JPH0616912A - Polyester resin composition - Google Patents

Abstract

PURPOSE: To obtain polyester resin composition of which heat and flame resistances are good, retention stability and flowability at the time of their molding are superior and pin press fitting strength of their molded products is improved, wherein the resin compositions is of polycyclohexanedimethyleneterephthalate base polyester.

CONSTITUTION: Resin compositions comprising (A) polyester resins of polycyclohexane dimethyleneterephthalate having an intrinsic viscosity of 0.5 to 2 dl/g and a repeating unit composing of a terephthalate residue and a 1,4- cyclohexanedimethanol residue in the amount of not less than 80 mole % in the polymer, (R) 2 to 30 wt.% (on total components) of an organic bromine compound having an average molecular weight of not less than 3,000, (C) 1 to 20 wt.% of antimony compound, (D) 0.05 to 5 wt.% of a multifunctional epoxy compound, (E) 0.5 to 20 wt.% of an elastomer comprising a copolymer of α-olefin and α,β-unsaturated carboxylic acid alkyl ester, and preferably (F) 0.05 to 2 wt.% of an organic phosphite or phosphonite compound of which not less than one P-O bond is bound to 6-30C aromatic groups.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition having excellent heat resistance and flame retardancy as well as excellent retention safety and fluidity during molding and excellent pin press-fit strength of a molded product.

[0002]

2. Description of the Related Art Polycyclohexane dimethylene terephthalate (PCT) has excellent mechanical properties and chemical resistance, and is a conventional thermoplastic polyester such as polybutylene terephthalate (PBT) and polyethylene terephthalate (PET). Since it has a higher heat distortion temperature than resin, it is expected to be applied to applications such as electric / electronic device parts, automobile parts and machine mechanism parts, which require heat resistance. In particular, when using resin materials for electrical and electronic applications, it is necessary to satisfy the flame retardancy stipulated in UL standards, and in the field of electronic connectors, etc., impart flame retardancy. Needless to say, even when the connector is assembled, the pin is often press-fitted when the connector is assembled, so that it is required to have sufficient pin press-fitting strength.

However, since the degree of polymerization of PCT is apt to be lowered during molding, it has a problem that mechanical properties are deteriorated due to molding retention for a short time, so that it is difficult to put it into practical use as a molding material. The tendency was particularly strong when the composition was flame-retardant. Further, since PCT has low toughness, it has been difficult to use it for a connector or the like that requires high pin press-fit strength.

To solve the former problem, a method has been proposed in which an epoxy compound or the like is added to polyethylene terephthalate, which is a similar terephthalic acid type polyester. As a method for improving the retention stability of PCT, a phenolic epoxy compound branched in three directions and a trifunctional allyl isocyanurate allyl compound are added (JP-A-63-221159), and a phenoxy resin is added. A method (US Pat. No. 4,837,254) and a method of adding a glycidyl ether ester compound (JP-A-3-9948) have been proposed.

Further, for flame retardation of similar polymers, a method of adding a low molecular weight flame retardant such as decabromodiphenyl ether or a method of adding brominated polycarbonate or brominated epoxy having a relatively high molecular weight. Have been proposed. Further, a method of adding a stabilizer to a blend of a PCT-based copolymer and a polycarbonate (JP-A-62-270653), a molded product which is not colored when heated by adding a heat stabilizer to the PCT-based copolymer ( The method for obtaining the publication No. 2-500033) is disclosed. Further, it has been proposed to add an ethylene-based elastomer to improve the crystallization rate of a PCT-based polymer (JP-A-2-53852).

[0006]

However, although it may be possible to prevent an apparent decrease in viscosity when used in PCT by adding an epoxy compound or the like, at that time, the mechanical properties still decrease, and the retention of PCT remains. It was difficult to truly prevent the deterioration of the degree of polymerization at that time and to exhibit the original high mechanical properties.

Further, although the oligomer type flame retardant can easily achieve flame retardancy satisfying the UL standard, the weld strength of the molded product is lowered, and it is difficult to obtain a molded product that can be practically used. Further, addition of a conventionally known elastomer has not been able to greatly improve the characteristics such as pin press-fit strength, which are sensitively affected by deterioration of physical properties during retention.

