JPH0433948A - Polycarbonate resin composition and impact-resistance improver for polycarbonate resin - Google Patents

Abstract

PURPOSE:To obtain a resin composition having especially improved thickness- dependent impact resistance without damaging excellent physical characteristics and mechanical properties, by blending a polycarbonate resin with an improver for impact resistance composed of a specific multi-phase structure thermoplastic resin. CONSTITUTION:A resin composition comprising (A) 100pts.wt. polycarbonate resin and (B) 1-100pts.wt. multi-phase structure thermoplastic resin which is composed of B1: 5-95wt.% copolymer consisting of a nonpolar alpha-olefin and a non-conjugated diene-based monomer or a polar vinyl-based monomer and B2: 95-5wt.% vinyl-based (co)polymer and having 0.001-10mum particle diameter of dispersed resin, such as a multi-phase structure thermoplastic resin obtained by impregnating an aqueous dispersion of the component B1 with a vinyl-based monomer, a radically (co)polymerizable organic peroxide and a radical polymerization initiator until the impregnation ratio reaches >=10wt.% and then heating to copolymerize the vinyl monomer with the peroxide.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to the excellent physical properties of polycarbonate resin,
It relates to a polycarbonate resin composition that maintains mechanical properties, has excellent impact resistance, and in particular has improved thickness dependence of impact resistance, and an impact resistance modifier for polycarbonate resin, and is suitable for electrical and electronic mechanical parts, precision parts, etc. It can be used in a wide range of fields such as mechanical parts and automobile parts.

[Conventional technology]

Polycarbonate resin has excellent mechanical properties such as toughness, flexibility, and impact strength, physical properties such as heat resistance and electrical properties, and dimensional accuracy of molded products, so it is used in automobile parts, electrical insulation materials,
Widely used for mechanical parts, various housings, etc.

However, the impact resistance of polycarbonate resin is highly dependent on the thickness; when the wall thickness is thin, the impact resistance is good, but when the wall thickness is thick, the impact resistance decreases significantly, so it is not suitable for thick molded products. The problem was that it could not be used.

Therefore, if it were possible to improve the thickness dependence of the impact resistance of polycarbonate resin, it would be possible to obtain thick-walled molded products with excellent physical properties, mechanical properties, dimensional accuracy, etc. of the polycarbonate resin. It becomes possible to develop applications in various fields.

In order to solve the thickness dependence of impact resistance of polycarbonate resin, JP-A-1-308449 discloses a method of blending a silane-modified polymer and a specific ethylene copolymer with a polycarbonate resin, and JP-A-1-308449 discloses a method of blending a silane-modified polymer and a specific ethylene copolymer with a polycarbonate resin. 3084
Publication No. 50 discloses a method of blending an epoxy-containing crosslinked copolymer with a polycarbonate resin, and each method has been shown to improve the thickness dependence of the polycarbonate resin.

[Problem to be solved by the invention]

However, although the thickness dependence of the impact resistance of polycarbonate resin is improved to some extent by the method of blending specific polymers as in JP-A-1-308449 and JP-A-1-308450, The poor compatibility between the polymer and polycarbonate resin not only impairs the excellent physical and mechanical properties of the polycarbonate resin, but also causes delamination of the obtained molded product and adhesion to the mold. There was a problem that it could cause

The present invention is characterized by the excellent physical properties of polycarbonate resin,
Maintains mechanical properties and has no delamination or adhesion phenomena.
In particular, it is an object of the present invention to provide a polycarbonate resin composition with improved thickness dependence of impact resistance and an impact resistance improver for polycarbonate resin.

[Means for solving problems]

Therefore, as a result of intensive research to solve these conventional problems, the present inventor found that a resin composition obtained by blending a specific multiphase thermoplastic resin with a polycarbonate resin has high impact resistance, especially impact resistance. It has been discovered that the thickness dependence of properties is significantly improved, and the physical properties, mechanical properties, and moldability are excellent, and the dispersibility of a specific multiphase structure layer thermoplastic resin into polycarbonate resin is also excellent. was completed.

That is, the first invention is a polycarbonate resin composition containing the following (1) (II).

(1) 100 parts by weight of polycarbonate resin, (II) 5 to 95% by weight of a copolymer consisting of a non-polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer;
Vinyl type (co) consisting of at least one vinyl monomer
Polyphase thermoplastic resin 1 to 95 to 5% by weight of a polymer and having a particle size of 0.001 to 10 μm in one dispersed resin
100 parts by weight.

