JP2001026710A - Thermoplastic resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin containing an aromatic polycarbonate and a saturated polyester resin which is excellent in moldability and impact resistance, excellent in heat resistance and rigidity, and excellent in retention heat stability. SOLUTION: The composition comprises the following components (A) and (B):
A thermoplastic resin composition comprising a composition containing predetermined amounts of the following components (C) and (D) based on parts by weight. (A) 5-95 parts by weight of aromatic polycarbonate (B) 5-95 parts by weight of saturated polyester (C) 0-50 parts by weight of partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer (D) Saturated with polyphenylene ether Melt kneading resin composition containing polyester 0.01 to 20 parts by weight (E) Inorganic filler 0 to 50 parts by weight

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic resin composition containing an aromatic polycarbonate and a saturated polyester resin as main components, and a method for producing the same.

[0002]

2. Description of the Related Art Aromatic polycarbonates are known as engineering plastics having excellent flame retardancy, heat resistance, dimensional stability, non-hygroscopicity and electrical properties, but are inferior in melt fluidity and difficult to mold. And the solvent resistance is insufficient. On the other hand, saturated polyester is a thermoplastic resin composition having excellent impact resistance, flexibility, and the like, but has a drawback in that it is inferior in rigidity, heat resistance, moldability, and appearance.

[0003] Therefore, it is conceivable to mix these two resins to obtain a resin excellent in moldability, impact resistance, heat resistance, cost and the like which has the advantages of both. However, a blend obtained by melt-kneading a polycarbonate resin and a saturated polyester in a usual manner is not necessarily sufficient in terms of impact resistance, appearance, moldability, balance of physical properties, and insufficient retention heat stability. Met.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide excellent moldability and impact resistance, and excellent heat resistance and rigidity.
It is still another object of the present invention to provide a thermoplastic resin composition containing an aromatic polycarbonate having excellent retention heat stability and a saturated polyester resin, and a method for producing the same.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and the gist of the present invention is that the following components (A) and (B) are combined with the following components in a total of 100 parts by weight. A thermoplastic resin composition comprising a composition containing a predetermined amount of (C) and (D). (A) 5-95 parts by weight of aromatic polycarbonate (B) 5-95 parts by weight of saturated polyester (C) 0-50 parts by weight of partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer (D) Saturated with polyphenylene ether Melt kneading resin composition containing polyester 0.01 to 20 parts by weight (E) Inorganic filler 0 to 50 parts by weight

Hereinafter, the present invention will be described in detail. (A) Aromatic polycarbonate As the aromatic polycarbonate, a thermoplastic aromatic polycarbonate polymer which may be produced by reacting an aromatic hydroxy compound or a small amount thereof with a phosgene or carbonic acid diester is used. Or a copolymer is mentioned.

As aromatic dihydroxy compounds, 2,2
2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -P-diisopropylbenzene, hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, and the like, Preferably, bisphenol A is used.

To obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-2,4,4
6-tri (4-hydroxyphenyl) heptene-2,
4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-
Tri (4-hydroxyphenylheptene-3,1,3,
5-tri (4-hydroxyphenyl) benzene, 1,
Polyhydroxy compounds represented by 1,1-tri (4-hydroxyphenyl) ethane or the like; 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol); 5-chlorisatin bisphenol; 7-dichlorisatin bisphenol, 5-
Bromoisatin bisphenol or the like may be used as a part of the aromatic dihydroxy compound.
It is 0.01 to 10 mol%, preferably 0.1 to 2 mol%.

In order to control the molecular weight, a monovalent aromatic hydroxy compound may be used, and m- and p-methylphenol, m- and p-propylphenol, p-tert-
Butylphenol and p-long-chain alkyl-substituted phenols. The aromatic polycarbonate resin is preferably a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or a resin derived from 2,2-bis (4-hydroxyphenyl) propane and another aromatic dihydroxy compound. Polycarbonate copolymer to be used.

The molecular weight of the aromatic polycarbonate resin is as follows:
Methylene chloride was used as a solvent, and the viscosity average molecular weight was 1 based on the solution viscosity measured at a temperature of 25 ° C.
6,000 to 30,000, preferably 18.0
00 to 23,000. As the aromatic polycarbonate resin, a mixture of two or more aromatic polycarbonate resins can be used.

(B) Saturated polyester As the saturated polyester, various polyesters can be used. For example, dicarboxylic acid, its lower alkyl ester or acid halide or acid anhydride derivative, glycol or dihydric phenol can be used in accordance with a usual method. And a thermoplastic polyester produced by condensing the same.

Examples of the dicarboxylic acid include aromatic dicarboxylic acid and aliphatic dicarboxylic acid. Specific examples of the aromatic dicarboxylic acid or aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid. acid,
Suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, p, p'-dicarboxydiphenylsulfone, p-carboxyphenoxyacetic acid, p-carboxyphenoxypropionic acid, p-carboxyphenoxybutyric acid, p-carboxyphenoxy Valeric acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, or the like, or a mixture of these carboxylic acids is exemplified.

Examples of the glycol include aliphatic glycols and aromatic glycols. Examples of the aliphatic glycol include linear alkylene glycols having 2 to 12 carbon atoms, such as ethylene glycol, 1,3-propylene glycol, and 1,4-propylene glycol. Butene glycol, 1,6-hexene glycol, 1,12-dodecamethylene glycol and the like. Examples of the aromatic glycol include p-xylylene glycol, and examples of the dihydric phenol include pyrocatechol, resorcinol, hydroquinone, and alkyl-substituted derivatives of these compounds. Other glycols include 1,4-cyclohexanedimethanol and the like.

