JPH05170844A - Hydrogenated diene copolymer and its composition - Google Patents

Abstract

PURPOSE:To prepare the title copolymer excellent in clarity, flexibility, and adhesive properties by hydrogenating a specified amt. of the double bonds of conjugated diene parts of a block copolymer which has a specific block structure and a plurality of polymer blocks in the molecule. CONSTITUTION:The title copolymer is prepd. by hydrogenating at least 80% of the double bonds of conjugated diene parts of a block copolymer which comprises 10-35wt.% polymer block A contg. at least 80wt.% vinyl arom. compd. units, 35-80wt.% conjugated diene block B contg. at least 80wt.% conjugated diene compd. units and a vinyl bond content in the diene compd. units of at least 70wt.%, and 5-40wt.% polybutadiene block C having a 1,2-vinyl bond content of up to 30wt.% and which has a block structure of A-(B-C)n, C-(B-A)m, or (C-B-A)1X (wherein n and m are each 1 or higher; l is 2 or higher, and X is a residue of a coupling agent) and a number-average mol.wt. of 40,000-700,000.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a hydrogenated diene copolymer obtained by hydrogenating a special block copolymer, and flexibility and transparency of the copolymer and a thermoplastic resin. The present invention relates to a hydrogenated diene-based copolymer composition having improved adhesion and the like.

[0002]

2. Description of the Related Art A diene-based copolymer having a double bond in the polymer is inferior in thermal stability, weather resistance and ozone resistance.
As a means for improving this, a method of hydrogenating an unsaturated double bond (hereinafter referred to as "hydrogenation") is known, and as a method thereof, for example, JP-B-43-19960 and JP-B-45-39275. JP-B-45-3555, JP-A-56-62805, JP-A-59-1.
33203 publication etc. are mentioned. The hydrogenated polymers obtained by these methods show expected heat resistance, weather resistance and ozone resistance, and are therefore often used for resin modification applications and the like. In addition, ethylene-α-olefin copolymers and the like are known as polymers having excellent thermal stability and weather resistance. However, when these polymers are blended with thermoplastics, transparency, flexibility,
It is insufficient to obtain a composition having a good balance of moldability and adhesiveness.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional technical problems, and when a pelletized product is obtained, pelletization is easy, and pellet blocking resistance is improved. And excellent heat resistance, weather resistance, ozone resistance, further as a modifier of other resins, hydrogenated diene-based copolymer and its properties that can improve properties such as transparency, flexibility, adhesion To provide a composition.

[0004]

DISCLOSURE OF THE INVENTION The present invention contains the polymer blocks A, B and C in the molecule (I) (provided that A
Is a polymer block segment containing 80% by weight or more of a vinyl aromatic compound, B is a conjugated diene block segment containing 80% by weight or more of a conjugated diene compound, and the vinyl bond content of the conjugated diene compound exceeds 70% by weight,
C is a polybutadiene block segment having a 1,2-vinyl bond content of 30% by weight or less) and a block structure of A- (BC) _n , C- (BA) _m , or (C- B-A) _{l From a} linear or branched block copolymer represented by X (where n and m are integers of 1 or more, l is an integer of 2 or more, and X is a coupling agent residue). , The content of the polymer block A is 10 to 35% by weight, the content of the polymer block B is 35 to 80% by weight,
And the content of the polymer block C is 5 to 40% by weight (however, A + B + C = 100% by weight), the number average molecular weight of the block copolymer is 40 to 700,000, and the double bond of the conjugated diene moiety is The present invention provides a hydrogenated diene-based copolymer in which 80% or more of the residues are hydrogenated (hereinafter referred to as "hydrogenated diene-based copolymer").

In the present invention, the hydrogenated diene copolymer is modified with at least one functional group (hereinafter referred to as "modified hydrogenated diene copolymer").
Is provided. Furthermore, the present invention provides (I) the hydrogenated diene-based copolymer and / or the modified hydrogenated diene-based copolymer 99 to 1 parts by weight, and (II) the thermoplastic resin 1 to 99 parts by weight [however, ( I) + (II) = 100 parts by weight] is provided as a main component, to provide a hydrogenated diene-based copolymer composition.

