Thermoplastic resin composition containing silan-treated foliated phyllosilicate and method for producing the same

The present invention provides a thermoplastic resin composition containing a thermoplastic resin and a silane-treated foliated phyllosilicate, the silane-treated foliated phyllosilicate being prepared by introducing a predetermined organosilane compound into a swellable layered silicate. According to the present invention, the silane-treated foliated phyllosilicate is prepared by introducing the organosilane compound into the swellable layered silicate after the basal spacing of the swellable layered silicate has been expanded, and is exfoliated as a number of fine layers dispersed uniformly in the thermoplastic resin composition of the present invention independently from one another. Thus, the present invention provides a thermoplastic resin composition excellent in mechanical properties, heat resistance, and the surface appearance of the resultant molded product.

TECHNICAL FIELD
 The present invention relates to a thermoplastic resin composition
 containing a thermoplastic resin and a silane-treated foliated
 phyllosilicate, and a method for producing the same.
 BACKGROUND ART
 In order to improved the mechanical properties, the heat resistance, and
 the like of a thermoplastic resin, a layered clay mineral such as talk and
 mica have been conventionally used as a filler (see Japanese Publication
 for Opposition No. 49-18615, Japanese Laid-Open Publication No. 55-16049,
 and Japanese Publication for Opposition No. 63-53222, for example). By
 adding a large amount of such layered clay mineral to a thermoplastic
 resin, the elastic modulus and the heat resistance of the resultant resin
 composition improves. However, a molded product obtained from the resin
 composition has the disadvantages of poor appearance, increased specific
 gravity, and poor color tone. Moreover, the strength, the tenacity, and
 the like of the resin composition are reduced due to insufficient
 dispersion of the layered clay mineral or insufficient adhesion between
 the layered clay mineral and the resin.
 A surface treatment agent has generally been used for improving the
 adhesion between a filler and a resin to prevent the reduction of
 strength, impact strength, and the like of a resin composition. For
 example, a composite of a layered clay mineral treated with a silane
 coupling agent and a polyester resin is disclosed (see Japanese Laid-Open
 Publication No. 51-24653 and Japanese Laid-Open Publication No. 51-24654,
 for example). However, the conventional surface treatment method has not
 yet provided a sufficient effect of improving the strength and the like of
 the resin composition. Further, even if the surface of the layered clay
 was treated, the layered clay mineral itself still has an aggregate
 structure. Therefore, the problems of poor appearance, increase in the
 specific gravity, and poor color tone of the resultant molded product
 remained unsolved.
 The layered clay mineral normally has an aggregate structure where about a
 hundred to several thousands of unit layers each having a thickness of
 about 1 nm are stratified. Therefore, in the above prior art technique,
 the layered clay mineral dispersed in the thermoplastic resin exists, not
 as foliated layers, but in the state of the aggregate structure.
 If such an aggregate structure of the layered clay mineral could be
 exfoliated to allow unit layers to be dispersed separately in the
 thermoplastic resin, the resultant resin would be strengthened by the
 addition of only a small amount of the layered clay mineral , and the
 problems of the poor appearance, the increase in the specific gravity, and
 the poor color tone of the resultant molded product would be overcome.
 However, no technique that can exfoliated the layered clay mineral to the
 state of foliated unit layers to disperse the unit layers in the
 thermoplastic resin uniformly by use of a silane-coupling agent so as to
 obtain a resin composition having excellent properties has yet been
 provided.
 DISCLOSURE OF THE INVENTION
 The object of the present invention is to intend to solve the
 above-described conventional problems and provide a thermoplastic resin
 composition excellent in mechanical properties (elastic modulus, strength,
 impact strength, and the like), heat resistance, and appearance of a
 molded product by exfoliating an aggregate structure of a layered clay
 mineral to disperse the layered clay mineral as a number of separate thin
 layers each having a size of the order of nanometers independently.
 As a result of intense examination for attaining the above object, the
 inventors of the present invention have completed the present invention.
 The thermoplastic resin composition of the present invention contains a
 thermoplastic resin (A) and a silane-treated foliated phyllosilicate (B),
 wherein the silane-treated foliated phyllosilicate (B) is prepared by
 introducing a organosilane compound (B2) represented by general formula
 (I):
EQU Y.sub.n SiX.sub.4-n (I)
 wherein n denotes an integer of 0 to 3, Y denotes independently a
 substituted or non-substituted hydrocarbon group having 1 to 25 carbon(s),
 and X denotes independently a hydrolyzable group or a hydroxyl group, into
 a swellable layered silicate (B1), and a value [R.sub.B300 ] is 20% or
 more when the value [R.sub.B300 ] is defined as a rate of layers of the
 silane-treated foliated phyllosilicate (B) of which equivalent area circle
 diameter [D] is 300 nm or less.
 In one embodiment, the thermoplastic resin (A) is at least one type
 selected from the group consisting of a thermoplastic polyester resin and
 a polycarbonate resin.
 In another embodiment, the swellable layered silicate (B1) is at least one
 type selected from the group consisting of smectite clay and swellable
 mica.
 In still another embodiment, the silane-treated foliated phyllosilicate (B)
 is prepared by introducing the organosilane compound (B2) after the basal
 spacing of the swellable layered silicate (B1) has been expanded.
 In still another embodiment, the content of the silane-treated foliated
 phyllosilicate (B) is 0.1 to 100 parts by weight with respect to 100 parts
 by weight of the thermoplastic resin (A).
 In still another embodiment. the ash content originated from the
 silane-treated foliated phyllosilicate (B) is 0.1 to 50% by weight.
 In a preferred embodiment, the value [R.sub.B300 ] is 500 nm or less when
 the [D.sub.B ] is defined as an average value of the equivalent area
 circle diameters of the silane-treated foliated phyllosilicate (B).
 In still another embodiment, a value [D.sub.B ]/[D.sub.B1 ] is 0.010 or
 less when the value [D.sub.B ] is defined as an average value of the
 equivalent area circle diameters of the silane-treated foliated
 phyllosilicate (B) and the value [D.sub.B1 ] is defined as an average
 value of the equivalent area circle diameters of the swellable layered
 silicate (B1).
 In still another embodiment, a value [N.sub.B ]/[N.sub.B1 ] is 300 or more
 when the value [N.sub.B ] is defined as the number of foliated layers of
 the silane-treated foliated phyllosilicate (B) per unit ash content and
 per unit area, and the value of [N.sub.B1 ] is defined as the number of
 the swellable layered silicate (B1) per unit ash content and per unit
 area.
 In still another embodiment, an average thickness of the foliated layers of
 the silane-treated foliated phyllosilicate (B) dispersed in the
 thermoplastic resin composition is 20 nm or less.
 In still another embodiment, 20% or more of layers of the silane-treated
 foliated phyllosilicate (B) dispersed in the thermoplastic resin
 composition have a layer thickness of 5 nm or less.
 In still another embodiment, a value [I.sub.B ]/[I.sub.B ] is 0.25 or less
 when the value [I.sub.B ] is defined as a diffraction intensity of the
 small angle X-ray diffraction originated from the silane-treated foliated
 phyllosilicate (B), and the value [I.sub.B ] is defined as a diffraction
 intensity of small angle X-ray diffraction originated from an aggregate
 structure of the swellable layered silicate (B1).
 In still another embodiment, the basal spacing of the silane-treated
 foliated phyllosilicate (B) in the thermoplastic resin composition is
 three times or more as large as an initial basal spacing of the swellable
 layered silicate (B1).
 According to another aspect of the present invention, the thermoplastic
 resin composition of the present invention contains a thermoplastic resin
 (A) and a silane-treated foliated phyllosilicate (B), wherein the
 silane-treated foliated phyllosilicate (B) is prepared by introducing a
 organosilane compound (B2) represented by general formula (I);
EQU Y.sub.n SiX.sub.4-n (I)
 wherein n denotes an integer of 0 to 3, Y denotes independently a
 substituted or non-substituted hydrocarbon group having 1 to 25 carbon(s),
 and X denotes independently a hydrolyzable group or a hydroxyl group, into
 a swellable layered silicate (B1) after the basal spacing of the swellable
 layered silicate (B1) has been expanded.
 According to still another aspect of the present invention, the
 thermoplastic resin composition of the present invention contains a
 thermoplastic resin (A) and a silane-treated foliated phyllosilicate (B),
 wherein the silane-treated foliated phyllosilicate (B) is prepared by
 introducing a organosilane compound (B2) represented by the above general
 formula (I) into a swellable layered silicate (B1), and an average
 thickness of the foliated layers of the silane-treated foliated
 phyllosilicate (B) dispersed in the thermoplastic resin composition is 20
 nm or less.
 According to still another aspect of the present invention, the
 thermoplastic resin composition of the present invention contains a
 thermoplastic resin (A) and a silane-treated foliated phyllosilicate (B),
 wherein the silane-treated foliated phyllosilicate (B) is prepared by
 introducing a organosilane compound (B2) represented by the above general
 formula (I) into a swellable layered silicate (B1), and 20% or more of
 layers of the silane-treated foliated phyllosilicate (B) dispersed in the
 thermoplastic resin composition has a layer thickness of 5 nm or less.
 According to still another aspect of the present invention, the
 thermoplastic resin composition of the present invention contains a
 thermoplastic resin (A) and a silane-treated foliated phyllosilicate (B),
 wherein the silane-treated foliated phyllosilicate (B) is prepared by
 introducing a organosilane compound (B2) represented by the above general
 formula (I) into a swellable layered silicate (B1), and a value [I.sub.B
 ]/[I.sub.B1 ] is 0.25 or less when the value [I.sub.B ] is defined as a
 diffraction intensity of small angle X-ray diffraction originated from the
 silane-treated foliated phyllosilicate (B), and the value [I.sub.B1 ] is
 defined as a diffraction intensity of small angle X-ray diffraction
 originated from an aggregate structure of the swellable layered silicate
 (B1).
 According to still another aspect of the present invention, the
 thermoplastic resin composition of the present invention contains a
 thermoplastic resin (A) and a silane-treated foliated phyllosilicate (B),
 wherein the silane-treated foliated phyllosilicate (B) is prepared by
 introducing a organosilane compound (B2) represented by the above general
 formula (I) into a swellable layered silicate (B1), and the basal spacing
 of the silane-treated foliated phyllosilicate (B) in the thermoplastic
 resin composition is three times or more as large as an initial basal
 spacing of the swellable layered silicate (B1).
 The method for producing a thermoplastic resin composition containing a
 thermoplastic resin (A) and a silane-treated foliated phyllosilicate (B)
 of the present invention includes the steps of: expanding the basal
 spacing of the swellable layered silicate (B1); and introducing a
 organosilane compound (B2) represented by the general formula (I):
EQU Y.sub.n SiX.sub.4-n (I)
 wherein n denotes an integer of 0 to 3, Y denotes independently a
 substituted or non-substituted hydrocarbon group having 1 to 25 carbon(s),
 and X denotes independently a hydrolyzable group or a hydroxyl group, into
 the swellable layered silicate (B1) of which basal spacing has been
 expanded, to prepare the silane-treated foliated phyllosilicate (B).
 In one embodiment, the method for producing a thermoplastic resin
 composition of the present invention further includes the steps of: mixing
 the silane-treated foliated phyllosilicate (B) with a monomer to obtain a
 mixture; and polymerizing the monomer in the mixture to obtain the
 thermoplastic resin (A).

BEST MODE FOR CARRYING OUT THE INVENTION
 The thermoplastic resin (A) used in the present invention can be any
 arbitrary thermoplastic resin. Examples of such a thermoplastic resin (A)
 include arbitrary thermoplastic resins such as thermoplastic polyester
 resins, polycarbonate resins, polyamide resins, polyolefin resins,
 polyarylate resins, vinyl polymer compounds, polyimide resins,
 polyphenylene sulfides, polyphenylene oxides, polyacetal, polysulfone,
 polyether sulfones, fluororesins, and polyolefin copolymers. The
 thermoplastic resin may be an elastomer or a rubber. One type or
 combinations of two or more types among these thermoplastic resins may be
 used. Thermoplastic polyester resins, polycarbonate resins, polyamide
 resins, and polyolefin resins are preferable. Thermoplastic polyester
 resins and polycarbonate resins are especially preferable.