In addition, the second invention provides at least one vinyl monomer,
At least one radical (co)polymerizable organic peroxide and a radical polymerization initiator are added, heated under conditions that substantially do not decompose the radical polymerization initiator, and the vinyl monomer is radically (co)polymerized. A copolymer consisting of a non-polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer is impregnated with a polar organic peroxide and a radical polymerization initiator, and the impregnation rate is as high as the first 10 times. % or more, the temperature of this aqueous suspension is raised to convert the vinyl monomer and radical (co)polymerizable organic peroxide into non-polar α-
A grafting precursor (A) copolymerized in a copolymer consisting of an olefin and a nonconjugated diene monomer or a polar vinyl monomer, or a grafting precursor (A) copolymerized with a nonpolar α-olefin and a nonconjugated A copolymer (B) consisting of a diene monomer or a polar vinyl monomer (B) 0 to 99% by weight, and/or a vinyl (co)polymer obtained by polymerizing at least one vinyl monomer. Combined (C) 0 to 99% by weight in advance from 100 to 99% by weight
This is an impact resistance modifier for polycarbonate resin, characterized in that the main component is a multi-phase structured thermoplastic resin obtained by melt-mixing in a range of 300°C.

Furthermore, the third invention is a copolymer suspension comprising a non-polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer, and at least one vinyl monomer and a radical. A polymerization initiator is added and heated under conditions that do not substantially cause decomposition of the radical polymerization initiator, and the vinyl monomer and radical polymerization initiator are combined with a non-polar α-olefin and a non-conjugated diene monomer or a polar polymerization initiator. When the copolymer consisting of a vinyl monomer is impregnated into the copolymer and the impregnation rate reaches the initial 10% or more, the temperature of this aqueous suspension is raised to convert the vinyl monomer into a non-polar A multiphase thermoplastic resin (D
), or (D), 0 to 99% by weight of a copolymer (B) consisting of a non-polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer, and/or at least 1
Mainly a multiphase thermoplastic resin obtained by melt-mixing 0 to 99% by weight of a vinyl (co)polymer (C) obtained by polymerizing seed vinyl monomers at a temperature of 100 to 300°C. This is an impact resistance modifier for polycarbonate resin, characterized in that it is used as a component.

The polycarbonate resin used in the present invention is 4
,4-dihydroxydiphenyl-2,2-propane (commonly known as bisphenol A). Polycarbonate, number average molecular weight 15,00
0 to 8o, ooo is preferred.

These polycarbonates can be manufactured by any method 1
For example, in the production of polycarbonate of 4,4-dihydroxydiphenyl-2,2-propane, 4,4-dihydroxydiphenyl-2,2-propane is used as the dioxy compound, and phosgene is added in the presence of an aqueous caustic alkali solution and a solvent. Examples include a method of manufacturing by blowing, and a method of manufacturing by transesterifying 4,4-dihydroxydiphenyl-2,2-propane and diester carbonate in the presence of a catalyst.

The copolymer composed of a non-polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer in the multiphase thermoplastic resin used in the present invention refers to one or two copolymers.
It is a polymer obtained by copolymerizing one or more nonpolar α-olefins with one or more nonconjugated diene monomers, or one or more polar vinyl monomers.

Examples of the nonpolar α-olefin monomers mentioned here include ethylene, propylene, butene-1,4-methylpentene-1, hexene-1, decene-1, octene-1, and the like. Further, as a non-conjugated diene monomer, for example, ethylidene norbornene.

1.4-hexadiene, 1,5-hexadiene, dicyclopentadiene, 2-methyl-1,5-hexadiene,
Examples include 1,4-cyclohebutadiene and 1°4-cyclooctadiene.

Examples of polar vinyl monomers include monomers having a vinyl group that can be copolymerized with nonpolar α-olefin monomers, such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, anhydride, etc. Maleic acid.

Itaconic acid, itaconic anhydride, bicyclo(2,2゜1)
α,β-unsaturated carboxylic acids such as -5-heptene-2,3-dicarboxylic acid, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate.

α, β-unsaturated carboxylic acid esters such as n-butyl methacrylate and isobutyl methacrylate, vinyl acetate, vinyl propionate, vinyl caproate.

Examples include vinyl esters such as vinyl caprylate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate.

Specific examples of copolymers made of the non-polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer include ethylene-propylene-ethylidene norbornene copolymer rubber, ethylene-propylene-1, 4-hexadiene copolymer rubber, ethylene-propylene-dicyclopentadiene copolymer rubber, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene- Isopropyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-isobutyl acrylate copolymer,
Ethylene-2-ethylhexyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-n-methacrylate
Examples include butyl copolymer, ethylene-isobutyl methacrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, and the like.

Specifically, the vinyl (co)polymer in the multiphase thermoplastic resin used in the present invention includes styrene, nuclear-substituted styrene such as methylstyrene, dimethylstyrene,
Ethylstyrene, isopropylstyrene, chlorstyrene, α-substituted styrenes such as α-methylstyrene, α-
Vinyl aromatic monomers such as ethylstyrene; C1-7 alkyl esters of acrylic acid or methacrylic acid.

