JPH01268751A - Thermoplastic resin composition and production thereof - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition, excellent in impact resistance, electrical characteristics, heat resistance, etc., and suitable as electrical, electronic, mechanical parts, etc., by blending a polyamide resin with a polyarylate resin and specific thermoplastic resin of a multilayered structure. CONSTITUTION:A thermoplastic resin composition obtained by blending 100pts. wt. total amount of (A) 99-1wt.% polyamide resin and (B) 1-99wt.% polyarylate resin with (C) 0.1-100pts.wt. thermoplastic resin, consisting of (C1) 5-95wt.% epoxy group-containing olefinic copolymer and (C2) 95-5wt.% vinylic (co)polymer prepared from one or more vinyl monomers and having a multilayered structure forming a dispersed layer with 0.001-10mum particle diameter of one (co)polymer thereof and (D) an inorganic filler in an amount of 0-150pts.wt. based on 100pts.wt. total amount of the components (A), (B) and (C).

Description

Detailed Description of the Invention [Field of Application in M Business] The present invention relates to a thermoplastic resin composition having excellent impact resistance, electrical properties, heat resistance, moldability, dimensional stability, etc., and a method for producing the same. The composition can be used in a wide range of fields such as electrical and electromechanical parts and automobile parts.

[Prior Art] Polyamide resins have excellent mechanical properties and moldability, but have a drawback in water resistance.

On the other hand, although polyarylate resins have excellent heat resistance, they have the disadvantage of poor impact resistance depending on their use, and their use may be subject to limitations.

[Problems to be Solved by the Invention] If a more excellent thermoplastic resin composition can be obtained by compensating for the disadvantages of polyamide resins and polyarylate resins with their respective advantages, new uses should open up. However, polyamide resins and polyarylate resins have poor affinity due to their different chemical structures, and in an attempt to solve this problem, Japanese Patent Laid-Open Nos. 11i2-277482 and 62-283146 A method is disclosed in which an epoxy-based ethylene copolymer and an acid anhydride-containing ethylene copolymer are used together. Although these polymers are effective for imparting impact strength, they require the use of acid anhydride-containing ethylene copolymers, which are soft polymers, to some extent, and the stiffness of the composition and the deflection temperature under load (heat The disadvantage is that the deformation temperature) tends to drop.

[Means for Solving the Problems] As a result of intensive research to solve these problems, the present inventors have found that a specific multilayer thermoplastic resin obtained from an epoxy group-containing olefin copolymer is used. As a result, the compatibility of polyamide resin and polyarylate resin was improved, and a thermoplastic resin composition with excellent mechanical properties, impact resistance, moldability, and dimensional stability was completed.

That is, the first invention comprises (I) 99 to 1% by weight of polyamide resin, (II) 1 to 93% by weight of polyarylate resin, and the above (I) + (I
I) 5 to 95 parts of (III) epoxy group-containing olefin copolymer per 100 parts by weight
% by weight and 95-5% by weight of a vinyl-based (co)polymer obtained from at least one vinyl monomer, with one (co)polymer forming a dispersed layer with a particle size of 0.001-10μ. 0.1 to 100 parts by weight of a multilayer thermoplastic resin, and 0 to 150 parts by weight of an inorganic filler (rl/) based on the above (I) + (II) + (I[[) too parts by weight] It is a thermoplastic resin composition made by blending the following.

Furthermore, a second invention includes adding an epoxy base to an aqueous suspension of an olefin copolymer, at least one vinyl monomer, at least one radical (co)polymerizable organic peroxide, and a radical polymerization initiator. The vinyl monomer, the radical (co)polymerizable organic peroxide, and the radical polymerization initiator are impregnated into the epoxy group-containing olefin copolymer by heating under conditions that do not substantially cause decomposition of the radical polymerization initiator. When the impregnation rate reaches the initial 50% by weight or more, the temperature of the aqueous suspension is raised and the vinyl monomer and the radical (co)polymerizable organic peroxide are co-coated with the epoxy group-containing olefin. Grafting precursor copolymerized in polymer (A) 1-100% by weight, epoxy base, *Olefin copolymer (B) 0-100% by weight
Polyamide resin (I) and polyarylate resin (II)
) or preliminarily melt-mix with (A), (B) and (C).
) is melt-mixed at a temperature of 100 to 300° C. to obtain a multi-phase structured thermoplastic resin (III), which is then melt-mixed with (I) and (II).

The polyamide resin (I) used in the present invention is not particularly limited, but includes ordinary aliphatic polyamides such as polycaproamide (nylon 6), polyhexamethylene adipamide (
Nylon 6/6), polyhexamethylene dodecamide (nylon 6/10), polyundecamethylene adipamide (
Nylon 11/6), polyhexamethylene dodecamide (
Nylon 6/12), polyundecaneamide (Nylon 11), polydodecanamide (Nylon 12), polytetramethylene adipamide (Nylon 4/6), or copolyamides containing these as main constituents; Hexamethylene terephthalamide (nylon 6T),
Polyhexamethylene isophthalamide (nylon θI)
, aromatic polyamides such as polymethaxylylenoa5sivamide (MXD6), etc. are used. Particularly preferred polyamide resins include nylon 6 and nylon 606.

