JPH1112451A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin compsn. which gives a molded item excellent in mechanical properties, heat resistance, and external appearance by compounding a thermoplastic polyester resin, a polycarbonate resin, and a specific clay composite in such a manner that the clay composite is dispersed with a specified average layer thickness or lower. SOLUTION: This compsn. contains a thermoplastic polyester resin, a polycarbonate resin, and a clay composite. The composite is prepd. by introducing a silane coupling agent of the general formula: Yn SiX4-n (wherein n is 0, 1, 2, or 3; Y is a 1-25C hydrocarbon group optionally substd.; X is a hydrolyzable or hydroxyl group; and when n or 4-n is 2 or higher, then each of n Y's or (4-n) Y's may be the same as or different from others) into a silicate compd. and is dispersed in an average layer thickness of 500Å or lower in the compsn. The silicate compd. is selected from among smectite clay minerals, swellable mica, and kaolin clay minerals.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic resin composition.

[0002]

2. Description of the Related Art Crystalline thermoplastic polyester resins represented by polyethylene terephthalate and polybutylene terephthalate have excellent mechanical properties, electrical properties, chemical resistance, When heated above the crystal melting temperature of the plastic polyester resin itself, it has the advantage of exhibiting good molding fluidity, but also has the disadvantage of poor impact resistance and dimensional stability.

On the other hand, polycarbonate resin has heat resistance,
As a thermoplastic resin having excellent impact resistance and toughness, it is widely used as a material for parts in industrial fields such as machinery, automobiles, electric and electronic fields. In particular, since aromatic polycarbonate resins have a high glass transition temperature, excellent heat resistance is expected.

However, a relatively high processing temperature of about 300 ° C. is generally required to ensure the molding fluidity of the aromatic polycarbonate resin. Requires extremely high injection speed and injection pressure. Also, aromatic polycarbonate resin,
When it comes in contact with various organic solvents, gasoline, etc., there is a problem in chemical resistance such as cracking, deformation, and dissolution of the molded product surface. In particular, when a molded body is manufactured by injection molding or the like, distortion is left inside the molded body due to molding at a relatively high injection speed and relatively high injection pressure, and cracks are remarkably generated at that portion. is there. Further, the polycarbonate resin has a problem in terms of weather resistance, and is not sufficient, for example, when the molded product surface is cracked or discolored to yellow when exposed to ultraviolet rays for a long period of time.

[0005] Therefore, for the purpose of complementing the drawbacks by utilizing the respective features, for example, Japanese Patent Publication No. 36-14 / 1986.
No. 035, JP-B-39-20434, JP-A-59-176345, JP-B-55-94350, JP-A-63-83158, and the like, a resin composition of a polyester resin and a polycarbonate resin. Is disclosed.

When a polyester resin and a polycarbonate resin are used as a composition as described above, the dimensional stability which is a problem of the polyester resin and the chemical resistance which is a problem of the polycarbonate resin are certainly improved. However, improvement in mechanical properties such as flexural modulus and heat resistance is not sufficient. This is because the polycarbonate resin and the polyester resin partially react with each other in the resin composition to generate a component having a relatively low glass transition temperature, or the crystallization of the polyester resin is inhibited due to the reaction. It is said that the degree of conversion decreases. Due to such a phenomenon, a composition having satisfactory chemical resistance cannot be obtained.

In order to improve the mechanical properties such as the flexural modulus and the heat resistance, inorganic fillers such as glass fibers, carbon fibers, glass flakes and glass beads have been added. However, although the heat resistance is certainly improved by the addition of the inorganic substance as described above, new strengths such as poor appearance of the molded article, poor dispersion of the inorganic substance, or a decrease in the toughness caused by poor adhesion between the inorganic substance and the resin, etc. Problems arise.

When an inorganic nucleating agent such as talc is added for the purpose of improving the crystallinity of the polyester resin,
Addition of a small amount is not sufficient in improving effect, and addition of a large amount causes problems such as poor appearance, strength, and decrease in fluidity. Further, when an organic nucleating agent such as a metal carboxylate is added, However, there arises a problem that the polycarbonate resin is decomposed and foamed.

[0009]

SUMMARY OF THE INVENTION In order to solve the above-mentioned conventional problems, the present invention provides a polyester resin and a polycarbonate which are excellent in mechanical properties and heat resistance and do not impair the appearance of a molded article. A thermoplastic resin composition comprising a thermoplastic polyester resin (A), a polycarbonate resin (B), and a clay composite (C). , clay complex (C) is, silicate compound (C1) in the general formula _{(I): Y n SiX 4} -n (I) ( wherein, n an integer of 0 to 3, Y is have a substituent A hydrocarbon group having 1 to 25 carbon atoms, X is a hydrolyzable group or a hydroxyl group, and when n or 4-n is 2 or more,
n Y or 4-n X may be the same or different, respectively.)
A thermoplastic resin composition wherein the clay composite (C) is dispersed in the thermoplastic resin composition at an average layer thickness of 500 ° or less (Claim 1); A thermoplastic resin composition comprising (A), a polycarbonate resin (B) and a clay composite (C), wherein the clay composite (C) is a silicate compound (C1) having the general formula (I): Y _n SiX _4-n (I) (wherein, n is an integer of 0 to 3, Y is a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, X is a hydrolyzable group or a hydroxyl group. Yes, if n or 4-n is 2 or more,
n Y or 4-n X may be the same or different, respectively.)
Is introduced, and the bottom spacing of the clay composite (C) dispersed in the thermoplastic resin composition is at least three times the initial bottom spacing of the silicate compound (C1). Thermoplastic resin composition (Claim 2), clay composite (C)
Can be obtained by adding the silane coupling agent (C2) after increasing the distance between the bottom surfaces of the silicate compound (C1) in the dispersion medium, and the introduced silane coupling agent ( The thermoplastic resin composition (Claim 3) according to claim 1 or 2, wherein the bottom space of the clay composite (C) is wider than the initial bottom space of the silicate compound (C1) by C2). The thermoplastic resin composition according to claim 1, 2 or 3, wherein the silicate compound (C1) is at least one selected from the group consisting of smectite group clay minerals, swellable mica, and kaolin group clay minerals. Claim | item 4), The thermoplastic polyester resin (A) is 1-99%.
(Weight%, the same applies hereinafter), the content of the polycarbonate resin (B) is 99 to 1%, and the total amount thereof is 100%.
The ash content of the thermoplastic resin composition according to claim 1, 2, 3 or 4 (claim 5) and the thermoplastic resin composition derived from the clay composite (C) is 0.1 to 50%. The present invention relates to a thermoplastic resin composition according to certain claims 1, 2, 3, 4, or 5.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The thermoplastic polyester resin (A) used in the present invention mainly comprises an acid component mainly composed of an aromatic dicarboxylic acid or an ester-forming derivative thereof, and a diol compound or an ester-forming derivative thereof. It is a conventionally known thermoplastic polyester resin produced by a reaction with a diol component as a component.

