JP2000313799A - Thermoplastic resin composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an inorganic fine particles-reinforced thermoplastic resin composition excellent in heat stability in moldability and processability and provide a method for producing the composition. SOLUTION: This composition comprises (A) polycarbonate-based resin, (B) a thermoplastic polyester-based resin and (C) basic inorganic fine particles in which the SiO2 unit occupies >=30 wt.%. In the composition, particles of numbers not smaller than total particle number × [an amount of the component B added/ (an amount of the component A added + an amount of the component B added) × 1.8] among total particles of the basic inorganic fine particles is present in a phase other than the polycarbonate-based resin phase. The composition is produced by using a kneader equipped with a vent port opened at atmospheric pressure between a first feed port and a second feed port, feeding >=30 wt.% inorganic compound (C) based on total raw material of the composition from the second feed port 3 and the balance of the raw material from the first feed port.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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 resins have high impact resistance,
It is a thermoplastic resin excellent in heat resistance and the like, and is widely used for parts in the fields of machinery, automobiles, electricity, and electronics, taking advantage of these features. However, there is a drawback that molding workability and chemical resistance are poor. On the other hand, a thermoplastic polyester resin is excellent in mechanical properties, electrical properties, chemical resistance, and the like, and exhibits good molding fluidity when heated to a temperature higher than its own crystal melting point.

[0003] In order to solve the above-mentioned problems in the polycarbonate resin, for example, Japanese Patent Publication No.
No. 035, JP-B-39-20434, JP-A-59-176345, etc., have proposed techniques of adding a thermoplastic polyester resin to a polycarbonate resin.

[0004] Also, Japanese Patent Application Laid-Open No. 4-85360 discloses that
A technique for improving the rigidity, dimensional stability, surface properties, low linear expansion coefficient, etc. of a resin composition by adding mica to such a mixture of a polycarbonate resin and a thermoplastic polyester resin is disclosed. Furthermore, WO97 / 319
No. 80 discloses that when a mixture of a polycarbonate resin and a thermoplastic polyester resin is made flame retardant with a phosphorus flame retardant, a silicate compound is added to improve the flame retardancy and heat resistance. Techniques are disclosed.

However, in these techniques, since the inorganic silicate compound generally shows basicity, if a polycarbonate-based resin obtained by adding an inorganic silicate compound to a polycarbonate resin is melted at a high temperature for a long period of time, the carbonate may be used. There is a drawback that the bond decomposition is promoted. As a result, the conventional technique has a problem that poor appearance such as silver occurs during molding at a high temperature. In addition, if the resin is kept at a high temperature for a long time during molding, the molecular weight is reduced due to decomposition of the resin, and the strength and long-term reliability of the obtained molded product are sometimes reduced.

[0006]

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

[0007]

The present inventors have found that inorganic silicate compounds exhibiting basicity do not relatively impair the stability of thermoplastic polyester-based compounds and are hardly affected by molding at high temperatures. Noting that there was no problem, we worked diligently. As a result, when the inorganic silicate compound is added to the polymer alloy composed of the polycarbonate-based resin / thermoplastic polyester-based resin, the inorganic silicate compound is dispersed so that the inorganic silicate compound is not present in the polycarbonate-based resin as much as possible. By controlling the state, it has been found that the thermal stability at the time of molding at a high temperature is greatly improved, and a high-performance resin composition can be obtained.

That is, according to the present invention, a polycarbonate resin (A) and a thermoplastic polyester resin (B)
When 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 SiO ₂ units
A thermoplastic resin composition containing 0.5 to 100 parts by weight of an inorganic compound (C) having a weight average particle diameter of 100 μm or less and occupying 0% by weight or more, and among all particles of the inorganic compound (C), , Total number of particles × [{addition amount of (B)} /
{The amount of (A) added + the amount of (B) added}] × 1.8 or more particles are a thermoplastic resin composition present in a phase other than the polycarbonate-based resin phase.

In the present invention, when the thermoplastic resin composition is produced by a kneading apparatus, a first supply port provided at the base of the kneading apparatus, a second supply port provided downstream of the first supply port, and Using a kneading device having at least a vent port opened to the atmospheric pressure provided at a position closer to the second supply port between the first supply port and the second supply port,
At least 30% by weight of the added amount of the inorganic compound (C) among the raw materials of the composition is supplied from the second supply port.
The remaining raw material is also supplied from the first supply port, and is also a method for producing a thermoplastic resin composition. Hereinafter, the present invention will be described in detail.

