JP2000212424A - Polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition excellent in rigidity, impact resistance, particularly appearance of its molding by improving insufficient points of a conventional polyester. SOLUTION: A polyester resin composition comprises to (A) 100 pts.wt. of a thermoplastic polyester; (B) 0.1-40 pts.wt. of a phyllosilicate wherein an exchangeable cation existing between layers is exchanged with an organic onium ion; and (C) 0.001-5 pts.wt. of at least one of a montanic acid compound and a lower molecular weight polyolefin. The composition is (A) a polybutylene terephthalate (co)polymer of a thermoplastic polyester wherein the terminal group of COOH is preferably not more than 50 eq/t and the intrinsic viscosity is 0.36-1.60.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyester molded article, which is excellent in rigidity and impact resistance, especially excellent in surface appearance, and is useful for various parts which require rigidity and impact resistance of a thin portion.

[0002]

2. Description of the Related Art Thermoplastic polyester resins have been recently developed for applications such as electric / electronic device parts, automobile parts, and machine / mechanical parts because of their excellent mechanical properties, heat resistance and chemical resistance.

However, when applied to parts having a thin portion and used under conditions where excessive external force or heat is applied, rigidity and impact resistance are insufficient, and impact modifiers and glass fibers and the like are not used. Fillers are being added. When an impact modifier is used, the impact resistance is improved to some extent, but there is a drawback that the rigidity and heat resistance are reduced. Further, the addition of a filler such as glass fiber has the disadvantage that the rigidity is improved but the toughness, especially the tensile elongation, is greatly reduced. Further, when a large amount of a filler or the like is added, there is a disadvantage that the surface appearance is deteriorated.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyester resin molded article which improves the insufficient properties of the conventional polyester resin and whose molded article is excellent in rigidity and impact resistance, especially in surface appearance. Aim.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have reached the present invention.

That is, the present invention relates to (A) 100 to 100 parts by weight of a thermoplastic polyester, and (B) 0.1 to 40 parts by weight of a layered silicate in which exchangeable cations existing between layers are exchanged with organic onium ions. And (C) at least one of a montanic acid compound and a low molecular weight polyolefin in an amount of 0.001 to 5 parts by weight.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polyester (A) used in the present invention is a non-liquid crystal obtained by a polycondensation reaction containing dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as main components. Or a liquid crystalline polymer or copolymer.

The above dicarboxylic acids include terephthalic acid,
Isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 5-
Alicyclics such as aromatic dicarboxylic acids such as sodium sulfoisophthalic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and dodecandioic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid And dicarboxylic acids and their ester-forming derivatives.

The diol component has 2 to 2 carbon atoms.
An aliphatic glycol of 0, ie ethylene glycol,
Propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,
6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, etc., or a long-chain glycol having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-
Examples include propylene glycol, polytetramethylene glycol, and the like, and ester-forming derivatives thereof. Examples of these polymers or copolymers,
Polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polypropylene terephthalate,
Polypropylene (terephthalate / isophthalate),
Polyethylene terephthalate, polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), bisphenol A (terephthalate / isophthalate), polybutylene naphthalate, polybutylene (terephthalate / naphthalate), polypropylene naphthalate, polyethylene naphthalate, poly Examples thereof include cyclohexane dimethylene terephthalate, polycyclohexane dimethylene (terephthalate / isophthalate), poly (cyclohexane dimethylene / ethylene) terephthalate, and poly (cyclohexane dimethylene / ethylene) (terephthalate / isophthalate).

Further, there may be mentioned a copolymer obtained by further copolymerizing a polyether component or an aliphatic polyester component. For example, polybutylene terephthalate / poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer,
Polybutylene terephthalate / poly (propylene oxide / ethylene oxide) glycol block copolymer,
Examples thereof include polybutylene terephthalate / isophthalate / poly (propylene oxide / ethylene oxide) glycol block copolymer, polybutylene terephthalate / polybutylene adipate block copolymer, and polybutylene terephthalate / poly-ε-caprolactone block copolymer.

