JP3400743B2 - Thermoplastic resin composition and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an inorganic fine particle reinforced thermoplastic resin composition having excellent thermal stability during molding and a method for producing the same.

[0002]

2. Description of the Related Art Polycarbonate-based resins have high impact resistance,
It is a thermoplastic resin having excellent heat resistance and is widely used for parts and the like in the fields of machines, automobiles, electric and electronic fields by taking advantage of these characteristics. However, it has a drawback that it is inferior in moldability and chemical resistance. On the other hand, the thermoplastic polyester-based resin has excellent mechanical properties, electrical properties, chemical resistance, etc., and exhibits good molding fluidity when heated above its own crystal melting point.

Therefore, in order to improve the above-mentioned problems in polycarbonate resins, for example, Japanese Patent Publication No. 36-14.
Japanese Patent Publication No. 035, Japanese Patent Publication No. 39-20434, Japanese Patent Publication No. 59-176345 and the like propose techniques for adding a thermoplastic polyester resin to a polycarbonate resin.

Further, in Japanese Patent Laid-Open No. 4-85360,
A technique for improving the rigidity, dimensional stability, surface property, low linear expansion coefficient, etc. of a resin composition by adding mica to a mixture of such a polycarbonate resin and a thermoplastic polyester resin is disclosed. Further WO97 / 319
In JP-A-80, when a mixture of a polycarbonate-based resin and a thermoplastic polyester-based resin is flame-retarded with a phosphorus-based flame retardant, a silicate compound is added to improve flame retardancy and heat resistance. The technology is disclosed.

However, in these techniques, since the inorganic silicate compound generally shows basicity, when a polycarbonate resin added with the inorganic silicate compound is melted at high temperature for a long time to form a carbonate, the carbonate It has the drawback of accelerating the breaking of bonds. As a result, the conventional technique has a problem that a defective appearance such as silver occurs during molding at high temperature. Further, if the resin is allowed to stay at a high temperature for a long time during the molding process, the molecular weight is lowered due to the decomposition of the resin, and the strength and long-term reliability of the obtained molded product may be lowered.

[0006]

SUMMARY OF THE INVENTION In view of the above situation, it is an object of the present invention to provide an inorganic fine particle reinforced thermoplastic resin composition having excellent thermal stability during molding and a method for producing the same. It is a thing.

[0007]

Means for Solving the Problems The present inventors have found that an inorganic silicate compound exhibiting basicity does not impair the stability relative to a thermoplastic polyester compound and is almost free from molding processes even at high temperatures. We paid close attention to the fact that there was no problem, and conducted a thorough study. As a result, when the inorganic silicate compound is added to the polymer alloy composed of the polycarbonate resin / thermoplastic polyester resin, the inorganic silicate compound is dispersed so that the inorganic silicate compound does not exist inside the polycarbonate resin as much as possible. The present invention has been completed by finding that controlling the state significantly improves the thermal stability at the time of molding at high temperature, and that a high-performance resin composition can be obtained.

That is, the present invention comprises a polycarbonate resin (A) and a thermoplastic polyester resin (B),
The weight ratio of (A) / (B) is 45/55 to 99/1, and the pH is 8.0 or more with respect to 100 parts by weight of the total of (A) and (B). Yes, 3 units of SiO ₂
A thermoplastic resin composition containing 0.5 to 100 parts by weight of an inorganic compound (C) having a weight average particle size of 100 μm or less, which accounts for 0% by weight or more, and is a total particle of the inorganic compound (C). , Total number of particles x [{addition amount of ((B)} /
The amount of {(A) added amount + (B) added amount} × 1.8 or more particles is the thermoplastic resin composition present in a phase other than the polycarbonate resin phase.

Further, according to the present invention, when the thermoplastic resin composition is produced by a kneading machine, a first supply port provided at the base of the kneading machine, a second supply port provided downstream of the first supply port, and Using a kneading device having at least a vent port provided at a position closer to the second supply port between the first supply port and the second supply port and opened to atmospheric pressure,
Of the raw material of the composition, 30% by weight or more of the added amount of the inorganic compound (C) is supplied from the second supply port,
The remaining raw materials are also the method for producing the thermoplastic resin composition, which is supplied from the first supply port. The present invention is described in detail below.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin composition of the present invention comprises
The raw material is three components of a polycarbonate resin (A), a thermoplastic polyester resin (B) and an inorganic compound (C).

The polycarbonate resin (A) to be added to the thermoplastic resin composition of the present invention is a polycarbonate obtained by polymerizing a divalent or higher valent phenol compound and phosgene or carbonic acid diester by a known method.