 The thermoplastic polyester resin is not specifically limited, but may be
 any arbitrary polyester resin prepared from, but not limited to, a
 dicarboxylic acid compound and/or an esterificationable derivative of
 dicarboxylic acid, and a diol compound and/or an esterificationable
 derivative of a diol compound. Specific examples of such a polyester resin
 include polyethylene terephthalate, polypropylene terephthalate,
 polybutylene terephthalate, polyhexamethylene terephthalate,
 polycyclohexane-1,4-dimethyl terephthalate, neopentyl terephthalate,
 polyethylene isophthalate, polyethylene naphthalate, polybutylene
 naphthalate, polyhexamethylene naphthalate, and copolymer polyesters
 thereof. These resins may be used individually or in combinations of two
 or more types.
 The polycarbonate resin is not specifically limited, but may be any
 arbitrary polycarbonate resin obtained by the reaction between a bivalent
 phenol compound and phosgene or between a bivalent phenol compound and a
 carbonic acid diester compound. Specific examples of such a polycarbonate
 resin include 2,2-bis-(4-hydroxyphenyl)propane type polycarbonate,
 2,2-bis-(3,5-dimetyl-4-hydroxyphenyl)propane type polycarbonate,
 1,1-bis(4-hydroxyphenyl)cyclohexane type polycarbonate,
 4,4'-dihydroxyphenyl ether type polycarbonate, 4,4'-dihydroxydiphenyl
 sulfide type polycarbonate, 4,4'-dihydroxydiphenyl sulfone type
 polycarbonate, bis(4-hydroxyphenyl)ketone type polycarbonate, and
 1,4-bis(4-hydroxyphenylsulfonyl)benzene. These resins may be used
 individually or in combinations of two or more types.
 The polyamide resin is not specifically limited, but may be any arbitrary
 polyamide resin. Specific examples of the polyamide resin included
 polycaproamide (Nylon 6), polytetramethylene adipamide (Nylon 46),
 polyhexaethylene adipamids (Nylon 66), polyhexamethylene sebacamide (Nylon
 610), polyhexamethylene dodecamide (Nylon 612), polyundecamethylene
 adipamide (Nylon 116), polyundecamide (Nylon 11), polydodecamide (Nylon
 12), polytrimethlhexamethylene terephthalamide (TMHT), polyhexamethylene
 terephthalamide (Nylon 6T), polyhexamethylene isophthalamide (Nylon 6I),
 polybis (4-aminocyclohexyl)methanedodecamide (Nylon dimethyl M12),
 polymethaxylylene adipamide (Nylon MXD6), polyundecamethylene
 hexahydroterephthalamide (Nylon 11TH), and copolymers thereof. These
 resins may be used individually or in combinations of two or more types.
 The polyolefin resin is not specifically limited, but may be any arbitrary
 polyolefin. Examples of the polyolefin include homopolymers of
 .alpha.-olefins including ethylene, a copolymer of two or more types of
 .alpha.-olefin (which includes any of a random copolymer, a block
 copolymer, a graft copolymer, and the like, and may be a mixture thereof),
 and olefin elastomers. Examples of the ethylene homopolymer includes
 low-density polyethylene (LDPE), high-density polyethylene (HDPE), and
 linear low-density polyethylene (LLDPE). Examples of polypropylene include
 not only a polypropylene homopolymer but also a copolymer of propylene and
 ethylene. The polyethylene and the polypropylene may include olefin
 elastomers. The olefin elastomer refers to a copolymer of ethylene and at
 least one type of .alpha.-olefin other than ethylene (e.g., propylene,
 1-butene, 1-hexene, and 4-methyl-1-pentene). Specific examples of the
 olefin elastomer include ethylene-propylene copolymers (EPR),
 ethylene-butene copolymers (EBR), and ethylene-propylene-diene copolymers
 (EPDM). These copolymers may be used individually or in combination of two
 or more types.
 The molecular weight of the thermoplastic resin (A) used in the present
 invention is selected in consideration of the molding flowability of the
 resin in the molding process and the properties of the final products.
 Excessively large and small molecular weights are not preferable. An
 optimal molecular weight is mainly determined based on the primary
 structure of the thermoplastic resin (A). Accordingly, a molecular weight
 suitable for each type of thermoplastic resin (A) should be set.
 The molecular weight of a thermoplastic polyester resin which can be
 suitably used in the present invention is set so that the logarithmic
 viscosity is 0.3 to 2.0 (dl/g), preferably 0.35 to 1.0 (dl/g), more
 preferably 0.4 to 1.8 (dl/g), as measured using a mixed solvent of
 phenol/tetrachloroethane (weight ratio: 5/5) at 25.degree. C. If the
 logarithmic viscosity is less than 0.3 (dl/g), the molded product of the
 resultant thermoplastic resin composition (C) tends to have low mechanical
 properties and impact resistance. If it exceeds 2.0 (dl/g), the
 processability such as the flowability in the molding process tends to be
 reduced.
 The molecular weight of a polycarbonate resin which can be suitably used in
 the present invention is set so that the weight average molecular weight
 (Mw) is 15000 to 80000, preferably 25000 to 75000, more preferably 30000
 to 70000, in terms of monodisperse polystyrene, as measured by gel
 permeation chromatography (GPC) using a tetrahydrofuran (THF) solvent at
 40.degree. C. If Mw is less than 15000, the molded product of the
 resultant thermoplastic resin composition (C) tends to have low mechanical
 properties and impact resistance. If it exceeds 80000, the processability
 such as the flowability in the molding process tends to be reduced.
 The molecular weight of a polyamide resin which can be suitably used in the
 present invention is desirably set so that the relative viscosity of 1.0%
 polyamide resin is 1.5 to 5.0 as measured using a 98% concentrated
 sulfuric acid at 25.degree. C. If the relative viscosity is less than 1.5,
 the molded product of the resultant thermoplastic resin composition (C)
 tends to have low mechanical properties and impact resistance. If it
 exceeds 5.0, the processability such as the flowability in the molding
 process tends to be reduced.
 Among said polyolefin resins, the molecular weight of polypropylene is
 desirably set so that the melt index is preferably 0.3 to 30 g/10 minutes,
 more preferably 0.5 to 15 g/10 minutes, as measured under a load of 2.16
 Kg at 230.degree. C., for example. If the melt index exceeds 30 g/10
 minutes, the processability such as the flowability in the molding process
 tends to be reduced.
 Silane-Treated Foliated Phyllosilicate (B)
 The silane-treated foliated phyllosilicate (B) used in the present
 invention refers to those prepared by introducing a organosilane compound
 (B2) represented by general formula (I):
EQU Y.sub.n SiX.sub.4-n (I)
 wherein n denotes an integer of 0 to 3, Y denotes independently a
 substituted or non-substituted hydrocarbon group having 1 to 25 carbon(s),
 and X denotes independently a hydrolyzable group or a hydroxyl group, into
 a swellable layered silicate (B1).
 Swellable Layered Silicate (B1)
 The swellable layered silicate (B1) may be any arbitrary swellable layered
 silicate normally used. Preferably, a silicate formed of a tetrahedral
 crystalline sheet mainly made of silicon oxide and an octahedral
 crystalline sheet mainly made of metal hydroxide are used. Examples of the
 swellable layered silicate include smectite clay and swellable mica.
 The smectite clay is a natural or synthetic mineral represented by the
 general formula:
EQU X.sub.0.2-0.6 Y.sub.2-3 Z.sub.4 O.sub.10 (OH).sub.2.nH.sub.2 O
 wherein X denotes at least one type selected from the group consisting of
 K, Na, 1/2Ca, and 1/2Mg, Y denotes at least one type selected from the
 group consisting of Mg, Fe, Mn, Ni, Zn, Li, Al, and Cr, and Z denotes at
 least one type selected from the group consisting of Si and Al, H.sub.2 O
 represents a water molecule which binds with an intercalated ion, and n
 markedly varies depending on the intercalated ion and the relative
 humidity. Specific examples of the smectite clay include montmorillonite,
 beidellite, nontronite, saponite, iron saponite, hectorite, sauconite,
 stevensite, bentonite, substituents or derivatives thereof, and mixtures
 thereof.
 The swellable mica is a natural or synthetic mineral represented by the
 general formula:
EQU X.sub.0.5-1.0 Y.sub.2-3 Z.sub.4 O.sub.10 (F, OH).sub.2
 wherein X denotes at least one type selected from the group consisting of
 Li, Na, K, Rb, Ca, Ba, and Sr, Y denotes at least one type selected from
 the group consisting of Mg, Fe, Ni, Mn, Al, and Li, Z denotes at least one
 type selected from the group consisting of Si, Ge, Al, Fe, and B. The
 swellable mica has the nature of swelling in water, a polar solvent
 soluble with water at an arbitrary ratio, or a mixed solvent of water and
 a polar solvent. Examples of the swellable mica include lithium type
 teniolite, sodium type teniolite, lithium type tetrasilicon mica, and
 sodium type tetrasilicon mica, substituents and derivatives thereof, and
 mixtures thereof.
 Vermiculites may also be used as the swellable mica. The vermiculites have
 two types: a 3-octahedron type and 2-octahedron type, and is represented
 by the general formula:
EQU (Mg, Fe, Al).sub.2-3 (Si.sub.4-x Al.sub.z)O.sub.10 (OH).sub.2.(M.sup.+,
 M.sup.2+1.sub.1/2).sub.x nH.sub.2 O
 where M denotes an exchangeable cation of an alkaline metal or alkaline
 earth metal such as Na and Mg, x denotes 0.6 to 0.9, and n denotes 3.5 to
 5.
 The swellable layered silicate (B1) is used individually or in combinations
 of two or more types. The crystal structure of the swellable layered
 silicate (B1) is desirably a structure with a high purity where layers are
 stratified regularly in the c-axis direction. However, a so-called mixed
 layer mineral where the crystal cycle is disturbed to allow a plurality of
 types of crystal structures to be mixed may also be used.
 Organosilane Compound (B2)
 the organosilane compound (B2) to be introduced into the swellable layered
 silicate (B1) may be any arbitrary organosilane compound preferably
 represented by general formula (I):
EQU Y.sub.n SiX.sub.4-n (I)
 wherein n denotes an integer of 0 to 3; Y is independently a substituted or
 non-substituted hydrocarbon group having 1 to 25 carbon(s), the
 substituent being at least one type selected from the group consisting of
 an ester group, and ether group, and epoxy group, an amino group, a
 carboxyl group, a carbonyl group, an amide group, a mercapto group, a
 sulfonyl group, sulfinyl group, a nitro group, a nitroso group, a nitrile
 group, a halogen atom, and a hydroxyl group; and X is independently a
 hydrolyzable group or a hydroxyl group, the hydrolyzable group being at
 least one type selected from the group consisting of an alkoxyl group,
 alkenyloxy group, a ketoxime group, an acyloxy group, an amino group, an
 aminoxy group, an amido group, and a halogen atom. The n Y's and 4-n X's
 may be respectively the same type or different types.
 The hydrocarbon group as used herein includes a linear or branched (i.e.,
 having a side chain), saturated or unsaturated, univalent or multivalent
 aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an
 alicyclic hydrocarbon group. Examples of the hydrocarbon group include an
 alkyl group, an alkenyl group, an alkinyl group, an aryl group (a phenyl
 group, a naphthyl group, etc.), and a cycloalkyl group.
 The "alkyl group" as used herein is intended to include a multivalent
 hydrocarbon group such as an "alkylene" group unless otherwise specified.
 Likewise, the alkenyl group, the alkynyl group, the aryl group (the phenyl
 group, the naphthyl group, etc.), and the cycloalkyl group, an arylene
 group (a phenylene group, a naphthylene group, etc,), and a cycloalkylene
 group, respectively.