[0010]

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

The polycarbonate resin (A) to be added to the thermoplastic resin composition of the present invention is a polycarbonate obtained by polymerizing a phenol compound having a valency of 2 or more and phosgene or a carbonic acid diester by a known method.

The divalent phenol compound is not particularly restricted but includes, for example, 2,2-bis (4-hydroxyphenyl) propane [commonly known as 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; dihydroxydiarylsulfones 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,
Dihydroxydiaryl ketones such as 4'-dihydroxybenzophenone; bis (4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide and the like Dihydroxydiaryl sulfides; dihydroxy diaryl 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 Dihydroxynaphthalenes such as naphthalene and 2,6-dihydroxynaphthalene; and the like. These may be used alone or in combination of two or more. Among them, bisphenol A is preferred.

The carbonic diester is not particularly limited.
For example, diaryl carbonates such as diphenyl carbonate; dialkyl carbonates 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, but may be a branched polycarbonate. The branching agent used to obtain this branched polycarbonate is not particularly limited,
For example, phloroglucin, melitic 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), benzophenonetetracarboxylic 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]- 4
-[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.

In some cases, the polycarbonate resin (A) may be a polycarbonate-polyorganosiloxane copolymer comprising 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, decanedicarboxylic acid and the like. It may be a system copolymer.

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

In order to obtain flame retardancy, the polycarbonate resin (A) may be a polycarbonate copolymer with a phosphorus compound or a polycarbonate resin end-blocked with a phosphorus compound. Is also good. Further, in order to enhance the weather resistance, a polycarbonate 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 from 0000 to 60000. 1000
When it is less than 0, the strength and heat resistance of the obtained resin composition are often insufficient. On the other hand, if it exceeds 60000,
In many cases, molding workability is insufficient. It is more preferably 15,000 to 45,000, and further preferably 180
00 to 35000.

In the thermoplastic resin composition of the present invention, one type of the polycarbonate resin (A) may be used alone, or two or more types may be used in combination.
When two or more kinds are used in combination, the combination is not particularly limited. For example, those having different monomer units, different copolymerization molar ratios, 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 divalent or higher carboxylic acid compound and a divalent or higher valent alcohol and / or phenol compound by a known method. It is a thermoplastic polyester obtained by polycondensation. Specifically, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and the like, but are not limited thereto. .

The divalent or higher carboxylic acid compound is not particularly limited, and examples thereof include divalent or higher 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, anthracenedicarboxylic acid, 4-4'-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, diphenylsulfondicarboxylic acid, trimesic acid, trimellitic acid, pyro Examples thereof include carboxylic acids such as melitic acid and derivatives thereof having ester forming ability. These may be used alone or in combination of two or more. Above all, terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid is preferred from the viewpoints of ease of handling, ease of reaction, and properties of the obtained resin composition.

The dihydric or higher valent alcohol and / or phenol compound is not particularly limited.
15 aliphatic compounds, an alicyclic compound having 6 to 20 carbon atoms,
Examples thereof include aromatic compounds having 6 to 40 carbon atoms and having two or more hydroxyl groups in a 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 '-Bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, derivatives thereof having an ester-forming ability, and the like. These may be used alone or in combination of two or more. Among them, ethylene glycol, butanediol or cyclohexane dimethanol is preferred from the viewpoints of ease of handling, ease of reaction, and properties of the obtained resin composition.

The thermoplastic polyester resin (B) is obtained by copolymerizing a known copolymerizable compound in addition to the carboxylic acid compound and the alcohol and / or phenol compound as long as the desired properties are not impaired. It may be obtained. Such copolymerizable compounds are not particularly limited, and include, for example, divalent or higher valent aliphatic carboxylic acids having 4 to 12 carbon atoms, divalent or higher valent alicyclic carboxylic acids having 8 to 15 carbon atoms, Ester-forming derivatives and the like. 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, and derivatives having an ester-forming ability thereof And the like. Other examples include oxyacids such as p-hydroxybenzoic acid or ester-forming derivatives thereof, and cyclic esters such as ε-caprolactone.

The thermoplastic polyester resin (B)
May be a thermoplastic polyester resin obtained by partially copolymerizing a polyalkylene glycol unit in a 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
Or, a random copolymer, a bisphenol A copolymerized polyethylene oxide addition polymer, a propylene oxide addition polymer, a tetrahydrofuran addition polymer, polytetramethylene glycol and the like can be mentioned.

