JPH0940852A - Polyester resin composition and molded article thereof - Google Patents

Abstract

(57) 【Abstract】 PROBLEM TO BE SOLVED: To have excellent mechanical properties, heat resistance and moldability, and also to be excellent in anisotropy of a molded product and pin press-fitting property.
Development of a thermoplastic resin composition useful for applications in the fields of electrical / electronic / electrical components and fields with strict dimensional accuracy. SOLUTION: Polybutylene terephthalate (50 to 97)
% By weight) Low crystalline thermoplastic polyester resin (3 to 50
% By weight) Based on a mixture (100 parts by weight) of a thermoplastic polyester elastomer (0-20% by weight), an organic bromine compound (1-60 parts by weight), an antimony compound (0.1-30 parts by weight), a fluoropolymer ( 0.01 to 5 parts by weight) and a glass filler (5 to 150 parts by weight).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fluidity during molding,
The present invention relates to a polyester resin composition having good mechanical properties and flame retardancy, extremely small anisotropy of a molded product, and improved pin press-fit strength, and a molded product thereof.

[0002]

2. Description of the Related Art Polybutylene terephthalate (PBT)
Since it has excellent mechanical properties and chemical resistance, it has recently been applied to applications such as electric / electronic equipment parts, automobile parts and mechanical mechanism parts, which require heat resistance. Furthermore, when using resin materials for these applications,
Needless to say, it is necessary to satisfy the flame retardancy stipulated in the UL standard, and further, in the field of electronic connectors, etc., it has good mechanical properties even when imparted with flame retardancy. Since pins are often pressed in when assembling, a molded product with small anisotropy is required in order to have sufficient pin press-fitting strength and to improve adhesion when connecting connectors. Japanese Patent Publication 61-5934
As disclosed in Japanese Patent Publication No. 7-72, for example, a method in which glass fiber and glass powder are used in combination with polyethylene terephthalate (PET), and as shown in Japanese Patent Publication No. 62-3869, for example, polyether ester or acrylonitrile-styrene copolymer is added to PBT. For example, a method using glass fiber and an inorganic filler having a specific particle size, a method using glass flakes or an inorganic solid and an epoxy compound as disclosed in JP-B-55-41699 and JP-B-55-41700, JP-A-63 −
As shown in 291947, for example, a method using a fluorine atom-containing compound and rubber having a specific particle size as a fireproofing agent, a method of using a filler, and a polycyclohexanedimethylene terephthalate copolymer as shown in JP-A-2-8243. A method using glass fiber and the like are disclosed.

However, although these polymers and fillers can provide materials satisfying a certain degree of anisotropy, flame-retardant materials have a problem that they do not exhibit sufficient strength against pin press-fitting during connector production. Not resolved.

[0004]

SUMMARY OF THE INVENTION Therefore, it is an object of the present invention to obtain a polyester resin composition having a flame retardancy and mechanical properties, in particular, a property of hardly causing cracking of a molded product when a pin is press-fitted, and a molded product thereof. To do.

[0005]

The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, have found that polybutylene terephthalate has a low crystalline thermoplastic polyester resin, a thermoplastic polyester elastomer, an organic bromine compound, and an antimony compound. By including a specific amount of polytetrafluoroethylene and an inorganic filler, it was found that a flame-retardant, mechanical property is excellent, and a molded product in which the pin press-fit strength of the molded product is remarkably improved is obtained, and the present invention has been achieved. did.

That is, the present invention provides "(A) polybutylene terephthalate 50 to 97% by weight (B) low crystalline thermoplastic polyester resin 3 to 50% by weight (C) thermoplastic polyester elastomer 0 to 20% by weight, the above ( A) (B) (C)
(D) 1 to 60 parts by weight of organic bromine compound (E) 0.1 to 30 parts by weight of (F) 0.01 to 5 parts by weight of fluororesin and (G) to 100 parts by weight of the mixture of
A polyester resin composition containing 5 to 150 parts by weight of an inorganic filler. ”.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Polybutylene terephthalate used in the present invention comprises terephthalic acid or an ester-forming derivative thereof and 1,4-butanediol or an ester-forming derivative as a main component and is subjected to a polycondensation reaction. The obtained polymer may contain a copolymerization component as long as the characteristics are not impaired.

Preferred examples of these polymers and copolymers are polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate). ), Polybutylene (terephthalate / naphthalate) poly (butylene / ethylene) terephthalate, etc., and they may be used alone or in combination of two or more.

