JPS60188451A - Thermoplastic elastomer - Google Patents

Abstract

PURPOSE:The titled elastomer having excellent heat resistance, oil resistance, and rubber elasticity, made by compounding a specified, modified hydrogenated copolymer with a polyamide-polyether copolymer by heating. CONSTITUTION:100pts.wt. hydrogenated product obtained by the hydrogenation, at 24-320 deg.C for 0.1-24hr under a pressure from atmospheric to 300atm in the presence of a hydrogenation catalyst, of a copolymer which has a number- average molecular weight of 10<4>-10<6> and consists of 2-60wt% vinyl aromatic compound (e.g. styrene) and 98-40wt% conjugated diene (e.g. 1,3-butadiene); and 0.001-20pts.wt. graft monomer selected from among unsaturated carboxylic acids (derivatives) are graft polymerized at 60-350 deg.C to obtain a modified hydrogenated copolymer (A). Then, 95-5wt% component A and 5-95wt% polyamide-polyether copolymer (B) are compounded at 150-370 deg.C.

Description

Detailed Description of the Invention The present invention relates to a modified hydrogenated copolymer (A) obtained by grafting an unsaturated carboxylic acid or a derivative thereof to a hydrogenated copolymer consisting of a vinyl aromatic compound and a conjugated diene compound, and a polyamide. -Regarding a thermoplastic elastomer mixed with a polyether copolymer (B), the thermoplastic elastomer having well-balanced properties such as heat resistance, oil resistance, and rubber elasticity.

Conventionally known thermoplastic elastomers include polytetramethylene terephthalate-polytetramethylene glycol-block copolymers and block copolymers of nylon-11, nylon-12, etc., and polyethylene glycol, polytetramethylene glycol, etc. Since it does not require vulcanization, has rubber-like properties, and has excellent processability, attempts have been made to use it for various purposes.

On the other hand, as another thermoplastic elastomer, JP-A-52-1
No. 50457 discloses a composition comprising a hydrogenated polystyrene-polybutadiene block copolymer blended with a polyamide polymer such as nylon-6 or nylon-66. However, this composition still has some shortcomings, such as the need for a different mixing method depending on the type of polyamide.

Further, JP-A-55-165931 discloses a thermoplastic polymer composition comprising a modified conjugated diene polymer in which an unsaturated carboxylic acid or a derivative thereof is added to a conjugated diene polymer, and polyamide. . However, this composition is relatively susceptible to deterioration due to heat, and therefore requires special consideration such as lowering the temperature during polymerization to avoid deterioration, and it becomes brittle in a short period of time when used in a high-temperature atmosphere. There are still some shortcomings, such as:

The present inventors grafted an unsaturated carboxylic acid or a derivative thereof to a hydrogenated copolymer consisting of a vinyl aromatic compound and a conjugated diene compound to obtain a modified product, and combined this with a polyamide/polyether copolymer. The thermoplastic elastomer obtained by mixing these under heating has a good balance of properties such as tensile strength, elongation, permanent set, and hardness, and also has excellent properties such as heat resistance, oil resistance, and rubber elasticity. They discovered this and arrived at the present invention.

That is, the present invention provides a modified copolymer obtained by graft copolymerizing a graft monomer selected from unsaturated carboxylic acids and derivatives thereof to part or all of a hydrogenated copolymer consisting of a vinyl aromatic compound and a conjugated diene compound. A modified hydrogenated copolymer (A) in which the proportion of the graft monomer is from about o, ooi to about 20 parts by weight per 100 parts by weight of the hydride of the copolymer;
It consists of a polyether copolymer (B) whose weight ratio (
The present invention relates to a thermoplastic elastomer characterized by being formed by mixing A)/(B) in a ratio of 9515 to 5/95 under heating.

Hydrogenated copolymers consisting of a vinyl aromatic compound and a conjugated diene compound, which are the origin of the modified product used in the present invention, include random copolymers consisting of a vinyl aromatic compound and a conjugated diene compound, linear , hydrides obtained by hydrogenating radial or branched block copolymers. Vinyl aromatic compounds include styrene, α-methylstyrene, vinyltoluene, p-tert-phthylstyrene,
Examples include vinylxylene, ethylvinylxylene, vinylnaphthalene, and mixtures thereof, and among these, styrene is particularly preferred. Examples of conjugated diene compounds include L,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, halogenated derivatives thereof, and mixtures thereof. A combination of conjugated diene compounds mainly consisting of is preferred, and butadiene is particularly preferred.