The liquid crystalline polyester forms an anisotropic molten phase composed of structural units selected from aromatic oxycarbonyl units, aromatic dioxy units, aromatic dicarbonyl units, ethylenedioxy units and the like. Polyester can be mentioned.

Examples of the aromatic oxycarbonyl unit include, for example, p-hydroxybenzoic acid, 6-hydroxy-2-
Examples of the structural unit generated from naphthoic acid and the aromatic dioxy unit include, for example, structural units generated from 4,4′-dihydroxybiphenyl, hydroquinone and t-butylhydroquinone, and examples of the aromatic dicarbonyl unit include terephthalic acid , Isophthalic acid, 2,6
Examples of the structural unit and aromatic iminooxy unit generated from -naphthalenedicarboxylic acid include a structural unit generated from 4-aminophenol. Specific examples include liquid crystalline polyesters such as copolymerized polyesters such as p-oxybenzoic acid / polyethylene terephthalate and p-oxybenzoic acid / 6-oxy-2-naphthoic acid.

Among these, polybutylene terephthalate, polypropylene terephthalate, polyethylene terephthalate, polycyclohexane dimethylene terephthalate, poly (cyclohexane dimethylene / ethylene) terephthalate, polybutylene naphthalate, polybutylene terephthalate poly (tetramethylene oxide) glycol And polybutylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol are preferably used, and particularly, polybutylene terephthalate, polybutylene terephthalate / poly (tetramethylene oxide) glycol Polyetherester copolymer and polybutylene terephthalate / isophthalate poly (te) La methylene oxide) glycol polyether ester copolymer of polybutylene terephthalate-based, such as (co) polymer is preferable, polybutylene terephthalate are preferred. These may be used alone or as a mixture of two or more.

The polybutylene terephthalate (co) polymer has an intrinsic viscosity of 0.36 to 1.60, particularly 0.52 to 1.25 when the O-chlorophenol solution is measured at 25 ° C. Are preferred. Furthermore, the polybutylene terephthalate (co) polymer is m-
Those having a COOH terminal group content of 0 to 50 eq / t (terminal group amount per ton of polymer) obtained by potentiometric titration of the cresol solution with an alkali solution can be preferably used from the viewpoint of durability.

In the present invention, the term (B) a layered silicate in which exchangeable cations present between layers have been exchanged with organic onium ions refers to (B-1) a layered silicate having exchangeable cations between layers. This is an inclusion compound in which a sex cation is replaced by (B-2) an organic onium ion.

(B-1) The layered silicate having exchangeable cations between layers has a width of 0.05 to 0.5 μm and a thickness of 6 to 1 μm.
It has a structure in which 5-angstrom plate-like materials are stacked, and has exchangeable cations between layers of the plate-like materials. The cation exchange capacity is 0.2 to 3 meq / g, and preferably the cation exchange capacity is 0.8 to 1.5 m
eq / g.

Specific examples of the layered silicate include various clay minerals such as smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and sauconite, vermiculite, halloysite, kanemite, keniyaite, zirconium phosphate, and titanium phosphate. And swelling mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica, etc., and may be natural or synthesized. . Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Na-type tetrasilicon fluorine mica and Li-type fluorine teniolite are preferred.

(B-2) Examples of the organic onium ion include an ammonium ion, a phosphonium ion, and a sulfonium ion. Among these, ammonium ions and phosphonium ions are preferable, and ammonium ions are particularly preferably used. The ammonium ion may be any of primary ammonium, secondary ammonium, tertiary ammonium and quaternary ammonium.

The primary ammonium ion includes decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like.

The secondary ammonium ion includes methyl dodecyl ammonium, methyl octadecyl ammonium and the like.

Examples of the tertiary ammonium ion include dimethyldodecylammonium and dimethyloctadecylammonium.

Examples of the quaternary ammonium ion include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, and benzalkonium; trimethyloctylammonium; Alkyl trimethyl ammonium ions such as trimethyl octadecyl ammonium, dimethyl dialkyl ammonium ions such as dimethyl dioctylammonium, dimethyl didodecyl ammonium, dimethyl dioctadecyl ammonium Trialkyl methyl ammonium ions such as trioctyl methyl ammonium and tridodecyl methyl ammonium Such as benzethonium ion having two benzene rings.