The hydrogenated diene-based copolymer of the present invention contains polymer blocks A, B and C in the molecule, but as the monomer unit constituting the block A, a vinyl aromatic compound is 80% by weight or more. , Preferably 90% by weight or more. Examples of the vinyl aromatic compound constituting the hydrogenated diene copolymer include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N.
-Diethyl-p-aminoethylstyrene, vinyl pyridine and the like are mentioned, and styrene and α-methylstyrene are particularly preferable. The other monomer constitutional units are not particularly limited, but 1,3-butadiene, isoprene,
2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3
-Conjugated diene compounds such as hexadiene, 4,5-diethyl-1,3-octadiene and chloroprene, especially 1,
3-Butadiene, isoprene and 1,3-pentadiene are preferred, and 1,3-butadiene is more preferred.
When the content of the vinyl aromatic compound is less than 80% by weight, the resulting hydrogenated diene-based copolymer is soft, and when formed into pellets, adhesion between the pellets easily occurs, and in producing the composition of the present invention, This will hinder operations such as blending and handling.

Block B contains the conjugated diene compound in an amount of 80% by weight or more, and the vinyl bond content of the conjugated diene compound (in this case, vinyl bond means 1,2-vinyl bond,
And 3,4-bond) are conjugated diene block segments exceeding 70% by weight, and when the vinyl bond content of the conjugated diene compound is 70% by weight or less, the composition with the thermoplastic resin finally obtained. The effect of improving flexibility is reduced. As the monomer unit constituting the block B, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-
Methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, chloroprene and the like can be mentioned, but hydrogenated diene-based copolymers that can be industrially used and have excellent physical properties To get coalesced, 1,3-
Butadiene, isoprene and 1,3-pentadiene are preferable, and 1,3-butadiene is more preferable. Examples of the monomer segment other than the conjugated diene compound include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-
Examples thereof include diphenyl styrene, N, N-diethyl-p-aminoethyl styrene, vinyl pyridine and the like, and styrene and α-methyl styrene are particularly preferable.

Block C is a polybutadiene block segment having a 1,2-vinyl bond content of 30% by weight or less, preferably 20% by weight or less. Block C 1,
When the content of 2-vinyl bond exceeds 30% by weight, the resin-like property is deteriorated and the obtained hydrogenated diene-based copolymer is soft,
In the case of pellets, the pellets are likely to adhere to each other, which hinders operations such as blending and handling in producing the composition of the present invention. In addition, the moldability of the composition obtained by blending with the thermoplastic resin decreases.

The hydrogenated diene-based copolymer of the present invention has a block structure of A- (B-C) _n , C- (B-A) _m , or (C-B-A) _l X (however, n , M is an integer of 1 or more,
1 is an integer of 2 or more, and X is a coupling agent residue), and is composed of a linear or branched block copolymer. The content of the polymer block A in the block copolymer is 10 to 35% by weight, and when the content is less than 10% by weight, the hydrogenated diene-based copolymer obtained is soft, and when pelletized, adhesion between pellets occurs. It is easy to do so, and in the production of the composition of the present invention, operations such as blending and handling are hindered. Further, the molding appearance of the composition obtained by blending with the thermoplastic resin is deteriorated. On the other hand, when it exceeds 35% by weight, the fluidity is lowered and the moldability and appearance of the obtained composition are deteriorated. The content of polymer block B is 3
5-80% by weight, preferably 40-80% by weight,
If it is less than 30% by weight, not only the effect of improving transparency and flexibility of the composition obtained by blending with the thermoplastic resin is lowered but also the effect of improving impact resistance is lowered, while if it exceeds 80% by weight, it is obtained. When the hydrogenated diene-based copolymer to be obtained is soft and formed into pellets, the pellets are likely to adhere to each other, which causes troubles in operations such as blending and handling in producing the composition of the present invention.

