JPH0478651B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a thermoplastic aromatic polyester resin composition that can provide molded articles with excellent mechanical properties, particularly improved impact resistance, and which can be used for electrical and electromechanical parts, automobile parts, etc. It can be used in a wide range of fields such as [Prior Art] Aromatic polyesters, such as polyethylene terephthalate and polybutylene terephthalate, have excellent heat resistance and mechanical properties, but their impact resistance, especially notched impact strength, is poor, so attempts have been made to improve them. Ta. Among them, JP-A-51-
Publication No. 144452, Japanese Patent Application Publication No. 1983-32045, Japanese Patent Application Publication No. 1987-32045
A method of blending a copolymer consisting of a monomer such as α-olefin and α,β-unsaturated acid glycidyl ester as shown in Publication No. 53-117049,
In the copolymer consisting of α-olefin and non-conjugated diene disclosed in JP-A-60-40154 etc., α,
A method of blending a modified polymer obtained by grafting monomers such as β-unsaturated acid glycidyl ester, or a combination of ethylene and α-olefin having 3 or more carbon atoms as shown in Japanese Patent Publication No. 57-54058. Methods such as blending modified polymers obtained by graft polymerizing α,β-unsaturated carboxylic acids, dicarboxylic acid anhydrides, or imide derivatives to polymers are not suitable for the purpose of improving impact resistance. Excellent. [Problems to be Solved by the Invention] However, the modified α-olefin copolymer used as the impact modifier is essentially a rubbery polymer for that purpose, and its glass transition temperature is below room temperature. belongs to. Therefore, in order to increase impact resistance, it is sufficient to increase the amount of modified α-olefin copolymer, but this results in an undesirable decrease in heat resistance, which is one of the characteristics of aromatic polyester. give. Furthermore, the aromatic polyester molded product blended with the modified α-olefin copolymer exhibits excellent impact resistance immediately after molding, but when annealed to remove distortion during molding, for example, the impact resistance decreases. It had the disadvantage that the value was extremely low. [Means for Solving the Problems] As a result of intensive research to solve these conventional drawbacks, the present inventors have developed a method that can be obtained by blending a specific multiphase thermoplastic resin with a thermoplastic aromatic polyester. The polyester resin composition has improved impact resistance while maintaining heat resistance, and also has improved impact strength after annealing. This discovery led to the completion of the present invention. That is, the first invention comprises () 50 to 99% by weight of thermoplastic aromatic polyester resin, () epoxy group-containing olefin copolymer portion 5
~95% by weight and vinyl (co)polymer portion 95~5
A graft copolymer consisting of % by weight,
A thermoplastic resin composition consisting of 50 to 1% by weight of a multiphase thermoplastic resin in which one (co)polymer part forms a dispersed phase with a particle size of 0.001 to 10 μm in the other (co)polymer part. be. Furthermore, a second invention is characterized in that at least one vinyl monomer, at least one radical (co)polymerizable organic peroxide, and a radical polymerization initiator are added to an aqueous suspension of epoxy group-containing olefin copolymer particles. is added and heated under conditions that do not substantially cause decomposition of the radical polymerization initiator, and the vinyl monomer, radical (co)polymerizable organic peroxide, and radical polymerization initiator are converted into an epoxy group-containing olefin copolymer. While impregnating into the particles, the total amount of impregnated material is 50% of the initial addition amount.
% by weight or more, the temperature of this aqueous suspension is raised to copolymerize the vinyl monomer and the radical (co)polymerizable organic peroxide in the epoxy group-containing olefin copolymer particles. The grafted precursor is melted and kneaded at a temperature range of 100 to 300°C, and the epoxy group-containing olefin copolymer portion is 5 to 95% by weight.
