JPH08253667A - Resin composition and molding having improved heat stability - Google Patents

Abstract

PURPOSE: To obtain the subject composition excellent in heat stability, rigidity, etc., and useful for a camera, etc., by compounding a composition consisting of a specific thermoplastic resin and a specific inorganic filler in combination with a specific epoxy resin or phenoxy resin and a specific silane coupling agent. CONSTITUTION: This resin composition is obtained by compounding (A) a composition composed of (i) 38-98wt.% of a thermoplastic resin containing at least 50wt.% of an aromatic polycarbonate resin in 100wt.% of a thermoplastic resin and (ii) 1-50wt.% of an inorganic filler (preferably, mica and/or talc) having reactivity with an aromatic polycarbonate resin in combination with (B) 0.1-10wt.% of a resin of at least one kind selected from an aromatic epoxy resin and a phenoxy resin and (C) 0.05-2wt.% of an epoxy silane coupling agent of the formula [R<1> is methyl or ethyl; R<2> is a 1-3C alkyl; R<3> is γ- glycidoxypropyl, etc.; (m+f(n)=3, (m)=1,0, (n)=2,3].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having improved thermal stability, and more specifically, to a thermoplastic resin containing an aromatic polycarbonate resin as a main component and having a reaction activity with respect to the aromatic polycarbonate resin. A camera, audio, which has very good thermal stability and excellent mechanical properties and rigidity when a composition containing an inorganic filler is melt processed.
The present invention relates to a resin composition useful in a wide range of industrial fields such as VTR and OA equipment.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins have excellent mechanical properties and are widely used as engineering plastics. Further, glass fibers, carbon fibers, etc. are blended in fields where dimensional accuracy and rigidity are required. Widely used.

In addition, regarding aromatic polyester resins such as polyethylene terephthalate resin or polybutylene terephthalate resin, various proposals have been made for compositions containing plate-like fillers such as glass flakes, mica and talc (Japanese Unexamined Patent Publication (Kokai) No.
4-83050 and JP-A-54-83051). However, when an inorganic filler having a reaction activity with respect to an aromatic polycarbonate resin such as talc or mica is added to the aromatic polycarbonate resin, the carbonate bond of the aromatic polycarbonate resin is broken during melt processing, and the aromatic polycarbonate resin is decomposed. As a result, when the composition in which talc or mica is added to an aromatic polycarbonate resin is melt-processed with an injection molding machine or the like, a decomposed product is ejected from a nozzle. There was a problem with thermal stability during melt processing, such as inability to measure.

[0004]

The object of the present invention is, in the case of a composition obtained by adding an inorganic filler having a reaction activity to an aromatic polycarbonate resin to a thermoplastic resin containing an aromatic polycarbonate resin as a main component, Focusing on the low thermal stability during melt processing, by combining at least one resin selected from an aromatic epoxy resin or a phenoxy resin and a specific epoxy silane coupling agent with this composition, a resin can be obtained. It is intended to provide a thermoplastic resin composition and a molded article which are improved in thermal stability of the composition and have excellent mechanical properties and rigidity.

[0005]

In order to achieve the above object, the present inventors have added an inorganic filler having a reaction activity to an aromatic polycarbonate resin to a thermoplastic resin containing an aromatic polycarbonate resin as a main component. When various epoxy resins or phenoxy resins were added to the composition described above and the improvement of thermal stability was examined, the improvement of the decrease in molecular weight was insufficient, and decomposition products were ejected during molding, resulting in insufficient improvement. It was Moreover, when various silane coupling agents were added and examined, the use of a specific silane coupling agent improved the molecular weight reduction, but it was not practical because the decomposition product was ejected during molding. . Obtaining these results, the inventors of the present invention have further studied, and as a result, a composition comprising a thermoplastic resin containing an aromatic polycarbonate resin as a main component and an inorganic filler having a reaction activity with respect to the aromatic polycarbonate resin. By adding a specific epoxy resin or phenoxy resin and a specific silane coupling agent together, it is possible to obtain a composition having improved thermal stability with less decrease in molecular weight and less spout of decomposition products during molding. Furthermore, they have found that they are also excellent in mechanical properties and rigidity, and have completed the present invention.

