JP2000109655A - Polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a low-density resin compsn. excellent in stiffness, toughness, and impact resistance by melt mixing and kneading a thermoplastic polyester with a nonfibrous inorg. filler and an org. compd. having a functional group reactive with the thermoplastic polyester. SOLUTION: This compsn. is prepd. by melt mixing and kneading 100 pts.wt. thermoplastic polyester, pref. a polyalkylene terephthalate, with a nonfibrous inorg. filler, pref. a silicate compd., pref. in an amt. of 0.1-40 wt.% (in terms of inorg. ash in the compsn.) and an org. compd., pref. in an amt. of 0.05-10 pts.wt., having at least one functional group reactive with the thermoplastic polyester. Pref., the org. compd. having at least one functional group reactive with the thermoplastic polyester is an olefin compd. (polymer) having a carboxylic anhydride group. Pref., the nonfibrous inorg. filler is a layered silicate having its interlayer exchangeable cations exchanged by org. onium ions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for improving the mechanical properties of a thermoplastic polyester, a non-fibrous inorganic filler and an organic compound having at least one functional group reactive with the thermoplastic polyester in a molecule. And a polyester resin composition.

[0002]

2. Description of the Related Art Conventionally, in order to improve the mechanical properties of a thermoplastic polyester resin, it has been practiced to incorporate a glass fiber or an inorganic filler into the resin. However, simply melting and kneading these inorganic fillers causes problems such as poor dispersion of the inorganic filler in the resin and poor interfacial adhesion, low impact resistance, and poor surface appearance. Therefore, in order to increase the affinity or bonding strength between the thermoplastic resin and the inorganic filler, there is a method of improving the dispersion of the filler in the resin by applying a coupling treatment such as an organic silane to the surface of the inorganic filler. However, it is only enough to improve the conformability between the resin and the inorganic filler, and has not been sufficiently improved. In addition, in order to obtain sufficient strength, it is necessary to increase the filling amount of a normal filler, and there is a problem that the obtained polyester resin composition has a high specific gravity.

[0003] On the other hand, clay minerals, which are a kind of inorganic layered compounds, have been tried for a long time as fillers. However, in ordinary mixing and kneading, secondary aggregation occurs, and uniform mixing in the polyester resin occurs. Dispersion was difficult. Japanese Unexamined Patent Publication No. 3-62846 discloses that uniform dispersion can be achieved by using an interlayer compound having a layered silicate as a host and an organic onium ion as a guest and a compatibilizer such as lactones, lactams and polymers thereof. Attempts have been made to improve the tensile strength, but an improvement in the tensile modulus has been observed, but it has not been satisfactory in terms of a reduction in impact strength due to the addition of a compatibilizer. Further, JP-A-7-16
Japanese Patent No. 6036 discloses a polyester resin composition comprising an interlayer compound having a layered silicate as a host and a specific quaternary ammonium salt as a guest, but improves rigidity but is satisfactory in toughness. I couldn't do it.

[0004]

SUMMARY OF THE INVENTION Accordingly, the present invention is to solve the above-mentioned problems, that is, to provide a polyester resin composition which has an excellent balance between rigidity and toughness and which can be reduced in weight due to a small amount of an inorganic substance added. The challenge is to obtain.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a thermoplastic polyester and a non-fibrous inorganic filler, in particular, an organic onium ion have been inserted between layers. The present inventors have found that the problem can be solved by further using a specific organic compound for the layered silicate thus obtained, and have reached the present invention.

That is, the present invention is to melt-knead (a) a thermoplastic polyester, (b) a non-fibrous inorganic filler, and (c) an organic compound having at least one functional group reactive with the thermoplastic polyester in a molecule. A polyester resin composition comprising:

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

[0008] (a) The thermoplastic polyester resin includes a thermoplastic polyester having an aromatic ring in a chain unit of a polymer. Specifically, it is generally used as an aromatic dicarboxylic acid (or an ester-forming derivative thereof). A polymer or copolymer obtained by a condensation reaction containing diol (or an ester-forming derivative thereof) and / or hydroxycarboxylic acid as a main component is exemplified.

Specific examples of preferred polyesters in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate,
Polyalkylene terephthalate such as polycyclohexane dimethylene terephthalate and polyhexylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polybutylene-2,6-naphthalenedicarboxylate, polyethylene-1,2-bis (phenoxy) ethane- In addition to 4,4'-dicarboxylate, polyethylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polybutylene terephthalate / decanedicarboxylate, poly (ethylene terephthalate / cyclohexane dimethylene terephthalate), polyethylene-4,4 ' Non-liquid crystalline polyesters such as dicarboxylate / terephthalate.

