JP2000080136A - Block copolymer and its polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polymer having good elasticity, excellent in weatherability, solvent resistance and heat resistance, and having good compatibility for both polar polymers and nonpolar polymers, and a polymer compsn. effectively demonstrating the merit of the polymer. SOLUTION: This block copolymer contains, in its main chain, polymer block A, polymer block B, and polymer block C. Wherein A is a crystalline polymer block which is prepared by adding hydrogen to not less than 80% of the unsaturated bonds of a butadiene polymer block having less than 20% 1,2-bond. B is a polymer block having a glass transition temp. not higher than 20 deg.C. C is a polymer block comprising a methacrylic acid ester unit or an acrylic acid ester unit, and having a glass transition temp. higher than 20 deg.C. This polymer compsn. contains the block copolymer and another polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel block copolymer and a polymer composition thereof. The block copolymer of the present invention has the properties of a thermoplastic elastomer and has polymethyl methacrylate (PMMA), ABS
It has excellent affinity with polar polymers represented by resins, polycarbonates (PC) and the like, affinity with nonpolar polymers represented by polyethylene and the like, weather resistance, solvent resistance and heat resistance. For this reason, the block copolymer can be used alone as a molding material, and further contains a modifier (eg, a polarity-imparting agent) for another polymer, and a polar polymer and a non-polar polymer. It can be used as a compatibilizer or the like in a polymer composition.

[0002]

2. Description of the Related Art Thermoplastic elastomers are used in automobile parts, electronic / electric parts, and construction / civil engineering applications as elastomeric materials having ease of molding.
In particular, polystyrene-polybutadiene-polystyrene block copolymer (SBS), polystyrene-hydrogenated polybutadiene-polystyrene block copolymer (SEB)
S), styrene-based thermoplastic elastomers represented by polystyrene-hydrogenated polyisoprene-polystyrene block copolymer (SEPS) (hereinafter sometimes referred to as “styrene-based TPE”) have stress-strain characteristics and the like. A wide range of materials are available, ranging from materials close to vulcanized rubber to materials close to plastic in the nature of
It is a material that is widely used industrially because the most suitable one can be selected according to the purpose from among them (for example, Komatsu Koei, “Thermoplastic Elastomers-Basics, Applications, Markets, and Future Prospects”). (See Nikkan Kogyo Shimbun, October 30, 1995).

However, styrene-based TPE is inferior in weather resistance and solvent resistance. Therefore, as a thermoplastic elastomer which has improved these disadvantages, for example, a block copolymer having a hydrogenated block of polybutadiene containing a large number of 1,4 bonds and a block of a hydrogenated polybutadiene containing a large number of 1,2 bonds is used. And a block copolymer having a polybutadiene hydrogenated block containing a large number of 1,4 bonds, a polybutadiene hydrogenated block containing a large number of 1,2 bonds, and a polystyrene block (hereinafter referred to collectively as " (Sometimes referred to as "hydrogenated 1,4-polybutadiene TPE") (for example, Macromolecules, Vol. 4 (No. 2), pp. 152-154 (1971), and JP-A 2-1.
No. 33406 (U.S. Pat. No. 5,206,301) and JP-A-3-128957 (U.S. Pat. No. 5,210,744).

[0004] By copolymerizing ethylene and a long-chain α-olefin (eg, 1-octene) using a metallocene-based polymerization catalyst, a polyolefin-based thermoplastic elastomer (hereinafter referred to as “metallocene-based TPE”) may be used. Is) manufactured. Metallocene-based TPEs exhibit elastomeric properties due to cohesion based on the crystallinity of the polyethylene part, and can be manufactured at low cost, and are widely used for the purpose of imparting toughness to polyolefin-based materials or their recycled products. Is starting to be.

[0005] As described above, styrene-based TPE is inferior in weather resistance and solvent resistance, but is superior in acrylic resin performance to these properties.
Alloys with PE have been proposed as soft materials having good weather resistance and solvent resistance.

A block copolymer comprising a hydrogenated block of a conjugated diene compound polymer and a methacrylic acid ester polymer block, and a block copolymer of a hydrogenated product of a conjugated diene compound polymer and a methacrylic acid ester polymer block And a block copolymer comprising an aromatic vinyl compound polymer block (hereinafter, these may be collectively referred to as "methacrylic ester-non-crystalline hydrogenated diene-based block copolymer"). (See, for example,
-250011 (European Patent Application Publication No. 0431706) and JP-A-4-227917 (U.S. Pat.
5278245) and the like)).

[0007]

However, the above-mentioned hydrogenated 1,4-polybutadiene-based TPE and the above-mentioned metallocene-based TPE have low affinity for polar polymers such as acrylic resins, and have poor compatibility and adhesion. Due to insufficient properties,
There are restrictions on applications. Furthermore, metallocene-based TPEs have the disadvantage that they have insufficient heat resistance and can exhibit lower physical properties under high-temperature conditions than under normal-temperature conditions. The above-mentioned alloys of styrene-based TPE and acrylic resin are inferior in heat resistance and, for example, have a low evaluation result in a compression set test. Further, the methacrylic acid ester-non-crystalline hydrogenated diene-based block copolymer has a drawback of poor solvent resistance.

