JPH07330972A - Olefin resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition which can give a molding excellent in impact strength, etc., by mixing a crystalline olefin resin having a specified bending modulus with a specified amount of a polycarbonate resin and a specified modified olefin elastomer. CONSTITUTION:An alpha, beta-unsaturated hydroxy carboxylic acid ester (e.g. 2- hydroxyethyl methacrylate in an amount of 0.01-20 pts.wt. another vinyl monomer (e.g. styrene) are grafted onto 100 pts.wt. olefin elastomer (e.g. ethylene/ propylene copolymer rubber) having a bending modulus (JISK7203) of 500kg/cm<2> or below at 23 deg.C to produce a modified olefin elastomer. 2-40 pts.wt. this elastomer is mixed with 100 pts.wt. mixture of 48-90wt.% crystalline olefin resin (e.g. polypropylene) having a bending modulus of 5000-40000kg/cm<2> at 23 deg.C and 52-10wt.% polycarbonate resin to produce the objective olefin resin composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin resin composition having excellent moldability, which gives a molded article excellent in impact resistance, heat resistance and solvent resistance. This molded product is used in a wide variety of fields such as packaging films, automobile parts, electric and electronic device parts such as switches, housings and hollow containers.

[0002]

2. Description of the Related Art Crystalline olefin resins represented by propylene resin and ethylene resin are excellent in molding processability, water absorption resistance, organic solvent resistance, etc., and have a low specific gravity and are inexpensive. However, its heat resistance is not so high, which hinders its use in engineering plastics. On the other hand, polycarbonate has excellent properties such as heat resistance, impact resistance, and dimensional stability, and is used in various applications as a molding material, but has poor melt flowability and is difficult to mold, and,
It has the drawback of poor water absorption resistance and organic solvent resistance. When a single resin material cannot sufficiently satisfy desired properties, a method of complementing insufficient properties by mixing another resin material is often used. As a result, if a resin composition having good properties of both polycarbonate and olefin resin and complementing the defects can be obtained, the field of application can be expanded.

However, since the polycarbonate having a polar group and the hydrophobic olefin resin are originally incompatible and have no affinity, when these two components are simply mixed, the two-phase structure The adhesion at the interface is not good. Therefore, the phase interface of the obtained molded product becomes a defect portion, and the mechanical strength such as impact resistance decreases. Further, the two phases are unlikely to be in a uniform and finely dispersed form, and when shear stress is applied during molding such as injection molding, delamination is likely to occur, and a molded product having a poor appearance is likely to be formed.

In order to solve the above problems, it has been proposed to blend a modified olefin resin having a functional group which reacts with the polycarbonate with a poorly reactive olefin resin into the polycarbonate. For example, JP-A-59-223742 discloses a resin composition in which 1 to 100 parts by weight of aromatic polycarbonate is mixed with 100 parts by weight of maleic anhydride-modified polypropylene. However, a molded article obtained from this resin composition has insufficient dispersibility and is easily delaminated, and its appearance and impact resistance are not practically satisfactory.

Further, a resin composition having improved surface peeling resistance (5 to 100 parts by weight of a polycarbonate resin mixed with 100 parts by weight of polyethylene or polypropylene modified with a hydroxyl group-containing (meth) acrylate such as hydroxy (meth) acrylate) ( JP-A-3-39344) or 5 to 95% by weight of a polycarbonate, 1 to 50 parts by weight of a styrene-based monomer in 100 parts by weight of a crystalline propylene-based resin, and a vinyl group containing a hydroxyl group such as 2-hydroxyethyl methacrylate. A resin composition (Japanese Patent Laid-Open No. 5-295221) containing 95 to 5% by weight of a modified propylene-based resin obtained by reacting 0.1 to 10 parts by weight of a monomer has been proposed.
However, the impact resistance of these resin compositions is still insufficient and further improvement is required.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides an olefin resin composition which is excellent in fluidity during molding, retention stability in a cylinder of an injection molding machine, impact strength, and a molded article having excellent appearance. With the goal

[0007]

The present invention provides (A) 23 ° C.
Flexural modulus at 5,000-40,000 kg /
cm ² of crystalline olefin resin 48 to 90% by weight and (B) polycarbonate resin 52 to 10% by weight 1
The present invention provides an olefin resin composition comprising (C) a modified olefin elastomer obtained by the following production method in an amount of 2 to 40 parts by weight based on 100 parts by weight. Production of component (C): 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.

