JPH07331053A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain a polycarbonate resin composition having excellent impact strength, weld strength, appearance, thermal aging resistance, etc. CONSTITUTION:This polycarbonate resin composition comprises (A) 5-98wt.% of a polycarbonate resin and (B) 50-2wt.% of a modified olefinic elastomer obtained by the following production method. The component B is a modified olefinic elastomer prepared by grafting 0.01-20 pts.wt. of a hydroxyl group- containing alpha, beta-unsaturated carboxylic acid ester and 0.1-20 pts.wt. of a styrenic monomer onto 100 pts.wt. of an olefinic elastomer having <=500kg/cm<2> modulus in flex (JIS K7,203) at 23 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition having excellent moldability, which gives a molded article excellent in heat aging resistance, low temperature impact strength and weld strength. This molded article is used in a wide variety of fields such as automobile parts such as instrument panels, ignition coils, manifolds and bumpers, and electrical and electronic parts such as switches, housings and containers.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins represented by 4,4'-dihydroxydiphenylalkane-based polycarbonate are widely used as molding resins for office equipment exterior members and electronic equipment members. This resin has excellent bending strength and thermal properties, but has low impact strength at low temperatures. As a means for improving the impact strength of polycarbonate at low temperatures, a resin composition obtained by blending 100 parts by weight of the polycarbonate with an ethylene / propylene block copolymer in a proportion of 50 parts by weight or less (Japanese Patent Publication No. 40-24191).
A resin composition in which 0.3 to 20 parts by weight of ethylene / propylene copolymer rubber or polyethylene or 0.3 to 20 parts by weight of ethylene / propylene / diene terpolymer rubber is mixed with 100 parts by weight of polycarbonate or polycarbonate. 57
No. 108152) has been proposed.

However, since a polycarbonate resin having a polar group and these hydrophobic olefin resins and olefin rubbers are originally incompatible and have no affinity, when these two components are simply mixed, The adhesion of the interface of the two-phase structure is not good. Therefore, the two phases are unlikely to be in a uniform and finely dispersed form, and the effect of improving the low temperature impact strength is low, and when shear stress is applied during molding such as injection molding, delamination is likely to occur.

In order to improve the compatibility of the two, 100 parts by weight of polycarbonate, 0.5 to 20 parts by weight of an unmodified crystalline polyolefin or ethylene / propylene copolymer rubber, and a maleic anhydride graft-modified polyolefin of 0. 1-40 parts by weight and inorganic fine powder 0.
Resin composition containing 1 to 80 parts by weight (Japanese Patent Publication No. 1-14
940) or 5 to 95% by weight of a polycarbonate, 1 to 50 parts by weight of a styrene-based monomer to 100 parts by weight of a crystalline propylene-based resin, and a hydroxyl group-containing vinyl monomer such as 2-hydroxyethyl methacrylate 0.1. Modified propylene resin obtained by reacting 10 to 10 parts by weight of 95 to 5% by weight
A resin composition containing JP-A-5-295221 has been proposed. However, even with these resin compositions, the effect of improving low temperature impact strength is not practically sufficient.

[0005]

SUMMARY OF THE INVENTION The present invention provides a molded article which is excellent in fluidity during molding, retention stability in the cylinder of an injection molding machine, heat aging resistance, weld strength, low temperature impact strength and appearance. It is intended to provide a polycarbonate resin composition to be given.

[0006]

The present invention provides a polycarbonate resin containing (A) 50 to 98% by weight of a polycarbonate resin and (B) a modified olefin elastomer obtained by the following production method in a proportion of 50 to 2% by weight. A composition is provided. Production of component (B): Flexural modulus at 23 ° C. (JIS
K7203) has α, β having a hydroxyl group in 100 parts by weight of an olefin elastomer having a weight of 500 kg / cm ² or less.
-A modified olefin elastomer obtained by graft-polymerizing 0.01 to 20 parts by weight of an unsaturated carboxylic acid ester and 0 to 50 parts by weight of another vinyl monomer.

