JPH0710921A - Epoxy-modified hydrogenated block polymer and its composition - Google Patents

Abstract

PURPOSE:To an industrially useful material which can be blended with a wider range of polymers in polymer alloy production by introducing an epoxy into a thermoplastic elastomer which is a hydrogenated block polymer. CONSTITUTION:A linear or branched block polymer which is made up of polybutadiene block segments (A) having a 1,2-vinyl bond content of 20% or lower and one or more block segments (B) consisting of polybutadiene or a vinylaromatic/butadiene copolymer and having a 1,2-vinyl bond content in the butadiene moieties of 30-95% and which has a block sequence represented by A-(B-A)n or (A-B)m (wherein (n) is 1 or larger and (m) is 2 or larger) is hydrogenated to obtain a hydrogenated block polymer (a) in which 30-90% of the butadiene moieties have been hydrogenated and which has a weight-average mol.wt., in terms of polystyrene, of 20,000-600,000. At least 90% of the remaining butadiene moieties of the polymer (a) are epoxidized to obtain the objective polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to interior and exterior parts of automobiles,
TECHNICAL FIELD The present invention relates to an epoxy-modified hydrogenated block polymer useful for various industrial parts and the like, and a composition thereof.

[0002]

2. Description of the Related Art In recent years, thermoplastic elastomers have attracted attention as injection-moldable elastomers, and compositions comprising polyolefin and ethylene-propylene rubber, compositions comprising polyolefin and acrylonitrile-butadiene copolymer rubber, etc. are known. However, these compositions have the drawback of being inferior in compression set, and have insufficient performance as an elastomer.

On the other hand, a hydrogenated styrene-butadiene triblock copolymer (SEBS) obtained by almost completely hydrogenating a butadiene block of a triblock copolymer of styrene and butadiene is a thermoplastic elastomer exhibiting excellent elastomer performance. It is known and an attempt has been made to obtain a characteristic thermoplastic elastomer composition by combining it with other resin components.

However, since SEBS has polystyrene as a block component, SEBS has the drawbacks of high hardness and poor chemical resistance.

Further, a hydrogenated stereoblock polymer obtained by hydrogenating a butadiene component of a stereoblock polymer composed of a polybutadiene segment having a small 1,2-vinyl structure and a polybutadiene segment having a large 1,2-vinyl structure is It is known to be a thermoplastic elastomer that exhibits excellent elastomer elasticity at room temperature.

Since this hydrogenated stereoblock polymer is a thermoplastic elastomer structurally regarded as polyethylene (PE) and ethylene-butene copolymer rubber (EB), it is flexible and excellent in chemical resistance. (Hereinafter referred to as "E-EB system TPE"). However,
This E-EB type TPE has a problem such as a decrease in mechanical strength at high temperature when used alone, and attempts have been made to obtain a composition having a comprehensive balance by combining it with other polymer components. .

For example, in JP-A-56-30455, a butadiene component of a diblock polymer composed of a polybutadiene segment having a small 1,2-vinyl structure and a polybutadiene segment having a large 1,2-vinyl structure is hydrogenated. A composition comprising E-EB-based TPE obtained as described above and polypropylene, polyethylene or the like has been proposed. This composition has improved tear strength at high temperatures, but its heat resistance was insufficient.

That is, since the E-EB TPE is essentially a saturated olefin polymer, it is poorly miscible with polymers other than polyolefin resins, and the blendable polymers are limited. Difficult to improve.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional technical problems, and it is an E-EB type TPE.
The purpose of the present invention is to introduce an epoxy into the polymer to broaden the selection of polymers to be alloyed and to provide an industrially useful material.

[0010]

The present invention provides (A) 1,2
A polybutadiene block segment having a vinyl bond content of 20% or less (hereinafter referred to as “block A”),
(B) Polybutadiene or vinyl aromatic compound-butadiene copolymer, which is a 1,2-butadiene unit
It is composed of a block segment having a vinyl bond content of 30 to 95% (hereinafter referred to as “block B”) and has a block structure of A- (BA) n or (AB) m (where n is 1 or more, m is 2 or more) and a polystyrene-converted weight average molecular weight obtained by hydrogenating a butadiene portion of a linear or branched block polymer (hereinafter referred to as “block polymer”) represented by 30 to 90% is 20,000 to An epoxy-modified hydrogenated block polymer (hereinafter referred to as "epoxy-modified hydrogenated polymer", characterized in that the residual butadiene portion of 600,000 hydrogenated block polymers (hereinafter referred to as "hydrogenated block polymer") was epoxidized by 90% or more. Block polymer ").