The divalent phenol compound is not particularly limited, and examples thereof include 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A] and bis (4-).
Hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl)
-(4-isopropylphenyl) methane, bis (3,5
-Dimethyl-4-hydroxyphenyl) methane, 1,1
-Bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane,
1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl)
Ethane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-
4-hydroxyphenyl) propane, 1-ethyl-1,
1-bis (4-hydroxyphenyl) propane, 2,2
-Bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) butane, 1,
4-bis (4-hydroxyphenyl) butane, 2,2-
Bis (4-hydroxyphenyl) pentane, 4-methyl-2,2-bis (4-hydroxyphenyl) pentane,
2,2-bis (4-hydroxyphenyl) hexane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane, 1,
10-bis (4-hydroxyphenyl) decane, 1,1
-Dihydroxydiarylalkanes such as bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane; 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl)
Dihydroxydiarylcycloalkanes such as cyclodecane; Dihydroxydiaryl sulfones such as bis (4-hydroxyphenyl) sulfone and bis (3,5-dimethyl-4-hydroxyphenyl) sulfone; Bis (4-
Dihydroxydiaryl ethers such as hydroxyphenyl) ether and bis (3,5-dimethyl-4-hydroxyphenyl) ether; 4,4′-dihydroxybenzophenone, 3,3 ′, 5,5′-tetramethyl-4,
Dihydroxydiarylketones such as 4'-dihydroxybenzophenone; bis (4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, etc. Dihydroxydiaryl sulfides; Dihydroxydiaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide;
Dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl; Dihydroxyarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene; Dihydroxybenzenes such as hydroquinone, resorcinol and methylhydroquinone; 1,5-dihydroxy Examples thereof include dihydroxynaphthalenes such as naphthalene and 2,6-dihydroxynaphthalene. These may be used alone or in combination of two or more. Among them, bisphenol A is preferable.

The carbonic acid diester is not particularly limited,
For example, diaryl carbonate such as diphenyl carbonate; dialkyl carbonate such as dimethyl carbonate and diethyl carbonate; These may be used alone or in combination of two or more.

The polycarbonate resin (A) is not limited to a linear polycarbonate and may be a branched polycarbonate. The branching agent used to obtain this branched polycarbonate is not particularly limited,
For example, phloroglucin, mellitic acid, trimellitic acid, trimellitic acid chloride, trimellitic anhydride, gallic acid, n-propyl gallate, protocatechuic acid, pyromellitic acid,
Pyromellitic dianhydride, α-resorcinic acid, β-resorcinic acid, resorcinaldehyde, isatin bis (o-cresol), benzophenone tetracarboxylic acid, 2,
4,4'-trihydroxybenzophenone, 2,2 ',
4,4'-tetrahydroxybenzophenone, 2,4
4'-trihydroxyphenyl ether, 2,2 ',
4,4'-tetrahydroxyphenyl ether, 2,
4,4'-trihydroxydiphenyl-2-propane,
2,2'-bis (2,4-dihydroxyphenyl) propane, 2,2 ', 4,4'-tetrahydroxydiphenylmethane, 2,4,4'-trihydroxydiphenylmethane, 1- [α-methyl-α- (4′-Dihydroxyphenyl) ethyl] -3- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α- (4′-dihydroxyphenyl) ethyl]- Four
-[Α ', α'-bis (4 "-hydroxyphenyl) ethyl] benzene, α, α', α" -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 2,6- Bis (2-hydroxy-5'-methylbenzyl) -4-methylphenol, 4,6-dimethyl-
2,4,6-Tris (4'-hydroxyphenyl) -2
-Heptene, 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) -heptane, 1,3,5
-Tris (4'-hydroxyphenyl) benzene, 1,
1,1-tris (4-hydroxyphenyl) ethane,
2,2-bis [4,4-bis (4'-hydroxyphenyl) cyclohexyl] propane, 2,6-bis (2'-
Hydroxy-5'-isopropylbenzyl) -4-isopropylphenol, bis [2-hydroxy-3-
(2'-hydroxy-5'-methylbenzyl) -5-methylphenyl] methane, bis [2-hydroxy-3-
(2'-hydroxy-5'-isopropylbenzyl)-
5-methylphenyl] methane, tetrakis (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) phenylmethane, 2 ', 4', 7-trihydroxyflavan, 2,4,4-trimethyl-2 ', 4 ', 7-
Trihydroxyflavan, 1,3-bis (2 ', 4'-
Dihydroxyphenylisopropyl) benzene, tris (4′-hydroxyphenyl) -amyl-s-triazine and the like can be mentioned.

