JP2682036B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Use The present invention provides impact resistance, heat resistance, weather resistance and molding processability, which are obtained by mixing a thermoplastic resin and a modified hydrogenated diene polymer. It relates to an excellent resin composition.

b. Conventional technology Conventionally, polyester, polycarbonate, polyoxymethylene, polyphenylene ether, styrene resin, etc. have been widely used as thermoplastic resins. For example, thermoplastic polyester resins, especially polybutylene terephthalate (hereinafter referred to as "PBT"), have well-balanced and good physical properties and excellent moldability, and are used for mechanical parts, electronic / electrical parts, automobile parts, etc. Widely used in the field. However, these thermoplastic resins have a major drawback of low notch impact strength. For example PBT
Shows good impact strength without a notch (notch), but with a notch, the impact strength remarkably decreases, which is an obstacle to expanding applications.

Therefore, various proposals have been made in order to improve the properties of these resins, particularly the impact resistance. For example, as an additive for improving the impact resistance of these thermoplastic resins, a conjugated diene compound-styrene copolymer (Japanese Patent Publication No. 46-
5229), a polymer obtained by grafting acrylonitrile and aromatic vinyl onto a conjugated diene rubber (Japanese Patent Publication No.
No.) etc. are proposed. However, since unsaturated bonds are present in these conjugated diene-based polymers, molded products obtained by adding this polymer are inferior in heat resistance and weather resistance, and the impact resistance is not sufficiently improved. Is. In order to improve the heat resistance and the weather resistance, it has been proposed to use a partially hydrogenated conjugated diene polymer (JP-A-60-130642), but the impact resistance is insufficient. However, the current situation is that the shortcomings have not been overcome yet.

c. Problems to be Solved by the Invention The present invention has been made against the background of the problems of the above-mentioned conventional techniques, and is excellent in properties such as impact resistance, heat resistance, weather resistance, and moldability, particularly excellent in impact resistance. Another object of the present invention is to provide a resin composition.

d. Means for Solving the Problem The gist of the present invention is a thermoplastic resin obtained by mixing 50 to 95 parts by weight of a thermoplastic resin (A) and 50 to 5 parts by weight of a modified hydrogenated diene polymer (B). In the resin composition.

Examples of the thermoplastic resin (A) include thermoplastic polyester resins such as aromatic polyesters and aliphatic polyesters such as polybutylene terephthalate and polyethylene terephthalate, polycarbonates, polyoxymethylene, polyphenylene ether, etc., or polystyrene, styrene-acnylonitrile copolymer. A styrene resin and an acrylic resin such as ABS resin, AES resin, and MBS resin can be used.

Of the above resins, the styrene resin is a homopolymer of a vinyl aromatic compound, or a copolymer with another monomer copolymerizable with the vinyl aromatic compound, or in the presence of a rubber-like polymer. , A vinyl aromatic compound or a graft copolymer obtained by polymerizing a vinyl aromatic compound and another copolymerizable monomer, or a mixture of at least two kinds thereof.

Examples of the vinyl aromatic compound include styrene, α-methylstyrene, methylstyrene, p-methylstyrene,
Vinyl xylene, chlorostyrene, bromostyrene, etc. are mentioned, and these are used by 1 type (s) or 2 or more types.

The copolymerizable monomer includes vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, which are used alone or in combination of two or more. Acrylonitrile is particularly preferred. Further, acrylic acid alkyl ester such as methyl acrylate, ethyl acrylate, propylene acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate; methoxyethyl. Acrylic acid alkoxyalkyl esters such as acrylate, ethoxyethyl acrylate, ethoxypropyl acrylate; methyl methacrylate, ethyl methacrylate, propylene methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl Sill methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, methacrylic acid alkyl esters such as benzyl methacrylate;
Unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; unsaturated acids such as acrylic acid and methacrylic acid; maleimide, N-methylmaleimide, N
Examples include α- or β-unsaturated dicarboxylic acid imide compounds such as -butylmaleimide, N- (P-methylphenyl) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc., which interfere with the object of the present invention. It is used in 1 type (s) or 2 or more types in the range without.