[0008]

When the resin composition is melted and kneaded, the hydroxyl group of the modified olefin elastomer of the component (C) and the carbonate bond of the polycarbonate resin of the component (B), which have an affinity for the crystalline olefin resin, are formed. The reaction produces a graft copolymer of an olefin elastomer and a polycarbonate resin, which serves as a compatibilizer (B).
It is presumed that the components form a fine and stable dispersion structure, and the component (C) acts as an interfacial reinforcing agent to improve the impact strength of the molded product, the appearance, the moldability of the composition, and the like.

(Detailed Description of the Invention) (A) Crystalline Olefin Resin The crystalline olefin resin is at least one type of α-olefin having 2 to 10 carbon atoms, or two or more types of polymers or copolymers. And the crystallinity at room temperature by X-ray diffraction is preferably 15% or more, more preferably 30 to 70%.
And has a melting point of 85 to 230 ° C., and JIS K 7
Bending elastic modulus according to 203 (measured at 23 ° C.) is 5,000 to
It is of 40,000 kg / cm ² . The decrease in crystallinity decreases the elastic modulus of the final composition. Further, this olefin resin needs to have a sufficient molecular weight as a molding resin at room temperature. For example, when propylene is the main component, the melt flow rate measured according to JIS K 6758 has a molecular weight corresponding to 0.01 to 500 g / 10 minutes, preferably 0.05 to 100 g / 10 minutes.

Examples of the above-mentioned α-olefin which is a constituent of the crystalline olefin resin include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1 and 4-methylpentene-1. , 3,3-dimethylpentene-1,3-methylhexene-1,4-methylhexene-1,4,4-dimethylhexene-1,5
-Methylhexene-1, allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexylbutene-1, vinylcyclopropane, vinylcyclohexane, 2-vinyl-bicyclo [2,2,1] heptane,
Heptene-1 or octene-1.

Among the above, preferred examples of α-olefin are ethylene, propylene, butene-1, pentene-1, hexene-1,3-methylbutene-1,4-methylpentene-1,3-methylhexene-1. Can be mentioned. Especially ethylene, propylene, butene-1,3
-Methylbutene-1 and 4-methylpentene-1 are preferred. In addition, as other components, 4-methyl-1,4-
Hexadiene, 5-methyl-1,4-hexadiene, 7
Non-conjugated dienes such as -methyl-1,6-toctadiene and 1,9-decadiene may be used as part of the polymerization component.

Specific examples of the crystalline olefin resin include propylene homopolymer, propylene / ethylene copolymer, propylene / ethylene / butene-1 copolymer, propylene / butene-1 copolymer and propylene / 4-. Methylpentene-1 copolymer, poly (4-methylpentene-
1), a propylene / 3-methylpentene-1 copolymer,
Examples include high-density polyethylene, linear medium-density polyethylene, linear low-density polyethylene, and propylene / 1,9-decadiene copolymer.

(B) Polycarbonate Resin Polycarbonate resin is produced by reacting an aromatic hydroxy compound or a small amount of 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.

Further, in order 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.

(C) Modified olefin elastomer The modified olefin elastomer has a flexural modulus of 500.
0.01 to 20 parts by weight of α, β-unsaturated carboxylic acid ester having a hydroxyl group and 0 to 5 other vinyl monomers per 100 parts by weight of olefin elastomer having a weight of not more than kg / cm ^2.
It is a modified olefin elastomer having a hydroxyl group obtained by graft polymerization of 0 part by weight.

Examples of the α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group for modifying the olefin elastomer include, for example, 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 or acrylic acid ester of 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 increase 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.

Examples of such other monomers include styrene and α
-Methylstyrene, α-methoxystyrene, methylstyrene, dimethylstyrene, 2,4,6-trimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, nitrostyrene, chloromethylstyrene, cyanomethylene, t-butylstyrene, vinylnaphthalene Aromatic vinyl monomers such as ethyl (meth) acrylate,
(Meth) acrylic acid ester monomers such as methyl (meth) acrylate, propyl (meth) acrylate, octyl (meth) acrylate; N-methyl (meth) acrylamide, N-methylol (meth) acrylamide (Meth) acrylamide monomers such as; cyanovinyl monomers such as acrylonitrile and methacrylonitrile; vinyl ester monomers such as vinyl butyrate; methyl vinyl ether,
Examples thereof include vinyl ether monomers such as ethyl vinyl ether and butyl vinyl ether; and heterocycle-containing vinyl compounds such as vinyl imidazole, vinyl oxazoline, vinyl pyridine and vinyl pyrrolidone. Two or more of these may be used in combination.