In some cases, the polycarbonate resin (A) may be a polycarbonate-polyorganosiloxane copolymer composed of a polycarbonate part and a polyorganosiloxane part. At this time, the degree of polymerization of the polyorganosiloxane part is preferably 5 or more.

Further, the polycarbonate resin (A) is a polycarbonate obtained by copolymerizing a linear aliphatic dicarboxylic acid such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and decanedicarboxylic acid. It may be a system copolymer.

As the terminal terminator used for polymerizing the polycarbonate resin (A), various known ones can be used. Specific examples include monohydric phenols such as phenol, p-cresol, pt-butylphenol, pt-octylphenol, p-cumylphenol and nonylphenol.

In order to obtain flame retardancy, the polycarbonate resin (A) may be a polycarbonate copolymer with a phosphorus compound, or may be a polycarbonate resin end-capped with a phosphorus compound. Good. Further, in order to enhance weather resistance, a polycarbonate-based copolymer with a dihydric phenol having a benzotriazole group may be used.

The viscosity average molecular weight of the polycarbonate resin (A) blended in the thermoplastic resin composition of the present invention is 1
It is preferably 0000 to 60,000. 1000
When it is less than 0, strength and heat resistance of the obtained resin composition are often insufficient. On the other hand, if it exceeds 60,000,
Molding processability is often insufficient. It is more preferably 15,000 to 45,000, and even more preferably 180.
It is 00-35000.

In the thermoplastic resin composition of the present invention, the polycarbonate resin (A) may be used alone or in combination of two or more.
When two or more kinds are used in combination, the combination is not particularly limited. For example, those having different monomer units, those having different copolymerization molar ratios, those having different molecular weights and the like can be arbitrarily combined.

The thermoplastic polyester resin (B) blended in the thermoplastic resin composition of the present invention comprises a carboxylic acid compound having a valence of 2 or more and an alcohol and / or phenol compound having a valence of 2 or more by a known method. It is a thermoplastic polyester obtained by polycondensation. Specific examples include, but are not limited to, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like. .

The divalent or higher carboxylic acid compound is not particularly limited, and examples thereof include divalent or higher valent aromatic carboxylic acids having 8 to 22 carbon atoms and ester-forming derivatives thereof. Specifically, for example, phthalic acid such as terephthalic acid and isophthalic acid; naphthalenedicarboxylic acid, bis (p
-Carboxyphenyl) methane, anthracene dicarboxylic acid, 4-4'-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, diphenylsulfonedicarboxylic acid, trimesic acid, trimellitic acid, pyro Examples thereof include carboxylic acids such as meritic acid and derivatives thereof having ester-forming ability. These may be used alone or in combination of two or more. Among them, terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid is preferable from the viewpoints of easy handling, easy reaction, physical properties of the obtained resin composition and the like.

The divalent or higher valent alcohol and / or phenol compound is not particularly limited, and has, for example, 2 to 2 carbon atoms.
15 aliphatic compounds, alicyclic compounds having 6 to 20 carbon atoms,
Examples thereof include aromatic compounds having 6 to 40 carbon atoms and compounds having two or more hydroxyl groups in the molecule, and ester-forming derivatives thereof. Specifically, for example, ethylene glycol, propylene glycol, butanediol, hexanediol, decanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediol, 2,2'-bis (4-hydroxyphenyl) propane, 2,2 Examples include ′ -bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, and derivatives thereof having ester-forming ability. These may be used alone or in combination of two or more. Among them, ethylene glycol, butanediol, or cyclohexanedimethanol is preferable from the viewpoints of easy handling, easy reaction, physical properties of the obtained resin composition, and the like.

The thermoplastic polyester resin (B) is obtained by copolymerizing, in addition to the above-mentioned carboxylic acid compound and alcohol and / or phenol compound, a known copolymerizable compound within a range that does not impair desired properties. It may be obtained. Such a copolymerizable compound is not particularly limited, and examples thereof include a divalent or more aliphatic carboxylic acid having 4 to 12 carbon atoms, a divalent or more alicyclic carboxylic acid having 8 to 15 carbon atoms, and the like. Examples thereof include ester-forming derivatives. Specifically, for example, dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, maleic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid, or derivatives thereof having ester forming ability. Etc. Other examples include oxyacids such as p-hydroxybenzoic acid or ester-forming derivatives thereof, cyclic esters such as ε-caprolactone, and the like.

Further, a thermoplastic polyester resin (B)
May be a thermoplastic polyester resin obtained by partially copolymerizing a polyalkylene glycol unit in the polymer chain. Such polyalkylene glycol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or
Alternatively, a random copolymer, a bisphenol A copolymerized polyethylene oxide addition polymer, the same propylene oxide addition polymer, the same tetrahydrofuran addition polymer, polytetramethylene glycol, etc. may be mentioned.