The term "main component" means that the ratio of each component in the acid component or the diol component is 80% or more, further 90% or more, and the upper limit is 100%.

The aromatic dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, orthophthalic acid,
2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid,
4,4'-diphenylsulfonedicarboxylic acid, 4,
Examples thereof include 4'-diphenylisopropylidene dicarboxylic acid and the like, and substituted substances thereof (for example, 5-methylisophthalic acid and the like) and derivatives thereof (for example, dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate) can also be used.

These may be used alone or in combination of two or more. A small amount (specifically, 2) that does not impair the properties of the obtained thermoplastic polyester resin
(About 0% or less), these aromatic dicarboxylic acids and the like may be used in combination with one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecane diacid, and sebacic acid. Also, oxyacids such as p-oxybenzoic acid and p-hydroxyethoxybenzoic acid, and ester-forming derivatives thereof can be used.

Among the above acid components, terephthalic acid, 2,6-naphthalenedicarboxylic acid and 4,4
4'-biphenyldicarboxylic acid is preferred, and terephthalic acid is particularly preferred.

The diol component includes ethylene glycol, propylene glycol, butylene glycol,
Aliphatic diols such as hexylene glycol and neopentyl glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and 2,2-bis (4
Aromatic diols such as (-hydroxyphenyl) propane and the like can also be used, and their substituted compounds can also be used.
Also, cyclic esters such as ε-caprolactone can be used. Two or more of these may be used in combination. Further, if the amount is a small amount (specifically, about 20% or less) that does not significantly lower the elastic modulus of the thermoplastic polyester resin, long chain diols (eg, polyethylene glycol, polytetramethylene glycol) and alkylenes of bisphenols may be used. An oxide addition polymer or the like (for example, an ethylene oxide addition polymer of bisphenol A) may be used in combination of one or more kinds.

Among the diol components, ethylene glycol, butylene glycol and 1,4-cyclohexanedimethanol are preferred from the viewpoint of the crystallinity, mechanical properties, and ease of handling during the reaction of the obtained thermoplastic polyester resin. Of these, ethylene glycol and butylene glycol are particularly preferred.

Specific examples of the thermoplastic polyester resin (A) include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, neopentyl terephthalate, polyethylene isophthalate, Examples include polyethylene naphthalate, polybutylene naphthalate, polyhexamethylene naphthalate, and the like, or a copolymerized polyester produced by using two or more kinds of acid components and / or diol components used for producing these resins.

The thermoplastic polyester resin (A) may be used alone or in combination of two or more of those having different constituent components and ratios and / or having different intrinsic viscosities.

Among the thermoplastic polyester resins (A), polyethylene terephthalate and polybutylene terephthalate are preferred in view of the mechanical properties, heat resistance and cost of the molded article obtained from the thermoplastic resin composition.

The thermoplastic polyester resin (A) has an intrinsic viscosity of 0.3 to 0.3 as measured at 25 ° C. using a phenol / tetrachloroethane (5/5 (weight ratio)) mixed solvent.
A value of about 2.0 (dl / g) is desirable. When the intrinsic viscosity is less than 0.3 (dl / g), the mechanical properties and impact resistance of the obtained molded article of the thermoplastic resin composition tend to be poor, and 2.0 (dl / g). If it is larger than g), processability such as fluidity during molding tends to be poor.

The polycarbonate resin (B) used in the present invention is a thermoplastic polycarbonate resin, and is an aromatic polycarbonate resin produced by reacting a dihydric phenol compound with phosgene or a dihydric phenol compound with a carbonic acid diester. Is preferred.

The constituent 2 of the polycarbonate resin (B)
Examples of the divalent phenol compound include 2,2-bis (4-hydroxyphenyl) propane (“bisphenol A”), bis (4-hydroxyphenyl) methane,
1,1-bis (4′-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -3,3,5
-Trimethylcyclohexane (“Bisphenol TM
C "), bis (4-hydroxyphenyl) cyclohexylmethane, 2,2-bis (4'-hydroxy-3,5 '
-Dibromophenyl) propane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) methane, 2,2-
Bis (4'-hydroxy-3 ', 5'-dimethylphenyl) propane, 1,1-bis (4'-hydroxyphenyl) -1-phenylethane, 4,4'-dihydroxydiphenyl ether, bis (4-hydroxy- 3,5-dimethylphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, 4,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfide, etc. Is raised. Further, a dihydric phenol compound having a benzotriazole group may be used to enhance the flame retardancy. Substitutes or derivatives of these dihydric phenol compounds may also be used. Two or more of these dihydric phenol compounds may be used in combination.

The carbonic acid diester compound includes
For example, bisalkyl carbonates such as dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, diphenyl carbonate, bis (2,4-dichlorophenyl) carbonate, bis (2,4,6- Bisaryl carbonates such as trichlorophenyl) carbonate, bis (2-nitrophenyl) carbonate, bis (2-cyanophenyl) carbonate, bis (4-methylphenyl) carbonate, bis (3-methylphenyl) carbonate, and dinaphthyl carbonate Is raised. Among the carbonic diesters, diphenyl carbonate, in terms of reactivity, safety, etc.,
Dimethyl carbonate is preferred.

Specific examples of the polycarbonate resin (B) include, for example, 2,2-bis (4-hydroxyphenyl) propane-type polycarbonate, 2,2-bis (3,
5-dimethyl-4-hydroxyphenyl) propane type polycarbonate, 1,1-bis (4-hydroxyphenyl) cyclohexane type polycarbonate, 4,4′-dihydroxyphenyl ether type polycarbonate, 4,
Examples thereof include 4'-dihydroxydiphenyl sulfide-type polycarbonate, 4,4'-dihydroxydiphenyl sulfone-type polycarbonate, bis (4-hydroxyphenyl) ketone-type polycarbonate, and 1,4-bis (4-hydroxyphenylsulfonyl) benzene.

The polycarbonate resin (B) may be used alone, or two or more components having different constituent components and ratios and / or different molecular weights may be used in combination.

Among the polycarbonate resins (B),
From the viewpoint of the mechanical properties, heat resistance and cost of the molded article obtained from the obtained thermoplastic resin composition, 2,2-bis (4-
(Hydroxyphenyl) propane-type polycarbonates are preferred.

The molecular weight of the polycarbonate resin (B) is
In gel permeation chromatography (GPC) measurement using a tetrahydrofuran (THF) solvent, 4
The weight average molecular weight (Mw) measured at 0 ° C is 15,000 to 80,000, preferably 30,000 to 65,000 in terms of monomolecular weight dispersed polystyrene. Mw is 1500
When the value is less than 0, the mechanical properties and impact resistance of the obtained thermoplastic resin composition tend to be poor. Workability tends to be poor.