 In general formula (I) above, examples of the compound where Y is a
 non-substituted hydrocarbon group having 1 to 25 carbons such as
 decyltrimethoxy silane; a compound where Y is a lower alkyl group having 1
 to 9 carbon(s) such as methyltrimethoxy silane; a compound where Y is an
 unsaturated hydrocarbon group such as 2-hexenyltrimethoxy silane; a
 compound where Y has a side chain such as 2-ethylhexyltrimethoxy silane; a
 compound where Y includes a phenyl group such as phenyltriethoxy silane; a
 compound where Y includes a naphthyl group such as
 3-.beta.-naphtylpropyltrimethoxy silane; and a compound where Y includes
 an arylalkyl group such as p-vinylhbenzltrimethoxy silane. In general
 formula (I) above, examples of a compound where Y is especially a vinyl
 group among the unsaturated hydrocarbon groups include vinyltrimethoxy
 silane, vinyltrichloro silane, and vinyltriacetoxy silane.
 In general formula (I) above, an example of a compound where Y is a group
 having an ester group having an ether group as a substituent include
 .gamma.-polyoxyethylenepropyltrimethoxy silane and 2-ethoxyethyltrimethoxy
 silane. An example of a compound where Y is a group having an epoxy group
 as a substituent includes .gamma.-glycidoxypropyltrimethoxy silane.
 Examples of a compound where Y is a group having an amino group as a
 substituent include .gamma.-aminopropyltrimethoxy silane,
 .gamma.-2-aminoethyl)aminopropyltrimethoxy silane, and
 .gamma.-anilinopropyltrimethoxy silane (NH.sub.2 C.sub.6 H.sub.4
 (CH.sub.2).sub.3 Si(OCH.sub.3).sub.3). An example of a compound where Y is
 a group having a carboxyl group as a substituent includes
 .gamma.-4-carboxyphenyl)propyltrimethoxy silane. An example of a compound
 where Y is a group having a carbonyl group as a substituent includes
 .gamma.-ureidopropyltriethoxy silane (H.sub.2 NCONH(CH.sub.2).sub.3
 Si(OC.sub.2 H.sub.5).sub.3). An example of a compound where Y includes an
 amido group as a substituent includes an acetylated compound from among
 the above-mentioned compound having an amino group. An example of a
 compound where Y is a group having a mercapto group as a substituent
 includes .gamma.-mercaptopropyltrimethoxy silane. An example of a compound
 where Y is a group having a sulfonyl group as a substituent includes
 .gamma.-phenylsulfonylpropyltrimethoxy silane. An example of a compound
 where Y is a group having a sulfinyl group as a substituent includes
 .gamma.-phenylsulfinylpropyltrimethoxy silane. An example of a compound
 where Y is a group having a nitro group as a substituent includes
 .gamma.-nitropropyltriethoxy silane. An example of a compound where Y is a
 group having a nitroso group as a substituent includes
 .gamma.-nitrosopropyltriethoxy silane. Examples of a compound where Y is a
 group having a nitryl group as a substituent include
 .gamma.-cyanoethyltriethoxy silane and .gamma.-cyanopropyltriethoxy
 silane. An example of a compound where Y is a group having a halogen as a
 substituent includes .gamma.-chloropropyltriethoxy silane. An example of a
 compound where Y is a group having a hydroxyl group as a substituent
 includes N,N-di(2-hydroxyethyl)amino-3-propyltriethoxy silane.
 In general formula (I) above, when X is a hydroxyl group, the hydroxyl
 group is in the form of a silanol group (SiOH). An example of the
 organosilane compound (B2) having a silanol group includes an oligomer of
 dimethylhydroxy silane represented by the formula below. In view of the
 reactivity with the swellable layered silicate (B1) and the convenience in
 handling of the organosilane compound (B2) itself, m is preferably an
 integer of 2 to 30.
 ##STR1##
 A substitution product or derivative of the organosilane compound (B2) may
 also be used. These organosilane compounds (B2) may be used individually
 or in combinations of two or more types.
 Preparation of Silane-Treated Foliated Phyllosilicate (B)
 The silane-treated foliated phyllosilicate (B) can be obtained by
 introducing the organosilane compound (B2) into the swellable layered
 silicate (B1) after the basal spacing of the swellable layered silicate
 (B1) is expanded.
 The basal spacing as used herein refers to a interlayer distance between
 adjacent unit layers of the swellable layered silicate or the resultant
 silane-treated foliated phyllosilicate. Actually, the basal spacing can be
 confirmed by a small angle X-ray diffraction (SAXS) method and the like.
 More specifically, the peak angle value of the X-ray diffraction performed
 for a dispersion composed of a dispersion medium and the swellable layered
 silicate (B1) (or for the swellable layered silicate in the aggregate
 state before being added to the dispersion medium) is measured by SAXS,
 and the basal spacing is calculated by using the resultant peak angle
 value and Bragg equation:
EQU 2d sin .theta.=n.lambda.
 wherein d denotes the basal spacing in a crystal, .theta. denotes an
 incident angle, n denotes a positive integer, and .lambda. denotes the
 wavelength of the X ray.
 The step of expanding the basal spacing of the swellable layered silicate
 (B1) is performed by dispersing the swellable layered silicate (B1) in the
 dispersion medium or by applying an external physical force to the
 swellable layered silicate (B1).
 In the case where the dispersion medium is used, water, a polar solvent
 soluble with water at any arbitrary ratio, or a mixed solvent of water and
 the polar solvent may be used as the dispersion medium. Examples of the
 polar solvent include: alcohols such as methanol, ethanol, and
 isopropanol; glycols such as ethylene glycol, propylene glycol, and
 1,4-butanediol; ketones such as acetone and methylethyl ketone; ethers
 such as diethylether and tetrahydrofuran; amido compounds such as
 dimethylformamide; and other solvents such as dimethylsulfoxide and
 2-pyrrolidone. These polar solvents may be used individually or in
 combinations of two or more types.
 The expansion of the basal spacing of the swellable layered silicate (B1)
 in the dispersion medium may be achieved by dispersing the swellable
 layered silicate (B1) in the dispersion medium through sufficient
 agitation. In order to efficiently expand the basal spacing of the
 swellable layered silicate, the mixture of the swellable layered silicate
 and the dispersion medium is preferably agitated at several thousand
 revolutions per minute.
 In the case where an external physical force is applied to the swellable
 layered silicate (B1) to exfoliate unit layers from adjacent unit layers,
 the external physical force may be applied by a general filler wet
 pulverization method. An example of the general filler wet pulverization
 method includes a method where hard particles are utilized. According to
 this method, hard particles, the swellable layered silicate (B1), and any
 arbitrary solvent are mixed and agitated to allow the hard particles and
 the swellable layered silicate (B1) to physically collide with each other
 and thus to separate unit layers of the swellable layered silicate (B1)
 from one another. The hard particles normally used are beads for filler
 pulverization. Examples of such beads include glass beads and zirconia
 beads. These beads for pulverization are not limited to glass and
 zirconia, but may be selected in consideration of the hardness of the
 swellable layered silicate (B1) or the material of the agitator. The
 particle size of the beads is preferably in the range of 0.1 to 6.0 mm
 dia. although it is not numerically limited since it is determined in
 consideration of the size of the swellable layered silicate (B1) and the
 like. The solvent used in this step is not specifically limited, but is
 preferably of a similar type to the dispersion medium described above.
 The basal spacing between adjacent layers of the swellable layered silicate
 (B1) after the expansion is preferably three times or more, more
 preferably five times or more, as large as the initial basal spacing of
 the swellable layered silicate (B1). An upper limit is not especially set.
 However, if the basal spacing is expanded by about ten times or more, the
 measurement of the basal spacing becomes difficult. The layers of the
 swellable layered silicate (B1) having such a basal spacing are
 substantially recognized as existing as unit layers. The initial basal
 spacing of the swellable layered silicate as used herein refers to the
 basal spacing of the swellable layered silicate before being added to the
 dispersion medium where unit layers are stratified on one another in the
 aggregate state.
 After the basal spacing of the swellable layered silicate (B1) has been
 expanded as described above, i.e., the unit layers in the aggregate state
 have been exfoliated to separate from one another so that they exist
 independently, the organosilane compound (B2) is introduced to the
 surfaces of the unit layers of the foliated swellable layered silicate
 (B1), so as to obtain the silane-treated foliated phyllosilicate (B).
 In the case of suing the dispersion medium the introduction of the
 organosilane compound is performed by adding the organosilane compound
 (B2) to the dispersion containing the swellable layered silicate (B1)
 having an expanded basal spacing and the dispersion medium and agitating
 the dispersion. When an efficient introduction of the organosilane
 compound (B2) is desired, the revolution of the agitation is preferably
 set at 1000 rpm or more, or the shear rate is preferably set at 500 (l/s)
 or more. Since the agitation at a revolution exceeding 25000 rpm or the
 shear rate of 500000 (l/s) or more is likely to provide no further
 improved effect, such excessive number of revolutions or shear rate is not
 required. In the case of applying an external physical force, the
 organosilane compound (B2) can be introduced by adding the organosilane
 compound (B2) to the swellable layered silicate (B1) while the swellable
 layered silicate is being applied with an external physical force (e.g.,
 it is being wet-pulverized). Alternatively, the organosilane compound (B2)
 may be introduced in the following manner: The swellable layered silicate
 (B1) of which basal spacing has been expanded due to an external physical
 force is added to the dispersion medium, and the organosilane compound
 (B2) is added to the resultant dispersion as in the case of using the
 dispersion medium described above.
 The introduction of the organosilane compound (B2) to the swellable layered
 silicate (B1) is realized by the reaction between the hydroxyl group on
 the surface of the swellable layered silicate (B1) and the hydrolyzable
 group or the hydroxyl group (X in formula (II) of the organosilane
 compound (B2). Although the reaction between the swellable layered
 silicate (B1) and the organosilane compound (B2) can proceed at room
 temperature satisfactorily, the reaction system may be heated as required.
 The maximum temperature for this heating may be set at any arbitrary
 temperature of less than the decomposition temperature of the organosilane
 compound (B2) used and less than the boiling point of the dispersion
 medium.
 when the organosilane compound (B2) introduced into the swellable layered
 silicate (B1) additionally includes a reactive functional group (a
 substituent of Y in formula (I)) such as an hydroxyl group, a carboxyl
 group, an amino group, an epoxy group, or a vinyl group, a compound which
 can react with such a reactive group may be further added to allow the
 compound to react with the reactive group. In this way, the length of a
 functional group chain of the organosilane compound (B2) introduced into
 the swellable layered silicate (B1) can be increased, and the polarity
 thereof can be modified. In the above case, the compound to be added may
 be, but is not limited to, the organosilane compound (B2) itself.
 Otherwise, any arbitrary compound may be used depending on the purpose.
 Examples of such a compound include an epoxy group containing compound, an
 amino group containing compound, a carboxyl group containing compound, an
 acid anhydride group containing compound, and a hydroxyl group containing
 compound.
 The amount of the organosilane compound (B2) used may be adjusted so that
 the affinity and the dispersiveness between the resultant silane-treated
 foliated phyllosilicate (B) and the resin (A) used. If required, a
 plurality of types of organosilane compounds (B2) having different
 functional groups may be used together. Accordingly, the added amount of
 the organosilane compound (B2) is not simply numerically limited, but
 preferably it is in the range of 0.1 to 200 parts by weight, more
 preferably in the range of 0.2 to 160 parts by weight, especially
 preferably in the range of 0.3 to 120 parts by weight, with respect to 100
 parts by weight of the swellable layered silicate (B1). If the amount of
 the organosilane compound (B2) is less than 0.1 parts by weight, the fine
 dispersion effect of the resultant silane-treated foliated phyllosilicate
 (B) tends to become insufficient. Even if it exceeds 200 part by weight,
 the effect improves no more. The addition exceeding 200 parts by weight is
 therefore unnecessary,
 The basal spacing of the silane-treated foliated phyllosilicate (B)
 obtained in the manner described above can be expanded compared with the
 initial basal spacing of the swellable layered silicate (B1) due to the
 presence of the introduced organosilane compound (B2). For example if the
 organosilane compound (B2) is not introduced, the swellable layered
 silicate (B1), of which the basal spacing has been expanded by being
 dispersed in the dispersion medium, will resume the original state where
 the unit layers aggregate with one another when the dispersion medium is
 removed. According to the present invention, however, by introducing the
 organosilane compound (B2) after the expansion of the basal spacing, the
 resultant silane-treated foliated phyllosilicate (B) can remain in the
 state where the basal spacing is expanded without the aggregation of the
 unit layers. The basal spacing of the silane-treated foliated
 phyllosilicate (B) is preferably expanded from the initial basal spacing
 of the swellable layered silicate (B1) by 1.5 times or more, more
 preferably by two times or more.
