JPH0198662A - Thermoplastic resin composition and its production - Google Patents

Abstract

PURPOSE:To facilitate the production of the title resin composition excellent in heat resistance, impact resistance, etc. and suitable for automobile parts, etc., by melt-mixing an aromatic polyester with a specified multiphase structure thermoplastic resin and an inorganic filler at a specified weight ratio. CONSTITUTION:A multiphase structure thermoplastic resin composed of 5-95wt.% ethylene copolymer selected from an ethylene/unsaturated carboxylic acid (alkyl ester) copolymer and an ethylene/vinyl ester copolymer and 95-5wt.% (co)polymer of at least one vinyl monomer (e.g., ethyl acrylate), wherein the (co)polymer forms a dispersed phase of a particle diameter of 0.001-10mum, is prepared. A thermoplastic resin composition is obtained by melt-mixing 50-1wt.% this resin with 50-99wt.% aromatic polyester resin and 0-150pts.wt., per 100pts.wt. total of these resins, inorganic filler (e.g., alumina).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic resin composition that can provide molded articles with excellent mechanical properties, particularly improved impact resistance, and a method for producing the same. The composition can be used in a wide range of fields such as industrial parts, electrical and electromechanical parts, and automobile parts.

[Prior art] Aromatic polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin are
Although it has excellent mechanical properties, heat resistance, and chemical resistance, it has poor impact resistance, especially notched impact strength, and attempts have been made to improve it. Among these, JP-A-51-144
452, JP-A-52-32045, and JP-A-53-117049, copolymers consisting of monomers such as α-olefin and α,β-unsaturated acid glycidyl ester are blended. Method, JP-A-60-4
α in the copolymer consisting of an α-olefin and a non-conjugated diene disclosed in Publication No. 0154 and the like.

A method of blending a modified polymer obtained by grafting monomers such as β-unsaturated acid glycidyl ester, or a combination of ethylene and an α-olefin having 3 or more carbon atoms as shown in Japanese Patent Publication No. 572-54058, etc. For polymers,
Methods such as blending modified polymers obtained by graft polymerization of α,β-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, if you want to increase the impact resistance, you can increase the content of the modified α-olefin copolymer, but this is not desirable because it reduces the heat resistance, which is one of the characteristics of aromatic polyester resins. 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. It had the disadvantage that it was extremely low.

[Means for Solving the Problems] As a result of our research to solve these conventional drawbacks, the present inventors have discovered a thermoplastic resin that is obtained by blending an aromatic polyester resin with a specific multiphase thermoplastic resin. The plastic resin composition has improved impact resistance while maintaining heat resistance, and also has improved impact strength during annealing, and it is optimal to melt and knead it in a specific hot island when manufacturing it. They discovered this and completed the present invention.

The first aspect of the present invention is as follows: (I) aromatic polyester resin 50 to 99 fff hanging %;
(II) At least one member selected from the group of ethylene-unsaturated carboxylic acid or alkyl ester copolymer thereof, or metal salt thereof, and dylene-vinyl ester copolymer.
5 to 95% by weight of a seed ethylene copolymer and at least 1
Vinyl (co)polymer 9 obtained from vinyl monomer of scale
A thermoplastic resin with a multiphase structure, consisting of 5 to 5% of polymers, in which one (co)polymer forms a dispersed phase with a particle size of 0.001 to 10 μm.
50-1 Booth%, and (I) + (I
F> It is a thermoplastic resin composition containing 0 to 100 small hanging parts of (1) inorganic filler per 1001 hanging parts.

Furthermore, the second invention of the present invention provides an aqueous solution of at least one ethylene copolymer selected from iT of an ethylene-unsaturated carboxylic acid or alkyl ester copolymer thereof or a metal salt thereof, and an ethylene-vinyl ester copolymer. At least one vinyl monomer, at least one radical (co)polymerizable organic peroxide, and a radical polymerization initiator are added to the suspension, and the radical polymerization initiator is substantially not decomposed (f4). The ethylene copolymer is impregnated with the vinyl monomer, the radical (co)polymerizable organic peroxide, and the radical polymerization initiator, and when the impregnation rate reaches the initial 50% by weight or more. Grafting precursor (A) 1 to 100 in which a vinyl monomer and a radical (co)polymerizable organic peroxide are copolymerized in an ethylene copolymer by raising the temperature of this aqueous suspension.
Small amount %, ■ At least one ethylene copolymer (B) selected from the group of dylene-unsaturated carboxylic acid or its alkyl ester copolymer or its metal salt, and ethylene-vinyl ester copolymer (B) 0 to 99 weight %,
and a vinyl-based (co)polymer (C) obtained by polymerizing at least one vinyl monomer in an amount of 0 to 99%, or melted and mixed with an aromatic polyester resin (I),
(A), (B) J5 and (C) in advance from 100 to 300
This is a method for producing a thermoplastic resin composition, which comprises melting and mixing in a temperature range of 0.degree. C. and roughly melting and mixing with a polyester resin.