For example, (meth)acrylic acid ester monomers such as methyl, ethyl, propyl, isopropyl, and butyl of (meth)acrylic acid; 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol (meth)acrylic acid hydroxyalkyl ester monomers such as monomethacrylate; vinyl cyanide monomers such as acrylonitrile or methacrylate; vinyl ester monomers such as vinyl acetate and vinyl propionate; Meth)acrylamide monomer; Vinyl monomers such as unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, and derivatives such as their amides, imides, esters, anhydrides, etc. It is a (co)polymer obtained by polymerizing one or more types of polymers.

Among these, vinyl aromatic monomers, vinyl cyanide monomers, (meth)acrylic acid ester monomers and vinyl ester monomers are preferably used. In particular, vinyl copolymers consisting of 0 to 50% by weight of vinyl cyanide monomers and 50 to 100% by weight of vinyl aromatic monomers, or vinyl containing 50% by weight or more of (meth)acrylate monomers. A system (co)polymer is the most preferred embodiment because it has good dispersibility in polycarbonate resin.

The thermoplastic resin with a multiphase structure as used in the present invention refers to a nonpolar α-
In a copolymer consisting of an olefin and a nonconjugated diene monomer or a polar vinyl monomer, and/or a vinyl (co)polymer matrix.

A vinyl (co)polymer, which is a different component, or a copolymer consisting of a nonpolar α-olefin and a nonconjugated diene monomer or a polar vinyl monomer is uniformly dispersed in a spherical shape. refers to something that exists.

The particle size of the dispersed polymer is 0.001 to 10 μm,
Preferably it is 0.01 to 5 μm. When the dispersed resin particle size is less than 0.001 μm or exceeds 5 μm,
(Not preferred because it has low dispersibility when blended with polycarbonate resin, resulting in deterioration of appearance or deterioration of mechanical properties, for example).

The number average degree of polymerization of the vinyl (co)polymer in the multiphase structured thermoplastic resin of the present invention is from 5 to 10,000°, preferably from 10 to
It is 5000.

If the number average degree of polymerization is less than 5, it is possible to improve the impact resistance of the thermoplastic resin composition of the present invention, but when blended with polycarbonate resin, dispersibility is low and mechanical properties are deteriorated. Therefore, it is undesirable. Moreover, if the number average degree of polymerization exceeds 10,000, it is not preferable because the melt viscosity is high, the moldability is decreased, and the surface gloss is decreased.

The multiphase thermoplastic resin of the present invention contains 5 to 95% by weight, preferably 20 to 95% by weight of a copolymer consisting of a nonpolar α-olefin and a nonconjugated diene monomer or a polar vinyl monomer.
It consists of 90% by weight. Therefore, the vinyl (co)polymer is 95 to 5% by weight, preferably 80 to 10% by weight.
If the amount by weight of the copolymer consisting of 9 non-polar α-olefin and a non-conjugated diene monomer or polar vinyl monomer is less than 5 weight %, the effect of improving impact resistance will be insufficient. Undesirable. Furthermore, if the copolymer consisting of a non-polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer exceeds 95% by weight, a sufficient effect of improving impact resistance can be obtained; This is not preferred because properties and heat resistance deteriorate.

When producing the multiphase structured thermoplastic resin used in the present invention, a generally well-known chain transfer method is used.

Although it can be produced by any grafting method such as ionizing radiation irradiation method, the most preferred method is.

It is based on one of the Niga methods listed below.

Hereinafter, the method for producing the multiphase thermoplastic resin used in the present invention will be specifically described in detail.

The first method is to prepare a copolymer 1 consisting of a non-polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer.
00 parts by weight of a radical (co)polymerizable organic peroxide represented by the following formula (a) or (b) is suspended in water, and separately 5 to 400 parts by weight of at least one vinyl monomer. or a mixture of two or more of the above vinyl monomers.
A radical (co)polymerization initiator with a decomposition temperature of 40 to 90°C to obtain a half-life of 10 hours and a radical (co)polymerization initiator of 0.1 to 10 parts by weight based on the vinyl monomer is used. 0.01 per 100 parts by weight of organic peroxide
~5 parts by weight of the vinyl monomer, the radical (co)polymerizable organic peroxide, and the radical are heated under conditions that do not substantially cause decomposition of the radical (co)polymerization initiator. A copolymer (co)polymer consisting of a non-polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer is impregnated with a (co)polymerization initiator. % or more, the temperature of this aqueous suspension is raised to convert the vinyl monomer and radical (co)polymerizable organic peroxide into non-polar α-olefin and non-conjugated diene monomer or polar A grafting precursor (A) is obtained by copolymerizing with a copolymer consisting of a vinyl monomer.

This grafted precursor (A) is also a thermoplastic resin with a multiphase structure. Therefore, this grafting precursor (A) may be directly melt-mixed with the polycarbonate resin (1) at a temperature in the range of 150 to 350°C.