 The introduction of the organosilane compound (B2) into the swellable
 layered silicate (B1) can be confirmed by a variety of methods. For
 example, the following method can be used for the confirmation. First, the
 silane-treated foliated phyllosilicate (B) is washed and rinsed using an
 organic solvent such as tetrahydrofuran and chloroform, to remove the
 organosilane compound (B2) which simply adsorbs to the silane-treated
 foliated phyllosilicate. After the wash, the silane-treated foliated
 phyllosilicate (B) is powdered with a mortar and the like and dried. The
 resultant silane-treated foliated phyllosilicate (B) is sufficiently mixed
 with powdered potassium bromide (KBr) at a predetermined ratio, and the
 mixture is pressed to obtain tablets. Then, an absorption band originated
 from the organosilane compound (B2) is measured by a transmission method
 using Fourier transform infrared spectrum (FT-IR). If an accurate
 measurement is desired or the amount of organosilane compound (B2) is
 small, the fully dried powdered silane-treated foliated phyllosilicate (B)
 itself is desirably measured by a diffuse reflectance infrared
 spectroscopy (DRIFT).
 The expansion of the basal spacing of the silane-treated foliated
 phyllosilicate (B) from the initial basal spacing of the swellable layered
 silicate (B1) can be confirmed by a variety of methods. For example, the
 following method can be used for the confirmation. That is, as described
 above, the silane-treated foliated phyllosilicate (B) is first washed and
 rinsed using an organic solvent to remove the organosilane compound (B2)
 which is adsorbed to the silane-treated foliated phyllosilicate, and then
 dried. Then, the expansion of the basal spacing can be confirmed by the
 small angle X-ray diffraction (SAXS) method and the like. According to
 this method, the peak angle value of the X-ray diffraction originated from
 the (001) plane of the powdered silane-treated foliated phyllosilicate (B)
 is measured by SAXS, and the Bragg equation is calculated using the
 resultant peak angle value, to obtain the basal spacing. The initial basal
 spacing of the swellable layered silicate (B1) is also measured in the
 same manner. These basal spacing are compared with each other to confirm
 the expansion of the basal spacing.
 As described above, the generation of the silane-treated foliated
 phyllosilicate (B) can be confirmed by confirming the introduction of the
 organosilane compound (B2) and the expansion of the basal spacing. In this
 way, according to the present invention, the affinity between the
 silane-treated foliated phyllosilicate (B) and the resin as a matrix can
 be enhanced by the introduction of the organosilane compound (B2) and the
 expansion of the basal spacing.
 Preparation of Thermoplastic Resin Composition (C)
 The thermoplastic resin composition (C) of the present invention is
 prepared so that the mixing amount of the silane-treated foliated
 phyllosilicate (B) is typically 0.1 to 100 parts by weight, preferably 0.2
 to 85 parts by weight, more preferably 0.5 to 0 parts by weight, with
 respect to 100 parts by weight of the thermoplastic resin (A). If the
 mixing amount of the silane-treated foliated phyllosilicate (B) is less
 than 0.1 parts by weight, the effect of improving the mechanical
 properties and the heat resistance is insufficient in some cases. If it
 exceeds 150 parts by weight, the appearance of a molded product, the
 flowability in the molding process, and the like tend to be degraded. The
 mixing amount is not limited to the above-described range since it can be
 appropriately selected depending on the final usage of the thermoplastic
 resin composition (C).
 The thermoplastic resin composition (C) of the present invention is
 prepared so that the ash content of the thermoplastic resin composition
 (C) originated from the silane-treated foliated phyllosilicate (B) is
 typically 0.1 to 50% by weight, preferably 0.2 to 45% by weight, more
 preferably 0.5 to 40% by weight. If the ash content is less than 0.1% by
 weight, the effect of improving the mechanical properties and the heat
 resistance is insufficient in some cases. If it exceeds 50% by weight, the
 appearance of a molded product, the flowability in the molding process,
 and the like tend to be degraded.
 The thermoplastic resin composition (C) may be produced by a method
 including the steps of preparing a mixture by mixing the previously
 prepared silane-treated foliated phyllosilicate (B) and a monomer (mixing
 step), and polymerizing the monomer in the resultant mixture to obtain the
 thermoplastic resin (A) (polymerization step).
 The monomer used in the above method may be any arbitrary monomer normally
 used for preparing a desired thermoplastic resin (A). The above-described
 dispersion medium used for the preparation of the silane-treated foliated
 phyllosilicate (B) and the monomer used may be the same.
 When the thermoplastic resin (A) is a polyester resin, the monomer used may
 include: an acid component having dicarboxylic acid and/or an
 esterificationable derivative thereof as a main component; and a diol
 component having a diol compound and/or an esterificationable derivative
 thereof as a main component.
 The dicarboxylic acid is preferably an aromatic dicarboxylic acid. Examples
 of the aromatic dicarboxylic acid include terephthalic acid, isophthalic
 acid, orthophthalic acid, 2,5-naphthalene dicarboxylic acid, 4,4'-biphenyl
 dicarboxylic acid, 4,4'-diphenylether dicarboxylic acid,
 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic
 acid, and 4,4'-diphenylisopropylidene dicarboxylic acid. Substituents and
 derivatives thereof may also be used. Oxyacids such as p-oxybenzoic acid
 and p-hydroxyethoxybenzoic acid, and esterificationable derivatives
 thereof may be used. A mixture of two or more types of these monomers may
 be used. One or more type(s) of aliphatic dicarboxylic acids such as
 adipic acid, azelaic acid, dodecanoic diacid, and sebacic acid may be
 mixed together with the above aromatic dicarboxylic acid, as long as the
 mixed amount is too small to degrade the properties of the resultant
 polyester resin.
 Examples of the diol component include: aliphatic diols such as ethylene
 glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl
 glycol; alicyclic diols such as 1,4-cyclohexanedimethanol; and aromatic
 diols such as 2,2-bis(4-hydroxyphenyl)propane. Substituents and
 derivatives thereof may also be used. A mixture of two or more types of
 these may also be used. At least one type of long-chain diols (e.g.,
 polyethylene glycol and polytetramethylene glycol), and alkylene oxide
 added polymers of bisphenols (e.g., an ethylene oxide added polymer of
 bisphenol A) may also be mixed, as long as the mixed amount is too small
 to degrade the properties of the resultant polyester resin.
 A cyclic ester such as .epsilon.-caprolactone may also be used as the
 monomer.
 When the thermoplastic resin (A) is a polycarbonate resin, the monomer used
 may include: a bivalent phenol component having a bivalent phenol compound
 and/or an esterificationable derivative thereof as a main component; and
 phosgene or carbonic acid diester compound.
 Examples of the bivalent phenol compound include
 bis(4-hydroxyphenylmethane), 1,1-bis(4-hydroxyphenyl)ethane,
 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane
 ("bisphenol A"), 2,2-bis(4-hydroxyphenyl)butane,
 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane,
 2,2-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane,
 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane,
 bis(4-hydroxy-3-methylphenyl)methane,
 bis(4-hydroxy-3-methylphenyl)phenylmethane,
 1,1-bis(4-hydroxy-3-methylphenyl)ethane,
 2,2-bis(4-hydroxy-3-methylphenyl)propane,
 2,2-bis(4-hydroxy-3-ethylphenyl)propane,
 2,2-bis(4-hydroxy-3-isopropylphenyl)propane,
 2,2-bis(4-hydroxy-3-sec-butylphenyl)propane,
 bis(4-hydroxyphenyl)phenylmethane,
 1,1-bis(4-hydroxyphenyl)-1-phenylethane,
 1,1-bis(4-hydroxyphenyl)-1-phenylpropane,
 bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)dibenzylmethane,
 4,4'-dihydroxydiphenylether, 4,4'-dihydroxydiphenylsulfone,
 bis(4-hydroxy-3,5-dimethylphenyl)sulfone, 4,4'-dihydroxydiphenylsulfide,
 4,4'-dihydroxybenzophenone, phenolphthalein, bis(4-hydroxyphenyl)methane,
 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane ("bisphenol TMC"),
 bis(4-hydroxypheny)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, and
 bis(4-hydroxy-3,5-dimethylphenyl)ether. A polymer which is copolymerized
 with a bivalent phenol having a benzotriazole group may also be used for
 enhancing the flame resistance. Substituents and derivatives, alkaline
 metal salts, and alkaline earth metal salts of these bivalent phenol
 compounds may also be used. A mixture of two or more types of these
 bivalent phenol compounds may also be used.
 Examples of the carbonic acid diester compound include: bisalkylcarbonates
 such as dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate,
 diisopropyl carbonate, and di-n-butyl carbonate; and bisarylcarbonates
 such as diphenyl carbonate, bis(2,4-dichlorophenyl) carbonate,
 bis(2,4,6-trichlorophenyl) carbonate, bis(2-nitrophenyl) carbonate,
 bis(2-cyanophenyl) carbonate, bis(4-methylphenyl) carbonate,
 bis(3-methylphenyl) carbonate, and dinaphtyl carbonate.
 For example, the mixing step of mixing the silane-treated foliated
 phyllosilicate (B) and the monomer as described above can be performed in
 the following manner. That is, the silane-treated foliated phyllosilicate
 (B) previously produced and isolated (i.e., the dispersion medium was
 removed) by the production method of the silane-treated foliated
 phyllosilicate (B) described above is added to the monomer, and
 sufficiently agitated to prepare a mixture. Alternatively, if the
 dispersion medium used in the production of the silane-treated foliated
 phyllosilicate (B) does not adversely influence the polymerization step,
 the dispersion medium may not be removed, and the dispersion containing
 the silane-treated foliated phyllosilicate (B) and the dispersion medium
 may be directly used to prepare the mixture. In the latter case, the
 organosilane compound (B2) is introduced into the swellable layered
 silicate (B1) in the dispersion medium according to the production method
 of the silane-treated foliated phyllosilicate (B) as described above, to
 prepare the silane-treated foliated phyllosilicate (B) and thus to obtain
 the dispersion containing the dispersion medium and the silane-treated
 foliated phyllosilicate (B). The monomer can then be added to the
 dispersion and sufficiently agitated to obtain a mixture. The dispersion
 medium itself may be the monomer as described above.
 Next, in the polymerization step, the monomer in the mixture obtained in
 the mixing step is polymerized by polymerization methods normally
 performed for various thermoplastic resins (A).
 When the thermoplastic resin (A) is a thermoplastic polyester resin, the
 polymerization step can utilize, for example, a melt polycondensation
 method described as follows. First, the mixture obtained in the mixing
 step is put in a polymerization reactor. Another monomer which constitutes
 the thermoplastic polyester resin may be added as required. The system is
 heated while agitating and mixing to be put in a melted state. Then, it
 can be decompressed to be subjected to a melt decondensation reaction. As
 a catalyst required for the polymerization reaction, one type or two or
 more types of metal oxides, carbonates, acetates, alcoholates, and the
 like may be added.