The aromatic polyester resin used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and is mainly 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 synthetic reaction.

The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, phthalic acid, 2.6-naphthalenedicarboxylic acid, 1.5-naphthalenedicarboxylic acid, bis(p-
Examples include carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4-diphenylneedledicarboxylic acid, 4,4-dicarboxylic acid, and 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 diol. Glycols, cyclohexanediol, etc., or long chain glycols with molecules 1400 to 6,000, i.e. polyethylene glycol, poly-1
, 3-propylene glycol, polytetramethylene gelcol, and mixtures thereof.

Preferred aromatic polyester resins 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 aromatic polyesters is measured at 25±0.1° C. as a concentration of 0.320 in 100 mj of trifluoric acid 11(25)/W methylene(75). Preferably, the intrinsic viscosity is 0.4 to 4. It is Odj/G. If it is less than 0.4 dJ/F, the aromatic polyester will not be able to exhibit sufficient mechanical strength, which is not preferable. Also 4,0
(If it exceeds jj/Q, the fluidity during melting will decrease and the surface gloss of the molded product will decrease, which is not preferable.

The ethylene copolymer used in the multiphase thermoplastic resin of the present invention is selected from the group consisting of (1) dylene-unsaturated carboxylic acid or its alkyl ester copolymer or its metal salt, and ethylene-vinyl ester copolymer. at least one ethylene copolymer comprising ethylene 5
0-99.5%, at least one monomer selected from the group of unsaturated carboxylic acids or their alkyl esters and/or vinyl esters 50-0.5% by weight, other unsaturated monomers 0 ~49.5% by weight of the copolymer or its metal salt, preferably produced by high-pressure radical polymerization.

At least one selected from the group of unsaturated carboxylic acids or their alkyl esters and/or vinyl esters! ! I! Monomers include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic Propyl acid, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, 9-n-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, methacryl Unsaturated carboxylic acid alkyl ester monomers such as stearyl acid, monomethyl maleate, monoethyl maleate, diethyl maleate, and monomethyl fumarate: vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, lauryl Examples include vinyl ester monomers such as vinyl acid, vinyl stearate, and vinyl trifluoroacetate.

Particularly preferred are ethyl acrylate and vinyl acetate. These monomers can be used even if mixed.

Specific examples of the above ethylene copolymers include ethylene/acrylic acid copolymers, ethylene/methacrylic acid copolymers,
Examples include random copolymers such as ethylene/acrylic acid/ethyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/vinyl acetate copolymer, and ethylene/vinyl acetate/ethyl acrylate copolymer. These ethylene copolymers can also be used as a mixture.

The random copolymer is preferably produced by high-pressure radical polymerization. That is, the production method uses 50 to 99.5% by weight of ethylene, 50 to 0% of at least one monomer selected from the group of unsaturated carboxylic acids or their alkyl esters and/or vinyl esters.
．． 5fffffi%, other unsaturated m-isomers 0-49.5@
m% of monomer mixtures in the presence of a radical polymerization initiator of 0.0001 to 1% by weight based on the total weight of all those monomers at a polymerization pressure of 500 to 4.0OOK! F/
ca! .

Preferably from 1,000 to 3,500'J/ci,
Reaction temperature 50-400°C, preferably 100-350°C
This is a method in which the monomers are brought into contact and polymerized simultaneously or in stages in the presence of a chain transfer agent and, if necessary, an auxiliary agent, on the wall of a tank or in a tubular reactor.

Examples of the above-mentioned radical m-intermediate initiators include conventional initiators such as peroxides, hydroperoxides, azo compounds, amine oxide compounds, and oxygen.

In addition, as a chain transfer agent, hydrogen, propylene, budene-1
．． 01 to C2o or higher saturated aliphatic hydrocarbons and halogen-substituted hydrocarbons, such as methane, ethane,
Propane, butane, isobutane, n-hexane, n-hebutane, cycloparaffins, chloroform and carbon tetrachloride, saturated aliphatic alcohols of C1 to C or higher, such as methanol, ethanol, buOpanol,
and isopropanol, C-C or higher saturated aliphatic carbonyl compounds such as carbon dioxide, acetone and methyl ethyl ketone, and aromatic compounds such as toluene, diethylbenzene Jj and xylene.

In addition, in the present invention, a graft copolymer obtained by modifying low, medium, or high density polyethylene or ethylene to α-olefin or copolymer with the unsaturated carboxylic acid, such as acrylic acid, maleic acid, maleic anhydride Fa, etc. Ionic crosslinking is achieved by reacting the polymer or the random or graft copolymer with a metal compound having a valence of 1 to 3 from groups f, ■, ■, ■-A and ■ of the periodic table. It also includes ethylene copolymers.

The above-mentioned metal compounds include nitrates, acetic acid M salts, oxides, hydroxides, methoxides, eth4sites, carbonates, and lignite W
I salts and the like are preferred.