The present invention also provides (a) 99 to 1% by weight of the epoxy-modified hydrogenated block polymer, and (b) 1 to 99% by weight of a thermoplastic resin and / or a rubbery polymer.
The present invention provides a thermoplastic polymer composition containing (hereinafter sometimes referred to as "thermoplastic polymer composition (I)").

The hydrogenated diene polymer used in the present invention comprises a polybutadiene block segment (A) having a 1,2-vinyl bond content of 20% or less and a polybutadiene or vinyl aromatic compound-butadiene copolymer. And the content of 1,2-vinyl bonds in the butadiene portion is 30
.About.95% of the block segment (B) and has a block structure of A- (BA) n or (AB) m.
(Provided that n is 1 or more and m is 2 or more), the butadiene portion of the linear or branched block polymer is 3
It is obtained by adding 0 to 90% hydrogen.

The block A becomes a crystalline block segment having a structure similar to that of ordinary low density polyethylene (LDPE) by hydrogenation.

The 1,2-vinyl structure in the block A is usually 20% or less, preferably 18% or less, more preferably 15% or less.

20% of 1,2-vinyl structure of block A
If it exceeds, the melting point of the crystal after the hydrogenation is remarkably lowered, and the mechanical properties of the modified hydrogenated block polymer obtained are inferior, which is not preferable.

Block B is polybutadiene or vinyl aromatic compound-butadiene copolymer,
By hydrogenation, it becomes a block segment having a structure similar to that of a rubber-like ethylene-butene copolymer or a vinyl aromatic compound-ethylene-butene copolymer.

Here, as the vinyl aromatic compound used in the block B, styrene, t-butylstyrene,
α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, N, N-diethyl-p
-Aminoethylstyrene, vinyl pyridine, etc. are mentioned, and styrene and α-methylstyrene are particularly preferable. The amount of the vinyl aromatic compound used is not more than 35% by weight, preferably not more than 30% by weight, more preferably not more than 25% by weight of the monomers constituting the block B. It is not preferable because the glass transition temperature rises and the mechanical properties of the resulting modified hydrogenated block polymer are inferior.

In addition, 1, of the butadiene portion of block B
The 2-vinyl structure is usually 30 to 95%, preferably 3
5 to 95%, more preferably 40 to 90%, 3
If it is less than 0% or more than 95%, after hydrogenation, it shows a crystal structure derived from a polyethylene chain or a polybutene-1 chain, respectively, and becomes a resinous property, resulting in poor mechanical properties of the modified hydrogenated block polymer obtained. Not good for

The ratio of the block A to the block B is 10 to 90% by weight, preferably 1 for the block A.
5 to 85% by weight, block B is 90 to 10% by weight, and preferably 85 to 15% by weight. When the content of the block A is less than 10% by weight and the content of the block B exceeds 90% by weight, the crystalline block segment is insufficient and the modified hydrogenated block polymer is inferior in mechanical properties, which is not preferable. Also,
When the amount of the block A exceeds 90% by weight and the amount of the block B is less than 10% by weight, the hardness of the modified hydrogenated block polymer increases and it becomes unsuitable as a thermoplastic elastomer, which is not preferable.

The polystyrene reduced weight average molecular weight of the entire block polymer is 20,000 to 600,000, preferably 50,000 to 550,000, more preferably 70,000 to 500,000, and 20,000.
If it is less than 0, the mechanical properties are insufficient, while if it exceeds 600,000, the hydrogenation reaction becomes difficult, which is not preferable.

In the hydrogenated block polymer of the present invention, it is necessary that at least 90%, preferably 95 to 100% of the double bonds in the butadiene portion of block A and block B are hydrogenated and saturated. If it is less than 90%, the heat resistance, weather resistance and ozone resistance are poor.