Examples of the rubber-like polymer include polybutadiene,
Diene rubber such as polyisoprene, styrene-butadiene copolymer, acrylonitrile-budadiene copolymer,
Ethylene-propylene, ethylene-butene, ethylene-
Propylene-non-conjugated diene terpolymers, non-diene rubbers such as acrylic rubber, and the like, one or two
Used in more than species.

When the monomer component is a mixture of a vinyl aromatic compound and another copolymerizable monomer, the proportion of the vinyl aromatic compound in the mixture is preferably 50% by weight or more, more preferably 70% by weight or more. If it is more than weight% and is in this range,
It is preferable because the moldability and the surface appearance of the molded product are further excellent.

The above acrylic resin is a homopolymer of (meth) acrylic acid alkyl ester, or a copolymer of (meth) acrylic acid alkyl ester and another copolymerizable monomer, or in the presence of a rubbery polymer. Is a (meth) acrylic acid alkyl ester or a graft copolymer obtained by polymerizing another monomer copolymerizable with the (meth) acrylic acid alkyl ester, or a mixture of at least two of them.

As the alkyl (meth) acrylate,
For example, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and the like can be mentioned, with preference given to methyl methacrylate.

The above-mentioned copolymerizable monomer corresponds to a monomer obtained by removing the (meth) acrylic acid alkyl ester from the copolymerizable monomer component represented by the styrene resin. As the rubber-like polymer, the rubber-like polymer represented by styrene resin is applicable.

In the case where the monomer component is a mixture of (meth) acrylic acid alkyl ester and another monomer copolymerizable,
The proportion of (meth) acrylic acid alkyl ester in the mixture is preferably 55% by weight or more, more preferably 70% by weight or more. Within this range, more excellent weather resistance can be obtained, which is preferable.

The content of the thermoplastic resin (A) in the resin composition of the present invention is 50 to 95 parts by weight (however, (A) + (B) = 100 parts by weight, the same applies hereinafter), preferably 60 to 85 parts by weight. If it is less than 50 parts by weight, the moldability of the resin composition is poor, while if it exceeds 95 parts by weight, the effect of improving the impact resistance and heat resistance of the resin composition is not observed, which is not preferable.

The modified hydrogenated diene-based polymer (B) is at least one conjugated diene polymer or at least one conjugated diene and a random diene copolymer containing 50% by weight or less of a vinyl aromatic compound, the (co) polymer A hydrogenated diene (co) polymer having a number average molecular weight of 5,000 to 1,000,000 and a vinyl bond content in the diene portion of 10% or more is obtained. At least one functional group selected from the group consisting of a carboxyl group or an anhydride thereof, an amino group, a hydroxyl group and an epoxy group based on 100 parts by weight of a hydrogenated diene polymer in which at least 70% of saturated bonds are hydrogenated. Unsaturated compounds containing groups 0.05
A modified hydrogenated diene polymer obtained by reacting ˜20 parts by weight can be used.

The modified hydrogenated diene-based polymer (B) is at least one conjugated diene polymer, or at least one conjugated diene and a random diene copolymer of a vinyl aromatic compound, and the diene portion is partially or A completely hydrogenated hydrogenated diene polymer is reacted with an unsaturated compound containing at least one functional group selected from the group consisting of a carboxyl group or its anhydride, an amino group, a hydroxyl group and an epoxy group. It is a copolymer.

Here, examples of the conjugated diene compound include butadiene, isoprene, pentadiene, and 2,3-dimethylbutadiene. Further, examples of the aromatic vinyl compound include styrene, paramethylstyrene, and α-methylstyrene.

Further, among the unsaturated compounds having a functional group, examples of the unsaturated compound having a carboxyl group include acrylic acid, methacrylic acid, maleic acid and fumaric acid. Among these, dicarboxylic acids may be acid anhydrides. Further, as the unsaturated compound having an amino group, for example, dimethylaminoethyl (meth)
Examples thereof include tertiary amino group-containing monomers such as acrylate, diethylaminoethyl (meth) acrylate and dibutylaminoethyl (meth) acrylate. Further, the unsaturated compound having a hydroxyl group is 1
-Hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate and the like can be mentioned.