Of these, if a styrene-based monomer such as styrene, α-methylstyrene or methylstyrene is 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 of 500 kg / cm ² or less, preferably 10 to 4 according to JIS K-7203 at room temperature.
It is a rubber-like polymer having a glass transition temperature of −10 ° C. or lower at 00 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), ethylene-butene-1 copolymer rubber and the like are preferable.

The method for modifying the olefin elastomer with the above-mentioned α, β-unsaturated carboxylic acid ester 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 the reaction efficiency, unreacted components and the like can be removed by adding an organic solvent such as xylene or the like, a chain transfer agent such as n-butyl mercaptan or carbon tetrachloride, or by 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.
It is 1 to 10 parts by weight. If the amount of the other vinyl monomer is less than 0.1 part by weight, there is no effect of improving the compatibility, and if it exceeds 50 parts by weight, the appearance of the molded article may be deteriorated or the mechanical strength may be decreased, which is preferable. Absent. 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 5/1. The above-mentioned modified olefin elastomer is JIS
The melt flow rate (MFR; 230 ° C., 2.16 kg load) measured according to K-7210 is 0.00
1 to 100 g / 10 minutes is preferable, and more preferably,
It is 0.01 to 50 g / 10 minutes.

Composition Ratio of Constituents The composition ratio of the crystalline olefin resin as the component (A) and the polycarbonate resin as the component (B) in the present invention is 90 to 48% by weight of the component (A) in the sum of the two. Preferably 80 to 48% by weight, more preferably 70 to 50% by weight
And component (B) is 10 to 52% by weight, preferably 20 to
52% by weight, more preferably 30 to 50% by weight.
If the content of the crystalline olefin resin is less than 48% by weight or the content of the polycarbonate resin exceeds 52% by weight, a molded article excellent in solvent resistance cannot be obtained, and conversely, the content of the crystalline olefin resin is 90%. When the content is more than 10% by weight or the content of the polycarbonate resin is less than 10% by weight, the heat resistance and bending rigidity of the obtained molded product are low.

The compounded amount of the modified olefinic elastomer having a hydroxyl group of the component (C) in the present invention is 2 with respect to 100 parts by weight of the total amount of the component (A) and the component (B).
-40 parts by weight, preferably 5-30 parts by weight, and more preferably 5-20 parts by weight. If the compounding amount of the component (C) is less than 2 parts by weight, the effect of improving the impact strength is small, and if it exceeds 40 parts by weight, the heat resistance and rigidity of the molded product are unfavorably increased.

Additional Components The thermoplastic resin composition of the present invention comprises the above component (A),
Components other than the components (B) and (C) can be contained. For example, a part (up to 90% by weight) of the modified olefin elastomer of the component (C) may be replaced with an unmodified olefin elastomer. Further, a part (up to 90% by weight) of the crystalline olefin resin as the component (A) is used as an α, β-unsaturated carboxylic acid ester having a hydroxyl group such as 2-hydroxyethyl methacrylate and a vinyl monomer such as styrene. It may be replaced by a graft-polymerized hydroxyl group-containing modified olefin resin.

Further, an organic / inorganic filler and a reinforcing agent, especially glass fiber, carbon fiber, 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-mentioned 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. In addition, as a phosphorus-based antioxidant, Sumilyzer-
TNP (Sumitomo Chemical Co., Ltd. trade name), Mark PEP36
(Trade name of ADEKA ARGUS), IRGAFOSS 168 (trade name of Ciba-Geigy), and the like.

Further, the resin composition may contain an impact modifier other than the modified olefin elastomer (C) used in the present invention in an amount of 5 to 30% by weight. As such impact modifier, styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber or hydrogenated products thereof, acrylic rubber, acrylic-styrene core shell rubber, ABS, AES and the like can be used. Further, the resin composition may contain polyphenylene ether, hydroxyalkylated polyphenylene ether, polyamide, polystyrene terephthalate, polyethylene / terephthalate and the like.