The hydrogenated block polymer in the present invention is preferably one in which 30 to 90% of the double bonds in the butadiene portion of block A and block B are hydrogenated.

The hydrogenated block polymer in the present invention is obtained by subjecting block A and block B to living anion polymerization in an organic solvent to obtain a block polymer, and then further hydrogenating this block polymer.

As the organic solvent, hydrocarbon solvents such as pentane, hexane, heptane, octane, methylcyclopentane, cyclohexane, benzene and xylene are used.

As the organic alkali metal compound which is a polymerization initiator, an organic lithium compound is preferable.

As the organic lithium compound, organic monolithium compounds, organic dilithium compounds and organic polylithium compounds are used. Specific examples of these are:
Ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, hexamethylene dilithium,
Butadienyl lithium, isoprenyl dilithium, etc. are mentioned, and are 0.02-0.2 per 100 weight part of monomers.
Used in parts by weight.

At this time, a Lewis base, such as an ether or an amine, specifically, diethyl ether, tetrahydrofuran, propyl ether, butyl ether, a higher ether, or the like, as a regulator for the microstructure, that is, the vinyl bond content of the conjugated diene portion, Polyethylene glycol ether derivatives such as ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl ether, and triethylene glycol dimethyl ether; examples of amines include tertiary amines such as tetramethylethylenediamine, pyridine, and tributylamine. To be

Further, the polymerization reaction is usually performed at -30 ° C to 1 ° C.
It is carried out at 50 ° C.

The polymerization may be carried out while controlling it at a constant temperature, or may be carried out at an elevated temperature without heat removal.

Any method may be used for forming the block polymer. Generally, the block A is first polymerized in the organic solvent using the polymerization initiator such as the alkali metal compound, and then the block B is polymerized. .

The block polymer thus obtained may be a block copolymer in which polymer molecules are extended or branched as represented by the following general formula by adding a coupling agent. Good.

A- (BA) n (AB) m (In the formula, n is 1 or more, preferably an integer of 2 to 4, and m is 2 or more, preferably 2 to 4). Examples of the coupling agent at this time include diethyl adipate, divinylbenzene, tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2-dibromoethane, and 1. , 4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4
-Benzene triisocyanate and the like.

The bond content of the vinyl aromatic compound in this block polymer is controlled by the amount of the monomer supplied during the polymerization in each stage, and the vinyl bond content of the conjugated diene is determined by varying the components of the micro-regulator. Is adjusted by.
Furthermore, the weight-average molecular weight can be calculated using a polymerization initiator such as n-.
It is controlled by the amount of butyllithium added.

The hydrogenated block polymer used in the present invention can be obtained by hydrogenating the block polymer polymerized as described above.

The hydrogenated block polymer according to the present invention is obtained by dissolving the block polymer thus obtained in an inert solvent and hydrogenating it at 20 to 150 ° C. under 1 to 100 kg / cm ² of pressurized hydrogen. It is carried out in the presence of a catalyst.

The inert solvent used for hydrogenation includes:
Hydrocarbon solvents such as hexane, heptane, cyclohexane, benzene, toluene, and ethylbenzene, and polar solvents such as methyl ethyl ketone, ethyl acetate, ethyl ether, and tetrahydrofuran are included.

As the hydrogenation catalyst, dicyclopentadienyl titanium halide, nickel organic carboxylate,
Hydrogenation catalyst consisting of organic carboxylates and organometallic compounds of Groups I to III of the periodic table, carbon, silica, nickel supported on diatomaceous earth, platinum, palladium,
Ruthenium, rhenium, rhodium metal catalyst and cobalt,
Nickel, rhodium, ruthenium complex, lithium aluminum hydride, p-toluenesulfonyl hydrazide, Zr-Ti-Fe-V-Cr alloy, Zr-Ti-Nb-Fe-V-Cr alloy, LaNi
Examples include hydrogen storage alloys such as ₅ alloys.

Among these hydrogenation catalysts, a catalyst composed of an organic carboxylic acid salt of organic lithium and cobalt, for example, a catalyst composed of n-butyllithium and cobalt octate is preferable. In this case, Li / Co ratio (molar ratio) =
2.0 to 2.5 / 1 is suitable.