That is, the present invention relates to (A) thermoplastic resin component 1
Thermoplastic resin (a component) in which at least 50% by weight is aromatic polycarbonate resin in (00% by weight), (B) inorganic filler (b component) having reaction activity with respect to aromatic polycarbonate resin, (C) aromatic At least one resin (component c) selected from epoxy resin or phenoxy resin and (D) an epoxy silane coupling agent represented by the following general formula (1) (component d)

[0007]

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[R ¹ is a methyl group or an ethyl group, R ² is an alkyl group having 1 to 3 carbon atoms, R ³ is a γ-glycidoxypropyl group or a β- (3,4-epoxycyclohexyl) ethyl group, m + n = 3, m = 1 or 0, n = 2 or 3], and the total of them is 1
When it is set to 00% by weight, a component is 38 to 98% by weight, b
A resin composition with improved thermal stability, characterized in that the components are in the range of 1 to 50% by weight, the c component is in the range of 0.1 to 10% by weight, and the d component is in the range of 0.05 to 2% by weight, and The present invention relates to a molded product obtained by molding a resin composition.

The aromatic polycarbonate resin used as the component a of the present invention is usually produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. Typical examples of dihydric phenols are 2,2
-Bis (4-hydroxyphenyl) propane [commonly known as bisphenol A], bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis ( 4-hydroxy-3,5-dibromophenyl) propane, 2,2- (4
Examples include -hydroxy-3-methylphenyl) propane and bis (4-hydroxyphenyl) sulfone. A preferred dihydric phenol is a bis (4-hydroxyphenyl) alkane, particularly preferably bisphenol A as a main raw material. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate, and the like, and specific examples thereof include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and a mixture thereof. In producing the polycarbonate resin, the dihydric phenol may be used alone or in combination of two or more kinds. Further, an appropriate molecular weight regulator, branching agent, catalyst for accelerating the reaction and the like can be used. 2 of the aromatic polycarbonate resin thus obtained
Mixing seeds or more is not a problem.

The thermoplastic resin other than the aromatic polycarbonate resin used as the component a of the present invention may be a resin which is usually used for obtaining a molded product. Examples of the thermoplastic resin include polyethylene,
Polypropylene, polyvinyl chloride, polystyrene, AB
General-purpose resins such as S resin and AS resin; polyacetal,
General-purpose engineering resins such as polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether and polyamide; high performance engineering resins such as polyphenylene sulfide, polysulfone, polyether sulfone, polyether-ether ketone, polyarylate, aromatic polyester and aromatic polyamide; Fluororesin, polyvinylidene chloride,
Specific resins such as polyvinyl alcohol, polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polymethylmethacrylate and polycellulose acetate can be mentioned, and these can be used alone or in combination of two or more. At least one thermoplastic resin selected from a graft copolymer obtained by grafting an aromatic vinyl compound and a vinyl cyanide compound to a diene rubber component, a polyester resin and a polyphenylene ether resin is contained in an amount of 50 to 0% by weight based on the total weight of the component a. % Is preferable.

The graft copolymer used in the present invention is a copolymer having a diene rubber component as a backbone and an aromatic vinyl compound component and a vinyl cyanide compound component graft-polymerized thereto. Examples of the diene rubber component include polybutadiene, polyisoprene and styrene-
Examples thereof include butadiene copolymers, and among them, polybutadiene is preferably used. Examples of the aromatic vinyl compound component grafted to these diene rubber components include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene and halogenated styrene, and among them, styrene is preferably used. Further, examples of the vinyl cyanide compound component include acrylonitrile, methacrylonitrile, chloroacrylonitrile, and the like, of which acrylonitrile is preferably used. Furthermore, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate and the like can be used. Among these graft copolymers, AB
S resin is preferably used.

These graft copolymers include bulk polymerization,
It may be produced by any of polymerization methods such as solution polymerization, suspension polymerization and emulsion polymerization, and the grafting method may be one-step grafting or multi-step grafting. Further, the graft copolymer can be used not only as one type but also as a mixture of two or more types.

The polyester resin used in the present invention is a resin obtained by a polycondensation reaction between a dicarboxylic acid component and a glycol component. Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbenedicarboxylic acid,
4,4-biphenyldicarboxylic acid, orthophthalic acid,
2,6-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4-diphenyl ether carboxylic acid,
4,4-diphenoxyethanedicarboxylic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3
Examples thereof include cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, which can be used alone or in combination of two or more kinds. Among these dicarboxylic acid components, terephthalic acid and isophthalic acid are preferably used alone or as a mixture thereof.

As the glycol component, for example, ethylene glycol, 1,2-propylene glycol, 1,3-
Propanediol, 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2,4,4-
Tetramethyl-1,3-cyclobutanediol, 1,4
-Butanediol, neopentyl glycol, 1,5-
Pentanediol, 1,6-hexanediol, 1,4
-Cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxy-3, 5-dibromophenyl) propane and the like can be mentioned, and these can be used alone or in combination of two or more kinds. Among these glycol components, ethylene glycol and 1,4-butanediol are preferably used.