Further, it has not been possible to obtain sufficient retention stability even by adding a conventionally known stabilizer. As a result of diligent studies to solve the above problems, the present inventors have found that
A flame retardant with a specific molecular weight is added to T, an antimony compound is added with a specific amount, a polyfunctional epoxy compound with a specific amount is added, a specific elastomer is further added, and a phosphorus-based compound is further added if necessary. Heat resistance,
The inventors have found that a composition having good flame retardancy, excellent retention stability and fluidity at the time of molding, and significantly improved pin press-fit strength of a molded product can be obtained, and arrived at the present invention.

[0009]

That is, the present invention is as follows.
(A) The repeating unit in which the terephthalic acid residue and the 1,4-cyclohexanedimethanol residue are bonded is 8 in the polymer.
Polycyclohexane dimethylene terephthalate type polyester resin occupying 0 mol% or more and having an intrinsic viscosity of 0.5 to 2.0, (b) an organic bromine compound having an average molecular weight of 3000 or more, and 2 to 30% by weight based on the total composition. , (C) antimony compound, 1 to 20% by weight based on the total composition, (d) polyfunctional epoxy compound, 0.05 to 5% by weight based on the total composition, and (e) α-olefin and α, β An elastomer substantially consisting of a copolymer with an unsaturated carboxylic acid alkyl ester, and a polyester resin composition comprising 0.5 to 20% by weight based on the total composition, and A polyester resin composition containing a specific organic phosphite or phosphonite compound.

The method for producing the polycyclohexanedimethylene terephthalate-based polyester in the present invention is not particularly limited, but it is possible to use terephthalic acid or a lower alkyl ester thereof in the presence or absence of a catalyst such as an organic titanium compound. A method obtained by polycondensing 1,4-cyclohexanedimethanol can be mentioned. The polymerization conditions include, for example, US Pat. No. 2,901,4
Conditions and the like described in the specification of No. 66 can be applied.

The acid component or diol component of the polycyclohexanedimethylene terephthalate polyester is 20
In the range of mol% or less, preferably 10 mol% or less, ifsotaric acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, methylterephthalic acid, 4, 4'-
Biphenyldicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 1,2-bis (4-carboxyphenoxy) -ethane, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, octadecanedicarboxylic acid, Other dicarboxylic acids such as dimer acid and 1,4-cyclohexanedicarboxylic acid or ethylene glycol, propylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol Those substituted with other diols such as 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol and 2,2-bis (2'-hydroxyethoxyphenyl) propane can also be used.

The cyclohexane ring which is a part of the 1,4-cyclohexanedimethanol residue of the polycyclohexanedimethylene terephthalate polyester used in the present invention has a cis / trans ratio (molar ratio) which is a ratio of cis structure and trans structure. ) Is preferably in the range of 60/40 to 10/90, more preferably 50/50 to 15 /.
The range is 85, more preferably 40/60 to 25/75. If the cis / trans ratio is 60/40 or more, the melting point of the polyester will be low, making it difficult to apply it to applications requiring heat resistance. On the other hand, if it is less than 10/90, the polyester will have a high melting point. Since the difference is too small, the difference between the decomposition temperature and the molding temperature becomes small, and it becomes difficult to improve the retention stability during molding even with the technique of the present invention.

The polycyclohexane dimethylene terephthalate polyester used in the present invention has an intrinsic viscosity of 0.5 when measured in an o-chlorophenol solution at 25 ° C.
To 2.0 dl / g, preferably 0.5 to 1.0 dl / g
g is preferable. Polycyclohexanedimethylene terephthalate polyester has an intrinsic viscosity of 0.5 dl / g
If it is less than 2.0, the mechanical properties are low, while if it exceeds 2.0 dl / g, the moldability tends to be poor.

The amount of terminal carboxyl groups of the polycyclohexanedimethylene terephthalate polyester is
The value before addition of the epoxy compound is preferably 100 equivalents / 10 ⁶ g-polymer or less, preferably 30 equivalents / 10 ⁶ g-polymer or less, and more preferably 15 equivalents / 10 ⁶ g-polymer or less. The amount of terminal carboxyl groups of the polycyclohexanedimethylene terephthalate-based polyester is, for example, Anal. Chem., 26.1614-1616 (1
954), and can be measured using the method of HA Pohl.