In addition, aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6
-Aminocaproic acid, 11-aminoundecanoic acid, 12
-Ammonium ions derived from aminododecanoic acid and the like.

Among these ammonium ions, preferred compounds include trioctylmethylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, benzalkonium and the like. These ammonium ions are generally available as a mixture, and the above compound names are the names of representative compounds containing small amounts of analogs. These may be used alone or as a mixture of two or more.

The (B) layered silicate in which exchangeable cations present between the layers are exchanged with organic onium ions for use in the present invention is (B-1) a layered silicate having an exchangeable cation between the layers. B-2) It can be produced by reacting an organic onium ion by a known method. Specific examples include a method based on an ion exchange reaction in a polar solvent such as water, methanol and ethanol, and a method based on directly reacting a liquid or molten ammonium salt with a layered silicate.

In the present invention, the amount of the organic onium ion with respect to the layered silicate is determined based on the dispersibility of the layered silicate, the thermal stability during melting, the gas during molding, and the suppression of generation of odor. Typically 0.4 for cation exchange capacity
The range is from 2.0 to 2.0 equivalents, but preferably from 0.8 to 1.2 equivalents.

Further, it is preferable to use these layered silicates by pre-treating them with a coupling agent having a reactive functional group in addition to the above-mentioned organic onium salt in order to obtain more excellent mechanical strength. Examples of the coupling agent having such a reactive functional group include an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound.

Particularly preferred are organic silane compounds, examples of which include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxy). Epoxy group-containing alkoxysilane compounds such as cyclohexyl) ethyltrimethoxysilane, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane,
ureido group-containing alkoxysilane compounds such as γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ- Isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyl Isocyanato group-containing alkoxysilane compounds such as trichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ Amino group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, .gamma.-hydroxypropyl trimethoxysilane, .gamma.
Hydroxyl-containing alkoxysilane compounds such as hydroxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, N
And carbon-carbon unsaturated group-containing alkoxysilane compounds such as -β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride.
In particular, a carbon-carbon unsaturated group-containing alkoxysilane compound is preferably used. The treatment of the layered silicate with these silane coupling agents can be carried out by adsorbing the silane coupling agent to the layered silicate in a polar solvent such as water, methanol, or ethanol, or a mixed solvent thereof, or by using a Henschel mixer or the like. A method in which a layered silicate is added to a high-speed stirring mixer, and the mixture is dropped and adsorbed in the form of an aqueous solution containing a silane coupling agent or an organic solvent while stirring, and the silane coupling agent is directly added to the layered silicate. Then, any method of mixing and adsorbing in a mortar or the like may be used. When the layered silicate is treated with a silane coupling agent, it is preferable to simultaneously mix water, acidic water, alkaline water and the like in order to promote the hydrolysis of the alkoxy group of the silane coupling agent. Further, in order to enhance the reaction efficiency of the silane coupling agent, water such as methanol or ethanol and an organic solvent that dissolves both the silane coupling agent may be mixed in addition to water. The reaction can be further promoted by heat-treating the layered silicate treated with such a silane coupling agent. When the layered silicate and the thermoplastic polyester are melt-kneaded without using a layered silicate with a coupling agent in advance, a so-called integral blending method of adding these coupling agents may be used.

In the present invention, (B) the amount of the layered silicate in which the exchangeable cation existing between the layers is exchanged with the organic onium ion is 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, particularly preferably. The range is 2 to 10 parts by weight.
If the amount is too small, the improving effect is small, and if it is too large, the toughness may decrease.

In the present invention, it is preferable to mix at least one of (C) a montanic acid compound and a low molecular weight polyolefin.