SUMMARY OF THE INVENTION It is an object of the present invention to provide not only a good elastomeric property, but also excellent weather resistance, solvent resistance and heat resistance, and a good affinity for each of a polar polymer and a non-polar polymer. To provide a novel polymer having the same. Another object of the present invention is to provide a novel polymer composition which utilizes these features and uses the polymer as a basic component, a modifier, a compatibilizer and the like.

[0009]

According to the present invention, one of the above objects is to provide at least one polymer block A, at least one polymer block B and at least one polymer block B in the main chain. This problem is solved by providing a block copolymer containing the following polymer blocks C.

A: a polymer block in which at least 80% of the unsaturated bonds of a butadiene-based polymer block having less than 20% of 1,2 bonds are hydrogenated and having crystallinity;

B: a polymer block having a glass transition point of 20 ° C. or less;

C: a polymer block mainly composed of methacrylate or acrylate units and having a glass transition point higher than 20 ° C.

Further, according to the present invention, the above-mentioned other object is as follows.
The problem is solved by providing a polymer composition containing the above block copolymer and at least one other polymer.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The block copolymer of the present invention comprises at least one polymer block A in the main chain (hereinafter, “polymer block A” may be referred to as “A block”), At least one polymer block B (hereinafter, “polymer block B” may be referred to as “B block”) and at least one polymer block C (hereinafter, “polymer block C” is referred to as “C block”). "May be referred to as").

The A block constituting the block copolymer of the present invention is formed by hydrogenating an unsaturated bond of a butadiene-based polymer block, but the butadiene unit in the butadiene-based polymer block before the hydrogenation is added. Is less than 20% (may be 0%),
In the hydrogenation, 80% or more (may be 100%) of the unsaturated bond is hydrogenated, and it is important that the polymer block after hydrogenation has crystallinity. The method of confirming the crystallinity is not necessarily limited.For example, in the case of differential scanning calorimetry, an endothermic peak is observed when the temperature is raised, and an exothermic peak is observed when the temperature is decreased, the crystal has crystallinity. Can be determined. If the A block is amorphous, the properties of the thermoplastic elastomer in the A block as a hard block are impaired, and the resulting block copolymer does not exhibit the function as a thermoplastic elastomer, which is not preferable. Butadiene polymer block 1, before hydrogenation
When the amount of two bonds is 20% or more, the A block after hydrogenation has no crystallinity, and the same disadvantages as described above occur, which is not preferable. Further, when the hydrogenation ratio of the unsaturated bond in the butadiene-based polymer block is less than 80%,
It is not preferable because the properties of the thermoplastic elastomer as a hard block are impaired, and the weather resistance and heat resistance of the block copolymer are impaired. From these viewpoints, regarding the A block, 1,2 in the butadiene unit in the butadiene-based polymer block before hydrogenation is used.
It is particularly preferred that the bond amount is 15% or less (or 0%) and 90% or more (or 100%) of the unsaturated bonds are hydrogenated.

In the present invention, the butadiene-based polymer block before hydrogenation of the A block is mainly composed of butadiene units (however, those having more than 80% are 1,1).
4 bond butadiene unit _(-CH 2 -CH = CH-CH
₂ -), and less than 20% 1,2-bond butadiene unit _{(-CH (CH = CH 2)} -CH 2 - is a polymer block consisting of) a), does not impair the gist of the present invention If it is a small amount, it may have a structural unit derived from another monomer such as another diene, vinyl aromatic compound, methacrylate, or acrylate.

The B block constituting the block copolymer of the present invention is a polymer block having a glass transition point of 20 ° C. or less. When the glass transition point of the B block is higher than 20 ° C., the properties of the thermoplastic elastomer as the soft block are impaired in the B block, and the obtained block copolymer does not exhibit the function as the thermoplastic elastomer. Therefore, it is not preferable. From this perspective,
More preferably, the B block has a glass transition point of 10 ° C. or less.

The glass transition point of the B block in the present invention is derived from the glass transition of the B block when the block copolymer is subjected to a differential scanning calorimetry at a rate of 10 ° C./min. This is the temperature at which a change in specific heat is observed.

