JP2000302850A - Manufacture of fire retardant polyester elastomer and composition of fire retardant polyester elastomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition not only showing excellence in fire retardation, antibacterial activity, dwelling stability during molding, weatherability, heat aging resistance and flexibility but having a good balance of strength and flexibility by block-copolymerizing a phosphorous compound so that the composition contains a specific amount of phosphorous. SOLUTION: A thermoplastic elastomer is a copolymer which comprises a polyester hard segment having a high melting point and a polymer segment having molecular weight of 400 to 6,000 and a low melting point. If a high polymer is prepared only from the segment having a high melting point, it shows a melting point of not less than 150 deg.C and if a high polymer is prepared only from a segment having a low melting point, it shows a melting point or a softening point of not more than 80 deg.C. An example of a phosphorous- containing compound which is used for introducing 500 to 50,000 ppm of a phosphorous atom in the polyester is represented by the formula (wherein R1 is a monovalent ester-forming group; R2 and R3 are each halogen, a 1-10C hydrocarbon group or R1; A is a 2 to 3 valent organic residual group; (n) is 1 or 2; 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 method for producing 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.

For the purpose of improving the above-mentioned problems, there is a method of adding a substance imparting flame retardancy during the production of a polymer and copolymerizing the same. Conventionally, various phosphorus compounds have been used (Japanese Patent Publication No. 55-55). No. 41610) has been proposed.
However, in these cases, there are problems such as insufficient flame retardancy and flexibility.

In recent years, a method of further adding a flame retardant represented by melamine cyanurate to a phosphorus compound copolymerized polyester has been proposed (JP-A-9-235480). When used for coalescence, 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 obtained, or high temperature and high humidity There is a problem that the flame retardant bleeds during use.

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.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a flame retardant which is excellent in all of flame retardancy, antibacterial properties, retention stability, weather resistance and heat aging resistance, and has a good balance of strength and flexibility. The present invention is to provide a thermoplastic polyester elastomer resin composition having a high viscosity.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to achieve excellent heat resistance without impairing the properties of the polyester elastomer, and as a result, have reached the present invention.
That is, the present invention has a phosphorus atom content of 500 to 50,000.
A method for producing a flame-retardant polyester elastomer, which comprises subjecting a phosphorus compound to block copolymerization in a method for producing a polyester elastomer in which a phosphorus compound is copolymerized so as to be ppm. A polyester elastomer composition comprising the flame-retardant polyester elastomer obtained by the above-mentioned production method.

According to the method of the present invention, the phosphorus atom content is 5
It is possible to obtain a thermoplastic polyester elastomer in which the phosphorus compound is block-copolymerized so as to have a concentration of from 00 to 50,000 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. .

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polyester elastomer in the present invention is a copolymer consisting of a high melting point hard polyester segment and a low melting point polymer segment having a molecular weight of about 400 to 6000, and only the high melting point polyester segment constituting component is used. The melting point when forming a high polymer at 150 ° C. or higher, and the melting point or softening point when measured only with the low melting point polymer segment constituents is 80 ° C. or less. It is united.

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

Examples of the low-melting polymer segment constituent 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.

When the phosphorus atom content in the polyester is 50,
As the phosphorus-containing compound to be used so as to be 0 to 50,000 ppm, a known compound can be used, and a phosphorus compound represented by the following general formula (Chemical Formula 1) is preferable.