The (C) montanic acid compound used in the present invention is a compound obtained by oxidizing, esterifying or metal-saltning a mixture containing an aliphatic monocarboxylic acid having 26 to 32 carbon atoms as a main component. , Montanic acid and 0.1
~ 1 equivalent of a metal oxide or hydroxide reacted with montanic acid and partially esterified with 0.1-1 equivalent of a dihydric alcohol having 2-4 carbon atoms in the alkylene group Or montanic acid in the alkylene group
Examples thereof include those partially esterified with 0.1 to 1 equivalent of a dihydric alcohol having 4 to 4 carbon atoms, and then neutralized with a metal oxide or hydroxide. The diol used here includes ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and the like. ~ 3 metals, such as sodium,
Beryllium, magnesium, calcium, lithium, aluminum and the like can be mentioned.

Specifically, montanic acid, calcium montanate, sodium montanate, montanic acid / ethylene glycol ester, montanic acid / glycerin ester, montanic acid / butylene glycol ester, montanic acid / butylene glycol ester calcium salt, montanic acid Acid / butylene glycol ester sodium salt;

The low-molecular-weight polyolefin (C) used in the present invention includes low-molecular-weight polyethylene, low-molecular-weight polypropylene, polyethylene oxide, and modified polyethylene, and has a viscosity average molecular weight of 500 to 5,000.
Those having an acid value in the range of 0 to 100 mgKOH / g can be preferably used. The oxidized polyethylene referred to here is obtained by heating and melting under appropriate conditions,
Or 2 while the oxidized polyethylene wax is melting.
The reaction is performed by adding a hydroxide of a valent metal. Preferred specific examples of the divalent metal salt include a magnesium salt, a calcium salt, a strontium salt and a barium salt. As the modified polyethylene here,
A compound obtained by grafting a compound having a carboxyl group and a carboxylic anhydride group.

In the present invention, these (C) montanic acid compounds and low molecular weight polyolefins may be used alone or in combination.
More than one species can be used in combination. (C) The content of the montanic acid compound and the low molecular weight polyolefin is as follows:
(A) 0.1 part by weight of thermoplastic polyester.
001 to 5 parts by weight are preferred.

In the present invention, an impact modifier may be further added. The impact modifier is not particularly limited as long as it can improve the impact resistance of the molded article. For example, at least one selected from the following impact modifiers can be used.

Specific examples include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer, ethylene-propylene Octene-1 copolymer, ethylene-acrylic acid copolymer and its alkali metal salt (so-called ionomer), ethylene-glycidyl acrylate copolymer,
Ethylene-alkyl acrylate copolymer (for example, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer), diene rubber (for example, polybutadiene, polyisoprene, polychloroprene)
And copolymers of diene and vinyl monomers (for example, styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene random copolymer, styrene- Isoprene block copolymer, styrene-isoprene-styrene block copolymer, polybutadiene grafted with styrene,
Butadiene-acrylonitrile copolymer), polyisobutylene and a copolymer of isobutylene and butadiene or isoprene, natural rubber, thiochol rubber, polysulfide rubber, acrylic rubber, polyurethane rubber, polyether rubber, epichlorohydrin rubber, polyester elastomer, Examples include polyamide elastomers.

Further, those having various degrees of cross-linking, those having a microstructure in various ratios such as cis structure and trans structure, those having a vinyl group or the like, or various average particle sizes (in the resin composition). And the like are also used.

Various (co) polymers such as random copolymers, block copolymers, and graft copolymers are all used as the impact modifier of the present invention.

Further, in preparing these (co) polymers, copolymerization with monomers such as other olefins, dienes, aromatic vinyl compounds, acrylic acid, acrylic acid esters and methacrylic acid esters is also required. It is possible.

Any of these copolymerization methods such as random copolymerization, block copolymerization, and graft polymerization can be used. Specific examples of these monomers include ethylene, propylene, styrene, chlorostyrene, α-methylstyrene, butadiene, isoprene, chlorobutadiene, butene-1, isobutylene, methyl acrylate,
Examples include acrylic acid, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, acrylonitrile, maleic anhydride, glycidyl methacrylate, dicyclopentadiene, and ethylidene norbornene.