The proportion of the thermoplastic polyester resin (A) in the thermoplastic polyester resin (A) and the polycarbonate resin (B) in the thermoplastic resin composition of the present invention is 1 to 99%, more preferably 5 to 95%, particularly preferably 5 to 95%. Is 10 to 90
% Is preferred. When the ratio is less than 1%, the effect of improving the chemical resistance and the like by using the thermoplastic polyester resin (A) tends to be insufficient. When the ratio is more than 99%, the polycarbonate resin (B) is used. There is a tendency that the effect of improving the dimensional stability and the like by using is insufficient.

The clay composite (C) used in the present invention is:
The silicate compound (C1) has a general formula (I): Y _n SiX _4-n (I) (wherein, n is an integer of 0 to 3, and Y is a carbon atom of 1 to 5 which may have a substituent. 25 is a hydrocarbon group, X is a hydrolyzable group or a hydroxyl group, and when n or 4-n is 2 or more,
n Y or 4-n X may be the same or different, respectively.)
Is introduced.

The silicate compound (C1) consists essentially of tetrahedral sheets of silicon oxide and octahedral sheets of metal hydroxide, such as, for example, smectite family clay minerals, swellable mica and kaolin And group clay minerals. The use of a smectite group clay mineral, a swellable mica or a kaolin group clay mineral as the silicate compound (C1) is effective in improving the dispersibility in a thermoplastic resin, improving the physical properties of the obtained thermoplastic resin composition, and easily obtaining the same. It is preferable from the point of view.

Specific examples of the smectite group clay mineral include natural or chemically synthesized hectorite, saponite, montmorillonite, stevensite, beidellite, nontronite, bentonite, and the like.
Or a substituted or derivative thereof, or a mixture thereof. The distance between the bottom surfaces of the smectite group clay mineral in the initial aggregation state is about 10 to 17 °, and the thickness of the smectite group clay mineral in the aggregation state is about 1000.
{1,000,000}.

The swellable mica has the property of swelling in water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent. For example, lithium teniolite, sodium teniolite Natural or chemically synthesized swellable mica, such as lithium tetrasilicic mica and sodium tetrasilicic mica,
Swellable mica having lithium ions or sodium ions between layers, or a substitute or derivative thereof, or a mixture thereof. The following equivalents of vermiculite can also be used. The distance between the bottom surfaces of the swellable mica in the initial state of aggregation is about 10 to 17 °, and the thickness of the swellable mica in the state of aggregation is about 1,000 to 10,000.
00 °.

Vermiculite includes a trioctahedral type and a dioctahedral type, and has a general formula (II): (Mg, Fe, Al) _2-3 (Si _4-x Al _x ) O ₁₀ (OH) _2. (M ⁺ , M ²⁺ _1/2 ) _x · nH ₂ O (II) (wherein, M is an exchangeable cation of an alkali or alkaline earth metal such as Na and Mg, x = 0.6-0. 9,
n = 3.5 to 5). The distance between the bottom surfaces of the vermiculite in the initial state of aggregation is about 10 to 17 degrees, and the thickness of the vermiculite in the state of aggregation is about 1000 to 5,000,000 degrees.

Examples of the kaolin group clay mineral include natural or chemically synthesized kaolinite, dickalite, halloysite or a substituted or derivative thereof,
Alternatively, a mixture thereof may be mentioned.

The synthetic kaolin group clay mineral can be produced, for example, by the following method.

For example, synthetic kaolinite can be precipitated by mixing colloidal silica and alumina sol in a kaolinite composition ratio as a starting material, setting the raw material concentration high in a hydrothermal treatment method, and treating at 150 to 300 ° C. (S. Tomura et al., Cl.
ays Clay Miner. , 33, 200 (19
85)). Synthetic halloysite can be obtained by leaching feldspar with a Soxhlet extractor or the like (WEE.
Parham, Clays Clay Miner,.
17, 13 (1969)). The kaolin group clay mineral has a bottom surface interval of about 7 to 12 ° in the initial aggregation state, and the kaolin group clay mineral in the aggregation state has a thickness of about 100 mm.
It is 0 ° to 100000 °.

The silicate compound (C1) may be used alone or in combination of two or more. Among these, montmorillonite, bentonite, hectorite, swelling mica having sodium ions between the layers and kaolinite are preferred, especially montmorillonite,
Swellable mica and kaolinite having sodium ions between the layers are preferred from the viewpoints of dispersibility in the thermoplastic resin, the effect of improving the physical properties of the obtained thermoplastic resin composition, and the availability.

The crystal structure of the silicate compound (C1) is c
It is desirable to have a high degree of purity, which is regularly stacked in the axial direction, but a so-called mixed-layer mineral in which the crystal cycle is disordered and a plurality of types of crystal structures are mixed may be used.

The silane coupling agent (C2) introduced into the silicate compound (C1) is a silane coupling agent represented by the general formula (I): Y _n SiX _4-n (I). In the general formula (I), n is an integer of 0 to 3, and Y is a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. When the hydrocarbon group having 1 to 25 carbon atoms has a substituent, examples of the substituent include a group bonded by an ester bond, a group bonded by an ether bond, an epoxy group, an amino group, and a carboxyl group. , A group having a carbonyl group at a terminal, an amide group, a mercapto group, a group bonded by a sulfonyl bond, a group bonded by a sulfinyl bond, a nitro group, a nitroso group, a nitrile group, a halogen atom and a hydroxyl group. . One of these may be substituted, or two or more may be substituted. Further, it may be substituted with one or two or more. X is a hydrolyzable group and / or a hydroxyl group;
Examples of the hydrolyzable group include one or more selected from the group consisting of an alkoxy group, an alkenyloxy group, a ketoxime group, an acyloxy group, an amino group, an aminoxy group, an amide group, and a halogen atom.

In the general formula (I), when n or 4-n is 2 or more, n Y or 4-n X may be the same or different.