In addition, metal ions include Na, K, Ca''++
++ ++a, Zn
, Ba , Fe”+ + +
+ + ・ + 1-Fe 1C
o %N+ Oyohiju++ A! It is J. Among these, especially Na+, ++
++ MO and Zn are preferred. These various metal compounds can be used in combination as necessary.

Specifically, the vinyl (co)polymer in the multiphase thermoplastic resin used in the present invention includes styrene, nuclear-substituted styrene such as methylstyrene, dimethylstyrene,
Ethylstyrene, isopropylstyrene, chlorstyrene, α-substituted styrenes such as α-methylstyrene, α-
Vinyl aromatic monomers such as ethylstyrene; C1-7 alkyl esters of acrylic acid or methacrylic acid, such as (meth)acrylic acid such as methyl, ethyl, propyl, isopropyl, and butyl esters of (meth)acrylic acid Ester monomer; (meth)acrylonitrile monomer; vinyl ester monomers such as vinyl acetate and vinyl propionate; (meth)acrylamide monomer; vinyl such as maleic anhydride and maleic acid monoesters and diesters 19 by polymerizing one or more monomers
It is a (co)polymer. Among these, vinyl aromatic monomers are particularly preferred.

The multiphase thermoplastic resin referred to in the present invention refers to an ethylene copolymer or a vinyl (co)m polymer matrix in which a vinyl (co)polymer or ethylene copolymer, which is a different component, is uniformly spherical. refers to things that are dispersed in

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

When the dispersed resin particle size is less than 0.001μ or 10
If it exceeds .mu.m, the dispersibility is poor when blended with an aromatic polyester resin, resulting in deterioration in appearance or lack of impact resistance improvement effect, which is undesirable.

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

Also, number average degree of polymerization/J: 10. If it exceeds oooJIj, the melt viscosity will be high, the moldability will be lowered, and the surface gloss will be lowered, which is not preferable.

The multiphase thermoplastic resin of the present invention is composed of 5 to 95% by weight, preferably 20 to 90% by weight of ethylene copolymer. Therefore, the vinyl (co)polymer is 95
~5 Φ foot%, preferably 80 to 10 Φ foot%.

If the ethylene copolymer content is less than 5% by weight, the compatibilization effect with the aromatic polyester resin will not be sufficiently exhibited, and if the ethylene copolymer content exceeds 95% by weight, the heat resistance and dimensional stability of the blend will deteriorate. I don't like it because it increases my IQ.

The multiphase structured thermoplastic resin of the present invention! The grafting method for producing II may be any of the generally well-known methods such as the chain transfer method and the ionizing radiation irradiation method, but the most preferred method is the method 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, ■Dylene-unsaturated carboxylic acid or its alkyl ester copolymer or its metal salt, ethylene-
suspending water in 100 parts by weight of at least one ethylene copolymer selected from the group of vinyl ester copolymers;
Separately, at least one vinyl monomer 5 to 400=I is added to the hanging part, and one or more radically (co)polymerizable organic peroxides represented by the following general formula (a) or (b) are added. 0.1 to 1 per 100 parts by weight of the vinyl monomer
0 weight and a half-life of 10 hours! : A radical polymerization initiator with a decomposition humidity of 40 to 90°C for a total of 1 vinyl monomer and a radical (co)degradable organic peroxide.
A solution of 0.01 to 5 parts by weight is added to 00 parts by weight and heated under conditions that substantially do not decompose the radical polymerization initiator. ) The ethylene copolymer is impregnated with a polymerizable ill peroxide and a radical initiator, and the impregnation rate is
When the weight of the aqueous suspension reaches % or more, the temperature of the aqueous suspension is controlled to copolymerize the vinyl monomer and the radically (co)producible organic peroxide in the ethylene copolymer to form a graft. A precursor (△) is obtained. This grafted precursor is also a multiphase thermoplastic.

Therefore, although this grafted precursor (A) may be directly melted and mixed with the aromatic polyester resin, it is most preferable to use a multiphase thermoplastic resin (If) obtained by kneading the grafted precursor. be.

That is, the grafting precursor (A) was heated to 100 to 300°C.
The resin is grafted by kneading while melting the resin to form a multiphase thermoplastic resin.

At this time, ethylene copolymer (B
) or a vinyl (co)polymer (C) and kneaded while melting, a multiphase thermoplastic resin can also be obtained.