Furthermore, various modified products of these (co) polymers can also be mentioned. For example, hydroxy or carboxy terminal modified polybutadiene, partially or completely hydrogenated styrene-butadiene, styrene-butadiene-styrene, styrene-isoprene or styrene-isoprene-styrene block copolymer, carboxy group, amino group, imino Group, epoxy group, amide group, vinyl group, isocyanate group and hydroxyl group
An impact modifier modified with one or two or more compounds selected from compounds containing a compound or an acid anhydride, a carboxylic acid ester and an oxazoline ring, for example, acrylic acid,
Ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene copolymer, styrene-butadiene copolymer (AB or AB) modified with hymic anhydride, glycidyl methacrylate, or maleic anhydride. B-A 'block, random, and graft copolymer) and its hydrogenated copolymer, styrene-isoprene copolymer (A-B or A-B-A' block, random, and graft copolymer) And hydrogenated copolymers thereof. For these modification methods, known techniques such as graft copolymerization and random copolymerization are used. One or two or more of these impact modifiers may be used.

In the diene rubber and the copolymer of the diene and the vinyl compound, those having various types of double bond microstructures (vinyl group, cis-1,4 bond, trans-1,4 bond) can be used in the present invention. Used as impact modifier.

Preferred impact modifiers include a copolymer of 40 to 100% by weight of butadiene and 60 to 0% by weight of styrene, 35 to 82% by weight of butadiene and 35 to 80% of acrylonitrile.
18% by weight of a copolymer, styrene-butadiene, and styrene-butadiene-styrene block copolymer (including all linear block copolymers, radial block copolymers, etc.), and hydrogenated products thereof, styrene -Isoprene, styrene-isoprene-styrene block copolymers and hydrogenated products thereof, styrene-grafted polybutadiene (polybutadiene or butadiene-styrene copolymer latex added with styrene and emulsion-polymerized with a radical initiator) ,
Ethylene-ethyl acrylate copolymer, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene-1 copolymer, ethylene-
Hexene-1 copolymer, ethylene-octene-1 copolymer, and those modified with maleic anhydride, glycidyl methacrylate, or styrene are available. At the time of modification, a radical generator such as benzoyl peroxide or t-butyl hydroperoxide can be added.

The addition amount of the impact modifier used in the present invention is 1 to 100 parts by weight of the thermoplastic polyester (A).
It is preferably from 50 to 50 parts by weight, more preferably from 3 to 40 parts by weight.

In the present invention, (A) an organic compound having at least one functional group reactive with the thermoplastic polyester in the molecule may be added. It is an organic compound having at least one functional group in the molecule that can chemically react with the terminal group of the thermoplastic polyester. Examples of the functional group include a carboxyl group and a terminal group of the thermoplastic polyester. There is no particular limitation as long as it is reactive with a hydroxyl group, but preferred examples are a carboxylic acid anhydride group and
Examples include an epoxy group, an isocyanate group, a carbodiimide group, and an oxazoline group.

Preferred compounds having one or more functional groups in the molecule include olefin compounds having carboxylic anhydride groups in the molecule, polymers of these olefin compounds, monoepoxy compounds, diepoxy compounds, and the like. Polyepoxy compound, isocyanate compound, diisocyanate compound, carbodiimide compound, polycarbodiimide compound, oxazoline compound,
Bisoxazoline compounds and the like can be mentioned.

Among these compounds, preferred compounds include olefin compounds having a carboxylic anhydride group in the molecule or polymers of these olefin compounds. Specific examples thereof include maleic anhydride, itaconic anhydride,
Examples include glutaconic anhydride, citraconic anhydride, aconitic anhydride, and polymers of these substituted olefin compounds. In the olefin compound polymer, olefins other than the olefin compound having a carboxylic anhydride group in the molecule, such as styrene, isobutylene, methacrylic acid ester, and acrylic acid ester, are copolymerized within a range that does not impair the effects of the present invention. Although it does not matter, it is preferable that the polymer is substantially composed of a polymer of an olefin compound having a carboxylic anhydride group in the molecule. The polymerization degree of the olefin compound polymer is preferably from 2 to 100,
0 is more preferable, and 2 to 20 is most preferable. Among them, maleic anhydride and polymaleic anhydride are most preferably used. As polymaleic anhydride,
For example, J. Macromol. Sci.-Revs. Macromol. Chem., C13
(2), 235 (1975) and the like can be used.