The content of the polymer block C is from 5 to 40% by weight, preferably from 5 to 35% by weight, and when the content is less than 5% by weight, the hydrogenated diene copolymer obtained is soft and, when made into pellets, pellets. Adhesion between the two is likely to occur, in producing the composition of the present invention, an operation such as blending,
It causes trouble in handling. Further, the molding appearance of the composition obtained by blending with the thermoplastic resin is deteriorated. On the other hand, when it exceeds 40% by weight, the effect of improving the transparency and flexibility of the composition obtained by blending with the thermoplastic resin decreases. Furthermore, the hydrogenated diene-based copolymer of the present invention has a number average molecular weight of 40,000 to 700,000, preferably 70,000 to 500,000, and if it is less than 40,000, the composition obtained by blending with a thermoplastic resin has a high resistance. The impact improving effect is reduced. on the other hand,
When it exceeds 700,000, the fluidity is lowered and the moldability and appearance of the resulting composition are deteriorated.

Further, it is necessary that 80% or more, preferably 90% by weight or more, of the double bond residues in the conjugated diene portion of the hydrogenated diene copolymer be hydrogenated. If it is less than 80% by weight, the weather resistance and heat resistance are insufficient.

The hydrogenated diene-based copolymer of the present invention is subjected to living anion polymerization in an organic solvent using an organic alkali metal compound as an initiator to obtain a block copolymer, and then hydrogenated to the block copolymer. It is obtained by performing (hydrogenation). As the organic solvent, hydrocarbon solvents such as pentane, hexane, heptane, cyclohexane and toluene are used. As the organic alkali metal compound that is a polymerization initiator, an organic lithium compound is preferable. Specific examples include n-butyllithium, sec-butyllithium, t-butyllithium, and the like, and the monomer 100
It is used in the range of 0.02 to 0.2 parts by weight per part by weight. Further, the adjustment of the vinyl bond content of the conjugated diene compound in the blocks B and C is adjusted by using a Lewis base such as ether or amine together with the organic solvent. Further, the polymerization reaction is usually -30 to
It is performed in the range of 150 ° C. Further, the polymerization may be carried out while controlling it at a constant temperature, or may be carried out at an elevated temperature without removing heat.

Any method may be used for forming the block copolymer, but generally, the block C is first prepared by using an initiator such as the organic alkali metal compound in the organic solvent.
And then block B is polymerized. Further, it can be obtained by subsequently polymerizing block A.
At this time, it is not always necessary to clearly distinguish the boundaries of the respective blocks. The bond content of the vinyl aromatic compound in the block A is adjusted by the amount of the monomer supplied during the polymerization. Further, the number average molecular weight is adjusted by the addition amount of the polymerization initiator.

(A)-(B) -obtained in this way
The block copolymer (C) may be a block copolymer in which a polymer molecular chain represented by the following general formula is extended or branched by adding a coupling agent. The block copolymer thus obtained is represented by the general formula [(C)-(B)-(A)] _1- X. [In formula, (A), (B), (C) is the same as the above, l is an integer greater than or equal to 2, X shows a coupling agent residue. Examples of this coupling agent include diethyl adipate, divinylbenzene, tetrachlorosilicon,
Examples thereof include butyltrichlorosilicon, tetrachlorotin, dimethylchlorosilicon, 1,2-dibromoethane, 1,4-chloromethylbenzene and tolylene diisocyanate. The preferred block structure of the block copolymer of the present invention is ABC, ( _CBAA ) ₁ X. The hydrogenated diene-based copolymer obtained by hydrogenating the block copolymer having this block structure is much more excellent in the effect intended by the present invention.