The polyarylate resin (II) used in the present invention is a polyester obtained from bisphenols and terephthalic acid and/or isophthalic acid.

RI R2R2' Rt 'wherein, X!
selected from the group consisting of t-0~l-3-1-8O2+, -co- or a hydrocarbon group having 1 to 10 carbon atoms, Rt~
R,, R,'', R2', R3' and R4' represent a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. When X represents a hydrocarbon group having 1 to 10 carbon atoms; , alkylene groups, branched alkyl groups, halogen-substituted alkyl groups, etc. Preferred hydrocarbon groups include methylene, ethylene, propylene, butylene, isopropylidene, cyclohexylmethylene, chloroedylene groups, and particularly preferably isopropylene groups. Also, NRI~R4, Rt', R2', R3
When ' and R4' represent a hydrocarbon group, the hydrocarbon group is preferably an alkyl group, particularly preferably a lower alkyl group. Such bisphenols include 4.4'-dihydroxydiphenyl ether, 4.
4'-dihydroxy-2,21-dimethyldiphenyl ether, 4.4'-dihydroxy-3,3'-dichlorodiphenyl ether, 4°4'-dihydroxydiphenyl sulfide, 4.4'-dihydroxydiphenyl sulfone, 4.4' -dihydroxydiphenylketone,
4゜4'-dihydroxydiphenylmethane, 1,2-bis(4'-hydroxyphenyl)ethane, 2,2-bis(4'-hydroxyphenyl)propane, 1,4-bis(4'-hydroxyphenyl)n- Butane, bis(4'
-hydroxyphenyl)cyclohexylmethane, 1,2
-bis(4'-hydroxyphenyl)-L 1,2-
) dichloroethane, etc. Among them, 2,2-bis(4'-hydroxyphenyl)propane, or bisphenol A, or 4,4'-dihydroxydiphenylsulfone, or bisphenol S, is most preferred.

On the other hand, terephthalic acid and isophthalic acid each individually
or used in combination.

The above-mentioned polyarylate resin is obtained by polymerizing the above-mentioned bisphenols and terephthalic acid and/or isophthalic acid, and the polymerization method may be any of ordinary interfacial polymerization, solution polymerization, or melt polymerization.

In addition, these polyarylate resins have a molecular weight of 5.0
00 to 70.000 is preferred.

The epoxy group-containing olefin copolymer used in the present invention is, in part, a binary polymer of an olefin and an unsaturated glycidyl group-containing monomer formed by high-pressure radical polymerization, or a monopolymer of an olefin and an unsaturated glycidyl group-containing monomer. mer and other unsaturated monomers, and
Ethylene is particularly preferred as the olefin in the copolymer, with 60 to 99.5% by weight of ethylene, 0.5 to 40% by weight of glycidyl monomer, and 0 to 3% of other unsaturated monomers.
A copolymer comprising 3.5% by weight is preferred.

Examples of the unsaturated glycidyl group-containing monomer include glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, monoglycidyl butenetricarboxylate, diglycidyl butenetricarboxylate, triglycidyl butenetricarboxylate, and α- chloroallyl, maleic acid, crotonic acid,
Examples include glycidyl esters such as fumaric acid, glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, glycidyloxyethyl vinyl ether, styrene-p-glycidyl ether, and p-glycidyl styrene, but particularly preferred is methacrylic acid. Examples include glycidyl and allyl glycidyl ether.

Other unsaturated monomers include at least one monomer selected from olefins, vinyl esters, α,β-ethylenically unsaturated carboxylic acids or derivatives thereof,
Specifically, olefins such as propylene, butene-1, hexene-1, decene-1, octene-1, styrene,
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, acrylic acid, methacrylic acid, esters of acrylic acid or methacrylic acid such as methyl, ethyl, propyl, butyl, 2-ethylhexyl, cyclohexyl, dodecyl, octadecyl, maleic acid,
Examples include maleic anhydride, itaconic acid, fumaric acid, maleic acid monoesters and diesters, vinyl ethers such as vinyl chloride, vinyl methyl ether, and vinyl ethyl ether, and acrylamide-based compounds, especially (meth)acrylic acid esters. is preferred.

Specific examples of the epoxy group-containing olefin copolymer include ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer,
Examples include ethylene/ethyl acrylate/glycidyl methacrylate copolymer, ethylene/-carbon oxide/glycidyl methacrylate copolymer, ethylene/glycidyl acrylate copolymer, ethylene/vinyl acetate/glycidyl acrylate copolymer, etc. . Among them, ethylene/
These are glycidyl methacrylate copolymer, ethylene/ethyl acrylate/glycidyl methacrylate copolymer, or ethylene/vinyl acetate/glycidyl methacrylate copolymer.

