer A: 60 parts by weight of dimethyl terephthalate, 1,
38 parts by weight of 4-butanediol, 37 parts by weight of poly (tetramethylene oxide) glycol having a molecular weight of about 1000, and 500 parts of a phosphorus compound (e) were added to the polymer to be produced.
ppm, and tetrabutyl titanate was added as a catalyst as metallic titanium at a concentration of 150 ppm with respect to the produced polymer, and a transesterification reaction was performed at 150 to 230 ° C. Next, 0.2 parts by weight of a hindered phenol-based stabilizer [Ciba Geigy KK; Irganox 1010] is added as a slurry of 1,4-butanediol to each of the produced oligomers, and 230 to 250 under a reduced pressure of 3 torr or less. The polymer was melt-polymerized at a temperature of ° C to obtain a polymer A.

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Example 2 Polymer B: 50 parts by weight of dimethyl terephthalate, 1,
31 parts by weight of 4-butanediol, 27 parts by weight of poly (tetramethylene oxide) glycol having a molecular weight of about 1500, and the following phosphorus compound (f) at 600 ppm based on the polymer.
And tetrabutyl titanate as a metal titanium as a catalyst.
ppm, and transesterified at 150 to 230 ° C. Next, 0.2 parts by weight of a hindered phenol-based stabilizer [Ciba Geigy Co., Ltd. product; Irganox 1010] was added as a slurry of 1,4-butanediol to each of the resulting oligomers, and 3 t
Melt polymerization was performed at 230 to 250 ° C. under reduced pressure of orr or less to obtain polymer B.

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Example 3 Polymer D: 45 parts by weight of dimethyl naphthalate, 1,
26 parts by weight of 4-butanediol, 30 parts by weight of poly (tetramethylene oxide) glycol having a molecular weight of about 1000, and the following phosphorus compound (g) were added to the polymer at 1000 pp.
m, and as a catalyst, titanium tetrabutyl titanate, 150 ppm with respect to the produced polymer.
And transesterified at 150 to 230 ° C. Next, a hindered phenol-based stabilizer [Ciba Geigy Co., Ltd. product; Ir]
ganox1010] 0.2 parts by weight of 1,4-
It was added as a slurry of butanediol, and melt-polymerized at 230 to 250 ° C. under a reduced pressure of 3 torr or less to obtain a polymer D.

[0037]

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Example 4 Polymer E: 50 parts by weight of dimethyl terephthalate, 1,
52 parts by weight of 4-butanediol, the same phosphorus compound (T) as in the example was added so as to be 5000 ppm with respect to the polymer, and tetrabutyl titanate was used as metal titanium as a catalyst so as to be 150 ppm with respect to the produced polymer. Then, a transesterification reaction was performed at 150 to 230 ° C. Next, a hindered phenol-based stabilizer [Ciba Geigy KK product;
x1010] 0.2 parts by weight of each was added as a slurry of 1,4-butanediol, and melt polymerization was performed at 230 to 250 ° C. under a reduced pressure of 3 torr or less to obtain a polymer F. Then, 70 parts by weight of polymer F and 50 parts by weight of ε-caprolactone were reacted with 1 part by weight of dibutyltin dilaurate as a catalyst under a nitrogen atmosphere at 220 to 240 ° C. for 2 hours to obtain polymer E.

[0039]

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Comparative Example 1 Polymer G: 50 parts by weight of dimethyl terephthalate, 1,
31 parts by weight of 4-butanediol, 27 parts by weight of poly (tetramethylene oxide) glycol having a molecular weight of about 1500, and tetrabutyl titanate as a metal titanium as a catalyst are added at 150 ppm to the produced polymer at 150 to 230 ° C. Was used to carry out a transesterification reaction. Next, a hindered phenol-based stabilizer [Ciba Geigy Co., Ltd. product; Irganox]
1010] 0.2 parts by weight of each were added as a slurry of 1,4-butanediol, and melt polymerization was performed at 230 to 250 ° C. under a reduced pressure of 3 torr or less to obtain a polymer G.