The hydrogenated diene-based copolymer of the present invention is prepared by dissolving the block copolymer thus obtained in an inert solvent, and heating it at 20 to 150 ° C. under 1 to 100 kg / cm ² of pressurized hydrogen. , Can be hydrogenated in the presence of a hydrogenation catalyst. As the inert solvent used for hydrogenation, hexane,
Hydrocarbon solvents such as heptane, cyclohexane, toluene and ethylbenzene, and polar solvents such as methyl ethyl ketone, ethyl acetate, ethyl ether and tetrahydrofuran are mentioned. As the hydrogenation catalyst, dicyclopentadienyl titanium halide, nickel organic carboxylate, cobalt organic carboxylate, and I to II of the periodic table.
Examples thereof include a combination with a Group I organometallic compound, and a metal hydride such as nickel, platinum, palladium, or rhodium supported on a carrier such as carbon. Further, hydrogenation with a hydride such as p-toluenesulfonyl hydrazide can be mentioned. The hydrogenation rate of the conjugated diene moiety is adjusted by changing the hydrogenation catalyst, the amount of the hydrogenated compound added, the hydrogen pressure during the hydrogenation reaction, and the reaction time.

From the hydrogenated block copolymer solution,
The hydrogenated diene-based copolymer can be easily isolated from the polymer solution by removing the residue of the catalyst and adding a phenol-based or amine-based antioxidant. Isolation of the hydrogenated diene-based copolymer is carried out, for example, by adding acetone or alcohol to a hydrogenated block copolymer solution to cause precipitation, and pouring the polymer solution into hot water with stirring to remove the solvent. It can be carried out by a method such as evaporation removal.

The hydrogenated diene-based copolymer composition of the present invention is
(I) 99 to 1 part by weight of the hydrogenated diene-based copolymer, preferably 95 to 2 parts by weight, more preferably 90 to 3 parts by weight, (II) 1 to 99 parts by weight of the thermoplastic resin, preferably 5
To 98 parts by weight, more preferably 10 to 97 parts by weight as a main component. The thermoplastic resin used in the present invention is not particularly limited, but includes polyethylene, high-molecular polyethylene,
High density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene (LLDPE),
Polypropylene, polybutene, polyisobutylene, high impact polystyrene (HIPS), polystyrene,
Non-polar thermoplastics such as polymethylstyrene, polymethylene, poly-4-methyl-pentene-1, and A
BS resin, acrylic resin, polyacrylamide, polyacrylic acid, polyacrylic acid alkyl ester, polymethacrylic acid alkyl ester, polymethacrylonitrile,
Acetal resin, polyoxymethylene, chlorinated polyethylene, coumarone / indene resin, cellulose, cellulose ester, fluorine resin, polyimide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polycarbonate, polysulfone,
Examples include polar thermoplastic resins such as polyphenylene oxide, polyvinyl ester, and polyvinyl acetate. Preferred thermoplastic resins are polypropylene, polyethylene, polycarbonate, polysulfone and polyphenylene oxide, and more preferably polypropylene and polyethylene.

The hydrogenated diene-based copolymer of the present invention is
It is also possible to introduce at least one functional group into the hydrogenated diene-based copolymer to use as a modified hydrogenated diene-based copolymer. For example, 100 parts by weight of a hydrogenated diene-based copolymer is added to a compound having an acid anhydride group or a carboxyl group, specifically acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid. , Α, β-unsaturated carboxylic acids such as itaconic anhydride, hymic acid, hymic acid anhydride, or anhydrides thereof,
Compounds having an epoxy group, specifically glycidyl (meth) acrylate, allyl glycidyl ether, vinyl glycidyl ether, and compounds having a hydroxy group, specifically hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, and A compound having an amino group, specifically, an unsaturated compound having at least one functional group selected from the group of diethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, vinylpyridine, etc. 0.0
Grafted with 1 to 20 parts by weight. As the grafting method, the method described in JP-B-39-6384 can be used. That is, a hydrogenated diene-based copolymer may be used instead of the olefin rubber, and a compound having various functional groups may be mixed and heated in a solid state to cause a reaction.

