JPH0480064B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Industrial Application] The present invention relates to a thermoplastic resin composition capable of providing molded articles with excellent mechanical properties, particularly improved impact resistance, and a method for producing the same. It can be used in a wide range of fields such as mechanical parts and automobile parts. [Prior art] Aromatic polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin have excellent mechanical properties and heat resistance, but their impact resistance, especially notched impact strength, is poor. Improvements have been attempted. Among these, JP-A-51-144452, JP-A-52-32045
A method of blending a copolymer consisting of monomers such as α-olefin and α,β-unsaturated acid glycidyl ester, disclosed in Japanese Patent Application Laid-Open No. 117049/1984, Japanese Patent Application Laid-open No. 40154/1982. A method of blending a modified polymer obtained by grafting a monomer such as an α,β-unsaturated acid glycidyl ester with a copolymer consisting of an α-olefin and a non-conjugated diene disclosed in publications, or 57−54058
In contrast to the copolymer of ethylene and α-olefin having 3 or more carbon atoms shown in the above publication, α,β-
Methods such as blending modified polymers obtained by graft polymerization of unsaturated dicarboxylic acids, dicarboxylic acid anhydrides, imide derivatives, etc. are relatively excellent for the purpose of improving impact resistance. [Problems to be Solved by the Invention] However, the modified α-olefin copolymer as the impact modifier is essentially a rubbery polymer for that purpose, and has a glass transition temperature below room temperature. It is something. Therefore, in order to increase the impact resistance, it is possible to increase the amount of the modified α-olefin copolymer, but this is not preferable because the heat resistance, which is one of the characteristics of aromatic polyester resins, decreases. Give results. Furthermore, the aromatic polyester resin 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. The disadvantage was 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 thermoplastic resin obtained by blending an aromatic polyester resin with a specific multiphase thermoplastic resin. The resin composition has improved impact resistance while maintaining heat resistance, and also has improved impact strength after annealing, and it is optimal to melt and knead at a specific temperature when manufacturing it. This discovery led to the completion of the present invention. That is, the first invention of the present invention comprises: () 50-99% by weight of a thermoplastic aromatic polyester resin, () 5-95% by weight of a non-polar α-olefin (co)polymer portion and a vinyl-based (co)polymer portion. 95～
5% by weight, and is a graft copolymer obtained by a specific method described below, in which the number average degree of polymerization of the vinyl (co)polymer portion is 5 to 10,000, and one (co)polymer The combined part is the other (co)
50 to 1% by weight of a multiphase thermoplastic resin that forms a dispersed phase with a particle size of 0.001 to 10 μm in the polymer part, and () 0 to 150 parts by weight of the above () + () for 100 parts by weight of the inorganic filler. A thermoplastic resin composition containing parts by weight. Furthermore, the second invention of the present invention provides an aqueous suspension of a nonpolar α-olefin copolymer containing at least one vinyl monomer, at least one radical (co)polymerizable organic peroxide, and a radical polymerizable organic peroxide. Add an initiator and heat under conditions that do not substantially cause decomposition of the radical polymerization initiator,