These epoxy group-containing olefin copolymers can be used as a mixture.

The method for producing an epoxy group-containing olefin copolymer by high-pressure radical polymerization includes the above-mentioned 60 to 99.5% by weight of ethylene,
One or more unsaturated glycidyl group-containing monomers 0.5-40
% by weight of at least one other unsaturated monomer 0-39.
5% by weight monomer mixture at a polymerization pressure of 500 to 4000 t/cJ, preferably 1000 t/cJ, in the presence of o,oooi to 1% by weight radical polymerization initiator, based on the total weight of all their monomers. ~3500 kg/c11 The monomer is reacted at a reaction temperature of 50 to 400°C, preferably 100 to 350°C, in the presence of a chain transfer agent and optionally an auxiliary agent in a tank or tube reactor. This is a method of contacting and polymerizing simultaneously or in stages.

Examples of the radical polymerization initiators include peroxides, hydroperoxides, azo compounds, amine oxide compounds,
Common initiators such as oxygen may be mentioned.

In addition, as a chain transfer agent, hydrogen, propylene, butene-
1,01 to C20 or higher saturated aliphatic hydrocarbons and halogen-substituted hydrocarbons, such as methane, ethane,
Propane, butane, isobutane, n-hexane, n-butane, cycloparaffins, chloroform, and carbon tetrachloride, saturated aliphatic alcohols from cI to Czo or higher, such as methanol, ethanol, propatool and isoproptool% Cl ” CQO or higher saturated aliphatic carbonyl compounds such as carbon dioxide, acetone and methyl ethyl ketone and aromatic compounds such as toluene, diethylbenzene and xylene.

Another example of the epoxy group-containing olefin copolymer of the present invention is a modified product obtained by adding the above-mentioned unsaturated glycidyl group-containing monomer to a conventional olefin homopolymer or copolymer.

The olefin polymers include homopolymers such as low-density, medium-density, and high-density polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, ethylene-propylene copolymers, and ethylene-butene-1. Copolymers with other α-olefins containing ethylene as the main component, such as copolymers, ethylene-hexene-1 copolymers, ethylene-4-methylpentene-1 copolymers, and ethylene-octene-1 copolymers. Copolymerization, propylene-based copolymers with other olefins such as propylene-ethylene block copolymers, and ethylene-vinyl acetate copolymers! copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, copolymer of ethylene and ester of acrylic acid or methacrylic acid such as methyl, ethyl, propyl, isopropyl, butyl, ethylene-maleic acid copolymer Also encompassed by the present invention are ethylene-propylene copolymer rubbers, ethylene-propylene-diene copolymer rubbers, liquid polybutadiene, ethylene-vinyl acetate-vinyl chloride copolymers, and mixtures thereof.

Multiphase structured thermoplastic resin (II
The epoxy group-containing olefin copolymer in I) specifically includes styrene, nuclear substituted styrene such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorstyrene, α-substituted styrene such as α-
Vinyl aromatic monomers such as methylstyrene and α-ethylstyrene; acrylic acid or methacrylic acid with 1 carbon number
~7 alkyl esters, such as (meth)acrylic acid ester monomers such as methyl, ethyl, propyl, isopropyl, butyl esters of (meth)acrylic acid; (meth)
Acrylonitrile monomer; vinyl ester monomer such as vinyl acetate and vinyl propionate; (meth)acrylamide monomer; one or more vinyl monomers such as maleic anhydride, maleic acid monoester, diester, etc. It is a (co)polymer obtained by polymerizing. Among these, a vinyl (co)polymer containing 50% by weight or more of a vinyl aromatic monomer is most preferred.

The multiphase structure thermoplastic resin (III) in the present invention refers to an epoxy group-containing olefin copolymer or a vinyl-based (co)
A polymer matrix in which a vinyl (co)polymer or an epoxy group-containing olefin copolymer, which is a different component, is uniformly dispersed in a spherical shape.

The particle size of the dispersed polymer is 0.001 to 10 μm1
Preferably it is 0.01 to 5 μm.

When the dispersed resin particle size is o, oot μm or no groove, or 1
If it exceeds 0 μm, dispersibility is poor when blended with polycarbonate resin and polyoxymethylene resin, and, for example, the appearance may deteriorate or impact resistance may not be improved, which is not preferable.

Vinyl (
The number average degree of polymerization of the co)polymer is 5 to 10,000, preferably 10 to 5,000.

If the number average degree of polymerization is less than 5 drops, it is possible to improve the impact resistance of the thermoplastic resin composition of the present invention, but it is not preferable because the heat resistance decreases. Moreover, if the number average degree of polymerization exceeds 10,000, the melt viscosity will be high, the moldability will be lowered, and the surface gloss will be lowered, which is not preferable.