The amount of the above-mentioned copolymerization component used in the thermoplastic polyester resin (B) is usually 2
It is 0% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less.

The thermoplastic polyester resin (B) is used to balance the physical properties of the resulting resin composition (for example, moldability).
It has 8 alkylene terephthalate units because of its excellent
It is preferably a polyalkylene terephthalate containing 0% by weight or more. It is more preferably polyalkylene terephthalate containing 85% by weight or more, and further preferably 90% by weight or more of the same unit.

The thermoplastic polyester resin (B) has a logarithmic viscosity (IV) of 0.30 to 2.00 dl / when measured at 25 ° C. in a mixed solvent of phenol / tetrachloroethane = 1/1 (weight ratio). It is preferably at least g. If the logarithmic viscosity is less than 0.30, the flame retardancy and mechanical strength of the molded product are often insufficient, and 2.00 dl / g
If it exceeds, the molding fluidity tends to decrease. It is more preferably 0.40 to 1.80 dl / g, still more preferably 0.50 to 1.60 dl / g.

In the thermoplastic resin composition of the present invention, the thermoplastic polyester resin (B) may be used alone or in combination of two or more. When two or more kinds are used in combination, the combination is not particularly limited. For example, copolymer components, different molar ratios, different molecular weights, etc. can be arbitrarily combined.

In the thermoplastic resin composition of the present invention, the mixing ratio [(A) / (B)] of the polycarbonate resin (A) and the thermoplastic polyester resin (B) is 45/55 by weight. ~ 99/1. If it is less than 45/55, dimensional stability, impact resistance, etc. tend to decrease,
If it exceeds 99/1, the thermal stability and solvent resistance of the resulting molded article tend to be reduced. Preferably from 51/49
95/5, more preferably 60/40 to 90/1
It is 0.

The inorganic compound (C) to be blended with the thermoplastic resin composition of the present invention has a pH of 8.0 or more and SiO ₂
The unit accounts for 30% by weight or more, and the weight average particle size is 10
It is an inorganic compound of 0 μm or less. This component is used for the purpose of improving various properties such as heat resistance, mechanical strength and elastic modulus while suppressing the anisotropy of the shrinkage ratio of the resin. When a flame retardant is added to the thermoplastic resin composition of the present invention to make it flame retardant, it is used for the purpose of enhancing the flame retardant effect.

SiO ₂ used as the inorganic compound (C)
The inorganic compound whose unit accounts for 30% by weight or more is not particularly limited, and examples thereof include magnesium silicate, aluminum silicate, calcium silicate, talc, mica, wollastonite, kaolin, diatomaceous earth, and smectite. Among them, mica, talc, kaolin or smectite is preferable because it has the effect of suppressing the anisotropy of the obtained molded product and is also excellent in heat resistance and mechanical strength.

The inorganic compound (C) has a weight average particle diameter of 1
The fine particles have a size of 00 μm or less. If it exceeds 100 μm,
The appearance of the obtained molded product is impaired, and the impact strength of the resin composition tends to decrease. Preferably from 1 nm
It is 70 μm, and more preferably 10 nm to 50 μm. In addition, the weight average particle diameter in the present invention is equivalent to the opening of the microsieve through which 50% by weight of the total weight of the powder subjected to the measurement has passed as a result of classifying the powder with various openings of the microsieve. It is defined by the value to

The shape of the inorganic compound (C) is not particularly limited, but typical examples thereof include powder, granules, needles and plates. This inorganic compound may be a natural product or a synthetic product. In the case of a natural product, the place of origin is not particularly limited and can be appropriately selected.

The inorganic compound (C) has a pH of 8.0 or higher. Since the polycarbonate resin (A) is stable even if an inorganic compound having a pH of less than 8.0 is added, it is not necessary to apply the technique of the present invention. In particular, the improvement effect of the present invention is great because the p of the inorganic compound (C) is
This is the case where H is 8.8 or more. The pH referred to in the present invention
Is a digital p based on JIS K-5101 B method.
It is a value measured by an H meter.

The inorganic compound (C) may be surface-treated with various surface-treating agents such as silane-treating agents in order to enhance the adhesiveness with the resin. The surface treatment agent is not particularly limited, and conventionally known ones can be used, but the epoxy group-containing silane coupling agent such as epoxysilane, and the amino group-containing silane coupling agent such as aminosilane are It is preferable because the physical properties are less likely to deteriorate. Besides, polyoxyethylene silane or the like can be used. The surface treatment method is not particularly limited, and a usual treatment method can be used.