Radicals represented by the general formulas (a) and (b) (
A co)polymerizable organic peroxide is a compound of the general formula [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, and 2ゝ7 R6 is a hydrogen atom or a carbon number 1 ~4 Al: λ-L (
, RR and RR are each an alkyl group having 314 8 9 1 to 4 carbon atoms, R5 and Rlo are 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. where m is 1 or 2 and n is 0.1 or 2. ] This is a compound represented by

Examples of the radical (co-)producible organic peroxide represented by the general formula (a) include t-bubblyberoxyacryloyloxyethyl carbonate, t-amylberoxyacryloyloxyethyl carbonate, t- Hexylberoxyacrylogol 4: Ethyl carbonate 1.
, 1.1.3.3-tetramethylbublber 4-diacrylic O yloxychloroethyl carbonate-1-, cumylberoxyacryloyloxyethyl carbonate-1-, p-isobutylper Axacryloyloxyethyl carbonate, t-butylperoxymethacryloyl carbonate-1~, t-amylperoxymethacryloylode I, ramidylbutylberoxymethacryloyloxyethyl carbonate, cumylberoxymethacryloyloxyethyl carbonate, p- Isobutylperoxymethacryloyloxyethyl carbonate i., V-butylperoxyacryloyloxyethoxyethoxyethyl carbonate, t-amylperoxyacryloyloxyethoxyethoxyethyl carbonate, t-hexylperoxyacryloyloxyethoxyethyl carbonate-1- , 1.1.3.3
-Tetramethylbutylberoxyacryloyloxyethoxyethoxyethyl carbonate, cumylberoxyacryloyloxyethoxyethyl carbonate, p-isobrobylperoxyacryloyloxyethoxyethoxyethyl carbonate-1, siebpulver Aximethacryloyloxyethyl carbonate : t-thiedyl carbonate, t-amylperoxyacryloyloxyethoxyethoxyethyl carbonate, t-hexylberoo 1-cymethacryloyloxyethoxyethyl carbonate 1-,1,1.3.3-tetramethylbutylberoxymethacryloyloxyethoxy ethyl carbonate
1., cumylberoxymethacryloyloxy■ toxyethyl carbonate, p-isopropylberoxymethacryloyl-1 ethoxyebur carbonate, t-butylberoxyacryloyloxyisobroyl carbonate, t-amylberoxymethacryloyloxyisobroyl carbonate, t-amylberoxymethacryloyloxy Roxyisopropyl carbonate, t-hexylberoxyacryloyloxyisobrobyl carbonate, 1.1.3.3-
Tetramethylbutylberoxyacryloyloxyisopropyl carbonate, cumylberoxyacryloyloxyisobutylh-bonate, p-isopropylperoxyacryloyloxyisopropyl carbonate, t-
butylberoxymethacryloyloxyisopropyl carbonate, t-amylberoxymethacryloyloxyisobropyl carbonate, t-hexylperoximetalylyloxyisopropyl carbonate-1., 1.1.
3.3-TetramethylbutylperAxymethacryloyl O
Examples include 1-xisopropyl carbonate, cumylperoxymethacryloyloxyisopropyl carbonate, and p-isobrobylperoxymethacryloyloxyisopropyl carbonate.

Furthermore, as a compound represented by general formula (b), t
-butylperoxyallyl carbonate t-amylperoxyallyl carbonate hexylperoxyallyl carbonate 3,3-te]-ramethylbubourberoxyallyl carbonate, p-menthaneperoxyallyl carbonate-1, cumylperoxyallyl carbonate,
t-Butyl peroxy methallyl carbonate - amyl peroxy methallyl carbonate, 1-hexyl peroxy methallyl carbonate 1,3,3-tetramethylbutylberoxy methallyl carbonate, p-menthamber A-methallyl carbonate, cumyl peroxy methallyl carbonate t-butylperoxyallyloxyethyl carbonate, t-amylberoxyallyloxyethyl carbonate-1-, t-bubourberoxymethallyloxyethyl carbonate, t-amylberoxymethallyloxyethyl carbonate, 1-hexylperoxymetallyloni 1-thyl blue carbonate, t-butylperoxyallyloxyisopropyl carbonate, t-amylperoxyallyloxyisopropyl carbonate,
-Hexylperoxyallyloxyisoprobyl J-
Examples include carbonate, t-butylperoxymetallyloxyisopropyl carbonate, t-hexylperoxymetallyloxyisopropyl carbonate, and the like.

Among them, t-butylberoxyacrylic O
Iroxyethyl carbonate, t-butyl methacryloyloxyethyl carbonate, t-butyl peroxyallyl carbonate, t-butyl peroxyallyl carbonate.

In the present invention, aromatic polyester resin 50 to 99
Weight ω%, preferably 60 to 95 weight R% is required. Therefore, the multiphase fS3i thermoplastic resin is 50-1% by weight
, preferably at a ratio of 40 to 5% by weight.

If the amount of aromatic polyester resin is less than 50% by weight, mechanical strength and heat resistance will deteriorate, which is not preferable. Furthermore, if the aromatic polyester resin exceeds 99% by weight, there is no effect of improving impact resistance, which is the objective of the present invention.

In the present invention, the resin component 1 containing the above (I) + (I)
The inorganic filler (II) can be blended in an amount of 0 to 100 fflω parts per 00 Lffi parts.