Other preferable polyesters include polyesters obtained by ring-opening polymerization of lactones, and specific examples include polypivalolactone and poly (ε-caprolactone). Still other preferred polyesters include polymers that form liquid crystals in the molten state (The The
rmotropic Liquid CrystalP
(Polymer). Representative polyesters in these categories include X7G from Eastman Kodak, Xyday (Zyder) from Dartco, Econol from Sumitomo Chemical, Vectra from Celanese, and the like.

As the saturated polyester, preferably,
Examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polynaphthalene terephthalate (PEN), poly (1,4-cyclohexane dimethylene terephthalate) (PCT), and liquid crystalline polyester.

The intrinsic viscosity of the saturated polyester is as follows: phenol / 1,1,2,2-tetrachloroethane = 60/40
0.5% as measured in a weight% mixed solution at 20 ° C.
5.0 dl / g, and more preferably 1.0 to 4.
0 dl / g, particularly preferably 2.0 to 3.5 dl.
/ G. When the intrinsic viscosity is less than 0.5 dl / g,
If the impact resistance is insufficient, and if it exceeds 5.0 dl / g, the moldability is reduced.

(C) Partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer The partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer includes a chain block [A] derived from an alkenyl aromatic compound. Block copolymer in which the aliphatic unsaturated group of the block [B] of the alkenyl aromatic compound-conjugated diene block copolymer having at least one chain block [B] derived from a conjugated diene is reduced by hydrogenation Is mentioned. Block [A]
The arrangement of the blocks [B] includes those having a linear structure or those having a branch structure, and those having a so-called teleblock structure. Partially hydrogenated alkenyl aromatic compounds-
In the structure of the conjugated diene block copolymer, a part thereof may include a random chain derived from a random copolymerized portion of the alkenyl aromatic compound and the conjugated diene.

The arrangement of the block [A] and the block [B] is preferably a diblock (A
-B block), triblock (ABA block), tetra block (ABAB block), pentablock (ABBABA block, BA-
BAB block) or those having a linear structure including those having a total of 6 or more blocks of A and B, more preferably diblock, triblock, and tetrablock.

Specific examples of the alkenyl aromatic compound include styrene, paramethylstyrene, α-methylstyrene, vinylxylene, vinyltoluene, vinylnaphthalene, divinylbenzene, bromostyrene, chlorostyrene, and mixtures thereof. Preferably, styrene, paramethylstyrene, α-methylstyrene, vinylxylene, vinyltoluene are used, and more preferably, styrene is used.

Specific examples of the conjugated diene include 1,3-butadiene, 2-methyl-1,3-butadiene, and 2,3-butadiene.
Examples thereof include dimethyl-1,3-butadiene, 1,3-pentadiene, and isoprene, and preferably include 1,3-butadiene and isoprene. In addition to these conjugated dienes, small amounts of lower olefinic hydrocarbons such as ethylene, propylene and 1-butene, dicyclopentadiene, and non-conjugated dienes may be contained.

The proportion of the repeating unit derived from the alkenyl aromatic compound in the partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer is preferably from 15 to 80% by weight, more preferably from 30 to 75% by weight.
%, Most preferably 55 to 70% by weight. When the proportion of the repeating unit derived from the alkenyl aromatic compound exceeds 80% by weight, impact resistance is insufficient, and when it is less than 10% by weight, rigidity and heat resistance tend to be insufficient.

In the partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer, the proportion of unsaturated bonds derived from the conjugated diene and remaining without hydrogenation in the aliphatic chain portion is 50% or less. Is preferably 20% or less, more preferably 10% or less. Also, up to about 25% of the aromatic unsaturated bonds derived from the alkenyl aromatic compound may be hydrogenated.

As a standard of the molecular weight of the partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer, the number average molecular weight measured by gel permeation chromatography and converted to polystyrene is preferably 5,000 to 500, 000 g / mol, more preferably 10,000 to 300,000 g / mol, and most preferably 30,000 to 200,000 g.
/ Mol.

As the partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer, there are those having a hydrogenated conjugated diene polymer chain portion and exhibiting crystallinity derived therefrom, and those exhibiting such crystallinity. Although a copolymer having a melting point of 150 ° C. or less or an amorphous copolymer having no definite melting point is preferable. Further, any glass transition temperature based on the hydrogenated conjugated diene polymer chain portion of these hydrogenated block copolymers can be used. As the partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer,
Sold easily under the trade name "Clayton G" from Shell Chemical Co., Ltd., under the trade name "Septon" from Kuraray Co., Ltd., and under the trade name "Tuftec" from Asahi Kasei Kogyo Co., Ltd. be able to.

(D) Melt-kneaded resin composition containing polyphenylene ether and saturated polyester (a) Polyphenylene ether Examples of polyphenylene ether include homopolymers and copolymers having a structure represented by the following general formula (2). .

[0026]

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Wherein Q ¹ represents a halogen atom, a primary or secondary alkyl group, a phenyl group, an aminoalkyl group, a hydrocarbonoxy group or a halohydrocarbon oxy group, and Q ² represents a hydrogen atom , A halogen atom, a primary or secondary alkyl group, a phenyl group, a haloalkyl group, a hydrocarbonoxy group or a halohydrocarbonoxy group, and m represents a number of 10 or more.)

