JPH0365833B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a polycarbonate resin composition,
Specifically, the present invention relates to a polycarbonate resin composition that has excellent solvent resistance, rigidity, and impact resistance, as well as various properties such as moldability and appearance.
This material is especially suitable for industrial materials such as automobile bumpers, etc.
It is useful as a material for home appliances. [Prior Art and Problems to be Solved by the Invention] Polycarbonate resins have conventionally been known as molding resins that have excellent physical properties such as rigidity and thermal properties. However, polycarbonate resin molded articles tend to develop cracks due to concentrated stress in the presence of certain solvents. Also,
The polycarbonate resin has a high melt viscosity, and therefore the molding temperature and molding pressure are high compared to other resins, which is considered to be a difficult point in molding. It has been proposed to blend various polyesters into polycarbonate resin in order to improve the solvent resistance and poor moldability of polycarbonate resin without significantly impairing the excellent physical properties inherent in polycarbonate resin. There is. For example, a composition in which polyalkylene terephthalate, which is a copolymerization of a difunctional carboxylic acid component and a diol component having a large amount of aromatic rings, is blended with a polycarbonate resin (Japanese Patent Publication No. 57-16137, Japanese Patent Publication No. 54
-37633, Japanese Patent Application Laid-Open No. 50-102648) has been proposed. However, since this composition has a high aromatic content in the diol component, it has drawbacks such as the occurrence of discoloration during molding, and is also economically disadvantageous because the diol component is expensive. Also known is a composition in which a polyalkylene terephthalate containing cyclohexanedimethanol as a diol component is blended with a polycarbonate resin (JP-A-53-94536), but this polyalkylene terephthalate has a large decrease in rigidity and is resistant to solvents. There are disadvantages in that the improvement in properties is insufficient and the composition is colored, which limits its uses. The applicant has already proposed a composition in which the solvent resistance of polycarbonate resin is improved by blending with polycarbonate resin a new polyester resin that uses a diol component consisting of polyalkylene glycol and alkylene glycol. (Gan Sho 60-9252). [Means for solving the problem] The present inventors have dramatically improved the solvent resistance by further blending a specific rubber into the above composition,
The present invention was completed based on the discovery that mechanical properties can also be improved. That is, the present invention provides (A) polycarbonate resin 30
~89% by weight, (B) 40-76% by weight of a difunctional carboxylic acid component, 10-24% by weight of an ethylene glycol component, and 45-5% by weight of a polyethylene glycol component; ) A rubber-like elastic body obtained by polymerizing one or more vinyl monomers in the presence of a rubber-like polymer consisting of an alkyl acrylate and/or an alkyl methacrylate, or an alkyl acrylate and/or an alkyl methacrylate. A copolymer obtained by copolymerizing methacrylate and a polyfunctional polymerizable monomer having a conjugated diene double bond with one or more vinyl monomers. The present invention provides a polycarbonate resin composition characterized by comprising 1 to 25% by weight of a rubber-like elastic material. The polycarbonate resin used as component (A) in the present invention has the following general formula: (Here, Z is a bond, or alkylene having 1 to 8 carbon atoms, alkylidene having 2 to 8 carbon atoms, or 5 carbon atoms.