Examples of the above-mentioned inorganic fillers include powder-like, tabular, scaly, acicular, spherical or hollow, fibrous, etc., 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; mica, glass plate, Sericy 1-, pyrolite, aluminum flakes metal foils such as, flat or scale-like fillers such as graphite; hollow fillers such as Nijirasu balloons, metal balloons, glass balloons, pumice; glass III, carbon fiber, graphite], fibers, whiskers,
Metal fiber, silicon carbide mt11, asbestos,
Examples include stonite mineral fibers.

If the filler blend ω exceeds 150 parts, it is not preferable because the impact strength of the molded product decreases.

In addition, the surface of the inorganic filler is treated with stearic acid, oleic acid, balmitic 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 at a temperature of 150 to 350°C, preferably 180 to 320°C. If the temperature is less than 150, the melting may be incomplete or the melt viscosity may be high, resulting in insufficient mixing and delamination, which is undesirable. Also 3
If the temperature exceeds 50°C, the resin may decompose or gel, which is undesirable.

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

In the present invention, other thermoplastic resins such as polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins,
Polycarbonate resin, polyamide resin, polyphenylene ether 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 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.

12 and XV<Multiphase Structure Thermoplastic Resin I [Production of A) Volume 1
2.50% pure water in a 65N stainless steel autoclave
(Add 2 liters of polyvinyl alcohol as a suspending agent.)
．． 50 dissolved. In this, ethylene/ethyl acrylate copolymer (containing ethyl acrylate 20% by weight) [trade name: LEXRON EEA A] is used as an ethylene copolymer.
700 g of -4200J (manufactured by Nippon Petrochemicals) was added and stirred and dispersed. Separately, benzoyl peroxide as a radical polymerization tJfl initiator "Product name: Niper-BJ (
(manufactured by NOF Corporation) 1.5a, t-butylberoxymethacryloyloxyethyl carbonate 6q as a radical (co)polymerizable organic peroxide was dissolved in styrene 300 (J) as a vinyl monomer, and this solution was dissolved in styrene 300 (J) as a vinyl monomer. The mixture was placed in an autoclave and stirred.

Next, the autoclave was heated to 60 to 65°C and stirred for 2 hours to impregnate the ethylene copolymer with a vinyl monomer containing a radical polymerization initiator and a radical (co)polymerizable organic peroxide. .

Next, after confirming that the total amount of the impregnated vinyl monomer, radical (co)polymerizable core peroxide, and radical polymerization initiator is 9% or more by weight,
The temperature was raised to 80-85°C and maintained at that temperature for 7 hours to complete polymerization, washed with water and dried to obtain a grafted precursor. The styrene polymer in this grafted precursor was extracted with ethyl acetate, and the number average degree of conjugation was determined by GPC to be 700.

Next, this grafted precursor is extruded at 200°C using a Laboplast Mill-axial extruder [manufactured by Toyo Seiki Seisakusho Co., Ltd.] at 200°C, and a grafting reaction is carried out to form a multiphase thermoplastic resin <IIA). ? Ta.

This multiphase 4M thermoplastic resin was examined using a scanning electron microscope rJE.
When observed using OL JSM T300J (product name, manufactured by JEOL Ltd.), the particle size was 0.1 to 0.2μ.
It was a thermoplastic resin with a multiphase structure in which true spherical resin of m was uniformly dispersed.

At this point, the grafting efficiency of the methyl methacrylate polymer was 65.7%.

Reference Example 2 (Manufacture of multiphase structure thermoplastic resin IIB) In Reference Example 1, methyl methacrylate monomer 300Q as a vinyl monomer was changed to styrene 300Q, and rl-dodecyl mercaptan was used as a molecular weight regulator. Reference Example 1 was repeated except that the polyphase structure thermoplastic resin nB was 111.

At this time, the number average Φ degree of the styrene polymer was 900, and the average particle size of the resin dispersed in this resin composition was 0.3 to 0.4 μm.

Polyethylene derephthalate 1 with an intrinsic viscosity of 2.2 dl/q
- (indicated as PET in the table), the multiphase structure thermoplastic resin obtained in 64 Examples 1 and 2 A or IIS was triblended for a predetermined amount, and the plastomill was set at 250°C.
The mixture was mixed using a shaft extruder [manufactured by Toyo Seiki Co., Ltd.].

Next, each test piece was created using an injection molding machine set at 250°C, and the notched isot impact strength at 25°C, the notched isot impact strength after annealing at 150°C for 3 hours, and the g/cd load were 18.6. The lower heat distortion temperature was measured. The results are shown in Table 1.

The test method is as follows.

(1) Izot impact value (notched): 1110 according to JIS (2) Deflection temperature under load: 7207 according to JIS (blank below) Table 1 In Example 1, multiphase structure thermoplastic resin is used for reference / Example 1
Example 1 was repeated except that the unmodified ethylene/ethyl acrylate copolymer (EEA) used in Example 1 was replaced. The results are shown in Table 2.

Test specimens were prepared and examined by repeating Example 1 in Table 2, except that the amount of the multiphase thermoplastic resin added was changed. The results are shown in Table 3.