These inorganic compounds (C) may be used alone or in combination of two or more having different average particle diameter, kind, surface treatment agent and the like.

The amount of the inorganic compound (C) used in the thermoplastic resin composition of the present invention is 0 based on 100 parts by weight of the total of the two components of the polycarbonate resin (A) and the thermoplastic polyester resin (B). 0.5 to 100 parts by weight. If it is less than 0.5 parts by weight, the heat resistance and mechanical strength of the obtained molded article will be reduced, and if it exceeds 100 parts by weight,
In addition to the impact resistance and surface property of the obtained molded article being lowered, kneading with the resin during melt kneading tends to be difficult. It is preferably 1 to 70 parts by weight, and more preferably 2 to 50 parts by weight.
Parts by weight.

A reinforcing filler other than the inorganic compound (C) can be further added to the thermoplastic resin composition of the present invention in order to further enhance the heat resistance and mechanical strength of the resin composition. Such a reinforcing filler is not particularly limited, and examples thereof include fibrous reinforcing agents such as glass fibers, carbon fibers and metal fibers; metal oxides such as titanium oxide and iron oxide; calcium carbonate, glass beads, glass powder, Ceramic powder,
Examples thereof include metal powder and carbon black. These reinforcing fillers may be used alone or in combination of two or more having different types, particle diameters, lengths, surface treatments and the like.

The reinforcing filler may be surface-treated in order to enhance the adhesiveness with the resin. The surface treatment agent used for performing such surface treatment is not particularly limited, but an epoxy group-containing silane coupling agent such as epoxysilane is preferable because it does not deteriorate the physical properties of the resin. The surface treatment method is not particularly limited, and a usual treatment method is used.

When these reinforcing fillers are used, the amount of addition is 1 part with respect to 100 parts by weight of the total of the polycarbonate resin (A) and the thermoplastic polyester resin (B).
It is less than 00 weight. If the addition amount exceeds 100 parts by weight, impact resistance is lowered and, in addition, moldability and flame retardancy may be lowered. It is preferably 50 parts by weight or less,
It is more preferably 10 parts by weight or less. Further, as the addition amount of these reinforcing fillers increases, the surface properties and dimensional stability of the molded product tend to deteriorate, so when these properties are emphasized, the addition amount of the reinforcing fillers should be adjusted. It is preferable to make it as small as possible.

To the thermoplastic resin composition of the present invention, a thermoplastic resin or a thermosetting resin other than the component (A) and the component (B) may be further added within a range not impairing the object of the present invention. . The resin of such an optional component is not particularly limited, and examples thereof include polyolefin resin, polyamide resin, polystyrene resin, polyphenylene sulfide resin, polyphenylene ether resin, polyacetal resin, polysulfone resin; polytetrafluoroethylene. And other fluorinated polyolefin resins. These may be used alone or in combination of two or more. When the resin of these optional components is added, the inorganic compound (C) may be present in the resin of these optional components in the thermoplastic resin composition of the present invention.

The resin of this optional component is preferably an elastic resin in order to enhance the impact strength of the obtained molded product. At least one glass transition point of this elastic resin is preferably 0 ° C. or lower, more preferably −20 ° C. or lower, because the obtained resin composition is excellent in the impact strength improving effect.

The elastic resin is not particularly limited, and examples thereof include dibutadiene rubbers such as polybutadiene, styrene-butadiene rubber, acrylonitrile-butadiene rubber and (meth) acrylic acid alkyl ester-butadiene rubber; acrylic rubber, ethylene-propylene rubber, Rubber-like polymers such as siloxane rubber; various polyolefin resins such as polyethylene and polypropylene; copolymerized polyolefin resins modified with various copolymer components such as ethylene-ethyl acrylate copolymer; ethylene-glycidyl methacrylate copolymer Modified polyolefin resins modified with various functional components such as

Further, this elastic resin contains the above-mentioned diene-based rubber and / or
Or, 10 to 90 parts by weight of at least one monomer selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds and (meth) acrylic acid alkyl esters with respect to 10 to 90 parts by weight of a rubber-like polymer, and It is preferable to add a rubbery copolymer obtained by polymerizing 10 parts by weight or less of another vinyl compound which is copolymerizable with these.

When the elastic resin is added, the addition amount is
It is usually 15 with respect to 100 parts by weight of the total of the polycarbonate resin (A) and the thermoplastic polyester resin (B).
The amount is not more than 10 parts by weight, preferably 0.1 to 12 parts by weight, and more preferably 0.2 to 10 parts by weight. If it exceeds 15 parts by weight, the rigidity, heat resistance, etc. tend to decrease.

