JPS591563A - Polyester resin composition - Google Patents

Abstract

PURPOSE:To provide a polyester resin compsn. having improved ductility while retaining flame retardance, mechanical properties and electrical properties, by blending antimony trioxide containing an arom. carboxylate ester deposited on its surface with a halogen-contg. polyester resin. CONSTITUTION:1-15pts.wt. antimony trioxide containing 0.1-10wt% (based on the quantity of antimony trioxide) arom. carboxylate ester deposited on its surface is blended with 100pts.wt. halogen-contg. polyester resin to obtain the titled compsn. Examples of the halogen-contg. polyester resins are halogen-contg. copolymer resins obtd. by copolymerizing terephthalic acid, a 2-10C alkylene glycol and an arom. halogen-contg. diol of the formula and resins obtd. by blending a polyester resin contg. no halogen with an arom. halogen-contg. flame retarder.

Description

[Detailed description of the invention] The present invention relates to polyester resin compositions.

This invention relates to a polyester resin composition that is flame retardant and has improved ductility.

A flame-retardant polyester resin composition is prepared by copolymerizing a halogen-containing copolyester resin, such as terephthalic acid or its ester-forming derivative, alkylene glycol or its ester-forming derivative, and a halogen-free aromatic diol. A composition in which antimony trioxide is blended as a flame retardant aid into the copolymerized polyester resin obtained by For some reason, compositions containing a halogen-containing copolymerized polyester resin, an aromatic halogen flame retardant, and antimony trioxide are known.

These flame-retardant polyester resin compositions have excellent mechanical and electrical properties and are widely used in electrical, electronic parts, and other applications, but they still lack sufficient ductility and bendability. It had a weak flaw. For example, in electric wire connectors, the flexible part that holds the metal contacts in the connector body often breaks, and in coil bobbins that have flanges at both ends, if a load is applied to the flanges by the winding, the flanges will break. There were inconveniences such as the base breaking.

As a result of intensive research in order to obtain a polyester resin composition that does not have the disadvantages of halogen-containing polyester resin, the present inventors have discovered that a specific compound is added to the surface of the halogen-containing polyester resin as antimony trioxide, which is added as a flame retardant additive. When antimony trioxide with M1-3- is used, the ductility can be improved without impairing the various physical properties of the halogen-containing polyester resin, such as flame retardancy, mechanical properties, and electrical properties. They discovered this and completed the present invention.

That is, the present invention aims to provide a polyester resin composition of great industrial value, and its gist is to provide a halogen-containing polyester resin with an aromatic carboxylic acid ester attached to the surface. This is a polyester resin composition containing antimony trioxide.

The present invention will be explained in detail below.

The halogen-containing polyester resin used in the present invention includes halogen-containing polyester resins fk and Wbru1.
Aii, halogen-free polyester resin covered above...
An example is one in which an aromatic halokene flame retardant is blended with a copolymerized polyester resin containing Rogun.

The halogen-containing copolyester resin has Qi 4 = phthalic acid or its ester-forming derivative, carbon number λ
-10 alkylene glycol or its ester-forming derivative, and a copolymer with a halogen-containing aromatic diol.

Terephthal pJ may also contain up to about 30 mol % of other polybasic acids such as 7-thalic acid, isophthalic acid, naphthalene dicarboxylic acid, adipic acid, sebacic acid, trimellitic acid. Furthermore, examples of its ester-forming derivatives include alkyl esters of the above acids such as d1 dimethyl terephthalate.

An alkylene glycol having -10 carbon atoms.

These include ethylene glycol, 7.3-propanediol, /, cuptanediol, /, 6-hexanediol, /, 10-decanediol, etc., and these contain less than 30 mol% of glycerin and pentaerythritol. It may also contain polyhydroxy compounds such as Furthermore, examples of the ester-forming derivative include ethylene oxide.

A halogen-containing aromatic diol is a compound represented by the general formula, and is produced by, for example, reacting halogenated bisphenol A with an alkylene oxide such as ethylene oxide or propylene oxide, or an alkylene halohydrin such as epichlorohydrin. be done.

Usually, R in the above general formula [1] is -0H2-OH2
- group or 10H-OH, - group, and X is bromine 0H.

or chlorine, specifically -12
-bis(y-(,2-hydroxyethoxy)-3,!-
cyfuromphenyl]furopane, 2,2-bis(y-(
a-hydroxyethoxy) 't'-dichlorophenyl]furopane, 2. +2-bis[gu(7i-hydroxypropoxy)-3,z-dibromphenyl]propane 1.2.2-bis[ter(3-hydroxypropoxy)-3,,t-dibromphenyl]furopane,
+2. ．． 2-bis[y-(3-hydroxypropoxy)
-3,s-dichlorophenyl]propane, λ, +2-
Bis[a-(,z-hydroxyethoxy)-3-bromphenyl]furopane, l,2-bis[<t-(,2-hydroxylaethoxy)-2,3,j,6-teto-bromphenyl]propane etc.