To accelerate this reaction, it is possible to react in the presence of a peroxide. Alternatively, in the block copolymer production stage before the hydrogenation, ethylene oxide, benzophenone, carbon dioxide, dialkylaminobenzaldehyde, 4,4 ′ is added to the active block copolymer terminal.
-OH, -COOH, -NR by stopping with a compound such as -dialkylaminobenzophenone, N-methyloxazolidinone, tolylene diisocyanate, diphenylmethane diisocyanate, carbon disulfide, tetraalkoxysilane, alkyltriphenoxysilane.
Functional groups such as ₂ groups, -NHR group, -NCO group, -Si (OR) n group (wherein R is alkyl or aryl, and n is an integer of 1 to 3) can be introduced.

In producing the composition of the present invention, the use of the hydrogenated diene copolymer and the modified hydrogenated diene copolymer is not particularly limited, but the thermoplastic resin used in the composition is not limited. May be distinguished by the type and purpose.
For example, in a composition with a thermoplastic resin having a polarity such as polyamide, it is better to use a modified hydrogenated diene copolymer modified with an acid anhydride group or the like to improve the impact resistance of the composition. Is further enhanced. Further, in the case of using a modified hydrogenated diene-based copolymer modified with an acid anhydride group or an -OH group in a composition with a nonpolar thermoplastic resin such as polypropylene or polyethylene,
The effect of improving coating strength and printability can be enhanced. The composition comprising the hydrogenated diene-based copolymer of the present invention and the thermoplastic resin, conventional auxiliary additives, such as antioxidants, heat stabilizers, ultraviolet absorbers, colorants, flame retardants, etc. It can be added.

Further, the hydrogenated diene copolymer of the present invention and the thermoplastic resin can be partially crosslinked. The method of partial cross-linking is not particularly limited, but generally, using a Banbury type kneader, a kneader type kneader, or a single-screw or twin-screw extruder, the (modified) hydrogenated diene copolymer and the 0.00 per 100 parts by weight of a composition comprising a plastic resin
100 to 300 in the presence of 1 to 0.5 parts by weight of peroxide.
Heat reaction to ℃.

In using the composition comprising the hydrogenated diene-based copolymer of the present invention and a thermoplastic resin, glass fiber, carbon fiber, metal fiber, glass beads, mica, calcium carbonate, potassium titanate whiskers, talc, Known fillers such as aramid fibers can be used alone or in combination. Further, in order to further soften the composition comprising the hydrogenated diene-based copolymer of the present invention and the thermoplastic resin, an oil or a plasticizer may be added as a softening agent. As oil, aromatic type, naphthene type,
Paraffin type can be used. Further, as the plasticizer, a phthalate type, an adipate type, a sebacate type, a phosphate type, a polyether type, or a polyester type can be used.

In producing a composition comprising the hydrogenated diene-based copolymer of the present invention and a polar thermoplastic resin having a functional group, the modified hydrogenated diene-based copolymer has excellent compatibility with the polar resin. However, when using a hydrogenated diene-based copolymer, during kneading with a polar resin, an acid anhydride group, a carboxy group, a hydroxy group, an amino group, an epoxy group, an oxazoline group, and a group of imide group An unsaturated compound having at least one functional group selected from the above, and a method of adding a peroxide if necessary, or an unsaturated compound having the functional group and a peroxide in advance in the hydrogenated diene copolymer. It is possible to use a method in which the graft product obtained by adding an oxide and heat treatment is blended with the polar resin. Further, in the production of a composition comprising a hydrogenated diene-based copolymer and a polar thermoplastic resin having a functional group, the compound having the functional group can be added as a compatibilizer.

The composition comprising the hydrogenated diene-based copolymer (modified hydrogenated diene-based copolymer) of the present invention and a thermoplastic resin is used as various molded articles by injection molding, extrusion molding, vacuum molding or the like. .. In particular, there are applications where softness and transparency are important, such as stationery, sports equipment, soft bumper materials, automobile interior materials, and electrical / electronic-related housing skin materials where softness is required. It is useful for applications such as various packaging materials, cases, and stationery.