The primary alkyl group for Q ¹ and Q ² includes methyl, ethyl, n-propyl, n-butyl, n-butyl
Amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl, 2-, 3- or 4-
Methylpentyl, heptyl and the like can be mentioned. As the secondary alkyl group, isopropyl, sec-butyl, 1
-Ethylpropyl and the like. Q ¹ is preferably an alkyl group or a phenyl group, particularly preferably an alkyl group having 1 to 4 carbon atoms, and Q ² is preferably a hydrogen atom.

The homopolymer of polyphenylene ether includes, for example, a polymer composed of 2,6-dimethyl-1,4-phenylene ether units. As the copolymer, the above unit and 2,3,6-trimethyl-1,4-
And a random copolymer comprising a combination with a phenylene ether unit. Many homopolymers or random copolymers have been described in patents and literature, and polyphenylene ethers containing molecular moieties that improve properties such as, for example, molecular weight, melt viscosity and / or impact strength are also preferred.

The intrinsic viscosity of the polyphenylene ether is preferably 0.2 to 0.2 as measured at 30 ° C. in chloroform.
0.8 dl / g, and more preferably 0.25 to
0.7 dl / g, most preferably 0.3 to 0.1.
6 dl / g. When the intrinsic viscosity is less than 0.2 dl / g, the impact resistance is insufficient, and when the intrinsic viscosity is 0.8 dl / g or more, the gel content is large and the appearance of the molded article is difficult.

(B) Saturated polyester As the saturated polyester in the melt-kneaded resin composition containing polyphenylene ether and saturated polyester, the saturated polyester described in the section of (B) Saturated polyester can be used. (B) The saturated polyester is (B)
It may be the same as or different from the saturated polyester.

(C) Phosphorous ester compound Examples of the phosphite ester compound include a phosphite triester compound. The phosphite triester preferably includes a compound represented by the following general formula (1) and a compound represented by the following general formula (3).

[0033]

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In the general formula (1), R ¹ represents an alkyl group having 1 to 20 carbon atoms or an aromatic group or a substituted aromatic group having 6 to 30 carbon atoms, preferably an aromatic group having 6 to 30 carbon atoms. Or a substituted aromatic group. n represents a number of 1 or 2; R ² represents an alkylene group or an arylene group having 2 to 18 carbon atoms when n is 1; and an alkyltetrayl group having 4 to 18 carbon atoms when n is 2. And R ¹ may be the same or different. Also, R ¹ and R ²
May be a substituent containing an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom.

Specific examples of R1 include methyl, ethyl, propyl, octyl, isooctyl, isodecyl, decyl, stearyl, lauryl, phenyl, 2-, 3- or 4-methylphenyl. Groups 2,4-,
2,6-dimethylphenyl group, 2,3,6-trimethylphenyl group, 2-, 3- or 4-ethylphenyl group, 2,4
-, 2,6-diethylphenyl group, 2,3,6-triethylphenyl group, 2,3- or 4-tert-butylphenyl group,
2,4-, 2,6-di-tert-butylphenyl group, 2,6-di-t
ert-butyl-6-methylphenyl group, 2,6-di-tert-butyl-6-ethylphenyl group, octylphenyl group, isooctylphenyl group, 2-, 3- or 4-nonylphenyl group, 2,4 -A dinorisphenyl group, a biphenyl group, a naphthyl group and the like.

When n is 1 as R2, for example,
Examples thereof include a 1,2-phenylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group. When n is 2, for example, tetrayl having a pentaerythrityl structure represented by the general formula (4) And the like.

[0037]

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In the general formula (4), R ^{6 to} R ¹³ are
Each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0039]

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In the general formula (3), R ³ , R ⁴ and R ⁵ each represent an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 30 carbon atoms or a substituted aromatic group. And an aromatic group having 6 to 30 carbon atoms or a substituted aromatic group. The substituent of R ³ , R ⁴ and R ⁵ may be a substituent containing an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom, respectively. Specific examples of R ³ , R ⁴ and R ⁵ include the groups shown as specific examples of R ¹ .

Specific examples of the phosphite compound include trioctyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triisooctyl phosphite, tris (nonylphenyl) phosphite, and tris ( 2,4-dinolylphenyl) phosphite, tris (2,4-di-ter)
t-butylphenyl) phosphite, triphenylphosphite, tris (octylphenyl) phosphite,
Diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, octyl diphenyl phosphite, dilauryl phenyl phosphite, diisodecyl phenyl phosphite, bis (nonylphenyl) phenyl phosphite, diisooctyl phenyl phosphite, diisodecyl pentaerythritol diphos Fight, dilauryl pentaerythritol diphosphite,
Distearyl pentaerythritol diphosphite,
(Phenyl) (1,3-propanediol) phosphite, (4-methylphenyl) (1,3-propanediol) phosphite, (2,6-dimethylphenyl)
(1,3-propanediol) phosphite, (4-t
tert-butylphenyl) (1,3-propanediol) phosphite, (2,4-di-tert-butylphenyl) (1,3-propanediol) phosphite,
(2,6-di-tert-butylphenyl) (1,3-
Propanediol) phosphite, (2,6-di-te)
rt-butyl-4-methylphenyl) (1,3-propanediol) phosphite, (phenyl) (1,2-ethanediol) phosphite, (4-methylphenyl)
(1,2-ethanediol) phosphite, (2,6-
Dimethylphenyl) (1,2-ethanediol) phosphite, (4-tert-butylphenyl) (1,2-
(Ethanediol) phosphite, (2,4-di-ter)
t-butylphenyl) (1,2-ethanediol) phosphite, (2,6-di-tert-butylphenyl)
(1,2-ethanediol) phosphite, (2,6-
Di-tert-butyl-4-methylphenyl) (1,2
-Ethanediol) phosphite, (2,6-di-te)
tert-butyl-4-methylphenyl) (1,4-butanediol) phosphite, diphenylpentaerythritol diphosphite, bis (2-methylphenyl) pentaerythritol diphosphite, bis (3-methylphenyl) pentaerythritol Diphosphite, bis (4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dimethylphenyl) pentaerythritol diphosphite, bis (2,6-dimethylphenyl) pentaerythritol diphosphite, bis (2 , 3,6-trimethylphenyl) pentaerythritol diphosphite, bis (2-tert-butylphenyl) pentaerythritol diphosphite, bis (3
-Tert-butylphenyl) pentaerythritol diphosphite, bis (4-tert-butylphenyl)
Pentaerythritol diphosphite, bis (2,4-
Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) penta Erythritol diphosphite, bis (2,
6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (biphenyl) pentaerythritol diphosphite, dinaphthylpentaerythritol diphosphite and the like. Can be

