JP3524271B2 - Resin composition and molded article comprising the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition and a molded article made of the resin composition. More specifically, it relates to a polycarbonate resin composition excellent in rigidity, melt flowability and low warpage and a molded article made of the same.

[0002]

2. Description of the Related Art Polycarbonate resin has excellent mechanical properties and is widely used as an engineering plastic. It is also widely used in fields where dimensional accuracy and rigidity are required by blending glass fiber or carbon fiber. Has been. However, there is a remarkable tendency in recent years to reduce the size and weight of home appliances, information devices, etc. Therefore, for example, the outer shell member thereof is extremely thin. Such a thin member is required to have low warpage in addition to dimensional accuracy and rigidity.
When the fibrous filler is blended, an extremely large warp occurs due to the anisotropy at the time of molding shrinkage accompanying the orientation of the fibrous filler even if the temperature of the mold is sufficiently controlled. To meet such demand for low warpage, a method is known in which a plate-like filler such as glass flakes is blended to reduce anisotropy at the time of molding shrinkage and reduce warpage. However, the plate-like filler alone has inferior rigidity as compared with the composition containing the fibrous reinforcing material, and if more plate-like filler is added in order to improve the rigidity, the specific gravity becomes high and the desired weight reduction is achieved. You will go backwards. Further, when the plate-like filler and the fibrous filler are combined in combination instead of only the plate-like filler, the anisotropy at the time of molding shrinkage does not decrease so much. That is, the low warpage is not improved so much. Therefore, it is necessary to increase the rigidity only with the plate-like filler without changing the amount. For this purpose, we have previously proposed a composition in which a plate-shaped filler-containing polycarbonate resin is mixed with an olefin wax having a carboxyl group or a derivative group thereof (Japanese Patent Application No. 7-4129). However, even in such a composition, there is a demand for improvement in rigidity equivalent to a composition containing a fibrous filler, and a polycarbonate resin composition excellent in such rigidity and having a low warp has not been obtained so far.

[0003]

An object of the present invention is to provide a polycarbonate resin composition which is excellent in rigidity, melt flowability and low warpage.

The present inventor has conducted extensive studies as a means to achieve the above object, and as a result, a resin composition comprising a polycarbonate resin and a specific amount of glass flakes, and an olefinic wax having a specific amount of a carboxyl group or a derivative group thereof were prepared. It was found that a polycarbonate resin composition excellent in rigidity and melt flowability and having low warpage can be obtained by adding a specific amount of polycaprolactone, and thus the present invention has been completed.

[0005]

The present invention provides 100 parts by weight of a resin composition comprising (A) 45 to 97% by weight of a polycarbonate resin and (B) 3 to 55% by weight of glass flakes,
A resin composition comprising (C) 0.02 to 3 parts by weight of an olefin wax having a carboxyl group and / or a derivative group thereof and (D) 0.5 to 12 parts by weight of polycaprolactone. It is related.

The polycarbonate resin which is the component (A) used in the present invention is an aromatic polycarbonate resin obtained by reacting a dihydric phenol and a carbonate precursor. Typical examples of dihydric phenols used here are 2,
2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), bis (4-hydroxyphenyl)
Methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2 -Bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
Bis (4-hydroxyphenyl) ether, 4,4'-
Examples thereof include dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone and the like. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred. As the carbonate precursor, for example, carbonyl halide, carbonate ester, haloformate and the like are used, and specific examples thereof include phosgene, diphenyl carbonate and dihaloformate of dihydric phenol. In producing a polycarbonate resin by reacting the above dihydric phenol and a carbonate precursor, the dihydric phenol may be used alone or in combination of two or more, and if necessary, a catalyst, a molecular weight modifier, Antioxidants and the like may be used. The polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a mixture of two or more polycarbonate resins.

However, when the total amount of dihydric phenol in the polycarbonate resin is 100 mol%, 70
It is preferable that the mol% or more of the dihydric phenol is bisphenol A.

The molecular weight of such a polycarbonate resin is
The viscosity average molecular weight is preferably 14,000 to 25,000, and particularly preferably 15,000 to 24,000. A polycarbonate resin having a viscosity average molecular weight of less than 14,000 is not preferable because it has insufficient strength. A polycarbonate resin having a viscosity average molecular weight of more than 25,000 is not preferable because it has poor melt fluidity and requires a high temperature for molding. The viscosity average molecular weight (M) in the present invention is 100 ml of methylene chloride and 0.7% of polycarbonate resin.
It is obtained by inserting the specific viscosity (η _sp ) obtained from a solution of g dissolved at 20 ° C. into the following equation. η _sp /c=[η]+0.45×[η] ² c [η] = 1.23 × 10 ⁻⁴ M ^0.83 (where [η] is the intrinsic viscosity, and c is the polymer concentration, 0.7). )

The basic means for producing a polycarbonate resin will be briefly described. In the solution method using phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and an organic solvent. As the acid binder, for example, a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. Further, for the purpose of accelerating the reaction, for example, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used, and as a molecular weight regulator, for example, an end capping agent such as phenol or an alkyl-substituted phenol such as p-tert-butylphenol can be used. It is desirable to use.
The reaction temperature is usually 0 to 40 ° C., the reaction time is several minutes to 5 hours,
The pH during the reaction is preferably maintained at 10 or higher.