From the viewpoint of moldability and mechanical properties, these polymers and copolymers have an intrinsic viscosity of 0.36 to 1.6 when measured in an o-chlorophenol solution at 25 ° C.
Those in the range of 0, particularly 0.52 to 1.25 are preferable.

Further, these polybutylene terephthalate polymers or copolymers have a COOH terminal group amount of 1 to 1 determined by potentiometric titration of an m-cresol solution with an alkaline solution.
Those in the range of 50 eq / t (amount of terminal group per ton of polymer) can be preferably used in terms of durability and anisotropy suppressing effect.

The low crystalline thermoplastic polyester resin (B) used in the present invention is a polymer obtained by a polycondensation reaction containing a dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming derivative as main components. Or a copolymer.

The dicarboxylic acid is terephthalic acid,
Isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-
Aromatic dicarboxylic acids such as sodium sulfoisophthalic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and dodecanedioic acid, alicyclic compounds such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Examples include dicarboxylic acids and their ester-forming derivatives.

The diol component has 2 to 20 carbon atoms.
Aliphatic glycol of ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6
-Hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, etc.,
Alternatively, long chain glycols having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like, and ester-forming derivatives thereof and the like can be mentioned.

Examples of these polymers or copolymers include polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / isophthalate), polyethylene terephthalate, polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), Bisphenol A (terephthalate / isophthalate), polybutylene (terephthalate / naphthalate), polyethylene naphthalate,
Polycyclohexane dimethylene terephthalate, polycyclohexane dimethylene (terephthalate / isophthalate), poly (cyclohexane dimethylene / ethylene)
Examples include terephthalate and poly (cyclohexane dimethylene / ethylene) (terephthalate / isophthalate). Among these (B) low crystalline thermoplastic polyester resins, from the viewpoint of moldability, fluidity, mechanical properties, particularly impact resistance and heat resistance of the polyester resin composition, ethylene glycol-derived structural units derived from diol are used. Structure 2
Those containing 0 mol% or more and 20 mol% of the structure derived from terephthalic acid in the structural unit derived from dicarboxylic acid are preferably used. In particular, the molar ratio of the cyclohexanedimethanol component to the ethylene glycol component is 50/50 to 80/20.
Poly (cyclohexane dimethylene / ethylene) terephthalate is preferably used.

As the index of low crystallinity of the low crystalline thermoplastic polyester resin (B) used in the present invention, 1/2 crystallization time in differential scanning calorimetry is used, and the present invention is used (A). Those which show no crystallization peak for 10 times or more as compared with polybutylene terephthalate are preferably used.

The low crystalline thermoplastic polyester resin (B) used in the present invention is an o-chlorophenol solution of 25.
Intrinsic viscosity is 0.36 to 1.55dl when measured at
/ G, particularly in the range of 0.52 to 1.25 dl / g is preferable from the viewpoint of mechanical properties and moldability.

In the present invention, a thermoplastic polyester elastomer may be blended for the purpose of improving the pin press-fit strength and impact resistance. As the thermoplastic polyester elastomer, a polyether ester block copolymer having a polyester having the same structure as the low crystalline thermoplastic polyester resin as a hard segment and a poly (alkylene oxide) glycol and / or an aliphatic polyester as a soft segment is used. Coalescence and polyester / ester block copolymers are preferably used.

Specific examples of the poly (alkylene oxide) glycol and the aliphatic polyester constituting the soft segment are polyethylene glycol, poly (1,2- and 1,3-propylene oxide) glycol, poly (tetramethylene oxide). ) Glycol, copolymer of ethylene oxide and tetrahydrofuran, polyethylene adipate, polybutylene adipate, poly-
ε-caprolactone, polyethylene sebacate, polybutylene sebacate and the like can be mentioned.

(C) The proportion of the soft segment and the hard segment of the thermoplastic polyester elastomer is
95/5 to 10/90 by weight, especially 90/10 to 30
It is preferably / 70.

As the thermoplastic polyester elastomer, those having Shore D hardness of 80 or less measured at 25 ° C. are preferably used.