The multiphase thermoplastic resin of the present invention can also be obtained by cross-fertilizing the grafted #precursor (A) while melting at 100 to 300°C. At this time, the grafting precursor (A)
Separately, a copolymer (B) or a vinyl (co)polymer (C) consisting of a non-polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer is mixed, and the mixture is melted. A multiphase thermoplastic resin can also be obtained by kneading. At this time, a copolymer (B) consisting of a nonpolar α-olefin and a nonconjugated diene monomer or a polar vinyl monomer and a vinyl (co)polymer (C) may be used together. . Most preferred is a thermoplastic resin with a multiphase structure obtained by kneading a grafted precursor.

The radical (co)polymerizable organic peroxide represented by the general formula (a) is one formula (in the formula, R□ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R2 is a hydrogen atom or a methyl group). , R3 and R4 are each an alkyl group having 1 to 4 carbon atoms, and Rs is an alkyl group having 1 to 12 carbon atoms.
represents an alkyl group, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. m is 1 or 2. ) is a compound represented by

In addition, the radical (co)polymerizable organic peroxide represented by the general formula (b) is a radical (co)polymerizable organic peroxide represented by the formula (wherein R6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R7 is a hydrogen atom or a methyl group. , R7 and R are each an alkyl group having 1 to 4 carbon atoms, and R1° is an alkyl group having 1 to 1 carbon atoms.
2 represents an alkyl group, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms, n is O
ll or 2. ) is a compound represented by

Examples of the radical (co)polymerizable organic peroxide represented by general formula (a) include t-butylperoxymethacryloyloxyethyl carbonate, t-amylperoxyacryloyloxyethyl carbonate, and t-hexylperoxy Acryloyloxyethyl carbonate, 1
, 1,3.3-tetramethylbutylperoxyacryloyloxyethyl carbonate, cumylperoxyacryloyloxyethyl carbonate, p-isopropylcumylperoxyacryloyloxyethyl carbonate, t
-butylperoxymethacryloyloxyethyl carbonate, t-amylperoxyacryloyloxyethyl carbonate, t-hexylperoxyacryloyloxyethyl carbonate, 1,1,3,3-tetramethylbutylperoxymethacryloyloxyethyl carbonate.

Cumylperoxyacryloyloxyethyl carbonate, p-isopropylcumylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-amylperoxyacryloyloxyethoxyethyl carbonate, t-hexylperoxyacryloyloxy Ethoxyethyl carbonate, 1,1,3,3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate, cumylperoxyacryloyloxyethoxyethyl carbonate, p-isopropylcumylperoxyacryloyloxyethoxyethyl carbonate, t-butylperoxy methacryloyloxyethoxyethyl carbonate, t
-Amylperoxyacryloyloxyethoxyethyl carbonate, t-hexylperoxyacryloyloxyethoxyethyl carbonate, 1,1,3゜3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate, cumylperoxyacryloyloxyethoxyethyl carbonate , p-isopropylcumylperoxyacryloyloxyethoxyethyl carbonate, 1-butylperoxyacryloyloxyisopropyl carbonate, t-amylperoxyacryloyloxyisopropyl carbonate, t-hexylperoxyacryloyloxyisopropyl carbonate, 1,1,3
, 3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate, cumylperoxyacryloyloxyisopropyl carbonate, p-isopropylcumylperoxyacryloyloxyisopropyl carbonate, t-butylperoxymethacryloyloxyisopropyl carbonate, t-amylperoxymethacryloyl Roxyisopropyl carbonate, t-hexylperoxyacryloyloxyisopropyl carbonate,
Examples include 1,1,3.3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate, cumylperoxyacryloyloxyisopropyl carbonate, and p-isopropylcumylperoxyacryloyloxyisopropyl carbonate.

Furthermore, as a compound represented by formula (b), t
-Butylperoxyallyl carbonate, t-amylperoxyallyl carbonate, 1-hexylperoxyallyl carbonate, 1,1゜3.3-tetramethylbutylperoxyallyl carbonate, cumylperoxyallyl carbonate, t-
Butyl peroxy methallyl carbonate, t-amyl peroxy methallyl carbonate, t-hexyl peroxy methallyl carbonate, 1,1.

3,3-Tetramethylbutylperoxymethallyl carbonate, P-menthaneperoxymethallyl carbonate, cumylperoxymethallyl carbonate, t-butylperoxyallyloxyethyl carbonate, t-amylperoxyallyloxyethyl carbonate, t-hexylperoxyalil carbonate Roxyethyl carbonate, t-butylperoxyallyloxyethyl carbonate, t-amylperoxyallyloxyethyl carbonate, t-hexylperoxymethallyloxyethyl carbonate, t-butylperoxyallyloxyisopropyl carbonate,
Examples include t-amylperoxyallyloxyisopropyl carbonate, t-hexylperoxyallyloxyisopropyl carbonate, t-butylperoxymetallyloxyisopropyl carbonate, t-amylperoxyallyloxyisopropyl carbonate, t-hexylperoxyallyloxyisopropyl carbonate, etc. be able to. Among these, preferred are t-butylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, and t-butylperoxyacryloyloxyethyl carbonate.
Butylperoxyallyl carbonate, t-butylperoxymethallyl carbonate 1-.