As used herein, the term "hydrocarbon group" means a linear or branched (ie, having a side chain) saturated or unsaturated, monovalent or polyvalent aliphatic hydrocarbon group, aromatic hydrocarbon group, or aliphatic hydrocarbon group. Means a cyclic hydrocarbon group, for example, an alkyl group, an alkylene group, an alkenyl group, an alkenylene group, an alkynyl group, an alkynylene group, a phenyl group, a phenylene group, a naphthyl group, a naphthylene group, a cycloalkyl group, a cycloalkylene group, etc. Can be

In the general formula (I), Y represents 1 to 2 carbon atoms.
Examples of the hydrocarbon group having a hydrocarbon group of No. 5 include those having a linear long-chain alkyl group such as decyltrimethoxysilane, those having a lower alkyl group such as methyltrimethoxysilane, and 2-hexenyltrimethoxy. One having an unsaturated hydrocarbon group such as silane, one having an alkyl group having a side chain such as 2-ethylhexyltrimethoxysilane, one having a phenyl group such as phenyltriethoxysilane, 3-β-naphthyl Examples include those having a naphthyl group such as propyltrimethoxysilane and those having an aralkyl group such as p-vinylbenzyltrimethoxysilane. When Y is a hydrocarbon group having 1 to 25 carbon atoms, particularly a group having a vinyl group, examples thereof include vinyltrimethoxysilane, vinyltrichlorosilane, and vinyltriacetoxysilane. Examples of the case where Y is a group having a group substituted with a group bonded by an ester bond include γ-methacryloxypropyltrimethoxysilane and the like. When Y is a group having a group substituted by a group linked by an ether bond, examples include γ-polyoxyethylenepropyltrimethoxysilane and 2-ethoxyethyltrimethoxysilane. When Y is a group substituted with an epoxy group, examples include γ-glycidoxypropyltrimethoxysilane. Examples of the case where Y is a group substituted with an amino group include γ-
Aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane and γ-
Anilinopropyltrimethoxysilane and the like can be mentioned. When Y is a group substituted with a group having a carbonyl group at the terminal, examples include γ-ureidopropyltriethoxysilane. Examples of the case where Y is a group substituted with a mercapto group include γ-
And mercaptopropyltrimethoxysilane. When Y is a group substituted with a halogen atom, examples include γ-chloropropyltriethoxysilane. When Y is a group having a group substituted with a group bonded by a sulfonyl bond, examples include γ-phenylsulfonylpropyltrimethoxysilane. When Y is a group having a group substituted by a group bonded by a sulfinyl bond, examples include γ-phenylsulfinylpropyltrimethoxysilane. When Y is a group substituted by a nitro group, examples include γ-nitropropyltriethoxysilane. When Y is a group substituted with a nitroso group, examples include γ
-Nitrosopropyltriethoxysilane and the like. When Y is a group substituted with a nitrile group, examples include γ-cyanoethyltriethoxysilane and γ-cyanopropyltriethoxysilane. When Y is a group substituted with a carboxyl group, examples include γ- (4-carboxyphenyl) propyltrimethoxysilane.

In addition to the above, a silane coupling agent (C2) in which Y is a group having a hydroxyl group can also be used. Such examples include N, N-di (2-hydroxyethyl) amino-3-propyltriethoxysilane and the like.

Substitutes and derivatives of the silane coupling agent (C2) can also be used. These silane coupling agents (C2) may be used alone or in combination of two or more.

The clay composite (C) used in the present invention comprises:
For example, after increasing the distance between the bottom surfaces of the silicate compound (C1) in the dispersion medium, the silane coupling agent (C2)
Is obtained by a method such as adding

Examples of the dispersion medium include water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent.

Examples of the polar solvent include alcohols such as methanol, ethanol and isopropanol, ethylene glycol, propylene glycol, and the like.
Glycols such as 1,4-butanediol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; amide compounds such as dimethylformamide; and other solvents such as dimethyl sulfoxide and 2-pyrrolidone. . These polar solvents may be used alone or in combination of two or more.

The distance between the bottom surfaces of the silicate compound (C1) in the dispersion medium can be increased by stirring and dispersing the silicate compound (C1) in the dispersion medium.
The distance between the bottom surfaces after the enlargement is 3 times or more, preferably 5 times or more, as compared with the initial distance between the bottom surfaces of the silicate compound (C1). Although there is no particular upper limit, the silicate compound (C1) is substantially present in a unit layer if the distance between the bottom surfaces is increased 30 times, so that it is not necessary to increase the silicate compound (C1) more than 30 times.

The initial distance between the bottom surfaces of the silicate compound (C1) is the distance between the bottom surfaces in a state where the unit layers are stacked on each other before the distance between the bottom surfaces is increased in the dispersion medium.

The distance between the bottom surfaces enlarged in the dispersion medium can be determined by small angle X-ray diffraction (SAXS) or the like. That is, the diffraction peak angle value of a dispersion comprising a dispersion medium and a silicate compound (C1) was measured by SAXS,
The bottom surface interval can be obtained by performing the calculation by applying the above expression.

As a method for efficiently increasing the distance between the bottom surfaces of the silicate compound (C1), stirring at several thousand rpm or more, or a method of applying a physical external force shown below can be mentioned.

The physical external force is applied by using a commonly-used method of pulverizing a filler. As a general method for finely pulverizing a filler, for example, a method using hard particles can be mentioned. in this way,
The hard particles, the silicate compound (C1), and an optional solvent are mixed and stirred, and the hard particles and the silicate compound (C1) are physically collided with each other to reduce the bottom distance of the silicate compound (C1). Enlarge to separate layers. Hard particles usually used are filler grinding beads, for example, glass beads or zirconia beads. These grinding beads are selected in consideration of the hardness of the silicate compound (C1) or the material of the stirrer, and are not limited to the glass beads or zirconia beads. Although the particle size is also determined in consideration of the size of the silicate compound (C1) and the like, it is not absolutely limited to a numerical value.
Those having a range of 1 to 6.0 mm are preferable. The solvent used here is not particularly limited, but for example, the above-mentioned dispersion medium is preferable.

As described above, after the bottom surface of the silicate compound (C1) is expanded to separate the layers, the silane coupling agent (C2) is added and stirred. As described above, the clay composite (C) is obtained by introducing the silane coupling agent (C2) to the surface of the silicate compound (C1) having the increased bottom surface spacing. In order to introduce the silane coupling agent (C2) more efficiently, the rotation speed of stirring should be 1000 rpm or more, or 50 rpm.
A shear rate of 0 (1 / s) or more is applied. The upper limit of the number of revolutions is 25000 rpm, and the upper limit of the shear rate is 5
00000 (1 / s). It is not necessary to stir at a value greater than the upper limit, since the effect tends to remain the same even if the stirring is performed at a value greater than the upper limit.

The introduction of the silane coupling agent (C2) into the silicate compound (C1) is carried out by combining a hydrolyzable group and / or a hydroxyl group of the silane coupling agent (C2) with a silicic acid having an increased bottom distance. The silane coupling agent (C2) is introduced into the silicate compound (C1) by reacting with a hydroxyl group present on the surface of the layer of the salt compound (C1).

When the introduced silane coupling agent (C2) has a reactive group such as a hydroxyl group, a carboxyl group, an amino group, an epoxy group or a vinyl group, the silane coupling agent is further added. The reaction can also be performed by adding a compound that reacts with the reactive group (C2). The silane coupling agent (C2) introduced into the silicate compound (C1) by the second reaction
It is also possible to lengthen the chain length of the functional group and to change the polarity. The compound added in the second reaction is not limited to the silane coupling agent (C2),
Any compound is used according to the purpose. Examples of these compounds include epoxy group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, acid anhydride-containing compounds, and hydroxyl group-containing compounds.