Among the copolymers consisting of a vinyl aromatic compound and a conjugated diene compound used as raw materials for hydrides, the random copolymers have a number average molecular weight of about 10.00.0 to about 1.
000,000, particularly preferably from about 20.00.0 to 300.000. Examples of block copolymers include block copolymers disclosed in JP-A-52-150457 or JP-A-5.3-71158, in which block copolymers made of vinyl aromatic compounds (
A block (Y) consisting of X) and (X:) and a conjugated diene compound (however, X and Xl may be the same or different) has a configuration such as X+Y-X-Y thick X, X-(-Y
-X→, Y (n is an integer of 1 to 10), and the like. Among these block copolymers, the end block is preferably a block made of a vinyl aromatic compound. The number average molecular weight of the block copolymer is preferably from about 10,000 to about 1.000.0
00, particularly preferably about 20,000 to about 30
It is in the range of 0.000. Further, the average molecular weight of each block consisting of a vinyl aromatic compound is preferably about 1,
000 to about 500.00.0, particularly preferably about 2.000 to about 300,000, and the average molecular weight of each block of conjugated diene compounds is preferably about 1,000 to about 500,000, particularly preferably ranges from about 2.000 to about 30.0.000.

In addition, the weight ratio of vinyl aromatic compound and conjugated diene compound in these random and block copolymers is
The range is preferably from about 2/98 to about 60/40, particularly preferably from about 10/90 to about 40/60.

In the present invention, hydrides obtained by hydrogenating these copolymers are used.

When hydrogenating a copolymer of a vinyl aromatic compound and a conjugated diene compound, it is preferable that 90% or more of the aliphatic double bonds are hydrogenated and 10% or less of the aromatic double bonds are hydrogenated. Especially preferred are those in which 99% or more of aliphatic double bonds are hydrogenated and 5% or less of aromatic double bonds are hydrogenated.

For hydrogenation, methods known to those skilled in the art can be employed. Examples of the hydrogenation catalyst include nickel on porous diatom, Raney nickel, copper dichromate, molybdenum sulfide, and catalysts in which platinum, palladium, etc. are supported on a carrier such as carbon. Hydrogenation at any pressure,
Temperature, e.g. atmospheric pressure to 300 atmospheres, usually 5 to 20
0.1 at temperatures between 24°C and 320°C at 0 atmospheric pressure
It can be carried out for 24 hours to 24 hours, preferably 0.2 to 10 hours.

Examples of copolymers consisting of a vinyl aromatic compound and a conjugated diene compound include styrene-butadiene random copolymer, styrene-isoprene random copolymer, butadiene-polystyrene-block copolymer, and polystyrene-polyisoprene- Examples include polystyrene-block copolymer, poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene)-block copolymer, and the like. Commercial products can also be used as these copolymers, and hydrides are also commercially available. These include, for example, Cariflex TR-1101, TR1107, TR4
113th Engineering Chemical Company Clayton G-6500, G6521, G1650
, G1652 Engineering Chemical Co., Ltd., and Hydrogenated Turprene Phillips Co., Ltd. are examples.

In order to graft-copolymerize a graft monomer selected from unsaturated carboxylic acids and derivatives thereof to a hydrogenated copolymer consisting of a vinyl aromatic compound and a conjugated diene compound, the hydrogenated copolymer and the graft monomer are It is carried out in the melt or in solution, with or without radical initiators.

Grafting monomers selected from unsaturated carboxylic acids and their derivatives include acrylic acid, methacrylic acid, α-
Ethyl acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endo-bicyclo(2,2,1)hept-5-ene-2,3-dicarboxylic acid (nadic acid) ■)
, unsaturated carboxylic acids such as methyl-endocys-bicyclo(2,2,1)hept-5-ene-2,3-dicarboxylic acid (methyl nadic acid), their acid halides, amides, imides, acid anhydrides , esters, and other derivatives, and specific examples include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid, and their acid anhydrides are particularly preferred.