Specific examples of the thermoplastic polyester elastomer (C) include polyethylene terephthalate / poly (tetramethylene oxide) glycol block copolymer, polyethylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer, poly Butylene terephthalate / poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / decanedicarboxylate / poly (tetramethylene oxide) glycol Block copolymer, polybutylene terephthalate / poly (propylene oxide / ethylene oxide) glycol block copolymer, polybutylene Terephthalate / isophthalate,
Poly (propylene oxide / ethylene oxide) glycol block copolymer, polybutylene terephthalate /
Decanedicarboxylate / poly (propylene oxide / ethylene oxide) glycol block copolymer, polybutylene terephthalate / poly (ethylene oxide)
Glycol block copolymer, polybutylene terephthalate / polyethylene adipate block copolymer, polybutylene terephthalate / polybutylene adipate block copolymer, polybutylene terephthalate / polybutylene sebacate block copolymer, polybutylene terephthalate / poly-ε- Preferred examples include caprolactone block copolymers.

Among these (C) thermoplastic polyester elastomers, polybutylene terephthalate / poly (tetramethylene oxide) glycol block copolymers, polybutylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymers are particularly preferable. , Polybutylene terephthalate / poly (propylene oxide / ethylene oxide) glycol block copolymer, polybutylene terephthalate / isophthalate
Poly (propylene oxide / ethylene oxide) glycol block copolymer, polybutylene terephthalate
A polybutylene adipate block copolymer and a polybutylene terephthalate / poly-ε-caprolactone block copolymer are preferably used.

The thermoplastic polyester elastomer (C) used in the present invention has a melt flow rate (MFR) at 200 ° C. of 3 to 40, particularly 5 to 15 from the viewpoint of mechanical properties and moldability. It is suitable. MFR
If it exceeds 40, the effect of improving cracks when press-fitting the pin is insufficient, and if MFR is less than 3, workability tends to be poor.

The amount of the polybutylene terephthalate (A) used in the present invention is 50 to 97% by weight, based on the total amount of (A), (B) and (C) optionally added, and is 70 to 70%. 91% by weight is preferred. Compounding amount is 97
If it exceeds 50% by weight, the effect of suppressing anisotropy will be insufficient and 50% by weight
If it is less than 100%, heat resistance and chemical resistance tend to be poor.

The blending amount of the low crystalline thermoplastic polyester resin (B) used in the present invention is 3 to 50 relative to the total of (A), (B) and (C) optionally added.
% By weight, preferably 9 to 30% by weight. The amount is 5
If it exceeds 0% by weight, heat resistance and chemical resistance become poor, and 3
If it is less than wt%, the effect of suppressing anisotropy tends to be insufficient.

The thermoplastic polyester elastomer (C) used in the present invention is optionally blended as described above. The blending amount thereof is 0 to 20% by weight, preferably 1 to 15% by weight, based on the total amount of (A), (B) and (C). If the blending amount exceeds 20% by weight, the rigidity and heat resistance tend to decrease.

Examples of the organic bromine compound (D) in the present invention include brominated polycarbonate, brominated epoxy resin,
Examples thereof include brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene, brominated bisphenol A and the like. Of these, brominated polycarbonates are preferable, and brominated polycarbonate copolymers containing unbrominated starting materials as copolymerization components are also preferably used.

As these polymers, those having a number average molecular weight of 1800 or more are preferable. When the molecular weight is low, mechanical properties are deteriorated, and the appearance of the molded product tends to be poor. Such a polymer can be produced using, for example, brominated bisphenol A or bisphenol A and brominated bisphenol A as raw materials.

Among the organic bromine compounds, the brominated polycarbonate copolymer is most preferable, and the molar ratio of bisphenol A / brominated bisphenol A structure is 9/1 to 1
Those in the range of / 9 can be particularly preferably used.

The amount of these organic bromine compounds added is 1 to 60 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the mixture of (A), (B) and (C). If the amount added is small, the flame retardancy tends to be insufficient, and the amount is not sufficient. If the amount is large, the mechanical properties of the composition tend to deteriorate.

When the antimony compound (E) used in the present invention is used in combination with the organic bromine compound, the flame retardancy can be synergistically improved. Various kinds of antimony compounds can be used. Specific examples include antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium antimonate, antimony phosphate, and the like, and antimony trioxide is particularly preferably used.
Furthermore, the antimony compound is not particularly limited, and those having various shapes and surface treatments can be used.

The addition amount of the antimony compound in the present invention is 0.1 to 30 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the mixture of (A), (B) and (C), and 0. If it is less than 1 part by weight, the flame retardant effect due to the combined use of the antimony compound is not sufficient, and if it exceeds 30 parts by weight, the mechanical properties are impaired, which is not preferable.