Specific examples of these polyester resins include polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, poly (ethylene terephthalate / cyclohexane dimethylene terephthalate) copolymer. , Poly (ethylene terephthalate / ethylene isophthalate) copolymer, poly (butylene terephthalate / butylene dodecadioate) polyester ether copolymer, polyarylate, and the like. These polyester resins may be used alone or in combination of two or more. May be used. Among these polyester resins, polyethylene terephthalate resin or polybutylene terephthalate resin is preferably used.

The polyphenylene ether-based resin used in the present invention is polyphenylene ether,
A modified polyphenylene ether obtained by blending the copolymer and another resin.

Examples of the polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether) and poly (2-methyl-6). -Phenyl-
1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and 2,6-dimethylphenol and other phenols (eg 2,3,6)
Examples of the copolymer include -trimethylphenol and 2-methyl-6-butylphenol).
6-dimethyl-1,4-phenylene ether) or a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable, and poly (2,6-dimethyl-1,4-phenylene ether) is preferable. Is more preferable. Further, by reacting the above polyphenylene ether with an α, β-unsaturated carboxylic acid or a derivative thereof, preferably in the presence of a radical generator, in a molten state, a dissolved state or a slurry state at a temperature of 80 to 350 ° C. The resulting polyphenylene ether (0.01 to 10% by weight may be grafted or added with an α, β-unsaturated carboxylic acid or a derivative thereof).

Examples of the modified polyphenylene ether blended with another resin include a blend of the above polyphenylene ether and a vinyl aromatic compound polymer or a polyamide resin, among which a vinyl aromatic compound polymer. Is preferred.

The vinyl aromatic compound polymer is a vinyl aromatic compound polymer or a vinyl aromatic compound-conjugated diene compound copolymer, and examples of the vinyl aromatic compound polymer are styrene and α-methylstyrene. , Α-ethyl styrene, o-methyl styrene, m-methyl styrene and nuclear alkyl-substituted styrenes such as p-methyl styrene or o-chloro styrene, m-chloro styrene, p-
Examples thereof include polymers of nuclear halogenated styrenes such as chlorostyrene, p-bromostyrene, dichlorostyrene, dibromostyrene, trichlorostyrene and tribromostyrene. Among them, polymers of styrene or α-methylstyrene are preferable. . Examples of vinyl aromatic compound-conjugated diene compound copolymer include styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer and methyl methacrylate-butadiene-styrene copolymer. Among these, styrene
Butadiene copolymers are preferred.

The polyphenylene ether-based resin was prepared by dissolving 0.5 g of this resin in 100 ml of chloroform,
The reduced viscosity measured at 0 ° C. is preferably in the range of 0.15 to 0.7.

Examples of the inorganic filler having a reactive activity with respect to the aromatic polycarbonate resin used as the component b of the present invention include talc, mica, alumina, wollastonite, rock wool and the like, preferably talc or mica. is there. The reaction activity as used herein means having a functional group having an activity of cleaving the carbonate bond of the aromatic polycarbonate resin in its molecular structure. For details, p measured according to JIS K5101
An inorganic filler having an H value of 8 or more, preferably 8.5 or more.

The talc used in the present invention is a pulverized product of magnesium silicate as a main component in the form of a thin plate or mica, and such talc may be used alone or mica. You may use it by mixing with. Further, such talc may be surface-treated with a silane coupling agent or the like, and may be granulated with a binder to form a granule. Specific examples of talc include talc PKP-80 manufactured by Fuji Talc Industry Co., Ltd., and these are easily available on the market.

The mica used in the present invention is a pulverized product of silicic acid compounds such as aluminum, potassium, magnesium, sodium and iron, and such mica may be used alone or mixed with talc. You may use it. Further, such mica may be surface-treated with a silane coupling agent or the like, and may be granulated with a binder to form a granule. Specific examples of the mica include Mica Powder (Mica Powder) A-41 of Yamaguchi Mica Industry Co., Ltd., which are easily available on the market.

The addition amount of talc and mica is from 1 to
50% by weight is preferable, and more preferably 5-40% by weight.
Is. If the added amount of talc and mica is less than 1% by weight, sufficient effects on mechanical properties and rigidity cannot be obtained.
If it exceeds the weight%, the moldability of the composition will be significantly reduced.