In the second method, 100 parts by weight of a copolymer consisting of a non-polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer is suspended in water.

Additionally, 5 to 400 parts by weight of at least one vinyl monomer. The decomposition temperature to obtain a half-life of 10 hours is 40-13
A radical (co)polymerization initiator at 0°C is mixed with vinyl monomer 1
Add a solution of 0.01 to 5 parts by weight per 00 parts by weight and heat under conditions that do not substantially cause decomposition of the radical polymerization initiator to completely remove the vinyl monomer and radical polymerization initiator. A copolymer consisting of a polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer is impregnated, and when the impregnation rate reaches the initial 10% by weight or more, the aqueous suspension is The temperature is raised to copolymerize the vinyl monomer in a copolymer consisting of a non-polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer to form a multiphase thermoplastic resin ( D) is obtained.

Even if this multiphase structured thermoplastic resin (D) is directly melt-mixed with the polycarbonate resin (1) in the range of 150 to 350°C, or the multiphase structured thermoplastic resin (D) is
The mixture may be kneaded while melting at ~300°C, and then melt-mixed with the polycarbonate resin (I) at a temperature of 150~350°C.

At this time, a copolymer (B) consisting of a non-polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer or a vinyl-based (
A multiphase thermoplastic resin can also be obtained by mixing the co)polymer (C) and kneading it while melting at 100 to 300°C. At this time, a copolymer (B
) and the vinyl (co)polymer (C) may be used together.

Although the purpose of the present invention can be achieved using any of these two manufacturing methods and is a preferred embodiment, the first method is particularly preferred. If anything,
The grafting efficiency of the multiphase structured thermoplastic resin is high and secondary aggregation due to heat does not occur, so performance is more effective and the resulting thermoplastic resin composition has improved physical properties, mechanical properties, and moldability. This is because it is superior in terms of etc.

In the present invention, the amount of the multiphase thermoplastic resin is 1 to 100 parts by weight, preferably 4 to 70 parts by weight, based on 100 parts by weight of the polycarbonate resin (1). If the amount of the multiphase thermoplastic resin is less than 1 part by weight, the effect of improving impact resistance, which is the objective of the present invention, is undesirable. Furthermore, if the amount of the multiphase thermoplastic resin exceeds 1.0 parts by weight, the mechanical strength and heat resistance will deteriorate, which is undesirable.

The thermoplastic resin composition of the present invention is prepared by heating the polycarbonate resin composition to 150 to 350°C, preferably 220 to 28°C.
Produced by mixing under melting conditions at 0°C. 15
If the temperature is lower than 0°C, melting may be insufficient or the melt viscosity may be high, resulting in insufficient mixing and phase separation or delamination may occur in the molded product, which is not preferable. Moreover, if the temperature exceeds 350°C, the resins to be mixed will decompose, resulting in coloring of the molded product and deterioration of mechanical properties, which is not preferable.

Melt mixing can be carried out using a mixing machine commonly used for mixing thermoplastic resins, such as a Banbury mixer, a pressure kneader, a single-screw extruder, a twin-screw extruder, or a mixing roll. A twin-screw extruder is particularly preferred from the viewpoints of performance and mechanical properties of the resin obtained.

The present invention further includes inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, organic flame retardants such as halogen-based and phosphorus-based flame retardants, calcium sulfate, and calcium silicate, without departing from the gist of the present invention.

Clay, diatomaceous earth, talc, alumina, silica sand, glass powder 1
Iron oxide, metal powder, graphite, silicon carbide.

Powder-like fillers such as silicon nitride, silica, boron nitride, aluminum nitride, carbon black, and molybdenum disulfide; metal powders such as mica, glass plates, sericite, pyrophyllite, and aluminum flakes, and flat or scaly materials such as graphite. Hollow fillers such as shirasu balloons, metal balloons, glass balloons, pumice, fibrous fillers such as glass fibers, carbon fibers, silicon carbide fibers, mineral fibers such as asbestos and wollastonite, titanium Inorganic fillers such as monocrystalline fibrous fillers such as acid potassium whiskers, calcium sulfate whiskers, carbon whiskers, organic fillers such as wood flour, antioxidants, ultraviolet inhibitors,
Additives such as lubricants, dispersants, coupling agents, foaming agents, crosslinking agents, colorants, and engineering plastics such as polyolefin resins, polyamides, polyesters, polyarylates, ABS resins, polyphenylene sulfide, and fluoroplastics are added. There is no problem.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

The Izot impact strength 9 flexural modulus measured in the Examples and Comparative Examples was measured in accordance with JIS shown below, and the appearance of the injection molded product was determined by the method below.