In order to improve the performance of the thermoplastic resin composition of the present invention, antioxidants such as phenolic antioxidants and thioether antioxidants; heat stabilizers such as phosphorus stabilizers and the like. Are preferably added alone or in combination of two or more. Further, if necessary, generally well known, stabilizers, lubricants, release agents, plasticizers, flame retardants other than phosphorus-based flame retardants, flame retardant aids, ultraviolet absorbers, light stabilizers,
Pigments, dyes, antistatic agents, conductivity-imparting agents, dispersants, compatibilizers, antibacterial agents, etc. may be added alone or in combination of two or more.

In the thermoplastic resin composition of the present invention,
Of all particles of the inorganic compound (C), the total number of particles x
[{Addition amount of (B)} / {Addition amount of (A) + addition amount of (B)} × 1.8 or more particles are present in a phase other than the polycarbonate resin phase. This enhances the thermal stability of the obtained thermoplastic resin composition when it is molded at high temperature. Among them, the total number of particles x 70% of all the particles of the inorganic compound (C), and the total number of particles x [{(B)
Addition amount} / {(A) addition amount + (B) addition amount} ×
2] and a larger number of particles are present in a phase other than the polycarbonate resin phase (however, in this case, the addition amount of (A) / (B) is 99). / 1 to 51/49). More preferably, the total number of particles x 8 among all particles of the inorganic compound (C)
0% and the total number of particles × [{(B) addition amount} / {(A) addition amount + (B) addition amount}] × 2, which is a larger number of particles is a polycarbonate type Exists in phases other than the resin phase (however, in this case, the amount of (A) added /
(B) is added in the range of 99/1 to 51/49). The larger the proportion of the inorganic compound (C) present in the phase other than the polycarbonate resin phase, the more the thermal stability during high temperature processing tends to be improved.

The number of particles of the inorganic compound (C) is measured by observing a cutting surface obtained by cutting the thermoplastic resin composition of the present invention with a transmission electron microscope, and measuring the inorganic compound (C) in the visual field. It is performed by measuring the number of particles (the total number of particles of the inorganic compound (C) and the number of particles of the inorganic compound (C) existing in a phase other than the polycarbonate resin phase) (here, the polycarbonate resin phase and Other phases can be distinguished by electron microscopy). Depending on the method for producing this composition, the dispersion state of the particles may differ between the surface layer and the inside, so there are three locations: near the surface layer (about 50 μm from the surface layer), in the center and near the middle of both. Is measured by a transmission electron microscope, and the average value of the values measured at these three points is used as the number of particles of the inorganic compound (C). Further, the width of the field of view of the electron microscope image used for the measurement is preferably about 100 times the area of the average particle diameter of the inorganic compound (C).

The method for producing the thermoplastic resin composition of the present invention is not particularly limited. For example, it can be produced by drying the above-mentioned components, additives, etc., and then melt-kneading them with a melt-kneader such as a single-screw or twin-screw extruder. When the compounding ingredients are liquid,
It can also be produced by adding it to the melt-kneader halfway using a liquid supply pump or the like.

As a preferred manufacturing method, when the thermoplastic resin composition of the present invention is manufactured by a kneading device, a first supply port provided at the base of the kneading device and a second supply port provided downstream of the first supply port. Port, and using a kneading device comprising at least a vent port provided at a position closer to the second supply port between the first supply port and the second supply port and opened to atmospheric pressure, Of the raw materials of the composition, 30% by weight or more of the added amount of the inorganic compound (C) is supplied from the second supply port, while the remaining raw materials are supplied from the first supply port. is there.

The manufacturing method of the present invention can be typically carried out using, for example, the apparatus shown in FIG. In FIG. 1, the first supply port 1 has a component (A), a component (B) and 70% by weight.
The following component (C) is added. The introduced raw materials are transported, kneaded and moved in the kneading device in the downstream direction. From the second supply port 3, 30% by weight or more of the component (C) is supplied. A vent port 2 is provided between the first supply port 1 and the second supply port 3 at a position close to the second supply port 3, and the vent port 2 is opened to atmospheric pressure. The raw materials are kneaded, transported downstream, and taken out from the take-out port 5.

By using such a manufacturing method,
The inorganic compound (C) is less likely to enter the polycarbonate resin phase even though the polycarbonate resin (A) and the thermoplastic polyester resin (B) are sufficiently kneaded. The thermoplastic resin composition having the dispersion state of (C) can be easily produced. In particular, when the whole amount of the inorganic compound (C) is supplied together with the components (A) and (B) from the common supply port, or even when the inorganic compound (C) is supplied from the second supply port, the atmospheric pressure is maintained. Dispersion control of the inorganic compound (C) in the resin phase can be easily performed as compared with the case where the released vent port is not used.