The aromatic epoxy resin and phenoxy resin used as the component c of the present invention are an epoxy resin and a phenoxy resin synthesized from an aromatic polyol and epihalogenohydrin. Specifically, it is an epoxy resin or a phenoxy resin synthesized from bisphenol A and epichlorohydrin. Specific examples of the epoxy resin include Epotote YD series manufactured by Tohto Kasei Co., Ltd., and specific examples of the phenoxy resin are manufactured by Tohto Kasei Co., Ltd.
There are phenothotes, etc., which are easily available on the market. The amount of the component c added is 0.1 to 10% by weight.
Is preferable, and more preferably 0.5 to 3% by weight.
If the amount added is less than 0.1% by weight, the thermal stability during melt processing will not be sufficient, and if it exceeds 10% by weight, the moldability of the composition will be significantly reduced.

The epoxy silane coupling agent used as the component d of the present invention is represented by the following general formula (1).

[0027]

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[R ¹ is a methyl group or an ethyl group, R ² is an alkyl group having 1 to 3 carbon atoms, R ³ is a γ-glycidoxypropyl group or a β- (3,4-epoxycyclohexyl) ethyl group, m + n = 3, m = 1 or 0, n = 2 or 3]. Among the epoxy silane coupling agents represented by the general formula (1), β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ are particularly preferable. -Glycidoxypropylmethyldiethoxysilane and the like. These may be used alone or in combination of two or more.

The amount of these epoxy silane coupling agents added is preferably 0.05 to 2% by weight, more preferably 0.5 to 1% by weight. If the amount of the epoxy silane coupling agent added is less than 0.05% by weight, the thermal stability during melt processing will not be sufficient, and if it exceeds 2% by weight, the moldability of the composition will be significantly reduced.

The composition of the present invention contains a flame retardant (for example, brominated bisphenol, brominated epoxy resin, brominated polystyrene, brominated polycarbonate, triphenyl phosphate, phosphonamide) within a range not impairing the object of the present invention. , Red phosphoric acid, etc.), flame retardant aids (eg, antimony trioxide, sodium antimonate, etc.), nucleating agents (eg, sodium stearate, ethylene-sodium acrylate copolymers, etc.), stabilizers (eg, phosphorus). Acid ester, phosphite ester, etc.), antioxidant (for example, hindered phenolic compound, etc.), light stabilizer, colorant, foaming agent, lubricant, release agent, antistatic agent, etc. may be blended. .

Any method may be used to produce the resin composition of the present invention. For example, a thermoplastic resin containing an aromatic polycarbonate resin as a main component, an inorganic filler having a reaction activity with respect to the aromatic polycarbonate resin, an aromatic epoxy resin or a phenoxy resin, an epoxy silane coupling agent, and other additives as appropriate. A method generally used in industry such as a method in which the agent is sufficiently mixed using a mixing means such as a V-type blender and then pelletized with a vent type uniaxial ruder is appropriately used.

The resin composition thus obtained can be molded by any method such as injection molding, extrusion molding, compression molding or rotational molding. The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

[0033]

Examples 1 to 8 and Comparative Examples 1 to 6 Thermoplastic resins containing aromatic polycarbonate resins shown in Tables 1 and 2 as main components, inorganic fillers having a reaction activity with respect to aromatic polycarbonate resins, and fragrances. Group epoxy resin and / or phenoxy resin, and epoxy silane coupling agent were mixed in a tumbler in the amounts (shown in% by weight) shown in Table 1 and Table 2, and a uniaxial ruder with a diameter of 30 mm [NAKATANI MACHINE CO., LTD. VSK- 30] and extruded at a cylinder temperature of 290 ° C. to obtain pellets. The pellets obtained are 105 ° C.
For 5 hours in a hot-air circulation dryer, and using an injection molding machine [FANUC T-150D] at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. to form a test piece molding mold for bending elastic modulus measurement. A test piece for flexural modulus measurement was obtained. Next, the flexural modulus was measured using this test piece. The method for evaluating the flexural modulus is as follows. The evaluation results are shown in Tables 3 and 4. Flexural modulus (kgf / cm ² ): ASTM D-790
Was measured according to.

The method for evaluating the thermal stability during melt processing is as follows.