 When the diol compound is contained in the mixture, the following method
 may also be used, in addition to the melt polycondensation method
 described above. That is, a thermoplastic polyester resin of a desired
 structure is added to the mixture, and the system is heated to near the
 melting point of the thermoplastic polyester resin. In this case, a
 thermoplastic polyester resin having a logarithmic viscosity of 0.3 to 2.0
 (dl/g) as measured in a mixed solvent of phenol-tetrachloroethane (weight
 ratio: 5/5) at 25.degree. C. is preferably used. According to the method,
 the thermoplastic polyester resin is made a monomer and/or an oligomer
 having about 2 to 15 repeating units due to the depolymerization reaction
 of the thermoplastic polyester resin with the diol compound. Then, the
 system is further sufficiently mixed, so that the silane-treated foliated
 phyllosilicate is uniformly dispersed in the system. Thereafter, the
 system is decompressed to be subjected to the melt polycondensation
 reaction. In this case, although the catalyst required for the reaction
 has been contained in the staring material resin, one type or two or more
 types of catalyst(s) similar to that used in the above melt
 polycondensation may be used additionally, as required.
 A solid state polymerization method may also be used, instead of the above
 melt polycondensation method. For example, the solid state polymerization
 method is performed in the following manner. That is, a polyester resin of
 a low degree of polymerization is obtained by the melt polycondensation
 reaction and solidified by cooling. After sufficient drying, the resin of
 a low degree of polymerization is heated to a temperature in the range
 from 150.degree. C. to the melting point of the resin under a flow of an
 inert gas such as nitrogen or under a decompressed atmosphere. While
 removing a generating diol compound and the like from the system, the
 resin of a low degree of polymerization is polymerized in the solid state
 to obtain a resin of a high degree of polymerization.
 When the thermoplastic resin (A) is a polycarbonate resin, the
 polymerization step can be performed, for example, by utilizing the
 following interfacial polymerization method. First, methylene chloride and
 phosgene are added to the mixture containing the alkaline metal salt of
 the bisphenol compound obtained in the mixing step described above. The
 mixture is then sufficiently agitated to allow a polycondensation reaction
 to occur at the interface between the alkaline aqueous phase and the
 methylene chloride phase. As the catalyst required for the interfacial
 polymerization method, one type or two or more types of aliphatic tertiary
 amine, alicyclic tertiary amine, aromatic tertiary amine, and the like may
 be added.
 A melt polymerization method may also be used in place of the interfacial
 polymerization method described above. An example of the melt
 polymerization method includes the following. First, a bisphenol compound
 is added to the mixture containing the carbonic acid diester compound
 obtained in the mixing step described above. The system is then heated to
 about 280.degree. C. to about 300.degree. C. while being sufficiently
 agitated, to allow for an ester exchange reaction in the melted state. As
 a catalyst required for the melt polymerization method, one type or two or
 more types of a simple substance, an oxide, a hydroxide, an amide
 compound, an alcoholate, and a phenolate of an alkali metal or an alkali
 earth metal, Sb.sub.2 O.sub.3, ZnO, PbO, an organic titanium compound, a
 quaternary ammonium salt, and the like may be added.
 The thermoplastic resin composition (C) of the present invention can also
 be produced directly by melt mixing the thermoplastic resin (A) and the
 silane-treated foliated phyllosilicate (B) using any of various types of
 melt mixers, in place of the method including the mixing step and the
 polymerization step as described above.
 Examples of the melt mixers include kneaders capable of providing a high
 shearing force to the system, such as a single screw extruder, a twin
 screw extruder, a Banbury mixer, and a roll. In particular, an engaging
 type twin screw extruder having kneading disks is preferable.
 Before the melt mixing, normally, the dispersion medium used in the
 production of the silane-treated foliated phyllosilicate (B) is removed.
 The removal of the dispersion medium, however, may be omitted if the
 dispersion medium does not cause an adverse effect such as degrading the
 thermoplastic resin (A), so that the silane-treated foliated
 phyllosilicate (B) including the dispersion medium can be used. Such a
 silane-treated foliated phyllosilicate (B) having the dispersion medium
 retained therein is preferable since it is effective for uniform
 dispersion in a resin.
 The thermoplastic resin (A) and the silane-treated foliated phyllosilicate
 (B) may be put in the melt mixer together at the same time for the melt
 mixing. Alternatively, the silane-treated foliated phyllosilicate (B) may
 be added to a pre-melted thermoplastic resin (A) for the melt mixing.
 The thermoplastic resin composition (C) of the present invention may be
 produced by the polymerization and the melt mixing as described above.
 However, when the thermoplastic resin (A) is easily dissolved in a
 solvent, e.g., when the thermoplastic resin (A) is a polycarbonate resin,
 a polyarylate resin, a vinyl polymer compound, or a polyphenyleneoxide
 resin, for example, the thermoplastic resin (A) may be dissolved in a
 dispersion of the silane-treated foliated phyllosilicate (B) dispersed in
 a solvent, and then the solvent may be removed by drying or the like.
 For example, when the polycarbonate resin described above is used as the
 thermoplastic resin (A), methylene chloride may be used as the solvent.
 The silane-treated foliated phyllosilicate (B) is added to the methylene
 chloride and mixed and dispersed therein by agitating. Then, the
 polycarbonate resin is added to and dissolved in the dispersion. By
 removing the methylene chloride by evaporating, the thermoplastic resin
 composition (C) of the present invention is obtained.
 An impact modifier such as polybutadiene, a butadiene-styrene copolymer,
 acrylic rubber, an ionomer, an ethylene-propylene copolymer, an
 ethylene-propylenedien copolymer, natural rubber, chlorinated butyl
 rubber, an .alpha.-olefin homopolymer, a copolymer of two or more types of
 .alpha.-olefins (including a random copolymer, a block copolymer, a graft
 copolymer, and the like and a mixture thereof), and an olefin elastomer
 may be added to the thermoplastic resin composition (C) of the present
 invention, as required. An acid compound such as maleic anhydride or an
 epoxy compound such as glycidyl methacrylate may be copolymerized and/or
 grafted to the above modifiers. The thermoplastic resin composition (C)
 may include any arbitrary resin other than the thermoplastic resin (A),
 such as an unsaturated polyester resin, a polyester carbonate resin, a
 liquid crystal polyester resin, a polyolefin resin, a polyamide resin, a
 gummous polymer reinforcing styrene resin, a polyphenylenesulfide resin,
 polyphenylenether resin, a polyacetal resin, a polysulfone resin, and a
 polyarylate resin, mixed therein individually or in combination of two or
 more types, as long as the properties such as the mechanical properties
 and the moldability of the resultant thermoplastic resin composition (C)
 are not reduced.
 The thermoplastic resin composition (C) of the present invention may
 further include an additive such as a pigment, a dye, a heat stabilizer,
 an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant,
 a plasticizer, a flame resistant agent, and an antistatic depending on the
 purpose thereof.
 Dispersion State of Silane-Treated Foliated Phyllosilicate (B) in
 Thermoplastic Composition (C)
 The structure of the silane-treated foliated phyllosilicate (B) dispersed
 in the thermoplastic resin composition (C) of the present invention
 obtained by the methods as described above is completely different from
 the aggregate structure like that of the swellable layered silicate (B1)
 before the mixing, where a number of unit layers are stratified. More
 specifically, the silane-treated foliated phyllosilicate (B) having an
 expanded basal spacing compared with that of the aggregate structure of
 the initial swellable layered silicate (B1) is mixed with the
 thermoplastic resin (A). By this mixing, the layers of the silane-treated
 foliated phyllosilicate are further exfoliated between one another,
 expanding the basal spacing. As a result, the silane-treated foliated
 phyllosilicate (B) is exfoliated into a number of very fine layers
 dispersed independently from one another in the thermoplastic resin
 composition (C). The dispersion state of the silane-treated foliated
 phyllosilicate (B) in the thermoplastic resin composition (C) can be
 represented by a variety of parameters as described below.
 Assume that a value [R.sub.B300 ] is defined as the rate of the number of
 unit layers of the silane-treated foliated phyllosilicate (B) having an
 equivalent area circle diameter [D] of 300 nm or less to the layers of the
 silane-treated foliated phyllosilicate (B) dispersed in the thermoplastic
 resin composition (C). The value [R.sub.B300 ] in the thermoplastic resin
 composition (C) of the present invention is preferably 20% or more, more
 preferably 35% or more, further more preferably 50% or more. If the value
 [R.sub.B300 ] is less than 20%, the effect of improving the mechanical
 properties and the thermal deformation resistance of the thermoplastic
 resin composition (C) tends to become insufficient.
 The equivalent area circle diameter [D] as used herein is intended to be a
 diameter of a circle having an area equal to the area of each of the unit
 layers dispersed in various shapes in an image obtained by a microscope or
 the like. The average value is intended to be a number average of the
 values of the diameters. The measurement of the equivalent area circle
 diameter [D] can be quantified by selecting any arbitrary region including
 100 or more dispersed layers in an image taken with a microscope or the
 like, imaging the region using an image processing apparatus, and
 processing by a computer. Accordingly, an average [D.sub.B ] of the
 equivalent area circle diameters of the silane-treated foliated
 phyllosilicate (B) can be quantified using a photograph showing the
 dispersion state of the silane-treated foliated phyllosilicate (B)
 obtained by taking a photograph of the thermoplastic resin composition (C)
 of the present invention with a transmission electron microscope (TEM).
 In the thermoplastic composition (C) of the present invention, the value
 [D.sub.B ] is preferably 500 nm or less, more preferably 450 nm or less,
 further more preferably 400 nm or less. When the value [R.sub.B300 ] is
 within the range described above and the value [D.sub.B ] is within the
 above range, the effect of improving the mechanical properties and the
 thermal deformation resistance of the thermoplastic resin composition (C)
 can be further increased. The lower limit of the value [D.sub.B ] is not
 specifically set, but since the effect hardly changes if the value
 [D.sub.B ] is less than about 10 nm, setting the value at less than 10 nm
 is unnecessary.
 The size of the silane-treated foliated phyllosilicate (B) exfoliated can
 be extremely thin and small compared with the size of the initial
 swellable layered silicate (B1) having the aggregate structure. That is,
 assuming that the value [D.sub.B ] is defined as an average of the
 equivalent area circle diameters of the silane-treated foliated
 phyllosilicate (B) in the thermoplastic resin composition (C) as described
 above and that a value [D.sub.B1 ] is defined as an average of the
 equivalent area circle diameters of the swellable layered silicate (B1),
 the value [D.sub.B ]/[D.sub.B1 ] is preferably 0.010 or less, more
 preferably 0.008 or less, further more preferably 0.005 or less. When the
 value [D.sub.B ]/[D.sub.B1 ] is less than 0.010, the effect of improving
 the mechanical properties and the thermal deformation resistance of the
 thermoplastic resin composition (C) further increases. The lower limit is
 not specifically set, but since the effect does not change if the value
 [D.sub.B ]/[D.sub.B1 ] is less than about 0.0001, setting the value at
 less than 0.0001 is unnecessary. The value [D.sub.B1 ] of the average
 equivalent area circle diameter of the initial swellable layered silicate
 (B1) having the aggregate structure can be obtained in the following
 manner, for example. That is, a resin composite including the
 thermoplastic resin (A) and the swellable layered silicate (B1), which has
 the same ash content as the thermoplastic resin composition (C), is
 prepared separately using a heat press or the like. A photograph of the
 resin composite showing the morphology of the swellable layered silicate
 (B1) therein is taken with an optical microscope. Using this photograph,
 the value [D.sub.B1 ] can be quantified, as in the quantification of the
 value [D.sub.B ].
 The number of layers of the silane-treated foliated phyllosilicate (B)
 dispersed in the thermoplastic resin composition (C) increases, compared
 with the number of layers of the initial swellable layered silicate (B1),
 since the silicate layers are exfoliated to exist independently from one
 another. More specifically, assuming that a value [N.sub.B ] is defined as
 the number of layers of the silane-treated foliated phyllosilicate (B) per
 unit ash content and per unit area and that a value [N.sub.B1 ] is defined
 as the number of layers of the swellable layered silicate (B1) per unit
 ash content and per unit area, a value [N.sub.B ]/[N.sub.B1 ] of the
 thermoplastic resin composition (C) of the present invention is preferably
 300 or more, more preferably 400 or more, further more preferably 500 or
 more. When the value [N.sub.B ]/[N.sub.B1 ] is within the above range, the
 number of layers of the silane-treated foliated phyllosilicate (B) which
 serve to enhance the properties of the thermoplastic resin composition (C)
 increases, thereby further increasing the effect of improving the
 mechanical properties and the thermal deformation resistance of the
 thermoplastic resin composition (C). The upper lime is not specifically
 set, but since the effect does not change if the value [N.sub.B
 ]/[N.sub.B1 ] exceeds about 50000, setting the value exceeding 50000 is
 unnecessary.
