JP2000302848A - Fire-retardant polyester elastomer resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition showing excellence in flame retardancy, antibacterial activity, flexibility, mechanical properties, dwelling stability during molding appearance and the like by specifying surface hardness, a critical oxygen index and elongation at break. SOLUTION: This composition shows surface hardness of not less than 60 to not more than 80, a critical oxygen index of not less than 22 and elongation at break (after treatment at 130 deg.C for 30 days) of not less than 200%. The composition is obtained from a thermoplastic polyester elastomer obtained by block-copolymerizing a phosphorous compound so that a content of a phosphorous atom becomes, for example, 500 to 50,000 ppm. The elastomer is preferably a copolymer comprising a polyester hard segment having a high melting point (an example: terephthalic acid) and a polymer segment having molecular weight of 400 to 6,000 and a low melting point [e.g. poly(ethyleneoxide)glycol]. The preferable example of the phosphorous-containing polyester is represented by the formula (wherein B is ethylene or butene; R2 and R3 are each halogen and a 1-10 C hydrocarbon; (n) is 4 to 10; and n2 and n3 are each 0 to 4).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to flame retardancy, heat resistance,
The present invention relates to a polyester elastomer (thermoplastic polyester type block copolymer) having excellent coloring properties, weather resistance, flexibility and antibacterial properties. 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, 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, antibacterial property, weather resistance and heat aging resistance. Have been. 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, there is a possibility that the flame retardant effect is lost due to poor appearance of the bleed due to the flame retardant, or the heat or light deterioration, resulting in flammability, and the thermoplastic polyester type block copolymer composition is used. However, there is a problem that flexibility, which is a feature of the method, is lost. Therefore, as a method for 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 auxiliary (Japanese Patent Publication No. 4-13132), Method of adding a brominated epoxy resin (Japanese Patent Publication No. Sho 5
No. 3-18068) has been proposed.

However, even in these cases, in order to impart flame retardancy, it is necessary to add a large amount of the above-described flame retardant, which results in poor molding due to gelation during high-temperature molding and mechanical properties caused by light. There is a problem of reduction and, in particular, lack of flexibility. Further, for the purpose of improving the above problems, there is a method of adding a substance imparting flame retardancy during the production of the polymer and copolymerizing,
Conventionally, a method using various phosphorus compounds (Japanese Patent Publication No. 55-4 / 1979)
No. 1610). However, in these cases, there are problems such as insufficient flame retardancy and flexibility.

In recent years, a method has been proposed in which a flame retardant represented by melamine cyanurate is further added to a phosphorus compound copolymerized polyester (Japanese Patent Application Laid-Open No. 9-235480). If the phosphorus content is increased until sufficient flame retardancy is obtained, or if a flame retardant is added, the balance between flexibility and strength required as an elastomer may not be achieved, or the flame retardant may be used at high temperature and high humidity. Bleed.

As described above, in the conventional method of copolymerizing a phosphorus-containing compound such as a phosphorus-containing dicarboxylic acid or a diol, flame retardancy can be obtained if the phosphorus compound is randomly copolymerized and a large amount of the phosphorus compound is copolymerized. , Mechanical properties were greatly reduced. On the other hand, if the copolymerization amount of the phosphorus compound is reduced, the mechanical properties can be maintained within a range in which there is no practical problem, but flame retardancy was not obtained. This is because when a phosphorus compound is copolymerized, it is copolymerized into a hard segment, and if the amount until the flame retardancy is achieved is randomly copolymerized, the crystallinity of the hard segment is reduced and the mechanical properties are reduced. This is considered to be due to problems such as poor heat resistance and reduced heat resistance.
On the other hand, if the amount of phosphorus satisfies these characteristics, sufficient flame retardancy could not be obtained. Further, if a low molecular weight flame retardant is added to compensate for this, not only the problem of bleed out but also the problem of deterioration in mechanical properties and heat resistance arises. In particular, under severe conditions of high temperature and high humidity, problems such as cracks often occur in parts where repeated bending and stretching loads are applied, probably due to weak crystallinity of the hard segment and difficulty in increasing the molecular weight. did. That is, at present, flame-retardant polyester elastomers that can withstand high-temperature, high-stress use have not been obtained.