Furthermore, examples of unsaturated compounds having an epoxy group include glycidyl (meth) acrylate, allyl glycidyl ether, vinyl glycidyl ether and the like. The unsaturated compounds having these functional groups can be used alone or in combination of two or more kinds.
Further, as the other unsaturated compound which can be copolymerized, a polyfunctional unsaturated compound can be mentioned. Specific examples of these include two or more functional groups, preferably 2
A compound having individual copolymerizable double bonds, specifically, non-conjugated divinyl compounds such as divinylbenzene, divinylxylene and divinyl ether, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol. Examples include polyvalent (meth) acrylate compounds such as propane triacrylate, unsaturated carboxylic acid esters such as vinyl (meth) acrylate, isopropenyl (meth) acrylate, and divinyl phthalate.

The content of these other copolymerizable unsaturated compounds in the rubbery copolymer is 0 to 10% by weight, preferably
It is 0.1 to 5% by weight, and is added as needed. On the other hand, if it exceeds 10% by weight, the degree of cross-linking of the rubbery copolymer becomes too large, and the mechanical strength of the obtained composition decreases.

The microstructure of the modified hydrogenated diene polymer (B) before modification and before hydrogenation has a vinyl bond content of 1,2-, 3,4-, etc. of 10% or more, preferably 20-80. %, Particularly preferably 20 to 50%. If it is less than 10%, the hydrogenated diene-based polymer takes on resinous properties, and the impact resistance of the resin composition deteriorates, which does not meet the object of the present invention.

The content of the aromatic vinyl compound in the diene polymer before the modification of the modified hydrogenated diene copolymer (B) and before hydrogenation is 50% by weight or less, preferably 35 to 5% by weight. . If it exceeds 50% by weight, the hydrogenated diene-based polymer has a resin-like property, and the impact resistance of the resin composition deteriorates, so that the object of the present invention is not met. Further, the diene-based polymer is a random copolymer in which aromatic vinyl compounds are bonded at random, and Corsov [IMKolthoff.J.Polymer Sci Vol 1
The content of the block-shaped polyvinyl aromatic compound according to the method of P429 (1946)] is 10% by weight or less, preferably 5% by weight or less, based on the total bound vinyl aromatic compounds.

The diene polymer may be either a linear polymer or a branched polymer, but a branched polymer is preferred from the viewpoint of improving processability and cold flow.

The molecular weight of the modified hydrogenated diene polymer (B) before modification and before hydrogenation is 5,000 to 1,000,000, preferably 30,000 to 300,000 in terms of number average molecular weight. If it is less than 5,000, the hydrogenated diene polymer will be liquid rather than rubber-like, and if it exceeds 1,000,000, the processability will tend to be reduced.

The molecular weight distribution (Mw / Mn) is preferably 10 or less, more preferably 5 or less, particularly preferably 1.
1 to 3. The hydrogenation rate of the olefinic unsaturated bond before modification of the modified hydrogenated diene polymer (B) is 70% or more, preferably 90% or more. If the hydrogenation rate is less than 70%, the effect of improving the weather resistance and heat resistance of the polymer will be insufficient, so that the purpose of the present invention will not be met.

The functional group-containing monomer (unsaturated compound) in the modified hydrogenated diene polymer (B) is 0.05 to 20% by weight, preferably 0.1 to 100% by weight of the hydrogenated diene polymer.
If the amount is less than 0.05% by weight, the resulting resin composition has poor impact resistance. On the other hand, if the amount exceeds 20% by weight, the thermoplastic resin (A) and the modified hydrogenated diene polymer (B) are When compounded, the dispersion state deteriorates, resulting in poor moldability.

The modified hydrogenated diene polymer (B) before modification and before hydrogenation can be obtained by anion living polymerization in a hydrocarbon solvent using, for example, an organolithium initiator. Further, the branched polymer can be obtained by adding a required amount of a tri- or higher functional coupling agent at the end of the polymerization and performing a coupling reaction.

