JP3332059B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition comprising a thermoplastic aromatic polycarbonate resin and a reinforced thermoplastic resin containing a glass-based filler. It has excellent strength, chemical resistance and heat resistance, and is suitable for automobile-related parts, OA equipment, home electric parts, medical parts, and miscellaneous goods.

[0002]

2. Description of the Related Art Conventionally, aromatic polycarbonate resins are:
Although widely used as a resin having excellent mechanical strength, impact strength, and heat resistance, it has disadvantages such as poor chemical resistance, fatigue resistance, fluidity, and light weight.

[0003] A polymer alloy of an aromatic polycarbonate resin and another thermoplastic resin is known to compensate for these drawbacks. However, when high rigidity and high strength are required, reinforcement of glass fiber or the like is required. Wood is needed. Conventionally, molded products obtained from molding materials in which a thermoplastic resin and a glass-based reinforcing material are each blended and blended with an aromatic polycarbonate resin have a large surface roughness, and are in the fields of automobile-related parts, OA equipment, home appliances parts, medical parts, and miscellaneous goods. In particular, there is a limit to the performance of a molded article requiring surface appearance.

As means for improving the surface condition of a molded article, various means such as selecting a glass-based filler as a reinforcing material, for example, a fiber diameter and a fiber length of glass fiber, and setting optimum molding conditions, etc. However, for molding materials containing a glass-based filler mixed with an aromatic polycarbonate resin and a thermoplastic resin, the glass-based filler can be used even if the optimal molding conditions are set or the fiber diameter and fiber length of the glass-based filler are changed. At present, there is a limit to the appearance of the surface of the material, and no satisfactory results have been obtained.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been made in view of the above circumstances, such as the floating of glass fibers in a molding material obtained by blending a thermoplastic aromatic polycarbonate resin, another thermoplastic resin, and a glass filler. The object of the present invention is to provide a molded article excellent in surface appearance by overcoming the defects of the surface appearance of the molded article.

[0006]

Means for Solving the Problems In view of the above-mentioned situation, the present inventors have conducted intensive studies to obtain molded articles having excellent rigidity, strength, chemical resistance, heat resistance and excellent surface appearance. Rigidity and strength by blending a predetermined ratio of thermoplastic aromatic polycarbonate resin with excellent heat resistance, glass filler reinforced thermoplastic resin with high rigidity and high strength, chemical resistance, and excellent moldability. The present invention has been found to obtain a molded article which solves the intended problem without lowering the molding quality.

The present invention relates to a reinforced thermoplastic resin containing 10 to 90% by weight of (a) a thermoplastic aromatic polycarbonate resin and (b) 5 to 50% by weight of glass fiber.
The present invention relates to a thermoplastic resin composition containing about 10% by weight. In other words, the present invention, when blending glass fiber as a reinforcing material with a thermoplastic aromatic polycarbonate resin, by forming a molding material comprising a thermoplastic resin composition blended with a reinforced thermoplastic resin to which glass fiber has been added in advance. An excellent molded product having excellent surface appearance can be obtained.

[0008] By adopting the compounding recipe according to the method of the present invention, the amount of resin adhering to the glass-based filler in the surface layer of the molded article increases, and the glass-based filler is submerged, so that the surface appearance is improved. It is considered to be. In addition,
In the present invention, as a means for obtaining a molding material, the resin composition comprising the above (a) and (b) is melt-kneaded by an extruder and pelletized. However, it was confirmed that the fiber length was not shortened as compared with the conventional formulation, and high rigidity and strength were maintained.

The thermoplastic aromatic polycarbonate resin in the present invention is a thermoplastic aromatic polycarbonate polymer obtained by reacting an aromatic dihydroxy compound or a small amount of the polyhydroxy compound with phosgene or a carbonic acid diester. The aromatic polycarbonate resin may be branched.

As the aromatic dihydroxy compound, specifically, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane (Tetramethylbisphenol A), 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane (tetrabromobisphenol A), 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxy Phenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl and the like, and among them, bisphenol A
Is preferred.

Examples of a branching agent for obtaining a branched aromatic polycarbonate resin include chloroglycine, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2,4 , 6-dimethyl-2,
4,6-tri (4-hydroxyphenyl) heptane,
2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3,4,6-dimethyl-2,4
6-tri (4-hydroxyphenyl) heptane, 1,
3,5-tri (4-hydroxyphenyl) benzene,
Polyhydroxy compounds exemplified by 1,1,1-tri (4-hydroxyphenyl) ethane and the like;
Bis (4-hydroxyaryl) oxindole (=
Isatin bisphenol), 5-chloroisatin bisphenol, 5,7-dichloroisatin bisphenol,
5-bromoisatin bisphenol and the like, and these branching agents are substituted for a part of the dihydroxy compound, for example, 0.1 to 2 mol% with a polyhydroxy compound.