The method of graft copolymerizing the graft monomer to the hydrogenated copolymer is not particularly limited, but the modified hydrogenated copolymer obtained may contain undesirable components such as gel, etc. It is desirable to avoid deterioration of processability due to a decrease in fluidity. For this purpose, when graft copolymerization is carried out by addition reaction under melt-mixing conditions using an extruder or the like, it is necessary to carry out the graft copolymerization in the presence of known stabilizers such as phenol-based, phosphorus-based, and amine-based stabilizers. desirable.

The reaction temperature for graft copolymerization is usually from 60 to about 35
It is carried out at 0°C, particularly preferably at about 100 to about 300°C. The addition ratio of the graft monomer is about 0.001 to about 20 parts by weight, particularly 0.01 to 10 parts by weight, based on 100 parts by weight of the hydrogenated block copolymer.
%, and the addition ratio of the radical initiator is similarly preferably 0.001 to 30 parts by weight, particularly preferably 0.01 to 20 parts by weight. By graft copolymerizing within such a range, the monomers from Graph 1 can be efficiently grafted onto the hydrogenated copolymer.

The modified hydrogenated copolymer prepared by the above method can be prepared by removing rigid substances such as gel-like substances as necessary, or by removing a copolymer consisting of a vinyl aromatic compound and a conjugated diene compound and/or its hydrogen. It is prepared by diluting it with chemicals. Particular preference is given here to using copolymer hydrides.

In the modified hydrogenated copolymer used in the present invention, the proportion of the graft monomer is about 0.001 to about 20 parts by weight, particularly preferably about 0.01 to about 20 parts by weight, based on 100 parts by weight of the modified hydrogenated copolymer. It is in the range of 10 parts by weight. 0.0
If the amount is less than 1 part by weight, the effect of improving physical properties will be small;
If it exceeds 0 parts by weight, gelation tends to occur during synthesis.

The polyamide/polyether copolymer (B) used in the present invention excludes polyamides consisting only of polyamide bonds. For example, the method disclosed in JP-A-56-65026 or cited therein It can be manufactured by a known method. Namely, ■ polycondensation of a polyamide (including oligomers) having both carboxyl end groups and a polyether having both hydroxyl end groups and/or amine end groups, and ■ polyamide having both amino end groups and a polyamide having both carboxyl end groups. Polycondensation of polyethers, 1. Polycondensation of polyamide-forming monomers such as lactams, ω-aminocarboxylic acids or equivalent dicarboxylic acids and diamines in the presence of dicarboxylic acids and polyethers with both hydroxyl and/or amino ends. It can be produced by condensation, (2) polycondensation of a polyamide-forming monomer and a polyether having carboxyl groups at both ends in the presence of a diamine, and the like.

Examples of raw material polyamides such as polyamides having both carboxyl terminal groups used in the above method amide (nylon 6.9), polyhexamethylene adipamide (nylon 6.10) and polyhexamethylene dodecanoamide (nylon 6.12) polybis(4-aminocyclohexyl)methandodecanamide, etc., and also lactams. poly-ε-caprolactam (nylon 6) produced by ring-opening polymerization of aminocarboxylic acids or by polycondensation of aminocarboxylic acids;
Polylaurinlactam (nylon 12) or poly-1
Examples include 1-aminoundecanoic acid (nylon 11).

diamines used to produce the polyamides mentioned above;
It is also possible to use copolymeric polyamides prepared by combining at least two or more dicarboxylic acids, lactam acids and aminocarboxylic acids, for example polymers made from adipic acid, isophthalic acid and hexamethylene diamine. . It is also possible to use blends of polyamides, such as mixtures of nylon 6.6 and nylon 6. Among these polyamides, polyhexamethylene adipamide (nylon 6.6), polyhexamethylene adipamide (nylon 6.10), poly-ε-caprolactam (nylon 6), polylaurin lactam ( Nylon 12), and poly-11-aminoundecanoic acid (Nylon 11)
etc. are preferable. As a method for introducing a carboxyl group or an amino group into the molecular terminal of these polyamides, a known method can be used in which the carboxyl group or amino group is introduced during or after the production of the polyamide.