The olefin compound having a carboxylic acid anhydride group in the molecule or a polymer of these olefin compounds used here may have an anhydride structure when substantially melt-kneaded with the thermoplastic polyester. The olefin compound or the polymer of the olefin compound is hydrolyzed and subjected to melt-kneading in the form of a carboxylic acid or an aqueous solution thereof, and subjected to a dehydration reaction by heating during the melt-kneading,
It may be melt-kneaded with the thermoplastic polyester substantially in the form of an acid anhydride.

Another preferred compound is an epoxy compound. Specific examples include monoepoxy compounds such as allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, glycidyl benzoate, glycidyl methacrylate, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl. Diglycidyl compounds such as ether, polypropylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol A type epoxy resin, diglycidyl phthalate ester, diglycidyl ester of cyclohexanedicarboxylic acid, glycidyl ether ester of oxybenzoate, etc., glycerol polyglycidyl ether, Trimethylolpropane diglycidyl ether, sorby Lumpur diglycidyl ether, and the like polyepoxy compounds such as glycidyl methacrylate / ethylene copolymer.

Among them, polyethylene glycol diglycidyl ether, bisphenol A type epoxy resin, glycidyl oxybenzoate and the like are preferable. These may be used alone or in combination of two or more.

The amount of the organic compound having at least one functional group reactive with the thermoplastic polyester used in the present invention in the molecule depends on the effect of improving toughness and moldability.
(A) 0.1 part by weight of thermoplastic polyester.
The amount is preferably from 0.05 to 10 parts by weight, more preferably from 0.1 to 5 parts by weight, further preferably from 0.1 to 5 parts by weight.
３3 parts by weight.

The composition of the present invention contains a small amount of another thermoplastic resin (for example, acrylic resin, fluororesin, polyphenylene sulfide, polyether ether ketone, polyacetal, polysulfone, polyphenylene oxide, etc.) as long as the object of the present invention is not impaired. And a thermosetting resin (for example, phenol resin, melamine resin, polyester resin, silicone resin, epoxy resin, etc.).

The composition of the present invention can be used by adding a small amount of another inorganic filler within a range not to impair the object of the present invention. The inorganic filler as used herein means a fibrous, particulate or flake-like filler, such as glass fiber, carbon fiber, mineral fiber, glass beads, glass flake, diatomaceous earth, mica, graphite, metal flake, and cellulite. Site, zeolite, dolomite, finely divided silica, feldspar powder, potassium titanate, shirasu balloon, magnesium hydroxide, aluminum hydroxide, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide,
Magnesium oxide, zirconium oxide, aluminum silicate, silicon oxide, aluminum oxide, iron oxide, barium titanate, calcium fluoride, boron nitride, silicon nitride, metal powder, novacurite, dawsonite, clay and carbon black. .

The resin composition of the present invention may contain a dye, a pigment, a plasticizer, a heat stabilizer, an ultraviolet absorber, a foaming agent, a flame retardant, and the like according to the application.

The method for producing the composition of the present invention is not particularly limited. For example, a thermoplastic polyester resin, a layered silicate in which exchangeable cations existing between layers have been exchanged with organic onium ions, and if necessary, A method is preferably used in which, after other additives are previously blended, the mixture is supplied to a hopper of a twin-screw extruder having one or more zones of a kneading block at a temperature equal to or higher than the melting point of the thermoplastic polyester resin and uniformly melt-kneaded. It is also preferable to provide a vent for the purpose of removing water and low-molecular-weight volatile components generated during melt-kneading.

The obtained polyester resin composition can be molded by any known method such as injection molding and extrusion molding.

[0057]

The present invention will be described in more detail with reference to the following examples.