It is particularly preferable to add 1 to 1 atom of antimony compound in the antimony compound to 2 to 5 atoms of bromine in the added organic bromine compound (D).

As the fluorine-based resin (F) used in the present invention, a fluorine-substituted polyolefin is usually used, and polytetrafluoroethylene is preferably used. Polytetrafluoroethylene is usually commercially available and is not particularly limited as long as it exhibits anisotropy improving effect on a molded product, but in the case of the present invention, one obtained by an emulsion polymerization method is preferable, and 2 Secondary particle size is 100-1500
Those in the range of μm are particularly preferable.

In general, polytetrafluoroethylene having a large secondary particle size has a large effect of improving anisotropy, but it aggregates during processing and mechanical properties and anisotropy are slightly improved.
An example in which a dispersant is used in combination is shown. However, the addition of the dispersant may remain as a volatile component in the molded product, and it tends to be difficult to obtain stable mechanical properties.

The present invention has a secondary particle diameter of 100 to 1500 μm.
By supplying those in the range of m to a twin-screw extruder having one or more kneading blocks together with components other than the inorganic filler, mechanically dispersing them, and then supplying the inorganic filler from a side feeder. Stable mechanical properties are obtained without using a dispersant together.

The polytetrafluoroethylene used in the present invention is available on the market as Polyflon F-103, F-104, F-201, manufactured by Daikin Industries, Ltd.
F-201L, F-203, F-302, and Teflon 6-J and 6C-J manufactured by Mitsui DuPont Fluorochemicals.

The amount of the fluorine-based resin (F) used in the present invention is 0.01 to 5 parts by weight, preferably 0.1 to 100 parts by weight of the mixture of (A), (B) and (C). If it is less than 0.01 part by weight, the effect of improving the anisotropy is not sufficient, and if it exceeds 5 parts by weight, the fluidity at the time of molding tends to be impaired, which is not preferable.

Examples of the (G) glass filler used in the present invention include glass fibers and glass powders, and it is preferable to use them in combination.

The glass fiber used in the present invention is not particularly limited as long as it is generally used for reinforcing a resin, and for example, long fiber type or short fiber type chopped strand, milled fiber or the like can be selected and used.
Further, the glass fiber may be coated or bundled with a thermoplastic resin such as ethylene / vinyl acetate copolymer or the like, or a thermosetting resin such as an epoxy resin or the like. The types of glass fiber are
Generally, it is not particularly limited as long as it is used for reinforcing the resin, but one having an average fiber diameter of 5 to 50 μm can be preferably used.

The glass powder used in the present invention is called glass foil or glass flake, and is not particularly limited as long as it is generally used for strengthening a resin, and the average particle diameter in the composition is 20 to 200 μm. The following can be preferably used.

The glass powder may be coated or bundled with a thermoplastic resin such as ethylene / vinyl acetate copolymer or the like, or a thermosetting resin such as an epoxy resin or the like.

These glass fillers are usually more effective when they are surface-treated with aminosilane or epoxysilane.

The function of the inorganic filler of the present invention is further improved by using the glass fiber and the glass powder together.
The combined ratio of glass fiber and glass powder is 90 / 10-2
It is 0/80% by weight, preferably 70/30 to 40/60% by weight.

In the present invention, the amount of the inorganic filler added is 5 per 100 parts by weight of the mixture of (A), (B) and (C).
˜150 parts by weight, preferably 10 to 120 parts by weight. When it is less than 5 parts by weight, the effect of improving mechanical properties is not sufficient, and when it exceeds 150 parts by weight, moldability is deteriorated, which is not preferable.

In addition to the above-mentioned essential components, it is also effective to add an olefinic elastomer to improve the pin press-fit strength. The blending amount is (A), (B), (C)
0.1 to 40 parts by weight is preferable to 100 parts by weight of the mixture. As the olefinic elastomer component, (i)
An epoxy group-containing copolymer comprising an olefin and an epoxy group-containing unsaturated monomer, (ii) an ethylene copolymer comprising ethylene and an α-olefin having 3 or more carbon atoms and / or a vinyl monomer, (iii) Examples thereof include hydrogenated or unhydrogenated conjugated dienes and aromatic vinyl block copolymers.