The reaction proceeds sufficiently at room temperature, but may be heated if necessary. The maximum temperature at the time of heating can be arbitrarily set as long as it is lower than the decomposition temperature of the silane coupling agent (C2) to be used and lower than the boiling point of the dispersion medium.

The amount of the silane coupling agent (C2) used depends on the affinity between the clay composite (C) and the thermoplastic polyester resin (A) or the polycarbonate resin (B), or the amount of the clay composite (C) in the resin. It can be adjusted so as to increase the dispersibility of C). If necessary, plural kinds of silane coupling agents (C2) having different functional groups can be used in combination. Therefore, the amount of the silane-based coupling agent (C2) to be added is not necessarily limited by numerical values, but is preferably 0.1 to 100 parts (parts by weight, the same applies hereinafter) of the silicate compound (C1). 1 to 200 parts, more preferably 0.2 to 160 parts, particularly preferably 0.3 to 1 part.
20 parts. If the amount of the silane coupling agent (C2) is less than 0.1 part, the clay composite (C) tends to be insufficiently finely dispersed in the thermoplastic resin composition. The effect does not change even if 200 parts or more are used.

The bottom spacing of the clay complex (C) obtained as described above is larger than the initial bottom spacing of the silicate compound (C1) due to the presence of the introduced silane coupling agent (C2). doing. The spacing between the bottom surfaces of the clay composite (C) is preferably 1.5 times or more, more preferably 2 times or more, as compared with the initial spacing between the silicate compounds (C1). .

As described above, the silane coupling agent (C
By introducing 2) and increasing the distance between the bottom surfaces, the dispersibility of the clay composite (C) in the resin serving as the matrix and the affinity for the resin serving as the matrix can be increased.

Here, the introduction of the silane coupling agent (C2) can be confirmed by various methods, and specific examples include the following methods.

First, the silane coupling agent (C2) simply adsorbed on the clay complex (C) is sufficiently washed and removed using an organic solvent such as tetrahydrofuran or chloroform. After washing, the clay composite (C) is powdered in a mortar or the like, and then dried sufficiently. Mix it well with a window material such as powdered potassium bromide (KBr) at a predetermined ratio,
Pressed tablets to make Fourier transform infrared spectroscopy (FT-IR)
The absorption band derived from the silane coupling agent (C2) introduced into the clay composite (C) by a transmission method or the like is measured. When more accurate measurement is desired, or when the amount of the introduced silane coupling agent (C2) is small, the sufficiently dried powdery clay complex (C) is diffused as it is. It is desirable to measure by a reflection method (DRIFT).

Further, it can be confirmed by various methods that the interval between the bottom surfaces of the clay composite (C) is larger than the initial interval between the bottom surfaces of the silicate compound (C1). There are various methods.

First, the silane coupling agent (C2) simply adsorbed on the clay composite (C) is washed with an organic solvent in the same manner as described above, dried and then subjected to a small-angle X-ray diffraction method (S
AXS) can be used to determine the bottom surface interval. According to this method, the diffraction peak angle derived from the (001) plane of the powdery clay composite (C) is measured by SAXS, and Bragg
By calculating by applying to the formula of
Similarly, the bottom surface interval of the silicate compound (C1) is also obtained,
By comparing the two, it can be confirmed that they have expanded.

As described above, the absorption band derived from the added silane coupling agent (C2) after washing with the organic solvent is observed by FT-IR or the like, and the bottom surface interval is determined by the silicate compound (C1 SAX)
By measuring with S or the like, it can be confirmed that the clay complex (C) is formed.

In the thermoplastic resin composition of the present invention, the compounding amount of the clay composite (C) is 0.1 to 100 parts with respect to 100 parts of the resin component comprising the thermoplastic polyester resin (A) and the polycarbonate resin (B). , And even 0.
The amount is preferably 2 to 80 parts, particularly preferably 0.5 to 60 parts. If the amount of the clay composite (C) is less than 0.1 part, the effect of improving mechanical properties and heat resistance tends to be insufficient,
If the amount exceeds 100 parts, the appearance of the molded body, the fluidity during molding, and the like tend to be impaired.

The ash content of the thermoplastic resin composition derived from the clay composite (C) is preferably 0.1 to 50%, more preferably 0.2 to 40%, and particularly preferably 0.5 to 35%. .
If the ash content is less than 0.1%, the effect of improving the mechanical properties and heat resistance tends to be insufficient, and if it exceeds 50%, the appearance of the molded article and the fluidity during molding tend to be impaired. is there.

The method for producing the thermoplastic resin composition of the present invention is not particularly limited. For example, it is produced by melt-mixing a thermoplastic polyester resin (A), a polycarbonate resin (B) and a clay composite (C) with a kneader.

Also, a method of producing a clay composite-containing polyester resin in which the clay composite (C) is dispersed in advance in the thermoplastic polyester resin (A) and then melt-mixing with the polycarbonate resin (B), or A method in which a clay composite-containing polycarbonate resin in which the clay composite (C) is dispersed in advance in B) is produced and then melt-mixed with the thermoplastic polyester resin (A). It can be produced by various methods such as a method of melt-mixing with a clay composite-containing polycarbonate resin.

Here, there is no particular limitation on the method for producing a clay complex-containing resin in which the clay complex (C) is dispersed in the resin in advance. Such a method includes, for example, mixing a polymerizable monomer and / or a polymerizable oligomer constituting a resin with a clay complex (C) to form a dispersion, and then dispersing the clay complex (C) in the dispersion. A method of polymerizing a polymerizable monomer and / or a polymerizable oligomer in the presence of the polymer (C), or dispersing the clay composite (C) in a good solvent for the resin, dissolving the resin, and then drying. The method can be obtained by various methods, such as a method of removing the solvent by using

Examples of the kneader include known kneaders capable of giving a high shearing force to a system such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, and a roll. Particularly, a meshing twin-screw extruder having a kneading disk portion is preferable.

The average layer thickness of the clay composite (C) dispersed in the thermoplastic resin composition of the present invention obtained as described above is 500 ° or less, preferably 400 ° or less, more preferably 300 ° or less. . The average layer thickness is 500
If it is larger than Å, the effect of improving mechanical properties and heat resistance is reduced. The lower limit of the average layer thickness is not particularly limited, but is about 10 ° because the thickness of the unit layer is about 10 °.