The amount of the copolymer component used in the thermoplastic polyester resin (B) is usually 2
0 wt% or less, preferably 15 wt% or less, more preferably 10 wt% or less.

[0027] The thermoplastic polyester resin (B) is used to balance the physical properties of the obtained resin composition (eg, moldability).
, The alkylene terephthalate unit is 8
Polyalkylene terephthalate containing 0% by weight or more is preferable. More preferably, it is a polyalkylene terephthalate containing 85% by weight or more, more 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 phenol / tetrachloroethane = 1/1 (weight ratio) mixed solvent. g or more. If the logarithmic viscosity is less than 0.30, the flame retardancy and mechanical strength of the molded product are often insufficient, and the viscosity is 2.00 dl / g.
If it exceeds 300, the molding fluidity tends to decrease. It is more preferably 0.40 to 1.80 dl / g, and still more preferably 0.50 to 1.60 dl / g.

In the thermoplastic resin composition of the present invention, as the thermoplastic polyester resin (B), one type may be used alone, or two or more types may be used in combination. When two or more kinds are used in combination, the combination is not particularly limited. For example, those having different copolymer components and different molar ratios, those having different molecular weights, and the like 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 on a weight basis. ９９99/1. If it is less than 45/55, dimensional stability and impact resistance tend to decrease,
If it exceeds 99/1, the resulting molded article tends to have reduced thermal stability and solvent resistance. Preferably 51 / 49-
95/5, more preferably 60/40 to 90/1.
0.

The inorganic compound to be blended in the thermoplastic resin composition of the present invention (C) has a pH of 8.0 or more, SiO ₂
The unit occupies 30% by weight or more, and the weight average particle diameter is 10
It is an inorganic compound of 0 μm or less. This component is used for the purpose of improving various physical properties such as heat resistance, mechanical strength, and elastic modulus while suppressing anisotropy of the shrinkage of the resin. In addition, 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 are preferred because they have the effect of suppressing the anisotropy of the obtained molded article and have excellent heat resistance and mechanical strength.

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

The shape of the inorganic compound (C) is not particularly limited, but typical examples include powder, granules, needles, and plates. This inorganic compound may be a natural product or a synthesized product. In the case of a natural product, there is no particular limitation on the place of production and the like, which can be appropriately selected.

The inorganic compound (C) has a pH of 8.0 or more. Since the polycarbonate resin (A) is stable even when an inorganic compound having a pH of less than 8.0 is added, the necessity of applying the technology of the present invention is small. Particularly, the improvement effect according to the present invention is large because the inorganic compound (C)
This is the case where H is 8.8 or more. In addition, pH referred to in the present invention
Is a digital p based on JIS K-5101 B method.
This is a value measured by an H meter.

Such an inorganic compound (C) may be subjected to a surface treatment with various surface treatment agents such as a silane treatment agent in order to enhance the adhesiveness to a resin. The surface treatment agent is not particularly limited, and conventionally known ones can be used.Epoxy group-containing silane coupling agents such as epoxy silane, and amino group-containing silane coupling agents such as amino silane are It is preferable because the physical properties are hardly reduced. In addition, polyoxyethylene silane or the like can be used. The surface treatment method is not particularly limited, and a usual treatment method can be used.

One of these inorganic compounds (C) may be used alone, or two or more of them having different average particle diameters, types, surface treatment agents and the like may be used in combination.

The amount of the inorganic compound (C) used in the thermoplastic resin composition of the present invention is 0 to 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. When the amount is less than 0.5 part by weight, the heat resistance and mechanical strength of the obtained molded article are reduced, and when the amount exceeds 100 parts by weight,
The impact resistance and surface properties of the obtained molded article are reduced, and it tends to be difficult to knead with the resin during melt kneading. Preferably it is 1 to 70 parts by weight, more preferably 2 to 50 parts by weight.
Parts by weight.