The organic bromine compound having an average molecular weight of 3000 or more in the present invention has a bromine atom in the molecule and has an average molecular weight of 3000 or more, preferably 5000 or more, and particularly preferably a bromine content of 30% by weight or more. . Specifically, a brominated epoxy compound or a brominated phenoxy compound (for example, a diepoxy compound or a brominated epoxy oligomer produced by a reaction between a brominated bisphenol A and epichlorohydrin or a reaction between a brominated epoxy compound and a brominated bisphenol A, Brominated epoxy polymer, brominated phenoxy polymer), poly (brominated benzyl acrylate), brominated polyphenylene ether,
Brominated bisphenol A / cyanuric chloride / brominated phenol condensate, and halogenated brominated polystyrene (linear type and crosslinked type), brominated polycarbonate (for example, polycarbonate produced from brominated bisphenol A as a raw material) Polymers, oligomers, and mixtures thereof having an average molecular weight of 3000 or more can be mentioned. Among them, brominated phenoxy, brominated polystyrene and brominated polyphenylene ether can be preferably used.

The addition amount of these organic bromine compounds having a molecular weight of 3000 or more is 2 to 30% by weight, preferably 7 to 20% by weight based on the total composition. If the amount added is less than 2% by weight, the flame retardancy is not sufficient, and if it exceeds 30% by weight, the mechanical properties of the composition tend to deteriorate, which is not preferable. The antimony compound used in the present invention has an average molecular weight of 300.
When used in combination with 0 or more organic bromine compounds, the flame retardancy is synergistically improved. Various kinds of antimony compounds can be used. Specific examples include antimony trioxide, antimony trioxide, antimony pentaoxide, antimony pentaoxide, sodium antimonate, and antimony phosphate. Sodium antimonate is preferable, and in particular, substantially anhydrous sodium antimonate heat-treated at a temperature of 550 ° C. or higher. Particularly preferred.

The amount of the antimony compound added in the present invention is 1 to 20% by weight, preferably 2 to 10% by weight based on the total composition.
If it is less than 1% by weight, the flame retardant effect due to the combined use of the antimony compound is not sufficient, and if it exceeds 20% by weight, the mechanical properties tend to be impaired, which is not preferable.
More preferably, it is added at a ratio of 1 antimony in the antimony compound to 2 to 5 atoms of bromine in the added flame retardant.

The epoxy compound used in the present invention is a compound containing two or more epoxy groups in one molecule. When the number of epoxy groups is one, the decrease in the molecular weight due to hydrolysis due to the decrease in the carboxyl groups of PCT is reduced, but it is not preferable because the effect of improving the retention stability during molding, which is the main object of the present invention, is not sufficient. . Further, in the case of two epoxy groups, it is necessary to add a large amount as compared with the case of an epoxy compound having a larger number of functional groups in order to improve the stability at the time of retention, so that the effect is exhibited by adding a small amount. Therefore, it is desirable to use a trifunctional or higher functional epoxy compound, especially a trifunctional to pentafunctional epoxy compound. In the case of conventionally known polyester resins such as PBT and PET, in general, when a trifunctional or higher functional epoxy compound is added, a remarkable cross-linking reaction occurs, and the moldability and physical properties often deteriorate due to thickening and gelation. . On the contrary, by utilizing such thickening, it has been used for extrusion molding and blow molding, which are applications other than injection molding. In the case of the PCT of the present invention, unlike the conventional PBT and PET, the decomposition rate is high at the melt molding temperature. Therefore, the use of the polyfunctional epoxy compound can effectively reduce the deterioration of the physical properties during the retention. The behavior is significantly different from that of the polyester resin.

Specific examples of epoxy compounds include:
1,6-hexanediol, neopentyl glycol,
Diglycidyl ethers of aliphatic diols such as polyalkylene glycols, sorbitol, sorbitan, polyglycerols, polyglycidyl ethers of aliphatic polyols such as pentaerythritol, diglycerol, glycerol and trimethylolpropane, cycloaliphatic rings such as cyclohexanedimethanol Formula Polyglycidyl ether of polyol, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, adipic acid, diglycidyl ester or polyglycidyl ester of aromatic polyvalent carboxylic acid such as sebacic acid, resorcinol, bis -(P-hydroxyphenyl) methane, 2,
2-bis- (p-hydroxyphenyl) propane, tris- (p-hydroxyphenyl) methane, 1,1,2,
Diglycidyl ether or polyglycidyl ether of polyhydric phenol such as 2-tetrakis (p-hydroxyphenyl) ethane, N, N-diglycidylaniline,
N, N-diglycidyl toluidine, N, N, N ', N'-
Tetraglycidyl-bis- (p-aminophenyl) N-glycidyl derivative of amine such as methane, triglycidyl derivative of aminophenol, triglycidyl tris
(2-Hydroxyethyl) isocyanurate, triglycidyl isocyanurate, orthocresol type epoxy, and phenol novolac type epoxy can be mentioned.