[0007]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, the following formula (1) was obtained.
The present invention has led to the invention of a flame-retardant thermoplastic polyester elastomer resin composition characterized by satisfying (3). (1) 60 ≦ Hs (Surface hardness Shore D) ≦ 80 (2) Limiting oxygen index (LOI) ≧ 22 (3) Elongation at break (after treatment at 120 ° C. for 30 days) ≧ 200%

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The polyester elastomer composition of the present invention has a surface hardness of 60 or more and 80 or less in Shore D. By increasing the hardness, it can be used even in applications requiring a high elastic modulus. The limiting oxygen index is 22 or more. By setting it to 22 or more, high flame retardancy can be exhibited even when a heating element or a flame is touched in a high-temperature environment. The limiting oxygen index is preferably 23 or more, more preferably 24 or more, and most preferably 25 or more. Further, the elongation at the time of cutting of the elongation measurement sample left at 30 ° C. for 30 days is 200% or more. Thereby, even when a polyester elastomer is used in a portion where a strong stress such as bending and elongation is applied under severe conditions of high temperature, occurrence of breakage or cracking can be suppressed.

The flame-retardant polyester elastomer composition of the present invention has, for example, a phosphorus atom content of 500 to 50,000.
It can be obtained from a thermoplastic polyester elastomer in which a phosphorus compound is block-copolymerized so as to be ppm. It is considered that the phosphorus content can be increased without greatly reducing the crystallinity of the hard segment by the block copolymerization of the phosphorus compound. In the case of a composition using this elastomer, it is possible to provide a thermoplastic polyester elastomer resin composition having particularly excellent retention stability and mechanical properties during molding, flame retardancy, antibacterial properties, durability and the like. .

The thermoplastic polyester elastomer in the present invention is preferably a copolymer comprising a high melting point hard polyester segment and a low melting point polymer segment having a molecular weight of 400 to 6000. It is a thermoplastic polyester-type block copolymer having a melting point of 150 ° C. or higher when formed into a united body, and a melting point or softening point of 80 ° C. or lower when measured only with the low melting polymer segment constituent components. Is preferred.

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.

Examples of low-melting polymer segment constituents having a molecular weight of 400 to 6000 include 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 adipate, polytetramethylene adipate, polyethylene sebacate, polyneopentyl sebacate, polytetramethylene dodeca Catenate, 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.

The phosphorus atom content is 500 to 50,000 ppm
As a method for obtaining a thermoplastic polyester elastomer in which a phosphorus compound is block-copolymerized so as to obtain, it is preferable to use a phosphorus-containing polyester as a starting material for copolymerizing phosphorus with the compound. As the phosphorus-containing polyester, a polyester of a phosphorus-containing dicarboxylic acid and a diol,
Examples include polyesters of a dicarboxylic acid and a phosphorus-containing diol, polyesters of a phosphorus-containing dicarboxylic acid and a phosphorus-containing diol, and polyesters of a phosphorus-containing oxyacid. The phosphorus-containing dicarboxylic acid may be in the form of an acid anhydride or may be an alkyl ester. The phosphorus-containing oxycarboxylic acid may be in the form of a lactone.

As the phosphorus-containing dicarboxylic acid, diol and oxycarboxylic acid, known ones as disclosed in JP-A-9-235480 can be used, and preferably phosphorus represented by the following general formula (Chemical Formula 1) is used. Contains compound.

[0015]

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(Wherein, R 1 is a monovalent ester-forming functional group, R 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, A represents a divalent or trivalent organic residue, and n1 represents 1 or 2, and n2 and n3 each represent an integer of 0 to 4.)

The phosphorus compound used for producing the flame-retardant thermoplastic elastomer is represented by the above-mentioned general formula (Chemical Formula 1). In the formula, R1 is specifically a carboxyl group, a hydroxyl group, A hydroxylalkoxycarbonyl group having 2 to 7 carbon atoms and a group represented by the following (Formula 2).

[0018]

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R 2 and R 3 are preferably a halogen atom such as a chlorine atom or a bromine atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an annealing group, and the above-mentioned monovalent ester-forming group. Are listed.
On the other hand, preferred as A are methylene, ethylene, 1,
Lower alkylene groups such as 2-propylene, 1,3-propylene, 1,4-butylene and 1,3-butylene;
-Arylene groups such as phenylene and 1,4-phenylene,
The following divalent groups such as 1,3-xylylene, 1,4-xylylene, and 1.4-benzylene, and the following (Formula 3) (R4 is a hydrogen atom or a lower alkyl group such as methyl and ethyl, n4 is 0
Or represents 1. ), A group represented by Chemical Formula 4, and the like. The above hydrocarbon group may be substituted by a halogen group such as a chlorine atom and a bromine atom.