The multiphase thermoplastic resin (II[) of the present invention is composed of an epoxy group-containing olefin copolymer in an amount of 5 to 95% by weight, preferably 20 to 90% by weight. Therefore, the vinyl (co)polymer is 95 to 5% by weight, preferably 80% by weight.
~10% by weight.

If the epoxy group-containing olefin copolymer is 5% by weight ungrooved, the compatibility with the polyarylate resin is insufficient,
If the content of the epoxy group-containing olefin copolymer exceeds 95% by weight, it is not preferable because the heat resistance and dimensional stability of the blend will be impaired.

The grafting method for producing the multiphase thermoplastic resin (III) of the present invention may be any generally well-known method such as the chain transfer method or the ionizing radiation method, but the most preferred method is the following. This is based on the method described. The reason for this is that the grafting efficiency is high and secondary aggregation due to heat does not occur, so performance is more effectively expressed.

Hereinafter, the method for producing the thermoplastic resin composition of the present invention will be specifically explained.

That is, 100% by weight of an epoxy group-containing olefin copolymer is suspended in water, and 5 to 400 parts by weight of at least one vinyl monomer is added to the following formula (a) or (b).
In order to obtain a half-life of 10 hours, one or a mixture of two or more radical (co)polymerizable organic peroxides represented by 0.1 to 10 parts by weight per 100 parts by weight of the vinyl monomer. A radical polymerization initiator having a decomposition temperature of 40 to 90°C is dissolved in 0.01 to 5 parts by weight per 100 parts by weight of the vinyl monomer and the radical (co)polymerizable organic peroxide. The vinyl monomer, the radical (co)polymerizable organic peroxide, and the radical polymerization initiator are added to the epoxy base and heated under conditions that do not substantially cause decomposition of the radical polymerization initiator. Impregnated with polymer,
When the impregnation rate reaches 50% or more, the temperature of the aqueous suspension is increased, and the vinyl monomer and the radical (co)polymerizable organic peroxide are mixed into the epoxy group-containing olefin copolymer. to obtain a grafted precursor (A). The multiphase thermoplastic resin (III) of the present invention can be obtained by kneading this grafted precursor (A) while melting at 100 to 300°C. Even if an epoxy group-containing olefin copolymer or a vinyl (co)polymer (C) is separately mixed with the grafted precursor at this time and kneaded while melting, a multilayered thermoplastic resin CI[r] can be obtained. I can do it.

Moreover, the grafting precursor (A) is also a multilayer thermoplastic resin. Therefore, this grafting precursor may be melt mixed directly with the polyamide resin and polyarylate resin.

The radical (co)polymerizable organic peroxides represented by formulas (a) and (b) above are - formula% formula% [wherein R1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms N] R2 and R7 are hydrogen atoms or methyl groups N R
e is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R3,
R4, RA, and R11 are each an alkyl group having 1 to 4 carbon atoms, and RISlRlo is an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or an alkyl group having 3 carbon atoms.
-12 cycloalkyl groups, m is 1 or 2, and n is 0, 1 or 2.

Examples of the radical (co)polymerizable organic peroxide represented by the general formula (a) include t-butylperoxyacryloyloxyethyl carbonate, t-amylperoxyacryloyloxyethyl carbonate, and t-hexylperoxyacrylate. (royloxyethyl carbonate), 1.1
, 3.3-Tetramethylbutylperoxyacryloyloxyethyl carbonate, cumylperoxyacryloyloxyethyl carbonate, p-isopropylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-
Amylperoxyacryloyloxyethyl carbonate, 1.1,3゜3-tetramethylbutylperoxymethacryloyloxyethyl carbonate, cumylperoxymethacryloyloxyethyl carbonate, p-isobrobylperoxymethacryloyloxyethyl carbonate, t-butylperoxy acryloyloxyethoxyethyl carbonate, t-amylperoxyacryloyloxyethoxyethyl carbonate, t-hexylperoxyacryloyloxyethoxyethyl carbonate), 1,
1,3゜3-Tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate, cumylperoxyacryloyloxyethoxyethyl carbonate, p-isopropylperoxyacryloyloxyethoxyethyl carbonate, t-butylperoxymethacryloyloxyethoxyethyl carbonate, t -amylperoxyacryloyloxyethoxyethoxyethyl carbonate, t-hexylberoxymethacryloyloxyethoxyethyl carbonate, 1,1,3.3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate,
Cumylperoxyacryloyloxyethoxyethoxyethyl carbonate, p-isopropylperoxyacryloyloxyethoxyethyl carbonate, t-butylperoxyacryloyloxyisopropyl carbonate, t-amylperoxyacryloyloxyisopropyl carbonate, t-hexylperoxyacryloyloxyisopropyl carbonate, 1,1,3.3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate, cumylperoxyacryloyloxyisopropyl carbonate, p-isopropylperoxyacryloyloxyisopropyl carbonate, t-butylperoxymethacryloyloxyisopropyl carbonate, 1-amylperoxyacryloyloxyisopropyl carbonate, t-hexylperoxyacryloyloxyisopropyl carbonate, 1゜1.3.3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate, cumylperoxyacryloyloxyisopropyl carbonate , p-isopropylperoxyacryloyloxyisopropyl carbonate, and the like.