The viscosity average molecular weight (M) of the pellets prepared by the method described above was measured. The viscosity average molecular weight of the pellets was determined by inserting the specific viscosity (η _sp ) obtained from a solution prepared by dissolving methylene chloride at 20 ° C. at a concentration of 0.7 g / dl into the following formula. η _sp /C=[η]+0.45[η] ² C [η] = 1.23 × 10 ⁻⁴ M ^0.83 where C = 0.7

Further, after producing a desired number of flexural modulus measuring test pieces, the test pieces are weighed, and the injection unit is retracted while the compositions shown in Tables 1 and 2 are retained in the cylinder. After leaving it as it was for 10 minutes, the injection unit was moved forward again to prepare a test piece for bending elastic modulus measurement. Part 1
The viscosity-average molecular weight of the first shot test piece molded after being left for 0 minutes was measured as a test piece after retention. After the retention, the difference (ΔM) between the viscosity average molecular weight of the test piece and the viscosity average molecular weight of the pellet was taken, and the thermal stability was evaluated by the difference (ΔM).

The method of evaluating the ejection of decomposed products during molding is as follows. When the test piece after retention was prepared by the method described above, the weight (g) of the ejected substance ejected from the nozzle while standing for 10 minutes was measured and used as the ejected substance weight.

The symbols showing the components shown in Tables 1 and 2 are as follows. PC: Aromatic polycarbonate resin (bisphenol A
Viscosity average molecular weight of 23,000 produced from and phosgene
Aromatic polycarbonate resin, Panlite L-1225 manufactured by Teijin Kasei Co., Ltd. ABS; Acrylonitrile-butadiene-styrene copolymer (UT-61 manufactured by Mitsui Toatsu Co., Ltd.) PBT; Polybutylene terephthalate resin (Teijin Co., Ltd. )
TRB-H) PPE; polyphenylene ether resin (poly (2,6-
Dimethyl-1,4-phenylene ether, manufactured by GEM
PPE) PS; polystyrene resin (Denka Styrol MW manufactured by Denki Kagaku Kogyo Co., Ltd.) Talc; talc having an average particle diameter of 1.8 μm (Microace P-3 manufactured by Nippon Talc Co., Ltd.) mica; mica having an average particle diameter of 40 μm ( Mica powder (mica powder) A-41) manufactured by Yamaguchi Mica Industry Co., Ltd. E-1; Aromatic epoxy resin (polymer obtained from bisphenol A and epichlorohydrin, epoxy equivalent 3,800 to 5,000 g / eq, Toto) Made by Kasei Co., Ltd.
Epotote YD-7020) E-2: Aromatic phenoxy resin (polymer obtained from bisphenol A and epichlorohydrin, hydroxyl group equivalent 0.35 eq / 100 g, Tohto Kasei Co., Ltd. Phenote YP-50) Si; epoxy silane cup Ring agent (γ-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.)
(Manufactured by KBM-403)

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

[Table 3]

[0042]

[Table 4]

[0043]

As is clear from Tables 3 and 4, the composition of the present invention comprises a thermoplastic resin containing an aromatic polycarbonate resin as a main component, and an inorganic filler having a reaction activity with respect to the aromatic polycarbonate resin. It is extremely useful because it has improved thermal stability when melt-processed a composition to which is added, and has excellent mechanical properties and rigidity.

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Claims (4)

[Claims] 1. A thermoplastic resin (component (a)) in which at least 50% by weight of (A) 100% by weight of the thermoplastic resin component is an aromatic polycarbonate resin, and (B) an inorganic material having a reaction activity with respect to the aromatic polycarbonate resin. Filler (b component), (C) at least one resin (component c) selected from aromatic epoxy resin or phenoxy resin, and (D) epoxy silane coupling agent represented by the following general formula (1) ( d component) [Chemical formula 1] [R ¹ is a methyl group or an ethyl group, R ² is an alkyl group having 1 to 3 carbon atoms, R ³ is a γ-glycidoxypropyl group or β
-(3,4-epoxycyclohexyl) ethyl group, m +
n = 3, m = 1 or 0, n = 2 or 3], and when the total of them is 100% by weight, a component is 38 to 98% by weight, and b component is Is 1-5
A resin composition with improved thermal stability, characterized in that 0% by weight, the c component is 0.1 to 10% by weight, and the d component is 0.05 to 2% by weight. 2. A thermoplastic resin other than the aromatic polycarbonate resin of the component a is at least selected from a graft copolymer obtained by grafting an aromatic vinyl compound and a vinyl cyanide compound on a diene rubber component, a polyester resin, and a polyphenylene ether resin. The resin composition with improved thermal stability according to claim 1, which is one type of thermoplastic resin. 3. The resin composition with improved thermal stability according to claim 1, wherein the component b is mica and / or talc. 4. A molded product obtained by molding the resin composition having improved thermal stability according to any one of claims 1 to 3.