and a vinyl (co)polymer portion of 95 to 5% by weight, and 1 to 50% by weight of this graft copolymer was added to 50 to 99% by weight of a thermoplastic aromatic polyester resin. This is a method for producing a thermoplastic resin composition, which comprises melting and mixing the thermoplastic resin composition. The aromatic polyester used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and whose main components are an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative). It is a polymer or copolymer obtained by a condensation reaction. The aromatic dicarboxylic acids mentioned here include terephthalic acid; isophthalic acid; phthalic acid; 2,6-naphthalene dicarboxylic acid; 1,5-naphthalene dicarboxylic acid; bis(p-carboxyphenyl)methane; anthracene dicarboxylic acid; , 4'-diphenyl dicarboxylic acid; 4,4'-diphenyl ether dicarboxylic acid; 1,2-bis(phenoxy)ethane 4,4'-dicarboxylic acid or their ester-forming derivatives. Diol components include aliphatic diols having 2 to 10 carbon atoms, namely ethylene glycol; propylene glycol; 1,4-butanediol; neopentyl glycol; 1,5-pentanediol; 1,6-hexanediol; Glycols such as cyclohexanediol, or long chain glycols with a molecular weight of 400 to 6000, ie, polyethylene glycol; poly-1,3-propylene glycol; polytetramethylene glycol, etc., and mixtures thereof. Preferred thermoplastic aromatic polyesters used in the present invention include polyethylene terephthalate; polypropylene terephthalate; polybutylene terephthalate; polyhexamethylene terephthalate; polyethylene-2,6-
Naphthalate; polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate and the like. More preferred are polyethylene terephthalate and polybutylene terephthalate. The intrinsic viscosity of these thermoplastic aromatic polyesters is determined at 25±0.10° C. as a concentration of 0.32 g in 100 ml of trifluoroacetic acid (25)/methylene chloride (75). Preferably the intrinsic viscosity is 0.4-4.0
dl/g. If it is less than 0.4 dl/g, the thermoplastic aromatic polyester will not be able to exhibit sufficient mechanical strength, which is not preferable. Moreover, if it exceeds 0.4 dl/g, the fluidity during melting will decrease and the surface gloss of the molded product will decrease, which is not preferable. The epoxy group-containing olefin copolymer constituting one polymer part of the graft copolymer, which is a multiphase thermoplastic resin used in the present invention, is composed of olefin and unsaturated glycidyl produced by high-pressure radical polymerization. It is a binary copolymer with a group-containing monomer or a tertiary or multi-component copolymer of an olefin and an unsaturated glycidyl group-containing monomer and other unsaturated monomers, and the olefin of the above copolymer Especially preferred is ethylene, with ethylene 60~
A copolymer consisting of 99.5% by weight, 0.5 to 40% by weight of a glycidyl group-containing monomer, and 0 to 39.5% by weight of other unsaturated monomers is preferred. As the unsaturated glycidyl group-containing monomer,
Glycidyl acrylate; glycidyl methacrylate; monoglycidyl itaconate; butene tricarboxylic acid monoglycidyl ester; butene tricarboxylic acid diglycidyl ester; butene tricarboxylic acid tricidyl ester; and α-chloroallyl, maleic acid, crotonic acid, fumaric acid, etc. Glycidyl esters or vinyl glycidyl ether; allyl glycidyl ether; glycidyloxyethylene vinyl ether; glycidyl ethers such as styrene-p-glycidyl ether; p-glycidyl styrene; particularly preferred are glycidyl methacrylate; acrylic glycidyl ether can be mentioned. 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-1; Hexene-1; Decene-1; Octene-1; Olefins such as styrene, vinyl acids; vinyl propylate; vinyl esters such as vinyl benzoate; acrylic acid; methacrylic acid; Methyl, ethyl, propyl, butyl, 2-ethylhexyl,
Esters such as cyclohexyl, dodecyl, octadecyl; maleic acid; maleic anhydride; itaconic acid; fumaric acid; maleic acid monoester,
and diesters; vinyl chloride; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; and ocrylic acid amide compounds, with acrylic esters being particularly preferred. Specific examples of the epoxy group-containing olefin copolymers include ethylene/glycidyl methacrylate copolymer; ethylene/vinyl acetate/glycidyl methacrylate copolymer; ethylene/ethyl acrylate/glycidyl methacrylate copolymer; Carbon monoxide/glycidyl methacrylate copolymer; ethylene/glycidyl acrylate copolymer;
Examples include ethylene/vinyl acetate/glycidyl acrylate copolymer. Among them, ethylene/glycidyl methacrylate copolymer is preferred. These epoxy-cocontaining olefin copolymers can be used in combination. The method for producing an epoxy group-containing olefin copolymer by high-pressure radical polymerization is the above-mentioned ethylene 60-99.5