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

The reinforcing filler may be subjected to a surface treatment in order to enhance the adhesiveness with the resin. The surface treatment agent used for performing such a surface treatment is not particularly limited, but an epoxy group-containing silane coupling agent such as epoxy silane is preferable because it does not reduce 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, they are added in an amount of 1 to 100 parts by weight of the total of the polycarbonate resin (A) and the thermoplastic polyester resin (B).
00 weight or less. If the amount exceeds 100 parts by weight, the impact resistance may decrease, and the formability and flame retardancy may decrease. Preferably not more than 50 parts by weight,
It is more preferably at most 10 parts by weight. Also, as the addition amount of these reinforcing fillers increases and the surface properties and dimensional stability of the molded article tend to deteriorate, when these characteristics are emphasized, the addition amount of the reinforcing fillers is reduced. It is preferred to minimize as much as possible.

The thermoplastic resin composition of the present invention may further contain a thermoplastic resin or a thermosetting resin other than the components (A) and (B) as long as the object of the present invention is not impaired. . The resin of such an optional component is not particularly limited. For example, polyolefin resin, polyamide resin, polystyrene resin, polyphenylene sulfide resin, polyphenylene ether resin, polyacetal resin, polysulfone resin; polytetrafluoroethylene And the like. These may be used alone or in combination of two or more. When these optional components are added, the inorganic compound (C) may be present in the optional components in the thermoplastic resin composition of the present invention.

This optional resin is preferably an elastic resin in order to increase the impact strength of the obtained molded article. The elastic resin preferably has at least one glass transition point of 0 ° C. or lower, more preferably −20 ° C. or lower, because the obtained resin composition has an excellent impact strength improving effect.

The elastic resin is not particularly restricted but includes, for example, diene rubbers such as polybutadiene, styrene-butadiene rubber, acrylonitrile-butadiene rubber, alkyl (meth) acrylate-butadiene rubber; acrylic rubber, ethylene-propylene rubber, Rubbery polymers such as siloxane rubber; various polyolefin resins such as polyethylene and polypropylene; copolymerized polyolefin resins modified with various copolymerization components such as ethylene-ethyl acrylate copolymer; ethylene-glycidyl methacrylate copolymer And the like, modified polyolefin-based resins modified with various functional components.

Further, in order to further increase the impact strength of the obtained molded article, this elastic resin is used for the above-mentioned diene rubber and / or
Or 10 to 90 parts by weight of at least one monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound and an alkyl (meth) acrylate based on 10 to 90 parts by weight of the rubbery polymer, and It is preferable that a rubbery copolymer obtained by polymerizing 10 parts by weight or less of another vinyl compound copolymerizable with these is added.

When an elastic resin is added, the amount added is
Usually, 15 parts with respect to 100 parts by weight of the total of the polycarbonate resin (A) and the thermoplastic polyester resin (B).
It is not more than 0.1 parts by weight, preferably 0.1 to 12 parts by weight, more preferably 0.2 to 10 parts by weight. If it exceeds 15 parts by weight, the rigidity and heat resistance 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; Are preferably added alone or in combination of two or more. Further, if necessary, generally well-known, stabilizers, lubricants, release agents, plasticizers, non-phosphorus-based flame retardants, flame retardant aids, ultraviolet absorbers, light stabilizers,
Pigments, dyes, antistatic agents, conductivity-imparting agents, dispersants, compatibilizers, antibacterial agents and the like may be added alone or in combination of two or more.

In the thermoplastic resin composition of the present invention,
Total number of particles of all particles of inorganic compound (C) ×
Particles of [{addition amount of (B)} / {addition amount of (A) + addition amount of (B)}] × 1.8 or more exist in phases other than the polycarbonate resin phase. Thereby, the thermal stability when the obtained thermoplastic resin composition is molded at a high temperature is improved. Above all, of all the particles of the inorganic compound (C), the total number of particles × 70% and the total number of particles × [｛(B)
｝ / ｛(A) + (B)｝ ×
2] is preferably present in a phase other than the polycarbonate resin phase (however, in this case, the added amount of (A) / the added amount of (B) is 99%). / 1 to 51/49). More preferably, among all the particles of the inorganic compound (C), the total number of particles × 8
0% and the total number of particles × [{(B) added amount / {(A) added amount + (B) added amount}] × 2, the larger number or more of the polycarbonate-based particles Exists in a phase other than the resin phase (however, in this case, the amount of (A) added /
(The addition amount of (B) is in the range of 99/1 to 51/49). The greater 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) was measured by observing the cut surface obtained by cutting the thermoplastic resin composition of the present invention with a transmission electron microscope, and measuring the number of particles of the inorganic compound (C) in the visual field. The measurement is performed by counting the number of particles (the total number of particles of the inorganic compound (C) and the number of particles of the inorganic compound (C) present in a phase other than the polycarbonate resin phase) (here, the polycarbonate resin phase, Other phases can be distinguished with an electron microscope). Note that, depending on the method for producing this composition, the dispersion state of particles may be different between the surface layer and the inside thereof. Therefore, there are three locations: near the surface layer (about 50 μm from the surface layer), at the center, and near the middle between the two. 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 visual field 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 and additives and then melt-kneading with a melt-kneading machine such as a single-screw or twin-screw extruder. Also, when the compounding component is a liquid,
It can also be manufactured by adding to a melt kneader in the middle using a liquid supply pump or the like.