[0025]

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 based on weight unless otherwise specified. In addition, various measurements in the examples were performed by the following methods. The bound vinyl aromatic content was measured by infrared analysis based on the absorption of the phenyl group at 679 cm ^-1 . The vinyl bond content of the conjugated diene was calculated by the Hampton method using an infrared analysis method. The hydrogenation rate of the conjugated diene was calculated from 100 MHz · ¹ H-NMR spectrum using ethylene tetrachloride as a solvent.

The molecular weight was determined in terms of polystyrene by gel permeation chromatography (GPC) at 135 ° C. using trichlorobenzene as a solvent. Melt flow rate (MFR) is JIS K72
230 ° C, load 2.16kg or 12.5 according to 10
It was measured in kg. The pellet blocking test is 55
Round pellets were prepared using mmφ, uniaxial extruder and hot cutter, and the load was 30 kg / cm ² , 7 in a constant temperature bath at 60 ° C.
Based on how the pellets clumped after 2 hours, they were ranked as follows. ◯: Almost does not solidify and easily disassembles. Δ: A little hardened, but can be loosened relatively easily. X: Hardened and difficult to loosen.

MFR (melt flow rate) is defined by JIS
According to K7210, it was measured at 230 ° C. and 2.16 kg. The IZOD impact value was measured according to JIS K7110. The flexural modulus was measured according to JIS K7203. The peeling strength of the coating film is obtained by degreasing a 2 mm-thick sheet obtained by injection molding with ethanol, applying a surface treatment with trichloroethane vapor, and applying a primer [RB291H manufactured by Nippon Bee Chemical Co., Ltd.]. Next, a polyurethane coating [R263, manufactured by Nippon Bee Chemical Co., Ltd.] was applied in a dry coating film thickness of about 50 μm, and after curing, the coating film was peeled 180 ° at a pulling speed of 30 mm / min, and the peel strength was measured.
Transparency was measured according to ASTM D1003. The DuPont impact value was measured with reference to JIS K7211. The tensile strength was measured according to JIS K7127.

Example 1 In an autoclave having an internal volume of 10 l, 5 k of cyclohexane was added.
g, 1,3-butadiene 900 g, and n-butyllithium 0.9 g were added, and the conversion reached 11% at 50 ° C.,
The polymer solution is cooled to 10 ° C. and tetrahydrofuran 2
00g was added and further polymerization was performed. Then, 100 g of styrene was added and the adiabatic polymerization was continued. After the polymerization was completed, the reaction solution was heated to 70 ° C. and n-butyllithium 0.4 was added.
5 g, 2,6-di-t-butyl-p-cresol 3.7
g, 0.5 g of bis (cyclopentadienyl) titanium dichloride, and 2 g of diethylaluminum chloride were added, and the mixture was reacted at a hydrogen pressure of 10 kg / cm ² for 1 hour. This reaction liquid was mixed in a large amount of methyl alcohol, and the solid substance that precipitated was collected and dried in a vacuum dryer to obtain a hydrogenated diene copolymer. The hydrogenated diene copolymer obtained had a hydrogenation ratio of 98% and a number average molecular weight of 130,000.
MFR (230 ℃, 2.16kg) is 4.1g / 10min
The 1,2-butadiene bond content of 1,3-butadiene measured at the end of the first stage 1,3-butadiene block polymerization was 12%, and the end of the second stage 1,3-butadiene block polymerization As a result of calculation from the 1,2-vinyl bond content measured in 1. and the 1,2-vinyl bond content in the first step, the 1,2-vinyl bond content of the 1,3-butadiene block in the second step was It was calculated to be 82%. This hydrogenated diene-based copolymer is referred to as "H-1". The H-1 thus obtained was pelletized with a 20 mmφ uniaxial extruder, and the blocking property of the pellet was measured. as a result,
There was no blocking of the pellet, and it was in a state that it could be easily loosened. The results are shown in Table 1.