From the above in Table 3, if the multiphase thermoplastic resin exceeds 50% by weight, the molded product will completely lose the properties of polyethylene terephthalate, and the amount of the multiphase thermoplastic resin added will be 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-1 was changed to polyethylene terephthalate having an intrinsic viscosity of 1.9 dl/q. The results are shown in Table 4.

Table 4 Actual: Example ratio: Comparative example In reference example 2, styrene 30 as the vinyl monomer
0Q was dissolved in 3,000 ml of benzene as a solvent, and 2.50 ml of n-dodecyl mercaptan was added as a molecular weight regulator.
A graft precursor was produced by repeating Reference Example 2, except that the following was added, and a multiphase thermoplastic resin ■C was obtained. At this time, the number average polymerization ratio of the styrene polymer is 4.2,
It was a liquid substance. Furthermore, as a result of observing this multiphase structured thermoplastic resin with an electron microscope, the dispersed particle size could not be confirmed.
It was estimated to be less than oiμm.

Comparative Example 13 Example 2 was repeated except that the multiphase structure thermoplastic resin ■C was used.

As a result, the Izotsu impact strength 4 with annealing notch
．． The deformation temperature was 56°C.

In Reference Example 1, the obtained grafted precursor 10o and the unmodified ethylene/ethyl acrylate copolymer were mixed into borini [brene terephthalate 1-] having an intrinsic viscosity of 2.2 dl/g.
Example 1 was repeated except triblended to 800%. As a result, the notched Izo impact strength before annealing was 5.8 g-cm/cm, and that after annealing was 5.8 g-cm/cm.
, IK(+-CIll/CI), and the heat distortion temperature was 77°C.

Supporting Example 1 A grafted precursor was obtained by repeating Reference Example 1 except that the radical (co)polymerizable organic peroxide was not used. The dispersed particle size of this grafting precursor is 0.1
It was ~0.3 μm.

Example 1 was repeated except that the grafted precursor was a multiphase thermoplastic resin. As a result, the notched Izo impact strength before annealing was 660 g-cm7 cm, after annealing it was 5.2 Kg-CI/c11+, and the heat distortion temperature was 80°C.

Example 11 Grafting precursor 100 (dispersed particle size 0.1 to 0.3 μm) obtained in Reference Example 1, unmodified ethylene/acrylic ethidyl copolymer 5q used in Reference Example 1, and styrene polymer (trade name " 5q of Dialex HF-55J (Mitsubishi Monsanto Chemical Co., Ltd.%1) and 80 g of the polyethylene terephthalate used in Example 1 were blended and then extruded at 260°C.Then, the physical properties were measured according to Example 1.As a result, The notched Izot impact strength before annealing was 5.3 g-cm/cIll, that after annealing was 5.4 Q-CII/C11l, and the thermal deformation QM was 79°C.

[51 Bright Effect] The thermoplastic resin composition of the present invention is a resin composition with high impact strength without a decrease in heat resistance f[, and is also characterized in that it can be easily made into 11 by simply mixing under melting conditions. . Furthermore, since the impact strength of the claw base 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 there is no decrease in impact strength after the molded product is heated, such as during 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, electronic/electrical parts, heat-resistant containers, and industrial parts.

procedure? In Official Book 1, Indication of the Case Patent Application No. 257680 of 1988 2, Title of the Invention Thermoplastic Resin Composition and Process for Producing the Same 3, Person Making the Amendment Relationship with the Case Name of Patent Applicant Title Japan Petrochemical Co., Ltd. 4 , Agent address: 1-1-5 Minami Aoyama-chome, Minato-ku, Tokyo Date of amendment order (self-initiated) (Starting point) 1920, Month, Day 6, Counterpoint of amendment 7, Contents of amendment (1) Patent claim The range will be corrected as shown in the attached sheet.

(2) Specification, page 12, line 14, rlooJ is r15
Correct it to 0j.

(3) Same, page 31, line 17, "0 to 100 parts by weight" is corrected to "0 to 150 parts by weight J.

(4) Table 4 on page 41 of the same is corrected as shown in the attached sheet.

Above 2, Claims (1) (I) 50 to 99% by weight of aromatic polyester resin, i) Ethylene-unsaturated carboxylic acid or its alkyl ester copolymer or its metal salt, ethylene-vinyl ester copolymer 95 to 95% by weight of at least one ethylene copolymer selected from the group of polymers and 95 to 95% by weight of at least one vinyl monomer.
5% by weight, and one (co)polymer has a particle size of 0.5% by weight.
50 to 1% by weight of a multiphase layered thermoplastic resin forming a dispersed phase of 0.001 to 10 μm, and 0 to 150 parts by weight of (III) an inorganic filler per 100 weight of the above (I) + (n). A thermoplastic resin composition containing.

(2) Aromatic polyester resin contains 40% terephthalic acid.
2. The thermoplastic resin composition according to claim 1, which comprises a dicarboxylic brewing component and a diol component containing mol% or more, and has an intrinsic viscosity of 0.4 to 4.0 dl/Q.