The (i) epoxy group-containing copolymer is
It can be produced by a known method such as a high pressure radical polymerization method, a solution polymerization method or an emulsion polymerization method using an olefin and an epoxy group-containing unsaturated monomer.

As the olefin, ethylene, propylene, butene-1 and the like can be preferably used. Examples of the epoxy group-containing unsaturated monomer include glycidyl ethers such as allyl glycidyl ether and 2-methylallyl glycidyl ether, and glycidyl esters. Specific examples of glycidyl ester include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylic acid, glycidyl itaconate,
And so on. Examples of preferred epoxy group-containing unsaturated monomers include glycidyl methacrylate and glycidyl acrylate. The copolymerization amount of the epoxy group monomer in the epoxy group-containing copolymer is 0.1 to 30% by weight, preferably 1 to 20% by weight. 40 more
Unsaturated monomers copolymerizable with the above-mentioned copolymers if the content is at most% by weight, that is, vinyl ethers, vinyl acetate, vinyl propionate and other vinyl esters, methyl, ethyl, propyl, butyl and other acrylic acid and methacrylic acid. Esters, acrylonitrile, styrene, carbon monoxide and the like may be copolymerized.

Preferred examples of the epoxy group-containing copolymer are ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, ethylene. / Glycidyl acrylate copolymer, ethylene / vinyl acetate / glycidyl acrylate copolymer, ethylene / glycidyl ether copolymer, etc. are mentioned, and among them, ethylene / glycidyl methacrylate copolymer is most preferable.

When the epoxy group-containing copolymer is used in the present invention, ethylene-based copolymer comprising ethylene and α-olefin having 3 or more carbon atoms and / or ethylene, α-olefin having 3 or more carbon atoms and non-conjugated diene are used. When the diene-based copolymer is used in combination, the mechanical properties can be further improved.

Specific examples of these copolymers include ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / pentene-1 copolymer, ethylene / propylene / butene-1 copolymer, ethylene. /propylene/
5-ethylidene-2-norbornene copolymer, ethylene / propylene / 1,4-hexadiene copolymer, ethylene / propylene / dicyclopentanediene copolymer, etc., among which ethylene / propylene copolymer and ethylene / butene -1 copolymer is preferred.

The ethylene-based or diene-based copolymer has a copolymerization ratio (molar ratio) of ethylene and an α-olefin having 3 or more carbon atoms of 40/60 to 99/1, preferably 70/30 to 95. / 5 mol%. The amount of non-conjugated diene in the diene-based copolymer is 0.1-10.
It is mol%, preferably 0.5 to 5 mol%.

The above ethylene-based copolymer or diene-based copolymer is added in an amount of 0.1 to 0.1% by weight of the epoxy group-containing copolymer.
It is preferably in the range of 4 times.

The ethylene copolymer (ii) is an ethylene copolymer obtained by copolymerizing ethylene with an α-olefin having 3 or more carbon atoms and / or a vinyl monomer. 3 carbon atoms in the (ii) ethylene-based copolymer
The above α-olefins are preferably propylene, butene-1, pentene-1, 3-methylpentene-1, octacene-1, etc. and / or vinyl-based monomers such as acryl such as methyl, ethyl, propyl and butyl. Examples of the acid or methacrylic acid ester, acrylonitrile, styrene, and the like. Among them, propylene, butene-
Methyl monoacrylate and ethyl acrylate are more preferred, and these can be used in combination of two or more kinds. Also,
In the unmodified ethylene-based polymer, a non-conjugated diene may be further copolymerized.

When the non-conjugated diene is not contained, the copolymerization ratio of ethylene and α-olefin having 3 or more carbon atoms is usually 4
0/60 to 99/1 (molar ratio), preferably 70/30
˜95 / 5 (molar ratio).

The copolymerization amount of the α-olefin having 3 or more carbon atoms in the ethylene copolymer containing a non-conjugated diene is usually 3 to 80 mol%, preferably 15 to 60 mol%.
The copolymerization amount of the conjugated diene is usually 0.1 to 15 mol%, preferably 0.5 to 10 mol%.

Specific examples of the ethylene-based copolymer include ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / pentene-1 copolymer, ethylene / propylene / butene-1 copolymer, ethylene / propylene/
Dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer And ethylene /
Propylene copolymer, ethylene / butene-1 copolymer,
An ethylene / methyl methacrylate copolymer and an ethylene / ethyl methacrylate copolymer can be preferably used.