 The value [N] which is the number of dispersed layers per unit ash content
 and per unit area can be obtained in the following manner, for example.
 First, any arbitrary region including 100 or more dispersed layers is
 selected on an image taken with a microscope or the like, and the number
 of dispersed layers present in the region, as well as the area of the
 region, are obtained. Separately from the above step, the ash content of
 the thermoplastic resin composition (C) originated from the dispersed
 layers is measured. The number of dispersed layers is divided by the area
 of the region and the ash content, to obtain the value [N]. Accordingly,
 the value [N.sub.B ] of the silane-treated foliated phyllosilicate (B) and
 the value [N.sub.B1 ] of the swellable layered silicate (B1) can be
 quantified using a photograph of the thermoplastic resin composition (C)
 taken with a transmission electronic microscope (TEM) or a photograph of
 the resin composite including the thermoplastic resin (A) and the
 swellable layered silicate (B1) taken with an optical microscope
 photograph, as in the measurement of the value [D] of the equivalent area
 circle diameter. The unit of area is not specifically limited as long as
 the same unit is used for the calculations of the value [N.sub.B ] and the
 value [N.sub.B1 ]. For example, any arbitrary unit such as .mu.m.sup.2,
 nm.sup.2, and .ANG..sup.2 may be used.
 As described above, in the thermoplastic resin composition (C) of the
 present invention, the silane-treated foliated phyllosilicate (B) is
 extremely finely dispersed compared with the initial aggregate structure
 of the swellable layered silicate (B1). If respective dispersed layers of
 the silane-treated foliated phyllosilicate (B) have a shape of thin
 plates, the properties such as the mechanical properties and the heat
 resistance of the thermoplastic resin composition (C) are further
 efficiently improved. More specifically, the average of the thicknesses of
 the layers of the silane-treated foliated phyllosilicate (B) in the
 thermoplastic resin composition (C) should be 20 nm or less, preferably 18
 nm or less, more preferably 15 nm or less. The lower limited is not
 specifically set, but may be about 1 nm.
 The measurement of the layer thickness can be quantified by selecting any
 arbitrary region including 100 or more dispersed layers of the
 silane-treated foliated phyllosilicate (B), as in the case of the value
 [D] of the equivalent area circle diameter and the value [N] of the number
 of dispersed layers described above, and measuring the thicknesses of the
 respective layers of the silane-treated foliated phyllosilicate (B). The
 average value is intended to be a number average thereof.
 When the rate of the independently dispersed layers of the silane-treated
 foliated phyllosilicate (B) having a layer thickness of 5 nm or less is
 20% or more, preferably 30% or more, with respect to the entire
 silane-treated foliated phyllosilicate (B), the mechanical properties and
 the thermal deformation resistance of the thermoplastic resin composition
 (C) can be more efficiently improved. The method for measuring the layer
 thickness is similar to that described above.
 The crystallinity of the silane-treated foliated phyllosilicate (B)
 dispersed in the thermoplastic resin composition (C) can be markedly
 reduced, compared with the crystallinity exhibited by the initial
 aggregate structure of the swellable layered silicate (B1). More
 specifically, in the X-ray diffraction measurement performed for the
 thermoplastic resin composition (C), assuming that a value [I.sub.B ] is
 defined as the diffraction intensity of the small angle X-ray diffraction
 originated from the silane-treated foliated phyllosilicate (B) and that a
 value [I.sub.B1 ] is defined as the diffraction intensity of the small
 angle X-ray diffraction originated from the initial aggregate structure of
 the swellable layered silicate (B1), a value [I.sub.B ]/[I.sub.B1 ] is
 preferably 0.25 or less, more preferably 0.23 or less, further more
 preferably 0.20 or less. When the value [I.sub.B ]/[I.sub.B1 ] is within
 the above range, the mechanical properties and the heat resistance of the
 thermoplastic resin composition (C) can be further improved. The lower
 limit is not specifically set. If the value [I.sub.B ] of the small angle
 X-ray diffraction intensity originated from the silane-treated foliated
 phyllosilicate (B) is so small that it becomes difficult to be
 distinguished from a base line or noise, the value [I.sub.B ]/[I.sub.B1 ]
 is 0, indicating that the silane-treated foliated phyllosilicate (B) has
 been substantially completely exfoliated and respective layers exist
 independently from one another. As in the case of the value [D.sub.B1 ],
 the value [I.sub.B1 ] can be obtained by separately preparing a resin
 composite including the thermoplastic resin (A) and the swellable layered
 silicate (B1), which has the same ash content as the thermoplastic resin
 composition (C), and performing the small angle X-ray diffraction
 measurement for the resin composite.
 The measurement of the small angle X-ray diffraction intensity [I] is
 performed by measuring the peak intensity or the integrated intensity of
 the small angle X-ray diffraction. The method for measuring the integrated
 intensity of the small angle X-ray diffraction is not specifically
 limited, but methods generally used, for example, include a method where
 the area is determined from a diffraction diagram obtained by the X-ray
 diffraction measurement, and a method using a count value. Examples of the
 method where the area is determined from a diffraction diagram include
 methods generally used such as a planimeter method, a weight method, and a
 trigonometric approximation method (peak height.times.half value width).
 Examples of the method using a count value include a 2.theta. sequential
 scan method, a 2.theta. step scan method, and a 2.theta. fixation method.
 It is preferable that the basal spacing of the exfoliated silane-treated
 foliated phyllosilicate (B) in the thermoplastic resin composition (C) is
 three times or more, preferably five times or more, as large as the basal
 spacing of the initial swellable layered silicate (B1) having the
 aggregate structure before the mixing. With such an expanded basal
 spacing, the mechanical properties and the heat resistance of the
 thermoplastic resin composition (C) can be improved more efficiently. The
 basal spacing can be measured in the manner as described above with
 respect to the preparation method of the silane-treated foliated
 phyllosilicate (B).
 The thermoplastic resin composition (C) of the present invention may be
 molded by injection molding or heat press molding. It may also be used for
 blow molding. Also, the thermoplastic resin composition (C) of the present
 invention can be used for biaxial extension films which can sustain the
 transparency and are excellent in the mechanical properties. Since molded
 products and films produced from the thermoplastic resin composition (C)
 of the present invention are excellent in appearance, mechanical
 properties, thermal deformation resistance, and the like, they are
 suitably used for automobile components, components of household electric
 appliances, components of precision machines, household daily necessities,
 package/container materials, magnetic recording tap substrates, and other
 general industrial materials.
 EXAMPLES
 Hereinbelow, the present invention will be described in more detail by way
 of examples. The present invention is however not limited to these
 examples.
 Material
 (Thermoplastic Resin (A))
 The following resins were used as obtained, without further purification.
 Polyethylene terephthalate (PET) resin:
 PEK2 manufactured by Kanebo, Ltd.
 (logarithmic viscosity (.eta.inh)=0.63 (dl/g))
 (Hereinbelow, referred to as PET.)
 Polybutylene terephthalate (PBT) resin:
 PBT120 manufactured by Kanebo, Ltd.
 (logarithmic viscosity (.eta.inh)=0.82 (dl/g))
 (Hereinbelow, referred to as PBT.)
 Polycarbonate (PC) resin:
 Taflon A-2200 manufactured by Idemitsu Petrochemical Co., Ltd.
 (weight average molecular weight (Mw)=45000)
 (Hereinbelow, referred to as PC.)
 (Monomer for Thermoplastic Resin (A))
 The following compounds were used as obtained, without further
 purification.
 Bishydroxyethyl terephthalate:
 NISSO BHET manufactured by Nisso Maruzen Chemical Co., Ltd.
 (Hereinbelow, referred to as BHET.)
 Dimethyl terephthalate:
 a best quality reagent manufactured by Wako Pure Chemical Industries, Ltd.
 (Hereinbelow, referred to as DMT.)
 Ethylene glycol:
 monoethylene glycol manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.
 (Hereinbelow, referred to as EG.)
 1,4-butanediol:
 1,4-butanediol manufactured by Toso Co., Ltd.
 (Hereinbelow, referred to as 1,4-BD.)
 (Swellable Layered Silicate (B1))
 As the montmorillonite, natural montmorillonite mined in Yamagata
 Prefecture, Japan (basal spacing=1.3 nm) was used.
 As the swellable mica, one synthesized in the following manner was used.
 Synthesis of swellable mica: Finely pulverized powders of 25.4 g of talc
 and 4.7 g of sodium silicofluoride were mixed and heated to 800.degree.
 C., to obtain 28.2 g of swellable mica (basal spacing=1.2 nm).
 (Organosilane Compound (B2))
 The following compounds were used as obtained, without further
 purification.
 .gamma.-(2-aminoethyl)aminopropyltrimethoxysilane
 .gamma.-glycidoxypropyltrimethoxysilane
 .gamma.-(polyoxyethylene)propyltrimethoxysilane
 Measurement Method
 (FT-IR)
 The silane-treated foliated phyllosilicate was added to tetrahydrofuran
 (THF) and agitated for 15 minutes, to wash off an adsorbing organosilane
 compound, and then centrifuged to separate the supernatant. This cleaning
 operation was repeated three times. About 1 mg of the silane-treated
 foliated phyllosilicate sufficiently dried and about 200 mg of KBr powder
 were sufficiently mixed with a mortar. A KBr disk for measurement was
 produced from the resultant mixture using a desk press. The measurement
 was then performed by a transmission method using an infrared
 spectroscope. An MCT detector was used as a detector with a resolving
 power of 4 cm.sup.-1 and scans of 100 times.
 (Transmission Electron Microscope (TEM))
 A thin section having a thickness of 80 to 100 nm was cut off from the
 sample using a microtome. The sample was measured using a transmission
 electron microscope (JEM-1200EX manufactured by JEOL, Ltd.) under an
 acceleration voltage of 80 kV.
 The average of the layer thicknesses was calculated by measuring the
 thicknesses of respective layers of the silane-treated foliated
 phyllosilicate in an arbitrary region of a TEM photograph of the
 thermoplastic resin composition of the present invention where 100 or more
 layers of the silane-treated foliated phyllosilicate are present and
 calculating a number average of the thicknesses.
 The value [N] of the number of layers per unit ash content and per unit
 area and the value [D] of the average of the equivalent area circle
 diameters were calculated by selecting an arbitrary region of the TEM
 photograph where 100 or more layers of the silane-treated foliated
 phyllosilicate are present and performing a processing using an image
 analyzer, PIAS III manufactured by Interquest Co.
 An optical microscope was optionally used in the observation of the
 morphology of the swellable layered silicate in the system produced in
 each of the comparative examples and production examples.
 (Small Angle X-Ray Diffraction (SAXS))
 The sample was measured with an X-ray generator (RU-200B manufactured by
 Rigaku Denki Co., Ltd.) using a target CuK.alpha. ray and an Ni filter
 under the conditions of a voltage of 40 kV, a current of 200 mA, a
 scanning angle 2.theta. of 0.2 to 16.0.degree., and a step angle of
 0.02.degree..
 The intensity [I] of the small angle X-ray diffraction was measured from
 the area of a diffraction diagram. When the diffraction diagram is
 difficult to be distinguished from a base line, that is, when the
 diffraction peak is very small, the rate of the X-ray diffraction
 intensity was set at 0%.
 The basal spacing was calculated by calculated by calculating the Bragg
 equation using the actual peak angle value of the small angle X-ray
 diffraction. When the confirmation of the peak angle value of the small
 angle X-ray diffraction is difficult, it was considered that the layers
 had been sufficiently exfoliated to substantially lose the crystallinity
 as described above, or that the confirmation was difficult since the peak
 angle value was about 0.8.degree. or less, giving the evaluation result of
 the basal spacing of &gt;10 nm.