~15 cycloalkylene, C5-15 cycloalkylidene, SO ₂ , SO, O, CO or R means a hydrogen, chlorine or bromine atom or a saturated alkyl group having 1 to 8 carbon atoms, and m represents a number from 0 to 4. ) It is a polymer having a structural unit represented by: This polycarbonate resin is produced by a solvent process, i.e., by the reaction of dihydric phenol with a carbonate precursor such as phosgene or by the reaction of dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of known acid acceptors, molecular weight modifiers, etc. It can be produced by a transesterification reaction with a carbonate precursor such as. Here, as divalent phenols that can be suitably used, there are bisphenols, and 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) is particularly preferred. In addition, bisphenol A
may be partially or entirely replaced with other dihydric phenols. Examples of divalent phenols other than bisphenol A include hydroquinone, 4,4'-dihydroxydiphenyl, bis(4
-hydroxyphenyl)alkane, bis(4-hydroxyphenyl)cycloalkane, bis(4-
Compounds such as hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) ether or bis(3,5-dibromo-4- Examples include halogenated bisphenols such as hydroxyphenyl)propane and bis(3,5-dichloro-4-hydroxyphenyl)propane. These dihydric phenols may be homopolymers or copolymers or blends of two or more dihydric phenols. Furthermore, the polycarbonate resin used in the present invention may be a thermoplastic randomly branched polycarbonate obtained by reacting a polyfunctional aromatic compound with a dihydric phenol and/or a carbonate precursor. From the viewpoint of mechanical strength and moldability, the polycarbonate resin used in the present invention preferably has a viscosity average molecular weight of 10,000 to 100,000, particularly
20,000 to 40,000 is suitable. The blending ratio of the polycarbonate resin, which is the component (A) above, is 30 to 89% by weight, preferably 40% by weight of the total amount of the composition.
~75% by weight. Next, in the present invention, a polyester ether elastomer comprising a bifunctional carboxylic acid component, an ethylene glycol component, and a polyethylene glycol component is used as component (B). The polyester ether elastomer used here has the following general formula: (In the formula, Ar is an aromatic hydrocarbon group, Z is a divalent group, and n is a number from 1 to 30.) A polyester ether elastomer mainly composed of aromatic dicarboxylate units represented by . The intrinsic viscosity of this polyester ether elastomer is usually 0.4 to 1.5 dl/g, preferably 0.5 to 1.22 dl/g. Here, examples of the difunctional carboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid. Among these, terephthalic acid is preferred, and other difunctional carboxylic acid components may be used in combination within a range that does not impair the effects of the present invention. These are, for example, aliphatic dicarboxylic acids and their ester-forming derivatives, such as oxalic acid, malonic acid, adipic acid, suberic acid, azelaic acid, sebacic acid or decanedicarboxylic acid. The proportion of these other dicarboxylic acid components should generally be within 20% by mole based on the total dicarboxylic acids. The polyester ether elastomer which is component (B) of the present invention has the above bifunctional carboxylic acid component 40 to
76% by weight, ethylene glycol component 10-24% by weight
and a polyethylene glycol component of 45 to 5% by weight, particularly 42 to 8% by weight. If the proportion of the polyethylene glycol component exceeds 45% by weight, the rigidity of the resin composition will decrease, and if it is less than 5% by weight, the solvent resistance will be insufficient, which is not appropriate. The polyester ether elastomer, which is component (B), is produced in accordance with a conventional method in the presence or absence of a polycondensation catalyst containing titanium, germanium, antimony, etc. This can be carried out by heating and polymerizing the components and discharging by-produced water, lower alcohols, etc. from the system. The blending ratio of component (B) as described above is 15% of the total amount of the composition.
-45% by weight, preferably 20-40% by weight. If the blending ratio of component (B) is less than 15% by weight, the improvement in solvent resistance of the resin composition will be insufficient, and
If it exceeds 45% by weight, it is not suitable because the impact resistance of the resin composition will be greatly reduced. Furthermore, in the present invention, a rubber-like elastic body is used as component (C). Here, as the rubber-like elastic body, those shown in the following are used. That is, there is a resin polymer obtained by polymerizing one or more vinyl monomers in the presence of a rubbery polymer comprising an alkyl acrylate and/or an alkyl methacrylate. Here, the alkyl methacrylate is preferably an alkyl group having 2 to 10 carbon atoms, and specifically, ethyl acrylate,
Examples include butyl acrylate, 2-ethylhexyl acrylate, and n-octyl methacrylate. Vinyl monomers reacted in the presence of this rubbery polymer include aromatic vinyl compounds such as styrene and α-methylstyrene; methyl acrylate,
It refers to monomers such as acrylic esters such as ethyl acrylate; and methacrylic esters such as methyl methacrylate and ethyl methacrylate, and one or more of these monomers are polymerized.