Further, a modified ethylene-based copolymer obtained by graft-reacting the following unsaturated carboxylic acid and its derivative on the ethylene-based copolymer may be used.

The unsaturated carboxylic acid is preferably acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, butenedicarboxylic acid, tetrahydrophthalic acid and the like. In addition, examples of their derivatives include alkyl esters, glycidyl esters, acid anhydrides or imides, and among these, glycidyl esters, acid anhydrides and imides are preferable.

Preferred specific examples of unsaturated carboxylic acids or their derivatives are maleic acid, fumaric acid, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylic acid, glycidyl itaconate, glycidyl citraconic acid, diglycidyl butenedicarboxylic acid, butenedicarboxylic acid. Monoglycidyl, diglycidyl tetrahydrophthalate, maleic anhydride, itaconic anhydride, citraconic anhydride, maleic acid imide, itaconic acid imide, citraconic acid imide and the like, especially glycidyl methacrylate,
Glycidyl tetrahydrophthalate, maleic anhydride, itaconic anhydride, maleic imide and the like can be preferably used. You may use these unsaturated monomers in combination of 2 or more types.

The above-mentioned (iii) olefin block copolymer is an olefin block copolymer of a conjugated diene and aromatic vinyl.

The conjugated dienes are 1,3-butadiene, isoprene (2-methyl-1,3-butadiene) and 2,3-
Dimethyl-1,3-butadiene, 1,3-butadiene, 1,3-pentadiene and the like are one kind or two or more kinds, and 1,3-butadiene and isoprene can be preferably used. Aromatic vinyl hydrocarbons include styrene and α-
One or more of methyl styrene, o-methyl styrene, p-methyl styrene, 1,3-dimethyl styrene, vinyl naphthalene and the like, and styrene and α-methyl styrene can be preferably used.

The hydrogenated olefin block copolymer means that at least 80% of the unsaturated content of the unhydrogenated olefin block copolymer is reduced by hydrogenation, and the aromatic double bond is The rate of reduction by hydrogenation is preferably 10% or less.

Preferred specific examples of the hydrogenated or unhydrogenated olefin block copolymer are hydrogenated or unhydrogenated styrene / butadiene / styrene triblock copolymer and hydrogenated or It is an unhydrogenated styrene / isoprene / styrene triblock copolymer, and among them, hydrogenated styrene / butadiene / styrene triblock copolymer is preferably used.

A modified hydrogenated or unhydrogenated olefinic block copolymer obtained by graft-reacting the above-mentioned unsaturated carboxylic acid or its derivative on the hydrogenated or unhydrogenated olefinic block copolymer may be used.

In contrast to the present invention, fillers (carbon fiber, ceramic fiber,
Ceramic beads, asbestos, wollastonite, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, fine silicic acid, feldspar powder,
Potassium titanate, shirasu balloon, calcium carbonate,
Magnesium carbonate, barium sulphate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dawsonite and clay etc.), antioxidant, UV absorber, heat stabilizer, nucleating agent, lubricant, release agent It may further contain at least one of a shaping agent, a colorant including a dye and a pigment, and a nucleating agent.

A small amount of another thermoplastic resin (for example, polyethylene, acrylic resin, polyamide, 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) (Combined) and the like can also be contained.

The method for producing the composition of the present invention is not particularly limited, but is preferably polybutylene terephthalate, a low crystalline thermoplastic polyester resin, a thermoplastic polyester elastomer, or a specific organic bromine above the melting point of polybutylene terephthalate. The compound, antimony compound, polytetrafluoroethylene and, if necessary, other additives are supplied from a hopper of a twin-screw extruder having one or more zones of kneading blocks, and an inorganic filler is supplied to the extruder from a side feeder. A method of uniformly melt-kneading is preferably used.

The composition obtained is generally known in injection molding,
It can be formed by any method such as extrusion.

Molded articles obtained from the composition of the present invention have excellent mechanical properties, flame retardancy and anisotropy, and have high pin press-fit strength. It can be used for various purposes such as precision machine parts such as machine parts.

[0071]

The present invention will be described in more detail with reference to the following examples.
All copies in the examples are on a weight basis.

The details of the low crystalline thermoplastic polyester resin, thermoplastic polyester elastomer, organic bromine compound, antimony compound and polytetrafluoroethylene used in the examples are shown in Table 1.