Further, examples of the polyether used in the above-mentioned methods (1) to (3) include polyethylene oxide, polypropylene oxide, polyofsacyclobutane, polytetrahydrofuran, and copolymers of ethylene oxide, propylene oxide, tetrahydrofuran, and the like. In order to introduce amino groups or carboxyl terminals into these polyethers, Japanese Patent Application Laid-Open No. 56-65026
This can be done by a known method cited in the above publication.

Furthermore, the dicarboxylic acids used in method (1) or (2) include aliphatic dicarboxylic acids such as succinic acid, adipic acid, pimelic acid, superric acid, sebacic acid and dodecanoic acid, aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid 4, and terephthalic acid. , isophthalic acid, and aromatic dicarboxylic acids such as knack dicarboxylic acid. Similarly, diamines include ethylenediamine,
Aliphatic diamines such as tetraethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, alicyclic diamines such as diaminocyclohexane, diaminomethylcyclohexane, piperazine, isophoronediamine, p-phenylenediamine, m-phenylene There are aromatic diamines such as diamine and xylylene diamine.

Furthermore, examples of the lactam include ε-prolactam, enantlactam, undecanolactam, and laurinlactam. In addition, as ω-aminocarboxylic acid,
6-aminocaproic acid, 11-aminoundecanoic acid, 1
Examples include 2-aminododecanoic acid.

Hardness: Using sheet (b), JTS K6301
Measured according to the following.

The composition ratio of the polyamide/polyether copolymer was calculated by quantifying the weight of nitrogen contained in the copolymer using elemental analysis.

Intrinsic viscosity of polyamide/polyether copolymer: 30
m-cresol/toluene (1/1 ratio) at °C
Measured in solution.

Molecular weight of polyamide/polyether copolymer: Calculated by quantifying terminal amino groups and carboxyl groups. The amino group was obtained by dissolving the polyamide/polyether copolymer in m-cresol and using thymol blue as an indicator at 0.
Electricity was applied with a 1N p-toluenesulfone@/m-cresol solution. The carboxyl group was obtained by dissolving the polyamide/polyether copolymer in benzyl alcohol, using phenolphthalein as an indicator, and adding 0.0% to the solution. lNNaOH/
Electricity was applied with a benzyl alcohol solution.

Furthermore, among the polyamide/polyether copolymers (B) used in the present invention, the weight of polyether (Ml
) and the total weight of polyamide chains (M2) (Ml/
M sand is preferably in the range of about 2/98 to about 98/2, preferably in the range of about 5/95 to about 95/5. When the weight ratio (M+/Mz) is less than 2/98, rubber properties such as permanent set and hardness are reduced. Moreover, if it exceeds 98/2, heat resistance, oil resistance, etc. will decrease.

In a particularly preferred embodiment of the polyamide/polyether copolymer (B), the molecular weight of the polyether segment is in the range of about 200 to about 100,000, particularly about 300 to about 50,000, and the polyamide segment The copolymer has a molecular weight ranging from about 300 to about 100,000, particularly from about 500 to about 50,000. Further, such a polyamide/polyether copolymer (B) is m-cresol/toluene-1/1wt
In many cases, it is soluble in a solvent with a ratio of 0.5 to 5.0.

As the polyamide/polyether copolymer (B),
For example, polyethylene oxide-nylon 6 copolymer, polypropylene oxide-nylon 6 copolymer, polytetrahydrofuran-nylon 76 6 6, 6 copolymer, polytetrahydrofuran-nylon 1
1 copolymer, polytetrahydrofuran-nylon 12 copolymer, ethylene oxide/propylene oxide copolymer-nylon 6 copolymer, and the like.

The thermoplastic elastomer of the present invention comprises a modified hydrogenated copolymer (A) and a polyamide/polyether copolymer (B).
), the weight ratio of which is in the range of 9515 to 5/95,
Particularly preferably, the mixture is mixed under heating in a range of 90/10 to 10/90. If the weight ratio is less than 5/95, rubber properties such as permanent set and hardness will deteriorate.

Moreover, when it exceeds 9515, heat resistance, oil resistance, etc. decrease.