[0020]

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[0021]

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The phosphorus-free diol component used in the phosphorus-containing polyester includes ethylene glycol, neopentyl glycol, propylene glycol, 1,3-
Propanediol, 1,4-butanediol, 1,6-
Examples thereof include hexanediol, cyclohexanedimethanol, and the like used for ordinary polyester resins. However, ethylene glycol, 1,4-butanediol, and cyclohexanedimethanol are preferred because they hardly lower the crystallinity of the hard segment.

Examples of the phosphorus-free dicarboxylic acid used for the phosphorus-containing polyester include those used for ordinary polyester resins such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, adipic acid and sebacic acid. From the aspect that does not reduce the
Terephthalic acid and naphthalenedicarboxylic acid are preferred. These phosphorus-containing polyester resins may be copolymerized with a small amount of a dicarboxylic acid component other than the phosphorus-containing dicarboxylic acid and a diol component other than the phosphorus-containing diol as long as the blocking property of the phosphorus compound is maintained.

The degree of polymerization of the phosphorus-containing polyester may be 2 or more, preferably 3 or more, and more preferably 4 or more. The upper limit is not particularly limited, but is preferably 50 or less, more preferably 30 or less, and particularly preferably 20 or less in the repeating unit.

Particularly preferred examples of these phosphorus-containing polyesters are shown as (Formula 5).

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(B is CH ₂ —CH ₂ or CH ₂ —CH ₂
Represents 2 ₂ —CH ₂ —CH ₂ , and R ₂ , R ₃ , n ₂ , and n ₃ are the same as those in the formula (1). n is 4-10. )

The phosphorus-containing polyester is used in an amount of 500 to 50,000 ppm as a phosphorus atom in the finally obtained polymer.
Preferably, it is used in an amount of preferably 1,000 to 30,000 ppm, more preferably 2,000 to 10,000 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 prepared by any known method, for example, a melt polymerization method, a solution polymerization method,
Solid phase polymerization can be applied. In the case of melt polymerization, a transesterification method or a direct polymerization method may be used. It is, of course, desirable to carry out solid phase polymerization after melt polymerization in order to improve the viscosity of the resin. After the polymerization of the polyester, the chain may be extended with an isocyanate compound or an epoxy compound. Preferably, it 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, a phosphorus-containing polyester to a temperature of about 150-260 ° C. in the presence of a catalyst, followed by a polycondensation reaction or esterification. A method of removing the water or methanol formed by the exchange reaction and heating the resulting prepolymer under vacuum to remove the excess low molecular weight diol to prepare a polyester type block copolymer having a high degree of polymerization, which is prepared in advance. After mixing and reacting the high-melting polyester segment-forming prepolymer and the low-melting polymer segment-forming prepolymer with a bifunctional compound that reacts with the terminal functional group of the prepolymer, the system is kept in a high vacuum, By removing volatile components, a polyester-type block copolymer is obtained. Method, high polymerization degree high melting polyester and lactone monomer heated mixing, and a method of the lactone while opening polymerization ester block copolymers.

As a method of adding the above-mentioned phosphorus-containing polyester as a starting material, it may be added at the time of transesterification, before polycondensation after transesterification or at a relatively early stage of polycondensation. Addition at the late stage of the reaction, heating roll, extruder, can also be mixed using a kneading machine such as a Banbury mixer, the above, even when added when the chain is extended with an isocyanate compound or an epoxy compound, the prepolymer May be added when a bifunctional compound reacting with the terminal functional group of the prepolymer is mixed and reacted. Although the addition method is not particularly limited, the present invention is achieved only when the phosphorus monomer is copolymerized as a block. Since the phosphorus-containing polyester is three-dimensionally bulky, randomization by transesterification after being introduced into the polyester as a block is relatively unlikely, but is left in a molten state for a long time after the phosphorus-containing polyester is reacted. Attention should be paid to the randomization of the phosphorus compound by transesterification.

Further, the flame-retardant polyester elastomer thus obtained may be added with known antioxidants such as hindered phenol-based, sulfur-based, and phosphorus-based additives, hindered amine-based, triazole-based, benzophenone-based, and the like. Benzoate, nickel, salicyl and other light stabilizers,
Antistatic agents, lubricants, molecular regulators such as peroxides, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, antacids, antibacterial agents, fluorescent brighteners, fillers, difficult A polyester elastomer composition can be obtained by adding one or more kinds of a flame retardant, a flame retardant auxiliary and the like.