Method for Preparing Composition and Molding Method The method for obtaining the thermoplastic resin composition of the present invention is not particularly limited, such as a melting method, a solution method and a suspension method, but in practice, a method of melt kneading is used. Is preferred. As the melt-kneading method, a kneading method generally used for thermoplastic resins can be applied. For example, the powdery or granular components are uniformly mixed with the additives described in the section of additional components, if necessary, by a Henschel mixer, ribbon blender, V-type blender, etc., and then uniaxial or multiaxial kneading. Extruder,
It can be kneaded with a roll, a Banbury mixer or the like.

The temperature of the melt-kneading 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 examples thereof include a method of kneading the crystalline olefin resin, the modified olefin elastomer, the polycarbonate resin and the additional component at once; A method of kneading an olefin elastomer and a polycarbonate resin and then kneading the remaining components; an olefin elastomer and an α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group, other copolymerizable monomers, and A method in which a modified olefin elastomer is kneaded with a radical initiator and then the remaining components are kneaded; an olefin elastomer and an α, β-unsaturated carboxylic acid ester monomer having a hydroxyl group, other copolymerizable other Monomer,
Any method such as a method of kneading the radical initiator, the polycarbonate resin, the crystalline olefin resin and the additional components in a batch, a method of kneading under reduced pressure, or the like may be used. Furthermore,
At the time of melt-kneading, an organic solvent such as chlorobenzene, trichlorobenzene or xylene, or a catalyst such as tetrakis (2-ethylhexoxy) titanium or dibutyltin oxide can be added. The molding method of the thermoplastic resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, injection molding, blow molding, extrusion molding, thermoforming, press molding, etc. Various molding methods can be applied.

[0039]

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 of 200 kg / cm ² ) is a twin-screw extruder (trade name: TEX-30) manufactured by Japan Steel Works, Ltd.
2-hydroxyethylmethacrylate 10 from a pre-stage vent provided in the middle of the extruder while kneading using a cylinder temperature of 180 ° C., a screw rotation speed of 300 rpm, a discharge rate of 70 g / min, and a reduced pressure of 750 mmHg.
A mixed solution of 0 parts by weight, 100 parts by weight of styrene, and 2 parts by weight of bis (t-butylperoxyisopropyl) benzene was added at a rate of 14 g / min using a transport pump, melt-kneaded, and formed into a strand from a die. It was extruded and cut into pellets. The constituent unit content of the obtained modified olefin elastomer (modified EPR-1) based on 2-hydroxyethyl methacrylate determined by the IR method was 0.42% by weight, and the constituent unit content based on styrene was 0.56% by weight. %Met. Also, JIS
MFR of pellets measured according to K7210 (2
(30 ° C.) was 1.82 g / 10 minutes.

Reference Example 2: 2-hydroxyethylmethacrylate
Rate-styrene graft modified ethylene-propylene
Preparation of polymer (modified EPR-2) In Reference Example 1, the addition amount of 2-hydroxyethyl methacrylate, styrene, and bis (t-butylperoxyisopropyl) benzene mixed solution was 28 g / min, and the screw rotation speed was 100 rpm. A modified elastomer (modified EPR-2) was produced in the same manner as in Reference Example 1 except that the modification was made. The content of structural units based on 2-hydroxyethyl methacrylate in the obtained modified elastomer was 1.20.
% By weight, the structural unit content based on styrene was 1.48% by weight, and the MFR of the pellet was 0.33 g / 10 minutes.

Reference Example 3: 2-hydroxyethylmethacrylate
Rate-graft modified ethylene-propylene copolymer (modified
Production of Modified EPR-3) A modified elastomer (modified EPR-3) was produced in the same manner as in Reference Example 1 except that styrene was not used and the screw rotation speed was changed to 100 rpm. The content of the constituent unit based on 2-hydroxyethyl methacrylate in the obtained modified elastomer was 0.81% by weight, and the MFR of the pellet was 1.17 g / 10 minutes.