% by weight, 0.5-40% by weight of one or more unsaturated glycidyl group-containing monomers, 0-39.5% by weight of at least one other unsaturated monomer, the total monomers thereof 0.0001-1% by weight based on the total weight of
Polymerization pressure in the presence of a radical polymerization initiator of 500 ~
4000Kg/cm ² , preferably 1000 to 3500Kg/cm ² , reaction temperature 50 to 400°C, preferably 100 to 350°C,
This is a method in which the monomers are brought into contact and polymerized simultaneously or in stages in a tank or tube reactor in the presence of a chain transfer agent and, if necessary, an auxiliary agent. Examples of the radical polymerization initiator include conventional initiators such as peroxides, hydroperoxides, azo compounds, amine oxide compounds, and oxygen. Chain transfer agents include hydrogen, propylene, butene-1, C ₁ to _{C 20} or higher saturated aliphatic hydrocarbons, and halogen-substituted hydrocarbons, such as
Methane, ethane, propane, butane, isobutane, n-hexane, n-heptane, cycloparaffins, chloroform and carbon tetrachloride, C ₁ ~
Saturated aliphatic alcohols of C ₂₀ or higher, such as methanol, ethanol, propanol,
and isopropanol, _C1 - _C20 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 above-mentioned olefin polymers include homopolymers such as low density, medium density, and high density polyethylene; polypropylene; polybutene-1; poly-4-methylpentene-1; ethylene-propylene copolymers;
Other α- containing ethylene as a main component such as ethylene-butene-1 copolymer; ethylene-hexene-1 copolymer; ethylene-4-methylpentene-1 copolymer; ethylene-octene-1 copolymer Copolymers with olefins, copolymers with other α-olefins containing propylene as a main component such as propylene-ethylene block copolymers; ethylene-vinyl acetate copolymers; ethylene-acrylic acid copolymers;
Ethylene-methacrylic acid copolymer; ethylene and methyl or ethyl acrylic acid or methacrylic acid;
Copolymers with esters such as propyl, isopropyl, butyl; ethylene-maleic acid copolymers;
Ethylene-propylene copolymer rubber; ethylene-
Propylene-diene copolymer rubber; liquid polybutadiene; ethylene-vinyl acetate-vinyl chloride copolymer and mixtures thereof, or mixtures thereof with different synthetic resins or rubbers are also included in the present invention. Specifically, the vinyl-based (co)polymer constituting the other polymer part of the graft copolymer, which is a multiphase thermoplastic resin used in the present invention, includes styrene, nuclear-substituted styrene, for example, methylstyrene. , dimethylstyrene, ethylstyrene, isopropylstyrene, chlorstyrene, α-substituted styrene; vinyl aromatic monomers such as α-methylstyrene, α-ethylstyrene; alkyl esters of acrylic acid or methacrylic acid having 1 to 7 carbon atoms; , (meth)acrylic acid ester monomers such as methyl, ethyl, propyl, isopropyl, butyl esters of (meth)acrylic acid;
Acrylonitrile; Monomer; Vinyl ester monomers such as vinyl acetate and vinyl propionate; (meth)acrylamide monomer; One or two types of vinyl monomers such as maleic anhydride, maleic acid monoesters and diesters, etc. It is a (co)polymer obtained by polymerizing more than one species. Among these, vinyl aromatic monomers, (meth)acrylic acid ester monomers, (meth)acrylonitrile monomers, and vinyl ester monomers are preferably used. In particular, a vinyl (co)polymer containing 50% by weight or more of a vinyl aromatic monomer or (meth)acrylic acid ester monomer is the most preferred embodiment because it has good dispersibility in thermoplastic aromatic polyester resin. It is. The multiphase thermoplastic resin referred to in the present invention refers to a graft copolymer in which one (co)polymer portion is uniformly dispersed in a spherical shape in the other (co)polymer portion. say. The particle size of the dispersed polymer is 0.001~10μ,
Preferably it is 0.01-5μ. Dispersed resin particle size
If it is less than 0.01 μm or more than 5 μm, the dispersibility is poor when blended with a thermoplastic aromatic polyester resin, resulting in poor appearance or lack of impact resistance improvement effect, which is undesirable. The number average degree of polymerization of the vinyl (co)polymer portion in the multiphase thermoplastic resin of the present invention is in the range of 5 to 10,000, preferably 10 to 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 be high, the moldability will be lowered, and the surface gloss will be lowered, which is not preferable. The thermoplastic resin having a multiphase structure according to the present invention has an olefin copolymer portion containing an epoxy group in an amount of 5 to 95% by weight, preferably 20 to 90% by weight. Therefore, the vinyl (co)polymer portion is 95 to 5% by weight, preferably 80 to 10% by weight. 5% by weight of olefin copolymer containing epoxy groups