To control the amount of vinyl bonds such as 1,2- and 3,4-bonds, ethers, tertiary amine compounds, alkoxides of alkali metals such as sodium and potassium, phenoxides, and sulfonates are used.

As the organic lithium initiator, n-butyl lithium,
For example, sec-butyllithium, tert-butyllithium, or the like is used. Examples of the hydrocarbon solvent include hexane, heptane, methylcyclopentane, cyclohexane, benzene, toluene, xylene, 2-methylbutene-1,2-
Methylbutene-2 or the like is used.

The polymerization may be a batch system or a continuous system, and the polymerization temperature is usually in the range of 0 to 120 ° C, and the polymerization time is in the range of 10 minutes to 3 hours. The coupling agent is a trifunctional or higher functional coupling agent, examples of which include tetrachlorosilicon,
Butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, tetrachlorogermanium, bis (trichlorosilyl) ethane, divinylbenzene, adipic acid diester, epoxidized liquid polybutadiene, epoxidized soybean oil, epoxidized linseed oil, tolylene diisocyanate, Examples thereof include diphenylmethane diisocyanate and 1,2,4-benzenetriisocyanate.

By hydrogenating the diene polymer thus polymerized, the hydrogenated diene polymer (B) of the present invention can be obtained.

The hydrogenation reaction of the hydrogenated diene-based polymer before modification of the present invention is carried out by dissolving the conjugated diene-based polymer in a hydrocarbon solvent,
1kg / cm ² ~100kg / cm ² pressurized water Motoka at 20 to 150 ° C., is carried out in the presence of a hydrogenation catalyst.

Examples of hydrogenation catalysts include catalysts in which noble metals such as palladium, ruthenium, rhodium, and platinum are supported on silica, carbon, and diatomaceous earth; complex catalysts such as rhodium, ruthenium, and platinum; organic carboxylic acids such as cobalt and nickel; and organic aluminum. Or a catalyst comprising organic lithium, dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyl titanium, dicyclopentadienyl titanium ditolyl, titanium compound such as dicyclopentadienyl titanium dibenzyl and lithium, aluminum, magnesium A hydrogenation catalyst comprising an organometallic compound is used.

A radical generator such as an organic peroxide is usually used in the reaction for modifying the hydrogenated diene polymer with a functional group-containing unsaturated compound. As the organic peroxide used as these functional group addition aids, 2,
5-Dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,2'-bis (t-butyl) Peroxy)
p-diisopropylbenzene, dicumyl peroxide, dit-butylperoxide, t-butylperoxybenzoate, 1,1-bis (t-butylperoxy)
-3,3,5-trimethylcyclohexane, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide,
Although there are p-chlorobenzoyl peroxide and the like, a dialkyl peroxide is more preferably selected and used.

The amount of organic peroxide to be added depends on the hydrogenated diene polymer
0.01 to 1.5 parts by weight, preferably 0.1 to 1.5 parts by weight per 100 parts by weight
1.0 parts by weight.

When the addition amount of the organic peroxide is less than 0.01 parts by weight, the grafting yield of the functional group is low, and when it exceeds 1.5 parts by weight, the cross-linking density of the hydrogenated diene polymer becomes high, and at the time of blending with the thermoplastic resin (A). The dispersed state deteriorates and the moldability becomes poor.

The graft reaction of the functional group to the hydrogenated diene-based polymer is performed by a pre-heated roll mill or Banbury mixer,
Using a closed kneader such as a pressure kneader or an extruder, the hydrogenated diene polymer and the unsaturated compound having a functional group are melt-mixed, and at the same time, an organic peroxide is added to functionalize the hydrogenated diene polymer. It can be carried out by grafting the group.

It can also be carried out by a method of copolymerizing a monomer having a functional group in the conjugated diene unit part in the rubber and further hydrogenating the copolymer.