Mixing under heat can be carried out in the presence of an organic diluent, but is usually carried out in its absence. It is not particularly necessary to add a catalyst during mixing.

With this mixture, some or all of the amino groups of the polyamide/polyether 8 copolymer (B) can be bonded to the graft monomer grafted to the modified hydrogenated copolymer (A) by amide bonds, imide bonds, etc. A linked copolymer is preferred. Water, alcohol, etc. produced as this reaction progresses can be removed by natural distillation using an inert gas such as nitrogen, or by distillation under reduced pressure.

When mixing (A) and (B) under heating, other additives such as colorants, stabilizers, inorganic fillers, organic fillers, etc. may be added at the beginning, intermediate or final stage. I can do it.

For mixing (A) and (B) or other additives, conventionally known devices such as a reactor with stirring blades,
- Kneading devices such as a shaft or twin screw extruder, a Banbury mixer, a kneader, and a mixing roll can be used alone or in combination.

The temperature of mixing under heating is preferably higher than the melting point of the modified hydrogenated copolymer (A) and the polyamide/polyether copolymer (B), particularly 150 to 370'
c, preferably at a temperature in the range of about 200 to about 350°C. If it is less than 150''c, the reaction between the amino groups of the polyamide and the graft monomer is slow.

Moreover, if the temperature exceeds 370°C, there are disadvantages such as side reactions such as decomposition and crosslinking. Further, the melt mixing under heating is carried out for about 2 minutes to about 10 hours, if necessary.

The above molten mixture can be used as it is in the thermoplastic elastomer of the present invention, or the unreacted modified hydrogenated copolymer (A) and polyamide/polyether copolymer (B) may be separated and removed. It is also possible to use only a copolymer of (A) and (B).

Among the thermoplastic elastomers provided by the present invention,
Intrinsic viscosity [η) (m-cresol/toluene-1/1
(weight ratio)) is about 0.2 to about 4.0, especially about 0.
5 to about 3.0 are particularly preferably used, and have well-balanced properties such as heat resistance, oil resistance, and rubber elasticity, and can be used alone or in combination with ■9 other additives for various purposes. used for.

The thermoplastic elastomer of the present invention improves the properties of conventional polyamide resins such as nylon 6.
It is also suitable for use in blending with these polyamide resins.

The thermoplastic elastomer of the present invention contains additives conventionally blended as modifiers for polyamide resins, such as hydrogenated polybutadiene, various polymers including polystyrene-hydrogenated polybutadiene-block copolymers, fiberglass, etc. Together with fillers, they can also be incorporated into polyamides to achieve a modifying effect, for example to improve impact resistance.

In these applications, when the thermoplastic elastomer of the present invention is blended, an organic diluent such as toluene, cyclohexane, N-methylpyrrolidone, hexamethylphosphoramide, etc. may be present, if necessary.

Additionally, additives that can be used in the present invention include:
Examples include colorants, stabilizers, softeners, plasticizers, blowing agents, lubricants, inorganic fillers, organic fillers, etc.10 More specifically, colorants include dyes such as nitrosine, cadmium sulfide, phthalocyanine, Examples include pigments such as carbon black and titanium oxide, and stabilizers include hindered phenol, hydroquinone, thioether,
Antioxidants and heat stabilizers such as phosphites and substituted products and combinations thereof; ultraviolet absorbers such as resorcinol, salicylate, benzotriazole, and benzophenone; higher fatty acids such as stearic acid and montanic acid, and their metal salts and esters; Various lubricants and mold release agents including derivatives such as Hafestel, stearyl alcohol and stearamide, flame retardant aids such as antimony oxide, antistatic agents such as sodium dodecylbenzenesulfonate and polyalkylene glycol, and crystallization promoters. Examples of inorganic fillers include fibrous materials such as glass fuzzy bars, carbon fibers, and ceramic fibers, plate-like materials such as mica, glass beads, silica, and titanic acid. Granular and powdered materials such as barium, hydrotalcite, and 2-zeolite are exemplified.

Organic fillers include fluororesins such as Teflon, wholly aromatic polyamide resin fibers such as Kevlar, and phenol resin fibers.