In a preferred production method, when the thermoplastic resin composition of the present invention is produced by a kneading apparatus, a first supply port provided at the base of the kneading apparatus and a second supply port provided downstream of the first supply port are provided. 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 the atmospheric pressure, 30% by weight or more of the added amount of the inorganic compound (C) among the raw materials of the composition is supplied from the second supply port, while the remaining raw materials are supplied from the first supply port. is there.

The production method of the present invention can be typically performed using, for example, the apparatus shown in FIG. In FIG. 1, components (A), (B) and 70% by weight
The following component (C) is charged. The input raw material is conveyed, kneaded and moved in the kneading apparatus 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 is opened to the atmospheric pressure. The raw material is conveyed downstream while being kneaded, and is taken out from the take-out port 5.

By using such a manufacturing method,
While sufficiently kneading the polycarbonate resin (A) and the thermoplastic polyester resin (B), the inorganic compound (C) does not easily enter the polycarbonate resin phase, so that the inorganic compound described above is used. The thermoplastic resin composition having the dispersed state of (C) can be easily produced. In particular, when the inorganic compound (C) is supplied collectively from the common supply port with the component (A) and the component (B), or when the inorganic compound (C) is supplied from the second supply port, the pressure is maintained at atmospheric pressure. Dispersion control of the inorganic compound (C) in the resin phase can be easily performed as compared with the case where the opened vent port is not used.

In this production method, the amount of the inorganic compound (C) supplied from the second supply port is at least 30% by weight of the total amount of the inorganic compound (C), but at least 50% by weight. It is more preferably 70% by weight or more, and the total amount of the inorganic compound (C) can be supplied from the second supply port.

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

The kneading apparatus used in the production method of the present invention is not particularly limited, and a known kneading apparatus can be used. Specifically, for example, TEX44 manufactured by Nippon Steel Works, Ltd.
The same direction meshing twin screw extruder etc. are mentioned. Among them, a twin-screw extruder is preferable for sufficiently kneading 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 rotations of the screws may be in the same direction or in opposite directions. This twin screw extruder has a first supply port 1 and a second supply port 3
In between, such as kneading disc or reverse screw structure,
Those having a structure for retaining the resin are more preferable. Immediately downstream of such a resin retention structure,
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 apparatus is generally 20 to 500 rpm. In general, the set temperature is appropriately set in a range from room temperature to 300 ° C. in a 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 examples thereof include molding methods generally used for thermoplastic resins, such as injection molding, blow molding, extrusion molding, vacuum molding, and the like. Press molding, calendar molding and the like can be used.

[0059]

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

[0060]Example 1  Bisphenol A type polycarbonate with viscosity average molecular weight of 22000
Polyethylene with 70 parts of carbonate resin and 0.70 relative viscosity
30 parts of terephthalate, EEA tree as other resin
Fat (Evaflex EE manufactured by DuPont-Mitsui Polychemicals)
A A709) 2 parts, and Adecasta as a stabilizer
EP-22, ADK STAB AO-60 and ADKSTA
0.2 parts each of Bu HP-10 (both trade names made by Asahi Denka)
After mixing with Super Floater, TE from TEPCO
X44 same direction meshing twin screw extruder with screw root
Feed from the hopper which is the first supply port provided nearby
Was. At a position before the second supply port, the screw has an angle of 90 ° C.
Insert the kneading disc
At the position where the lock section is finished, insert the vent port opened to atmospheric pressure
Provided. Side feeder installed right next to vent
Mica (Yamaguchi) from the second supply port with the side feeder
A-21S made by mica, weight average particle diameter 20 μm, pH =
9.0) 20 parts were forcibly pressed. Second supply port and screw
-A vacuum vent connected to the vacuum pump
The mouth was provided. Screw rotation speed 150rpm, time
The dripping amount was set to 60 kg / hr. Set temperature is
The temperature near one supply port is 100 ° C.
The temperature before the kneading disk was set to 270 ° C. D
From the loading disc to the atmospheric pressure release vent
At 70 ° C, the pressure between the atmospheric pressure release vent port and the second supply port is 2
At 65 ° C, the distance from the second supply port to the screw tip is 26
It was set to 0 ° C. Under these conditions, sample pellet for evaluation
Obtained.