 (Ash Content)
 The ash content of the thermoplastic resin composition originated from the
 silane-treated foliated phyllosilicate was measured in compliance with JIS
 K7052.
 Since the ash content of the thermoplastic resin used in examples,
 comparative examples, and reference examples are substantially 0, the
 measured ash content is concluded to be the ash content originated from
 the silane-treated foliated phyllosilicate.
 (Preparation of Test Piece)
 After being dried, the thermoplastic resin composition was injection-molded
 using an injection molding machine with a mold clamping pressure of 75 t
 at a resin temperature of about 260 to 280.degree. C., to prepare a test
 piece having a dimension of about 10.times.100.times.6 mm.
 (Load Deflection Temperature)
 The load deflection temperature of the test piece obtained by the injection
 molding when it is under a load of 1.85 MPa was measured in compliance
 with ASTM D-648.
 (Flexural Properties)
 The flexural strength and the flexural elastic modulus of the test piece
 obtained by the injection molding were measured in compliance with ASTM
 D-790.
 (Surface Appearance of Molded Product)
 The gloss and color tone of the test piece obtained by the injection
 molding were visually observed. The evaluation results were represented by
 O, .DELTA., and x as follows:
 O: Glossy and no dots in color tone
 .DELTA.: The transparency is lost or the color tone is non-uniform.
 x: The transparency is lost and the color tone is non-uniform.
 (Measurement of Logarithmic Viscosity)
 After a polyester resin composition was dried at 140.degree. C. for four
 hours, about 100 mg thereof was accurately weighed. Then, the polyester
 resin composition was added to and dissolved in 20 ml of a mixed solvent
 of phenol/1,1,2,2-tetrachloroethane (weight ratio: 5/5) at 120.degree. C.
 The viscosity of the solution was measured with an automatic viscosity
 measuring apparatus (Viscotimer manufactured by Rauda Co.) using a
 Ubbelohde viscometer, and the logarithmic viscosity (.eta.inh) was
 calculated from the equation below. The measurement temperature was
 25.degree. C.
 .eta.inh={1n(t/t.sub.0)}/C (I)
 wherein t denotes the measured value of the solution, t.sub.0 denotes the
 measured value of the mixed solvent, and C denotes the concentration
 (g/dl).
 Production Example 1
 Montmorillonite, 150 g, was dispersed in 6800 g of pure water by agitating
 at 5000 rpm for three minutes using a high-seed agitator. Thereafter, 15 g
 of .gamma.-(2-aminoethyl)aminopropyltrimethoxysilane was dropped in using
 a pipette, and the resultant mixture was agitated at a revolution of 6000
 rpm for two hours, to obtain a slurry (slurry a) composed of a
 silane-treated foliated phyllosilicate and water.
 A portion of the slurry was dried and pulverized to obtain a silane-treated
 foliated phyllosilicate (silane-treated foliated phyllosilicate a). The
 resultant silane-treated foliated phyllosilicate had a basal spacing of
 2.6 nm. The silane-treated foliated phyllosilicate was washed with THF and
 then measured by FT-IR. As a result, absorption bands originating from a
 primary amino group, a secondary amino group, and an ethylene group were
 observed.
 The silane-treated foliated phyllosilicate and the slurry obtained in
 Production Example 1 are referred to as "silane-treated foliated
 phyllosilicate a" and "slurry a", respectively.
 Production Example 2
 Montmorillonite, 150 g, was dispersed in 4500 g of pure water by agitating
 at 5000 rpm for three minutes using a high-speed agitator. Thereafter, 15
 g of .gamma.-glycidoxypropyltrimethoxysilane hydrolyzed with a mixed
 solvent of ethanol/water (weight ratio: 9/1) adjusted to a pH of 5.0 was
 dropped in using a simplified pipette. The resultant mixture was agitated
 at a shear rate of 20000 (1/s) for three hours, to obtain a slurry (slurry
 b) composed of a silane-treated foliated phyllosilicate and water.
 A portion of the slurry as dried and pulverized to obtain a silane-treated
 foliated phyllosilicate (silane-treated foliated phyllosilicate b). The
 resultant silane-treated foliated phyllosilicate had a basal spacing of
 2.0 nm. The silane-treated foliated phyllosilicate was washed with THF and
 then measured by FT-IR. As a result, absorption bands originating from an
 epoxy ring (ethyleneoxide group), an ether group, and a methylene group
 were observed.
 The silane-treated foliated phyllosilicate and the slurry obtained in
 Production Example 2 are referred to as "silane-treated foliated
 phyllosilicate b" and "slurry b", respectively.
 Production Example 3
 Montmorillonite, 150 g, was dispersed in 4500 g of pure water by agitating
 at 5000 rpm for three minutes using a high-speed agitator. Thereafter, 15
 g of .gamma.-polyoxyethylenepropyltrimethoxysilane hydrolyzed with water
 adjusted to a pH of 4 with hydrochloric acid was dropped in using a
 simplified pipette. The resultant mixture was agitated at a shear rate of
 20000 (1/s) for two hours, to obtain a slurry (slurry c) composed of a
 silane-treated foliated phyllosilicate and water.
 A portion of the slurry was dried and pulverized to obtain a silane-treated
 foliated phyllosilicate (silane-treated foliated phyllosilicate c). The
 resultant silane-treated foliated phyllosilicate had a basal spacing of
 2.4 nm. The silane-treated foliated phyllosilicate was washed with THF and
 then measured by FT-IR. As a result, absorption bands originating from an
 ether group and an ethylene group were observed.
 The silane-treated foliated phyllosilicate and the slurry obtained in
 Production Example 3 are referred to as "silane-treated foliated
 phyllosilicate c" and "slurry c", respectively.
 Production Example 4
 Swellable mica, 150 g, was dispersed in 3500 g of pure water by agitating
 at 6000 rpm for six minutes using a high-speed agitator. Thereafter, 25 g
 of .gamma.-(2-aminoethyl)aminopropyltrimethoxysilane was dropped in using
 a simplified pipette. The resultant mixture was agitated at a shear rate
 of 30000 (1/s) for three hours, to obtain a slurry (slurry d) composed of
 a silane-treated foliated phyllosilicate and water.
 A portion of the slurry was dried and pulverized to obtain a silane-treated
 foliated phyllosilicate (silane-treated foliated phyllosilicate d). The
 resultant silane-treated foliated phyllosilicate had a basal spacing of
 1.8 nm. The silane-treated foliated phyllosilicate was washed with THF and
 then measured by FT-IR. As a result, absorption bands originating from a
 primary amino group, a secondary amino group, and a methylene group were
 observed.
 The silane-treated foliated phyllosilicate and the slurry obtained in
 Production Example 4 are referred to as "silane-treated foliated
 phyllosilicate d" and "slurry d", respectively.
 Production Example 5
 Montmorillonite, 150 g, was sprayed with 15 g of
 .gamma.-(2-aminoethyl)aminopropyltrimethoxysilane using a spray and left
 for one hour to mix therewith, so as to obtain treated montmorillonite.
 The treated montmorillonite had a basal spacing of 1.3 nm which was the
 same as the basal spacing of the untreated initial montmorillonite. The
 treated montmorillonite was washed with THF and then measured by FT-IR. As
 a result, absorption bands originating from a primary amino group, a
 secondary amino group, and an ethylene group were observed.
 The treated montmorillonite obtained in Production Example 5 is referred to
 as "treated montmorillonite a'".
 Production Examples 6 to 16
 Powdered thermoplastic resin, 100 g, and swellable layered silicate of
 amounts shown in Table 1 below were blended in the dry state. Using 15 g
 of each of the resultant mixtures, a molded product with a dimension of
 about 10.times.100.times.3 mm composed of the thermoplastic resin and the
 swellable layered silicate was produced using a heat press under the
 molding conditions (temperature and pressure) shown in Table 1.
 TABLE 1
 Production Examples
 6 7 8 9 10 11 12 13 14 15
 16
 Thermoplastic resin PET PBT
 PC
 Swellable Mont- Mixing 3.6 6.2 15.0 32.0 115 3.6 6.2 15.0
 6.0
 layered moril- amount g
 silicate lonite (parts by 3.6 6.2 15.0 32.0 115 3.6 6.2 15.0
 6.0
 wt.)
 Swellable Mixing 6.2
 6.0
 mica amount g
 (parts by 6.2
 6.0
 wt.)
 Molding Temperature (.degree. C.) 270 240
 280
 condition Pressure (kg/cm.sup.2) 800 800
 800
 Ash content (wt. %) 3.4 5.8 13.2 24.3 53.0 6.0 3.4 5.9 13.2
 5.7 5.8
 Example 1
 Slurry a, 400 g, produced in Production Example 1 and 3000 g of
 bishydroxyethyl terephthalate (hereinbelow, referred to as BHET) were put
 in an autoclave provided with a distilling tube and mixed, and agitated at
 a temperature of about 120.degree. C. for about three hours. While being
 further agitated for about one hour, the mixture was decompressed to
 remove water, so as to prepare a BHET slurry (containing a minute amount
 of water) essentially composed of silane-treated foliated phyllosilicate a
 and BHET.
 Thereafter, 7.5 g of a hindered phenol stabilizer (AO60 manufactured by
 Asahi Denka Kogyo K.K.; hereinbelow, referred to as AO60) and 0.45 of
 antimony trioxide (Sb.sub.2 O.sub.3 ; hereinbelow, referred to as Sb.sub.2
 O.sub.3) as polymerization catalyst were added to the slurry, to
 polymerize BHET at a polymerization reaction temperature of 280.degree. C.
 under decompression, thereby to produce polyethylene terephthalate (PET).
 Thus, a thermoplastic polyester resin composition containing
 silane-treated foliated phyllosilicate a was produced. The logarithmic
 viscosity of the PET in the thermoplastic polyester resin composition was
 0.59 (dl/g).
 TEM observation was performed for a test piece obtained by the injection
 molding of the resultant thermoplastic polyester resin composition, to
 obtain, with respect to the dispersed silane-treated foliated
 phyllosilicate, the value [R.sub.B300 ]of the rate of dispersed layers
 having an equivalent area circle diameter of 300 nm or less with respect
 to the entire silane-treated foliated phyllosilicate, the value [D.sub.B ]
 of the average of the equivalent area circle diameters, the value [N.sub.B
 ]of the number of layers of the silane-treated foliated phyllosilicate per
 unit ash content and per unit area, the average value of the layer
 thicknesses, and the rate of layers having a thickness of 5 nm or less
 with respect to the entire dispersed layers. FIG. 1 shows a TEM photograph
 of the thermoplastic polyester resin composition obtained in Example 1. As
 is apparent from FIG. 1, the layers of the silane-treated foliated
 phyllosilicate are dispersed in the resin phase in the state of very thin
 layers without aggregating with one another.
 The SAXS measurement was performed for the injection-molded test piece of
 the thermoplastic polyester resin composition, to obtain the value
 [I.sub.B ]of the intensity of the small angle X-ray diffraction
 originating from silane-treated foliated phyllosilicate a and the basal
 spacing of silane-treated foliated phyllosilicate a. A small angle X-ray
 diffraction diagram of the thermoplastic polyester resin composition
 obtained in Example 1 is shown in FIG. 2. As is shown in FIG. 2, no peak
 of crystallinity originating from the silane-treated foliated
 phyllosilicate was observed. This indicates that the layers were not
 aggregated with one another but were dispersed independently. The
 evaluation result of the basal spacing in this case was set as &gt;10 nm.
 The optical microscope observation and the SAXS measurement were performed
 for the molded product obtained in Production Example 6. The results were
 evaluated in the manner described above, and the value [D.sub.B
 ]/[D.sub.B1 ], the value [N.sub.B ]/[N.sub.B1 ], and the value [I.sub.B
 ]/[I.sub.B1 ] were obtained.
 Other evaluation items include the ash content of the thermoplastic
 polyester resin composition originating from the silane-treated foliated
 phyllosilicate, and the load deflection temperature, the flexural
 strength, the flexural elastic modulus, and the visual surface finishing
 of the injection-molded test piece.