[Izot impact strength JIS K-7110 The test was carried out on Izot test specimens with a thickness of 12.7 m and 3°2-.

[Flexural modulus] JIS K-7203 Test speed 2 wm / SoiB [Appearance of injection molded product] Regarding the appearance of the injection molded product, presence or absence of delamination was visually determined.

Reference example 1 (Production of multiphase structure thermoplastic resin A) Internal volume 5Ω
Put 2,500 g of pure water into a stainless steel autoclave, and add 2.5 g of polyvinyl alcohol as a suspending agent.
was dissolved. In this, a copolymer consisting of a non-polar α-olefin and a non-conjugated diene (trade name: Mitsui Elastomer K-97204, manufactured by Mitsui Petrochemical Industries, Ltd., ethylene-propylene-diene copolymer rubber Mooney viscosity (M
L I+4,100℃) 40, Iodine value 22) 70
0g was added and stirred to disperse. Separately, 1.5 g of benzoyl peroxide (trade name "Niper", manufactured by NOF Corporation) was added as a radical polymerization initiator, and 6 g of t-butylperoxymethacryloyloxyethyl carbonate was added as a radical (co)polymerizable organic peroxide. The polymer was dissolved in 210 g of styrene monomer and 90 g of acrylonitrile monomer, and this solution was poured into the autoclave and stirred. Then autoclave for 60-65
The nonpolar α-olefin polymer was impregnated with a vinyl monomer containing a radical polymerization initiator and a radical (co)polymerizable organic peroxide by raising the temperature to ℃ and stirring for 2 hours. Impregnated vinyl monomer, radical (
After confirming that the total amount of co)polymerizable organic peroxide and radical polymerization initiator is at least 10% by weight, the temperature is raised to 80-85°C and maintained at that temperature for 7 hours. Polymerization was completed, washed with water and dried to obtain a grafted precursor. The styrene-acrylonitrile copolymer in this grafted precursor was extracted with ethyl acetate, and GPC
As a result of measuring the number average degree of polymerization, it was 880.

Next, this grafted precursor was extruded at 180° C. using a Laboplast Mill-shaft presser (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to cause a grafting reaction, thereby obtaining a multiphase thermoplastic resin A.

This multiphase thermoplastic resin was examined using a scanning electron microscope (rJE).
OL JSM T300J, manufactured by JEOL Ltd.)
It was found to be a thermoplastic resin with a multiphase structure in which perfectly spherical resin particles each having a diameter of 0.3 to 0.4 μm were uniformly dispersed.

At this time, the grafting efficiency of the styrene-acrylonitrile copolymer was 80.5% by weight.

Reference Example 2 (Production of Multiphase Structure Thermoplastic Resin B) In Reference Example 1, 210 g of styrene monomer as the vinyl monomer
A multiphase structure thermoplastic resin B was obtained in accordance with Reference Example 1, except that 300 g of styrene monomer was used instead of 90 g of acrylonitrile monomer.

At this time, the number average degree of polymerization of the styrene polymer was 830, and the average particle diameter of the resin dispersed in this resin composition was 0.2 to 0.3 μm.

Reference Example 3 (Manufacture of multiphase structure thermoplastic resin C) In Reference Example 1, 210 g of styrene monomer as the vinyl monomer
And instead of 90 g of acrylonitrile monomer, 300 g of methyl methacrylate monomer was used, and 0.6 g of n-dodecyl mercaptan was added as a molecular weight regulator.
A multiphase thermoplastic resin C was obtained according to Reference Example 1.

At this time, the number average degree of polymerization of the methyl methacrylate polymer was 890, and the average particle diameter of the resin dispersed in this resin composition was 0.3 to 0.4 μm.

Reference Example 4 (Manufacture of thermoplastic resin with multiphase structure) In Reference Example 1, a copolymer consisting of a non-polar α-olefin and a polar vinyl was used instead of a copolymer consisting of a non-polar α-olefin and a non-conjugated diene. The multilayer structure was prepared according to Reference Example 1, except that the composite material (trade name: "8 stone Rexron EVA V-270J, manufactured by Nippon Petrochemical Co., Ltd., ethylene-vinyl acetate copolymer, vinyl acetate content, 15% by weight)" was used. A structural thermoplastic resin was obtained.

At this time, the number average degree of polymerization of the styrene-acrylonitrile copolymer was 880. The average particle size of the resin dispersed in this resin composition was 0.3 to 0.4 μm.

Reference Example 5 (Manufacture of multi-phase structure thermoplastic resin E) In Reference Example 1, a copolymer consisting of a non-polar α-olefin and a polar vinyl was used instead of a copolymer consisting of a non-polar α-olefin and a non-conjugated diene. Combination (Product name: ``8 Stone Rexron''
A multilayer thermoplastic resin E was obtained according to Reference Example 1, except that EEAA-4200J, manufactured by Nippon Petrochemical Co., Ltd., ethylene-ethyl acrylate copolymer, ethyl acrylate content 20% by weight) was used. Ta.