Furthermore, as a compound represented by formula (b), t
-Butylperoxyallyl carbonate, t-amylperoxyallyl carbonate, t-hexylperoxyallyl carbonate, 1.1.3.3-tetramethylbutylperoxyallyl carbonate, p-menthane peroxyallyl carbonate, cumylperoxyallyl carbonate, t- -butylperoxymethallyl carbonate, t-amylperoxymethallyl carbonate, t-
Hexylperoxymethallyl carbonate, 1,1.3
．． 3-tetramethylbutylperoxymethallyl carbonate, p-menthane peroxymethallyl carbonate,
Cumylperoxymethallyl carbonate, t-butylperoxyallyloxyethyl carbonate, t-amylperoxyallyloxyethyl carbonate, t-butylperoxymethallyloxyethyl carbonate, t-amylperoxyallyloxyethyl carbonate, t-hexylperoxyallyloxyethyl carbonate Roxyethyl carbonate, t-butylperoxyallyloxyisopropyl carbonate,
Examples include t-amylperoxyallyloxyisopropyl carbonate, -hexylperoxyallyloxyisopropyl carbonate, t-butylperoxymethallyloxyisopropyl carbonate, t-hexylperoxymethallyloxyisopropyl carbonate, and the like.

Among them, preferred are t-butylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-butylperoxyallyl carbonate, and t-butylperoxymethallyl carbonate.

In the present invention, the above (I) + (II) + (I
0 to 150 parts by weight per 100 parts by weight of the resin component containing II)
Up to parts by weight of inorganic fillers (IV) can be included.

Examples of the above-mentioned inorganic fillers include powder-like, tabular, scaly, needle-like, spherical, hollow, and fibrous forms,
Specifically, calcium sulfate, calcium silicate, clay,
Diatomaceous earth, talc, alumina, silica sand, glass powder, iron oxide,
Metal powder, graphite, silicon carbide, silicon nitride, silica,
Powder-like fillers such as boron nitride, aluminum nitride, and carbon black; Flat or scaly fillers such as mica, glass plates, sericite, pyrolite, metal foils such as aluminum flakes, and graphite; glass balloons, metal balloons, Examples include hollow fillers such as glass balloons and pumice; mineral fibers such as glass fibers, carbon fibers, graphite fibers, whiskers, metal fibers, silicon carbide fibers, asbestos, and wostonite.

If the blending amount of the filler exceeds 150 parts by weight, the mechanical strength such as impact strength of the molded article will decrease, which is not preferable.

In addition, the surface of the inorganic filler contains stearic acid, oleic acid,
It is preferable to perform surface treatment using palmitic acid or a metal salt thereof, paraffin wax, polyethylene wax or a modified product thereof, an organic silane, an organic borane, an organic titanate, or the like.

The thermoplastic resin composition of the present invention comprises the above (1)+(II)
+ Produced by melt-mixing (III) at a temperature of 200 to 350°C, preferably 200 to 320°C.

The melt-mixing method can be carried out using a commonly used kneading machine such as a mixing roll, a Banbury mixer, a Nigu mixer, a kneading extruder, a twin-screw extruder, or a roll. Regarding the order of melt-mixing, all components may be melt-mixed at the same time, or polyamide resin (I) or polyarylate resin (II) and multilayer thermoplastic resin (I) may be melt-mixed in advance.
After melt-mixing with II), it may be melt-mixed with another resin.

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, antioxidants, ultraviolet inhibitors, lubricants, dispersants, etc., without departing from the gist of the present invention. Additives such as foaming agents, foaming agents, crosslinking agents, and coloring agents may be added.

The present invention includes the following embodiments.

(1) The epoxy group-containing olefin copolymer contains 60 to 99.5% by weight of ethylene, 40 to 0.5% by weight of glycidyl (meth)acrylate, and 0 to 39% of other unsaturated monomers.
The thermoplastic resin composition according to claim 1, which is a copolymer containing 5% by weight.

(2) The multilayer thermoplastic resin contains at least one vinyl monomer and the following general formula (a) or (b) C112:C-C-0~(CH2-C1l-0), -f
l knee 0~0~C-R5III 1111 R□ ORQOR4 --------------<a)012:C-C
H* -0~(GHQ-Cto0)--C-0~0~C-
Rt.