[0007]

[Function] By melting and kneading the resin composition,
The hydroxyl group of the modified olefin elastomer of the component (B) reacts with the carbonate bond of the polycarbonate resin of the component (A) to form a block copolymer and / or a graft copolymer of the olefin elastomer and the polycarbonate resin, It is presumed that this serves as a compatibilizing agent and the component (B) forms a fine and stable dispersion structure, which improves the mechanical strength, appearance and moldability of the composition.

(Detailed Description of the Invention) (A) Polycarbonate Resin The polycarbonate resin (A) is produced by reacting an aromatic hydroxy compound or a small amount of a polyhydroxy compound with phosgene. It is also produced by transesterifying an aromatic dihydroxy compound or a small amount of this polyhydroxy compound with a carbonic acid diester. If necessary, a trifunctional or higher functional compound of a branching agent and a molecular weight modifier are also provided for the reaction. This aromatic polycarbonate resin is a thermoplastic aromatic polycarbonate resin which may be branched or unbranched.

Examples of aromatic dihydroxy compounds include:
2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A), tetramethylbisphenol A, tetrabromobisphenol A, bis (4
-Hydroxyphenyl) -p-isopropylbenzene,
Hydroquinone, resorcinol, 4,4'-dihydroxyphenyl, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis ( 4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl)
Examples thereof include ethane and 1,1-bis (4-hydroxyphenyl) cyclohexane, and bisphenol A is particularly preferable.

To obtain a branched aromatic polycarbonate resin, phloroglucin, 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-
3,2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ) Polyhydroxy compounds exemplified by ethane and the like, and 3,3-bis (4-hydroxyaryl) oxindole [= isatin (bisphenol A)], 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like are mentioned above. A part of the dihydroxy compound, for example, 0.1 to 2 mol% is replaced with the polyhydroxy compound.

Further suitable monovalent aromatic hydroxy compounds for controlling the molecular weight are m- and p-methylphenol, m- and p-propylphenol, p-bromophenol, p-tertiary-butylphenol and p-long-chain alkyl-substituted phenol and the like. A preferable aromatic polycarbonate resin is a bis (4-hydroxyphenyl) alkane compound, particularly preferably a polycarbonate containing bisphenol A as a main raw material. A polycarbonate copolymer obtained by using two or more kinds of aromatic dihydroxy compounds in combination and a branched polycarbonate resin obtained by using a small amount of trivalent phenol compounds can also be mentioned as a preferable example (Japanese Patent Laid-Open No. 63- No. 30524,
56-55328, JP-B-55-414, 60
-25049, Japanese Patent Publication No. 3-49930). The aromatic polycarbonate resin may be used as a mixture of two or more kinds.

The preferred molecular weight of the polycarbonate resin is GP because of the balance of heat resistance, mechanical strength, moldability and the like.
The weight average molecular weight (Mw) in terms of polystyrene measured by C is in the range of 10,000 to 150,000, more preferably in the range of 15,000 to 100,000, and most preferably in the range of 35,000 to 80,000. preferable.

(B) Modified Olefin Elastomer The modified olefin elastomer (B) is an olefin elastomer 1 having a flexural modulus of 500 kg / cm ² or less.
A modified olefin elastomer having a hydroxyl group obtained by graft-polymerizing 0.01 to 20 parts by weight of an α, β-unsaturated carboxylic acid ester having a hydroxyl group and 0 to 50 parts by weight of another vinyl monomer to 00 parts by weight. Is.