Further, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-te
rt-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and the like. Further, the thermoplastic resin composition of the present invention may contain a compound generated by hydrolysis or thermal decomposition of the phosphite compound.

(D) Phosphate Compound As the phosphate compound in the present invention, a compound represented by the following general formula (5) or (6) can be mentioned.

[0044]

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In the formula, R ¹⁴ , R ¹⁵ and R ¹⁶ each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted by an alkyl group; And j represent 0 or 1, respectively.

The phosphate compound represented by the above general formula (5) can be produced from phosphorus oxychloride or the like by a known method. Specific examples of the phosphate compound represented by the general formula (5) include triphenyl phosphate, tricresyl phosphate, diphenyl 2-ethylcridyl phosphate, tri (isopropylphenyl) phosphate, diphenyl methylphosphonic acid, diethyl phenylphosphonic acid, and phosphoric acid. Examples include diphenylcresyl and tributyl phosphate.

[0047]

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Wherein R ¹⁷ , R ¹⁸ , R ¹⁹ and R
²⁰ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, p, q, r and s are each 0 or 1, y is an integer of 1 to 5, and X represents an arylene group.

The phosphorus compound represented by the general formula (6) is a condensed phosphoric ester in which y is 1 to 5, and for a mixture of condensed phosphoric esters in which m is different, y is an average value of the mixture. Become. X represents an arylene group, for example, a group derived from a dihydroxy compound such as resorcinol, hydroquinone, and bisphenol A. As a specific example of the phosphorus compound represented by the general formula (6), when resorcinol is used as the dihydroxy compound, phenyl resorcin polyphosphate, cresyl resorcin polyphosphate, phenyl cresyl resorcin polyphosphate, Xylyl resorcin polyphosphate, phenyl-Pt-butylphenyl resorcin polyphosphate, phenyl isopropylphenyl resorcin polyphosphate, cresyl xylyl resorcin polyphosphate, phenyl isopropylphenyl diisopropylphenyl resorcin polyphosphate, etc. No.

(E) Inorganic Filler As the inorganic filler, those having an average particle diameter of 5 μm or less, preferably 4 μm or less, particularly preferably 2.5 μm or less are preferable. Here, the average particle size is an average maximum particle size of primary particles measured by observation with an electron microscope. The shape of the inorganic filler is spherical, cubic, granular, needle-like, plate-like,
There are various types such as a fibrous shape, and any of them can be used. Among them, a plate-like shape is preferable from the viewpoint of the balance between physical properties of rigidity and impact resistance and the effect of improving dimensional stability.

Examples of the inorganic filler include groups I to V of the periodic table.
Group III metal elements (eg, Fe, Na, K, Cu, M
g, Ca, Zn, Ba, Al, Ti) or a simple substance of silicon element, oxide, hydroxide, carbon salt, sulfate, silicate,
Sulfites, various viscosity minerals composed of these compounds, and others, specifically, for example, titanium oxide, zinc oxide, barium sulfate, silica, calcium carbonate, iron oxide,
Alumina, calcium titanate, aluminum hydroxide,
Magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium sulfate, sodium sulfate, calcium sulfite, calcium silicate, clay wollastonite, glass beads, glass powder, silica sand, silica stone, quartz powder,
Examples include whitebait, diatomaceous earth, white carbon, iron powder, aluminum powder, and the like. These may be used in combination of two or more. Among them, talc, mica, kaolin clay diatomaceous earth and the like having an average particle size of 5 μm or less are particularly preferable because they are plate-shaped.

The inorganic filler may be used without any treatment, but for the purpose of increasing the affinity with the resin or the interfacial bonding strength, an inorganic surface treating agent, a higher fatty acid or a derivative thereof such as an ester or a salt thereof (for example, stearic acid) , Oleic acid, palmitic acid, calcium stearate, magnesium stearate, aluminum stearate, stearic acid amide, ethyl stearate, methyl stearate, calcium oleate, calcium oleate,
Oleic acid ethyl ester, calcium palmitate,
Palmitic acid amide, palmitic acid ethyl ester, etc.)
And coupling agents (eg, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-
Aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc .; titanium coupling agent (for example, isopropyltriisos) Thiaroyl titanate, isopropyl trilauryl myristyl titanate, isopropyl isostearoyl dimethacryl titanate, isopropyl tridiisooctyl phosphate titanate, etc.) can be used.