Hindered phenolic antioxidants Hindered phenolic antioxidants which can be incorporated in 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 that 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.

Phosphorus-based antioxidants Examples of the phosphorous-based antioxidants which 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, salicylic acid, etc., which can be incorporated in the resin composition of the present invention. Triazole, benzophenone, benzoate, nickel, salicylic acid, etc. 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 agents Examples of antistatic agents that can be incorporated into the resin composition of the present invention include glycerin fatty acid (C8-C22) ester, sorbitan fatty acid (C8-C22) ester, and propylene glycol fatty acid (C8-C22). ) Esters, sucrose fatty acid (C8-C22) esters, citrate mono (di or tri) stearyl ester, pentaerythritol fatty acid (C8-C18) esters, trimethylolpropane fatty acid (C8-C18) S, polyglycerin fatty acid ( C8-C22) ester, polyoxyethylene (20 mol) glycerin fatty acid (C12-C18) ester, oilyoxyethylene (20 mol) sorbitan fatty acid (C12-
C18) ester, polyethylene glycol fatty acid (C8
To C22) esters, polyoxyethylene fatty alcohol (C12 to C20) ethers, polyoxyethylene (4 to 5)
0 mol) alkyl (C4 or more) phenyl ether, N,
N-bis (2-hydroxyethyl) fat (C8-C18)
Nonionic surfactants such as amines, condensation products of fatty acids and diethanolamine, polyoxypropylene polyoxyethylene block polymers, polyethylene glycol and polypropylene glycol; alkyl (C10
~ C20) sulfonates (Na, K, NH4), alkyl naphthalene sulfonates (Na), sodium dialkyl (C4 -C16) sulfonatesuccinates, alkyl (C8
To C20) anionic surfactants such as sulfate (Na, K, NH4) and fatty acid (C8 to C22) salts (Na, K, NH4); zwitterionic interfaces such as N-acyl (C8 to C18) sarcosinate Activator; and other auxiliaries such as polyacrylic acid and its sodium salt.

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 blended in the resin composition of the present invention include 1,3,2,4-di-benzylidene-sorbitol and 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 which 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 which can be incorporated in 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.

Further, in order to further increase the flame retardancy and to make the limiting oxygen index 25 or more, it is possible to add a known low molecular weight flame retardant. Examples of the low molecular weight flame retardant include phosphorus-based, halogen-based, and the like.
Salts of a triazine compound represented by melamine cyanurate and cyanuric acid or isocyanuric acid, or ammonium polyphosphate are preferred.

In the case of long-term use under high temperature and high humidity, the above-mentioned additive of a low molecular organic compound having a molecular weight of 1000 or less may bleed and deteriorate the appearance. In order to prevent this, the amount of the organic low molecular weight additive is preferably 12% by weight or less, more preferably 10% by weight or less, still more preferably 7% by weight or less, and most preferably 5% by weight or less.
Weight percent or less.

[0044]

Next, the present invention will be described with reference to the following examples.
Physical properties were evaluated by the following methods. Surface hardness (Hs) ASTM-D-2240 method Tensile strength JIS K6251 method Tensile elongation (after heat treatment at 130 ° C for 30 days) JIS K6251 method Stress at 50% elongation JIS K6251 method Melt viscosity: Melt flow index (MFI) ASTM- D-1238 Combustion test UL-94V test method (Sample thickness 1/16 inch, combustion time is sample 5
The book shows the total combustion time after each two-time flame contact. ) Flame retardancy test UL94 test method Limiting oxygen index (LOI) method JIS K7201 (A-1) method TGA 5% weight loss temperature Heating rate 20 ° C / min Bloom 80 ° C × 30 days storage Sample (Judged visually) Antibacterial JIS L1902 (Staphylococcus aureus)

Example 1 76 parts by weight of dimethyl terephthalate, 54 parts by weight of 1,4-butanediol, 10 parts by weight of poly (tetramethylene oxide) glycol having a molecular weight of about 1000, and the following phosphorus-containing polyester (Chemical Formula 6, n = 7 to 8) ) To polymer
2,000 ppm, and tetrabutyl titanate as titanium as a catalyst was added at 150 ppm with respect to the produced polymer.
Was used to carry out a transesterification reaction. 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. Polymer A was obtained by performing melt polymerization at ℃.

[0046]

Embedded image

Example 2 A polymer B was obtained in the same manner as in Example 1 except that the addition time of the phosphorus-containing polyester (Chem. 6) was changed to 15 minutes before the end of the transesterification reaction.