Reference Example 1 (B-1) Na-type montmorillonite (Kunimine Industries: Knipia F,
100 g of a cation exchange capacity (120 meq / 100 g) was stirred and dispersed in 10 liters of warm water, and 30.2 g of 12-aminododecanoic acid hydrochloride (equivalent to the cation exchange capacity) was added.
Was dissolved in 2 L of warm water and stirred for 1 hour. The resulting precipitate was separated by filtration and washed with warm water. This washing and filtration were repeated three times, and the obtained solid was vacuum-dried at 80 ° C. to obtain a dried organic layered silicate.

Reference Example 2 (B-2) Na-type montmorillonite (Kunimine Industries: Knipia F,
100 g of a cation exchange capacity (120 meq / 100 g) was stirred and dispersed in 10 liters of warm water, and 2 L of warm water in which 50.5 g (equivalent to the cation exchange capacity) of benzyldimethyloctadecyl ammonium chloride was added, and added for 1 hour. Stirred. Then, in the same manner as in Reference Example 1,
Drying yielded benzyldimethyloctadecyl ammonium montmorillonite.

Reference Example 3 (B-3) 100 g of Na type synthetic mica (COPE CHEMICAL: ME-100, cation exchange capacity 80 meq / 100 g) was added to warm water 1
The mixture was stirred and dispersed in 0 liter, and 2 L of warm water in which 47 g (equivalent to the cation exchange capacity) of dimethyldioctadecyl ammonium chloride was dissolved, and the mixture was stirred for 1 hour. Thereafter, it was recovered, washed and dried in the same manner as in Reference Example 1 to obtain an organically modified layered silicate.

Evaluation Items and Measurement Methods Tensile test: Evaluated in accordance with ASTM D638 using an ASTM No. 1 dumbbell test piece having a thickness of 1 mm. Bending test: Evaluated according to ASTM D790 using a bar-shaped test piece of イ ン チ inch (about 12.7 mm) × 5 inches (about 127 mm) × 1/4 inch (about 6.35 mm). Impact test: An Izod impact test piece having a thickness of 1/8 inch (about 3.18 mm) was evaluated according to ASTM D256. Surface characteristics: The gloss was measured by using an ASTM No. 1 dumbbell test piece having a thickness of 1 mm, and the degree of reflection of the luminous body was visually observed.

Examples 1 to 10 and Comparative Examples 1 to 6 Polybutylene terephthalate (hereinafter referred to as PBT) having an intrinsic viscosity of 1.2 and a COOH terminal group of 35 eq / t, an organic compound obtained in the reference example shown in Table 1. After the layered silicate and other additives shown in Table 1 were blended and pre-blended by a tumbler mixer, the cylinder temperature was set to 250 ° C.
Melt and kneaded with EX-30 twin screw extruder (Nippon Steel Works)
A resin composition was obtained.

After the resulting composition was pelletized, 11
It was dried with hot air at 0 ° C. for 8 hours, and injection-molded at a cylinder temperature of 270 ° C. and a mold temperature of 40 ° C. to obtain test pieces.

[0064]

[Table 1]

From the results of the examples and comparative examples in Table 2, it is clear that molded articles having better rigidity and impact resistance and excellent surface appearance can be obtained as compared with the comparative examples.

[0066]

The molded article obtained from the polyester resin composition of the present invention is excellent in rigidity and impact resistance, and particularly excellent in surface appearance, and thus is useful for various parts requiring rigidity and impact resistance in thin portions.

Claims (2)

[Claims] (1) 0.1 to 40 parts by weight of a layered silicate obtained by exchanging an exchangeable cation existing between layers with an organic onium ion for (A) 100 parts by weight of a thermoplastic polyester; ) A polyester resin composition comprising 0.001 to 5 parts by weight of at least one of a montanic acid compound and a low molecular weight polyolefin. 2. The polyester according to claim 1, wherein (A) the thermoplastic polyester is a polybutylene terephthalate (co) polymer, the COOH terminal group is 50 eq / t or less, and the intrinsic viscosity is 0.36 to 1.60. Resin composition.