In the transesterification reaction (melting method) using a carbonic acid diester as a carbonate precursor, a predetermined ratio of a dihydric phenol is heated and stirred with a carbonic acid diester in the presence of an inert gas to produce an alcohol or a phenol compound. Is distilled out. The reaction temperature will differ depending on the boiling point of the alcohol or phenol to be produced, but is usually in the range of 120 to 300 ° C. The reaction is completed by depressurizing from the initial stage while distilling off the produced alcohol or phenols. Further, a catalyst for transesterification reaction can be usually used to accelerate the reaction. Examples of carbonic acid diesters used in this transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and the like, with diphenyl carbonate being particularly preferred.

The glass flakes used as the component (B) in the composition of the present invention have an average particle size of 10 to 1,
000 μm is preferable, and when the average particle size is (a) and the thickness is (b), the (a) / (b) ratio is preferably 5 to 500, more preferably 6 to 450. , 7 to 400 are particularly preferable. If the average particle size is less than 10 μm or the (a) / (b) ratio is less than 5, the rigidity tends to be insufficient, and the average particle size is 1,000 μm.
When the ratio exceeds (a) / (b) exceeds 500, the appearance tends to be insufficient.

The glass flakes are preferably surface-treated with a silane coupling agent or the like. By this surface treatment, the decomposition of the polycarbonate resin can be suppressed and the adhesion can be improved. The silane coupling agent here is the following general formula

[0013]

[Chemical 1]

In the formula, Y is a group having reactivity or affinity with the resin matrix such as an amino group, an epoxy group, a carboxylic acid group, a pinyl group, a mercapto group and a halogen atom, and R _{1 to} R
Each of ₄ represents a single bond or an alkylene group having 1 to 7 carbon atoms, and an amide bond, an ester bond, an ether bond or an imino bond may be present in the alkylene molecular chain.
X _{1 to} X ₃ are each a hydrogen atom, a halogen atom or an alkoxy group, at least two of X _{1 to} X ₃ are a halogen atom or an alkoxy group, and the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. . Specific examples of the silane compound include vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane and β- (3,4-
Epoxycyclohexyl) ethyltrimethoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β
(Aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ- Examples thereof include mercaptopropyltrimethoxysilane and γ-chloropropyltrimethoxysilane. Further, it is preferable that the glass flakes are granulated or bundled with a binder such as an acrylic resin, a urethane resin, an epoxy resin, an unsaturated polyester resin, or the like from the viewpoint of easy handling. However, the above-mentioned glass flake average particle size range and thickness range are not applied to the granular or focused product obtained by such granulation or focusing. The blending amount of the component (B) is 3 to 55% by weight in the resin composition including the polycarbonate resin (A) and the component (B). 3% by weight
If it is less than 50%, the effect of improving the rigidity is insufficient, and if it is more than 55% by weight, the moldability deteriorates, and it becomes difficult to obtain the target thin-walled molded product.

In the present invention, the carboxyl group derivative in the olefin wax having a carboxyl group and / or its derivative group used as the component (C) is a carboxylic acid anhydride group, a metal salt of a carboxylic acid, or an alkyl ester of a carboxylic acid. , Aryl esters and the like. The carboxyl group or its derivative group may be bonded to any part of the olefin wax, and the concentration thereof is not particularly limited.
The range of 0.1 to 6 meq / g is preferable. 0.1
If it is less than meq / g, the rigidity and impact resistance will be insufficiently improved, and if it is more than 6 meq / g, the thermal stability of the olefin wax itself will be deteriorated.

The (C) olefin wax is, for example, Diacarna PA30, PA208 [manufactured by Mitsubishi Chemical Corporation], high wax acid treatment type 2203A,
1105A [manufactured by Mitsui Petrochemical Industry Co., Ltd.] and the like. This olefin wax may be used alone or in combination of two or more kinds. The compounding amount of the (C) olefin wax is 0.02 to 3 parts by weight, preferably 0.03 to 1 part by weight, per 100 parts by weight of the composition comprising the components (A) and (B). If it is less than 0.02 parts by weight, the rigidity and impact resistance are not sufficiently improved, and if it is more than 3 parts by weight, the tensile strength is greatly reduced and the rigidity is also reduced.