Among these, particularly effective ones are polyglycidyl ethers of aliphatic polyols, tris- (p
-Hydroxyphenyl) methane triglycidyl ether, 1,1,2,2-tetrakis- (p-hydroxyphenyl) ethane tetraglycidyl ether, and triglycidyl tris (2-hydroxyethyl) isocyanurate are excellent and are preferably used. it can.

The monomer type epoxy contained in the above may be added not only as a monomer but also in the form of an oligomer or polymer formed by condensation of epoxy groups or in the form of a mixture thereof. The degree of polymerization of the condensate is preferably 1 to 20, more preferably 1 to 10. Further, different types of epoxies may be mixed and used.

The method for producing the epoxy compound used in the present invention is not particularly limited. A conventionally known method,
For example, “Encyclopedia of Polymer Science & Engineer
ing ", John Willey & Sons, New York, Epoxy Resin
It can be produced by the method described in the section s or its reference. The addition amount of the epoxy compound in the present invention is 0.
It is from 05 to 5% by weight, preferably from 0.1 to 3% by weight. If the addition amount is less than 0.05% by weight, the effect of improving the molding retention stability, dry heat deterioration resistance, etc. is small.
When the content exceeds the weight%, the mechanical properties of the polycyclohexane dimethylene terephthalate polyester are impaired, which is not preferable. Also, among epoxy resins,
Compared to glycidyl ether type epoxy compounds, the glycidyl ester type and N-substituted glycidyl derivative compounds are
Generally, since the reactivity is high, it is preferable to reduce the addition amount as compared with the glycidyl ether type.

The addition amount of the epoxy compound is as follows after addition to polycyclohexanedimethylene terephthalate.
The amount of terminal carboxyl groups of polycyclohexanedimethylene terephthalate is 30 equivalents / 10 ⁶ g-polymer or less,
Desirably, it is necessary to add 20 equivalents / 10 ⁶ g-polymer or less in such a proportion that molding fluidity, retention stability, and
It is preferable from the viewpoint of improving dry heat deterioration resistance.

The α-olefin component of the elastomer used in the present invention includes ethylene, propylene and butene-1.
And ethylene is most preferred. As the α, β-unsaturated carboxylic acid alkyl ester, an ester of acrylic acid or methacrylic acid and a monohydric alcohol having 1 to 8 carbon atoms is preferably used. Specific examples thereof include esters such as methyl, ethyl, propyl, hexyl, 2-ethylhexyl and octyl. Examples of suitable alkyl acrylates and alkyl methacrylates are methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate and butyl methacrylate, with methyl acrylate and ethyl acrylate being particularly preferred. The amount of the α, β-unsaturated carboxylic acid alkyl ester copolymerized with the elastomer is preferably 5 to 60% by weight, more preferably 10 to 50% by weight. Other than that, it is possible to copolymerize a copolymerizable vinyl-based monomer as long as the effect of the present invention is not impaired. In particular, a copolymerization component showing an effect of lowering the glass transition temperature of the elastomer can be preferably used for improving the toughness at low temperature.

The amount of the elastomer component added in the present invention is 0.5 to 20% by weight, preferably 1 to 10% by weight, based on the total composition. If the addition amount is less than 0.5% by weight, the effect of improving the toughness of the polymer is not sufficient, and if it exceeds 20% by weight, the heat distortion temperature tends to be lowered, which is not preferable. In the composition of the present invention, by adding an epoxy compound to a specific flame retardant composition and further adding a specific elastomer, the retention stability and the characteristics against pin press-fitting are greatly improved, but further, the phosphorus-based compound described below. It is preferable to use in combination because the characteristics can be further improved. The organic phosphite or phosphonite used in the present invention has at least one P—O bond bonded to an aromatic group. Such compounds are represented by chemical formulas (1) and (2).

[0026] Here, at least one of R ₁ , R ₂ and R ₃ is an aromatic group having 6 to 30 carbon atoms, and other R ₁ , R ₂ and R 3
₃ is hydrogen or an aliphatic group having 1 to 30 carbon atoms.

[0027] Here, at least one of R ₄ , R ₅ and R ₆ is an aromatic group having 6 to 30 carbon atoms, and other R ₄ , R ₅ and R 6
₆ is hydrogen or an aliphatic group having 1 to 30 carbon atoms.