(3) The thermoplastic resin having a multiphase structure is composed of at least one vinyl monomer and the following general formula (a) or (b) R1 [wherein R1 is a hydrogen atom or an atom having 1 to 2 carbon atoms] 1
/L/ M, R2, R7 are hydrogen atoms or methyl groups, R
6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, RR and RR are alkyl W having 1 to 5 carbon atoms, phenyl group, alkyl Represents a 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. ) At least one radical (co)polymerizable organic peroxide represented by is selected from the group of ethylene-unsaturated carboxylic acid or its alkyl ester polymer or its metal salt, and ethylene-vinyl ester copolymer. 1 to 100% by weight of grafting precursor (A) copolymerized in at least one ethylene copolymer particle, ethylene-unsaturated carboxylic acid or its alkyl ester copolymer or its metal salt, ethylene-vinyl ester A vinyl-based (co)polymer obtained by (co)polymerizing at least one ethylene copolymer (B) 0 to 99% by weight selected from the group of copolymers and at least one vinyl monomer. A mixture consisting of 0 to 99% by weight of polymer (C) and/or dissolved 8! The thermoplastic resin composition according to claim 1, which is a grafted product obtained by mixing.

(4) 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 intermediate, (meth)acrylonitrile monoconvex, and vinyl ester monomer. The thermoplastic resin composition described in .

(5) The ethylene copolymer is ethylene 50-99,
5% by weight, 50-0% by weight of at least one monomer selected from the group of unsaturated carboxylic acids or their alkyl and/or vinyl esters, 0-49% by weight of other unsaturated monomers. 4. The thermoplastic resin composition according to any one of claims 1 to 3, which is a copolymer or a metal salt thereof consisting of 5% polyester.

(6) The vinyl (co)polymer contains 5 of the vinyl monomers.
6. The thermoplastic resin composition according to claim 1, wherein 0% or more of the thermoplastic resin composition comprises a (meth)acrylic acid ester monomer.

(7) an aqueous suspension of at least one ethylene copolymer selected from the group of ethylene-unsaturated carboxylic acid or its alkyl ester copolymer or its metal salt, and ethylene-vinyl ester copolymer; One type of vinyl monomer, at least one type of radical (co)polymerizable organic peroxide, and a radical polymerization initiator are added, and heated under conditions in which decomposition of the radical polymerization initiator does not substantially occur. The monomer, the radical (co)polymerizable organic peroxide, and the radical polymerization initiator are impregnated into the ethylene copolymer, and when the impregnation rate reaches 50% by weight or more, the aqueous suspension is Grafting precursor (A > 1 to 1
At least one ethylene copolymer (B) selected from the group of ethylene-unsaturated carboxylic acid or its alkyl ester copolymer or its metal salt, ethylene-vinyl ester copolymer (B) 0-99 and at least 1) 0 to 99% by weight of a vinyl (co)polymer (C) obtained by polymerizing 1 vinyl monomer with an aromatic polyester resin (I), or
(A), (B) and (C) in advance at 100-300°C
A method for producing a thermoplastic resin composition, which comprises melting and mixing the composition in the following range, and further melting and mixing it with a polyester resin.

(8) The radical (co)polymerizable organic peroxide has the following general formula (a) or (b) (blank below) [In the formula, R1 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and RR is hydrogen atom or methyl group, R6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, RR and R8, R9
each represents an alkyl group having 3 to 4 carbon atoms, RR 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. and n is 0.1 or 2. 8. The method for producing a thermoplastic resin composition according to claim 7, wherein F is a mixture of one or more peroxycarbonate compounds represented by F.

(9) Aromatic polyester resin contains 40% of terephthalic acid.
9. The thermoplastic resin composition according to claim 7 or 8, which comprises a dicarboxylic acid component and a diol component in an amount of mol% or more, and has an intrinsic viscosity of 0.4 to 4 and Odl/Q.

(10) Vinyl monomer is vinyl aromatic type fig (4
, (meth)acrylic acid ester monomer, (meth)acrylonitrile monomer, and vinyl ester monomer (iii). A method for producing a thermoplastic resin composition according to any one of items 1 to 9.

(11) The ethylene copolymer has ethylene 50 to 99%
．． 5% by weight, 50-0.5% by weight of at least one monomer selected from the group of unsaturated carboxylic acids or their alkyl esters and/or vinyl esters, 0-49% by weight of other unsaturated monomers. 11. A method for producing a thermoplastic resin composition as set forth in any one of claims 7 to 10, which is a copolymer containing 5 mm% of gold fi or its gold fi salt.

(12) Vinyl (co)polymer is vinyl monomer,
12. The method for producing a thermoplastic resin composition according to any one of claims 7 to 11, wherein 50% by weight or more is composed of a hanging body for (meth)acrylic ester.