The method for mixing the resin composition of the present invention is not particularly limited. For example, a method of mixing the thermoplastic resin (A) and the modified hydrogenated diene polymer (B) using a mixer such as a roll, a Banbury mixer, an intermixer, or the modified hydrogenated diene polymer (B) in advance. Pellets, crumbs or powders, dry blend this with the thermoplastic resin (A) with a mixer such as a Henschel mixer or tumbler, and then melt mix with a mixer such as an extruder. In any case, the conditions and the apparatus may be selected so that the respective components are sufficiently dispersed and mixed.

The resin composition of the present invention includes conventional auxiliary additives such as flame retardants, mold release agents, antioxidants, weather resistance imparting agents, antistatic agents, heat stabilizers, colorants, plasticizers and reinforcing agents. , Crosslinker,
Surfactants, lubricants, nucleating agents and the like can be added.
Further, fillers such as calcium carbonate, kaolin, talc, asbestos and glass fibers, thermoplastic resins other than the above used in the present invention, such as polystyrene resin, ethylene-vinyl acetate copolymer resin, polyxylene resin, polyvinyl acetate resin. , Polyvinylidene chloride, fluorine resin, polyacrylonitrile, urethane resin, polyvinyl ketone, polyamide resin, polycarbonate resin, polyacetal resin, polyethylene, polypropylene, polyvinyl chloride, ABS resin, AES resin, MBS resin, acrylic resin,
It is also possible to blend a polyether resin, or an α, β-unsaturated nitrile-conjugated diene-based copolymer rubber other than the above used in the present invention, an ethylene-α-olefin copolymer rubber, or a rubber such as a modified product thereof. It is possible to add it in an amount of 0 based on 100 parts by weight of the resin composition of the present invention.
~ 20 parts by weight are preferred.

The resin composition of the present invention thus obtained is superior to impact resistance, heat resistance and molding processability in comparison with ordinary thermoplastic resins, and therefore LED lamps, relay cases, switches, connectors, coil bobbins. , Telecommunications parts such as resistors, computer parts, telephone exchange parts, condenser cases, tuners, terminal blocks, timer cases; hair dryers, irons, shavers, egg boilers, coffee makers, VTR parts, microwave oven parts, TV
For household electrical parts such as parts, audio parts, compact discs, refrigerator parts, air conditioner parts, word processors, lighting covers, etc .: For precision mechanical parts such as camera bodies, camera parts, clock parts, strobe parts, binoculars, microscope parts, projector parts, etc. : Power tools, vending machine parts, handler bellows, elevator parts, escalator parts,
Motor cases, oil filter cases, pump parts, bolts, nuts, gears, cams, fiber bobbins, counter frames, office computer parts, register parts, calculator parts, typewriter parts, drafting machine parts, facsimile parts, copier parts, etc. For machine-related parts: For automobiles and vehicles, car heater fans, bumpers, instrument panels, instrument panels, motorcycle windshields, headlights, taillights, windbreaks, rail insulation parts, vehicle armrests, curtain covers, wiper covers,
It is especially useful for automobile / vehicle related parts such as mold grips, meter needles and wheel covers, as well as leisure related parts such as surf riders and golf equipment, various covers, surface treatment agents and applications.

e. Examples Next, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to these. Hereinafter, the ratio (parts by weight) to 100 parts by weight of the polymer is shown in PHR units.

Sample 1: (1) Cyclohexane degassed and dehydrated in a 5 l autoclave
After charging 2500 g, 150 g of styrene and 350 g of 1,3-butadiene, 2.5 g of tetrahydrofuran and 0.34 g of n-butyllithium were added, and the temperature was raised to 30 to 80 ° C to carry out polymerization. After the conversion reached approximately 100%, SiCl ₄ 0.
14 g was added. After that, 2,6-di-tert-butylcatechol was added and the solvent was removed by a steam stripping method.
A polymer was obtained by drying on a 120 ° C. hot roll. The styrene-butadiene copolymer thus obtained has a vinyl bond content.
The content was 30%, the styrene content was 30% by weight, and the branched polymer having 3 or more branches was 56% by weight. The number average molecular weight by GPC analysis is 2
00,000 and Mw / Mn were 1.5.