The inorganic filler further includes glass fibers. The glass fibers preferably have an average diameter of 15 μm or less, and those having an average diameter of 1 to 10 μm further increase the balance of physical properties (heat resistance stiffness, impact strength) and further reduce molding warpage deformation / reheating warpage deformation. It is preferred in that respect. The method for producing the glass fiber is, for example, as follows. First, the melted glass is formed into glass balls of a predetermined size called marble, which are softened by heating in a spinning furnace called pushing, and are allowed to flow down from a number of nozzles of the furnace table. While stretching, the sizing agent is adhered by immersion in a sizing agent coating device provided in the middle of the sizing agent, bundled, dried and wound up by a rotating drum. At this time, the average diameter of the glass fiber is set to a predetermined size by adjusting the nozzle diameter, the take-up speed, the take-off atmosphere temperature, and the like.

Although the length of the glass fiber is not specified, roving supply, chopped strand of about 1 to 8 mm, and the like are also preferable. The number of bundles in this case is usually 100 to
5000 are preferred. The average length after kneading is 0.
If it can be obtained in a thickness of 1 mm or more, it may be a milled fiber or a ground pulverized product called glass powder or a continuous single fiber sliver. The composition of the raw material glass is preferably non-alkali, and one of the examples is E glass. If the average diameter of the glass fiber exceeds 15 μm, the degree of improvement in mechanical strength decreases, and the amount of warpage in molding increases, which is not preferable. Here, the average diameter is observed with an electron microscope or the like,
"Average" indicates a number average.

The sizing agent is usually composed of a film forming agent, a surfactant, a softener, an antistatic agent, a lubricant and the like, but may be a surface treatment agent alone. When using glass fibers, various coupling agents can be used for the purpose of increasing the affinity with the resin or the interfacial bonding force. The coupling agent usually includes a silane-based, chrome-based, titanium-based coupling agent and the like. Above all, those containing a silane coupling agent such as epoxysilane such as γ-glycidoxypropyltrimethoxysilane; vinyltrichlorosilane; aminosilane such as γ-aminopropyltriethoxysilane are preferable. At this time, it is possible to combine the treatment with various surfactants such as nonionic, cationic and anionic types and dispersants such as fatty acids, metal soaps and various resins in view of improvement in mechanical strength and kneading properties. preferable.

<Composition Ratio of Constituent Components> The composition ratio of components (A) to (E) in the thermoplastic resin composition of the present invention is such that the total amount of component (A) and component (B) is 100 parts by weight. Is as follows. The proportion of the aromatic polycarbonate of the component (A) is 5 to 95 parts by weight, preferably 15 to 9 parts by weight.
0 parts by weight, more preferably 30 to 80 parts by weight. The proportion of the saturated polyester of the component (B) is 5 to 95.
Parts by weight, preferably 10 to 85 parts by weight, more preferably 20 to 70 parts by weight. When the proportion of the component (A) is less than 5 parts by weight, the impact resistance is insufficient, and 9
If it exceeds 5 parts by weight, the moldability is insufficient and the component (B)
Is less than 5 parts by weight, moldability is insufficient,
If it exceeds 95 parts by weight, the impact resistance is insufficient.

The proportion of the partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer of the component (C) is 0 to 100 parts by weight of the total of the components (A) and (B).
50 parts by weight. If the proportion of the component (C) exceeds 50 parts by weight, the appearance and moldability of the molded product tend to be insufficient. The proportion of the component (C) is preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight, and most preferably 100 parts by weight of the total of the components (A) and (B). It is 2 to 20 parts by weight.

The proportion of the melt-kneaded resin composition containing the polyphenylene ether of the component (D) and the saturated polyester is based on 100 parts by weight of the total of the components (A) and (B).
0.01 to 20 parts by weight. If the amount is less than 0.01 part by weight, the effect of improving the impact resistance and fluidity of the resin composition is insufficient. If the amount is more than 20 parts by weight, the appearance of the molded article tends to be difficult. The proportion of the component (D) is preferably 0.1 with respect to 100 parts by weight of the total of the component (A) and the component (B).
To 20 parts by weight, more preferably 0.5 to 15 parts by weight, and most preferably 1 to 10 parts by weight.

Component (D) In the melt-kneaded resin composition containing polyphenylene ether and saturated polyester, (a)
The ratio of the polyphenylene ether to the saturated polyester (b) is such that the polyphenylene ether is 20 to 95 parts by weight, the saturated polyester is 5 to 80 parts by weight, and the total of the components (a) and (b) is 100 parts by weight. It is. If the polyphenylene ether is less than 20 parts by weight, impact resistance and heat resistance tend to be insufficient, and if it exceeds 95 parts by weight, impact resistance and fluidity tend to be insufficient. The ratio of (a) polyphenylene ether and (b) saturated polyester is preferably 30 to 90%.
Parts by weight and the saturated polyester is 10 to 70 parts by weight, more preferably 55 to 55 parts by weight of polyphenylene ether.
85 parts by weight and 15 to 45 parts by weight of saturated polyester.