Examples of the α, β-unsaturated carboxylic acid ester-based monomer having a hydroxyl group for modifying the olefin-based elastomer include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxymethyl-3-hydroxypropyl methacrylate, 2-hydroxymethyl-3-hydroxypropyl acrylate, 2,2-dihydroxymethyl −
3-hydroxypropyl methacrylate, 2,2-dihydroxymethyl-3-hydroxypropyl acrylate, methacrylic acid ester or acrylic acid ester of an oligomer of ethylene glycol or propylene glycol having 4 to 40 carbon atoms, bis (2-hydroxyethyl) malate, Bis (2-hydroxyethyl) fumarate, bis (2-hydroxypropyl) fumarate, bis (2-hydroxypropyl) fumarate, bis (2,3)
-Dihydroxypropyl) malate, bis (2,3-dihydroxypropyl) fumarate, bis (2-hydroxymethyl-3-hydroxypropyl) malate, bis (2-hydroxymethyl-3-hydroxypropyl) fumarate, bis (2,2) -Dihydroxymethyl-3-hydroxypropyl) maleate, bis (2,2-dihydroxymethyl-3-hydroxypropyl) fumarate, maleic acid or fumaric acid ester of an oligomer of ethylene glycol or propylene glycol having 4 to 40 carbon atoms, and the like. To be The maleic acid or fumaric acid ester is not limited to those in which two carboxyl groups are esterified with two co-hydroxyalkyl groups as described above, and those in which only one is esterified are similar monomers. Can be illustrated as

The above α, β-unsaturated carboxylic acid ester monomers having a hydroxyl group can be used alone or in combination of two or more kinds. Among these, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, methacrylic acid or acrylic acid ester of an oligomer of ethylene glycol or propylene glycol having 4 to 40 carbon atoms, and the like. preferable.

In order to enhance the grafting efficiency of the α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group onto the olefin elastomer, it is useful to use another vinyl monomer in combination. Such other monomers include styrene, α-methylstyrene, α-methoxystyrene,
Methylstyrene, dimethylstyrene, 2,4,6-trimethylstyrene, chlorostyrene, dichlorostyrene,
Aromatic vinyl monomers such as bromostyrene, nitrostyrene, chloromethylstyrene, cyanostyrene, t-butylstyrene, vinylnaphthalene; ethyl (meth) acrylate, methyl (meth) acrylate, propyl (meth) acrylate , (Meth) octyl acrylate etc. (meth)
Acrylic ester type monomers; (meth) acrylamide type monomers such as N-methyl (meth) acrylamide, N-methylol (meth) acrylamide; cyanovinyl type monomers such as acrylonitrile and methacrylonitrile; vinyl butyrate etc. And vinyl ether-based monomers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether; and heterocyclic ring-containing vinyl compounds such as vinyl imidazole, vinyl oxazoline, vinyl pyridine, and vinylpyrrolidone.
Two or more of these may be used in combination.

Of these, if styrene-based monomers such as styrene, α-methylstyrene and methylstyrene are used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the olefin elastomer, the components (A) and (B) will be used. The compatibility with the components is further improved. The olefin elastomer used in the present invention has a flexural modulus at 23 ° C. according to JIS K-7203 of 500 kg / cm ² or less, preferably 10 to
It is a rubber-like polymer having a glass transition temperature of −10 ° C. or lower at 400 kg / cm ² .

Specific examples of these rubbery polymers include:
Homopolymers of olefins such as polybutadiene, polyisoprene, and polyisobutylene, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene-butene 1 copolymers, ethylene-butadiene copolymers, ethylene-isoprene Copolymers, ethylene-chloroprene copolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl acrylate copolymers such as copolymers of ethylene and organic acid esters, etc. Examples thereof include copolymers with different olefins or diolefins.

These copolymers are random copolymers,
Any of a block copolymer, a graft copolymer and an alternating copolymer may be used. These olefin elastomers may be used alone or in combination of two or more. Among these, ethylene-propylene copolymer rubber (EPR), ethylene-propylene-diene copolymer rubber (EPDM), and ethylene-butene-1 copolymer rubber are preferable.