Further, if necessary, molecular weight control can be used. As such a molecular weight control agent, a monovalent aromatic hydroxy compound is used. The monovalent aromatic hydroxy compound includes m- and p-methylphenol,
Preferred are m- and p-propylphenol, p-bromophenol, p-tert-butylphenol and p-long chain alkyl-substituted phenols.

The aromatic polycarbonate resin is typically a bis (4-hydroxyphenyl) alkane-based compound, particularly a polycarbonate containing bisphenol A as a main raw material. Two or more aromatic dihydroxy compounds are used in combination. Examples of the obtained polycarbonate copolymer include a branched polycarbonate obtained by using a small amount of a trivalent phenol compound in combination. In the present invention, the aromatic polycarbonate resin may be used as a mixture of two or more kinds.

In the present invention, the thermoplastic resin in the reinforced thermoplastic resin in which the glass filler is blended includes:
Generally, any material can be used as long as it can be blended with the aromatic polycarbonate resin. For example, thermoplastic polyester,
Polystyrene resin, polyarylene ester resin,
One or a mixture of two or more selected from a polyolefin resin, a diene resin, a polyamide resin, a polyether resin, a polysulfone resin, a polyphenylene resin, and the like. Alternatively, an aromatic polycarbonate resin to be blended may be used.

The thermoplastic polyester is a polymer obtained by reacting an aromatic dicarboxylic acid or a diester thereof with a glycol or an alkylene oxide by a known method. Specifically, terephthalic acid or dimethyl terephthalate is used. , Naphthalenedicarboxylic acid, dimethyl naphthalenedicarboxylate as the main component of the aromatic dicarboxylic acid, ethylene glycol, butanediol,
Examples thereof include polyethylene terephthalate, polytetramethylene terephthalate (= polybutylene terephthalate), polyethylene naphthalate, and polytetramethylene naphthalate (= polybutylene naphthalate) obtained by reacting cyclohexanedimethanol or ethylene oxide. The thermoplastic polyester may be a copolymer, for example, a copolymer of cyclohexane dimethanol with terephthalic acid and isophthalic acid, and a copolymer of cyclohexane dimethanol and a copolymer of ethylene glycol with terephthalic acid. Can be.

The thermoplastic polyester used in the present invention has an intrinsic viscosity (intrinsic viscosity) of 0.4 or more, usually 0, as measured at 30 ° C. in a mixed solvent of phenol and tetrachloroethylene in a weight ratio of 6: 4. It is preferably from 0.5 to 1.5, and if it is less than 0.4, the improvement of impact resistance and chemical resistance becomes insufficient.

Examples of the polystyrene resin include polystyrene (PS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-ethyl methacrylate copolymer (AES resin), and maleic acid-butadiene-styrene. Copolymer (M
BS resin), maleic acid-acrylonitrile-styrene copolymer (MAS resin), acrylic acid-acrylonitrile-styrene copolymer (AAS resin), styrene-butadiene block copolymer, styrene-maleic anhydride copolymer, etc. desirable.

Examples of the polyarylene ester resin include:
A polymer or copolymer obtained by subjecting a dihydric phenol or a derivative thereof and an aromatic dicarboxylic acid or a derivative thereof to a condensation reaction as a main raw material. As the dihydric phenol used herein, the same aromatic dihydroxy compound as exemplified for the aromatic polycarbonate resin is preferably used, and the derivative of the dihydric phenol is obtained by combining the dihydric phenol with a fatty acid or an aromatic carboxylic acid. Is a diester of As the aromatic dicarboxylic acid, the same ones as exemplified for the production of the thermoplastic polyester are preferably used.

Examples of the polyolefin resin include high-density polyethylene resin, low-density polyethylene resin, linear low-density polyethylene resin, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, and ethylene-acrylate ester as polyethylene resins. Copolymers, ethylene-glycidyl (meth) acrylate copolymers and the like are desirable. Desirable polypropylene resins include polypropylene, propylene-vinyl acetate copolymer, propylene-vinyl chloride copolymer and the like.

Examples of the diene-based resin include monomers having a diene structure such as 1,2-polybutadiene resin and trans-1,4-polybutadiene resin alone or copolymers with monomers copolymerizable therewith. Is a mixture of

The polyamide resin is preferably an aminocarboxylic acid compound alone, a copolymer of a dicarboxylic acid compound and a diamine compound, or a polymer obtained by ring-opening polymerization of α, ω-caprolactam.

The polyether resin is preferably a polyphenylene ether resin.

The present is added to the thermoplastic resin in the invention <br/> glass fibers with an average fiber 2~30μm, especially length 3-1
0mm chopped strand, length 30-1000μ
m milled fiber or roving type can be used.

The amount of glass fiber added may be selected within the range of 5 to 50% by weight based on the amount of the thermoplastic resin, and if it is less than 5%, dimensional stability (low shrinkage), strength or Inferior in rigidity, not functioning as glass reinforced material. On the other hand, if the content exceeds 50% by weight, molding becomes difficult due to insufficient fluidity, and friction of the cylinder becomes severe, which is economically disadvantageous.