If it is less than that, the effect of improving impact resistance will be insufficient, which is not preferable. Moreover, if the epoxy group-containing olefin copolymer portion exceeds 95% by weight, a sufficient effect of improving impact resistance can be obtained, but heat resistance decreases, which is not preferable. The grafting method for producing the multiphase thermoplastic resin of the present invention may be any of the generally well-known methods such as chain transfer method and ionizing radiation irradiation, but the most preferred method is as follows. This is based on the method shown. 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 parts by weight of epoxy group-containing olefin copolymer particles are suspended in water, and 5 to 400 parts by weight of at least one type of vinyl monomer are added with a radical represented by the following general formula (a) or (b). One type or mixture of two or more types of (co)polymerizable organic peroxides is added in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the vinyl monomer, and the decomposition temperature is 40°C to obtain a half-life of 10 hours. ~
A total of 100 ℃ of radical polymerization initiator with vinyl monomer and radical (co)polymerizable organic peroxide at 90℃
A solution containing 0.01 to 5 parts by weight per part by weight is added and heated under conditions that do not substantially cause decomposition of the radical polymerization initiator to dissolve vinyl monomers and radical (co)polymerizable organic polymers. An oxide and a radical polymerization initiator are impregnated into epoxy group-containing olefin copolymer particles, and when the impregnation rate reaches 50% by weight or more, the temperature of this aqueous suspension is increased to increase the vinyl monomer content. A grafting precursor is obtained by copolymerizing the polymer and a radical (co)polymerizable organic peroxide in epoxy group-containing olefin copolymer particles.
By melting and kneading this grafted precursor at 100 to 300°C, the graft copolymer used in the present invention can be obtained. Therefore, even if this grafted precursor is directly melt-mixed with a thermoplastic aromatic polyester resin,
As a result, the grafted precursor becomes a graft copolymer. In addition, in the present invention, vinyl (co-) which is produced as a by-product during the production of the grafted precursor or graft copolymer
It does not matter if a polymer or an unreacted epoxy group-containing olefin copolymer is contained. Furthermore, a graft precursor or a graft copolymer mixed with a vinyl (co)polymer or an epoxy co-containing olefin copolymer may also be used. Most preferred is to use a graft copolymer. What is required in the present invention is that the graft copolymer is finally contained in a predetermined amount in the thermoplastic resin. In the above manufacturing method, if the impregnation rate is less than 50% by weight, the proportion of the vinyl (co)polymer part that effectively contributes as a component of the graft copolymer will decrease, and only the graft copolymer will be used. In some cases, it is necessary to separate unimpregnated components and homopolymers, which is disadvantageous from an economic point of view. The method for measuring the impregnation rate is to take out a predetermined amount of epoxy group-containing olefin copolymer particles from the reaction vessel, measure the heated residue, and calculate the impregnation rate from the difference in weight before and after heating. can. The radical (co)polymerizable organic peroxide represented by the general formula (a) above is the general formula [In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R ₃ and R ₄ are each an alkyl group having 1 to 4 carbon atoms, R ₅
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, and m is 1 or 2. Also, a radical (group) represented by the above general formula (b)
Polymerizable organic peroxide has the general formula [In the formula, R ₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₇ is a hydrogen atom or a methyl group, R ₈ and R ₉ are each an alkyl group having 1 to 4 carbon atoms,
R ₁₀ is an alkyl group having 1 to 12 carbon atoms, a phenyl group,
represents an alkyl-substituted phenyl group or a cycloalkyl group having 3 to 12 carbon atoms, and n is 0, 1 or 2. Specifically, as the radical (co)polymerizable organic peroxide represented by the general formula (a), t-butylperoxyacryloyloxyethyl carbonate;