[0061]Comparative Example 1  The same blending components as in Example 1 were used. Ishinaka iron as a kneading machine
Using an 80 mm single screw extruder HS80 manufactured by Kosakusho,
Do not have a part with a stagnation structure)
All the ingredients were added all at once. Screw tip
A decompression vent connected to a decompression pump is provided in the foreground.
Was. Screw rotation speed 200rpm, discharge amount per hour
Was set to 180 kg / hr. The set temperature is the same as in the first embodiment.
It was set to have the same tendency. Under these conditions, the evaluation sun
A pull pellet was obtained.

[0062]Particle abundance ratio  The obtained pellet with a diameter of about 3.6 mm is cut at the center.
And 50 μm from the pellet surface of the section, the center of the pellet
Part and three places of about 1 mm from the center of the pellet
Observation with a transmission electron microscope was performed. Three images
Each of the inorganic particles (my
F) The number of
Count the number of particles (mica), (measured in three images
Of the number of inorganic particles other than the polycarbonate phase
Total) / (sum of the number of inorganic particles measured in the three images)
Total) was calculated.

[Formation of Test Piece] Each of the obtained sample pellets was put into a Toshiba 75t molding machine at a set temperature of 280 ° C., and the molding cycle was 127 mm × 12.7 in 30 seconds.
A test piece having a size of 3.2 mm and a thickness of 3.2 mm was formed. Further, a test piece was similarly molded in a 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
Was used to measure the Izod impact strength. For each test piece
(The impact test of the test piece obtained by the cycle 30 minutes
Value) / (Impact test of test piece obtained by 30 seconds cycle)
(Experimental value) × 100. Table 1 shows the results.
The larger the value, the better the retention heat stability of the resin composition.
Have been.

[0065]Molecular weight  After the obtained molded product is pulverized, it is stirred for one day in a chloroform solvent.
Stirred. Using the obtained solution, a GPC measuring device (solvent chloro
Resin in terms of polystyrene by Holm, RI detector)
Was measured for molecular weight. For each specimen, (Cycle 3
Weight average of the resin contained in the test piece obtained at 0 minutes
Weight) / (included in the test piece obtained by 30 seconds cycle)
(Weight average molecular weight of the resin to be obtained) × 100. This
Table 2 shows the results. The larger this number, the more the resin composition
The heat stability of the material is excellent.

[0066]

[Table 1]

[0067]Example 2 and Comparative Example 2  Mica of Example 1 and Comparative Example 1 (Mica Yamaguchi A-21)
S) instead of montmorillonite (Kunimine Industries)
Kunipia-F, weight average particle diameter 20 μm, pH = 10.
0) 100 parts of γ-aminopropyltriethoxy
Use the surface treated with 1 part of silane, and add 3 parts.
Parts, except that the parts were made as described in Example 1 and Comparative Example 1.
The fabrication method and the evaluation method were implemented. 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 has excellent staying heat stability during molding at a high temperature.

[0070]

Since the present invention has the above-mentioned constitution, a basic inorganic compound is added to improve the rigidity, dimensional stability, surface properties, low linear expansion coefficient, etc. of the thermoplastic resin composition. In addition, a thermoplastic resin composition having excellent retention heat stability during molding at a high temperature can be obtained. Such a thermoplastic resin composition can be suitably used for injection-molded articles such as home appliances, OA equipment parts, AV equipment parts, and the like.

[Brief description of the drawings]

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

[Explanation of symbols]

 1; first supply port 2; vent port opened to atmospheric pressure 3; second supply port 4; depressurized vent port 5; take-out port 6;

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F201 AA24 AA28 AB16 AB22 AL03 AR12 AR15 BA01 BC01 BC02 BC12 BC37 BD05 BK26 BK36 BQ01 BQ07 BQ16 4J002 CF05X CF06X CF07X CF08X CF10X CG01W CG02W DJ006 DJ036 DJ046 DJ0016 FB 010 GQ00

Claims (3)

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