As described above, the silane-based coupling agent (C2) is introduced into the silicate compound (C1) to form the clay composite (C). Although it is larger than the initial distance between the bottom surfaces, the distance between the bottom surfaces of the clay composite (C) dispersed in the thermoplastic resin composition of the present invention is further expanded, and the initial distance between the silicate compound (C1) and the clay compound (C1) is small. Enlarged three times or more, preferably four times or more, as compared with the bottom surface interval. If the ratio is less than 3 times, the clay composite (C) is difficult to disperse uniformly, and as a result, the effect of sufficiently improving the mechanical properties and heat resistance of the thermoplastic resin composition cannot be obtained. The upper limit of the distance between the bottom surfaces of the clay composite (C) dispersed in the thermoplastic resin composition of the present invention is not particularly limited, but when it is about 10 times or more, the effect of improving mechanical properties and heat resistance is improved. Hardly change.

The layer thickness of the clay composite (C) can be determined, for example, by using a transmission electron microscope or the like. Further, the bottom surface interval can be easily obtained from the measurement of the bottom surface interval of the (001) plane by small angle X-ray diffraction (SAXS). The distance between the bottom surfaces can be determined by calculating the diffraction peak angle value in SAXS by applying the Bragg equation.

The clay composite (C) may be dispersed in any one of the resin phases constituting the thermoplastic resin composition of the present invention, or may be dispersed in two or more phases. Good.

The thermoplastic resin composition of the present invention may contain, if necessary, polybutadiene, butadiene-styrene copolymer, acrylic rubber, ionomer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer,
Natural rubber, chlorinated butyl rubber, homopolymer of α-olefin, copolymer of two or more α-olefins (random, block, graft, etc., any copolymer, or a mixture thereof) ) Or an impact modifier such as an olefin-based elastomer can be added. These may be modified with an acid compound such as maleic anhydride or an epoxy compound such as glycidyl methacrylate.

Further, any other thermoplastic resin or thermosetting resin such as an unsaturated polyester resin, a polyester carbonate resin, a liquid crystal polyester resin, a polyolefin resin, or the like, as long as the properties such as mechanical properties and moldability are not impaired. A polyamide resin, a rubbery polymer reinforced styrene resin, a polyphenylene sulfide resin, a polyphenylene ether resin, a polyacetal resin, a polysulfone resin, or the like may be added alone or in combination of two or more.

Further, according to the purpose, the thermoplastic resin composition of the present invention may contain pigments, dyes, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, flame retardants and antistatics. An additive such as an agent may be added.

The thermoplastic resin composition of the present invention may be molded by an injection molding method, a hot press molding method or a blow molding method. Further, the thermoplastic resin composition of the present invention,
It may be formed into a biaxially stretched film that maintains transparency and has excellent mechanical properties.

The molded articles and films produced from the thermoplastic resin composition of the present invention are excellent in appearance, mechanical properties, heat-resistant deformation properties, etc., and therefore, for example, automobile parts, household electric appliance parts, precision mechanical parts, It is suitably used for household goods, packaging and container materials, magnetic recording tape base materials, and other general industrial materials.

[0080]

The composition of the present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention thereto.

The main raw materials used in Examples and Comparative Examples are shown below.

As the thermoplastic polyester resin (A) and the polycarbonate resin (B), the following resins were used without purification.

Thermoplastic polyester resin (A) PET: polyethylene terephthalate manufactured by Kanebo Co., Ltd., trade name PBK2, logarithmic viscosity (η _inh ) = 0.63
dl / g

Polycarbonate resin (B) PC: polycarbonate manufactured by Idemitsu Petrochemical Co., Ltd., trade name: Toughlon A-2200, weight average molecular weight (Mw)
= 45000

Silicate Compound (C1) Montmorillonite: Unpurified natural montmorillonite from Akita Prefecture, spacing between bases = 13 ° Swelling mica: A finely pulverized product of 25.4 g of talc and 4.7 g of sodium silicofluoride was mixed. , 28.2 g of swelling mica obtained by heat treatment at 800 ° C., base spacing = 12
Å ・ Kaolinite: Natural kaolinite from Georgia, USA, base spacing = 7Å

Silane Coupling Agent (C2) The following silane coupling agent was used without purification. Γ- (2-aminoethyl) aminopropyltrimethoxysilane: A-1120 manufactured by Nippon Unicar Co., Ltd. γ-glycidoxypropyltrimethoxysilane: A-187 manufactured by Nippon Unicar Co., Ltd. γ- ( Polyoxyethylene) propyltrimethoxysilane: manufactured by Nippon Unicar Co., Ltd., A-1230

The evaluation methods in Examples and Comparative Examples are summarized below.

(FT-IR) 1.0 g of the clay complex was added to 50 ml of tetrahydrofuran (THF), and the mixture was stirred for 15 minutes to wash and remove the adsorbed silane coupling agent, and then centrifuged to remove the supernatant. The washing operation of separating was repeated three times. After washing, about 1 mg of the sufficiently dried clay complex and about 200 mg of KBr powder are sufficiently mixed using a mortar, and then the K for measurement is measured using a tabletop press.
A Br disk was prepared. Subsequently, the measurement was carried out by a transmission method using an infrared spectrometer (8100M, manufactured by Shimadzu Corporation). The detector was an MCT detector with a resolution of 4 cm ^-1 and the number of scans was 100.

(Measurement of Layer Thickness by Transmission Electron Microscope (TEM)) Using a microtome, a test piece of a thermoplastic resin composition produced by an injection molding machine (IS-75E, manufactured by Toshiba Machine Co., Ltd.) was used to measure 80 to 80%. A flake having a thickness of 100 nm was cut out. Transmission electron microscope (manufactured by JEOL Ltd., JEM-1)
200EX) at an acceleration voltage of 80 kV. The average value of the layer thickness was determined by measuring the layer thickness of each clay composite in a portion where 100 or more clay composites exist in the microscopic image, and averaging them.

Further, in a portion where 100 or more clay composites are present, the layer thickness is 50 ° with respect to the total number of clay composites.
The ratio of the number of the following layers was determined.

(Measurement of Bottom Spacing by Small Angle X-ray Diffraction Method (SAXS)) X-ray Generator (RU-R, manufactured by Rigaku Corporation)
200B), target CuKα ray, Ni filter, voltage 40 kV, current 200 mA, scanning angle 2θ =
The initial spacing of the silicate compound, the spacing of the clay composite, and the spacing of the clay composite in the resin composition under the measurement conditions of 0.2 to 16.0 ° and a step angle of 0.02 °. Was measured.

(Ash content) The ash content of the thermoplastic resin composition derived from the clay composite was measured according to JIS K7052.

(HDT) The pelletized thermoplastic resin composition was dried (140 ° C., 5 hours),
Injection molding with a resin temperature of about 280 ° C., a gauge pressure of about 10 MPa, and an injection speed of about 50% using an injection molding machine (TOSHIBA MACHINE Co., Ltd., IS-75E) of about 10 × 100 × 6.
mm test pieces were prepared. The HDT of the obtained test piece is A
Measured according to STMD-648.