The thermoplastic resin composition obtained by blending the components (a) and (b) of the present invention contains,
If desired, various additives such as stabilizers, pigments, dyes and lubricants and various fillers such as reinforcing materials such as inorganic or organic fibrous substances can be blended, and further impair the properties of the resin composition of the present invention. Other resin components can be blended within the range not

In order to prepare a molding material comprising a reinforced thermoplastic resin containing a glass fiber of the present invention and a resin composition in which the reinforced thermoplastic resin is mixed with an aromatic polycarbonate resin, a conventionally known method is adopted. Machine,
A method of kneading with a mixer, roll or the like such as Banbury or Henschel is appropriately selected.

[0027]

EXAMPLES The composition of the present invention will be described below more specifically based on examples. The present invention is not limited to these.

Examples 1 to 3 and Comparative Examples 1 and 2 Aromatic polycarbonate resin from bisphenol A (trade name Iupilon S-manufactured by Mitsubishi Gas Chemical Co., Ltd.)
2000; molecular weight 25,000) (a), glass fiber reinforced aromatic polycarbonate resin (Mitsubishi Gas Chemical Co., Ltd., trade name Iupilon GS2020M) (a-
GF), glass fiber (fiber diameter 6 μm) reinforced polybutylene terephthalate resin (manufactured by Polyplastics Co., Ltd., trade name: Duranex RSX2105; GF30% by weight) (b-1), glass fiber (fiber diameter 13 μm) reinforced polybutylene Terephthalate resin (manufactured by Polyplastics Co., Ltd., trade name: Duranex 3300; GF30)
% By weight) (b-2), polybutylene terephthalate resin (Polyplastics Co., Ltd., trade name: Duranex 2002) (c), chopped strand glass fiber (fiber diameter: 6 μm) (manufactured by Nippon Electric Glass Co., Ltd.) Product name
ECS03T531DE) (GF-1), chopped strand glass fiber (fiber diameter 13 μm) (trade name ECS03T531P, manufactured by Nippon Electric Glass Co., Ltd.) (GF-
2) were mixed in a tumbler in the ratio (% by weight) shown in Table 1 and extruded into pellets by a single-screw vented extruder, and the pellets were heated at 120 ° C. in a hot air drier.
After drying for 5 hours or more, a test piece for measuring physical properties was injection-molded at a resin temperature of 260 ° C. and a mold temperature of 80 ° C.

The physical properties were measured as follows. Tensile strength: measured in accordance with ASTM D-638. Flexural strength: Measured according to ASTM D-790. Deflection temperature under load; measured according to ASTM D-648.

As for the surface roughness, a disk having a diameter of 100 mm is used.
Surface roughness meter (Surfcom 554A, manufactured by Tokyo Seimitsu Co., Ltd.)
, The center line average roughness Ra, the maximum height Rt, and the 10-point average roughness Rz were measured. The numerical value of the surface roughness is a numerical value when the upper stage is scaled parallel to the resin flow direction, and a numerical value when the lower stage is scaled perpendicular to the resin flow direction. Molded article using resin composition of the present invention and conventional method
FIGS. 1 and 2 show the state of the surface roughness of the molded article according to the comparative example.

The surface gloss was measured by UG manufactured by Suga Test Instruments Co., Ltd.
According to V-5D, the incident angle and the light receiving angle are each adjusted to 60 degrees, and the glossiness is measured. The numerical value of the surface glossiness is a numerical value when the upper part is irradiated with a light beam parallel to the resin flowing direction, and a lower numerical value is a value when the light beam is irradiated perpendicularly to the resin flowing direction.

[0032]

Industrial Applicability The thermoplastic resin composition of the present invention can provide a molded article having excellent surface smoothness and good appearance.

[0033]

[Table 1]

[Brief description of the drawings]

FIG. 1 shows the surface roughness of a molded article obtained from the resin composition of the present invention in a scale with respect to the resin flow direction.

FIG. 2 shows a surface roughness of a molded product obtained from a resin composition according to a conventional method (comparative example) in a scale with respect to a resin flow direction.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kazuo Okazaki 5-6-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Inside the Engineering Center of Mitsubishi Engineering-Plastics Corporation (72) Inventor Hidehiko Kamano 5-6-Higashi-Hachiman, Hiratsuka-shi, Kanagawa No. 2 Mitsubishi Engineering Plastics Co., Ltd. Technical Center Examiner Satoshi Morikawa (56) References JP-A-4-80249 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 69/00

Claims (2)

(57) [Claims] 1. A heat obtained by blending (a) 10 to 90% by weight of a thermoplastic aromatic polycarbonate resin and (b) 90 to 10% by weight of a reinforced thermoplastic resin containing 5 to 50% by weight of glass fiber. Plastic resin composition. 2. A molded article comprising the resin composition according to claim 1 and having excellent surface appearance.