-amylperoxyacryloyloxyethyl carbonate; t-hexyloxyacryloyloxyethyl carbonate; 1,1,3,3-tetramethylbutylperoxyacryloyloxyethyl carbonate; cumylperoxyacryloyloxyethyl carbonate; p-isopropylc Milperoxyacryloyloxyethyl carbonate; t
-butylperoxymethacryloyloxyethyl carbonate; t-amylpenyloxymethacryloyloxyethyl carbonate; t-hexylperoxymethacryloyloxyethyl carbonate;
1,1,3,3-tetramethylbutylperoxymethacryloyloxyethyl carbonate; cumylperoxymethacryloyloxyethyl carbonate; p-isopropylcumylperoxymethacryloylxyethyl carbonate; t-butylperoxyacryloyloxyethoxyethyl carbonate; -amylperoxyacryloyloxyethoxyethoxyethyl carbonate; t-hexylperoxyacryloyloxyethoxyethoxyethyl carbonate; 1,1,3,3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate; cumylperoxyacryloyloxyethoxyethyl carbonate; p-isopropylcumylperoxyacryloyloxyethoxyethoxyethyl carbonate; t-butylperoxymethacryloyloxyethoxyethoxyethyl carbonate; t-amylperoxyacryloyloxyethoxyethyl carbonate; t-hexylperoxymethacryloyloxyethoxyethyl carbonate; 1,1, 3,3
-Tetramethylbutylperoxymethacryloyloxyethoxyethoxyethyl carbonate; cumylperoxymethacryloyloxyethoxyethoxyethyl carbonate; p-isopropylcumylperoxymethacryloyloxyethoxyethyl carbonate; t-
Butylperoxyacryloyloxyisopropyl carbonate; t-amylperoxyacryloyloxyisopropyl carbonate; t-hexylperoxyacryloyloxyisopropyl carbonate; 1,1,3,3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate; cumylperoxyacrylate Loyloxyisopropyl carbonate; p-isopropylcumyl peroxyacryloyloxyisopropyl carbonate; t-butylperoxymethacryloyloxyisopropyl carbonate; t-amylperoxymethacryloyloxyisopropyl carbonate; t-hexylperoxymethacryloyloxyisopropyl carbonate; 1,1 , 3,3-tetramethylbutylperoxymethacryloyloxyisopropyl carbonate; cumylperoxymethacryloyloxyisopropyl carbonate; p
Examples include -isopropylcumylperoxymethacryloyloxyisopropyl carbonate. Furthermore, as a compound represented by general formula (b), t-butyl peroxyallyl carbonate;
t-amyl peroxyallyl carbonate; t-
Hexylperoxyallyl carbonate; 1,
1,3,3-tetramethylbutyl peroxyallyl carbonate; p-menthane peroxyallyl carbonate; cumyl peroxyallyl carbonate; t-butyl peroxy methallyl carbonate; t-amyl peroxy methallyl carbonate; t-hexyl peroxy methallyl carbonate; 1,1,3,3-tetramethylbutylperoxymethallyl carbonate; p-menthane peroxymethallyl carbonate; cumyl peroxymethallyl carbonate; t-butylperoxyallyloxyethyl carbonate; t-amylperoxyallyloxyethyl carbonate; -hexylperoxyallyloxyethyl carbonate; t-
Butylperoxymethallyloxyethyl carbonate; t-amylperoxymethallyloxyethyl carbonate; t-hexylperoxymethallyloxyethyl carbonate; t-butylperoxyallyloxy, isopropyl carbonate; t-amylperoxyallyloxyisopropyl carbonate; t-hexylperoxyallyloxy Examples include isopropyl carbonate; t-butylperoxymetallyloxyisopropyl carbonate; t-amylperoxymetallyloxyisopropyl carbonate; t-hexylperoxymethallyloxyisopropyl carbonate. Among them, preferred are t-butylperoxyacryloyloxyethyl carbonate; t-butylperoxymethacryloyloxyethyl carbonate; t-butylperoxyallyl carbonate; and t-butylperoxymethallyl carbonate. In the present invention, the thermoplastic aromatic polyester resin is required in an amount of 50 to 99% by weight, preferably 60 to 95% by weight. Therefore, the amount of multiphase thermoplastic resin is 50 to 1% by weight, preferably 40 to 5% by weight. If the content of the thermoplastic aromatic polyester resin is less than 50% by weight, mechanical strength and heat resistance will deteriorate, which is undesirable. Moreover, if the content of the thermoplastic aromatic polyester resin exceeds 99% by weight, the effect of improving impact resistance, which is the objective of the present invention, is undesirable. The thermoplastic resin composition of the present invention is produced by melting and mixing thermoplastic aromatic polyester resin compositions at 150 to 350°C, preferably 180 to 320°C. If the temperature is lower than 150°C, melting may be insufficient, melt viscosity may be high, mixing may be insufficient, and phase separation or delamination may appear in the molded product, which is not preferable. Moreover, if the temperature exceeds 350°C, the resin to be mixed will decompose and the molded product will be colored, which is not preferable. 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, metal powder, talc, glass fiber,
Organic or inorganic fillers such as carbon fiber and wood flour; additives such as antioxidants, ultraviolet inhibitors, lubricants, dispersants, coupling agents, foaming agents, crosslinking agents, and coloring agents; and other polyolefin resins and polyamides. , polycarbonate, ABS resin, polyphenylene ether, polyphenylene sulfide, and other engine nearing plastics may be added. [Example] Next, the present invention will be explained in more detail with reference to Examples. Reference example 1 (Production of multiphase structure thermoplastic resin A) In a stainless steel autoclave with a volume of 5,