As the polycaprolactone used as the component (D) in the present invention, those generally known at present as flow modifiers for polycarbonate resins and the like are used, and the production method and the structure of the terminal blocking are not particularly limited. Absent.
The number average molecular weight is 3,000 to 30,000.
It is preferably about 0. If it is less than 3,000, the thermal stability is adversely affected, and if it is more than 30,000, the effect of improving the rigidity is somewhat insufficient. The compounding amount is 0.1 parts by weight per 100 parts by weight of the composition comprising the components (A) and (B).
5 to 12 parts by weight. If it is less than 0.5 parts by weight, the effect of improving the rigidity is not sufficient, and if it is more than 12 parts by weight, the heat resistance and strength are adversely affected.

The resin composition of the present invention contains a halogen-based flame retardant, a flame retardant aid, a drip-preventing agent, a heat stabilizer, a light stabilizer, a release agent, a colorant, within a range that does not impair the object of the present invention. A lubricant, a foaming agent and the like can be added in an effective expression amount, if necessary. Examples of the halogen-based flame retardant include brominated bisphenol carbonate oligomer, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, brominated polystyrene, and the like, and flame retardant aids include antimony trioxide and sodium antimonate. Can be mentioned. Further examples of the anti-drip agent include polytetrafluoroethylene having a fibrillation-forming ability, examples of the heat stabilizer include phosphate ester, phosphite ester, and hindered phenol-based antioxidant, and examples of the light stabilizer include: Examples thereof include hindered piperidine derivatives, phenyl salicylate derivatives, 2-hydroxybenzophenone derivatives, and the like. Examples of the release agent include polyethylene wax, acid-modified polyethylene wax, 1-alkene polymer and fatty acid ester compound. Further, other fillers such as mica, talc, calcium carbonate, carbon black, and metal powder may be blended depending on the purpose, and, for example, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polyamide, acrylic resin, A thermoplastic resin such as wholly aromatic polyester, phenoxy resin, or epoxy resin, or an elastic body may be blended. Among these, particularly, phosphoric acid esters for the purpose of improving thermal stability, phosphorous acid esters, heat stabilizers such as hindered phenolic antioxidants, hindered piperidine derivatives for the purpose of improving weather resistance, and phenyl. It is preferable to add a light stabilizer such as a salicylate derivative or a 2-hydroxybenzophenone derivative.

Any method may be used to produce the resin composition of the present invention. For example, (A) a polycarbonate resin, (B) a glass flake, (C) an olefin wax having a carboxyl group or a derivative group thereof and (D) a polycaprolactone, and optionally other additives at the same time or in any order, for example, a tumbler. , V type blender,
Nauta mixer, Banbury mixer, kneading roll,
A method of mixing with an extruder or the like is appropriately adopted. The polycarbonate resin composition thus obtained is molded by any molding method, but the injection molding method is particularly preferable.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below with reference to Examples. In addition, the part in an Example is a weight part and evaluation was performed by the following method. (1) Flexural modulus (kgf / cm ² ): After bending the test piece, it was left at 23 ° C. and 50% RH for 48 hours, and then A
It was measured according to STM D-790. (2) Impact value (kgf · cm / cm): After molding the impact test piece and leaving it in an atmosphere of 23 ° C. and 50% RH for 48 hours, A
STM D-256 (with Izod notch, thickness 3.
2 mm). (3) Anisotropy of molding shrinkage (%): width 50 mm x length 1
23mm at 50% R after forming a square plate of 00mm x thickness 4mm
After being left in an H atmosphere for 24 hours, the square plate size was measured by a three-dimensional measuring machine [manufactured by Mitutoyo Co., Ltd.] to calculate the molding shrinkage rate. As a measure of anisotropy, a value obtained by subtracting the value in the flow direction from the value in the direction perpendicular to the molding shrinkage was calculated.
The closer it is to 0, the less anisotropy and good low warpage. (4) Flow characteristics (cm): flow path thickness 2 mm, flow path width 8 mm
The Archimedean type spiral flow length of the above was measured by an injection molding machine [SG150U manufactured by Sumitomo Heavy Industries, Ltd.] with a cylinder temperature of 290 ° C, a mold temperature of 100 ° C, and an injection pressure of 1200.
It was measured in kgf / cm ² . (5) Specific gravity: measured according to ASTM D792.