The vinyl monomer, radical (co)polymerizable organic peroxide, and radical polymerization initiator are impregnated into the nonpolar α-olefin (co)polymer until the total amount of the impregnated material is 50% of the initial addition amount. % by weight or higher, the temperature of this aqueous suspension is raised to co-incorporate the vinyl monomer and the radical (co)polymerizable organic peroxide in the nonpolar α-olefin (co)polymer. The polymerized grafting precursor is melted at a temperature of 100 to 300°C to obtain a graft copolymer, and 50 to 1% by weight of this graft copolymer is further melted and mixed with 50 to 99% by weight of a thermoplastic aromatic polyester resin. A method for producing a thermoplastic resin composition comprising mixing. The thermoplastic aromatic polyester resin used in the present invention is a polyester that has an aromatic ring in the chain unit of the polymer, and is composed of 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 in which the main component is a condensation reaction. The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis(p-carboxyfer)methane, anthracenedicarboxylic acid, 4, Examples include 4'-diphenyl ether dicarboxylic acid, 1,2-bis(phenoxy)ethane 4,4'-dicarboxylic acid, and ester-forming derivatives thereof. Diol components include aliphatic diols having 2 to 10 carbon atoms, such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, and decamethylene diol. Examples thereof include glycol, cyclohexanediol, etc., or long chain glycols with a molecular weight of 400 to 6000, such as polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc., and mixtures thereof. Preferred thermoplastic aromatic polyester resins used in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene-2,6-
Examples include 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 aromatic polyesters is trifluoroacetic acid (25)/methylene chloride (75) 100
Measured at a concentration of 0.32 g in ml at 25±0.1°C. Preferably, the intrinsic viscosity is 0.4 to 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 4.0 dl/g, the fluidity during melting will decrease and the surface gloss of the molded product will decrease, which is not preferable. The nonpolar α-olefin (co)polymer constituting one polymer part of the graft copolymer used in the present invention refers to one or more α-olefin (co)polymers
This is a polymer obtained by (co)polymerizing an olefin monomer and a non-conjugated diene monomer. The α-olefin monomers mentioned here include ethylene, propylene, butene-1,4-methylpentene-
1, hexene-1, decene-1, octene-1, and the like. Examples of non-conjugated diene monomers include ethylidenenorbornene, 1,4-hexadiene, dicyclopentadiene, and the like. Specific examples of the non-polar α-olefin (co)polymers include homopolymers such as high, medium, and low density polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and ethylene-propylene copolymers. , ethylene-butene-1 copolymer,
Ethylene and carbon atoms of 3 to 3, such as ethylene-hexene-1 copolymer and ethylene-octene-1 copolymer
12 copolymer with α-olefin, ethylene-propylene copolymer rubber, ethylene-propylene-
Examples include ethylidene norbornene copolymer rubber, ethylene-propylene-1,4-hexadiene copolymer rubber, and ethylene-propylene-dicyclopentadiene copolymer rubber. Preferably, a low density ethylene (co)polymer having a density in the range of 0.85 to 0.95 g/ ^cm3 , an ethylene-propylene copolymer rubber having a Mooney viscosity of 15 to 90, a Mooney viscosity of 15 to 120 and an iodine value of 4 to 4. 30 ethylene-propylene-diene copolymer rubber. Note that the Mooney viscosity is a value determined according to JIS K-6300 (100°C). Specifically, the vinyl (co)polymer constituting the other polymer part of the graft copolymer used in the present invention includes styrene; nuclear substituted styrene such as methylstyrene, dimethylstyrene, ethylstyrene, isopropyl Styrene, chlorstyrene; α-substituted styrene; vinyl aromatic monomers such as α-methylstyrene, 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 monomers; vinyl acetate, vinyl propionate, etc. vinyl ester monomer; (meth)acrylamide monomer; (co)polymer obtained by polymerizing one or more vinyl monomers such as maleic anhydride, maleic acid monoester, diester, etc. It is a combination. Among these, vinyl aromatic monomers (meth)acrylonitrile monomers and vinyl ester monomers are particularly preferably used. In particular, vinyl (co)polymers containing 50% by weight or more of vinyl aromatic monomers or (meth)acrylic acid ester monomers are the most preferred embodiment because they have good dispersibility in thermoplastic aromatic polyester resins. be. The graft copolymer used in the present invention has a multiphase structure in which one (co)polymer portion is uniformly dispersed in another (co)polymer portion in a spherical shape. The particle size of the dispersed polymer part is 0.001~