In this manufacturing method, the amount of the inorganic compound (C) supplied from the second supply port is 30% by weight or more, but 50% by weight or more of the total amount of the inorganic compound (C) added. Is more preferable, and more preferably 70% by weight or more, and the total addition amount of the inorganic compound (C) can be supplied from the second supply port.

In the above kneading device, the position of the vent port 2 opened to the atmospheric pressure is particularly limited as long as it is between the first supply port 1 and the second supply port 3 and closer to the second supply port 3. Not done. Further, a depressurized vent port 4 can be further provided downstream of the second supply port 3.

The kneading device used in the manufacturing method of the present invention is not particularly limited, and a known kneading device can be used. Specifically, for example, TEX44 manufactured by Japan Steel Works, Ltd.
A twin-screw extruder that meshes in the same direction may be used. Of these, a twin-screw extruder is preferable in order to sufficiently knead the polycarbonate resin (A) and the thermoplastic polyester resin (B). The twin-screw extruder is not particularly limited,
Conventionally known ones can be used. The rotation of the screw may be in the same direction or in the opposite direction. This twin-screw extruder has a first supply port 1 and a second supply port 3
Between the kneading disk or the reverse screw structure,
It is more preferable that the resin has a structure for retaining the resin. Immediately downstream of the structure for retaining such resin,
A vent port 2 opened to the atmospheric pressure may be provided.

In the production method of the present invention, the screw rotation speed of the kneading device is generally 20 to 500 rpm. In addition, generally, the set temperature is appropriately set in the range from room temperature to 300 ° C in the section from the first supply port to the second supply port, and is 250 to 300 ° C after the second supply port. The residence time of the resin in the kneading device may be 0.1 to 10 minutes.

The molding method of the thermoplastic resin composition of the present invention is not particularly limited, and for example, molding methods generally used for thermoplastic resins such as injection molding, blow molding, extrusion molding, vacuum molding, Press molding, calendar molding, etc. can be used.

[0059]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Further, in the following, "parts" means parts by weight and "%" means% by weight unless otherwise specified.

[0060]Example 1 Viscosity average molecular weight 22,000 bisphenol A type polycarbonate
Polycarbonate with 70 parts of carbonate resin and relative viscosity of 0.70
30 parts of terephthalate, EEA resin as other resin
Fat (Eva Flex EE manufactured by Mitsui DuPont Polychemical Co., Ltd.
A A709) 2 parts and Adecasta as a stabilizer
Buep EP-22, ADEKA STAB AO-60 and ADEKA STA
Bu HP-10 (all are Asahi Denka brand names) 0.2 parts each
After mixing with a super floater, TE of Japan Steel Works
X44 Same-direction meshing twin screw extruder with screw root
Input from the hopper, which is the first supply port provided nearby
It was 90 ° C on the screw in front of the second supply port
Insert the kneading disc of the
At the position where the end of the
Provided. Side feeder installed right next to the vent
Then, use the side feeder to feed mica from the second supply port (Yamaguchi
A-21S manufactured by Mica, weight average particle diameter 20 μm, pH =
9.0) 20 parts was forcedly pressed. Second supply port and screw
-At the middle part between the tip and the
It has a door. Screw rotation speed 150 rpm, time
The discharge rate was set to 60 kg / hr. Set temperature is first
The temperature near one supply port is 100 ° C, and the set temperature is gradually increased.
The temperature in front of the kneading disc was set to 270 ° C. D
2 from the holding disk to the atmospheric pressure release vent port
At 70 ℃, from the atmospheric pressure open vent port to the second supply port 2
26 ° C from the second inlet to the screw tip at 65 ° C.
It was set to 0 ° C. Sample pellets for evaluation under these conditions
Obtained.

[0061]Comparative Example 1 The same formulation components as in Example 1 were used. Ishinaka iron as a kneading machine
Using the 80 mm single screw extruder HS80 manufactured by Kogaku
-There is no part with retention structure)
All the ingredients were added at once. Screw tip
A pressure reducing vent connected to the pressure reducing pump is provided in front
It was Screw rotation speed 200 rpm, discharge rate per hour
Was set to 180 kg / hr. The set temperature is the same as in Example 1.
It was set to have a similar tendency. Under this condition, the evaluation sun
Pull pellets were obtained.

