JPH01113456A - Thermoplastic resin composition and its production - Google Patents

Abstract

PURPOSE:To make it possible to form a thermoplastic resin composition excellent in moldability, heat resistance, impact resistance, etc., by mixing an aromatic polyester resin with a polycarbonate resin with the aid of a specified multiphase-structure thermoplastic resin as a compatibilizer. CONSTITUTION:This thermoplastic resin composition comprises 99-1wt.% aromatic polyester resin (A), 1-99wt.% polycarbonate resin (B), and 0.1-100pts. wt., per 100 pts.wt. in total of components A and B, multiphase-structure thermoplastic resin (C) which comprises 5-95wt.% epoxy group-containing olefin copolymer and 95-5wt.% vinyl (co)polymer obtained from at least one vinyl monomer and in which either (co)polymer forms a dispersed phase of a particle diameter of 0.001-10mum and 0-150 pts.wt., per 100 pts.wt. in total of components A, B and C, inorganic filler (D).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a thermoplastic resin composition with excellent heat resistance and impact resistance, and is applicable in a wide range of fields such as automobile parts, electrical and electromechanical parts, etc. It is used.

[Prior Art] Aromatic polyester resins have excellent properties such as moldability, chemical resistance, dimensional stability, and weather resistance, and are widely used in various molded products. However, the deflection temperature under load was low and there was a problem with heat resistance, which sometimes limited its use.

On the other hand, although polycarbonate resin has excellent characteristics such as heat resistance and mechanical properties, improvements in moldability, chemical resistance, etc. are desired.

If thermoplastic resins with even more excellent characteristics can be obtained by compensating for the respective disadvantages of aromatic polyester resins and polycarbonate resins with other advantages, new uses can be expected to open up.

[Problems to be Solved by the Invention] However, aromatic polyester and polycarbonate resin have different chemical structures and therefore have extremely poor compatibility.To improve this, for example, Japanese Patent Application Laid-Open No. 60-231757 discloses glycidyl. A method using group-containing copolymers is disclosed. According to this method, it is said that a composition with high impact strength and little decrease in dry heat deterioration resistance can be obtained, but if the stability of the product is increased by roughly reducing the decrease in impact strength due to heat treatment, It is possible to expand the range of uses.

[Means for solving the problems] As a result of intensive research to solve the above problems, the present invention has been made based on the following:
By blending a specific multiphase thermoplastic resin with aromatic polyester resin and polycarbonate resin as a compatibilizer, the compatibility between aromatic polyester resin and polycarbonate resin is improved, resulting in excellent moldability of aromatic polyester resin. We have now completed a thermoplastic resin composition that has both impact resistance and chemical resistance and the excellent heat resistance and mechanical properties of polycarbonate resin.

That is, the first invention of the present invention comprises (I) 99 to 1% by weight of an aromatic polyester resin, (II) 1 to 99% by weight of a polycarbonate resin, and based on 100 parts by weight of the above (I) + (II). , (III)-Epoxy group-containing olefin copolymers 5 to 9
5% by weight and 95-5% by weight of a vinyl-based (co)polymer obtained from at least one vinyl monomer, one (co)polymer being a dispersed phase with a particle size of o, ooi ~ 10 μm. 0.1 to 100 parts by weight of a thermoplastic resin with a multiphase structure forming the composition, and 0 to 150 parts by weight of an inorganic filler (rV) per 100 parts by weight of the above (I) + (II) + (III). It is a thermoplastic resin composition made by blending.

Furthermore, a second invention includes 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. In addition, the vinyl monomer, the radical (co)polymerizable organic peroxide, and the radical polymerization initiator are converted into an 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 this aqueous suspension is increased to combine the vinyl monomer and the radical (co)polymerizable organic peroxide. Grafting precursor (A) 1 to 100 copolymerized in an epoxy group-containing olefin copolymer
Weight %, epoxy group-containing olefin copolymer (B) 0-
99% by weight and 0 to 99% by weight of vinyl (co)polymer (C) obtained by polymerizing at least one vinyl monomer are melted with aromatic polyester resin (I) and polycarbonate resin (II). (A) and (B) in advance.
) and (C) are melt-mixed at a temperature of 200 to 300°C to obtain a multi-phase structure thermoplastic resin (I This is the manufacturing method.

The aromatic polyester resin (I) used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and is composed of aromatic dicarbon II (or its ester-forming derivative) and diol (or its ester-forming derivative). It is a polymer or copolymer obtained by a condensation reaction containing as a main component.

The aromatic dicarboxylic acids mentioned here include terephthalic acid,
Isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1.5-naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-dicarboxylic acid Examples include acids or ester-forming derivatives thereof.