Table 4 Actual: Example Ratio: Comparative example

Claims (12)

[Claims] (1) selected from the group of (I) aromatic polyester resin 50 to 99% by weight, (II) ethylene-unsaturated carboxylic acid or its alkyl ester copolymer or its metal salt, ethylene-vinyl ester copolymer Consisting of 5-95% by weight of at least one ethylene copolymer and 95-5% by weight of a vinyl (co)polymer obtained from at least one vinyl monomer, one (co)polymer being 50 to 1% by weight of a multiphase layered thermoplastic resin forming a dispersed phase with a particle size of 0.001 to 10 μm, and (III) 0 inorganic filler per 100 parts by weight of the above (I) + (II). -100 parts by weight of a thermoplastic resin composition. (2) Aromatic polyester resin contains 40% terephthalic acid.
The thermoplastic resin composition according to claim 1, which comprises a dicarboxylic acid component and a diol component in an amount of mol % or more, and has an intrinsic viscosity of 0.4 to 4.0 dl/g. (3) A thermoplastic resin with a multiphase structure contains at least one vinyl monomer and the following general formula (a) or (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (a) ▲ Numerical 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. ] At least one radical (co)polymerizable organic peroxide represented by is selected from the group of ethylene-unsaturated carboxylic acid or its alkyl ester copolymer or its metal salt, and ethylene-vinyl ester copolymer. Grafting precursor (A) copolymerized in at least one ethylene copolymer particle, 1 to 100% by weight, ethylene-unsaturated carboxylic acid or its alkyl ester copolymer or its metal salt, ethylene-vinyl A vinyl-based (co) polymer obtained by (co)polymerizing at least one ethylene copolymer (B) 0 to 99% by weight selected from the group of ester copolymers and at least one vinyl monomer. The thermoplastic resin composition according to claim 1, which is a mixture and/or a grafted product comprising 0 to 99% by weight of polymer (C). (4) 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. (5) The ethylene copolymer has ethylene of 50 to 99.
5% by weight, 50-0.5% by weight of at least one monomer selected from the group of unsaturated carboxylic acids or their alkyl esters and/or vinyl esters, 0-49.5% by weight of other unsaturated monomers. The thermoplastic resin composition according to any one of claims 1 to 3, which is a copolymer or a metal salt thereof consisting of % by weight. (6) The vinyl (co)polymer contains 5 of the vinyl monomers.
6. The thermoplastic resin composition according to any one of claims 1 to 5, wherein 0% by weight or more consists of a (meth)acrylic acid ester monomer. (7) an aqueous suspension of at least one ethylene copolymer selected from the group of ethylene-unsaturated carboxylic acid or its alkyl ester copolymer or its metal salt, and ethylene-vinyl ester copolymer; One type of vinyl monomer, at least one type of radical (co)polymerizable organic peroxide, and a radical polymerization initiator are added, and heated under conditions in which decomposition of the radical polymerization initiator does not substantially occur. The monomer, the radical (co)polymerizable organic peroxide, and the radical polymerization initiator are impregnated into the ethylene copolymer, and when the impregnation rate reaches 50% by weight or more, the aqueous suspension is Grafting precursor (A) obtained by copolymerizing a vinyl monomer and a radical (co)polymerizable organic peroxide in an ethylene copolymer by raising the temperature. 0 to 99% by weight of at least one ethylene copolymer (B) selected from the group of saturated carboxylic acid or its alkyl ester copolymer or its metal salt, ethylene-vinyl ester copolymer, and at least one kind 0 to 99% by weight of a vinyl (co)polymer (C) obtained by polymerizing a vinyl monomer is melted and mixed with an aromatic polyester resin (I), or the (A), (B) and (C) 100-300
A method for producing a thermoplastic resin composition, which comprises melting and mixing at a temperature within a range of °C, and further melting and mixing with a polyester resin. (8) 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 7, which is one or a mixture of two or more peroxycarbonate compounds represented by: (9) Aromatic polyester resin contains 40% of terephthalic acid.
9. The thermoplastic resin composition according to claim 7, which comprises a dicarboxylic acid component and a diol component in an amount of mol% or more, and has an intrinsic viscosity of 0.4 to 4.0 dl/g. (10) The vinyl monomer is one or two selected from the group consisting of vinyl aromatic monomers, (meth)acrylic acid ester monomers, (meth)acrylonitrile monomers, and vinyl ester monomers. The method for producing a thermoplastic resin composition according to any one of claims 7 to 9, wherein the thermoplastic resin composition is one or more types of vinyl monomers. (11) The ethylene copolymer has ethylene 50 to 99%
．． 5% by weight, 50-0.5% by weight of at least one monomer selected from the group of unsaturated carboxylic acids or their alkyl esters and/or vinyl esters, 0-49.5% by weight of other unsaturated monomers. % by weight of a copolymer or a metal salt thereof. (12) Vinyl (co)polymer is vinyl monomer,
The method for producing a thermoplastic resin composition according to any one of claims 7 to 11, wherein 50% by weight or more consists of a (meth)acrylic acid ester monomer.