In order to copolymerize the above three components to produce a copolymerized polyester resin, the above three components are charged during transesterification or esterification, followed by a polycondensation reaction, in accordance with conventionally known polyester resin production methods. Alternatively, terephthal rM or an ester-forming derivative thereof is reacted with an alkylene glycol or an ester-forming derivative thereof to produce bishydro 7-xyalkyl terephthalate or its low l metal compound, which is then reacted with the general formula shown above. A method in which a halogen-containing aromatic diol represented by [I] is added and a polycondensation reaction is performed can be adopted.

The type and amount of the halogen-containing aromatic diol used in the copolymerization are such that the halogen content of the obtained co-polyester resin is 3 to 1%, preferably 1 to 7%.
It is selected so that it is 0% by weight.

If the halogen content of the copolymerized polyester resin is too low, the flammability (M) will not be sufficient, whereas if it is too high, the mechanical properties will be impaired, which is not preferable.

The halogen-free polynisder resin contains the above-mentioned terephthalic acid or its ester-forming vj conductor and the carbon number - ~/
θ alkylene glycol or its ester forming property I
It is a compound obtained by MM combination of compound II and polyester resin according to the conventionally known manufacturing method of polyester resin, and typical examples include polyethylene terephthalate, polybutylene
8- Examples include phthalate.

Examples of aromatic halogen flame retardants include hexabromobenzene, pentabromotoluene, and other halogenated diphenyls such as tetrabromodiphenyl, thecabrom diphenyl, tetrabrom diphenyl ether, thecabrom diphenyl ether, and thecaprom diphenyl sulfone. Class s +21'-bis(terhydroxy-3,j-dibromphenyl)furopane (tetrabromobisphenol A), J,, 2-bis(couglycidoxy-3,j-dibromphenyl)propane or lower compound thereof () 10-glycanated bisphenol A-type epoxy resin), -z+,z-bis(9-hydroxyethoxy-3,j-dibromphenyl)propane, 2. ．． 2
- Bis(4t-acetoxyphenyl)furopane, polycarbonate oligomers of tetrabromobisphenol A, derivatives of bisphenol A, tetrabromophthalic anhydride, tribromophenol condensates, polypentabromobenzyl acrylate, brominated polystyrene, Examples include condensates of tetrabromobisphenol A, cyanuric acid, and tribromophenol.

The amount of these aromatic halogen-based flame retardants to be used is based on the assumption that the halogen content of the halogen-containing polyester resin blended with the aromatic halogen flame retardant is /~/1M-fjA%, <ke3~/θkabata%. It is better to do so.

If this level is too much, the flame retardance will not be sufficient, and on the other hand, if it is too much, the mechanical properties will be impaired.

Antimony trioxide with an ester of aromatic carboxylic acid attached to the surface is prepared by thoroughly mixing a fine powder of trihyantimony, for example, a fine powder of /~Δ/ with an ester of aromatic carboxylic acid. One example is one in which an ester of aromatic carboxylic acid is completely adhered to the surface of fine antimony oxide powder.

Esters of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid,
Examples include esters of alcohols and aromatic carboxylic acids such as trimesic acid and naphthalene dicarboxylic acid, and esters of aromatic dicarboxylic acids, aromatic tricarboxylic acids,
Esters with alcohols having 3 to 3θ carbon atoms are preferred.

Specifically, dibutyl phthalate, dioctyl phthalate, dioctyl phthalate, dioctyl phthalate, diisooctyl phthalate, di(,2-ethylhexyl) phthalate, dinonyl phthalate, didecyl phthalate, diindecyl phthalate, diindecyl phthalate, didodecyl phthalate. , esters of phthalic acid such as ditridecyl phthalate, diphenyl phthalate, dibenzyl phthalate, butylbenzyl phthalate, octyldecyl phthalate, esters of isophthalic acid such as di(-monoethylhexyl) isophthalate, diisooctylisophthalate, Examples include esters of trimellitic acid such as (,2-ethylhexyl) trimellitate, trioctyl trimellitate, and triindecyl trimellitate.

=11- The amount of these aromatic carboxylic acid esters σ) attached is 1 to 0.1 to 70% by weight, preferably about 4 to 4% by weight, based on antimony trioxide. This lowers the rigidity of the ester resin and impairs the original properties of the resin.

For example, as above-mentioned antimony trioxide,
Backed by Matsuku Geen Co., Ltd., trademark: Matsuku Geen L, particle size/, 6~. 2. Those with θμ are commercially available and are suitable for use in the composition of the present invention.