[0073]

[Table 1]

Examples 1 to 9 and Comparative Examples 1 to 7 Polybutylene terephthalate having an intrinsic viscosity of 0.92, Table 1
Low crystallinity thermoplastic polyester resin, thermoplastic polyester elastomer, organic bromine compound, antimony compound and polytetrafluoroethylene as shown in Table 2 were compounded in the ratio shown in Table 2, and a kneading block was incorporated in 2 zones in front of the side feeder. Temperature set at 250 ℃ 45
The mixture was supplied to a mmφ twin-screw extruder, and the inorganic filler was supplied from a side feeder of the extruder to melt-knead into pellets.

Processing temperature of 250 using the obtained pellets
C., mold temperature 80.degree. C., molding cycle (injection time / cooling time / intermediate time) 8/10/5 seconds, and 1/8 "t tensile test pieces were molded and subjected to a tensile test according to ASTM D638.

Subsequently, a UL combustion test piece (1/32 "× 1/2" × 5 ") was molded under the same molding conditions, and a vertical combustion test was performed according to the UL94 standard.

Continuing, 1.5 mm × 2.8 mm pitch
1.6 mm using a test piece obtained by molding a pin press-fitting test piece having a thickness of 3 mm with ten 1.5 mm square holes
A brass bar of 1.6 mm was inserted into each square hole, and the number of cracked square holes was examined.

Subsequently, the thickness is 1 mm, the length is 80 mm and the width is 80.
A mm square plate was molded with a film gate mold, and vertical and horizontal molding shrinkage rates were measured with a universal projector.

Finally, the thickness is 2 mm, the length is 100 mm and the width is 5 mm.
A box having a size of 0 mm and a depth of 15 mm was formed, and the releasing force was measured using a pressure sensor.

The results are shown in Tables 2 and 3.

[0081]

[Table 2]

[0082]

[Table 3]

From the results shown in Tables 2 and 3, the molded articles of the present invention are
Compared with the comparative example, the flame retardancy and mechanical properties are excellent, and the anisotropy is small and the pin press-fit strength is remarkably improved, which is excellent.

It is obvious that it is suitable for electrical / electronic connector applications and molded articles having dimensional accuracy.

[0085]

The molded product obtained from the molding resin of the present invention has excellent mechanical properties, heat resistance and moldability.
Since the molded product has excellent anisotropy and pin press-fitting properties, it is useful for applications in the fields of electrical / electronic / electrical components and fields with strict dimensional accuracy.

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Claims (8)

[Claims] 1. (A) Polybutylene terephthalate 50-97
% By Weight (B) Low Crystalline Thermoplastic Polyester Resin 3-5
0% by weight (C) thermoplastic polyester elastomer 0-20
%, 100 parts by weight of the mixture of (A), (B) and (C) above, 1 to 60 parts by weight of (D) organic bromine compound (E) 0.1 to 30 parts by weight of (F) fluorine-based compound 0.01 to 5 parts by weight of resin and 5 to 15 (G) glass filler
A polyester resin composition containing 0 part by weight. 2. The low crystalline thermoplastic polyester resin (B) comprises 20 mol% or more of a structure derived from ethylene glycol in a structural unit derived from a diol and 20 mol% of a structure derived from terephthalic acid in a structural unit derived from a dicarboxylic acid. The polyester composition according to claim 1, which is contained. 3. The organic bromine compound (D) has a number average molecular weight of 18
The polyester resin composition according to claim 1 or 2, which is a brominated polycarbonate of 00 or more. 4. The fluorine-based resin (F) has a secondary particle diameter of 100.
The polyester resin composition according to any one of claims 1 to 3, wherein the polyester resin composition is polytetrafluoroethylene having a size of -1500 m. 5. The polyester resin composition according to claim 1, which contains glass fiber and glass powder as the glass filler (G). 6. A glass powder having a particle size of 20 to 2 in the composition.
The polyester resin composition according to claim 5, wherein the polyester resin composition is in a range of 00 μm. 7. The low crystalline thermoplastic polyester resin (B) is a poly (cyclohexanedimethylene / ethylene) having a molar ratio of a structure derived from cyclohexanedimethanol to a structure derived from ethylene glycol of 50/50 to 80/20. It is terephthalate, The polyester resin composition in any one of Claims 1-6 characterized by the above-mentioned. 8. A polyester molded product obtained by molding the polyester resin composition according to claim 1.