Examples 2 to 10 By the same method as in Example 1, monomer species, monomer amount,
It was prepared by varying the amount of catalyst, polymerization temperature and polymerization time. Using these hydrogenated diene-based copolymers, a pellet blocking test was conducted in the same manner as in Example 1. The results are shown in Tables 1-2.

Example 11 A block copolymer was polymerized in the same manner as in Example 1 except that 0.9 g of n-butyllithium was used.
When 100% of all the monomers were polymerized, 0.2 g of tetrachlorosilicon was added and reacted for about 10 minutes. At this point, 25% of the block copolymer has been coupled,
An increase in molecular weight was observed. The increased molecular weight was about 3.5 times that before the addition of the coupling agent, and the coupled copolymer was in a form in which four block copolymers were bonded around the coupling agent residue ( H-11). After that, a pellet blocking test was performed in the same manner as in Example 1. The results are shown in Table 2.

Example 12 A block copolymer was polymerized in the same manner as in Example except that 1.1 g of n-butyllithium was used. When 100% of all monomers were polymerized, methyldichlorosilicon was used. 1.0g was added and it reacted for about 20 minutes. At this point, 95% of the block copolymer has been coupled,
An increase in molecular weight was observed. The increased molecular weight was about 1.95 times before the addition of the coupling agent, and the coupled copolymer was in a form in which two block copolymers were bonded around the coupling agent residue ( H-12). After that, a pellet blocking test was performed in the same manner as in Example 1. The results are shown in Table 2.

Comparative Examples 1 to 9 In the same manner as in Example 1, K-1 to K-9 shown in Table 3 were used.
The amount of the monomer, the amount of the catalyst, and the polymerization temperature were varied so that the hydrogenated diene-based copolymer of was obtained. Using these hydrogenated diene-based copolymers, a pellet blocking test was conducted in the same manner as in Example 1. The results are shown in Table 3. As can be seen from Table 3, in the hydrogenated diene copolymers of Comparative Examples 2 and 5-8, pellet blocking was observed, and in Comparative Examples 1, 3-4 and 9, pellet blocking was not generated. However, as shown in Comparative Example 10 and thereafter, the blending with other resins is not preferable because the modification effect is inferior to that of the hydrogenated diene-based copolymers of Examples.

Examples 13 to 24 (Production of composition with non-polar thermoplastic resin) H-1 to 12 obtained in Examples 1 to 12 and polypropylene resin: PP-1 [Mitsubishi Petrochemical Co., Ltd. ), BC-0
3] using a 4-liter Banbury type kneader
Mixed in a weight ratio of 5/75. The mixed composition was formed into a sheet and then cut into square pellets for the following evaluation. (Physical Properties of Injection Molded Product) A test piece was prepared from the composition obtained above using a 6.5 oz. In-line screw type injection molding machine. The injection molding conditions are shown below. Injection pressure: 500 kg / cm ² (secondary pressure: 400 kg / cm ² ) Molding temperature: 240 ° C. Cooling temperature: 40 ° C. Each physical property was measured using the obtained test piece. The measurement results are shown in Tables 4-5. (Physical Properties of Sheet Molded Product) Hydrogenated diene-based copolymer pellets obtained in Examples 1 to 12 and polypropylene resin: PP-2 [XF1800 manufactured by Chisso Petrochemical Co., Ltd.] were prepared by the same method as described above. After blending in a weight ratio of 10/90 to obtain pellets, 2
A 0 mmφ extruder-150 mm T die was used to make a 0.5 mm thick sheet. In the sheet forming, the sheet thickness was adjusted with two mirror-finished rolls. The roll temperature was adjusted to 50 ° C. The physical properties of the obtained sheet are shown in Tables 4-5.

Examples 25 to 27 Using the hydrogenated diene copolymer (H-1) of Example 1, the composition was changed and the physical properties were measured. By increasing the amount of the hydrogenated diene-based copolymer, it is possible to obtain a composition having more excellent flexibility and transparency. The results are shown in Table 5.