As a method for blending antimony trioxide with an aromatic carboxylic acid ester attached to the surface into a halogen-containing polyester resin, various known methods can be adopted.For example, a method of tri-blending the above-mentioned two, Examples of methods include melt-kneading the blend using an extruder, Banbury mixer, etc., and forming pellets.

The composition of the present invention has sufficient flame retardancy, mechanical properties, and electrical properties, and has improved ductility, so it is extremely valuable as an engineering plastic.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

In the examples, "parts" and "%J" indicate "parts by weight" and "% by weight," respectively.

In addition, the flammability is UL-2<l (Underwrite
er'5 Laboratories, Engineering nc, )
The full results of the vertical combustion test, tensile strength and tensile elongation rate of A8TMD63? The results are shown below.

Examples/and Comparative Examples/Polybutylene lentilthalate having an intrinsic viscosity of 7.2 (manufactured by Mitsubishi Chemical Corporation, trademark, 100 parts of NOVADOL J0.2,
<Melting point obtained by polymerizing nttaprom benzyl acrylate in a propylene glycol solvent using benzoyl peroxide as a catalyst/θ! ~770°C, bromine content 70. and 77 parts of polybentabromobenzyl acrylate (%), and 3 parts of antimony trioxide (manufactured by McGeehn Co., trade name, McGeehn L) with 7% indecyl 7-thaleate attached to the surface of the antimony trioxide. 2 using an Ω extruder (manufactured by Isuzu Koki ■)! The mixture was melt-kneaded at θ°C and extruded into pellets.

This Beretwo, 3. J'oz injection molding machine (manufactured by Nissaya Jushi Kogyo ■, TS-/θθ type), combustion test piece, and AST
Using a test piece mold specified by M, the resin temperature was 260.
Injection molding was performed at a mold temperature of θ°C, an injection time of 70 seconds, and a cooling time of 20 seconds.

The combustible tensile strength and tensile elongation of the obtained molded article were as shown in Table 1 below.

For comparison, antimony trioxide with no deposits on the surface (manufactured by Kingdom Seirin) was used (-).
Comparative example /) is also written.

Table 1 Examples-~j and Comparative Examples-~j 700 parts of dimethyl terephthalate, 66 parts of Z-fundiol, and -2,2-bis[tar(,z-hi)'
+:+Kissy 3. Intrinsic viscosity θ obtained by copolymerizing s-sifromphenyl)]propane/part,! ! , halogen-containing copolyester resin ioom with 6% bromine content
, the same antimony trioxide used in Example/! ,? and the flame retardant shown in Table 2 below were mixed, and molding was carried out in the same manner as in Example.

The flammability, tensile strength and tensile elongation of the obtained molded article were as shown in Table 2 below.

15- For comparison, the results when antimony oxide was used as antimony trioxide on the same surface as that used in Comparative Example (Comparative Example)
~ri is also written.

16- Example 6 and Comparative Example 1g The same non-rogen-containing polyester resin/θO part and antimony trioxide s and tr parts as used in Example- were mixed, and I was prepared in the same manner as in Example. The molding was done with.

The flammability, tensile strength and tensile elongation of the obtained molded article were as shown in Table 3 below.

For comparison, the same table r111 used as antimony trioxide in Comparative Example 1 also shows the slag (comparative example 6) when antimony trioxide without horns was used.

Table 3

Claims (1)

[Scope of Claims] (1) A polyester resin composition obtained by blending antimony trioxide with an ester of aromatic carboxylic acid adhered to the surface of a polyester resin containing nitrogen. (2) The halogen-containing polyester resin is (a) terephthalic acid or its ester-forming visiting conductor, (1)) an alkylene glycol having 2 to /θ carbon atoms or its ester-forming visiting conductor, and (Q) general formula % formula. The polyester resin composition according to claim 1, which is a halogen-containing copolyester resin obtained by copolymerizing a halogen-containing aromatic diol expressed in %. (3) The halogen-containing polyester resin is a halogen-free polyester resin "Ifc", which is a polyester mMb obtained by blending an aromatic halogen flame retardant with the halogen-containing copolyester resin. (4) An ester of an aromatic octacarboxylic acid, an aromatic dicarboxylic acid or an aromatic tricarboxylic acid, and a carbon number j to 3.
Claim No. 0 which is an ester with alcohol of
1) The polyester resin composition as described in item (3) without item. (5) The adhesion amount of aromatic carboxylic acid ester is 0.0% relative to antimony trioxide. /~101% by weight of the polyester resin composition according to claims (1) to (4). (6) The blending amount of antimony trioxide is /~/ with respect to 1 part of halogen-containing polyester resin/θθ! The polyester resin composition according to claims (1,)-1-(5), which is in parts by weight.