Particularly preferred are polybutylene terephthalate, polyethylene terephthalate, and polyethylene-2,6-naphthalenedicarboxylate. These polyester resins can be used to obtain necessary properties such as moldability, heat resistance, toughness, and surface properties. Accordingly, it is practically preferable to use it as a mixture.

The degree of polymerization of these thermoplastic polyesters is not limited, but polybutylene terephthalate is 0.5%.
% O-chlorophenol solution at 25 ° C. has an intrinsic viscosity in the range of 0.80 to 1.9, especially 1.0 to 1.
In the case of polyethylene terephthalate, the intrinsic viscosity measured under the same conditions as above is preferably in the range of 0.36 to 1.60, particularly preferably in the range of 0.52 to 1.35.

In the present invention, the non-fibrous inorganic filler (b) may be a non-fibrous inorganic filler such as a plate, a rod (for example, having a major axis / minor axis ratio of 10 or less), and a granular (eg, spherical). That is, specifically, silicate compounds such as wallastite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, alumina silicate, layered silicate represented by montmorillonite, alumina, etc. Metal compounds such as silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate,
Fillers such as carbonates such as dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide and silica These may be hollow, and two or more of these fillers may be used in combination. Preferred fillers among these are talc,
Wollastenite, kaolin, silicate compounds such as layered silicates represented by montmorillonite, etc., especially ductility, in order to impart good rigidity, kaolin, layered silicates represented by montmorillonite, etc. are most preferred .

Further, when a layered silicate having exchangeable cations between layers is used as the layered silicate, the layered silicate which has been exchanged between the layers by an organic onium ion is used. Is preferred. The layered silicate in which the exchangeable cation existing between the layers is exchanged with the organic onium ion means (b-1) an exchangeable cation of the layered silicate having an exchangeable cation between the layers, (b- 2)
Inclusion compound replaced by organic onium ions.

(B-1) The layered silicate having exchangeable cations between layers is 0.05 to 0.5 μm in width and 6 to 1 in thickness.
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 smectite-based clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, and vermiculite, various clay minerals such as halloysite, kanemite, keniyaite, zirconium phosphate, and titanium phosphate. Swelling synthetic mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluoromica, Li-type tetrasilicon fluoromica, and the like, whether natural or synthesized. good. 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.

Examples of the secondary ammonium ion include methyl dodecyl ammonium, methyl octadecyl ammonium and the like.

Examples of the tertiary ammonium ion include dimethyldodecylammonium and dimethyloctadecylammonium.

The quaternary ammonium ions include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, trioctylmethylammonium, trimethyloctylammonium, and trimethyldodecylammonium. , Alkyltrimethylammonium ions such as trimethyloctadecylammonium, dimethyldioctylammonium, dimethyldidodecylammonium,
And dimethyldialkylammonium ions such as dimethyldioctadecylammonium.

In addition to these, aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine,
-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, ammonium ions derived from 12-aminododecanoic acid, and the like.

In the present invention, (b) the layered silicate in which the exchangeable cations present between the layers are exchanged with the organic onium ion is (b-1) a layered silicate having an exchangeable cation between the layers. 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 from the viewpoint of the dispersibility of the layered silicate, the thermal stability during melting, the suppression of generation of gas and odor during molding, and the like. 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.

It is preferable to use these non-fibrous inorganic fillers after pretreatment with a coupling agent having a reactive functional group 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 are 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.

In the treatment of the non-fibrous inorganic filler with these coupling agents, the coupling agent is adsorbed on the non-fibrous inorganic filler in a polar solvent such as water, methanol or ethanol, or a mixed solvent thereof. A method in which a non-fibrous inorganic filler is added to a high-speed stirring mixer such as a Henschel mixer, and the mixture is dropped and adsorbed in the form of an aqueous solution containing a coupling agent or an organic solvent with stirring. Any method may be used, in which a coupling agent is directly added to the inorganic filler in the form of a mixture and mixed and adsorbed in a mortar or the like. When the non-fibrous inorganic filler is treated with a coupling agent, it is preferable to simultaneously mix water, acidic water, alkaline water and the like in order to promote hydrolysis of the alkoxy group of the coupling agent. Further, in order to enhance the reaction efficiency of the coupling agent, water such as methanol or ethanol and an organic solvent which dissolves both the coupling agent may be mixed in addition to water. The reaction can be further promoted by heat-treating the non-fibrous inorganic filler treated with such a coupling agent. In addition, when the non-fibrous inorganic filler and the thermoplastic polyester are melt-kneaded without previously treating the non-fibrous inorganic filler with the coupling agent, a so-called integral blending method is used in which these coupling agents are added. May be used.