The method for modifying the olefin-based elastomer with the above-mentioned α, β-unsaturated carboxylic acid ester-based monomer having a hydroxyl group and another copolymerizable monomer is not particularly limited. And α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group are allowed to coexist with another copolymerizable monomer, and reacted in the presence or absence of a radical generator such as an organic peroxide. There are a method of irradiating, a method of irradiating ultraviolet rays and radiation, a method of contacting with oxygen and ozone, and the like.

As the radical generator, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-
Dimethylhexane-2,5-dihydroperoxide, benzoyl peroxide, dicumyl peroxide, 1,3
-Organic and inorganic peroxides such as bis (t-butylperoxy-isopropyl) benzene, t-butylperoxybenzoate, dibutyl peroxide, methyl ethyl ketone peroxide, potassium peroxide, hydrogen peroxide, 2,
2'-azobisisobutyronitrile, 2-2'-azobis (isobutyramide) dihalide, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], azodi-t-butane An azo compound such as, a carbon radical generator such as dicumyl, and the like can be used. These radical generators can be appropriately selected in relation to the modifier and the reaction form. Further, two or more kinds can be used in combination.

The amount of the radical generator used is 0 to 30 parts by weight, preferably 0 to 10 parts by weight, based on 100 parts by weight of the olefin elastomer. The temperature during the graft copolymerization is usually 30 to 350 ° C., preferably 5
The range of 0 to 300 ° C. and the modification reaction time are 50 hours or less, preferably 0.5 minutes to 24 hours. The graft reaction may be carried out in any of a solution state, a molten state and a suspension state. Furthermore, during melt modification by an extruder or the like,
For the purpose of improving reaction efficiency, unreacted components and the like can be removed by adding an organic solvent such as xylene or kneading under reduced pressure.

The content of the α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group introduced into the olefin elastomer is 0.01 to 20 parts by weight, preferably 0.1% by weight based on 100 parts by weight of the olefin elastomer. 05-10
The range is parts by weight. If the content of the α, β-unsaturated carboxylic acid ester-based monomer having a hydroxyl group is less than 0.01 part by weight, the effect of improving the compatibility is small, and if it exceeds 20 parts by weight, there is a problem in molding processability due to gelation or the like. It may occur or the appearance of the molded product may be deteriorated, which is not preferable.

The content of the other vinyl monomer introduced into the olefin-based elastomer depends on the olefin-based elastomer 10
0.1 to 50 parts by weight, preferably 0.
2 to 10 parts by weight. If the amount of the other vinyl monomer is less than 0.1 part by weight, the effect of improving the compatibility is not sufficient, and if it exceeds 50 parts by weight, the appearance of the molded product may be deteriorated or the mechanical strength may be lowered. , Not preferable. And the preferable mixing ratio of the α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group and the styrene monomer is 1/5 to 5 /
It is 1. The above-mentioned modified olefin elastomer is J
The melt flow rate (MFR; 230 ° C., 2.16 kg load) measured according to IS K-7210 was 0.
001 to 100 g / 10 minutes is preferable, and 0.01 to 50 g / 10 minutes is more preferable.

Composition Ratio of Constituent Components The polycarbonate resin of the component (A) in the present invention is
50 to 98% by weight, preferably 65 to 95, in the resin composition
Used in a weight percentage. If it is less than 50% by weight, the heat resistance and bending rigidity of the molded product are not sufficient. If it exceeds 98% by weight, improvement in low temperature impact strength and heat aging resistance is insufficient.
The modified olefin elastomer as the component (B) is used in the resin composition in an amount of 50 to 2% by weight, preferably 35 to 5% by weight. If it exceeds 50% by weight, the flexural modulus decreases significantly, and if it is less than 2% by weight, the retention stability of the resin composition is poor and the resulting molded article has low low-temperature impact strength.

