JPH0366345B2 - - 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 have the disadvantage of being susceptible to cracking when subjected to concentrated stress in the presence of certain solvents. In addition, the polycarbonate resin has a high melt viscosity,
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 low moldability, which are disadvantages 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 bifunctional 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,
No. 54-37633, Japanese Unexamined Patent Publication No. 50-102648) have 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 a new polyester resin using a diol component consisting of polyalkylene glycol and alkylene glycol into polycarbonate resin (patent application). (Sho 60-9252). [Means for Solving the Problems] The present inventors have discovered that by further blending a polyester resin and a rubber-like elastic body into the above composition, the solvent resistance can be dramatically improved and the mechanical properties can also be improved. They discovered this and completed the present invention. That is, the present invention provides (A) polycarbonate resin 40
~90% by weight, (B) difunctional carboxylic acid component 40-76% by weight, alkylene glycol component 10-24% by weight, and polyalkylene glycol component 45-5% by weight
Polyester ether elastomer consisting of 5~
30% by weight, (C) 2 to 40% by weight of polyester resin, and (D) one or more vinyl monomers in the presence of a rubbery polymer consisting of alkyl acrylate and/or alkyl methacrylate. A rubber-like elastic body obtained by polymerization, or a copolymer obtained by copolymerizing an alkyl acrylate and/or alkyl methacrylate with a polyfunctional polymerizable monomer having a conjugated diene type double bond, The present invention provides a polycarbonate resin composition characterized by comprising 2 to 25% by weight of a rubbery elastic body obtained by polymerizing one or more vinyl monomers. 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 alkylidene having 5 to 8 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 prepared by a solvent process, i.e., the reaction of a dihydric phenol with a carbonate precursor such as phosgene or the reaction of a 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. It can be produced by a transesterification reaction with a carbonate precursor such as. Here, as dihydric phenols that can be suitably used, there are bisphenols, and 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) is particularly preferred. Also, 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 40 to 90% by weight, preferably 40% by weight of the total amount of the composition.
~75% by weight. Next, in the present invention, as component (B), a polyester ether elastomer consisting of a bifunctional carboxylic acid component, an alkylene glycol component, and a polyalkylene glycol component is used. 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 alone. . The intrinsic viscosity of this polyester ether elastomer is usually
It is 0.4 to 1.5 d/g, preferably 0.5 to 1.2 d/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. Next, there are no particular restrictions on the alkylene glycol component, but specific examples include ethylene glycol, propylene-1,2-glycol, propylene-1,
3-glycol, butylene-1,4-glycol, butylene-2,3-glycol, hexane-
1,6-diol, octane-1,8-diol, neopentyl glycol or decane-1,
Aliphatic diols having 2 to 15 carbon atoms such as 10-diol can be used. Among them, ethylene glycol and butylene glycol are preferred. In addition, polyalkylene glycol components include diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and poly(alkylene oxide)-α,ω- such as poly(tetramethylene oxide)-α,ω-diol.
Diols and ethylene oxide and 1,2-
A variety of propylene oxide random or block copolymers can be used. Among them, the average molecular weight is 300-8000, preferably 400-8000.
3000 polyethylene glycol and polytetramethylene glycol are preferred. The polyester ether elastomer which is component (B) of the present invention has the above bifunctional carboxylic acid component 40 to
76% by weight, 10-24% by weight of alkylene glycol component and 45-5% by weight, especially 42-8% by weight of polyalkylene glycol component. If the proportion of the polyalkylene 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, component (B), is produced in accordance with a conventional method in the presence or absence of a polycondensation catalyst containing titanium, germanium, antimony, etc., using a difunctional carboxylic acid component, an alkylene glycol component, and a polyalkylene This can be carried out by heating and polymerizing the glycol component and discharging by-product water, lower alcohol, etc. from the system. The blending ratio of component (B) as described above is 5% of the total amount of the composition.
~30% by weight. Here, the blending ratio of component (B) is 5
If it is less than 30% by weight, the improvement in solvent resistance of the resin composition will be insufficient, and if it exceeds 30% by weight, the impact resistance of the resin composition will be greatly reduced, which is not appropriate. Next, in the present invention, a polyester resin is used as component (C). Various polyester resins can be used here, but polyester resins obtained by polycondensing a bifunctional carboxylic acid component and an alkylene glycol component are particularly suitable. Here, as the bifunctional carboxylic acid component and the alkylene glycol component, those explained for the component (B) above can be mentioned. Particularly suitable as such polyester resin are polyethylene terephthalate and polybutylene terephthalate. The polyester resin, component (C), 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 bifunctional carboxylic acid component and the alkylene glycol component, and discharging by-product water, lower alcohol, etc. from the system. The blending ratio of component (C) as described above is 2% of the total amount of the composition.