Diol components include aliphatic diols having 2 to 10 carbon atoms, ie, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-bentanediol, 1,6-hexanediol, and decamethylene glycol. Diglycol, cyclohexanediol, etc., or molecular weight 400-6.0
00 long steel glycols, such as polyethylene glycol, poly-1J3-propylene glycol, polytetramethylene gelcol, etc., and mixtures thereof.゛Specifically, preferred aromatic polyester resins used in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene-2.6-naphthalate, and polyethylene-1.2-bis. Examples include (phenoxy)ethane-4,4-monodicarboxylate. More preferred are polyethylene terephthalate and polybutylene terephthalate.

The intrinsic viscosity of these thermoplastic aromatic polyesters is trifluoroacetic acid 1 (25>/methylene chloride (75) 100
Measured at 25±0.1° C. as a concentration of 0.32 g in rl. Preferably, the intrinsic viscosity is 0.4 to 4. Odj)
/g. If it is less than 0.4 dl110, the aromatic polyester will not be able to exhibit sufficient mechanical strength, which is not preferable.

4 again.

If it exceeds 0dll/Q, the fluidity during melting will decrease,
This is not preferred because the surface gloss of the molded product decreases.

The polycarbonate resin (II> used in the present invention is 4
．． 4,4-dioxydiallylalkane polycarbonate including 4-dihydroxydiphenyl-2,2-propane (commonly known as bisphenol), but especially 4,4-dihydroxydiphenyl-2,2-propane polycarbonate. , number average molecule n15.000
-so, ooo are preferred. These polycarbonates are manufactured by any method. For example, 4, 4-
For the production of dihydroxydiphenyl-2,2-10pan polycarbonate, 4,4-dihydroxydiphenyl-2 is used as the dioxy compound.

A method of producing phosgene using 2-propane in the presence of an aqueous caustic alkali solution and a solvent, or 4
, 4-dihydroxydiphenyl-2.

An example of the method is a method of transesterifying 2-propane and a carbonic acid diester in the presence of a catalyst.

The epoxy group-containing olefin copolymer in the multiphase thermoplastic resin used in the present invention is, in part, a binary copolymer of an olefin and an unsaturated glycidyl group-containing monomer produced by high-pressure radical polymerization, or It is a ternary or multi-component copolymer of an olefin, an unsaturated glycidyl group-containing monomer, and other unsaturated monomers, and the olefin in the copolymer is particularly preferably ethylene, with ethylene having 60 to 99
．． A copolymer containing 5% by weight of glycidyl group-containing monomers, 0.5 to 40% by weight of glycidyl group-containing monomers, and 0 to 39.5% by weight of other unsaturated monomers is preferred.

The unsaturated glycidyl group-containing monomers include glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, monoglycidyl butene tricarboxylate, diglycidyl butene tricarboxylate ester triglycidyl rubonate, and α-chloroallyl, Examples include glycidyl esters such as maleic acid, crotonic acid, and fumaric acid, glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, glycidyloxyethyl vinyl ether, styrene-p-glycidyl ether, and p-glycidyl styrene. Preferred examples include glycidyl methacrylate and acrylic glycidyl ether.

Other unsaturated monomers include at least one monomer selected from olefins, vinyl esters, α,β-ethylenically unsaturated carboxylic acids or derivatives thereof, and specifically propylene, butene, etc. -1, hexene-1,
Olefins such as decene-1, octene-1, and styrene, vinyl esters such as vinyl acetate, vinyl propionate, and vinyl benzoate, acrylic acid, methacrylic acid, methyl and ethyl acrylic acid or methacrylate,
Esters such as propyl, butyl, 2-ethylhexyl, cyclohexyl, dodecyl, octadecyl, maleic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid monoesters and diesters, vinyl chloride,
Examples include vinyl ethers such as vinyl methyl ether and vinyl ethyl ether, and acrylic acid amide compounds, with acrylic esters being particularly 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 these, preferred are ethylene/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 ethylene 60-99, 5% by weight,
One or more unsaturated glycidyl group-containing monomers 0.5-40
% heavy, at least one other unsaturated monomer 0-39.
A monomer mixture of 5% by weight was polymerized at a polymerization pressure of 500-y 4.000 Kg/cd in the presence of a radical polymerization initiator of 0,0001 to 1% by weight based on the total weight of all their monomers.
, preferably 1.000 to 3.500 Kg/cd1 reaction humidity 50 to 400°C, preferably 100 to 350'C, in the presence of a chain transfer agent and optionally an auxiliary agent, seed type or tube type reaction. This is a method in which the monomers are brought into contact and polymerized simultaneously or in stages in a vessel.

Examples of the radical polymerization initiator include conventional initiators such as peroxides, hydroperoxides, azo compounds, amine oxide compounds, and oxygen.