Additional Components The polycarbonate resin composition of the present invention may contain components other than the above components (A) and (B). For example, a part (up to 90% by weight) of the modified olefin elastomer of the component (B) may be replaced with an unmodified olefin elastomer. Furthermore, crystalline polyolefin such as polypropylene and polyethylene, acrylic rubber,
Acrylic-styrene core shell rubber, ABS, AES,
The resin composition may contain 1 to 48% by weight of polyphenylene ether, hydroxyalkylated polyphenylene ether, polyamide, polybutylene terephthalate, polyethylene terephthalate and the like.

Further, organic / inorganic fillers, reinforcing agents, particularly glass fibers, carbon fibers, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica and the like are added to the resin composition in an amount of 5 to 40% by weight. This is effective in improving rigidity, heat resistance, dimensional accuracy, dimensional stability, and the like. For practical use, various coloring agents and their dispersants are also 1 to
It can be used in a proportion of 10% by weight.

In addition, non-resinous additives may optionally be included to improve chemical and physical properties. For example, hindered phenol-based antioxidants, phosphorus-based antioxidants such as phosphite, amine-based antioxidants, benzotriazole-based UV absorbers, benzophenone-based UV absorbers, aliphatic carboxylic ester-based lubricants, paraffin Examples include lubricants, flame retardants, release agents, antistatic agents, colorants and the like.

Specific examples of the above hindered phenolic antioxidants include 2,6-ditertiary butyl-p-cresol, Irganox 1076 (trade name of Ciba Geigy), Sumilizer GM (trade name of Sumitomo Chemical Co., Ltd.). ) Etc. Further, as the phosphorus-based antioxidant, Sumilizer TNP (trade name of Sumitomo Chemical Co., Ltd.), Mark PEP36
(Trade name of ADEKA ARGUS), IRGAFOSS 168 (trade name of Ciba-Geigy), and the like.

Method for Preparing Composition and Molding Method The method for obtaining the polycarbonate resin composition of the present invention is not particularly limited, but may be a melting method, a solution method, a suspension method or the like.
Practically, the method of melt kneading is preferable. As a melt-kneading method, a kneading method generally used for polycarbonate resins can be applied. For example, the powdery or granular components are uniformly mixed together with the additives described in the section of additional components, if necessary, using a Hengel mixer, ribbon blender, V-type blender, etc., and then uniaxial or multiaxial. It can be kneaded with a kneading extruder, roll, Banbury mixer, or the like.

The melting and kneading temperature of each component is 100
In the range of ℃ to 400 ℃, preferably 120 ℃ to 300
It is in the range of ° C. Further, the kneading order and method of the respective components are not particularly limited, and for example, a method of kneading the modified olefin elastomer, the polycarbonate resin and the additional component at once, a part or the whole amount of the modified olefin elastomer and the polycarbonate resin. After kneading, the remaining components are kneaded, and an olefin elastomer and an α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group, another copolymerizable monomer and a radical initiator are kneaded. To obtain a modified olefin elastomer, and then kneading the remaining components, an olefin elastomer, an α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group, another copolymerizable monomer, and radical initiation. Agent, polycarbonate resin, additional components, and the like at once, or under reduced pressure. It may be.
Further, during the melt-kneading, an organic solvent such as chlorobenzene, trichlorobenzene, xylene or the like, or a catalyst such as tetrakis (2-ethylhexoxy) titanium or dibutyltin oxide can be added. The method of molding the polycarbonate resin composition of the present invention is not particularly limited, and molding methods generally used for polycarbonate resins, that is, various molding methods such as injection molding, hollow molding, extrusion molding, thermoforming, and press molding. The law is applicable.