Furthermore, these monomers are polymerized with other vinyl monomers, such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate. The polymerization reaction can be carried out by various methods such as bulk polymerization, suspension polymerization, and emulsion polymerization, and those produced by emulsion polymerization are particularly preferred. It is necessary that the resin polymer thus obtained contains the above-mentioned rubber component in an amount of 20% by weight or more. Specifically, such a resin polymer is
Examples include MAS resin elastomers such as graft copolymers of 60 to 80% by weight of n-butyl acrylate, styrene, and methyl methacrylate. above
Examples of the MAS resin elastomer include the product name "KM-330" manufactured by Rohm & Haas, and the product name "Metablane W529" manufactured by Mitsubishi Rayon Co., Ltd. These can be used as component (C) of the present invention. In addition, one type of vinyl monomer or There are resin polymers obtained by polymerizing two or more types. Here, as the alkyl acrylate and alkyl methacrylate, those mentioned above are used. In addition, examples of polyfunctional polymerizable monomers having conjugated diene type double bonds include conjugated diene compounds such as butadiene, and compounds having non-conjugated double bonds in addition to conjugated diene type double bonds in one molecule. can be mentioned. Specifically, such compounds include, for example,
1-Methyl-2-vinyl-4,6-heptadien-1-ol; 7-methyl-3-methylene-1,
6-octadiene; 1,3,7-octatriene, etc. When copolymerizing the above alkyl acrylate and/or alkyl methacrylate with a polyfunctional polymerizable monomer having a conjugated diene type double bond, an aromatic vinyl compound such as styrene or α-methylstyrene may be used as necessary. ; Adding vinyl monomers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl ester compounds such as vinyl acetate and vinyl propionate; vinyl ether compounds such as methyl vinyl ether; and vinyl halogenated compounds such as vinyl chloride. You can also do that. Furthermore, a crosslinking agent such as ethylene dimethacrylate or divinylbenzene may be added. In addition, when producing a copolymer by copolymerizing the above alkyl acrylate and/or alkyl methacrylate with a polyfunctional polymerizable monomer having a conjugated diene type double bond, the conjugated diene type double bond The polyfunctional polymerizable monomer should be used in a proportion of 0.1 to 20% by weight, preferably 1 to 10% by weight, in the copolymer. The vinyl monomers to be polymerized with the copolymer thus obtained include those listed above, and one or more of these may be used. The polymerization reaction can be carried out by various methods such as bulk polymerization, suspension polymerization, and emulsion polymerization, and those produced by emulsion polymerization are particularly preferred. The resin polymer obtained as described above is used according to the present invention.
It can be used as component (C). Preferred examples of such resin polymers are shown below. The first method is to copolymerize an alkyl (meth)acrylate such as n-butyl acrylate, 2-ethylhexyl acrylate, or methyl methacrylate with butadiene and a small amount of a crosslinking agent such as ethylene dimethacrylate or divinylbenzene by a conventional method. It is a graft copolymer obtained by adding a vinyl monomer such as styrene, acrylonitrile, vinyl chloride, etc. as a graft component monomer to the obtained latex, and graft polymerizing it by a conventional method. The second method is to copolymerize the above-mentioned alkyl (meth)acrylate with a compound having a non-conjugated double bond in addition to a conjugated diene type double bond in one molecule, and use the resulting latex. This is a graft copolymer obtained by adding the above-mentioned vinyl monomer as a graft component monomer and carrying out graft polymerization by a conventional method. Incidentally, the graft polymerization may be carried out in one stage, or may be carried out in multiple stages by changing the constituent components of the graft component monomer in multiple stages. More specifically, such resin polymers include:
MABS resins such as graft copolymers obtained by adding styrene and methyl methacrylate to a rubber latex obtained by copolymerizing octyl acrylate and butadiene in a ratio of 7:3 (the former: the latter = 7:3). There is an elastic body. The above MABS resin elastomers include "HIA 15", "HIA 28", and "HIA 30" manufactured by Kureha Chemical Industry Co., Ltd.