+ 1111R,R,OR9 -------------(b) [In the formula, %R1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R2 and R7 are a hydrogen atom or a methyl group, R11
is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R3'%
R4 and Ra, Re are each an alkyl group having 1 to 4 carbon atoms, R6 and R10 are an alkyl group having 1 to 12 carbon atoms,
Phenyl group, alkyl-substituted phenyl group or carbon number 3-
12 cycloalkyl groups, m is 1 or 2, and n is 0, 1 or 2] At least one radical (co)polymerizable organic peroxide represented by Grafting precursor (B) copolymerized in the combined particles 1-100
Weight%, epoxy group-containing olefin copolymer (A) 0 to 99% by weight, and vinyl-based (co)polymer (C) obtained by (co)polymerizing at least one vinyl monomer 0 to 93% by weight % of a mixture and/or a grafted product.

(3) The vinyl monomer is a vinyl aromatic monomer, (meth)
The thermoplastic resin composition according to claim 1, characterized in that the thermoplastic resin composition is one or more vinyl monomers selected from the group consisting of acrylonitrile monomers and vinyl ester monomers.

(4) The vinyl (co)polymer contains 5 of the vinyl monomers.
The thermoplastic resin set and acid product according to claim 1, wherein 0% by weight or more is comprised of a vinyl aromatic monomer.

(5) The radical (co)polymerizable organic peroxide has the following general formula (a) or (b) CHa"C-C-0~(C1lla-CH-0), -C
-0~0~C-ReIII 11
11Rs OR20R4 -------------(a) Ck=C-CH2-0~(CH2-CH-0)n-C-
0-0-C-R+.

Rs R70Re---
-=------(b) [In the formula, RI is a hydrogen atom or an alkyl a having 1 to 2 carbon atoms, R1 and R7 are a hydrogen atom or a methyl group, and Re is a hydrogen atom or an alkyl having 1 to 4 carbon atoms. group, R3, R4
and Ra and Re each represent an alkyl group having 1 to 4 carbon atoms, R6 and R1° each represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms, m is 1 or 2, and n is 011 or 2. The thermoplastic composition according to claim 2, wherein the composition is one or a mixture of two or more peroxycarbonate compounds. manufacturing method.

(6) Vinyl monomer is vinyl aromatic monomer, (meth)
Production of a thermoplastic resin composition according to claim 2, characterized in that it is one or more vinyl monomers selected from the group consisting of acrylonitrile monomers and vinyl ester monomers. Method.

(7) The epoxy group-containing olefin copolymer contains 60 to 99.5% by weight of ethylene and 40 to 0.5% by weight of glycidyl (meth)acrylate, 0 to 3B of other unsaturated monomers,
3. The method for producing a thermoplastic resin composition according to claim 2, wherein the copolymer contains 5% by weight.

(8) The vinyl (co)polymer contains 5 of the vinyl monomers.
3. The method for producing a thermoplastic resin composition according to claim 2, wherein 0% by weight or more is comprised of a vinyl aromatic monomer.

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

! (Manufacture of multilayer thermoplastic resin (III)) 2,500 g of pure water was placed in a stainless steel autoclave with a capacity of 5 mm, and 2.5 g of polyvinyl alcohol was added as a suspending agent.
was dissolved. In this, 00 g of ethylene/methacrylic acid copolymer (glycidyl methacrylate content: 15% by weight) "Product name: Rexval J-3700J [: manufactured by Nippon Petrochemicals Co., Ltd.]" was added as an epoxy group-containing olefin copolymer. Dispersion was carried out by stirring under a nitrogen atmosphere.

Benzoyl peroxide as another radical polymerization initiator "Product name Niper BJ [manufactured by NOF Corporation] 1
．． 5g1 t- as a radical (co)polymerizable organic peroxide
6 g of butylperoxymethacryloyloxyethyl carbonate was dissolved in 300 g of styrene as a vinyl monomer, and this solution was poured into the autoclave and stirred.

Next, the autoclave was heated to 60 to 65°C and stirred for 2 hours to mix the vinyl monomer containing the radical polymerization initiator and the radical (co)polymerizable organic peroxide into the epoxy group-containing olefin copolymer. impregnated with. Next, the total amount of the impregnated vinyl monomer, radical (co)polymerizable organic peroxide, and radical polymerization initiator is
After confirming that the content is 0% by weight or more, 80~8%
The temperature was raised to 5° C. and maintained at this temperature for 7 hours to complete polymerization, followed by washing with water and drying to obtain a grafted precursor (A).

The styrene polymer of this grafted precursor was extracted with ethyl acetate, and the number average degree of polymerization was measured by GPC.
It was 00.

Next, this grafted precursor was extruded at 200° C. using a Laboplast Mill-axial extruder “Gen Toyo Seiki Seisakusho Co., Ltd.” to cause a grafting reaction, thereby obtaining a multilayered thermoplastic resin (IIf).