[0032]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the following, parts and percentages are based on weight. In addition, it is an α, β-unsaturated carboxylic acid ester graft-polymerized on the modified olefin elastomer.
The content of -hydroxyethyl methacrylate and styrene was determined by the following method. 0.3 g of modified olefin elastomer obtained by melt modification was added to 30 m of xylene.
After heating and dissolving in 1 ml, the product was reprecipitated and purified in 250 ml of methanol. Then, the purified modified olefin elastomer is molded into a film by using a press, and an IR spectrum is measured by infrared spectroscopy (hereinafter referred to as “IR method”) to obtain an absorption and aromatic ring at 1724 cm ⁻¹ derived from carbonyl. It was quantified from the calibration curve prepared in advance from the absorption at 700 cm ⁻¹ derived from

Reference Example 1: 2-hydroxyethylmethacrylate
Rate-styrene graft modified ethylene-propylene
Production of polymer (modified EPR-1) Ethylene-propylene copolymer elastomer manufactured by Nippon Synthetic Rubber Co., Ltd. (trade name EPO1; MFR at 230 ° C. is 3.
5 g / 10 min, flexural modulus 200 kg / cm ² ) 40
g, 2-hydroxyethyl methacrylate 2 g, styrene 2 g and bis (t-butylperoxyisopropyl)
After mixing 0.06 g of benzene, a twin-screw kneader (trade name: Labo Plastomill) manufactured by Toyo Seiki Seisakusho Co., Ltd. was used to melt-knead for 3 minutes at a temperature of 180 ° C. and a screw rotation speed of 180 rpm, and this kneaded product Was crushed to obtain pellets.

The content of the constitutional unit based on 2-hydroxyethyl methacrylate obtained by the IR method in the obtained modified olefin elastomer (modified EPR-1) pellets was 0.97% by weight, and the constitutional unit content of styrene was 0. 6
It was 7% by weight. In addition, the MFR at 230 ° C. of the pellet measured according to JIS K-7210 is 0.08.
It was g / 10 minutes.

Reference Example 2: 2-hydroxyethylmethacrylate
Rate-styrene graft modified ethylene-propylene
Production of polymer (modified EPR-2) Ethylene-propylene copolymer elastomer manufactured by Nippon Synthetic Rubber Co., Ltd. (trade name EPO1; MFR at 230 ° C. is 3.
5 g / 10 min, flexural modulus 200 kg / cm ² ) 40
g, 4-hydroxyethyl methacrylate 4 g, styrene 4 g and bis (t-butylperoxyisopropyl)
After mixing 0.08 g of benzene, a twin-screw kneader (trade name: Labo Plastomill) manufactured by Toyo Seiki Seisakusho Co., Ltd. was used, and the temperature was 180 ° C. and the screw rotation speed was 30 rpm.
Melt and knead for 1 minute, screw rotation speed 180 rpm
The mixture was melted and kneaded for 1.5 minutes, and the kneaded product was crushed to obtain pellets.

The content of the constitutional unit based on 2-hydroxyethyl methacrylate obtained by the IR method in the pellet of the obtained modified olefin elastomer (modified EPR-2) was 1.54% by weight, and the constitutional unit content of styrene was 1. Four
It was 3% by weight. Further, the MFR at 230 ° C. of the pellet measured according to JIS K-7210 is 0.04.
It was g / 10 minutes.

Reference Example 3: 2-hydroxypropylmethac
Relate-styrene graft modified ethylene-propylene
Production of Copolymer (Modified EPR-3) In Reference Example 1, 2-hydroxypropyl methacrylate was used instead of 2-hydroxyethyl methacrylate, and the amount of bis (t-butylperoxyisopropyl) benzene used was 0.04 g. A modified olefin elastomer (modified EPR-3) was produced in the same manner except that the above was changed to. The content of the constituent unit based on 2-hydroxypropyl methacrylate in the modified elastomer is 0.50% by weight,
Constituent unit content based on styrene is 0.47% by weight, MF
R was 1.06 g / 10 minutes.

Reference Example 4: 2-hydroxyethylmethacrylate
Rate-graft modified ethylene-propylene copolymer (modified
Production of Modified EPR-4) A modified elastomer (modified EPR-4) was produced in the same manner as in Reference Example 1 except that styrene was not used. The content of the constituent unit based on 2-hydroxyethyl methacrylate in the modified elastomer is 0.53% by weight, and the MFR is 1.02 g.
/ 10 minutes.