The hydrogenation rate of the double bond of the butadiene portion of the hydrogenated block polymer in the present invention is determined by changing the addition amount of the hydrogenation catalyst or the hydrogenation compound, or the hydrogen pressure or the reaction time during the hydrogenation reaction. Adjusted.

From the hydrogenated block polymer solution:
The hydrogenated block polymer can be easily isolated from the polymer solution by removing the residue of the catalyst and adding a phenol-based or amine-based antioxidant.

The hydrogenated block polymer can be isolated by, for example, adding acetone or alcohol to the polymer solution to cause precipitation, or pouring the polymer solution into hot water with stirring to remove the solvent by distillation. It can be carried out.

The epoxy-modified hydrogenated block polymer of the present invention is obtained by epoxidizing the residual butadiene portion of the hydrogenated block polymer produced as described above by 90% or more.

In order to obtain the epoxy-modified hydrogenated block polymer of the present invention, it is necessary to epoxidize the hydrogenated block polymer using peracids, hydroperoxides and the like. Examples of peracids include formic acid, peracetic acid, perbenzoic acid, and trifluoroperacetic acid. The hydroperoxides include hydrogen peroxide, t-butyl hydroperoxide, cumene peroxide and the like.

Next, the thermoplastic polymer composition of the present invention is
(A) It contains 99 to 1% by weight of the epoxy-modified hydrogenated block polymer, and (b) 1 to 99% by weight of a thermoplastic resin and / or rubbery polymer.

The thermoplastic resin in the component (b) used in the present invention is a generic term for a thermoplastic resin that can be melted by heating to be molded into an arbitrary shape. Specific examples of this thermoplastic resin include:
Polyolefin resin, polyamide resin such as nylon 4,6, nylon 6, nylon 6,6, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, crystalline thermoplastic polymer such as polyamide elastomer and polyester elastomer, AB
Amorphous thermoplastics such as rubber modified polymers such as S resin, AES resin, AAS resin, MBS resin, anion-styrene copolymer, styrene-methylmethacrylate copolymer, polystyrene, polymethylmethacrylate, polycarbonate, polyphenyleneoxide, etc. Polymer or a graft polymer in which another polymer is graft-polymerized to a polymer unit having a C 2-8 α-monoolefin as a main repeating structural unit, for example, ethylene-propylene copolymer and acrylonitrile-styrene copolymer. Is a graft polymer graft-polymerized, an ethylene-butene copolymer is graft-polymerized with an acrylonitrile-styrene copolymer, an ethylene-butene copolymer is graft-polymerized with a butyl acrylate-methyl methacrylate copolymer. Polymer, a graft polymer obtained by graft-polymerizing a methyl methacrylate copolymer on an ethylene-butene copolymer, and the like. Particularly, polyamide resin, polyester resin, polycarbonate, polyamide elastomer, polyester elastomer, etc. Preferred as a component for improving the properties.

Among these thermoplastic resins, preferably, a crystalline thermoplastic polymer and a polymer having a main repeating structural unit of α-monoolefin having 2 to 8 carbon atoms are graft-polymerized with another polymer. Polymers may be mentioned.

The rubbery polymer which is the other component constituting the component (b) is a general term for natural rubber and synthetic rubber. Specific examples of this rubbery polymer include:
Styrene butadiene rubber and its hydrogenated product, isoprene rubber, nitrile rubber and its hydrogenated product, chloroprene rubber, butyl rubber, ethylene-propylene rubber,
Ethylene-propylene-diene rubber, ethylene-butene rubber, ethylene-butene-diene rubber, acrylic rubber,
α, β-unsaturated nitrile-acrylic acid ester-conjugated diene copolymer rubber, chlorinated polyethylene rubber, fluororubber, silicone rubber, urethane rubber, epichlorohydrin rubber, polysulfide rubber, styrene-butadiene block polymer and hydrogenated product thereof Etc. are mentioned as typical ones.

Among these rubbery polymers, preferably hydrogenated products of styrene-butadiene rubber, hydrogenated products of nitrile rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene rubber,
Ethylene-butene-diene rubber, acrylic rubber, chlorinated polyethylene rubber, fluorine rubber, silicone rubber, urethane rubber, epichlorohydrin rubber, polysulfide rubber, styrene-butadiene block polymer hydrogenated product, α, β
-Unsaturated nitrile-acrylic acid ester-conjugated diene copolymer rubber, and other rubbers having a substantially low degree of saturation or unsaturation, and modified rubbers having functional groups added thereto.