2500 g of pure water was added, and 2.5 g of polyvinyl alcohol was further dissolved therein as a suspending agent. In this, 700 g of ethylene/glycidyl methacrylate copolymer (glycidyl methacrylate content 15% by weight) "Lexpar J-3700" (trade name, manufactured by Nippon Petrochemical Co., Ltd.) was added as epoxy group-containing olefin copolymer particles. , stirred and dispersed. Separately, benzoyl peroxide "Niper B" as a radical polymerization initiator
(Product name, manufactured by NOF Corporation) 1.5g, Radical (co)
6 g of t-butylperoxymethacryloyloxyethyl carbonate as a polymerizable organic peroxide and n-dodecyl mercaptan as a molecular weight regulator.
0.6 g was dissolved in 300 g of methyl methacrylate 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 impregnate the vinyl monomer containing the radical polymerization initiator and the radical (co)polymerizable organic peroxide into the epoxy group-containing ethylene copolymer. I let it happen. Next, after confirming by the following measurement method that the total amount of the impregnated vinyl monomer, radical (co)polymerizable organic peroxide, and radical polymerization initiator is at least 50% by weight, The temperature was raised to 80-85°C and maintained at that temperature for 7 hours to complete the polymerization.
A grafted precursor was obtained by washing with water and drying. The methyl methacrylate polymer in this grafted precursor was extracted with ethyl acetate, and the number average degree of polymerization was measured by GPC and found to be 700. Next, this grafted precursor was processed using a Labo Plast Mill uniaxial extruder [manufactured by Toyo Seiki Seisakusho Co., Ltd.].
Multiphase structure thermoplastic resin A was obtained by extrusion at 200°C and grafting reaction. This multiphase thermoplastic resin was examined using a scanning electron microscope "JEOL JSM T300 (product name, manufactured by JEOL Ltd.)".
As a result of observation, it was found to be a thermoplastic resin with a multiphase structure in which truly spherical resin particles with a particle size of 0.1 to 0.2 μm were uniformly dispersed. At this time, the grafting efficiency of the methyl methacrylate polymer was 68.8% by weight. Method for Measuring Impregnation Rate Approximately 1 g of epoxy group-containing olefin copolymer particles (pellets) are taken out from the reaction vessel, the moisture on the surface is wiped off, and the weight is accurately measured. Next, after heating the particles at 200°C for 15 minutes, their weight is accurately measured and the impregnation rate is determined from the following formula. Impregnation rate (%) = weight of pellet before heating - weight of pellet after heating / theoretical impregnation amount of vinyl monomer solution x 10
0 The theoretical impregnation amount of vinyl monomer solution is: weight of pellet before heating x amount of vinyl monomer solution used/amount of pellets used + amount of vinyl monomer solution used mer, a radical (co)polymerizable organic peroxide, and a radical polymerization initiator. In this example, the impregnation rate was 53.8%. Reference Example 2 (Manufacture of multiphase structure thermoplastic resin B) In Reference Example 1, 300 g of methyl methacrylate monomer as the vinyl monomer was changed to 300 g of styrene, and n-dodecyl mercaptan was used as the molecular weight regulator. A multiphase structure thermoplastic resin B was obtained by repeating Reference Example 1, except that it was not used. At this time, the number average degree of polymerization of the styrenic polymer is
900, or the average particle size of the resin dispersed in this resin composition was 0.3 to 0.4μ. Examples 1 to 6 Polyethylene terephthalate with an intrinsic viscosity of 2.2 dl/g was dry-blended with a predetermined amount of the multiphase structure thermoplastic resin A or B obtained in Reference Examples 1 to 2, and uniaxially extruded in a plastomill set at 250°C. The mixture was mixed using a machine [manufactured by Toyo Seiki Seisakusho Co., Ltd.]. Next, each test piece was prepared using an injection molding machine set at 250℃, and the notched isot impact strength at 25℃, the notched isot impact strength after annealing at 150℃ for 3 hours, and the heat under a load of 18.6Kg/cm ² were measured. The deformation temperature was measured. The results are shown in Table 1.