[0062]Particle abundance ratio Cut the resulting pellet with a diameter of about 3.6 mm at the center
50 μm from pellet surface of section, center of pellet
Part and about 3 mm from the center of the pellet
Observation with a transmission electron microscope was performed. Three images
Inorganic particles present in the polycarbonate phase (My
F) and the presence of other than the polycarbonate phase
Measure the number of particles (mica), (measured with 3 images
Of the number of inorganic particles present in the non-polycarbonate phase
Total) / (sum of the number of inorganic particles measured in 3 images)
The total value was calculated.

[Molding of test piece] Each of the obtained sample pellets was put into a Toshiba 75t molding machine having a preset temperature of 280 ° C, and 127 mm x 12.7 in a molding cycle of 30 seconds.
mm × thickness 3.2 mm A test piece was molded. Further, the test piece was similarly molded in the molding cycle of 30 minutes under the same temperature conditions and the like.

[0064]Impact test Notched Izod test after cutting the specimen in the center
The Izod impact strength was measured at. Regarding each test piece
(The impact test of the test piece obtained by 30 minutes cycle
Value) / (impact test of the test piece obtained by the cycle of 30 seconds
The value of (test value) × 100 was determined. The results are shown in Table 1.
The larger this value, the better the retention heat stability of the resin composition.
Has been.

[0065]Molecular weight After crushing the obtained molded product, it is stirred in a chloroform solvent for 1 day.
I stirred. The obtained solution was used in a GPC measuring device (solvent chloro
Resin in terms of polystyrene by form and RI detector)
Was measured. For each test piece (cycle 3
Weight average content of resin contained in the test piece obtained in 0 minutes
Content) / (included in test pieces obtained by 30 seconds cycle)
The value of (weight average molecular weight of resin) × 100 was determined. This
The results are shown in Table 2. The larger this value is, the resin composition
The retention heat stability of the product is excellent.

[0066]

[Table 1]

[0067]Example 2 and Comparative Example 2 Mica of Example 1 and Comparative Example 1 (Yamaguchi mica A-21
Instead of S), montmorillonite (made by Kunimine Industries Co., Ltd.)
Kunipia-F, weight average particle diameter 20 μm, pH = 10.
0) 100 parts of γ-aminopropyltriethoxy
Use the one surface-treated with 1 part of silane, and add 3
Made in the same manner as in Example 1 and Comparative Example 1 except that
A manufacturing method and an evaluation method were carried out. The results are shown in Table 2.
You

[0068]

[Table 2]

From the results shown in Tables 1 and 2, it can be seen that the thermoplastic resin composition of the present invention is excellent in retention heat stability during molding at high temperature.

[0070]

EFFECTS OF THE INVENTION Since the present invention has the above-mentioned constitution, a basic inorganic compound is added to improve the rigidity, dimensional stability, surface property, low linear expansion coefficient and the like of the thermoplastic resin composition. Also, it is possible to obtain a thermoplastic resin composition which is excellent in residence heat stability during molding at high temperature. Such a thermoplastic resin composition can be suitably used for injection molded products such as home electric appliances, OA equipment parts, AV equipment parts and the like.

[Brief description of drawings]

FIG. 1 is a side view showing an example of a kneading device that can be used in the manufacturing method of the present invention.

[Explanation of symbols]

1; First supply port 2; Vent opening to atmospheric pressure 3; Second supply port 4; Depressurized vent port 5: outlet 6; drive motor

Claims (3)

(57) [Claims] 1. A polycarbonate resin (A) and a thermoplastic polyester resin (B) are contained at a weight ratio of (A) / (B) of 45/55 to 99/1, and
Inorganic compound (C) having a weight average particle diameter of 100 μm or less and having a pH of 8.0 or more and a SiO ₂ unit accounting for 30% by weight or more based on 100 parts by weight of the total of (A) and (B). A thermoplastic resin composition containing 0.5 to 100 parts by weight, wherein, in all particles of the inorganic compound (C),
Total number of particles × [addition amount of {(B)} / {addition amount of (A) +
Addition amount of (B)}] × 1.8 or more particles are present in a phase other than the polycarbonate resin phase, the thermoplastic resin composition. 2. When manufacturing the thermoplastic resin composition according to claim 1 in a kneading device, a first supply port provided at the base of the kneading device, a second supply port provided downstream of the first supply port, And, using a kneading device having at least a vent port opened to atmospheric pressure, which is provided at a position closer to the second supply port between the first supply port and the second supply port,
Of the raw materials of the composition, the addition amount of the inorganic compound (C) is 3
A method for producing a thermoplastic resin composition, characterized in that 0% by weight or more is supplied from the second supply port, while the remaining raw materials are supplied from the first supply port. 3. The manufacturing method according to claim 2, wherein the kneading device is a twin-screw extruder.