Comparative Example 2 Polymer H: 50 parts by weight of dimethyl terephthalate, 1,
31 parts by weight of 4-butanediol, 27 parts of poly (tetramethylene oxide) glycol having a molecular weight of about 1500, and tetrabutyl titanate as metal titanium as a catalyst.
The resulting polymer was added at a concentration of 150 ppm, and transesterification was performed at 150 to 230 ° C. Next, as a phosphorus compound, 10 parts by weight of triphenyl phosphate and a hindered phenol-based stabilizer [Ciba Geigy Co., Ltd. product; Irganox 1010] are added to the resulting oligomer.
0.2 parts by weight of each were added as a slurry of 1,4-butanediol, and the pressure was reduced to 230 to 3 torr or less.
The melt polymerization was carried out at 250 ° C., but the viscosity increased and became a gel, and the desired polymer could not be obtained.

Comparative Example 3 Polymer I: To a polymer G obtained in Comparative Example 1, 10 parts by weight of triphenyl phosphate was added using a twin screw extruder to obtain a polymer I.

Comparative Example 4 Polymer J: To a polymer G obtained in Comparative Example 1, 8 parts by weight of diethyl benzenephosphonate was added using a twin screw extruder to obtain a polymer J.

Example 4 Polymer K: Polymer K was obtained by adding 2 parts by weight of melamine cyanurate to polymer A obtained in Example 1 using a twin screw extruder.

Example 5 Polymer L: To a polymer B obtained in Example 2, 8 parts by weight of melamine cyanurate was added using a twin screw extruder to obtain a polymer L.

Comparative Example 5 Polymer M: To Polymer G obtained in Comparative Example 1, 10 parts by weight of triphenyl phosphate and 5 parts by weight of melamine cyanurate were added using a twin screw extruder to obtain polymer M. .

A test piece was prepared from the polymer obtained as described above by injection molding and subjected to physical property measurement. The results are shown in Tables 1 to 3.

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

[0050]

According to the present invention, since a phosphorus compound having a specific structure is copolymerized and contains a triazine compound and / or derivative, flame retardancy, flexibility, molding retention stability, appearance, etc. Is obtained, whereby a polyester elastomer resin composition having a very excellent value is obtained.

Claims (4)

[Claims] (A) An aromatic dicarboxylic acid as a main acid component, an aliphatic and / or alicyclic dihydroxy compound as a main glycol component, a low melting polymer segment having a molecular weight of 400 to 6000, and a phosphorus atom content. Is 500-10
A thermoplastic polyester type block copolymer in which a phosphorus compound is copolymerized so as to be 000 ppm, and (b) a triazine-based compound and / or a derivative thereof;
A flame-retardant polyester elastomer resin composition satisfying (3). (1) 40 ≦ Hs (Surface hardness Shore D) ≦ 70 (2) 20 ≦ Limited oxygen index ≦ 27 (3) TGA (5% weight loss) ≧ 350 ° C. 2. The flame-retardant polyester elastomer composition according to claim 1, wherein the compound having a phosphorus atom is represented by the following general formula (A). Embedded image (Wherein, R ₁ is a monovalent ester-forming functional group;
₂ and R ₃ are the same or different groups, and each is a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, R ₁
A represents a divalent or trivalent organic residue.
N ₁ represents 1 or 2, and n ₂ and n ₃ each represent an integer of 0 to 4. ) 3. The flame-retardant polyester elastomer resin composition according to claim 1, wherein the triazine-based compound and / or the derivative (b) thereof is represented by any one of formulas (b) to (d). Embedded image Embedded image Embedded image (Wherein R ₁ , R ₂ , and R ₃ are a hydrogen atom, an amino group, an alkyl group, an annealing group, and a phenyl group, and R ₁ , R ₂ , and R 3
₃ may be the same or different. ) 4. The triazine compound and / or its derivative (b) is melamine cyanurate in powder form,
The flame-retardant polyester elastomer resin composition according to claim 3, wherein the powder has an average particle diameter of 2 µm to 100 µm when an image of the powder taken by a scanning electron microscope (SEM) is analyzed by an image analyzer. .