10 μm, preferably 0.01 to 5 μm. If the dispersed resin particle size is less than 0.001 μm or more than 10 μm, the dispersibility is poor when blended with thermoplastic aromatic polyester resin, which is undesirable because, for example, the appearance may deteriorate or the effect of improving impact resistance may be insufficient. . The number average degree of polymerization of the vinyl (co)polymer portion of the graft copolymer used in 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 graft copolymer used in the present invention has a nonpolar α
- from 5 to 95% by weight of the olefin (co)polymer portion;
Preferably it consists of 20 to 90% by weight. Therefore, the vinyl (co)polymer portion is 95 to 5% by weight, preferably 80 to 10% by weight. If the nonpolar α-olefin (co)polymer portion is less than 5% by weight, the effect of improving impact resistance will be insufficient, which is not preferable. If the nonpolar α-olefin (co)polymer portion exceeds 95% by weight, a sufficient effect of improving impact resistance can be obtained, but heat resistance and dispersibility will decrease. A specific grafting method for producing the graft copolymer used in the present invention is as shown below. 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 nonpolar α-olefin (co)polymer particles are suspended in water, and separately 5 to 400 parts by weight of at least one vinyl monomer are mixed with the following general formula (a) or (b). 0.1 to 10 parts by weight of one or a mixture of two or more radical (co)polymerizable organic peroxides to 100 parts by weight of the vinyl monomer, and decomposition to obtain a half-life of 10 hours. Temperature is 40~
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. While impregnating nonpolar α-olefin (co)polymer particles with an oxide and a radical polymerization initiator, when the total amount of the impregnated particles reaches 50% by weight or more of the initial addition amount, this aqueous suspension The vinyl monomer and the radical (co)polymerizable organic peroxide are copolymerized in the nonpolar α-olefin (co)polymer particles to obtain a grafted precursor. This grafted precursor
The graft copolymer used in the present invention can be obtained by kneading while melting at 100 to 300°C. Therefore, even if this grafted precursor is directly melted and kneaded with a thermoplastic aromatic polyester resin, the resulting grafted precursor becomes a graft copolymer. In addition, if the impregnation rate is less than 50% by weight in the above manufacturing method, the proportion of the vinyl (co)polymer part that effectively contributes as a component of the graft copolymer is small, that is, the vinyl (co)polymer part Since the amount of homopolymer increases, separation takes time and is economically disadvantageous. The method for measuring the impregnation rate is to collect non-polar α-
Take out a predetermined amount of olefin (co)polymer particles,
By measuring the heating residue, it can be easily determined from the difference in weight before and after heating. The graft copolymer obtained as described above has a nonpolar α-olefin (co)polymer portion of 5
~95% by weight and vinyl (co)polymer portion is 95~5%
% by weight, and the vinyl (co)polymer portion has a number average degree of polymerization of 5 to 10,000, preferably 10 to 10,000.
5000 range. In addition, this graft copolymer becomes a thermoplastic resin with a multiphase structure because one (co)polymer part forms a dispersed phase with a particle size of 0.001 to 10 μm in the other (co)polymer part. .
This graft copolymer is added to 50 to 99% by weight of a thermoplastic aromatic polyester resin in a proportion of 50 to 1% by weight, and if necessary, an inorganic filler is added in an amount of up to 150 parts by weight per 100 parts by weight of the mixture. The thermoplastic resin composition of the present invention can be obtained by melting and kneading. 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 is an alkyl group having 1 to 12 carbon atoms, a phenyl group,