The following can be mentioned as specific examples of such compounds. Tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylene phosphonite, bis (2,4-di-t-butyl) Phenyl) pentaerythritol-di-phosphite, bis (2,6-
Di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis
(4,6-di-t-butylphenyl) octyl phosphite, 4,4'-butylidene-bis (3-methyl-6-t
-Butylphenyl-di-tridecyl) phosphite,
1,1,3-Tris (2-methyl-4-ditridecylphosphite-5-t-butyl-phenyl) butane, tris (mixed mono and di-nonylphenyl) phosphite, tris (nonylphenyl) phosphite , 4,
4'-isopropylidene bis (phenyl-dialkyl phosphite) and the like, and tris (2,4-di-t-
Butylphenyl) phosphite, 2,2-methylenebis
(4,6-di-t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t) -Butylphenyl) -4,4'-
Biphenylene phosphonite and the like can be preferably used.

In the present invention, these specific organic phosphite or phosphonite compounds can be used alone or in combination of two or more, and the content thereof is 0.05 based on the total amount of the polyester resin composition. To 2% by weight, preferably 0.1 to 1% by weight, more preferably 0.1 to 0.5. If it is less than 0.05% by weight, the effect of suppressing branching due to epoxy and the effect of improving the retention stability are not sufficient, and if it is more than 2% by weight, the retention stability of the polyester is lowered, which is not preferable.

It is necessary to wait for future research to find out why the addition of a specific phosphorus compound to the composition containing the polyfunctional epoxy compound or the like can significantly improve the deterioration of the physical properties at the time of retention. The formation of a branched structure is suppressed by the addition of the compound as compared with the case where the compound is not added, which correlates with the fact that the retention stability is significantly improved as compared with the case where the epoxy compound is simply added. It is thought that it is. The addition of a phosphorus compound has the effect of reducing the decrease in crystallization rate as compared with the case where only an epoxy compound is added, but the addition of a phosphorus compound also suppresses the formation of a branched structure. It is highly likely that this is due to an accident.

In the constitution of the present invention, (a) PCT polyester, (b) organic bromine compound having a molecular weight of 3000 or more, (c) antimony compound, (d) polyfunctional epoxy compound, (e) α-olefin. It is necessary to include an elastomer composed of α and β-unsaturated carboxylic acid alkyl ester, and the object of the present invention can be achieved only by including these elastomers. It is preferable to further contain a specific phosphorus compound in the composition of the present invention, because the residence stability can be dramatically improved.

Even when the composition of the present invention is used in combination with the epoxy compound of the present invention, a compound such as another epoxy compound, an oxazoline compound, a carbodiimide compound or an aziridine compound which can further improve the hydrolysis resistance of polyester is used. Good. It is preferable to use a reinforcing filler for the present invention because rigidity, heat resistance and the like are further improved. The preferred reinforcing filler is fibrous,
Means a particulate or flake filler, for example,
Glass fiber, glass beads, glass flake, carbon fiber, ceramics fiber, asbestos, wollastonite, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, fine silicic acid, feldspar powder, potassium titanate, silas balloon , Calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dawsonite, and clay, and these can be used in combination of two or more. Among these reinforcing fillers, especially glass fiber, glass beads, wollastonite, mica,
Clay and talc are suitable, and glass fiber and glass beads are particularly preferably used.

The fiber diameter of the glass fiber is preferably 2 to 20 μm, particularly preferably 6 to 15 μm. The glass fibers have an average length of 0. 1 when dispersed in a polymer.
It is preferable that the distance is about 05 to 1 mm, particularly 0.1 mm to 0.5 mm. The composition of the present invention is a conventional additive, for example, an antioxidant, within a range that does not impair the object of the present invention.
At least one kind of ultraviolet absorber, heat stabilizer, lubricant, template, coloring agent including dyes and pigments, nucleating agent and flame retardant can be further contained.

In addition, a small amount of another thermoplastic resin (for example, polyethylene, acrylic resin, fluororesin, polyamide,
Polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, polyether ether ketone resin, liquid crystal polyester resin,
Polyacetal, polycarbonate, polysulfone, polyphenylene oxide, etc., thermosetting resin (eg phenol resin, melamine resin, polyester resin, silicone resin, epoxy resin etc.) and soft thermoplastic resin (eg ethylene / vinyl acetate copolymer, polyester elastomer) , Ethylene / propylene terpolymer, ethylene / butene-1 copolymer, etc.) and the like.