At this time, the number average degree of polymerization of the styrene-acrylonitrile copolymer was 870, and the average particle diameter of the resin dispersed in this resin composition was 0.2 to 0.3 μm.

Reference Example 6 (Production of Multiphase Structure Thermoplastic Resin F) 67% by weight of the grafted precursor obtained in Reference Example 1 was added with non-polar α-
Copolymer consisting of olefin and non-conjugated diene (trade name: Mitsui Elastomer 19720J, manufactured by Mitsui Petrochemical Industries, Ltd., ethylene-propylene-diene copolymer rubber)
Mooney viscosity (ML I+4,100°C) 40. Iodine value: 22) 33% by weight was extruded at 180°C using a Laboplast Mill-screw extruder (manufactured by Toyo Seiki Co., Ltd.) to obtain a multiphase thermoplastic resin F.

At this time, the average particle diameter of the resin dispersed in the resin composition was 0.4 to 0.5 μm.

Reference Example 7 (Production of multiphase structure thermoplastic resin G) Internal volume 51
2 in a stainless steel autoclave.

2,500 g of pure water was added, and 2.5 g of polyvinyl alcohol was further dissolved therein as a suspending agent. In this solution, 5 g of benzoyl peroxide (trade name: Niper BJ, manufactured by NOF Corporation) as a radical polymerization initiator was dissolved in 700 g of styrene monomer as a vinyl monomer and 300 g of acrylonitrile monomer. The autoclave was charged into the autoclave and stirred.Then, the autoclave was heated to 80~
The temperature was raised to 85°C, maintained at that temperature for 7 hours to complete polymerization, washed with water and dried to obtain a styrene-acrylonitrile copolymer as a vinyl copolymer. The number average degree of polymerization of this styrene-acrylonitrile copolymer is 85
It was 0.

71% by weight of the grafted precursor obtained in Reference Example 1;
29% by weight of the styrene-acrylonitrile copolymer obtained by the above method as a vinyl copolymer was heated to 18% by weight using a Laboplast Mill-screw extruder (newly manufactured by Toyo Seiki Co., Ltd.).
A multiphase thermoplastic resin G was obtained by extrusion at 0°C.

At this time, the average particle diameter of the resin dispersed in this resin composition was 0.4 to 0.5 μm.

Reference Example 8 (Manufacture of multiphase structure thermoplastic resins H and I) Reference Example 1 except that t-butylperoxymethacryloyloxyethyl carbonate as the radical (co)polymerizable organic peroxide is not used. A multiphase structure thermoplastic resin H was obtained according to .

At this time, the number average degree of polymerization of the styrene-acrylonitrile copolymer was 860, and the average particle diameter of the resin dispersed in this resin composition was 0.4 to 0.5 μm.

This thermoplastic resin H with a multiphase structure was extruded at 180° C. using a Laboplast Mill-screw extruder (manufactured by Toyo Seiki Co., Ltd.) to obtain a thermoplastic resin I with a multiphase structure.

Reference Example 9 (Manufacture of multiphase thermoplastic resin J) A copolymer consisting of 67% by weight of the multiphase thermoplastic resin H obtained in Reference Example 8, a nonpolar α-olefin, and a nonconjugated diene (
Product name: Mitsui Elastomer K-9720J, manufactured by Mitsui Petrochemical Industries, Ltd., ethylene-propylene-diene copolymer rubber Mooney viscosity (ML I+4, 100°C) 40
, iodine value 22) 33% by weight was extruded at 180° C. using a Laboplast Mill-axial extruder (manufactured by Toyo Seiki Co., Ltd.) to obtain a multiphase structure thermoplastic resin J.

At this time, the average particle diameter of the resin dispersed in the resin composition was 0.5 to 0.6 μm.

Reference Example 10 (Manufacture of multiphase structure thermoplastic resin) Reference Example 8
871% by weight of the multiphase thermoplastic resin obtained in Reference Example 7 and the styrene obtained in Reference Example 7 as a vinyl copolymer.
29% by weight of acrylonitrile copolymer was heated to 180°C using a Laboplast Mill-screw extruder (newly manufactured by Toyo Seiki Co., Ltd.).
A thermoplastic resin K having a multiphase structure was obtained by extrusion.

At this time, the average particle diameter of the resin dispersed in this resin composition was 0.5 to 0.6 μm.