When this multilayered thermoplastic resin was observed using a scanning electron microscope (trade name: JEOL JSM T300J [manufactured by JEOL Ltd.), the particle size was 0.3 to 0.
It was a multilayered thermoplastic resin in which 4 μm true spherical resin was uniformly dispersed.

Nylon 6/6 [Amilan CM3001-N manufactured by Toshiku Co., Ltd.] as a disaster & epolyamide resin, reduced viscosity 0.85d 17
The polyarylate of g [obtained from bisphenol A/terephthalic acid/isophthalic acid (molar ratio of terephthalic acid/isophthalic acid 50150)] and the multilayer structure thermoplastic resin (III) obtained in Reference Example in the proportions shown in Table 1 The mixture was melted and mixed. The melt mixing method uses a cylinder temperature of 280°C.
The mixture was supplied to a co-directional twin-screw extruder (manufactured by Plastic Engineering Research Institute Co., Ltd.) with a screw diameter of 30 cm, and melt-mixed in the cylinder.

The mixed resin was granulated, dried at 150° C. for 3 hours, and then injection molded into test pieces.

The size of the test piece and the test method are as follows.

Izotsu impact value (with notch): 13mmXG5mmXG+wm (JIS K71
10) Load deflection temperature 13imX130mmX6mm (JIS K7
207) Bending strength 1010mmX130X4mm (JIS KI
li75B) Layer peeling state: Observe the fractured surface of the molded product,
Ranked as follows:

◎: No peeling at all O: Slight peeling of solder ×: Peeling (marked below) Fruit 1st 1L: The grafted multilayer thermoplastic resin of the above example was obtained in the reference example. Table 2 shows examples in which the grafted precursor was used.

This case also shows the same effect as the grafted multilayer thermoplastic resin.

~ In addition to the above examples, the average fiber length is 5. hm, diameter l
Table 3 shows an example in which Oμ intestinal glass fiber was blended.

Table 4 shows examples using acid anhydride-modified polyethylene and ethylene/glycidyl methacrylate copolymer, in addition to the above examples.

Table 3 [Effects of the Invention] The thermoplastic resin composition of the present invention is a resin composition with improved heat resistance, impact resistance, moldability, electrical properties, and chemical resistance. It has the characteristic that it can be easily manufactured by simply mixing it.

Patent applicant: Nippon Petrochemical Co., Ltd. May 10, 1999 1. Indication of the case: 1988 Patent Application No. 97649 2. Name of the invention: Thermoplastic resin composition and its manufacturing method 3. Relationship Name of applicant: Nippon Petrochemical Co., Ltd. 4, agent address: 1-1-5, Minami-Aoyama-chome, Minato-ku, Tokyo, date of amendment order (voluntary): Showa date: 7, content of amendment (1) Patent claim Correct the range as shown in the attached sheet.

■ In the description, on the following page and line, "multilayer" is corrected to "polymorphic".

Page row 6 11-12 20 13, 15 3f3 2.3.7, 1439
2.4 ■ Same as above, on page 6, line 15, "monomer" is corrected to "monomer".

(2) "Olefin alone" on page 15, line 5 is corrected to "olefin alone".

■ "Olefin polymer" in line 8 of the same page is corrected to "olefin homopolymer or copolymer."

■ "To the present invention" in the first line of page 18 is deleted.

■ "Polycarbonate resin and" from line 16 to line 17 on page 17 are deleted.

■ On the same page, line 17, "polyoxymethylene" is corrected to "polyarylate."

■ In the same text, page 18, lines 11 to 12, "consisting of. Therefore" is corrected to "and."

(lO) In the same page, line 13, ``1%'' is corrected to ``consists of 1%''.

(11) Same, page 20, lines 8 and 13, change “kneading” to “
"Kneading," he corrected.

(12) Same, on the following page and line, "p-isopropylperoxy" is corrected to "p-isopropylcumylperoxy".

Page row 22 16-17 23 3-4, 13 24 2-3, 11-12 (I3) same,
Insert the following sentence between lines 16 and 17 on page 26.

In the present invention, the amounts of (I) and (II) are selected depending on the intended use of the composition.

That is, if the purpose is to maintain the characteristics of polyamide resin while improving its drawbacks of water absorption and heat resistance, the polyamide resin should be used in an amount of 50 to 99% by weight, preferably 60 to 95% by weight.
is necessary.

The reason is that if the polyamide resin is less than 50% by weight, the moldability, mechanical properties, and impact resistance, which are the characteristics of polyamide resin, will be impaired, and if it exceeds 99% by weight, the water absorption, which is one of the objectives of the present invention, will be impaired. This is because there is no effect of improving heat resistance.

Further, if the purpose is to improve the impact resistance, which is a drawback of polyarylate resin while maintaining its characteristics, the polyarylate resin needs to be contained in an amount of 50 to 99% by weight, preferably 60 to 95% by weight.