(2) The conjugated diene-based copolymer polymerized in (1) was charged into a 3 l autoclave to prepare a 15% cyclohexane solution.
After substituting the system with nitrogen, the catalyst solution of nickel naphthenate: n-butyllithium: tetrahydrofuran = 1: 8: 20 (molar ratio), which had been prepared in a separate container in advance, was added to the olefin portion.
It was prepared so that the amount of nickel was 1 mol with respect to 2000 mol. Thereafter, hydrogen was introduced into the reaction system, and a hydrogenation reaction was performed at 70 ° C. After controlling the hydrogenation rate from the absorption and consumption of hydrogen, the hydrogen in the system was replaced with nitrogen, and the antioxidant 2,6-di-tert-butylparacresol was added to 1PHR.
Was added. After repeating contact removal and solidification, roll drying was carried out by a conventional method to obtain a hydrogenated diene polymer having a hydrogenation rate of 95%.

Sample 2: A styrene-butadiene copolymer having a vinyl bond content of 30% by weight and a styrene content of 30% by weight was obtained in the same manner as in (1) of Sample 1 except that the coupling reaction was not performed. This was treated in the same manner as in Sample 1 (2) to obtain a hydrogenated diene copolymer having a hydrogenation ratio of 98%.

Samples 3 to 6: In the same manner, hydrogenated diene-based copolymers shown in Table 1 were obtained.

The analytical values in the above table were determined as follows.

-The bound styrene content was determined from a calibration curve by an infrared method based on the absorption of a phenyl group at 679 cm- ¹ .

-The vinyl bond content was determined by an infrared method (Morello method).

-Molecular weight, molecular weight distribution, and coupling efficiency (C / E) were determined by gel permeation chromatography (GPC).

The hydrogenation rate was calculated from the decrease in the unsaturated bond portion of the ¹ H-NMR spectrum at 100 MHz measured at a concentration of 15% using ethylene tetrachloride as a solvent.

Example 1 The component (B) was obtained by using the sample 2 described in Table 1 above and performing graft polymerization according to the following procedure.

That is, 100 parts of Sample 2 was adjusted to 190 ° C with a mixer (HAAKE RHEOCORD SYSTEM40 RHEOM manufactured by HAAKE BUCHLER).
IX MIXER600) and after 2 minutes, 2.5 parts of maleic anhydride was added, and after melting and mixing, organic peroxide [2,5-dimethyl-2,5-di (t-butylperoxy) hexane; NOF Corporation] 0.15 part of Perhexa 25B manufactured by Co., Ltd. was added, and kneading was continued for 5 minutes to obtain a component (B).

Polybutylene terephthalate as a thermoplastic polyester resin (A) (Novadur 50 manufactured by Mitsubishi Kasei Co., Ltd.)
Using 10), 80 parts by weight of the component (A) and 20 parts by weight of the component (B) previously pelletized by shredding were stirred by a tumbler so that the contents became uniform. Mixer adjusted to 240 ℃ (HAAKE BUC
It was put into a HAKE company HAAKE PHEOCORD SYSTEM40 EXTRUDER) and melt-mixed. The extrudate obtained is pelletized by a pelletizer and is molded by an injection molding machine (250 ° C) to prepare Izod impact test pieces, and Izod impact test (after normal value and heat aging, after weathering test) JIS
It carried out according to K7110. The heat aging resistance was evaluated by using a Gar oven and evaluating the Izod impact strength after exposing the Izod test piece in the air at 120 ° C for 120 hours. The weather resistance test uses a sunshine weatherometer and the Izod test piece is tested with a black panel temperature of 83.
The Izod impact strength was evaluated after 500 hours of exposure in an arc at ℃.

The moldability was evaluated by visually inspecting the surface gloss after injection molding. O marks have good gloss, and X marks have poor gloss.

 Table 2 shows the results.