The thermoplastic polymer composition of the present invention comprises (a)
The main component is an epoxy-modified hydrogenated block polymer, and (b) a thermoplastic resin such as a polyester resin or a polyamide resin and / or a rubbery polymer, and the mixing ratio thereof is (a) component 99 to 1 weight. %, Preferably 95 to 5% by weight, more preferably 90 to 10% by weight, component (B) 1 to 99% by weight, preferably 5 to 95% by weight, more preferably 10 to 90% by weight.

Here, if the content of the component (a) exceeds 99% by weight, the effect of improving the physical properties is insufficient, while if it is less than 1% by weight, various physical properties as an elastomer are inferior, which is not preferable. If the amount of the component (b) is less than 1% by weight, the effect of improving the physical properties due to the addition of the component (b) is not recognized,
On the other hand, if it is used in excess of 99% by weight, the characteristics as a thermoplastic elastomer will be lost, which is not preferable.

Further, in the present invention, the composition is designed by taking advantage of the unique property of the epoxy-modified hydrogenated diene polymer as the component (a), that is, the property of acting as a compatibilizing agent between different polymers. You can also do it. In general, when a block polymer is used as a compatibilizer, it is known that the addition amount thereof is about several% by weight. The minimum amount of component (a) used in the present invention is 1% by weight.
This is because it is considered to use the component (a) as a compatibilizer.

That is, when the component (a) is used as a compatibilizer, a thermoplastic resin and a rubbery polymer are used together as the component (b).

Since the epoxy-modified hydrogenated block polymer of the present invention has an epoxy, it is generally incompatible with a polymer having a polyolefin structure through a chemical reaction between functional groups. It functions as a compatibilizer. Examples of the thermoplastic resin incompatible with the polyolefin resin, in which the modified block polymer of the present invention effectively acts as a compatibilizer, include polyamide resins such as nylon 4, 6, nylon 6, nylon 6,6, and polyethylene terephthalate. Polyester resin such as polybutylene terephthalate, polycarbonate, polyamide elastomer, polyester elastomer and the like.

Examples of the rubbery polymer which is incompatible with the polyolefin resin include acrylic rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic acid ester-unsaturated diene copolymer rubber, urethane rubber and the like. be able to.

Even when the component (a) is used as a compatibilizer, a thermoplastic resin and / or a rubbery polymer other than the above may be blended.

With the thermoplastic polymer composition of the present invention, a thermoplastic elastomer exhibiting excellent performance can be obtained by simply kneading the above-mentioned components (a) and (b). When the rubber polymer is an essential component as the component (b), or when the component (a) is the rubber component and the thermoplastic resin is the component (b), the rubber component as the component (i) and And / or (b) by kneading (heat-melt kneading) the components (a) to (b) while applying shear deformation in the presence of a component that crosslinks the rubbery polymer. It is possible to obtain a composition having further excellent performance (hereinafter sometimes referred to as “composition (II)”).

The cross-linking agent used here is one that is used for cross-linking ordinary rubbers, for example, those described in "Cross-linking Agent Handbook" (written by Shinzo Yamashita, Tosuke Kaneko, Taiseisha). Can be used.

As the preferable cross-linking agent, sulfur, sulfur compounds, p-benzoquinone dioxime, p, p'-
Resin vulcanizing agents such as dibenzoylquinone dioxime, 4,4'-dithio-bis-dimorpholine, poly-p-dinitrosobenzene, tetrachlorobenzoquinone, alkylphenol-formaldehyde resin, brominated alkylphenol-formaldehyde resin, ammonium benzoate, Examples thereof include bismaleimide compounds, diepoxy compounds, dicarboxylic acid compounds, diol compounds, diamine compounds, amino resins, organic metal salts, metal alkoxides, organic metal compounds and organic peroxides.

These cross-linking agents can be used alone or as a mixture. Further, depending on the type of the cross-linking agent, the cross-linking may proceed more efficiently by using it in combination with other compounds.