In addition, as a chain transfer agent, hydrogen, propylene, butene-1
, 01 to C2o or higher, such as methane, ethane, propane, butane, isobutane, n-hexane, n-heptane, cycloparaffins, chloroform and carbon tetrachloride, C1 to C2o or higher saturated aliphatic alcohols such as methanol, ethanol, propatool,
and isopropanol, C1-C2o or higher saturated aliphatic carbonyl compounds such as carbon dioxide, acetone and methyl ethyl ketone, and aromatic compounds such as toluene, diethylbenzene and xylene.

The epoxy group-containing olefin copolymers of the present invention include homopolymers such as low density, medium density, and high density polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, ethylene-propylene copolymers, Ethylene-
With other α-olefins whose main component is ethylene, such as butene-1 copolymer, ethylene-hexene-1 copolymer, ethylene-4-methylpentene-1 copolymer, and ethylene-octene-1 copolymer. copolymers of propylene with other α-olefins, such as propylene-ethylene block copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic Acid copolymers, copolymers of ethylene and esters of acrylic acid or methacrylic acid such as methyl, ethyl, propyl, isopropyl, butyl, ethylene-
Maleic acid copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, liquid polybutadiene, ethylene-vinyl acetate-vinyl chloride copolymer and mixtures thereof, or synthetic resins different from these, or Mixtures with rubber are also included in the invention.

Specifically, the vinyl-based (co)polymer in the multiphase thermoplastic resin used in the present invention includes styrene-nuclear substituted styrene, such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, and chlorstyrene. , α-substituted styrene, such as α-methylstyrene,
It is a (co)polymer obtained by mixing one or more of vinyl aromatic monomers such as α-ethylstyrene and (meth)acrylonitrile monomers.

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

The particle size of the dispersed polymer is 0.001 to 10 μm1
Preferably 6 is 0.01 to 5 μm.

When the dispersed resin particle size is less than o, ooiμm or 1
If it exceeds 0 μm, the aromatic polyester resin and the polycarbonate resin will not be sufficiently compatible, resulting in a decrease in impact resistance and delamination.

The number average degree of polymerization of the vinyl (co)polymer in the multiphase thermoplastic resin of the present invention is 5 to io, ooo, preferably 10 to
The range is 5,000.

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 it is not preferable because the heat resistance decreases.

Moreover, if the number average degree of polymerization exceeds 10.000, the melt viscosity will increase, moldability will decrease, and surface gloss will decrease, which is not preferable.

The multiphase thermoplastic resin of the present invention has an epoxy group-containing olefin copolymer of 5 to 95%, preferably 20 to 9%.
It consists of 0% by weight. Therefore, vinyl (
The co)polymer has a weight R% of 95 to 5%, preferably 80 to 10% by weight.

If the content of the epoxy group-containing olefin copolymer is less than 5%, the effect of improving impact resistance will be insufficient, which is not preferable.

Moreover, if the epoxy group-containing olefin copolymer exceeds 95% by weight, the heat resistance and dimensional stability of the thermoplastic resin composition of the present invention will be impaired, which is not preferable.

The grafting method for producing the multiphase thermoplastic resin of the present invention may be any generally well-known method such as chain transfer method or ionizing radiation irradiation method, but the most preferred method is as shown below. It depends on the method. The reason for this is that the grafting efficiency is high and secondary aggregation due to heat does not occur, so performance is more effective.

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

That is, 100 parts by weight of an epoxy group-containing olefin copolymer is suspended in water, and 5 to 400 parts by weight of at least one type of vinyl monomer is added to the following general formula (a) or (b).
) 1 of the radical (co)polymerizable organic peroxide represented by
A radical polymerization initiator whose decomposition temperature is 40 to 90°C to obtain a half-life of 10 hours, in which the species or a mixture of two or more species is used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the vinyl monomer. A solution in which 0.01 to 5 parts by weight of the vinyl monomer and the radical (co)polymerizable organic peroxide are dissolved is added to 100 parts by weight in total, and the radical polymerization initiator is substantially decomposed. vinyl monomer,
When an epoxy group-containing olefin copolymer is impregnated with a radical (co)polymerizable organic peroxide and a radical polymerization initiator, and the impregnation rate reaches the initial 50i11% or more,
The temperature of this aqueous suspension is raised to copolymerize the vinyl monomer and the radically (co)polymerizable organic peroxide in the epoxy group-containing olefin copolymer to form a grafting precursor (
A) is obtained. This grafted precursor is also a multiphase thermoplastic. Therefore, this grafted precursor (A)
may be directly melt-mixed with aromatic polyester resin and polycarbonate resin.