When the phosphite compound (c) is blended in the melt-kneaded resin composition containing polyphenylene ether and saturated polyester, the ratio of (c) the phosphite compound is (a) polyphenylene ether and (b) For a total of 100 parts by weight of the saturated polyester,
0.1 to 10 parts by weight. When the proportion of the phosphite is less than 0.1 part by weight, the effect as a compatibilizing improver is small, and the effect of improving the physical properties tends to be insufficient. . The proportion of (c) the phosphite is preferably 0.2 to 9 parts by weight, more preferably 0.3 to 9 parts by weight, based on 100 parts by weight of the total of (a) polyphenylene ether and (b) the saturated polyester. 8 parts by weight.

When the phosphate compound (d) is blended in the melt-kneaded resin composition containing polyphenylene ether and saturated polyester, the ratio of (d) the phosphate compound is as follows: (a) polyphenylene ether and (b) saturated polyester. 5 to 12 parts per 100 parts by weight of
0 parts by weight. If the proportion of the phosphoric acid ester is less than 5 parts by weight, the effect of fluidity tends to decrease, and if it exceeds 120 parts by weight, heat resistance tends to decrease. (D) The ratio of the phosphoric ester is (a) polyphenylene ether and (b)
It is preferably from 8 to 100 parts by weight, more preferably from 10 to 9 parts by weight, based on 100 parts by weight of the saturated polyester.
0 parts by weight.

The inorganic filler of the component (E) is used in an amount of 0 to 50 based on 100 parts by weight of the total of the components (A) and (B).
Parts by weight. If it exceeds 50 parts by weight, the retention heat stability deteriorates. The ratio of component (E) is determined by comparing component (A) with component (B).
Is preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight with respect to 100 parts by weight in total.

<Additional Components> Examples of the additional components in the thermoplastic resin composition of the present invention include an impact resistance improving material, a filler and a reinforcing agent. Examples of the impact resistance improver include polyolefin resins such as polyethylene and polypropylene, α-olefin rubber, styrene rubber, acrylic rubber, silicon rubber, MBS and core-shell polymers. The ratio of the impact modifier is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the total of the components (A) and (B).

Examples of the filler and the reinforcing agent include an organic filler, an inorganic filler, an organic reinforcing agent, and an inorganic reinforcing agent. Specific examples thereof include glass fiber, mica, talc, and the like.
Wollastonite, potassium titanate, calcium carbonate,
Silica and the like. The compounding of filler and reinforcing agent is
It is effective in improving rigidity, heat resistance, dimensional accuracy, etc. The mixing ratio of the filler and the reinforcing agent is preferably from 1 to 5 based on 100 parts by weight of the total of the component (A) and the component (B).
0 parts by weight, more preferably 5 to 40 parts by weight.

The additional components in the resin composition of the present invention can further include various known auxiliaries.
The ratio of the additional component is 0.01 to 100 parts by weight of the total of the component (A) and the component (B), the content of the antioxidant, the weather resistance improver, the alkali soap, the metal soap and the hydrotalcite is 0.01 to 100 parts by weight. About 5 parts by weight, about 5 to 30 parts by weight of a plasticizer and a fluidity improver, about 0.5 to 2 parts by weight of a nucleating agent,
About 5 to 50 parts by weight of the flame retardant, about 0.1 to 10 parts by weight of the anti-dripping agent, and about 0.5 to 5 parts by weight of the colorant and its dispersant. If necessary,
Styrene resin, thermoplastic resin such as polyamide resin,
For a total of 100 parts by weight of the component (A) and the component (B),
About 1 to 30 parts by weight can be added.

<Production Method of Thermoplastic Resin Composition> The production method of the resin composition of the present invention is not limited to a specific method, but is preferably by melt-kneading, and is generally used for thermoplastic resins. A kneading method can be applied. As an example of the production method, after the component (D) is pelletized or powdered by a melt-kneading method or the like, the components (A), (B) and (C) are added, if necessary, to additional components and the like. In addition, after uniformly mixing with a Henschel mixer, a ribbon blender, a V-type blender or the like, the mixture can be kneaded with a single-screw or multi-screw kneading extruder, a roll, a Banbury mixer, a Labo Plast mill (Bradbender), or the like. Each component including the additional component may be fed to the kneader at one time or may be sequentially fed, or a premix of two or more components selected from each component including the additional component may be used. Good.

The kneading temperature and the kneading time can be arbitrarily selected depending on the desired conditions such as the type of the resin composition and the kneading machine, but the kneading temperature is about 150 to 350 ° C. and the kneading time is 20 minutes.
It is preferably about 10 minutes or less. When the temperature exceeds 350 ° C. or 20 minutes, thermal deterioration of the aromatic polycarbonate or polyphenylene ether becomes a problem, and the physical properties and appearance of the molded product may be deteriorated.

In the production of the thermoplastic resin composition of the present invention, other components can be added in addition to the above components (A) to (D). Examples of the additional component include a plasticizer having a plasticizing effect on an aromatic polycarbonate resin.Specifically, for example, aromatic hydrocarbons such as benzene, toluene, and xylene, heptane, chains such as cyclohexane, and the like. Cyclic aliphatic hydrocarbons, chlorobenzene, dichlorobenzene, trichlorobenzene, halogenated hydrocarbons such as dichloromethane, dioxane, ethers such as diethyl ether, cyclohexanone, ketones such as acetophenone, ethyl acetate, esters such as propiolactone, Nitriles such as acetonitrile and benzonitrile,
Examples include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and sec-butanol, and nitrobenzene and sulfolane. These can be used alone or as a mixture. The plasticizer having a plasticizing effect on the aromatic polycarbonate resin is preferably a compound having a solubility parameter in the range of 7 to 11.5.