The method for producing the composition of the present invention is not particularly limited, but preferably, at a melting point of the polycyclohexanedimethylene terephthalate type polyester or higher, the polycyclohexanedimethylene terephthalate type polyester, a specific organic bromine compound, an antimony compound, Examples thereof include a method in which an epoxy compound, an elastomer, and optionally a phosphorus compound, and other additives are melt-kneaded uniformly using an extruder.

The composition obtained is generally known in injection molding,
It can be molded by any method such as extrusion molding. Molded articles obtained from the composition of the present invention have excellent heat resistance, mechanical properties and chemical resistance, and can be used in various applications such as precision equipment parts such as electric / electronic parts, automobile parts and machine parts. Can be used.

[0037]

The present invention will be described in more detail with reference to the following examples.
All parts in the examples are based on weight. Examples 1-5, Comparative Examples 1-5 Cyclohexanedimethanol residue cis / trans ratio =
35/75, intrinsic viscosity 0.82, terminal carboxyl group amount 21 equivalents / 10 ⁶ g-Polycyclohexanedimethylene terephthalate (PCT) which is a polymer, chopped strand type glass fiber (10 μmφ, length 3 mm) 30 Wt%, sodium antimonate 6 wt%, the following organic bromine compounds, (A-1) to (A-4), epoxy compounds (B-1) to (B-4), elastomer (C-
1) to (C-2), and phosphorus compounds (D-1) to (D
-3) was dry-blended using a V blender as shown in Table 1, and then melt-kneaded and pelletized using a twin-screw extruder set at 300 ° C. to obtain a resin composition. Also, the composition was subjected to an injection molding machine having an injection capacity of 5 ounces, a processing temperature of 300 ° C., a mold temperature of 120 ° C.,
Molding cycle (injection time / cooling time / intermediate time), 10
/ 15/10 seconds (molding cycle (a)), and 10 /
Molded in 15/100 seconds (molding cycle (b)),
A 1/8 "tensile test piece was obtained.

For these test pieces, ASTM D63
A tensile test was performed according to No. 8 to evaluate the tensile strength. In the molding cycle (a), UL combustion test pieces (1/16 "
X1 / 2 "x5") was molded and subjected to a vertical combustion test according to UL94 standard. In addition, the injection molding condition (a) is 1.3.
With 10 square holes of 1.5mm x 1.5mm with mm pitch,
A pin press-fitting test piece having a thickness of 3 mm was obtained. Using the obtained test piece, a 1.6 mm × 1.6 mm brass square rod was inserted into each square hole, and the number of cracked square holes was examined.

Further, in order to evaluate the formability, a length of 80 mm,
A small box with a width of 30 mm, a depth of 20 mm, and a wall thickness of 2 mm is set at a mold temperature of 1
Molding was carried out at 30 ° C., and the minimum molding cycle in which a molded product could be molded was obtained to evaluate the high cycle property. The results are shown in Table 1.

[0040]

[0041]

The molded product obtained from the polyester composition of the present invention has excellent heat resistance and flame retardancy, excellent retention stability and fluidity during molding, and excellent pin press-fit strength of the molded product.・ Electronic equipment parts, automobile parts, machinery
It is useful as a mechanical part.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08L 63:00 8830-4J 23:00) 7107-4J (72) Inventor Hidetoshi Otata Nagoya, Aichi Prefecture 1 Toray Co., Ltd. Nagoya Plant, 9-9 Oemachi, Minato-ku, Japan (72) Inventor Jiro Kumagi 1-9 Toe Co., Ltd. Nagoya, Minato-ku, Aichi Prefecture

Claims (2)

[Claims] 1. A repeating unit in which (a) a terephthalic acid residue and a 1,4-cyclohexanedimethanol residue are combined occupies 80 mol% or more of the polymer and has an intrinsic viscosity of 0.5 to.
Polycyclohexane dimethylene terephthalate-based polyester resin of 2.0, (b) organic bromine compound having an average molecular weight of 3000 or more, 2 to 30% by weight based on the total composition,
(C) antimony compound, 1 to 20% by weight based on the total composition, (d) polyfunctional epoxy compound, 0.
05-5% by weight, and (e) α-olefin and α, β
An elastomer consisting essentially of a copolymer with an unsaturated carboxylic acid alkyl ester, 0.5-2 based on the total composition
A polyester resin composition comprising 0% by weight. 2. At least one P—O bond has 6 carbon atoms.
To 30 organic phosphite or phosphonite compounds bonded to aromatic groups in addition to 0.0 to total composition.
The polyester resin composition according to claim 1, wherein the polyester resin composition is added in an amount of 5 to 2% by weight.