The multiphase thermoplastic resin of the present invention can also be obtained by kneading the grafted precursor (A) while melting at 100 to 300°C. At this time, the grafting precursor (A>
A multiphase thermoplastic resin can also be obtained by separately mixing an epoxy group-containing olefin copolymer or a vinyl (co)polymer and kneading the mixture while melting. The most preferred is a multi-phase structured thermoplastic resin obtained by kneading a grafting precursor - the radical (co)polymerizable organic peroxide represented by the general formula (a) is represented by the general formula %) [In the formula, R is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R2 is a hydrogen atom or a methyl group, R3 and R4 are each an alkyl group having 1 to 4 carbon atoms, and R5 is an alkyl group having 1 to 4 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, m
is 1 or 2. ] This 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 general formula (% 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, R8 and R9 are each an alkyl group having 1 to 4 carbon atoms, and R is a methyl 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, and n is 0, 1 or 2. ] This is a compound represented by

Examples of the radical (co)polymerizable organic peroxide represented by the general formula (a) include t-amylberoxyacryloyloxyethyl carbonate and t-amylberoxyacryloyloxyethyl carbonate. , t-hexylperoxyacryloyloxyethyl carbonate, 1.1
．． 3.3-Tetramethylbutylperoxyacryloyloxyethyl carbonate, cumylperoxyacryloyloxyethyl carbonate, p-isopropylcumylperoxyacryloyloxyethyl carbonate, t-butylberoxymethacryloyloxyethyl carbonate, t-amylber Oxymethacryloyloxyethyl carbonate, t-hexylperoxyacryloyloxyethyl carbonate, 1.1.3.3-detramethylbutylperoxymethacryloyloxyethyl carbonate,
cumylberoxymethacryloyloxyethyl carbonate, p-isopropylcumylperoxyacryloyloxyethyl carbonate, t-butylperoxyacryloyloxyethoxyethyl carbonate, t-amylperoxyacryloyloxyethoxyethyl carbonate,
t-hexylperoxyacryloyloxyethoxyethoxyethyl carbonate, 1.1.3.3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate, cumylberoxyacryloyloxyethoxyethyl carbonate, p-isobrobylcumylperoxiethyl carbonate Chryloyloxyethoxyethoxyethyl carbonate, t-butylperoxyacryloyloxyethoxyethoxyethyl carbonate, t-amylperoxyacryloyloxyethoxyethyl carbonate, t-hexylperoxyacryloyloxyethoxyethyl carbonate, 1.1゜3.3-
Detramethylbutylberoxymethacryloyloxyethoxyethoxyethyl carbonate, cumylberoxymethacryloyloxyethoxyethoxyethyl carbonate, p-isopropylcumylberA゛xymethacryloyloxyethoxyethoxyethyl carbonate-1~, t-butylperoxyacryloyloxyisopropyl carbonate, t-amylperoxyacryloyloxyisopropyl carbonate, t-hexylperoxyacryloyloxyisopropyl carbonate, peroxyacryloyloxyisopropyl carbonate, cumylperoxyacryloyloxyisopropyl carbonate, p-isobrobylcumylperoxyacryloyl Roxyisobutyl carbonate, t-butylperoxymethacryloyloxyisopropyl carbonate,
t-7 milberoxymethacrylate, t-hexylperoxyacryloyloxyisopropyl carbonate, 1.1.3.3-detramethylbutylperoxymethacryloyloxyisopropyl carbonate, cumylperoxyacryloyloxyisopropyl carbonate, p-isobrobylcumylberoxymethacryloyloxyisopropyl carbonate, and the like.

Furthermore, as a compound represented by general formula (b), t
-butylperoxyallyl carbonate, t-amylperoxyallyl carbonate, t-hexylperoxyallyl carbonate 3,3-tetramethylbutylperoxyallyl carbonate, p-menthane peroxyallyl carbonate t-butylperoxymethallyl carbonate - amylperoxymethallyl carbonate, t-hexylperoxymethallyl carbonate 1,3.3-tetramethylbutylperoxymethallyl carbonate, p-menthamberoxymethallyl carbonate, cumylperoxymethallyl carbonate tyl carbonate, t-amylperoxyallyloxyethyl carbonate, t-Hexylperoxyaryloxyethyl carbonate, t-butylberoxymethallyloxyethyl carbonate, 1-amylberoxymethacryloyloxyethyl carbonate, t-hexylperoxyacryloyloxyethyl carbonate, t-butylberoxyacryloyloxyisobro building carbonate,
t-amylperoxyallyloxyisopropyl carbonate, t-butylperoxyallyloxyisopropyl carbonate, t-butylberoxymethacryloxyisopropyl carbonate, t-
Examples include amylperoxymethacryloyOxyisopropyl carbonate, t-hexylperoxymethacryloyyOxyisopropyl carbonate, and the like.