Examples 1 to 4 and Comparative Examples 1 to 6 After dry-blending the components shown in Table 1 in the amounts shown in the table, a single screw extruder with a screw diameter of 30 mm and having a vent [VSK-manufactured by Freesia Macross Co., Ltd.] 30] and melt-kneaded at a cylinder temperature of 300 ° C. to uniformly knead the entire composition, and then pellets were obtained by strand cutting. The pellets were dried at 110 ° C. for 6 hours by a hot air circulation dryer, and then an injection molding machine [SG150 manufactured by Sumitomo Heavy Industries, Ltd.]
U], a bending test piece, an impact test piece and an anisotropic test piece of molding shrinkage were molded and evaluated at a cylinder temperature of 300 ° C. and a mold temperature of 100 ° C. Moreover, the Archimedes type spiral flow length of the obtained pellet was measured.

The evaluation results are shown in Table 1. The symbols of the components used in Table 1 are shown below. PC-1: Polycarbonate resin having a viscosity average molecular weight of 19500 [Panlite L-1225L manufactured by Teijin Chemicals Co., Ltd.] PC-2: Polycarbonate resin having a viscosity average molecular weight of 15500 [Panlite L-1225L manufactured by Teijin Chemicals Co., Ltd.]
L] GFL; glass flake [REFG manufactured by Nippon Sheet Glass Co., Ltd.
-101, thickness 2 to 6 µm, average particle diameter 600 µm, average particle diameter / thickness = 100 to 300] GFB; glass fiber [3PE-45 manufactured by Nitto Boseki Co., Ltd.]
5, fiber diameter 13 μm, average fiber length 3 mm] OW; copolymer of 1-alkene and maleic anhydride having a concentration of a carboxyl group and / or its derivative group of about 1 meq / g [manufactured by Mitsubishi Kagaku KK] 30M] PCL; polycaprolactone having a number average molecular weight of 10,000 [Plaxel H1P manufactured by Daicel Chemical Industries, Ltd.] ST; trimethyl phosphate [TM manufactured by Daihachi Chemical Co., Ltd.]
P]

[0023]

[Table 1]

From the comparison between Example 1 and Comparative Example 1, the blending of polycaprolactone (PCL) improved the flexural modulus (rigidity) and increased the fluidity.
Also in the comparison between Example 2 and Comparative Example 2, the addition of polycaprolactone (PCL) improves rigidity and fluidity. In the comparison between Example 2 and Comparative Example 3, the rigidity is remarkably improved and the fluidity is enhanced by blending the olefin wax (OW) having a carboxyl group and the polycaprolactone (PCL). In the comparison between Example 2 and Comparative Example 4, when glass fibers (GFB) are blended with glass flakes (GFL), the anisotropy is significantly reduced and the warpage is deteriorated. From the comparison between Example 3 and Comparative Example 5, polycaprolactone (P
By blending CL), the rigidity is greatly improved and the fluidity is also increased. From the comparison between Example 4 and Comparative Example 6, the rigidity cannot be improved by blending only polycaprolactone (PCL).

[0025]

The polycarbonate resin composition of the present invention is excellent in rigidity, low anisotropy (low warpage) and fluidity, and satisfies both high rigidity and low anisotropy (low warpage) at the same time. It is suitable as a material for manufacturing a CD tray, a tray for a CD changer, a disk cartridge, etc., which must be done, and the industrial effect produced by the material is exceptional.

Claims (6)

(57) [Claims] 1. (A) Polycarbonate resin 45 to 97
100 parts by weight of a resin composition consisting of 3 to 55% by weight of (B) glass flake and (B) an olefin wax having (C) a carboxyl group and / or its derivative group.
02 to 3 parts by weight and (D) polycaprolactone 0.5 to 1
A resin composition comprising 2 parts by weight. 2. The component (A) polycarbonate resin is
70 mol% when the total dihydric phenol is 100 mol%
The viscosity average molecular weight obtained by reacting a dihydric phenol composed of 2,2-bis (4-hydroxyphenyl) propane with a carbonate precursor is 14,000 to 25.0.
The resin composition according to claim 1, which is a polycarbonate resin of 00. 3. When the glass flakes of the component (B) have an average particle diameter of 10 to 1,000 μm, the average particle diameter is (a), and the thickness is (b), (a) / (b). Ratio is 5
The resin composition according to claim 1 or 2, which is a glass flake of about 500. 4. The olefin wax as the component (C) comprises:
The concentration of the carboxyl group and / or its derivative group in the wax is 0.1 to 1 g of the olefin wax.
The resin composition according to any one of claims 1 to 3, which is an olefin wax in a range of 6 meq / g. 5. The number average molecular weight of the polycaprolactone as the component (D) is 3,000 to 30,000.
The resin composition according to claim 1. 6. A molded product obtained by melt-molding the resin composition according to claim 1.