[0043]Reference Example 4: 2-hydroxyethyl methacrylate
Rate-styrene graft modified propylene-ethylene
Production of polymer (modified PP-1) (for comparison) Crystalline propylene-ethylene copolymer manufactured by Mitsubishi Yuka Co., Ltd.
[Product name: Mitsubishi Polypro EC9 (density 0.90 g /
cm³, Flexural modulus is 12,000 kg / cm ², MF
R is 0.5 g / 10 minutes) 2,000 g, 2-hydroxy
100 g of ethyl methacrylate, 100 g of styrene and
Bis (t-butylperoxyisopropyl) benzene 2
After mixing 0 g with a super mixer, twin screw extruder
(Manufactured by Japan Steel Works, trade name: TEX-30 type)
Cylinder temperature 180 ℃, screw speed 250
Knead under the conditions of rpm and discharge rate of 5 kg / hour,
Extrude in a strand shape, cut it, and
Got Obtained modified polypropylene (modified PP-1)
Based on 2-hydroxyethylmethacrylate in
Unit content is 1.13% by weight, structural unit based on styrene
Content is 1.25% by weight, pellet MFR (230 ℃,
2.16 kg load) was 26.3 g / 10 minutes.

Reference Example 5: 2-hydroxyethyl methacrylate
Of rate graft modified polypropylene (modified PP-2)
Production (for comparison) Propylene homopolymer powder manufactured by Mitsubishi Petrochemical Co., Ltd. (230 ° C)
MFR: 1 g / 10 minutes, melting point: about 164 ° C., flexural modulus: 12,000 kg / cm ² ) 2,000 g, 2-hydroxyethyl methacrylate 100 g, and t-butyl peroxybenzoate 10 g were mixed with a super mixer. Melt kneading was carried out in the same manner as in Reference Example 4, extruded in a strand shape, and cut to produce pellets. 2- in the obtained modified polypropylene (modified PP-3)
The content of structural units based on hydroxyethyl methacrylate is 1.94% by weight, and the pellet MFR is 40.3 g / 1.
It was 0 minutes.

Aromatic Polycarbonate Resin A 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 elastomer Maleic acid modified EPR manufactured by Mitsubishi Oil Chemical Co., Ltd. (trade name: Modic, maleic anhydride content 1.2% by weight, MFR 1.0 g / 10 min at 190 ° C., “MAH-EPR” in the table) (Abbreviation) was used.

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 Propylene homopolymer manufactured by Mitsubishi Petrochemical Co., Ltd. [trade name: Mitsubishi Polypro MA6 (MFR 1.4 g / 10 min, density 0.90 g / cm ³ ; MA6 ").

Propylene-ethylene block copolymer Propylene-ethylene copolymer manufactured by Mitsubishi Petrochemical Co., Ltd. [trade name, Mitsubishi Polypro EC9; MFR 0.5 g / 10 min,
The density was 0.90 g / cm ³ , and in the table, abbreviated as “PP-EC9”] was used.

Example 1 2-hydroxyethyl methacrylate obtained in Reference Example 1
Styrene-grafted ethylene-propylene copolymer (modified EPR-1) 20 parts by weight, polycarbonate resin 50 parts by weight and propylene-ethylene copolymer (PP-EC9)
50 parts by weight were kneaded with a twin-screw kneader (Labo Plastomill manufactured by Toyo Seiki Seisaku-sho, Ltd.) 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]
The impact resistance of a test piece injection-molded at a temperature of 260 ° C. was measured and evaluated by the following method. The measurement results are shown in Table 1.

(1) Impact 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 [manufactured by Custom Scientific Co., 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. During the kneading and molding, the polycarbonate resin and the resin composition were dried at 100 ° C. for 5 hours immediately before that.

Examples 2 to 7 and Comparative Examples 1 to 8 Test pieces were obtained by injection molding in the same manner as in Example 1 except that the ratio of the resin composition was changed as shown in Table 1. Table 1 shows the impact strength of this test piece.

[0054]

[Table 1]

[0055]

As is clear from the examples and comparative examples,
The olefin resin composition of the present invention gives a molded article having excellent impact resistance.

Claims (2)

[Claims] 1. (A) The flexural modulus at 23 ° C. is 5,
000 to 40,000 kg / cm ² of crystalline olefin resin 48 to 90% by weight and (B) polycarbonate resin 52 to 10% by weight to 100 parts by weight, (C) modification obtained by the following production method 2-4 olefin elastomers
An olefin resin composition characterized by being blended in a proportion of 0 parts by weight. Production of component (C): 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 olefin resin composition according to claim 1, which is used in a ratio of 20 parts by weight.