Among them, t-butylperoxyacrylic O
yloxyethyl carbonate, t-butylberoxymethacryloyloxyethyl carbonate, t-butylperoxyallyl carbonate: t-butylperoxymethallyl carbonate.

In the present invention, the front &! (I)+ (II)+ (II
O to 150 parts by weight of the inorganic filler (IV) can be blended with 100 parts by weight of the resin component containing I).

Examples of the above-mentioned inorganic fillers include powder-like, tabular, scaly, acicular, spherical or hollow, and fibrous, and specific examples include calcium sulfate, calcium silicate, clay, diatom, talc, alumina, Powder-like fillers such as silica sand, glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon black, etc.: mica, glass plate, sericite, bi-0 fluorite, aluminum flakes metal foils, flat or scale-like fillers such as graphite Nijiras balloons, metal balloons, glass balloons, hollow fillers such as pumice, glass fibers, carbon Ill, graphite fibers, whiskers, gold Ia miscellaneous, silicone carbon Examples include bite fibers, asbestos, and mineral fibers such as wolstonite.

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

In addition, the surface of the inorganic filler is treated with stearic acid, oleic acid, palmitic acid or their metal salts, paraffin wax, polyethylene wax or modified products thereof, organic silane, organic borane, organic titanate, etc. It is preferable to apply

The thermoplastic composition of the present invention is produced by melting and mixing an aromatic polyester resin and a polycarbonate resin at a temperature in the range of 200 to 300°C.

The melt-mixing order may be such that all the components are melt-mixed at the same time, or after the aromatic polyester resin or polycarbonate resin and the multiphase thermoplastic resin are melt-mixed in advance,
It may be melt-mixed with another resin.

The melt-mixing method can be carried out using a commonly used kneading machine such as a Banbury mixer-1 pressure kneader-1 kneading extruder, a twin-screw extruder, or a mixing roll.

In the present invention, other thermoplastic resins such as polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins,
Polyamide resin, polyphenylene sulfide resin,
Porsulfone resin, natural rubber, synthetic rubber, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, organic flame retardants such as halogen-based and phosphorus-based, organic flame retardants such as metal powder, talc, glass fiber, carbon fiber, and wood powder. Alternatively, additives such as inorganic fillers, antioxidants, ultraviolet inhibitors, lubricants, coupling agents, dispersants, foaming agents, crosslinking agents, and coloring agents may be added.

[Example] Next, the present invention will be explained in more detail with reference to Examples.

Reference example 1 [Manufacture of multiphase structure thermoplastic resin (IIIA)]
Pure water 2.5 in a stainless steel autoclave with a capacity of 51
000 was added, and 2.5 g of polyvinyl alcohol was further dissolved therein as a suspending agent. Add 700 q of ethylene/glycidyl methacrylate copolymer (containing glycidyl methacrylate 115% to 115%) as an epoxy group-containing olefin copolymer (trade name: Lexpar J-3700J (manufactured by Nippon Petrochemicals)), and Separately, benzoyl peroxide (trade name: Niper BJ (manufactured by NOF Corporation, 10 hour half-life temperature 74°C) 1.5a, radical (co)polymerizable organic 6q of t-butylperoxymethacryloxyethyl carbonate as an oxide was dissolved in 300 g of styrene as a vinyl monomer, and this solution was poured into the autoclave and stirred.The autoclave was then heated to 60 to 65°C. The vinyl monomer containing the radical polymerization initiator and the radical (co)polymerizable organic peroxide was impregnated into the epoxy group-containing ethylene copolymer by stirring at 2 hours.Then, the impregnated vinyl monomer After confirming that the total amount of polymer, radical (co)polymerizable organic peroxide, and radical polymerization initiator is at least 50% by weight, the temperature is raised to 80 to 85 ° C.
The polymerization was completed by maintaining the temperature for 7 hours, followed by washing with water and drying to obtain a grafted precursor (HA'). When the styrene polymer in this grafted precursor was extracted with ethyl acetate and the number average degree of polymerization was measured by GPC, it was found to be 390.
It was 0. Next, this grafted precursor was processed using a Labo Plast Mill-Screw Extruder [manufactured by Toyo Seiki Seisakusho Co., Ltd.] for 24 hours.
A multiphase thermoplastic resin (IIIA>) was obtained by extrusion at 0° C. and grafting reaction.

This multiphase thermoplastic resin was examined using a scanning electron microscope (rJEO).
When observed using L JSM T300J (trade name, manufactured by JEOL Ltd.), it was found to be a multiphase thermoplastic resin in which perfectly spherical resin particles with a particle diameter of 0.3 to 0.4 μm were uniformly dispersed.