[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 in the production of the flame-retardant thermoplastic elastomer in the present invention is represented by the above-mentioned general formula (Chemical Formula 1). Hydroxyl group, 2-C
7 and a group represented by the following (Chemical 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 are represented by the following chemical formula (R4 is a hydrogen atom or a lower alkyl group such as methyl or ethyl, and n4 is 0
Or represents 1. ), A trivalent group represented by the following (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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In the present invention, the phosphorus-containing polyester represented by the general formula (Chemical Formula 1) contains 500 to 50,000 ppm, preferably 1,000 to 30,000 ppm, and more preferably 200 to 50,000 ppm of phosphorus atoms in the finally obtained polymer.
It is appropriate to use it so that it is contained at 0 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 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 for adding the above phosphorus-containing compound, even if it is added during the transesterification reaction, it may be added before the polycondensation after the transesterification or at a relatively early stage of the polycondensation reaction or at a later stage of the polycondensation reaction. Addition, when performing a chain extension reaction with an isocyanate compound, an epoxy compound, or the like, when mixing a prepolymer with a bifunctional compound that reacts with a terminal functional group of the prepolymer, and the like, without limitation. The method is not particularly limited as long as it is a method in which the phosphorus compound is introduced in the block, but preferably added after the middle and / or late stages of the polycondensation reaction in order to keep the blockability of the phosphorus-containing monomer in the polymer high. preferable. In addition, it is also possible to mix using a kneader such as a heating roll, an extruder, a Banbury mixer, and the addition method is not particularly limited, but the present invention is not limited to that the phosphorus-containing monomer is copolymerized as a block. Achieved. Normally, even if a dicarboxylic acid or diol is added at a later stage during the polycondensation reaction, the dicarboxylic acid or the diol bonds randomly in the polymer chain, but the phosphorus-containing dicarboxylic acid or the phosphorus-containing diol is subjected to transesterification due to steric hindrance. It is difficult for the polymer to be incorporated into the main chain.For example, when a phosphorus-containing dicarboxylic acid is added to a state where the polymer chain and the diol are present in the reaction system, the reaction between the phosphorus-containing dicarboxylic acid and the diol is likely to occur. It is considered that the phosphorus compound is introduced in 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 can be used as a known additive such as a hindered phenol-based, sulfur-based, phosphorus-based antioxidant, hindered amine-based, triazole-based, benzophenone-based, or 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 into 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 antioxidants Examples of 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 stabilizers The hindered amine light stabilizers that can be incorporated in the resin composition of the present invention include 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 acids which can be incorporated in the resin composition of the present invention. 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 in 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 in 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 deactivators The metal deactivators which can be incorporated in the resin composition of the present invention include 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 The nucleating agent that can be incorporated in the resin composition of the present invention includes 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 which can be incorporated into 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 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.

In order to further improve the flame retardancy, a known low molecular weight flame retardant may be added. Known low-molecular-weight flame retardants include phosphorus-based and halogen-based flame retardants, and a salt of a triazine-based compound represented by melamine cyanurate with cyanuric acid or isocyanuric acid is preferred.

[0038]

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 Flame retardancy test UL94 test method Combustion test UL-94V test Method The thickness of the sample was 1/16 inch, and the burning time was the sum of the burning time after two flames in each of five samples. Limiting oxygen index (LOI) method JIS K7201 (A-1) method TGA 5% weight loss temperature Bloom 80 ° C x 30 days storage sample (determined visually) Heating rate 20 ° C / min Antibacterial JIS L1902 (Staphylococcus aureus)

Example 1 65 parts by weight of dimethyl terephthalate, 27 parts by weight of 1,4-butanediol, 50 parts by weight of poly (tetramethylene oxide) glycol having a molecular weight of about 1,000, and a polymer formed as titanium tetrabutyl titane as a catalyst 150 to 23 ppm,
A transesterification reaction was performed at 0 ° 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. Polymer A was obtained by melt-polymerizing at ℃, adding the following phosphorus-containing polyester (Chemical Formula 5) to the polymer at 5000 ppm at the latter stage of the polycondensation, and subjecting the phosphorus-containing monomer to block copolymerization.

Example 2 A polymer B was obtained by adding 5 parts by weight of melamine cyanurate to the polymer A obtained in Example 1 using a twin screw extruder.

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COMPARATIVE EXAMPLE 1 65 parts by weight of dimethyl naphthalate, 27 parts by weight of 1,4-butanediol, 50 parts by weight of poly (tetramethylene oxide) glycol having a molecular weight of about 1,000, and 5000 ppm of the above phosphorus compound (formula 5) based on the polymer And added as a catalyst as tetrabutyl titanate titanium 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; 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 C.

COMPARATIVE EXAMPLE 2 65 parts by weight of dimethyl naphthalate, 27 parts by weight of 1,4-butanediol, 50 parts by weight of poly (tetramethylene oxide) glycol having a molecular weight of about 1000, and 15,000 ppm of the above phosphorus compound (formula 5) based on the polymer And added as a catalyst as tetrabutyl titanate titanium 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; 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 D.

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.

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[Table 1]

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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 CF151 FD010 FD040 FD070 FD100 FD130 FD170 FD180 FD200 4J029 AA02 AA03 AA05 AB07 AC03 BA02 BA03 BA05 BA08 BA10 BB06A BD06A BF20 BF25 BF27 BH03 CA02 CA06 CB05 CHB CB06 DC06 CCB EG09 HA01 HB01 HB02 KB02 KB22 KD01 KE02 KE03 KE05 KE09 KE12 KE15

Claims (2)

[Claims] Claims: 1. A phosphorus atom content of 500 to 50,000 ppm
A method for producing a polyester elastomer in which a phosphorus compound is copolymerized so as to obtain a flame-retardant polyester elastomer, wherein the phosphorus compound is subjected to block copolymerization. 2. A polyester elastomer composition comprising the flame-retardant polyester elastomer obtained by the production method according to claim 1.