-40% by weight, preferably 3-30% by weight. If the blending ratio of component (C) is less than 2% by weight, the rigidity and solvent resistance of the resin composition will be insufficient, and if it exceeds 40% by weight, the solvent resistance and impact resistance of the resin composition will be insufficient. It is not suitable as it reduces the quality. Further, in the present invention, a rubber-like elastic body as component (D) is used. Here, as the rubber-like elastic body, those shown below 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, as the alkyl acrylate and alkyl methacrylate, those having an alkyl group having 2 to 10 carbon atoms are suitable, and specifically, ethyl acrylate,
Examples include butyl acrylate, 2-ethylhexyl acrylate, n-octyl methacrylate, and the like. Vinyl monomers reacted in the presence of this rubbery polymer include aromatic vinyl compounds such as styrene and α-methylstyrene; acrylic esters such as methyl acrylate and ethyl acrylate; methyl methacrylate and methacrylic acid. It refers to monomers such as methacrylic esters such as ethyl, and one or more of these monomers are polymerized. Further, 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. Here, the polymerization reaction is bulk polymerization,
It can be carried out by various methods such as 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. Examples of such resin polymers include MAS resin elastomers such as graft copolymers of 60 to 80% by weight of n-butyl acrylate, styrene, and methyl methacrylate, and copolymers of styrene and methyl methacrylate. Examples include MS resin elastomer which is a combination. The MAS resin elastic body mentioned above is manufactured by Rohm & Haas under the trade name "KM-".
330", product name "Metablane" manufactured by Mitsubishi Rayon Co., Ltd.
W529" etc. (D) of the present invention
Can be used as an ingredient. In addition, one type of vinyl monomer or There are resin polymers obtained by polymerizing two or more types. 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 is The polyfunctional polymerizable monomer with
It should be used in a proportion of 0.1 to 20% by weight, preferably 1 to 10% by weight. 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 (D). Preferred examples of such resin polymers are shown below. The first method is to copolymerize butadiene with an alkyl (meth)acrylate such as n-butyl acrylate, 2-ethylhexyl acrylate, or methyl methacrylate, and a small amount of a crosslinking agent such as ethylene dimethacrylate or divinylbenzene by a conventional method. This 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 carrying out graft polymerization 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 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. There is an elastic body. Furthermore, there are MBS resin elastomers such as graft copolymers obtained by adding styrene to rubber latex obtained by copolymerizing methyl methacrylate and butadiene and performing graft polymerization. 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. Furthermore, other rubber-like elastic bodies, such as ABS resin elastic bodies, can also be used as the component (D) of the present invention. The blending ratio of component (D) of the present invention as described above is 2 to 25% by weight, preferably 2 to 20% by weight of the total amount of the composition.
It is. If the blending ratio of component (D) is less than 2% by weight, solvent resistance will be insufficient.
Undesirable. Furthermore, if the blending ratio of component (D) exceeds 25% by weight, the rigidity of the resin composition will decrease and the appearance will become poor, which is not suitable. The polycarbonate resin composition of the present invention may contain various inorganic fillers, additives, other rigid 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, garbon 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. Commonly used flame retardants, mold release agents, antistatic agents, colorants and the like can be mentioned. Other synthetic resins include polyethylene, polypropylene, polystyrene, AS resin,
Various resins such as ABS resin and polymethyl methacrylate can be mentioned. Examples of the elastomer include isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-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 automotive field such as automobile bumpers, and in the home appliance field. Molded products can be manufactured. [Example] Next, the present invention will be explained in detail with reference to Examples. Examples 1 to 14 and Comparative Examples 1 to 8 After drying predetermined amounts of polycarbonate resin (PC resin), polyester ether elastomer, polyester resin, and rubber-like elastic body shown in Table 1, they were chip-blended and put into an extruder. The mixture was fed and kneaded at a temperature of 260 to 300°C to form pellets. Table 1 shows the test results for the pellets obtained. In addition, the test method and its evaluation were performed by 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 is expressed as the elongation at break (%) with respect to the original test piece when a tensile test is 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 consisting of (A) 40-90% by weight of polycarbonate resin, (B) 40-76% by weight of difunctional carboxylic acid component, 10-24% by weight of alkylene glycol component, and 45-5% by weight of polyalkylene glycol component. 5 to 30% by weight, (C) 2 to 40% by weight of polyester resin, and (D) one or two vinyl monomers in the presence of a rubbery polymer consisting of alkyl acrylate and/or alkyl methacrylate. A rubber-like elastic body obtained by polymerizing the above, or a copolymer obtained by copolymerizing an alkyl acrylate and/or alkyl methacrylate with a polyfunctional polymerizable monomer having a conjugated diene type double bond. A polycarbonate resin composition comprising 2 to 25% by weight of a rubber-like elastic body obtained by polymerizing one or more vinyl monomers.