If the polyarylate resin is less than 50% by weight, the heat resistance and dimensional stability of the polyarylate resin cannot be exhibited, and if it exceeds 99% by weight, there is no effect of improving impact resistance, which is one of the objectives of the present invention, and this is not preferred. .

The multiphase structured thermoplastic resin of the present invention has (I)+(II)1
It can be used in an amount of 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight.

If 0.1 part by weight of the multiphase thermoplastic resin is not grooved, it is not preferable because there is no compatibilizing effect, the impact strength decreases, and delamination occurs in the molded product, deteriorating the appearance. Also, 100
If the amount exceeds 1 part by weight, the heat resistance of the composition decreases, which is not preferable. ” (14) “Copolymer (
"A)" is corrected to "Copolymer (B)."

(15) In the same page, line 8, “or grafted product” is changed to “
or a grafted product obtained by melt-mixing them.”

(1B) Same, page 33, line 9, “thermoplastic composition” is changed to “
"Thermoplastic resin composition" is corrected.

(17) Ibid., page 35, line 13, “becomes more than that” is 1
That’s all,” he corrected.

(18) Table 1 on page 38 and Table 3 on page 41 are corrected as shown in the attached sheet.

Above 2, Claims (1) (I) 99-1% by weight of polyamide resin, (II)
1-99% by weight of polyarylate resin and the above (I) +
(III) epoxy group-containing olefin copolymer 5 to 85 to (II) too parts by weight
% by weight and 85 to 5% by weight of a vinyl-based (co)polymer obtained from at least one vinyl monomer, one of the (co)polymers forming a dispersion with a particle size of o, oot to lOμm. 0.1-100 parts by weight of a multiphase-structured thermoplastic resin, and 0-150 parts by weight of (IV) an inorganic filler based on the above (I) + (II) + (III) too parts by weight. A thermoplastic resin composition.

(2) Adding at least one type of vinyl monomer, at least one type of radical (co)polymerizable organic peroxide, and a radical polymerization initiator to an aqueous suspension of an epoxy group-containing olefin copolymer; The olefin copolymer is impregnated with the vinyl monomer, the radical (co)polymerizable organic peroxide, and the radical polymerization initiator by heating under conditions that do not substantially cause decomposition of the epoxy base. When the percentage reaches above the initial 50% by weight, the temperature of the aqueous suspension is increased to dissolve the vinyl monomer and radicals (
Co) Grafting precursor (A) obtained by copolymerizing a polymerizable organic peroxide in an epoxy group-containing olefin copolymer
1 to 100% by weight, an epoxy group-containing olefin copolymer (B) 0 to 99% by weight, and a vinyl (co)polymer (C) obtained by polymerizing at least one type of vinyl polymer (C) 0 to 99% by weight. 99% by weight of polyamide resin (I) and polyarylate resin (II)
) or preliminarily melt-mix with (A), (B) and (C).
) are melt-mixed in the range of 100 to 300'C17) to obtain a multiphase structured thermoplastic resin (III).
A method for producing a thermoplastic resin composition comprising melt-mixing with I).

Table 3

Claims (2)

[Claims] (1) (I) 99-1% by weight of polyamide resin, (II)
1 to 99% by weight of polyarylate resin and the above (I)+
(III) 5 to 95% by weight of an epoxy group-containing olefin copolymer and 35 to 5% by weight of a vinyl (co)polymer obtained from at least one vinyl monomer based on 100 parts by weight of (II). , on the other hand (
Co) 0.1 to 100 parts by weight of a multilayer thermoplastic resin in which the polymer forms a dispersed layer with a particle size of 0.001 to 10 μm, and 100 parts by weight of the above (I) + (II) + (III). In contrast, (IV) a thermoplastic resin composition containing 0 to 150 parts by weight of an inorganic filler. (2) Adding at least one vinyl monomer, at least one radical (co)polymerizable organic peroxide, and a radical polymerization initiator to an aqueous suspension of an epoxy group-containing olefin copolymer; The vinyl monomer, the radical (
Co) A polymerizable organic peroxide and a radical polymerization initiator are impregnated into an epoxy group-containing olefin copolymer, and when the impregnation rate reaches the initial 50% by weight or more, the temperature of this aqueous suspension is raised. , vinyl monomer and radical (co)
Grafting precursor (A) 1-1 obtained by copolymerizing a polymerizable organic peroxide in an olefin copolymer containing an epoxy group
00% by weight, 0 to 1% by weight of an epoxy group-containing olefin copolymer (B), and 0 to 39% by weight of a vinyl (co)polymer (C) obtained by polymerizing at least one vinyl monomer. , polyamide resin (I) and polyarylate resin (II)
) or preliminarily melt-mix with (A), (B) and (C).
) at a temperature of 100 to 300°C to obtain a multiphase thermoplastic resin (III), which is then melt-mixed with (I) and (II).