It represents an alkyl-substituted phenyl group or a cycloalkyl group having 3 to 12 carbon atoms, and 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 defined by 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-hexylperoxyacryloyloxyethyl carbonate; 1,1,3,3-tetramethylbutylperoxyacryloyloxyethyl carbonate; cumylperoxyacryloyloxyethyl carbonate; p-isopropylc Milperoxyacryloyloxyethyl carbonate; t-butylperoxymethacryloyloxyethyl carbonate; t-amylperoxymethacryloyloxyethyl carbonate; t-hexylperoxymethacryloyloxyethyl carbonate; 1,1,3,3-tetramethylbutylperoxy methacryloyloxyethyl carbonate; cumylperoxymethacryloyloxyethyl carbonate; p-isopropylcumylperoxymethacryloyloxyethyl carbonate; t-butylperoxyacryloyloxyethoxyethyl carbonate; t-amylperoxyacryloyloxyethoxyethyl carbonate; -hexylperoxyacryloyloxyethoxyethoxyel carbonate; 1,1,3,3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate; cumylperoxyacryloyloxyethoxyethoxyethyl carbonate; p-isopropylcumylperoxyacryloyloxyethoxy Ethyl carbonate; t-butylperoxymethacryloyloxyethoxyethoxyethyl carbonate; t-amylperoxymethacryloyloxyethoxyethyl carbonate; t-hexylperoxymethacryloyloxyethoxyethyl carbonate; 1,1,
3,3-tetramethylbutylperoxymethacryloyloxyethoxyethoxyethyl carbonate; cumylperoxymethacryloyloxyethoxyethoxyethyl carbonate; p-isopropylcumylperoxymethacryloyloxyethoxyethyl carbonate; t-butylperoxyacryloyloxyisopropyl carbonate; t- Aluminum peroxyacryloyloxyisopropyl carbonate; t-
hexylperoxyacryloyloxyisopropyl carbonate; 1,1,3,3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate; cumylperoxyacryloyloxyisopropyl carbonate; p-isopropylperoxyacryloyloxyisopropyl carbonate; t-butylperoxymethacrylate Loyloxyisopropyl carbonate; t-aluminum peroxymethacryloyloxyisopropyl 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 peroxy acrycarbonate;
t-amyl peroxyallyl carbonate; t-
Hexyl peroxyallyl carbonate; 1,
1,3,3-tetramethylbutyl peroxyallyl carbonate; p-menthane peroxyallyl carbonate; cumyl peroxyallyl carbonate; butyl peroxymethallyl carbonate;
t-aluminum peroxymethallyl carbonate; t
-hexylperoxymethallyl 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-butylperoxyallyloxyisopropyl carbonate; t-amylperoxyallyloxyisopropyl carbonate;
-hexylperoxyallyloxyisopropyl carbonate; t-butylperoxymethallyloxyisopropyl carbonate; t-amylperoxymethallyloxyisopropyl carbonate; t-
Examples include hexylperoxymetallyloxyisopropyl carbonate. Among them, preferred are t-butylperoxyacryloyloxyethyl carbonate; t-butylperoxymethacryloyloxyethyl carbonate; t-butylperoxyacrylic carbonate; and t-butylperoxymethallyl carbonate. In the present invention, the amount of thermoplastic aromatic polyester resin is 50 to 99% by weight, preferably 60 to 95% by weight. Therefore, the polyphase structure thermoplastic resin is 50 to 1
It is blended in a proportion by weight, preferably 40 to 5% by weight. If the thermoplastic aromatic polyester resin is less than 50% by weight, mechanical strength and heat resistance will decrease, which is not preferable. Furthermore, if the thermoplastic aromatic polyester resin exceeds 99% by weight, the effect of improving impact resistance, which is the object of the present invention, is undesirable. In the present invention, 0 to 150 parts by weight of an inorganic filler () can be blended with 100 parts by weight of the resin component containing the above ()+(). Examples of the above-mentioned inorganic fillers include granular, tabular, scaly, acicular, spherical or hollow, and fibrous fillers, and specific examples include calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, and silica sand. , glass powder, iron oxide, metal powder, graphite,
Powder-like fillers such as silicon carbide, silicon nitride, silica, 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. Material: shirasu balloon,
Examples include hollow fillers such as metal balloons, 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 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 may contain stearic acid, oleic acid, palmitic acid, or a metal salt thereof.
It is preferable to perform surface treatment using paraffin wax, polyethylene wax or modified products thereof, organic silane, organic borane, organic titanate, or the like. The thermoplastic resin composition of the present invention comprises a thermoplastic aromatic polyester resin and a multiphase structured thermoplastic resin.