Reference Example 5: 2-hydroxypropyl acryl
Rate-styrene graft modified ethylene-propylene
Preparation of Polymer (Modified EPR-5) In Reference Example 1, modified elastomer (modified EPR-5) is used in the same manner as in Example 2 except that 2-hydroxypropyl acrylate is used instead of 2-hydroxyethyl methacrylate.
Was manufactured. The content of the constitutional unit based on 2-hydroxypropyl acrylate in the modified elastomer is 0.60% by weight, the content of the constitutional unit based on styrene is 0.41% by weight,
The MFR was 0.62 g / 10 minutes.

Reference Example 6 (for comparison): 2-hydroxyethyl
-Methacrylate-styrene graft modified propylene-
Production of ethylene copolymer (modified crystalline PP) Mitsubishi Yuka Co., Ltd. crystalline propylene-ethylene copolymer "Mitsubishi Polypro BC8" (trade name, ethylene content about 9% by weight, density 0.90 g / cm ³ , bending elastic modulus is 1
0,600 kg / cm ² , MFR 1.8 g / 10 minutes)
2,000 g, 2-hydroxyethyl methacrylate 1
After mixing 00 g, styrene 100 g, and bis (t-butylperoxyisopropyl) benzene 20 g with a super mixer, a cylinder temperature of 180 was obtained using a twin-screw extruder (manufactured by Japan Steel Works, trade name: TEX-30 type).
The pellets were obtained by kneading at a temperature of 250 ° C., a screw rotation speed of 250 rpm, and a discharge rate of 5 kg / hour. The content of structural units based on 2-hydroxyethyl methacrylate in the obtained modified crystalline polypropylene (modified crystalline PP) was 1.0.
5% by weight, the structural unit content based on styrene was 1.19% by weight, and the MFR of the pellet was 11.7 g / 10 minutes.

Reference Example 7 (for comparison): Glycidyl metaac
Relate graft modified ethylene-propylene copolymer
Production of (GMA-EPR) A modified elastomer (GMA-EPR) was produced in the same manner as in Reference Example 4 except that glycidyl methacrylate was used instead of 2-hydroxyethyl methacrylate. The content of the structural unit in the modified elastomer based on glycidyl methacrylate determined by the IR method is 0.
58% by weight, MFR was 0.87 g / 10 minutes.

Aromatic polycarbonate resin Polycarbonate resin manufactured by Mitsubishi Gas Chemical Co., Inc. (trade name: Iupilon S2000; abbreviated as "PC" in the table) was used. Maleic anhydride modified ethylene-propylene copolymer gills
Stormer Mitsubishi Yuka Co., Ltd. maleic acid modified EPR (trade name: modic, maleic anhydride content 1.2 wt%, MFR 1.0 g / 10 min at 190 ° C., abbreviated as “MAH-EPR” in the table) Using.

Unmodified ethylene-propylene copolymer
Lastomer Japan Synthetic Rubber Co., Ltd. ethylene-propylene copolymer elastomer (trade name: EPO1, 230 ° C. MFR3.
5 g / 10 minutes, abbreviated as "EPR" in the table) was used. Propylene homopolymer Crystallized propylene homopolymer manufactured by Mitsubishi Yuka Co., Ltd. [trade name: Mitsubishi Polypro MA8 (MFR 0.8 g / 10
Minute, density 0.90 g / cm ³ , abbreviated as "PP" in the table. )]

Propylene-ethylene block copolymer Propylene-ethylene copolymer manufactured by Mitsubishi Petrochemical Co., Ltd. [trade name: Mitsubishi Polypro BC8D (MFR: 1.2 g / 10
Min, density 0.90 g / cm ³ , abbreviated as “EPP” in the table. )] High-density polyethylene Polyethylene manufactured by Mitsubishi Petrochemical Co., Ltd. [Product name: Mitsubishi Polyethylene HY540; MFR is 1.1 g / 10 min (190 ° C
2.16 kg load), density 0.960 g / cm ³ , abbreviated as "HDPE" in the table. ] Was used.