<Method of Forming Resin Composition> The method of forming the resin composition of the present invention is not particularly limited.
Molding methods generally used for thermoplastic resins, that is, injection molding, hollow molding, extrusion molding, molding methods such as press molding can be applied, as a preferred molding method, hollow,
Extrusion molding and the like can be mentioned.

[0070]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Raw Materials Used in Examples and Comparative Examples (1) Aromatic polycarbonate resin: manufactured by Mitsubishi Engineering-Plastics Corporation, Iupilon S-2000,
Viscosity average molecular weight 23,000. (Hereinafter, also referred to as PC) (2) Polybutylene terephthalate: manufactured by Kanebo Co., Ltd.
BT124 (injection molding grade), intrinsic viscosity 2.4.
(Hereinafter, also referred to as PBT)

(3) Partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer: Kraton G1652 (St content: 29 wt%, solution viscosity (2
0 wt% toluene solution 25 ° C.): 550 cps), Clayton G1651 (St content: 33 wt%, melt viscosity: 2000 cps). (4) Polyphenylene ether: poly (2,6-dimethyl-1,4-phenylene ether), manufactured by Japan Polyether Co., Ltd., having an intrinsic viscosity of 0.53 dl / g measured in chloroform at 30 ° C. (Hereinafter also referred to as PPE)

(5) Phosphite compound: bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, trade name MARK PEP-36, manufactured by Asahi Denka Co., Ltd. (6) Phosphate ester: triphenyl phosphate (TPP), manufactured by Daihachi Chemical Co., Ltd. (7) Inorganic filler: calcium silicate, trade name: Vistal, manufactured by Otsuka Chemical Co., Ltd.

(8) MFR: Measured at 280 ° C. under a load of 2.16 kg using an MFR tester manufactured by Techno Seven. (9) Flexural modulus: ISO R178-1974 Pr
according to oscure12 (JIS K7203),
It was measured using an Instron tester. (10) Izod impact strength: ISO R180-19
The measurement was carried out using an Izod impact tester manufactured by Toyo Seiki Seisaku-Sho, Ltd., in accordance with the 69 (JIS K7110) Notched Izod Impact Strength Measurement Method.

(11) Heat retention stability: cylinder temperature 2
After staying in a molding machine at 80 ° C. for 30 minutes, the appearance (generation of silver streaks) of an injection-molded molded sheet (100 squares) was evaluated. The evaluation results are as follows: 場合 when no silver is generated, ○ when slight silver is generated (20% or less of sheet area), Δ when silver is generated (70 to 20% of sheet area), and silver generated Was large (70% or more of the sheet area).

[Examples 1 to 4] The components of component (D) were thoroughly mixed and stirred with a supermixer at the mixing ratio shown in Table 1 in advance, and then this was mixed with a vented Nippon Steel Corporation.
Using a TEX44 twin-screw extruder to reduce the pressure to 10 Torr from a vent port installed downstream of the first hopper, and to knead under a kneading condition of a set temperature of 210 ° C. and a screw rotation speed of 250 rpm, to obtain a melt-kneaded resin composition And pelletized. This was dried with a hot air drier at 105 ° C. for 8 hours. Next, the obtained pellets of the component (D) and the components (A), (B), (C) and (E) were sufficiently mixed and stirred by a super mixer at the mixing ratio shown in Table 1. This is then replaced with a TE ventilated TE
Using an X44 twin-screw extruder, the pressure was reduced to 10 Torr from the vent port installed downstream of the first hopper, and the set temperature was 2
Under a kneading condition of 30 ° C. and a screw rotation number of 250 rpm, the mixture was melt-kneaded and pelletized as a composition. The obtained pellets were dried with a hot air drier at 120 ° C. for 4 hours,
Various evaluations were performed. The results are shown in Table 1.

Example 5 Each component of component (D) was previously
Mixing, stirring, melt-kneading, pelletizing as a melt-kneaded resin composition and drying in the same manner as in Example 1 at the compounding ratios shown in Table 1. Next, pellets of the obtained component (D),
The components (A), (B) and (C) were mixed, stirred, melt-kneaded, pelletized as a composition and dried in the same manner as in Example 1 at the mixing ratios shown in Table 1, and various evaluations were made. Was carried out. The results are shown in Table 1.

[0077]

[Table 1]

[Comparative Examples 1 to 3] The components shown in Table 2 were sufficiently mixed and stirred at a mixing ratio shown in Table 2 using a super mixer, and then these were mixed with a ventilated Nippon Steel Corporation.
Using a TEX44 twin-screw extruder to reduce the pressure to 10 Torr from a vent port installed downstream of the first hopper, melt-knead under a kneading condition of a set temperature of 230 ° C. and a screw rotation speed of 250 rpm, and pelletize as a composition. It has become. The obtained pellets were dried with a hot air drier at 120 ° C. for 4 hours, and various evaluations were performed. Table 2 shows the results. [Comparative Example 4] PBT-1 and PEP-36 were previously prepared as shown in Table-2.
In the same manner as in Example 1, the mixture was mixed, stirred, melt-kneaded, pelletized as a melt-kneaded resin composition, and dried. Next, the obtained pellets, component (A), component (B) and component (C) were mixed, stirred and melt-kneaded in the mixing ratio shown in Table 2 in the same manner as in Example 1 to obtain a composition. Pellets, dried, and various evaluations were performed. Table 2 shows the results.