The thermoplastic polymer composition containing the components (a) and (b) of the present invention described above can be used in a conventional kneading machine such as a rubber mill, a Brabender mixer, a Banbury mixer, a pressure kneader, or a twin screw. Although an extruder or the like can be used, a closed type or an open type, which can be replaced by an inert gas, is preferable.

The kneading temperature is a temperature at which all the components to be mixed are melted, and is usually 140 to 300 ° C., preferably 160 to 280 ° C.
Further, the kneading time depends on the type and amount of the constituents and the kneading device, and therefore cannot be unconditionally discussed. It takes about 40 minutes.

Further, when kneading, each component may be kneaded at once, or a multistage divided kneading method in which after kneading optional components and then adding the remaining components and kneading .

In the thermoplastic polymer composition of the present invention, if necessary, various additives such as an antioxidant, a heat stabilizer, an ultraviolet absorber, an inorganic filler such as silica, talc and carbon, a plasticizer, A softening agent such as oil can be blended and used.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.

In the examples, parts and% are
Unless otherwise specified, it is based on weight. Examples 1 to 3 (Preparation of epoxy modified hydrogenated block polymer) 300 g of hydrogenated block polymer A was added to a reactor with a jacket.
Cyclohexane (1500 g) was charged and dissolved while maintaining the reaction temperature at 30 ° C., and 30% peracetic acid solution in ethyl acetate 172 was used.
g was continuously dropped and reacted. Peracetic acid reaction rate is 99%
The reaction was completed when the above was reached. It was reprecipitated with methanol and dried to obtain the resulting epoxy-modified hydrogenated block polymer. Epoxy modified polymer I
And the epoxy equivalent was 465.

Epoxy modified polymer II was prepared by using hydrogenated block polymer B instead of hydrogenated block copolymer A described above.
(Epoxy equivalent 705), Epoxy modified polymer III using hydrogenated block copolymer C (epoxy equivalent 1050)
Got

Number average hydrogenated block in block B in block A 1,2-vinyl 1,2-vinyl A / B / A hydrogenation rate copolymer bond content (%) bond content (%) (× 10) ³ ) (%) A 12 45 30/140/30 65 B 13 80 60/120/60 75 C 10 56 25/200/25 80 This polymer is formed into a sheet with a hot roll and then press-formed to form one side. A 10 cm square plate was cut out with a dumbbell cutter to give a test piece for measurement.

The physical property evaluation test is conducted according to JIS K63.
It was carried out according to 01. The results are shown in Table 1.

In Examples 4 to 10 and Comparative Examples 1 to 4, the epoxy-modified hydrogenated block polymer alone was added to Laboplast mill whose temperature was adjusted to 190 ° C. according to the formulation shown in Table 1.
(A) Epoxy modified hydrogenated block polymer and (b)
A thermoplastic resin and / or a rubbery polymer or a hydrogenated block polymer alone was added and mixed at 80 rpm for about 10 minutes. This mixture was discharged, formed into a sheet with a hot roll, and then press-formed into a square plate with a side of 10 cm, which was cut out with a dumbbell cutter to give a test piece for measurement.

When a crosslinking agent is added, (a)
After confirming that the components and (b) were completely melted, they were added. After the addition of the crosslinking agent, mixing was continued at 80 rpm after observing the axial torque with the torque meter attached to the Labo Plastomill.
Minute mixing was continued and discharged. In most cases, it took less than 20 minutes from addition of the crosslinking agent to discharge.

The physical property evaluation test is conducted according to JIS K630.
It carried out according to 1. The results are shown in Tables 1 and 2.

In Table 1, Examples 1 to 3 are Production Examples of the epoxy modified hydrogenated block polymer of the present invention, and Examples 4 to 10 are shown.
Are production examples of the thermoplastic polymer composition of the present invention, and all have excellent physical property values.

On the other hand, Comparative Examples 1 to 3 are composition examples using an unmodified hydrogenated block polymer as the component (a), and the elongation at break is poor and not suitable for practical use.

Comparative Example 4 is an example using a hydrogenated styrene-butadiene-styrene block polymer to which 3% of maleic anhydride was added. The mechanical properties were almost the same, but the melt viscosity was It was high and inferior in workability.