Example 3 A polymer C was obtained in the same manner as in Example 1 except that the addition amount of the chemical formula (6) was changed to a phosphorus content of 4500 ppm. Further, 2 parts by weight of melamine cyanurate was added to the polymer C using a twin screw extruder to obtain a polymer D.

Example 4 A polymer E was obtained in the same manner as in Example 3, except that the amount of melamine cyanurate was changed to 4.5 parts by weight.

Example 5 A polymer F was obtained in the same manner as in Example 3, except that the amount of melamine cyanurate was changed to 7.5 parts by weight.

[0051]

Embedded image Comparative Example 1 76 parts by weight of dimethylnalephthalate, 54 parts by weight of 1,4-butanediol, 10 parts by weight of poly (tetramethylene oxide) glycol having a molecular weight of about 1,000, and the above-mentioned phosphorus compound (Formula 7) was adjusted to 5000 ppm based on the polymer. And tetrabutyl titanate as titanium as a catalyst was added at a concentration of 150 ppm with respect to the produced polymer, and a transesterification reaction was performed at 150 to 230 ° C. Next, a hindered phenol-based stabilizer [Ciba Geigy KK product;
x1010] 0.2 part by weight of each was added as a slurry of 1,4-butanediol, and melt polymerization was carried out at 230 to 250 ° C. under a reduced pressure of 3 torr or less to obtain a polymer G.

COMPARATIVE EXAMPLE 2 76 parts by weight of dimethyl naphthalate, 54 parts by weight of 1,4-butanediol, 10 parts by weight of poly (tetramethylene oxide) glycol having a molecular weight of about 1,000, and 15,000 ppm of the above phosphorus compound (Formula 7) based on the polymer Then, tetrabutyl titanate was used as a catalyst, and titanium was added so as to be 150 ppm with respect to the produced polymer, and a transesterification reaction was performed at 150 to 230 ° C. Next, a hindered phenol-based stabilizer [Ciba Geigy Co., Ltd. product; Irgan]
ox1010] 0.2 parts by weight of each as a slurry of 1,4-butanediol, and melt-polymerized at 230 to 250 ° C. under a reduced pressure of 3 torr or less to obtain polymer H
I got

COMPARATIVE EXAMPLE 3 76 parts by weight of dimethyl terephthalate, 54 parts by weight of 1,4-butanediol, 10 parts by weight of poly (tetramethylene oxide) glycol having a molecular weight of about 1000, and titanium as a catalyst using tetrabutyl titanate as a catalyst. 150 ppm with respect to 150 ppm
A transesterification reaction was performed at 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. ° C
And 5 parts by weight of triphenyl phosphate and 5 parts by weight of melamine cyanurate were added to the obtained polymer using a twin-screw extruder to obtain a polymer I.

A test piece was prepared from the polymer obtained above by injection molding and / or extrusion molding, and was subjected to measurement of physical properties. Table 1 shows the results.

[0055]

[Table 1]

[0056]

According to the present invention, since a phosphorus compound is subjected to block copolymerization, a polyester elastomer resin having extremely excellent flame retardancy, antibacterial properties, flexibility, mechanical properties, molding retention stability, appearance, etc. A composition is obtained.

Continued on the front page F-term (reference) 4J002 CF001 CF031 CF101 CF151 CF181 CF191 CF201 FD010 FD040 FD070 FD100 FD130 FD170 FD200 4J029 AA01 AB07 AC03 AE01 BA02 BA03 BA04 BA05 BA07 BA08 BA10 BB06A BD07A BF25 BH03 CA06 CB05 DC3 JA093 JA123 JA203 JA283 JA293 JB123 JB153 JB163 JB173 JB183 JB193 JB233 JB303 JC033 JC043 JC123 JC133 JC233 JC283 JC343 JC353 JC483 JC573 JD05 JD06 JE063 JE093 JE133 JE153 JE162 JE182 JE183 JE223 JF023 JF033 JF043 JF073 JF123 JF133 JF143 JF153 JF163 JF183 JF193 JF213 JF223 JF313 JF323 JF373 JF383 JF473 JF563

Claims (1)

[Claims] 1. A flame-retardant thermoplastic polyester elastomer resin composition which satisfies the following formulas (1) to (3). (1) 60 ≦ Hs (Surface hardness Shore D) ≦ 80 (2) Limiting oxygen index (LOI) ≧ 22 (3) Elongation at break (after treatment at 120 ° C. for 30 days) ≧ 200%