Example 2 Using the hydrogenated diene-based polymer shown in Table 1 as Sample 2, graft polymerization was performed in advance according to the following procedure to prepare the component (B), and then the resin composition was prepared in the same manner as in Example 1. The product was prepared and the composition was evaluated.

That is, the graft reaction was carried out by
The mixture was put into the mixer adjusted to 90 ° C., 2.5 minutes later, 2.5 parts of glycidyl methacrylate was added, and after melting and mixing, an organic peroxide [2,5-dimethyl-2,5-di (t-butylperoxy)] was added. Hexane; manufactured by NOF CORPORATION, Perhexa 25B]
0.15 parts was added and kneading was continued for 5 minutes to obtain the composition (B) component of the present application. Table 2 shows the results.

Example 3 Using the hydrogenated diene-based polymer shown in Table 1 as Sample 2, graft polymerization was performed in advance according to the following procedure to prepare the component (B), and then the resin composition was prepared in the same manner as in Example 1. The materials were adjusted and the composition was evaluated.

That is, for the graft reaction, 100 parts of the above sample 2 was charged into the mixer adjusted to 190 ° C., and after 2 minutes, 2.5 parts each of maleic anhydride and divinylbenzene were added, and after mixing, an organic peroxide (2,5- Dimethyl-2,5-di (t-butylperoxy) hexane: manufactured by NOF CORPORATION (Perhexa 25B)
Component (B) was obtained by adding 0.15 part and continuing kneading for 5 minutes. Table 2 shows the results.

Example 4 Maleic anhydride was graft-polymerized in the same manner as in Example 1 except that the hydrogenated diene-based polymer shown as Sample 4 in Table 1 was used to prepare a resin composition and evaluate the composition. went. Table 2 shows the results.

Comparative Example 1 A resin composition was prepared in the same manner as in Example 1 except that the hydrogenated diene-based polymer shown in Table 1 as a sample 2 was used before the hydrogenation and the functional group was not graft-polymerized. Was prepared and the composition was evaluated. Table 2 shows the results.

Comparative Example 2 Using the diene copolymer before hydrogenation used in Comparative Example 1, maleic anhydride graft polymerization was carried out in the same manner as in Example 1, a resin composition was prepared and compounding evaluation was carried out. Table 2 shows the results.

Comparative Example 3 Using the hydrogenated diene polymer shown in Table 1 as Sample 2, a resin composition was prepared in the same manner as in Example 1 except that the functional group was not graft-polymerized, and the composition was evaluated. Table 2 shows the results.

Comparative Example 4 A compounding evaluation was performed in the same manner as in Example 1 except that only polybutylene terephthalate (Novadul 5010 manufactured by Mitsubishi Kasei Co., Ltd.) was used. Table 2 shows the results.

Example 5 A resin composition was prepared in the same manner as in Example 1 except that the hydrogenated diene polymer shown as Sample 3 in Table 1 was used, and the composition was evaluated. Table 2 shows the results.

Comparative Example 5 In the preparation of Sample 1, without using tetrahydrofuran, first charge 75 g of styrene into a 5 l autoclave.
-Butyllithium was added as a catalyst to polymerize styrene, then 350 g of butadiene was added and polymerized, and finally 75 g of styrene was added and polymerized to obtain a styrene-butadiene block copolymer (Sample 7). .

The obtained block copolymer was hydrogenated in the same manner as in Sample 1 to obtain a hydrogenated diene block copolymer. This hydrogenated diene block copolymer was used in place of the diene polymer, maleic anhydride was reacted in the same manner as in Example 1 to prepare a resin composition, and the composition was evaluated. Table 2 shows the results.

Example 6 30 parts by weight of the modified hydrogenated diene-based copolymer (component (B)) obtained by the method shown in Example 1 and a polycarbonate resin (Upilon S-2000 manufactured by Mitsubishi Gas Chemical Co., Inc .; (A)) Ingredients) 70 parts by weight of a closed type mixer (HAAKE BUCHLER RH
EOMIX MIXER600) was melted and kneaded at 190 ° C. and 60 rpm for 5 minutes to obtain a resin composition. The resin composition thus obtained was compression-molded for 5 minutes with an electric heating press heated to 200 ° C. to prepare an Izod impact test piece. Impact value is normal
37.2kg ・ cm / cm, 120 ℃ × 120 hours 34.5k after air heating aging
g · cm / cm.