Example 1 2-hydroxyethyl methacrylate obtained in Reference Example 1
20 parts by weight of styrene-grafted ethylene-propylene copolymer (modified EPR-1) and polycarbonate resin 80
Using a biaxial kneader (Labo Plastomill manufactured by Toyo Seiki Seisakusho Co., Ltd.), the parts by weight were kneaded at a temperature of 250 ° C. and a screw rotation speed of 180 rpm for 5 minutes, and then pulverized to obtain granular pellets.

The characteristics of the obtained pellets are measured by using an injection molding machine [Custom Scientific (Custom Science).
manufactured by CS), CS183MMX minimax]
A test piece injection-molded at a temperature of 300 ° C. was measured and evaluated by the following method. The measurement results are shown in Table 1. During the kneading and molding, the polycarbonate resin and the resin composition were dried at 100 ° C. for 5 hours immediately before that.

(1) Impact resistance strength: A test piece having a length of 31.5 mm, a width of 6.2 mm and a thickness of 3.2 mm was injection-molded, and the Izod impact tester [made by Custom Scientific, Minimax CS was used. -138TI type],
The notched Izod impact strength (notch tip R = 0.25 mm, depth = 1.2 mm) at 30 ° C. was measured. (2) Weld strength: Using an injection mold having runners that allow resin to flow in from both sides, the center part has a contact weld and the parallel part length is 7 mm and the parallel part diameter is 1.5 mm.
Test piece for tensile strength measurement of the welded part of the test piece was injection molded, and the tensile tester [Custom Scientific Co., CS
-183TE] was used to perform a tensile test under the condition of a tensile speed of 1 cm / min to measure the stress at break.

(3) Appearance of molded products: The test pieces molded in (1) above were evaluated for delamination and appearance. Those having no practical problems are indicated by ◯, those requiring improvement are indicated by Δ, and extremely defective ones are indicated by ×. (4) Thermal aging resistance (impact strength after heat treatment): (1) above
The test piece molded in 1. was heat treated in a heating oven set at a temperature of 120 ° C. for 29 hours, and the notched Izod impact strength at 23 ° C. was measured by the same method as in (1) above. (5) Elastic modulus: A test piece having a length of 51 mm, a width of 5 mm, and a thickness of 2 mm was injection-molded, and a solid viscoelasticity measuring device (RSAII, manufactured by Rheometrics Far East Co., Ltd.) was used at a frequency of 1 Hz at 23 ° C. The value of storage elastic modulus (E ') was determined.

Examples 2 to 12 and Comparative Examples 1 to 8 Evaluations were made in the same manner as in Example 1 except that the compounding ratio of the resin composition used in the pellets was changed as shown in Table 1 or Table 2. The results are shown in Table 1 or Table 2.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

EFFECT OF THE INVENTION The polycarbonate resin composition of the present invention gives a molded article excellent in impact strength, weld strength, appearance, heat aging resistance and the like.

Claims (2)

[Claims] 1. (A) Polycarbonate resin 50 to 98
%, And (B) a polycarbonate resin composition containing the modified olefin elastomer obtained by the following production method in a proportion of 50 to 2% by weight. Production of component (B): flexural modulus at 23 ° C. (JIS
K7203) has α, β having a hydroxyl group in 100 parts by weight of an olefin elastomer having a weight of 500 kg / cm ² or less.
-A modified olefin elastomer obtained by graft-polymerizing 0.01 to 20 parts by weight of an unsaturated carboxylic acid ester and 0 to 50 parts by weight of another vinyl monomer. 2. The other vinyl monomer is styrene, and is 0.1 to 100 parts by weight of the olefin elastomer.
The polycarbonate resin composition according to claim 1, which is used in a ratio of 20 parts by weight.