In the case where the non-fibrous inorganic filler is a layered silicate having exchangeable cations between layers, the above-mentioned coupling is carried out after forming an inclusion compound in which exchangeable cations are exchanged with organic onium ions. Preferably, a treatment is applied.

In the present invention, the content of (b) the non-fibrous inorganic filler is 0.1% as the amount of inorganic ash in the composition of the present invention.
-40% by weight, preferably 1-30% by weight, particularly preferably 3-15% by weight. If the ash content is too small, the effect of improving the physical properties is small, and if the ash content is too large, the toughness may decrease. The inorganic ash content is a value obtained by incinulating 2 g of the thermoplastic resin composition in an electric furnace at 500 ° C. for 3 hours.

In the present invention, (c) the organic compound having at least one functional group reactive with the thermoplastic polyester in the molecule refers to the functional group capable of chemically reacting with the terminal group of the thermoplastic polyester. Is an organic compound having one or more in a molecule. The functional group is not particularly limited as long as it is reactive with a carboxyl group or a hydroxyl group which is a terminal group of the thermoplastic polyester.
Preferred examples include a carboxylic anhydride group, an epoxy group, an isocyanate group, a carbodiimide group, and an oxazoline group. Preferred compounds having one or more of these functional groups in the molecule include olefin compounds having a carboxylic anhydride group in the molecule, or polymers of these olefin compounds, monoepoxy compounds, diepoxy compounds, and polyepoxy compounds. , Isocyanate compounds, diisocyanate compounds, carbodiimide compounds, polycarbodiimide compounds, oxazoline compounds, bisoxazoline compounds, and the like.

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 anhydride group in the molecule or a polymer of these olefin compounds used here may have an anhydride structure substantially when melt-kneaded with a 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 polyamide resin substantially in the form of an acid anhydride.

Another preferred compound as the component (c) is an epoxy compound. Specific examples thereof include allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether,
Monoepoxy compounds such as glycidyl benzoate and glycidyl methacrylate, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol A type epoxy resin, Diglycidyl compounds such as glycidyl phthalate, diglycidyl cyclohexanedicarboxylate, glycidyl ether oxybenzoate, glycerol polyglycidyl ether, trimethylolpropane diglycidyl ether, sorbitol diglycidyl ether, glycidyl methacrylate / ethylene copolymer, etc. And the like.

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

The amount of the organic compound (c) having at least one functional group reactive with the thermoplastic polyester in the molecule used in the present invention is (a) the thermoplastic polyester 1
0.05 to 10 parts by weight with respect to 00 parts by weight is preferable,
Further, it is preferably in the range of 0.1 to 5 parts by weight,
More preferably, it is 0.1 to 3 parts by weight. If the amount is too small, the effect of improving the toughness tends to be small, and if it is too large, the moldability tends to deteriorate.

In the present invention, the method of melt-kneading (a) the thermoplastic polyester and (b) the non-fibrous inorganic filler is not particularly limited, as long as mechanical shearing can be performed in the molten state of the thermoplastic polyester. Good. The processing method may be either a batch method or a continuous method, but a continuous method capable of continuous production is preferable from the viewpoint of working efficiency. Further, there is no limitation on the method of adding the organic compound having at least one functional group reactive with the thermoplastic polyester in the molecule, and (a) the thermoplastic polyester and (b) the non-fibrous inorganic filler are used. A method of pre-blending before melt-kneading, a method of adding (a) and (b) during melt-kneading, and the like can be given. The specific kneading apparatus is not limited, but an extruder, particularly a twin-screw extruder, is preferable in terms of productivity. 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 resin composition of the present invention can be produced by a so-called master batch method. For example, (a) a part of the thermoplastic polyester, (b) a non-fibrous inorganic filler, and (c) an organic compound having at least one functional group reactive with the thermoplastic polyester in a molecule are melt-kneaded in advance. There is a method of melt kneading the master batch pellets and the remaining master batch pellets and the remaining thermoplastic polyester (a).
The master batch pellets and the remaining thermoplastic polyester pellets (a) may be mixed and directly subjected to melt molding.