At this time, the grafting efficiency of the styrene polymer was 77.
It was 1% by weight.

1 亙■ 1 [Multiphase structure thermoplastic resin 1 [Production of B] In Reference Example 1, styrene 300Q as the vinyl monomer was changed to methyl methacrylate mono-omega monomer, and n-dodecyl mercaptan 0 was used as the molecular weight regulator. Reference Example 1 was repeated except that .69 was used to obtain a multiphase structure thermoplastic resin (IIIB
) was obtained.

Examples 1 to 8 Polycarbonate resin with a number average molecular weight of 162.000, polybutylene terephthalate with an intrinsic viscosity of 3.56 J/a (
(shown as POT in the table) and the multiphase thermoplastic resin obtained in Reference Example were melt-mixed in the proportions shown in Table 1. - The melt-mixing method involved supplying the materials to a co-directional twin-screw extruder (manufactured by Plastic Engineering Research Institute Co., Ltd.) with a screw diameter of 30 em set at a cylinder temperature of 250°C, and melt-mixing within the cylinder. After the mixed resin is granulated, it is heated to 150°C.
After drying for 3 hours, test pieces were prepared by injection molding. The size of the test piece is as follows.

Izotsu impact test piece 13m+1X 651111X
61m (with notch) Load deflection temperature test piece 13mm x 130em x
6+am The test method is as follows.

(1) Izot impact value (notched): 7110 according to JIS (2) Deflection temperature under load: 7201 according to JIS For chemical resistance, observe the appearance after immersing the test piece in methanol at 75°C for 30 days. did.

Q...No change.

Δ...Cracks occur on the surface Some of it is eluted.

X: Significant surface elution.

Examples 9 to 14 Table 2 shows examples in which the grafted multiphase thermoplastic resin of the above Examples was replaced with the grafted precursor obtained in the Reference Example. This case also shows the same effect as the grafted multiphase thermoplastic resin.

Table 3 shows an example in which glass fibers having an average length of 5.0 μm and a diameter of 10 μm were added to the above examples.

Separately from the above examples, Table 4 shows examples using ethylene-glycidyl methacrylate copolymers.

Table 1 Table 2 Table 3 Table 4 *Glycidyl methacrylate content: 15% by weight [Effects of the invention] The thermoplastic resin composition of the present invention takes advantage of the respective advantages of aromatic polyester resin and polycarbonate resin,
It is a resin composition with excellent heat resistance, rain impact resistance, and adhesive properties.

Therefore, it can be widely used, for example, in automobile parts, electrical/electronic parts, industrial parts, etc.

Patent applicant: Nippon Petrochemical Co., Ltd. Procedural amendment (to the Patent Office examiner) 1. Indication of the case: Patent Application No. 271275 of 1988 2. Name of the invention Thermoplastic resin composition and its manufacturing method 3. Amendments to be made Patent applicant name Nippon Petrochemical Co., Ltd. 4, agent address 1-1-5 Minami-Aoyama-chome, Minato-ku, Tokyo, date of amendment order (voluntary) (starting address) Month, Day 6, 1939; Target of amendment 7, content of amendment (1) The scope of claims is amended as shown in the attached sheet.

(2) "Acetic acid" on page 16, line 15 of the specification is replaced with "acetic acid J
I am corrected.

(3) Add the following sentence between lines 10 and 11 on page 31.

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 aromatic polyester resin while improving its drawbacks such as impact resistance, heat resistance, and rigidity, aromatic polyester resin should be used in an amount of 50 to 99% by weight, preferably 60 to 95% by weight. is necessary.

The reason for this is that if the aromatic polyester resin is less than 50% by weight, the moldability, chemical resistance, and weather resistance, which are characteristics of aromatic polyester resin, will be impaired, and if it exceeds 99% by weight, one of the objectives of the present invention will not be achieved. This is because it does not have the effect of improving certain impact resistance, heat resistance, and rigidity.

In addition, if the purpose is to maintain the characteristics of polycarbonate resin while improving its drawbacks such as chemical resistance and weather resistance, polycarbonate resin should be used in a proportion of 50 to 99% by weight, preferably 60%.
~95% by weight is required.

If the polycarbonate resin is less than 50%, the heat resistance, impact resistance, and rigidity of the polycarbonate resin cannot be exhibited.
If it exceeds 99%, it is not preferable because it does not have the effect of improving moldability, chemical resistance, and weather resistance, which are one of the objectives of the present invention.