(Flexural Modulus) The flexural modulus of a test piece produced in the same manner as in the case of HDT was determined according to ASTM D-790.
Was measured according to

(Surface Appearance of Molded Article) The glossiness and color tone of the test piece prepared in the same manner as in the case of HDT were visually observed and evaluated according to the following criteria.

：: glossy, no unevenness in color tone Δ: devitrified or non-uniform color tone ×: devitrified and non-uniform color tone

Production Example 1 150 g of montmorillonite was added to 6000 g of pure water, and the mixture was stirred and dispersed at 5,000 rpm for 5 minutes using a high-speed stirrer. Thereafter, 15 g of γ- (2-aminoethyl) aminopropyltrimethoxysilane was gradually dropped with a simple pipette, and the mixture was stirred at 5000 rpm for 2 hours,
A slurry of the clay composite was obtained.

The clay composite was confirmed by separating, drying, and pulverizing a solid content from the slurry, having an average layer thickness of 85 °, a bottom surface interval of 38 °, and washing with THF by FT-IR. As a result of the measurement, absorption bands derived from primary amino groups, secondary amino groups and ethylene groups were observed.

The clay composite and slurry obtained in Production Example 1 are referred to as clay composite Ca and slurry Ca, respectively.

Production Example 2 150 g of swellable mica was added to 4000 g of pure water, and the mixture was stirred and dispersed at 5,000 rpm for 5 minutes using a high-speed stirrer. After that, 20 g of γ- (2-aminoethyl) aminopropyltrimethoxysilane was gradually dropped using a simple pipette, and the mixture was stirred at a shear rate of 6000 (1 / s) for 3 hours to obtain a clay composite slurry.

The clay composite was confirmed by separating solids from the slurry, drying and pulverizing to obtain an average layer thickness of 1%.
55 °, the spacing between the bottom surfaces was 28 °, and the product washed with THF was measured by FT-IR.
The measurement was performed by observing absorption bands derived from secondary amino groups and methylene groups.

The clay composite and slurry obtained in Production Example 2 are referred to as clay composite Cb and slurry Cb, respectively.

Production Example 3 150 g of kaolinite was added to 2000 g of pure water, and the mixture was stirred and dispersed at 5,000 rpm for 5 minutes using a high-speed stirrer.
Thereafter, 30 g of γ- (2-aminoethyl) aminopropyltrimethoxysilane was gradually dropped using a simple pipette, and the mixture was stirred at a shear rate of 10,000 (1 / s) for 3 hours to obtain a slurry of a clay composite.

The clay composite was confirmed by separating solids from the slurry, drying and pulverizing to obtain an average layer thickness of 1%.
45 °, the interval between the bottom surfaces was 20 °, and the product washed with THF was measured by FT-IR. As a result, an absorption band derived from a primary amino group, a secondary amino group and a methylene group was observed. .

The clay composite and slurry obtained in Production Example 3 were replaced with clay composite Cc and slurry C, respectively.
-C.

Production Example 4 150 g of montmorillonite was added to 6000 g of pure water, and the mixture was stirred and dispersed at 5,000 rpm for 5 minutes using a high-speed stirrer. After that, ethanol / pH adjusted to 5.0 with hydrochloric acid /
15 g of γ-glycidoxypropyltrimethoxysilane hydrolyzed with a water (9/1 weight ratio) mixed solvent is gradually dropped with a simple pipette, and stirred at a shear rate of 4000 (1 / s) for 3 hours to obtain a clay complex. Was obtained as a slurry.

The clay composite was confirmed by separating solids from the slurry, drying and pulverizing to obtain an average layer thickness of 1%.
The measurement was performed by FT-IR on a sample washed with THF at 20 ° and a bottom surface interval of 39 °. As a result, absorption bands derived from an epoxy ring (ethylene oxide group), an ether group and a methylene group were observed. Was.

The clay composite and slurry obtained in Production Example 4 are referred to as clay composite Cd and slurry Cd, respectively.

Production Example 5 180 g of montmorillonite was added to 7000 g of pure water, and the mixture was stirred and dispersed at 5,000 rpm for 5 minutes using a high-speed stirrer. Thereafter, 20 g of γ-polyoxyethylenepropyltrimethoxysilane hydrolyzed with water adjusted to pH 4.0 with hydrochloric acid was gradually dropped with a simple pipette, and the shear rate was 4
By stirring at 000 (1 / s) for 3 hours, a slurry in which the clay composite was dispersed was obtained.

The clay composite was confirmed by drying and pulverizing the slurry, obtaining an average layer thickness of 100 °, a bottom surface interval of 39 °, and washing with THF to obtain FT-I.
The measurement was carried out by observing absorption bands derived from ether groups and ethylene groups as a result of measurement by R.

The clay composite and slurry obtained in Production Example 5 were replaced with clay composite Ce and slurry C, respectively.
-E.

Production Example 6 γ- (2-aminoethyl) was added to 150 g of montmorillonite.
15 g of aminopropyltrimethoxysilane was sprayed using a spray and mixed for 1 hour.

The silane-treated montmorillonite had an average layer thickness of 49300 ° and a bottom space of 13 °. Also T
The silane-treated montmorillonite after washing with HF is
As a result of measurement by T-IR, absorption bands derived from primary amino groups, secondary amino groups and ethylene groups were observed.

The montmorillonite obtained in Production Example 6 is referred to as silane-treated montmorillonite Cf.

Production Example 7 γ-polyoxyethylenepropyltrimethoxysilane 2 in which methoxy groups were hydrolyzed in 150 g of montmorillonite
0 g was sprayed using a spray and mixed for 1 hour.

The silane-treated montmorillonite had an average layer thickness of 45600 ° and a bottom space of 13 °. The silane-treated montmorillonite washed with THF was measured by FT-IR, and as a result, absorption bands derived from ether groups and ethylene groups were observed.

The montmorillonite obtained in Production Example 7 is referred to as silane-treated montmorillonite Cg.

Examples 1 to 5 The clay composites Ca to Cc, P obtained in Production Examples 1 to 3
ET, PC and ADK STAB PEP36 (phosphorus-based stabilizer manufactured by Asahi Denka Kogyo KK) were dry-blended at the weight ratios shown in Table 1 and rotated using a co-rotating twin-screw extruder having a kneading disk portion. Several hundred rpm, temperature 2
The mixture was melted and mixed at 60 ° C. to produce a thermoplastic resin composition. The ash content of the obtained thermoplastic resin composition, the average layer thickness and bottom spacing of the clay composite dispersed, the high load HD of the test specimen
T, flexural modulus, and surface properties were evaluated. Table 1 shows the results
Shown in

Examples 6 and 7 Production Examples 1 and 4 were carried out in an autoclave equipped with a distillation tube.
Slurry (slurry C-a or slurry C
-D) 6000 g, bishydroxyethyl terephthalate (BHET: manufactured by Nisso Maruzen Chemical Co., Ltd., NISSO)
-BHET), stirred at about 100 ° C. for about 3 hours, and further decompressed while stirring for about 1 hour to remove water to remove B comprising the clay complex and BHET.
A HET slurry (containing a trace amount of water) was prepared.