Further, the polyester resin composition of the present invention may contain various conventional additives such as glass fiber, carbon fiber, acicular inorganic filler such as acicular wollastenite, as long as the object of the present invention is not impaired. Impact modifiers such as elastomers, crystal nucleating agents, coloring inhibitors, antioxidants such as hindered phenols and hindered amines, mold release agents such as ethylenebisstearylamide and higher fatty acid esters, plasticizers, heat stabilizers, lubricants , UV inhibitors, colorants,
Additives such as flame retardants can be added.

The polyester resin composition of the present invention can be easily formed into a molded product by ordinary processing methods such as extrusion molding and injection molding. In this case, the molded article obtained from the polyester resin composition of the present invention has a small amount of filler, exhibits a high flexural modulus and is excellent in impact strength, and thus is suitable for various engineering parts and structural materials.

[0040]

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

Evaluation Items and Measurement Method Tensile test: Evaluated according to ASTM D638 using an ASTM No. 1 dumbbell specimen having a thickness of 1/8 ″.

Bending test: Evaluated according to ASTM D790 using a bar-shaped test piece of １ ／ ″ × 5 ″ × １ ／ ″.

Impact test: An Izod impact test piece having a thickness of 1/8 "was evaluated according to ASTM D256.

Reference Example 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 2 L of warm water in which 48 g (equivalent to the cation exchange capacity) of trioctylmethylammonium chloride was dissolved, 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 2 100 g of Na-type synthetic mica (COPE CHEMICAL: ME-100, cation exchange capacity 80 m equivalent / 100 g) was added to warm water 1
The mixture was stirred and dispersed in 0 L, and 2 L of warm water in which 34 g (equivalent to the cation exchange capacity) of benzyldimethyloctadecyl ammonium chloride was added, 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 a dried organically modified layered silicate.

Reference Example 3 An organically modified layered silicate was produced in the same manner as in Reference Example 1, using 100 g of montmorillonite and 30.2 g (equivalent to the cation exchange capacity) of 12-aminododecanoic acid hydrochloride as in Reference Example 1. did.

Reference Example 4 An organically modified layered silicate was produced in the same manner as in Reference Example 1, except that 100 g of Na-type synthetic mica and 47 g of dimethyldioctadecyl ammonium chloride (equivalent to the cation exchange capacity) were used as raw materials. .

Example 1 95.6 parts by weight of polybutylene terephthalate having an intrinsic viscosity of 1.2 in an o-chlorophenol solution at a concentration of 0.5% measured at 25 ° C. After 4.4 parts by weight of silicate and 0.2 parts by weight of maleic anhydride were blended and pre-blended by a tumbler mixer, a TEX-30 type twin screw extruder (Nippon Steel Works) with a cylinder temperature set to 250 ° C was used. The mixture was melt-kneaded to obtain a resin composition. The resulting composition was pelletized, dried with hot air at 110 ° C. for 8 hours, and injection-molded at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. to obtain a test piece. When 2 g of the test piece was ashed in an electric furnace at 500 ° C. for 3 hours to determine the amount of inorganic ash,
3.0 wt%. Table 1 shows the evaluation results of the mechanical properties.

Example 2 A composition was obtained by melt kneading in the same manner as in Example 1 except that polymaleic anhydride having an average molecular weight of 8 was used instead of maleic anhydride in Example 1, and a composition was obtained. Physical properties were evaluated.

Example 3 In Example 1, bisphenol A was used instead of maleic anhydride.
Epoxy resin (oiled shell epoxy: Epicoat 81)
Except for using item 9), melt kneading was performed in the same manner as in Example 1 to obtain a composition, and after injection molding, physical properties were evaluated.

Example 4 A composition was obtained by melt-kneading in the same manner as in Example 1 except that diepoxy oxybenzoate (Ueno Pharmaceutical: U-QUICK-103) was used instead of maleic anhydride. After the injection molding, the physical properties were evaluated.

Examples 5 to 7 The same polybutylene terephthalate as used in Example 1, the layered silicate prepared in Reference Examples 2 to 4, and (c)
Compounds corresponding to the components were blended according to the formulation shown in Table 1, and a composition was obtained by melt-kneading in the same manner as in Example 1 and then subjected to molding evaluation.