(All items indicate product names.) etc. are preferably used. The blending ratio of component (C) of the present invention as described above is 1 to 25% by weight, preferably 5 to 20% by weight of the total amount of the composition.
It is. If the blending ratio of component (C) is less than 1% by weight, the impact resistance and solvent resistance of the resin composition will decrease, and if it exceeds 25% by weight, the rigidity of the resin composition will decrease and the appearance will deteriorate. This is not appropriate as it will result in defects. The polycarbonate resin composition of the present invention may contain various inorganic fillers, additives, other synthetic resins, elastomers, etc., as necessary, as long as they do not impede the purpose of the present invention. First, the inorganic filler added for the purpose of increasing the mechanical strength, durability, or weight of the polycarbonate resin composition includes, for example, glass fiber,
Examples include glass beads, glass flakes, carbon black, calcium sulfate, calcium carbonate, calcium silicate, titanium oxide, alumina, silica, asbestos, talc, clay, mica, and quartz powder. The additives include, for example, phosphite-based and phosphate-based antioxidants, benzotriazole-based and benzophenone-based ultraviolet absorbers, and aliphatic carboxylic acid ester-based and paraffin-based external lubricants. Examples include commonly used flame retardants, mold release agents, antistatic agents, colorants, etc. Other synthetic resins include polyethylene, polypropylene, polystyrene, AS resin,
Examples of resins include ABS resin, polyester, and polymethyl methacrylate. Also,
Elastomers include isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-
Examples include propylene rubber and acrylic elastomer. The polycarbonate resin composition of the present invention can be obtained by blending and kneading the above-mentioned components. Blending and kneading can be carried out by conventional methods, such as a ribbon blender, Henschel mixer, Banbury mixer, drum tumbler, single-screw extruder, twin-screw extruder, co-kneader, multi-screw extruder, etc. be able to. The appropriate heating temperature during kneading is usually 250 to 300°C. The thus obtained polycarbonate resin composition can be molded using various known molding methods, such as injection molding, extrusion molding, compression molding, calendar molding, and rotary molding, to produce molded products in the automobile field such as automobile bumpers, and in the home appliance field. Molded products can be manufactured. Next, the present invention will be explained in detail with reference to examples. Examples 1 to 14 and Comparative Examples 1 to 7 After drying predetermined amounts of polycarbonate resin (PC resin), polyester ether elastomer, and rubber-like elastic body shown in Table 1, they were chip-blended and fed to an extruder. The mixture was kneaded at a temperature of 270 to 280°C and pelletized. After drying the obtained pellets, they were injection molded (mold temperature 80-90°C) to obtain test pieces. Table 1 shows the test results for the obtained test pieces. In addition,
The test method and its evaluation were performed using the following method. (1) Solvent resistance Using a JIS No. 1 dumbbell under a surface strain of 0.7%,
Toluene/isooctane/methanol=42.5/
After immersing in a mixed solvent of 42.5/15 (volume%) for 5 minutes,
It was expressed as elongation (%) relative to the original test piece when a tensile test was performed at 50 mm/min. (2) Izotsu impact strength Conforms to ASTM D256 (3) Flexural modulus Conforms to JIS K6719

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Claims (1)

[Claims] 1 Polyester ether elastomer 15 consisting of (A) 30-89% by weight of polycarbonate resin, (B) 40-76% by weight of difunctional carboxylic acid component, 10-24% by weight of ethylene glycol component, and 45-5% by weight of polyethylene glycol component. A rubber-like elastic body obtained by polymerizing one or more vinyl monomers in the presence of a rubber-like polymer consisting of ~45% by weight and (C) alkyl acrylate and/or alkyl methacrylate, or alkyl acrylate and/or alkyl methacrylate;
Rubber-like elasticity obtained by polymerizing one or more vinyl monomers with a copolymer obtained by copolymerizing a polyfunctional polymerizable monomer having a conjugated diene type double bond. A polycarbonate resin composition comprising 1 to 25% by weight of the polycarbonate resin composition.