Examples 1 to 14 The polycarbonate resin (trade name "Panlite L-1250J manufactured by Teijin Kasei Ltd.") was mixed with the polyphase structure thermoplastic resin obtained in Reference Examples 1 to 10 in the proportions shown in Tables 1 to 2. Resin A-
and the grafting precursor obtained in Reference Example 1 were triblended in a predetermined amount, and the mixture was triblended using a co-directional twin-screw extruder (manufactured by Kurimoto Iron Works Co., Ltd., model KRC Kneader S-1) set at 270°C. Mixed. Next, an in-line screw injection molding machine (manufactured by Debuta Kikai Kogyo Co., Ltd.) was set at 275°C.

TS-35-FV25 type) was prepared for each test piece, and the Izod impact strength 1 flexural modulus and appearance of the molded product were evaluated. The results are shown in Tables 1 and 2.

Comparative Examples 1 to 8 Examples 1.4 to 7.12, except that the amount of the multiphase thermoplastic resin added was changed as shown in Table 3.
Test pieces were prepared according to 4 to 7.12, and the Izot impact strength, flexural modulus, and appearance of the molded product were examined.

The results are shown in Table 3.

Comparative Examples 9 to 13 In Example 1, instead of the multiphase thermoplastic resin,
Ethylene-propylene-diene copolymer rubber, ethylene-
Test pieces were prepared and examined in accordance with Example 1, except that vinyl acetate copolymer and ethylene-ethyl acrylate copolymer were used in the amounts shown in Table 4.

The results are shown in Table 4.

When the amount of the multiphase thermoplastic resin exceeds 100 parts by weight based on 100 parts by weight of the polycarbonate resin, the molded product completely loses the mechanical and physical properties of the polycarbonate resin. Furthermore, it has become clear that if the amount of the multiphase thermoplastic resin added is less than 1 part by weight per 100 parts by weight of the polycarbonate resin, there is no effect of the addition.

In addition, the multiphase structured thermoplastic resin of the present invention has extremely good dispersibility in polycarbonate resin, and the appearance of the molded product is similar to that of delamination.
It became clear that the phenomenon was not observed.

The composition can be used in a wide variety of applications, such as automobile parts, home appliance parts, precision mechanical parts, and the like.

〔Effect of the invention〕

The polycarbonate resin composition of the present invention has mechanical properties,
It is a resin composition with excellent thermal properties and high impact resistance even in thick-walled products, and can be easily manufactured by simply mixing while melting.

Furthermore, since the degree of impact resistance is determined by the blending ratio of the multiphase thermoplastic resin to be mixed, it is possible to easily produce a wide variety of products in small quantities.

Claims (3)

[Claims] (1) A polycarbonate resin composition containing the following (I) and (II). (I) 100 parts by weight of polycarbonate resin, (II) 5 to 95% by weight of a copolymer consisting of a non-polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer;
Vinyl type (co) consisting of at least one vinyl monomer
Multiphase thermoplastic resin 1 to 1 consisting of 95 to 5% by weight of a polymer and having a dispersed resin particle size of 0.001 to 10 μm
100 parts by weight. (2) At least one vinyl monomer, a radical (co-)
At least one polymerizable organic peroxide and a radical polymerization initiator are added and heated under conditions that substantially do not cause decomposition of the radical polymerization initiator. A copolymer consisting of a non-polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer is impregnated with an oxide and a radical polymerization initiator, and the impregnation rate reaches 10% by weight or more. When the temperature of this aqueous suspension is increased, vinyl monomers and radicals (
A grafting precursor (A
), or (A), 0 to 99% by weight of a copolymer (B) consisting of a non-polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer, and/or at least 1
A multiphase structure layer thermoplastic resin obtained by melt-mixing 0 to 99% by weight of a vinyl (co)polymer (C) obtained by polymerizing seed vinyl monomers in advance at a temperature of 100 to 300°C. An impact resistance modifier for polycarbonate resin, characterized by being a main component. (3) At least one vinyl monomer and a radical polymerization initiator are added to an aqueous suspension of a copolymer consisting of a nonpolar α-olefin and a nonconjugated diene monomer or a polar vinyl monomer. In addition, the vinyl monomer and radical polymerization initiator are heated under conditions that do not substantially cause decomposition of the radical polymerization initiator, and the vinyl monomer and the radical polymerization initiator are combined with the non-polar α-olefin and the non-conjugated diene monomer or polar vinyl monomer. When the impregnation rate reaches the initial 10% by weight or more, the temperature of this aqueous suspension is raised to mix the vinyl monomer with the non-polar α-olefin. A thermoplastic resin with a multiphase structure (D) obtained by copolymerization in a copolymer consisting of a conjugated diene monomer or a polar vinyl monomer, or (
D) is a copolymer (B) consisting of a non-polar α-olefin and a non-conjugated diene monomer or a polar vinyl monomer.
~99% by weight, and/or vinyl-based (co)polymer (C) obtained by polymerizing at least one vinyl monomer (C) 0
An impact modifier for polycarbonate resin, characterized in that the main component is a thermoplastic resin with a multiphase structure layer obtained by melt-mixing 99% by weight in advance at a temperature of 100 to 300°C.