Comparative Example 1 A composition was obtained in the same manner as in Example 1 except that maleic anhydride was not used, and a composition was obtained. After injection molding, physical properties were evaluated.

Comparative Example 2 A composition was obtained by melt-kneading in the same manner as in Example 1 except that the untreated montmorillonite used in Reference Example 1 was used as a layered silicate, and a composition was obtained. .

Comparative Example 3 The procedure of Example 6 was repeated except that polycaprolactone (Daicel Chemical: Praxel H1P) was used in place of the diepoxy oxybenzoate. Was done.

Comparative Example 4 The procedure of Example 7 was repeated except that no polymaleic anhydride was used, and the mixture was melt-kneaded to obtain a composition, which was then evaluated for molding.

[0057]

[Table 1]

[0058]

[Table 2]

Example 8 The same PBT as used in Example 1 was used, and calcined kaolin having an average particle diameter of 0.8 μm (aminosilane-treated kaolin) surface-treated with N-2- (aminoethyl) -3-aminopropyltrimethoxysilane ) And maleic anhydride were mixed according to the formulation shown in Table 3 and melt-kneaded in the same manner as in Example 1 to obtain a composition, which was evaluated for molding.

Example 9 The same PBT as used in Example 1, calcined kaolin (kaolin treated with methacryloxysilane) having an average particle diameter of 0.8 μm and surface treated with γ-methacryloxypropyltrimethoxysilane, and maleic anhydride were used. The composition was mixed according to the formulation shown in Table 3, melt-kneaded in the same manner as in Example 1 to obtain a composition, and the composition was evaluated.

Comparative Examples 5 and 6 A composition was obtained in the same manner as in Examples 8 and 9 except that maleic anhydride was not used, and the molding was evaluated.

[0062]

[Table 3]

[0063]

Industrial Applicability The polyester resin composition of the present invention has both excellent rigidity and toughness, excellent rigidity such as flexural modulus and strength even with a small amount of inorganic ash, and excellent balance with impact strength. Therefore, it is suitable for molded articles such as automobile parts, electric / electronic parts, building materials, furniture, and daily necessities.

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Claims (11)

[Claims] 1. An organic compound having (a) a thermoplastic polyester, (b) a non-fibrous inorganic filler and (c) an organic compound having at least one functional group reactive with the thermoplastic polyester in a molecule is melt-kneaded. A polyester resin composition comprising: 2. The polyester resin composition according to claim 1, wherein (b) the non-fibrous inorganic filler is a silicate compound. 3. The polyester according to claim 1, wherein (b) the non-fibrous inorganic filler is a layered silicate obtained by exchanging exchangeable cations existing between layers with organic onium ions. Resin composition. 4. The polyester resin composition according to claim 1, wherein (b) a non-fibrous inorganic filler is contained in an amount of 0.1 to 40% by weight based on the amount of inorganic ash in the composition. object. 5. The compounding amount of the organic compound having at least one functional group reactive with the thermoplastic polyester in the molecule is 0.05 to 10 parts by weight based on 100 parts by weight of the thermoplastic polyester. 2. The unit according to claim 1, wherein
5. The polyester resin composition according to any one of items 1 to 4. 6. The polyester resin composition according to claim 1, wherein (a) the thermoplastic polyester resin is a polyalkylene terephthalate. 7. The organic compound having at least one functional group reactive with the thermoplastic polyester in a molecule thereof is a carboxylic acid anhydride group and / or an epoxy group. The polyester resin composition according to claim 1. (C) The organic compound having at least one functional group reactive with the thermoplastic polyester in the molecule is an olefin compound having a carboxylic anhydride group in the molecule or a polymer of the olefin compound. The polyester resin composition according to any one of claims 1 to 7, wherein 9. The method according to claim 1, wherein the organic compound having at least one functional group reactive with the thermoplastic polyester in the molecule is maleic anhydride and / or polymaleic anhydride. The polyester resin composition according to any one of items 1 to 8, above. 10. The polyester resin composition according to claim 1, wherein (b) the non-fibrous inorganic filler is treated with a coupling agent having a reactive functional group. (B) The non-fibrous inorganic filler is a layered silicate obtained by exchanging exchangeable cations existing between layers with organic onium ions and further treating with a coupling agent having a reactive functional group. 2. The method according to claim 1, wherein:
0. The polyester composition according to any one of the above.