Softeners include process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, petroleum softeners such as petrolatum; coal tar softeners such as coal tar and coal tar pitch; castor oil, linseed oil, and rapeseed oil. , fatty oil-based softeners such as coconut oil: tall oil; sub-oil;
Examples include waxes such as beeswax, carnauba wax, and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate, and zinc laurate; and synthetic polymeric substances such as petroleum resins.

Plasticizers include phthalate esters, adipate esters, sebacate esters, phosphoric acid esters, etc., and tackifiers include coumaroindene resin, terpene/phenol resin, xylene/formalin resin, etc. The blending amount of these additives is determined as appropriate, but when blending fillers such as inorganic fillers and organic fillers, approximately 100 parts by weight of the composition consisting of (A) and (B) 0.
It is preferred to melt mix in a proportion of 1 to about 200 parts by weight, particularly about 1 to about 150 parts by weight.

Polymers used as additives include polybutadiene, polyisoprene, or their hydrides, ethylene propylene rubber, ethylene propylene diene rubber, styrene butadiene rubber, hydrogenated styrene butadiene rubber, or acrylic acid, maleic anhydride, etc. Modified rubber graft copolymerized with polyethylene, polypropylene, ethylene-1-butene copolymer, ethylene-4
-α-olefin resins such as methyl-1-pentene copolymer and 4-methyl-1-pentene-decene copolymer,
Or elastomer, polymethacrylic acid, acrylic resin such as ethylene-ethyl acrylate copolymer, ionomer resin such as zinc salt of ethylene-methacrylic acid copolymer, ethylene-vinyl acetate copolymer, polyacecool, polyryoku 3 Examples include -bonate, polysulfone, polyphenylene oxide, fluororesin, phenol resin, melamine resin, unsaturated or saturated polyester resin, silicone resin, and epoxy resin.

The amount of the above-mentioned additives can be determined as appropriate depending on the application.
For example, it can be used for various molded products, such as industrial parts, by methods such as injection molding and extrusion molding.

Next, the present invention will be explained with reference to Examples.

In the Examples, the following methods were used for molding and evaluating the physical properties of the products.

Molding: The composition consisting of dried (A) and (B) was molded using a press molding machine at a molding temperature of 240°C, a molding pressure of 50 kgZc, and a nitrogen atmosphere of 11X11X0.05 cm'fal and 5X5.
A sheet having a shape of X O, 3 cm (bl) was prepared.

Tensile test: A bell-shaped test piece with a length of 5 cm and a width of 0 and 5 cm with a parallel portion 5 4 was punched out from the sheet of (a), and tested using an Instron tensile tester model 1122.
The test was carried out under the conditions of 3'C and a crosshead speed of 50 mm/min.

Permanent set: Based on the hysteresis curve of the tensile test. That is, the test piece was stretched 100% at a crosshead speed of 50 mm/min, and then the crosshead was lowered to the position before the test at the same speed, and the sample was further stretched to 100%. In this test, the strain remaining during the second stretching was defined as permanent strain.

Glass transition point Tg: Measured using a dynamic mechanical analyzer (DMA) model 981 manufactured by DuPont.

Melting point Tm: Measured using a differential scanning calorimeter model DSC-2 manufactured by PerkinElmer.

Vicat softening point: Using sheet (b), JIS
K72066 Reference Example 1 <Synthesis of maleic anhydride modified product of hydride of styrene-butadiene-block copolymer> Hydrogenated styrene-butadiene block copolymer ( Hereinafter referred to as rSEBSJ, the shell
460 parts by weight of 652 (trade name: Kraton G), manufactured by Chemical Company, styrene content 29%, and 1800 ml of xylene were added and heated to 140°C to melt. After dissolution, 400 ml of a xylene solution containing 34.5 g of maleic anhydride and 100 ml of a xylene solution containing 6.22 g of dicumyl peroxide
ml was added dropwise from the dropping funnel over 4 hours. After the dropwise addition was completed, the reaction was further carried out at 140°C for 2 hours,
The contents were poured into acetone, and the precipitate was collected by filtration, washed with acetone, and then dried at 100°C under reduced pressure for one day.