【table】

[Table] Comparative Examples 1 to 4 Example 1 was repeated except that the multiphase thermoplastic resin was replaced with the unmodified epoxy group-containing olefin copolymer pair used in Reference Example 1. The results are shown in Table 2.

【table】

[Table] Comparative Examples 5 to 9 Test pieces were prepared and examined by repeating Example 1 except that the amount of the multiphase thermoplastic resin added was changed. The results are shown in Table 3.

[Table] From the above, if the multiphase thermoplastic resin exceeds 50% by weight, the molded product loses its properties of polyethylene terephthalate, and if the amount of the multiphase thermoplastic resin added is less than 1% by weight, It became clear that the addition had no effect. Examples 7 to 8, Comparative Examples 8 to 12 Example 1 was repeated except that polyethylene terephthalate in Example 1 was changed to polybutylene terephthalate having an intrinsic viscosity of 1.9 dl/g. The results are shown in Table 4.

[Table] Reference Example 3 (Manufacture of multi-phase structure thermoplastic resin C) In Reference Example 2, 300 g of styrene as a vinyl monomer was dissolved in 300 g of benzene as a solvent, and further added n-dodecyl mercaptan as a molecular weight regulator. A grafted precursor was produced by repeating Reference Example 2, except that 2.5 g was added, and a multiphase thermoplastic resin C was obtained. The number average degree of polymerization of the styrene polymer at this time was 4.1, and it was a liquid material. Furthermore, as a result of observing this multiphase structured thermoplastic resin with an electron microscope, the dispersed resin particle size was found to be 0.001μ or less, but this could not be confirmed. Comparative Example 13 Example 2 was repeated except that the multiphase thermoplastic resin A was changed to the multiphase thermoplastic resin C. As a result, the impact strength of notched Izotsu before annealing was 5.0Kg・cm/cm,
After annealing, it was 2.8 kg·cm/cm, and the heat distortion temperature was 68°C. Example 9 Grafting precursor 10 obtained in Reference Example 1
Example 1 was repeated except that 10 g of the unmodified epoxy group-containing olefin copolymer were dry blended with 80 g of polyethylene terephthalate having an intrinsic viscosity of 2.2 dl/g. As a result, the impact strength of notched Izotsu before annealing was 6.5Kg・cm/
cm, notched izot impact strength after annealing
The heat distortion temperature was 7.8Kg・cm at 76℃. Example 10 A grafted precursor was obtained by repeating Reference Example 1 except that the radical (co)polymerizable organic peroxide was not used. The dispersed particle diameter of this grafted precursor was 0.1 to 0.3 μm. This grafting precursor was used as a multi-phase thermoplastic resin, and Example 1 was repeated and studied except for the above. As a result, the impact strength of notched Izotsu before annealing was 5.5Kg・cm/
cm, notched izot impact strength after annealing
It was 5.6Kg・cm/cm, and the heat distortion temperature was 81℃. [Effects of the Invention] The thermoplastic resin composition of the present invention is a resin composition with high impact strength without deterioration in heat resistance, and can be easily produced by simply mixing while melting. Furthermore, since the degree of impact strength is determined by the blending ratio of the multiphase thermoplastic resin mixed, it is possible to easily produce a wide variety of products in small quantities. Another feature is that the impact strength does not decrease even after the molded product is heated, such as through annealing. From the above points, the thermoplastic resin composition of the present invention can be used in a wide range of applications, such as automobile parts, home appliance parts, and heat-resistant containers.