It is produced by kneading while melting at 150-350°C, preferably 180-320°C. If the temperature is less than 150℃,
Insufficient melting or high melt viscosity,
This is not preferable because mixing becomes insufficient and phase separation or layer peeling appears in the molded product. 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. Melting and mixing methods include Banbury mixer, pressure kneader, kneading press, twin screw extruder,
This can be carried out using a commonly used kneader such as a roll. In the present invention, other thermoplastic resins such as polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins, polycarbonate resins,
Polyamide resin, polyphenylene ether resin, polyphenylene sulfide resin, porsulfone resin, natural rubber, synthetic rubber, or inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, organic flame retardants such as halogen type and phosphorus type. Additives such as , antioxidants, ultraviolet inhibitors, lubricants, dispersants, foaming agents, crosslinking agents, and colorants 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) 2500 g of pure water was placed in a stainless steel autoclave of container 5, and 2.5 g of polyvinyl alcohol was further dissolved therein as a suspending agent. Low-density ethylene polymer (trade name: Mitsui Nisseki Polyethylene Polyethylene) was added to this as non-polar α-olefin (co)polymer pellets.
700 g of "LD F41" (manufactured by Nippon Petrochemicals) was added and stirred and dispersed. Separately, benzoyl peroxide as a radical polymerization initiator "Product name: Niper B"
(manufactured by NOF Corporation) 1.5g and n as a molecular weight regulator
-Dodecyl mercaptan 1.5g, radical (co)
6 g of t-butylperoxymethacryloyloxyethyl carbonate as a polymerizable organic peroxide was dissolved in 300 g of methyl methacrylate as a vinyl monomer, and this solution was poured into the autoclave and stirred. Next, raise the temperature of the autoclave to 60-65℃, and
By stirring for a period of time, a vinyl monomer containing a radical polymerization initiator and a radical (co)polymerizable organic peroxide was impregnated into the low density ethylene polymer pellets. Next, after confirming by the following measurement 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 is lowered. The temperature was raised to 80-85° C., maintained at that temperature for 7 hours to complete polymerization, washed with water and dried to obtain a grafted precursor. The methyl methacrylate polymer in this grafted precursor was extracted with ethyl acetate and GPC
The number average degree of polymerization was measured to be 700. Next, this grafted precursor was heated at 200°C using a Laboplast Mill single-screw extruder [manufactured by Toyo Seiki Seisakusho Co., Ltd.].
A multiphase thermoplastic resin (A) was obtained by extrusion and grafting reaction. When this multiphase thermoplastic resin was observed using a scanning electron microscope "JEOL JSM T300" (manufactured by JEOL Ltd.), it was found that it was a multiphase thermoplastic resin in which true spherical resin with a particle size of 0.1 to 0.2 μm was uniformly dispersed. It was hot. At this time, the grafting efficiency of the methyl methacrylate polymer was 53% by weight. Method for Measuring Impregnation Rate Approximately 1 g of nonpolar α-olefin (co)polymer pellets are taken out from the reaction vessel, and after wiping off the moisture on the surface, the weight is accurately measured. Next, after heating this pellet at 200°C for 15 minutes, its 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 100 The theoretical impregnation amount of vinyl monomer solution is calculated as follows: Weight of pellet before heating x Vinyl monomer solution used Amount of polymer solution/Amount of pellets used + Amount of vinyl monomer solution used Vinyl monomer solution represents a mixture of vinyl monomer, radical (co)polymerizable organic peroxide, and radical polymerization initiator. . In this example, the impregnation rate was 56.3%. Reference Example 2 (Production of Multiphase Structure Thermoplastic Resin B) In Reference Example 1, 300 g of methyl methacrylate monomer as a vinyl monomer was replaced with 300 g of styrene monomer.
Multiphase structure thermoplastic resin B was obtained by repeating Reference Example 1 except for changing to g and not using a molecular weight regulator.