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

If the polyphase structure thermoplastic resin has a hanging part of less than 0.11, the compatibilization effect will be reduced! 1i It is not preferable because impact strength decreases and delamination occurs in the molded product, deteriorating the appearance. Also, 1
If it exceeds 0.00 parts by weight, the heat resistance of the composition decreases, which is not preferable. J (4) Same, page 38, lines 12 to 13, “ethylene-
"glycidyl methacrylate" is corrected to "ethylene-glycidyl methacrylate".

(5) Table 1 on page 39 of the same is corrected as shown in the attached sheet.

(6) Table 2 on page 40 of the same is corrected as shown in the attached sheet.

(7) Table 3 on page 41 of the same is corrected as shown in the attached sheet.

(8) Table 4 on page 42 of the same is corrected as shown in the attached sheet.

Above 2, Claims (1) (I) 99 to 1% by weight of aromatic polyester resin, (II) 1 to 99% by weight of polycarbonate resin, and based on 100 parts by weight of the above (I) + (I[) (III) Epoxy group-containing olefin copolymer 5 to 95
% of serious injury and 95-5% by weight of a vinyl-based (co)polymer obtained from at least one vinyl monolayer, one of the (co)polymers forming a dispersed phase with a particle size of 0.001-10 μm. 0.1 to 100 parts by weight of a thermoplastic resin with a multiphase structure, and 0 to 150 parts by weight of an inorganic filler (IV) to 100 parts by weight of the above (I) + (II) + (III). Plastic resin composition.

(2) The thermoplastic resin with a multi-phase structure comprises at least one vinyl monomer and the following general formula (a) or (b) [wherein R1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, RR is a hydrogen atom or a methyl group, 2'7 R6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R3
, R4, R8, and R9 each represent an alkyl group having 1 to 4 carbon atoms, and RR represents an alkyl group having 1 to 5 10 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 0.1 or 2. ] Grafting precursor (A) 1 to 100 in which at least one radical (co)polymerizable organic peroxide represented by is copolymerized in epoxy group-containing olefin copolymer particles.
Weight %, epoxy group-containing olefin copolymer (B) 0-
A mixture consisting of 99% by weight and 0 to 99% by weight of a vinyl (co)polymer (C) obtained by (co)polymerizing at least one vinyl monomer and/or %tl@? 11”
The thermoplastic resin composition according to claim 1, which is a grafted product formed by:

(3) 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% by weight of other unsaturated monomers.
Claims 1 to 5 are copolymers consisting of 5% by weight.
Thermoplastic resin composition according to any one of Item 3.

(4) The vinyl (co)polymer contains 5 of the vinyl monomers.
The thermoplastic resin composition according to claim 2 or 3, wherein 0% by weight or more of the thermoplastic resin composition comprises a vinyl aromatic monomer.

(5) The vinyl monomer is a vinyl aromatic monomer, (meth)
Claim 1 or 2 is one or more vinyl monomers selected from the group consisting of acrylic acid ester monomers, (meth)acrylonitrile monomers, and vinyl ester monomers. The thermoplastic resin composition described in .

(6) Add 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, and perform radical polymerization. The vinyl monomer, the radical (
Co) Impregnating an epoxy group-containing olefin copolymer with a polymerizable organic peroxide and a radical polymerization initiator, and when the impregnation rate reaches the initial 50% or more, the temperature of this aqueous suspension is increased. Grafting precursors (A) 1 to 10 in which a vinyl monomer and a radical (co)polymerizable organic peroxide are copolymerized in an epoxy group-containing olefin copolymer.
0% by weight, epoxy group-containing olefin copolymer (B) 0
~99% by weight, and 0~99% by weight of beer-based (co)polymer (C) obtained by polymerizing at least one vinyl monomer, aromatic polyester resin (I) and polycarbonate resin (n ) or melt-mix with (A), (8) in advance.
and (C) in the range of 200 to 300°C to obtain a multiphase structure thermoplastic resin (I[I), and a thermoplastic resin composition comprising (I) and (I) melt-mixed. Production method.

(7) The radical (co)polymerizable organic peroxide has the following general formula (a) or (b) [wherein R1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R2 and R7 are hydrogen atoms or Methyl group, R6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms 1, RR and R
8 and R9 each represent an alkyl group having 1 to 4 carbon atoms, R5 and Rlo represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a dichlorofurkyl group having 3 to 12 carbon atoms, m is 1.
or 2, and n is 0, 1 or 2. ] The method for producing a thermoplastic resin composition according to claim 6, which is one or a mixture of two or more peroxycarbonate compounds represented by:

(8) The vinyl monomer is a vinyl aromatic monomer, (meth)
Claim 6 or 7 is one or more vinyl monomers selected from the group consisting of acrylic acid ester monomers, (meth)acrylonitrile monomers, and vinyl ester monomers. A method for producing a thermoplastic resin composition as described in Section 1.