[0079]

[Table 2]

Example 6 Each component of component (D) was previously
At the compounding ratio shown in Table 3, similarly to Example 1, the mixture was stirred, melt-kneaded, pelletized as a melt-kneaded resin composition, and dried. Next, pellets of the obtained component (D),
The components (A) and (B) were mixed, stirred, melt-kneaded, pelletized as a composition and dried in the same manner as in Example 1 at the mixing ratios shown in Table 3, and various evaluations were performed. The results are shown in Table 1.

Example 7 Each component of component (D) was
At the compounding ratio shown in Table 3, similarly to Example 1, the mixture was stirred, melt-kneaded, pelletized as a melt-kneaded resin composition, and dried. Next, pellets of the obtained component (D),
The components (A), (B) and (E) were mixed, stirred and melt-kneaded in the mixing ratios shown in Table-3, pelletized as a composition, dried and evaluated in the same manner as in Example 1. Was carried out. The results are shown in Table-3.

[Comparative Example 5] The components shown in Table 2 were sufficiently mixed and stirred with a super mixer at the mixing ratio shown in Table 3, and then this was mixed with TE ventilated TE-manufactured by Nippon Steel Corporation.
Using an X44 twin-screw extruder, the pressure was reduced to 10 Torr from the vent port installed downstream of the first hopper, and the set temperature was 2
Under a kneading condition of 30 ° C. and a screw rotation number of 250 rpm, the mixture was melt-kneaded and pelletized as a composition. The obtained pellets were dried with a hot air drier at 120 ° C. for 4 hours,
Various evaluations were performed. The results are shown in Table-3.

[0083]

[Table 3]

[0084]

Industrial Applicability The thermoplastic resin composition of the present invention has excellent fluidity and impact resistance, excellent rigidity and heat resistance, and excellent heat retention stability. It can be widely used in the fields of electronic equipment parts, general industrial parts, home electric appliances and the like, and is useful in various applications.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 53:02 71:12) (72) Inventor Shinji Kodoko 5-6-1 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture No. Mitsubishi Engineering Plastics Co., Ltd. Technology Center (72) Inventor Tsuneaki Iwakiri 5-6-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa F-term in Mitsubishi Engineering Plastics Co., Ltd. Technical Center 4J002 BP013 CF00X CF004 CF05X CF06X CF07X CF08X CG00W CH07W CH074 DA066 DE076 DE076 DE106 DE116 DE136 DE146 DE186 DE236 DG046 DG056 DJ006 DJ016 DJ036 DL006 EW048 EW067 FA046 FA086 FB086 FD016 FD207 FD208

Claims (6)

[Claims] 1. A total of 100 of the following components (A) and (B):
A thermoplastic resin composition comprising a composition containing predetermined amounts of the following components (C) and (D) based on parts by weight. (A) 5-95 parts by weight of aromatic polycarbonate (B) 5-95 parts by weight of saturated polyester (C) 0-50 parts by weight of partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer (D) Saturated with polyphenylene ether Melt kneading resin composition containing polyester 0.01 to 20 parts by weight (E) Inorganic filler 0 to 50 parts by weight 2. A total of 100 of the following components (A) and (B):
A thermoplastic resin composition comprising a composition containing predetermined amounts of the following components (C) and (D) based on parts by weight. (A) 5-95 parts by weight of an aromatic polycarbonate (B) 5-95 parts by weight of a saturated polyester (C) 0.5-50 parts by weight of a partially hydrogenated alkenyl aromatic compound-conjugated diene block copolymer (D) polyphenylene ether Kneading resin composition containing 0.1 and 20 parts by weight of a saturated polyester 3. The melt-kneaded resin composition of the component (D) is a composition containing a predetermined amount of the following component (c) based on 100 parts by weight of the total of the following components (a) and (b). Item 1
Or the thermoplastic resin composition according to 2. (A) 5-80 parts by weight of a saturated polyester (b) 20-95 parts by weight of a polyphenylene ether (c) 0.1-10 parts by weight of a phosphite compound 4. A composition in which the melt-kneaded resin composition of the component (D) contains predetermined amounts of the following components (c) and (d) based on 100 parts by weight of the total of the following components (a) and (b): The thermoplastic resin composition according to claim 1, which is made of a product. (A) polyphenylene ether 20 to 95 parts by weight (b) saturated polyester 5 to 80 parts by weight (c) phosphite compound 0.1 to 10 parts by weight (d) phosphate compound 5 to 120 parts by weight 5. The thermoplastic resin composition according to claim 3, wherein (c) the phosphite compound is a phosphite compound represented by the following general formula (1). Embedded image (Wherein, R ¹ represents an alkyl group having 1 to 20 carbon atoms or an aromatic group or a substituted aromatic group having 6 to 30 carbon atoms;
Represents a number of 1 or 2, and when n is 1, R ² represents an alkylene group or an arylene group having 2 to 18 carbon atoms;
When n is 2, it represents an alkyltetrayl group having 4 to 18 carbon atoms, R ¹ may be the same or different, and the substituents of R ¹ and R ² are an oxygen atom, a nitrogen atom, a sulfur atom Alternatively, it may be a substituent containing a halogen atom. ) 6. The melt kneading of the polyphenylene ether and the saturated polyester constituting the component (C) is carried out in a range of 150 to 150.
The method for producing a thermoplastic resin composition according to any one of claims 1 to 5, wherein the method is performed at a temperature of 350 ° C.