I got it. At this time, the number average degree of polymerization of the styrene polymer is 900,
Further, the average particle diameter of the resin dispersed in this resin composition was 0.3 to 0.4 μm. Examples 1-6 For polyethylene terephthalate (expressed as PET) with an intrinsic viscosity of 2.2 dl/g, reference examples 1-6
Multiphase structure thermoplastic resin A or B obtained in 2.
were dry blended in a predetermined amount, and melted and kneaded using a Plastomill single screw extruder [manufactured by Toyo Seiki Seisakusho Co., Ltd.] set at 250°C. Next, each test piece was made using an injection molding machine set at 250°C, and the notched Izo impact strength at 25°C, Izo impact strength after annealing at 150°C for 3 hours, and heating deformation under a load of 18.6 Kg/cm ² were measured. Temperature was measured. In addition, the presence or absence of delamination was observed by observing the fractured surface of the molded product. The results are shown in Table 1.

[Table] Izot impact strength: Comparative examples with notches 1 to 4 Example 1 was repeated except that the multiphase thermoplastic resin was replaced with the unmodified low-density ethylene polymer used in Reference Example 1. . Second result
Shown in the table.

【table】

[Table] Izo impact strength: Comparative examples with notches 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] Izot impact strength: Notched From the above, when the multiphase thermoplastic resin exceeds 50% by weight, the composition loses all the properties of a thermoplastic aromatic polyester resin, and furthermore, when the multiphase thermoplastic resin It has become clear that if the amount added is less than 1% by weight, there is no effect of the addition. Examples 7-8, Comparative Examples 10-12 Example 1 was repeated except that the polyethylene terephthalate in Example 1 was changed to polyethylene terephthalate (indicated as PBT) having an intrinsic viscosity of 1.9 dl/g. The results are shown in Table 4.

【table】

[Table] Izot impact strength: Notched Reference Example 3 (Production of multiphase 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 then a molecular weight modifier was added. A graft precursor was produced by repeating Reference Example 2, except that 2.5 g of n-dodecylmerkaoutane was added as a substitute, and a multiphase thermoplastic resin C was obtained. At this time, the number average degree of polymerization of the styrene polymer was 4.1, and it was a liquid material. Further, as a result of observing this multiphase structured thermoplastic resin C using an electron microscope, the dispersed particle size was estimated to be 0.001 μm or less, but could not be confirmed. Comparative Example 13 Example 2 was repeated except that the multiphase thermoplastic resin A of Example 2 was changed to the multiphase thermoplastic resin C. As a result, the notched isot impact strength before annealing was 3.7 kg·cm/cm, that after annealing was 2.1 kg·cm/cm, and the heat distortion temperature was 55°C. Example 9 Grafting precursor 10 obtained in Reference Example 1
g and 10 g of unmodified low density ethylene polymer, polyethylene terephthalate with an intrinsic viscosity of 2.2 dl/g
Example 1 was repeated except that 80 g was dry blended. As a result, the impact strength of the notched Izotsu before annealing was 5.8Kg・cm/cm, and that after annealing was
The weight was 5.0Kg·cm/cm, and the heat distortion temperature was 75°C. Moreover, there was no delamination. Example 10 A grafting precursor was obtained by repeating Reference Example 1 except that the radical (co)polymerizable organic peroxide used in Reference Example 1 was not used and t-butyl allyl carbonate was used. The dispersed resin particle diameter of this grafted precursor was 0.1 to 0.3 μm. This grafting precursor was used as a multiphase thermoplastic resin, and Example 1 was repeated except for the investigation. As a result, the notched isot impact strength before annealing was 3.8 Kg·cm/cm, that after annealing was 3.7 Kg·cm/cm, the heat distortion temperature was 83°C, and no delamination was observed. Example 11 Grafting precursor 10 obtained in Reference Example 1
g (dispersed particle size 0.1 to 0.3 μm), 5 g of the unmodified low-density ethylene polymer used in Reference Example 1, styrene polymer (trade name "Dialex HF-55",
(manufactured by Mitsubishi Monsanto Chemical Co., Ltd.) and 80 g of the polyethylene terephthalate used in Example 1 were dry blended, and then extruded at 260°C. Next, the physical properties were measured according to Example 1, and the results showed that the notched Izot impact strength before annealing was 3.5 Kg・cm/cm;