Comparative Examples 10 to 12 In Example 13, an ethylene-propylene copolymer [EP02P manufactured by Nippon Synthetic Rubber Co., Ltd.], an ethylene-butene-1 copolymer was used instead of the hydrogenated diene copolymer. [Japan Synthetic Rubber Co., Ltd., EBM2041P], hydrogenated triblock copolymer [Asahi Kasei Co., Ltd., Tuftec H
1041: SEBS] was used to obtain a composition pellet with polypropylene resin-1 in the same manner as above. Subsequently, an injection-molded article was produced in the same manner as in Example 13, and the physical properties were measured. The results are shown in Table 6. From these comparisons, the hydrogenated diene-based copolymer of the present invention is more flexible than the conventionally used ethylene-propylene copolymer, ethylene-butene-1 copolymer, or hydrogenated triblock copolymer. It turns out that it is excellent.

Comparative Examples 13 to 21 In the same manner as in Example 13, K-1 to K- shown in Table 3 were obtained.
Injection-molded products and sheet-molded products were produced using the hydrogenated diene-based copolymer of 9 and each physical property was measured. The results are shown in Tables 6-7. From the above comparative examples, any composition using a hydrogenated diene-based copolymer that deviates from the requirements of the present invention results in lacking any of the specific properties of the present invention. Comparative Examples 22 to 23 Table 7 shows the cases where only the hydrogenated diene copolymer (H-1) or the thermoplastic resin was used. Injection molding of H-1 was possible, but the molding appearance was poor. Sheet formation was impossible.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

[0041]

[Table 5]

[0042]

[Table 6]

[0043]

[Table 7]

[0044]

INDUSTRIAL APPLICABILITY The present invention is a composition comprising a specific hydrogenated diene-based copolymer, or a thermoplastic resin with the specific hydrogenated diene-based copolymer, and has flexibility, transparency and adhesiveness as compared with conventional compositions. It is an excellent hydrogenated diene-based copolymer composition that also has the following: That is, the polymer blocks A, B, and C are contained in the molecule, 80% by weight or more of the block A is composed of a vinyl aromatic compound, and the block B is a conjugated diene compound showing a high vinyl bond. Is a low vinyl bond. This copolymer is highly hydrogenated, making it easy to pelletize, improve pellet blocking resistance, and when blended with a thermoplastic resin,
It exhibits the above-mentioned excellent characteristics.

Front page continued (72) Inventor Yasuhiko Takemura 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (3)

[Claims] 1. A polymer block A, B and C is contained in the molecule (I) (wherein A is a vinyl aromatic compound).
A polymer block segment containing 0% by weight or more, B is a conjugated diene block segment containing a conjugated diene compound in an amount of 80% by weight or more and the vinyl bond content of the conjugated diene compound exceeds 70% by weight, and C is 1,2-vinyl. (A polybutadiene block segment having a bond content of 30% by weight or less) and a block structure of A- (BC)
_n , C- (B-A) _m , or (C-B-A) _l X (where n and m are integers of 1 or more, l is an integer of 2 or more, and X is a coupling agent residue) Polymer block A comprising a linear or branched block copolymer represented by
Is 10 to 35% by weight, the content of the polymer block B is 35 to 80% by weight, and the content of the polymer block C is 5 to 40% by weight (where A + B + C = 100% by weight). , The block copolymer has a number average molecular weight of 4 to
700,000 and 80% of the double bond residues in the conjugated diene moiety
The above is hydrogenated diene copolymer. 2. A hydrogenated diene-based copolymer obtained by modifying the hydrogenated diene-based copolymer according to claim 1 with at least one functional group. 3. (I) Claim 1 and / or claim 2
99 to 1 parts by weight of the hydrogenated diene-based copolymer described above, and 1 to 99 parts by weight of (II) thermoplastic resin [provided that (I) +
(II) = 100 parts by weight] as a main component.