From elemental analysis, maleic acid-modified 5EBS contains 5EBS1.
00 parts by weight of maleic reference example 2 <Synthesis of maleic anhydride modified product of styrene-butadiene block copolymer> Styrene-butadiene block copolymer (hereinafter referred to as rsB
sJ, manufactured by Shell Chemical Company, trade name CARIFLEX T R1101 (styrene content 30%) 460 parts by weight, maleic anhydride 34.5 g, dicumyl peroxide 6
．． A reaction similar to that in Reference Example 1 was carried out using 22 g. As a result, maleic acid-modified SBS to which 1.0 part by weight of maleic acid was added per 100 parts by weight of 5BS was produced.

Reference example 3 <Synthesis of polyamide/polyether copolymer> Stirrer,
6-Aminocaproic acid 174 was added to a reactor equipped with a nitrogen introduction tube.
．． 1g (1,33 mole), bisaminopropyl polytetrahydrofuran (B A P -PTHF, manufactured by BASF, molecular weight 750) 86.2 g (0,11 mole)
le), introducing sebacic acid (0.11 mole). The mixture was heated under a nitrogen atmosphere to 260° C. with stirring for 2 hours. Thereafter, the mixture was heated and stirred at 260° C. for 3 hours. Furthermore, the system was depressurized and under high vacuum (3mm
ml, and the reaction was continued for 1 hour with stirring. As a result, a very viscous melt was produced. The melt was cooled and removed. As a result of examining the composition of the polyamide/polyether copolymer thus synthesized, the weight composition ratio of the polyamide component and the polyether component was 60/40.

In addition, the intrinsic viscosity is 1.55 dl/g, and the melting point is 198
It was °C.

Also, 6-aminocaproic acid, BAP-PTHF
Synthesis of polyamide/polyether copolymers was carried out in the same manner by changing the molar ratio of sebacic acid. Ether copolymers were used and mixed in the proportions shown in Table 2. This mixture was heated under a nitrogen atmosphere for 20
mmψ extruder (single screw, Dalmage type screw, L/D
= 28), and a melt blend (pellet shape) was prepared at a cylinder temperature of 150 to 230°C.

The pellets were vacuum dried at 60° C. for one day, then press-molded to prepare test pieces for measuring physical properties, and the physical properties were measured. The results are shown in Table 2.

Comparative Example 1 The maleic acid-modified SBS synthesized in Reference Example 2 and Nylon-6 (manufactured by Toshishiku Co., Ltd., Alamine CM1021XF) were mixed in the proportions shown in Table 2. This mixture was prepared in Example 1.
After kneading using an extruder under the same conditions as above, the mixture was press-molded and its physical properties were measured. The results are shown in Table 2. Incidentally, the melt blend product at the end of kneading was significantly colored.

Comparative Example 2 Unmodified 5EBS and polyether/polyamide copolymer sample T-1 shown in Reference Example 3 were mixed in the proportions shown in Table 2. After kneading this mixture using an extruder under the same conditions as in Example 1, the composition ratio of maleic acid-modified 5RBS and polyamide-polyether copolymer was determined according to the present invention as shown in Table 2. and by changing the polyether content in the polyamide-polyether copolymer,
The physical properties can be balanced at will.

Further, in comparison with Comparative Example 1, Example 2 has a better balance of heat resistance, mechanical strength, and rubber elasticity. Furthermore, it can be seen that in Comparative Example 1, significant coloring occurred during extrusion kneading and heat resistance was poor. In addition, in Example 2, compared to Comparative Example 2,
Improved compatibility and improved mechanical properties.

Applicant: Mitsui Petrochemical Industries, Ltd. Agent Kazu Yamaguchi 5

Claims (1)

[Claims] (1) A modified copolymer obtained by graft copolymerizing a graft monomer selected from unsaturated carboxylic acids and derivatives thereof to part or all of the hydrogenated copolymer consisting of a vinyl aromatic compound and a conjugated diene compound. A modified hydrogenated copolymer (A) and a polyamide/polyether copolymer (B) in which the proportion of the graft monomer is 0.001 to 20 parts by weight based on 100 parts by weight of the hydrogenated copolymer. ) and mixed under heating at a weight ratio of (A)/(B) in the range of 9515 to 5/95.