Comparative Example 6 Example 6 except that only the polycarbonate resin was used.
Evaluation was performed in the same manner as described above. Izod impact value is 25.5kgcm / cm in the normal state, 8.6kg after heating and aging at 120 ° C for 120 hours
cm / cm.

Example 7 Same as Example 6 except that 80 parts by weight of polyacetal resin (Duracon M25-01; (A) component manufactured by Polyplastics Co., Ltd.) and 20 parts by weight of modified hydrogenated diene copolymer (Sample 2) were used. Was blended and evaluated. Impact value is normal
15.2kg ・ cm / cm, 120 ℃ / 120 hours after air heating aging 12.8kg
・ It was cm / cm.

Comparative Example 7 Evaluation was performed in the same manner as in Example 7 except that only the polyacetal resin was used. The impact value was 5.4 kg · cm / cm in the normal state and 5.0 kg · cm / cm after heat aging.

Example 8 80 parts by weight of polyphenylene ether resin (Noryl 731J manufactured by Engineering Plastics Co., Ltd .; (A) component) and 20 parts by weight of modified hydrogenated diene copolymer (sample 2) were adjusted to 260 ° C. in a closed mixer. After melt-kneading at 60 rpm for 4 minutes and pelletizing, an Izod impact test piece was molded by an injection molding machine (290 ° C). Impact value is 19.5 in normal state
kg ・ cm / cm, 120 ℃ × 120 hours 20.8kg ・ c after air heating aging
It was m / cm.

Comparative Example 8 Except that only polyphenylene ether resin was used,
Evaluation was carried out in the same manner as in Example 8. Impact value is 10.1 in normal state
kg · cm / cm, 9.2 kg · cm / cm after heat aging.

Examples 9 and 10 Instead of the polybutylene terephthalate of Example 1,
A resin composition was prepared in the same manner as in Example 1 except that the styrene resin or acrylic resin shown in Table 3 was used,
The composition was evaluated. The results are shown in Table-3.

f. Effects of the Invention According to the present invention, it is possible to provide a resin composition excellent in properties such as impact resistance, heat resistance, weather resistance, and moldability, particularly impact resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 67/00 C08L 67/00 69/00 69/00 71/12 71/12 (72) Inventor Koji Engyo 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) Reference JP-A-58-27740 (JP, A) JP-A-63-118369 (JP, A) JP-A-SHO 62-86048 (JP, A) JP-A-2-651 (JP, A) Special Table 3-501133 (JP, A)

Claims (1)

(57) [Claims] 1. A composition obtained by mixing 50 to 95 parts by weight of a thermoplastic resin (A) and 50 to 5 parts by weight of a modified hydrogenated diene polymer (B), wherein the thermoplastic resin (A ) Is a thermoplastic polyester resin,
At least one resin selected from the group consisting of polycarbonate, polyoxymethylene, polyphenylene ether, styrene resin, and acrylic resin, wherein the modified hydrogenated diene polymer (B) is at least one conjugated diene polymer. Or a random diene copolymer of at least one conjugated diene and 50% by weight or less of a vinyl aromatic compound (however, the content of the block-shaped polyvinyl aromatic compound is 10% by weight in the total bonded vinyl aromatic compound).
It is as follows. ) And having a number average molecular weight of 5,000 to 1,00
And a hydrogenated diene (co) polymer having a vinyl bond content of 10% or more in its diene part, wherein at least 70% of the olefinically unsaturated bond of the (co) polymer is With respect to 100 parts by weight of the hydrogenated hydrogenated diene polymer, an unsaturated compound having at least one functional group selected from the group consisting of a carboxyl group or an acid anhydride thereof, an amino group, a hydroxyl group and an epoxy group 0 .
A thermoplastic resin composition, which is obtained by reacting 05 to 20 parts by weight.