Table 1 Example 1 2 3 4 5 6 7 8 9 10 Block polymer type amount Epoxy modified polymer type ABCAABCAAC amount 100 100 100 60 70 30 5 40 40 80 Thermoplastic resin type (6) (7) (6) (6) (8) (9) (8) Amount 40 30 30 50 60 60 20 Rubber polymer type (10) (10) Amount 40 45 Crosslinking agent-containing resin Vulcanizing agent (1) 1.0 1.0 Chloride Tin dihydrate 0.2 0.2 t-PBO (3) 0.8 0.5 0.8 TAC (4) 1.0 BMI (5) 1.0 Example 1 2 3 4 5 6 7 8 9 10 10 Physical properties Tensile strength 150 200 100 310 320 250 210 160 250 150 (Kg / cm2) Elongation at break 1000 1000 1000 460 450 490 420 760 510 900 (%) 100% elongation Permanent elongation (%) 15 16 15 20 30 25 30 20 25 20 Hardness 80 72 64 95 100 89 93 90 93 82 (JIS A) Tensile strength retention rate at 80 ° C 40 35 30 70 70 65 75 75 75 55 (%) Table 2 Comparative Example 1 2 3 4 Block polymer type AAB amount 60 70 5 Epoxy modified polymer type ( 11) Quantity 60 Thermoplastic resin type (6) (7) (6) (6) Quantity 40 30 50 40 Rubbery polymer type (10) Amount 45 Crosslinking agent compound Resin vulcanizing agent Tin chloride dihydrate t-PBO TAC BMI The substances in parentheses in Tables 1 and 2 above are as follows.

(1) Alkylphenol-formaldehyde resin (2) (3) Di-t-butylperoxide (4) Triaryl isocyanurate (5) Bismaleimide (6) Rilsan AMNO (Toray, Nylon 12) (7) Toray PBT 1401-X06 (8) PIBIFLEX 46CM (Dutral, polyester elastomer) (9) Grelax A-25
0 (Dainippon Ink, polyamide elastomer)
(10) JSR EP57P (Nippon Synthetic Rubber, ethylene-propylene rubber) (11) Shell, Kraton G1650 with 3% maleic anhydride grafted
Modified SEBS

[0077]

The epoxy-modified hydrogenated block polymer of the present invention has an excellent compatibility with polyamides, polyesters and the like even though it has an olefin structure, and a polymer blend using the block polymer is used in the industry. It is possible to meet a wide range of various performance requirements from customers.

In particular, the thermoplastic polymer composition of the present invention utilizing the performance of this epoxy-modified hydrogenated block polymer as a thermoplastic elastomer is a composition which has never been obtained. Parts include interior skin materials, rack and pinion boots, bellows, vacuum connectors, tubes, side moldings, headrests, regulators, armrests, shift lever boots, weather strips, air spoilers, suspension boots, belt covers, wheel covers, knobs, Bumpers, site shields, bumper moldings, etc.
Industrial parts include hydraulic hoses, air tubes, rubber hoses, out covers, various gaskets, containers, O-
It can be used for rings, packing materials, various color tiles, floor materials, furniture, skin materials for home appliances, anti-electric materials, sporting goods, especially grip skin materials.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C08L 101/00 LTA

Claims (2)

[Claims] 1. The (A) 1,2-vinyl bond content is 20%.
A polybutadiene block segment, which is (B)
A polybutadiene or vinyl aromatic compound-butadiene copolymer comprising a block segment having a butadiene portion having a 1,2-vinyl bond content of 30 to 95%, and having a block structure of A- (BA) n or (A
-B) A polystyrene-equivalent weight average molecular weight obtained by hydrogenating the butadiene portion of the linear or branched block polymer represented by m (where n is 1 or more and m is 2 or more) by 30 to 90%. An epoxy-modified hydrogenated block polymer, wherein 90% or more of the residual butadiene portion of 20,000 to 600,000 hydrogenated block polymer is epoxidized. 2. A thermoplastic containing 99 to 1% by weight of the epoxy-modified hydrogenated block copolymer according to claim 1 and (B) 1 to 99% by weight of a thermoplastic resin and / or a rubbery polymer. Polymer composition.