Next, 2.1 g of a hindered phenol-based stabilizer (AO60, manufactured by Asahi Denka Kogyo KK) and antimony trioxide (Sb ₂ O ₃ : Nippon Seiko Co., Ltd.) as a polymerization catalyst
0.1 g of PATOX-H) was added thereto, and PET was polymerized under reduced pressure (0.5-5.0 torr) at 280 ° C. to obtain a clay composite-containing PET.

The PET containing the clay composite Ca is called a clay composite-containing PET Ca, and the PET containing the clay composite Cd is called a clay composite-containing PET Cd.

Dry blending of 850 g of the obtained clay composite-containing PET Ca or Cd, 1640 g of PC and 7 g of ADK STAB PEP36 was carried out to prepare Examples 1 to 3.
A thermoplastic resin composition was obtained by melt-mixing in the same manner as in Example 5, and evaluated. Table 1 shows the results.

Example 8 180 g of the clay complex Ce obtained in Production Example 5 was dispersed in 7000 g of methylene chloride by stirring at 5000 rpm for 30 minutes. Then, 2100 g of PC was added, stirred and dissolved to obtain a mixed solution. The solvent was removed from the mixed solution by drying to obtain a clay complex-containing PC.

The obtained PC 2280 containing the clay complex
g, 900 g PET and ADK STAB PEP36
9 g was dry blended, melt-mixed in the same manner as in Examples 1 to 5, and evaluated. Table 1 shows the results.

[0125]

[Table 1]

Comparative Example 1 900 g of PET, 2100 g of PC and 969 g of Adekastab PEP 369 were dry-blended, melt-mixed as in Examples 1 to 5, and evaluated. Table 2 shows the results.

Comparative Example 2 A resin composition was evaluated in the same manner as in Example 1 except that the silane-treated montmorillonite Cf obtained in Production Example 6 was used instead of the clay composite C-1. The results are shown in Table 2.

Comparative Example 3 A resin composition was evaluated in the same manner as in Example 6 except that silane-treated montmorillonite Cf was used instead of slurry Ca. Table 2 shows the results.

The PET containing the silane-treated montmorillonite Cf was replaced with the silane-treated montmorillonite-containing PE.
Called TC-f.

Comparative Example 4 Example 8 was repeated except that the silane-treated montmorillonite Cg obtained in Production Example 7 was used instead of the clay composite Ce.
A resin composite was produced and evaluated in the same manner as in the above. Table 2 shows the results.

Comparative Example 5 900 g PET, 2100 g PC, milled fiber (EFH7531, manufactured by Central Glass Co., Ltd.) 18
0 g and Adekastab PEP369 g were dry-blended, melt-mixed as in Example 1, and evaluated. Table 2 shows the results.

Comparative Example 6 900 g of PET, 2100 g of PC, talc (Micro Ace K-1 manufactured by Nippon talc Co., Ltd., bottom space 9 °) 1
80 g and Adekastab PEP369 g were dry-blended, melt-mixed as in Example 1, and evaluated. Table 2 shows the results.

Comparative Example 7 900 g of PET, 2100 g of PC, sodium pt-butyl benzoate (carboxylate crystal nucleating agent) 9
g and Adekastab PEP369 g were dry-blended and melt-mixed in the same manner as in Example 1. However, because of foaming, the properties could not be evaluated.

[0134]

[Table 2]

[0135]

As described above, the silicate compound (C1) in which the unit layer remains agglomerated is converted into a silane coupling agent (C).
It is difficult to improve the mechanical properties and heat resistance even using the material treated in 2). In addition, it is difficult to balance physical properties and surface appearance of a molded article even when a fibrous reinforcing agent or an inorganic nucleating agent is added. Can not.

In contrast, in the case of the thermoplastic resin composition of the present invention, the distance between the bottom surfaces of the silicate compound (C1) was increased in a dispersion medium, and then the silane coupling agent (C2) was added. By finely dispersing the obtained clay composite (C) in a resin, a molded article having excellent mechanical properties, heat resistance and surface appearance of the molded article is provided.

Claims (6)

[Claims] 1. A thermoplastic resin composition comprising a thermoplastic polyester resin (A), a polycarbonate resin (B) and a clay composite (C), wherein the clay composite (C) comprises:
The silicate compound (C1) has a general formula (I): Y _n SiX _4-n (I) (wherein, n is an integer of 0 to 3, and Y is a carbon atom of 1 to 5 which may have a substituent. 25 is a hydrocarbon group, X is a hydrolyzable group or a hydroxyl group, and when n or 4-n is 2 or more,
n Y or 4-n X may be the same or different, respectively.)
Wherein the clay composite (C) is dispersed in the thermoplastic resin composition at an average layer thickness of 500 ° or less. 2. A thermoplastic resin composition comprising a thermoplastic polyester resin (A), a polycarbonate resin (B) and a clay composite (C), wherein the clay composite (C) comprises:
The silicate compound (C1) has a general formula (I): Y _n SiX _4-n (I) (wherein, n is an integer of 0 to 3, and Y is a carbon atom of 1 to 5 which may have a substituent. 25 is a hydrocarbon group, X is a hydrolyzable group or a hydroxyl group, and when n or 4-n is 2 or more,
n Y or 4-n X may be the same or different, respectively.)
And the bottom surface interval of the clay composite (C) dispersed in the thermoplastic resin composition is at least three times the initial bottom surface interval of the silicate compound (C1). Thermoplastic resin composition. 3. A clay composite (C) obtained by adding a silane coupling agent (C2) after increasing a bottom surface interval of a silicate compound (C1) in a dispersion medium. Yes, the introduced silane coupling agent (C
3. The thermoplastic resin composition according to claim 1, wherein the distance between the bottom surfaces of the clay composite (C) is larger than the initial distance between the bottom surfaces of the silicate compound (C1). 4. The thermoplastic material according to claim 1, wherein the silicate compound (C1) is at least one selected from the group consisting of smectite group clay minerals, swellable mica, and kaolin group clay minerals. Resin composition. 5. The thermoplastic polyester resin (A) is 1 to
99% by weight, and 99% by weight of the polycarbonate resin (B).
The thermoplastic resin composition according to claim 1, 2, 3 or 4, wherein the total amount is 100% by weight. 6. The thermoplastic resin composition according to claim 1, wherein the ash content of the thermoplastic resin composition derived from the clay composite (C) is 0.1 to 50% by weight. .