After annealing, it was 3.3 Kg·cm/cm, the heat distortion temperature was 84°C, and no delamination was observed. [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 is characterized in that it can be easily manufactured simply by mixing under melting conditions. 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. Furthermore, it is also characterized in that the impact strength does not decrease even after the molded product is heated, such as by annealing. 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)

[Scope of Claims] 1 () 50-99% by weight of thermoplastic aromatic polyester resin, () 5-95% by weight of non-polar α-olefin (co)polymer portion and 95-95% by weight of vinyl-based (co)polymer portion
5% by weight, and is a graft copolymer obtained by the following method, in which the number average degree of polymerization of the vinyl (co)polymer part is 5 to 10,000, and one (co)polymer part is 50 to 1% by weight of a multiphase thermoplastic resin that forms a dispersed phase with a particle size of 0.001 to 10 μm in the other (co)polymer part, and () inorganic to 100 parts by weight of the above () + () A thermoplastic resin composition containing 0 to 150 parts by weight of a filler. The graft copolymer comprises 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. ) A graft obtained by melt-mixing a grafting precursor obtained by copolymerizing at least one radical (co)polymerizable organic peroxide represented by in nonpolar α-olefin (co)polymer particles. It's a monster. 2 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. 3 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 1, which is a vinyl monomer. 4 The nonpolar α-olefin (co)polymer has a density
The thermoplastic resin composition according to claim 1, which is a low density ethylene polymer having a density ranging from 0.85 to 0.94 g/cm ³ . 5. The thermoplastic resin composition according to claim 1, wherein the nonpolar α-olefin (co)polymer is an ethylene-propylene copolymer rubber or an ethylene-propylene diene copolymer rubber. 6 The vinyl (co)polymer part is 50% by weight.
The thermoplastic resin composition according to claim 1, which comprises a polymer portion based on a (meth)acrylic acid ester monomer. 7 Adding at least one vinyl monomer, at least one of the following radical (co)polymerizable organic peroxides, and a radical polymerization initiator to an aqueous suspension of nonpolar α-olefin copolymer particles, The vinyl monomer, the radical (co)polymerizable organic peroxide, and the radical polymerization initiator are converted into nonpolar α-olefin copolymer particles by heating under conditions that do not substantially cause decomposition of the radical polymerization initiator. During impregnation, when the total amount of the impregnated material reaches 50% or more by weight of the initial addition amount, the temperature of this aqueous suspension is increased, and the vinyl monomer and radical (co)polymerizable organic peroxide are added. The grafted precursor is copolymerized in nonpolar α-olefin (co)polymer particles, and the resulting grafted precursor is melted and kneaded in the range of 100 to 300°C to form a nonpolar α-olefin (co)polymer.
- Consists of 5 to 95% by weight of an olefin (co)polymer part and 95 to 5% by weight of a vinyl (co)polymer part, and the number average weight of the vinyl (co)polymer part is 5 to 10,000; , obtain a graft copolymer 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, and heat 50 to 1% by weight of the graft copolymer. A method for producing a thermoplastic resin composition, which comprises melting and kneading 50 to 99% by weight of a plastic aromatic polyester resin. 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. ) is a peroxycarbonate compound represented by 8 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 9 The nonpolar α-olefin (co)polymer has a density
8. The method for producing a thermoplastic resin composition according to claim 7, wherein the thermoplastic resin composition is a low density ethylene polymer having a density ranging from 0.85 to 0.94 g/cm ³ . 10. The method for producing a thermoplastic resin composition according to claim 7, wherein the nonpolar α-olefin (co)polymer is an ethylene-propylene copolymer rubber or an ethylene-propylene-diene copolymer rubber. 11. The method for producing a thermoplastic resin composition according to claim 7, in which the vinyl (co)polymer portion is a polymer portion in which 50% by weight or more is based on a (meth)acrylic acid ester monomer. .