(9) The epoxy group-containing olefin copolymer contains 60 to 99.5% by weight of ethylene, 40 to 0.5111% of glycidyl (meth)acrylate, and 0 to 39% of other unsaturated monomers.
．． Claim 6 which is a copolymer consisting of 5% by weight
A method for producing a thermoplastic resin composition according to any one of items 1 to 8.

(10) Vinyl (co)polymer is vinyl monomer,
7. The method for producing a thermoplastic resin composition according to claim 6, wherein 50% by weight or more is comprised of a vinyl aromatic monomer.

Table 1 Table 2 Table 3 Table 4

Claims (10)

[Claims] (1) (I) Aromatic polyester resin 99-1% by weight
, (II) 1 to 99% by weight of a polycarbonate resin, and (III) 5 to 95% by weight of an epoxy group-containing olefin copolymer and at least one vinyl monomer based on 100 parts by weight of the above (I) + (II). A thermoplastic resin with a multiphase structure, consisting of 95 to 5% by weight of a vinyl-based (co)polymer obtained from a polymer, and one of the (co)polymers forming a dispersed phase with a particle size of 0.001 to 10 μm. 0.1 to 100 parts by weight, and 0 to 150 parts by weight of (IV) an inorganic filler to 100 parts by weight of the above (I) + (II) + (III). (2) A thermoplastic resin with a multi-phase structure contains at least one vinyl monomer and the following general formula (a) or (b) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(a) ▲Mathematical formulas, chemical formulas, There are tables etc.▼(b) [In the formula, R_1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R_2 and R_7 are hydrogen atoms or a methyl group, R_
6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R_3
, R_4 and R_8, R_9 each have 1 to 4 carbon atoms.
The alkyl group, R_5, R_1_0 represents 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 0, 1 Or 2. ] Grafting precursor (A) 1 to 100 in which at least one radical (co)polymerizable organic peroxide represented by is copolymerized in epoxy group-containing olefin copolymer particles.
Weight%, epoxy group-containing olefin copolymer (B) 0-99% by weight, and vinyl-based (co)polymer (C) obtained by (co)polymerizing at least one vinyl monomer 0-99 % by weight and/or a grafted product. (3) 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.
Claims 1 to 5 are copolymers consisting of 5% by weight.
Thermoplastic resin composition according to any one of Item 3. (4) The vinyl (co)polymer contains 5 of the vinyl monomers.
The thermoplastic resin composition according to claim 2 or 3, wherein 0% by weight or more of the thermoplastic resin composition comprises a vinyl aromatic monomer. (5) The vinyl monomer is a vinyl aromatic monomer, (meth)
Claim 1 or 2 is one or more vinyl monomers selected from the group consisting of acrylic acid ester monomers, (meth)acrylonitrile monomers, and vinyl ester monomers. The thermoplastic resin composition described in . (6) Add 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, and perform radical polymerization. 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. , a grafting precursor (A) in which a vinyl monomer and a radical (co)polymerizable organic peroxide are copolymerized in an epoxy group-containing olefin copolymer.
1 to 100% by weight, epoxy group-containing olefin copolymer (B) 0 to 99% by weight, and vinyl (co)polymer obtained by polymerizing at least one vinyl monomer (C) 0 to 99% by weight is melt-mixed with aromatic polyester resin (I) and polycarbonate resin (II), or preliminarily mixed with said (A) and (B).
) and (C) in a temperature range of 200 to 300°C to obtain a multiphase thermoplastic resin (III), and then melt-mixing the resin with (I) and (II) to produce a thermoplastic resin composition. Method. (7) The radical (co)polymerizable organic peroxide has the following general formula (a) or (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (b ) [In the formula, R_1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R_2 and R_7 are a hydrogen atom or a methyl group, R_
6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R_3
, R_4 and R_8, R_9 each have 1 to 4 carbon atoms.
The alkyl group, R_5, R_1_0 represents 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 0, 1 Or 2. ] The method for producing a thermoplastic resin composition according to claim 6, which is one or a mixture of two or more peroxycarbonate compounds represented by: (8) The vinyl monomer is a vinyl aromatic monomer, (meth)
Claim 6 or 7 is one or more vinyl monomers selected from the group consisting of acrylic acid ester monomers, (meth)acrylonitrile monomers, and vinyl ester monomers. A method for producing a thermoplastic resin composition as described in Section 1. (9) 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.
Claims 6 to 5 are copolymers consisting of 5% by weight.
A method for producing a thermoplastic resin composition according to any one of Item 8. (10) Vinyl (co)polymer is vinyl monomer,
7. The method for producing a thermoplastic resin composition according to claim 6, wherein 50% by weight or more is comprised of a vinyl aromatic monomer.