 The above evaluation results are shown in Table 2 below.
 Example 2
 PET was produced by polymerization in the manner described in Example 1,
 except that 2700 g of slurry b produced in Production Example 2 was used,
 to produce a thermoplastic polyester resin composition containing
 silane-treated foliated phyllosilicate b, and the resultant composition
 was evaluated. The evaluation results are shown in Table 2 below.
 The logarithmic viscosity of PET in the thermoplastic polyester resin
 composition produced in Example 2 was 0.60 (dl/g).
 Example 3
 PET was produced by polymerization in the manner described in Example 1,
 except that 2700 g of slurry c produced in Production Example 3 was used,
 to produce a thermoplastic polyester resin composition containing
 silane-treated foliated phyllosilicate c, and the resultant composition
 was evaluated. The evaluation results are shown in Table 2 below.
 The logarithmic viscosity of PET in the thermoplastic polyester resin
 composition produced in Example 3 was 0.60 (dl/g).
 Example 4
 Slurry a produced in Production Example 1, 400 g, and 3000 g of 1,4-BD were
 put in an autoclave provided with a distilling tube and sufficiently
 mixed. Thereafter, the mixture was agitated at a temperature of about
 120.degree. C. for about three hours. While being further agitated for
 about one hour, the mixture was decompressed to remove water, so as to
 prepare a 1,4-BD slurry (containing a minute amount of water) essentially
 composed of silane-treated foliated phyllosilicate a and 1,4-BD.
 Thereafter, 1765 g of DMT, 6.0 g of AD60, and 0.42 g of titanium
 tetrabutoxide (Ti(OBu).sub.4) as an ester exchange catalyst were put in
 the autoclave. A rectifying column was attached to the autoclave, and the
 mixture was agitated at a reaction temperature of about 190.degree. C. for
 about four hours, to allow DMT and 1,4-BD to perform ester exchange with
 each other to produce bishydroxybutyl terephthalate (hereinbelow, referred
 to as BHBT).
 Thereafter, the rectifying column was removed, BHBT was then polymerized
 under decompression to produce polybutylene terephthalate (PBT) at
 260.degree. C. of polymerization temperature, and thus to produce a
 thermoplastic polyester resin composition containing silane-treated
 foliated phyllosilicate a. The resultant composition was evaluated in the
 manner described in Example 1, except that the system produced in
 Production Example 12 was used in place of the system produced in
 Production Example 6. The results are shown in Table 2 below.
 The logarithmic viscosity of PBT in the thermoplastic polyester resin
 composition produced in Example 4 was 0.82 (dl/g).
 Example 5
 Slurry a produced in Production Example 1, 14000 g, and 5000 g of EG were
 mixed and agitated at a temperature of about 130.degree. C. for about four
 hours. While being further agitated for about one and a half hours, the
 mixture was decompressed to remove water, so as to prepare an EG slurry
 (containing a minute amount of water) essentially composed of
 silane-treated foliated phyllosilicate a and EG.
 Thereafter, the EG slurry, 5000 g of PET, and 15 g of a hindered phenol
 stabilizer were put in a horizontal continuous polymerization reactor via
 a supply port thereof, and agitated at 30 rpm at a temperature of
 280.degree. C. for about three hours, so as to depolymerize PET while
 removing ethylene glycol from the system. Then, the system was
 decompressed and generated ethylene glycol was removed from the system, to
 allow for polycondensation reaction to obtain PET. Thus, a thermoplastic
 polyester resin composition containing silane-treated foliated
 phyllosilicate a was produced and continuously released from a spout of
 the reactor. The resultant composition was evaluated in the manner
 described in Example 1, except that the system produced in Production
 Example 7 was used in place of the system produced in Production Example
 6. The results are shown in Table 2 below.
 The logarithmic viscosity of PET in the thermoplastic polyester resin
 composition produced in Example 5 was 0.64 (dl/g).
 Example 6
 PBT was polymerized in the manner described in Example 5, except that
 1,4-BD was used in place of EG, PBT was used in place of PET, and the
 temperature of the polymerization reactor was set at 260.degree. C., to
 produce a thermoplastic polyester resin composition containing
 silane-treated foliated phyllosilicate a. The resultant composition was
 evaluated in the manner described in Example 1, except that the system
 produced in Production Example 13 was used in place of the system produced
 in Production Example 6. The results are shown in Table 2 below.
 The logarithmic viscosity of PBT in the thermoplastic polyester resin
 composition produced in Example 6 was 0.83 (dl/g).
 Example 7
 PET was polymerized in the manner described in Example 5, except that 7000
 g of slurry d produced in Production Example 4 was used in place of slurry
 a, to produce a thermoplastic polyester resin composition containing
 silane-treated foliated phyllosilicate d. The resultant composition was
 evaluated in the manner described in Example 1, except that the system
 produced in Production Example 11 was used in place of the system produced
 in Production Example 6. The results are shown in Table 2 below.
 The logarithmic viscosity of PET in the thermoplastic polyester resin
 composition produced in Example 7 was 0.65 (dl/g).
 Example 8
 Using 10000 g of slurry a and 1950 g of BHET, a BHET slurry (containing a
 minute amount of water) essentially composed of silane-treated foliated
 phyllosilicate a and BHET was prepared, as described in Example 1.
 Thereafter, 4.5 g of AO60 and 0.2 g of Sb.sub.2 O.sub.3 were added to
 effect polymerization as described in Example 1, to obtain a composition
 essentially composed of silane-treated foliated phyllosilicate a and PET
 having a low molecular weight and a logarithmic viscosity of 0.27 (dl/g).
 The composition was solidified by cooling and sufficiently dried. The
 resultant composition was subjected to solid-phase polymerization under a
 decompression of about 0.5 torr at 200 to 210.degree. C. for nine hours,
 to increase the molecular weight of the PET and thus to produce a
 thermoplastic polyester resin composition containing silane-treated
 foliated phyllosilicate a. The resultant composition was evaluated in the
 manner described in Example 1, except that the system produced in
 Production Example 8 was used in place of the system produced in
 Production Example 6. The results are shown in Table 2 below.
 The logarithmic viscosity of PET in the thermoplastic polyester resin
 composition produced in Example 8 was 0.61 (dl/g).
 Example 9
 A thermoplastic polyester resin composition containing silane-treated
 foliated phyllosilicate b was produced in the manner described in Example
 8, except that 6750 g of slurry b was used in place of slurry a. The
 resultant composition was evaluated in the manner described in Example 1
 except that the system produced in Production Example 8 was used in place
 of the system produced in Production Example 6. The results are shown in
 Table 2 below.
 The logarithmic viscosity of PET in the thermoplastic polyester resin
 composition produced in Example 9 was 0.62 (dl/g).
 Example 10
 PBT was polymerized using 10000 g of slurry a, 2250 g of 1,4-BD, 1330 g of
 DMT, 0.32 g of Ti(OBu).sub.4, and 4.5 of AO60 in a manner as described in
 Example 4, to obtain a composition essentially composed of silane-treated
 foliated phyllosilicate a and the PBT having a low molecular weight and a
 logarithmic viscosity of 0.29 (dl/g).
 The composition was subjected to solid-phase polymerization as described in
 Example 8, to increase the molecular weight of the PBT and thus to produce
 a thermoplastic polyester resin composition. The resultant composition was
 evaluated in the manner described in Example 1, except that the system
 produced in Production Example 14 was used in place of the system produced
 in Production Example 6. The results are shown in Table 2 below.
 The logarithmic viscosity of PBT in the thermoplastic polyester resin
 composition produced in Example 10 was 0.79 (dl/g).
 Example 11
 Slurry a was dried and pulverized to obtain powdered silane-treated
 foliated phyllosilicate a.
 Then, 480 g of silane-treated foliated phyllosilicate a, 1500 g of PET, of
 AO60 were dry-blended. The mixture was molten and mixed using a
 unidirectional engaging type twin screw extruder provided with a kneading
 disk at 100 rpm at a set temperature of 250 to 270.degree. C., so as to
 produce a thermoplastic polyester resin composition containing
 silane-treated foliated phyllosilicate a. The resultant composition was
 evaluated in the manner described in Example 1 except that the system
 produced in Production Example 9 was used in place of the system produced
 in Production Example 6. The results are shown in Table 2 below.
 Reference Examples 1 and 2
 PET and PBT test pieces were obtained by injection molding, and the load
 deflection temperature, the flexural elastic modulus, and the surface
 finishing were evaluated. The results are shown in Table 2 below.
 TABLE 2

Ref.
 Examples
 Example Comparative Examples
 12 13 14 15
 3 6 7
 Thermoplastic resin PC PC PC PC
 PC PC PC
 Inorganic compound Silane-treated Silane-treated Silane-treated
 Silane-treated -- Montmoril- Treated
 Type foliated phyllo- foliated phyllo- foliated phyllo-
 foliated phyllo- lonite montmorillonite a'
 silicate a silicate b silicate c silicate d
 (parts by weight) 6.0 6.0 6.0 6.0
 0 6.0 6.0
 Ash content (wt. %) 5.8 5.8 5.8 5.9
 0 5.8 5.7
 [R.sub.8330 ] (%) 71 67 53 91
 0 0
 [D.sub.8 ] (nm) 218 296 512 91
 3050 2950
 [D.sub.8 /D.sub.81 ] .times. 10.sup.-3 5.45 7.40
 8.53 2.28 76.3 73.8
 [N.sub.8 ](pcs./wt % .multidot. .mu.m.sup.2) 2.52 2.34
 1.67 5.17 0.025 0.029
 [N.sub.8 /N.sub.81 ] value 890 827 590
 1827 8.83 10.3
 Avevage layer 8.6 7.8 13.6 2.3
 2650 2320
 thickness (nm)
 Ratio of 5 nm or 59 50 32 89
 0 0
 less thick layers
 [I.sub.8 /I.sub.81 ] .times. 10.sup.-2 14.3 16.7
 20.2 0 92.9 91.3
 Basal spacing (nm) 6.8 6.5 4.8 &gt;10
 1.3 1.3
 Load deflection 161 162 156 164
 134 134 135
 temperature (.degree. C.)
 Flexural strength 148 151 148 156
 107 108 109
 (MPa)
 Flexural elastic 3680 3760 3050 3980
 2210 2220 2230
 modulus (MPa)
 Surface finishing .smallcircle. .smallcircle. .smallcircle. .smallcircle.
 .smallcircle. .DELTA. .DELTA.
 INDUSTRIAL APPLICABILITY
 According to the present invention, the silane-treated foliated
 phyllosilicate (B) obtained by introducing the organosilane compound (B2)
 into the swellable layered silicate (B1) after the basal spacing of the
 swellable layered silicate (B1) has been expanded is used as a filler for
 the thermoplastic resin composition. When the silane-treated foliated
 phyllosilicate is included in the thermoplastic resin composition (C),
 layers of the silane-treated foliated phyllosilicate are exfoliated,
 further expanding the basal spacing. As a result, the silane-treated
 foliated phyllosilicate (B) exists in the thermoplastic resin composition
 (C) as a number of very fine layers dispersed independently from one
 another. Thus, according to the present invention, the thermoplastic resin
 composition (C) excellent in various properties such as the mechanical
 properties (elastic modulus, strength, tenacity, etc.), heat resistance,
 and the surface appearance of molded products can be obtained only by
 adding a small amount of the silane-treated foliated phyllosilicate (B).
 In the conventional technique, the swellable layered silicate (B1) in the
 state of an aggregate structure where layers are stratified with one
 another, or the swellable layered silicate (B1) in the state of an
 aggregate structure treated with the organosilane compound (B2) is used as
 a filler for the thermoplastic resin composition. Accordingly, the elastic
 modulus and the heat resistance are not improved by adding a small amount
 of such a filler. On the contrary, if a large amount of the filler is
 added, the surface finishing, the strength, the impact strength, and the
 like of the resultant molded product are degraded. Balancing these
 properties has been difficult.