Claims (1)

[Claims] 1 () Thermoplastic aromatic polyester resin 50~
99% by weight and () Epoxy group-containing olefin copolymer portion 5
~95% by weight and vinyl (co)polymer portion 95~5
A graft copolymer consisting of % by weight,
A thermoplastic resin composition comprising 50 to 1% by weight of a multiphase thermoplastic resin in which one (co)polymer portion forms a dispersed phase with a particle size of 0.001 to 10 μm in the other (co)polymer portion. 2. The graft copolymer has at least one vinyl monomer and the following general formula (a) or (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 are each an alkyl group having 1 to 4 carbon atoms, and R ₅ and R ₁₀ are an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or an alkyl group having 3 to 12 carbon atoms. represents a cycloalkyl group, m is 1
or 2, and n is 0, 1 or 2. ) is a grafted product obtained by melting and kneading a grafting precursor obtained by copolymerizing at least one radical (co)polymerizable organic peroxide represented by in epoxy group-containing olefin copolymer particles. Thermoplastic resin composition according to claim 1. 3 The thermoplastic aromatic polyester resin consists of a dicarboxylic acid component and a diol component containing 40 mol% or more of terephthalic acid, and has an intrinsic viscosity of 0.4 to 4.0.
dl/g of the thermoplastic resin composition according to claim 1. 4. The thermoplastic resin composition according to claim 1, wherein the vinyl copolymer portion is a polymer portion in which 50% by weight or more is based on a (meth)acrylic acid ester monomer. 5 The epoxy group-containing olefin copolymer contains 60 to 99.5% by weight of ethylene, 40 to 0% by weight of glycidyl (meth)acrylate, and 0 to 0% of other unsaturated monomers.
Thermoplastic resin composition according to any one of claims 1 and 2, which is a copolymer based on 39.5% by weight. 6 The vinyl monomer is one or more selected from the group consisting of vinyl aromatic monomers, (meth)acrylic acid ester monomers, (meth)acrylonitrile monomers, and vinyl ester monomers. The thermoplastic resin composition according to claim 2, which is a vinyl monomer. 7 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 epoxy group-containing olefin copolymer particles to perform radical polymerization. The vinyl monomer, the radical (co)polymerizable organic peroxide, and the radical polymerization initiator are impregnated into the epoxy group-containing olefin copolymer particles by heating under conditions that substantially do not cause decomposition of the initiator. Tsutsu,
When the total amount of the impregnated material reaches 50% by weight or more of the initial addition amount, the temperature of this aqueous suspension is increased to dissolve the vinyl monomer and the radical (co)polymerizable organic peroxide. Grafting precursor copolymerized in olefin copolymer particles containing epoxy groups
It is melted and kneaded in a temperature range of 100 to 300°C, and is composed of 5 to 95% by weight of an epoxy group-containing olefin copolymer part and 95 to 5% by weight of a vinyl-based (co)polymer part, and one (co)polymer part is A graft copolymer () in which the combined part forms a dispersed phase with a particle size of 0.001 to 10 μm in the other (co)polymer part is obtained, and 1 to 50% by weight of the graft copolymer is mixed with a thermoplastic aromatic polyester. A method for producing a thermoplastic resin composition, which comprises melting and mixing 50 to 99% by weight of a resin. 8 The radical (co)polymerizable organic peroxide has the following general formula (a) or (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 are each an alkyl group having 1 to 4 carbon atoms, and R ₅ and R ₁₀ are an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or an alkyl group having 3 to 12 carbon atoms. represents a cycloalkyl group, m is 1
or 2, and n is 0, 1 or 2. 8. The method for producing a thermoplastic resin composition according to claim 7, wherein the thermoplastic resin composition is one or a mixture of two or more peroxycarbonate compounds represented by: 9 The vinyl monomer is one or more selected from the group consisting of vinyl aromatic monomers, (meth)acrylic acid ester monomers, (meth)acrylonitrile monomers, and vinyl ester monomers. 8. The method for producing a thermoplastic resin composition according to claim 7, wherein the vinyl monomer is 10 The thermoplastic aromatic polyester resin consists of a carboxylic acid component containing 40 mol% or more of terephthalic acid and a diol component, and has an intrinsic viscosity of 0.4 to 4.0.
dl/g. The method for producing a thermoplastic resin composition according to claim 7. 11 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% of other unsaturated monomers.
8. The method for producing a thermoplastic resin composition according to claim 7, wherein the copolymer is based on .about.39.5% by weight. 12. The method for producing a thermoplastic resin composition according to claim 7, wherein the vinyl copolymer portion is a polymer portion in which 50% by weight or more is based on a (meth)acrylic acid ester monomer.