As long as the B block has a glass transition point observed at a substantially single temperature of 20 ° C. or less, even if it is composed of a homopolymer composed of a single type of monomer, a plurality of types of single block may be used. It may be composed of a copolymer composed of monomers. As an example of the polymer constituting the B block, the 1,2 bond amount is 20% or more (may be 100%).
(Preferably polybutadiene having 1,2 bonds of 30% or more (may be 100%)), diene polymers such as polyisoprene; polyhexyl methacrylate, octyl polymethacrylate, decyl polymethacrylate, polymethacryl Lauryl acid, polymethacrylic acid 2-
Methacrylic acid ester-based polymers such as ethylhexyl and polymethoxymethyl methacrylate; polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polybutyl acrylate, polyacrylic acid s-
Butyl, polyheptyl acrylate, polyacrylic acid 3-
Examples include acrylic acid ester polymers such as pentyl, polyhexyl acrylate, octyl polyacrylate, decyl polyacrylate, lauryl polyacrylate, 2-ethylhexyl polyacrylate, and 2-methoxyethyl acrylate. However, when the B block is composed of the diene-based polymer, 80% or more (or 100%) of the unsaturated bonds in the diene-based polymer may be hydrogenated from the viewpoint of the weather resistance of the obtained block copolymer. The polymer is preferably a polymer obtained by hydrogenating 90% or more (or 100%) of unsaturated bonds. Further, the above-mentioned exemplified polymer has a glass transition point of 20 ° C. or less within a range of diene,
Other monomers such as a vinyl aromatic compound, methacrylate, and acrylate may be copolymerized.

The C block constituting the block copolymer of the present invention is a polymer block mainly composed of a methacrylate unit or an acrylate unit and having a glass transition point higher than 20 ° C. Where C
The glass transition point of the block is a temperature at which a change in the specific heat derived from the glass transition of the C block is observed when the block copolymer is subjected to differential scanning calorimetry at a rate of 10 ° C./min. . In the C block, the methacrylate unit and / or the acrylate unit are preferably 80% by weight or more (1
00% by weight), more preferably 90% by weight
(May be 100% by weight). When the glass transition point of the C block is 20 ° C. or lower, the property of the thermoplastic elastomer as a hard block is impaired in the C block, and the obtained block copolymer does not exhibit the function as the thermoplastic elastomer, which is preferable. Absent.
In this respect, the C block more preferably has a glass transition point of 40 ° C. or higher.

Preferred examples of the polymer constituting the C block include polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, poly-s-butyl methacrylate, poly-t-butyl methacrylate, poly-methacrylic acid. Methacrylate polymers such as cyclohexyl acrylate, polyisobornyl methacrylate, and polyglycidyl methacrylate; and acrylate polymers such as t-butyl polyacrylate, polyhexyl methacrylate, and isobornyl methacrylate. it can. As long as the glass transition temperature of the C block is higher than 20 ° C., structural units derived from other monomers such as butadiene in addition to the methacrylate unit and / or the acrylate unit. May be included.

The arrangement of the block A, block B and block C in the block copolymer of the present invention is not necessarily limited, but the block copolymer has a main chain in that the elastomeric property can be sufficiently exhibited. At least a portion of which has at least one polymer block B
Preferably has a structure located between at least one polymer block A and at least one polymer block C, and at least a part of the formula

[0023]

[A]-[B]-[C]

(Where [A] represents a polymer block A, [B] represents a polymer block B, [C] represents a polymer block C, and solid lines (-) represent the polymer at both ends. (Indicates that the blocks are directly connected by a chemical bond or are connected via a partial structure derived from a coupling agent.)

It is more preferred to have the structure shown by

The block copolymer of the present invention has a hydroxyl group, a carboxyl group, an amino group,
It may have a functional group such as an epoxy group. Furthermore, the block copolymer of the present invention has, in its molecular main chain,
It has a partial structure derived from a polymer block different from the A block, B block and C block, and a coupling agent such as 1,2-dibromoethane, bis (bromomethyl) benzene, silicon tetrachloride, and tin chloride. Is also good.

Representative examples of the combination of polymer blocks in the block copolymer of the present invention include the following (1) to
(8) can be mentioned.

(1) (hydrogenated polybutadiene having a low 1,2 bond content)-(hydrogenated polybutadiene having a high 1,2 bond content)-(polymethyl methacrylate)

(2) (hydrogenated product of polybutadiene having a low 1,2 bond content)-(hydrogenated product of polyisoprene)
-(Polymethyl methacrylate)

(3) (hydrogenated polybutadiene having a small amount of 1,2 bonds)-(hydrogenated isoprene-butadiene copolymer)-(polymethyl methacrylate)

(4) (hydrogenated polybutadiene having a low 1,2 bond content)-(polylauryl methacrylate)-
(Polymethyl methacrylate)

(5) (a hydrogenated product of polybutadiene having a low 1,2 bond content)-(polyethyl 2-methyhexyl methacrylate)-(polymethyl methacrylate)

(6) (a hydrogenated product of polybutadiene having a low 1,2 bond content)-(n-butyl polyacrylate)-
(Polymethyl methacrylate)

(7) (hydrogenated polybutadiene having a low 1,2 bond amount)-(hydrogenated polybutadiene having a high 1,2 bond amount)-(hydrogenated polybutadiene)
-(Polymethyl methacrylate)

(8) (hydrogenated polybutadiene having a low 1,2 bond content)-(hydrogenated isoprene-butadiene copolymer)-(hydrogenated polybutadiene)-
(Polymethyl methacrylate)

The number average molecular weight of the block copolymer of the present invention is not necessarily limited, but is preferably in the range of 20,000 to 1,000,000. In the block copolymer of the present invention, the molecular weight distribution represented by the ratio of (weight average molecular weight) / (number average molecular weight) is preferably in the range of 1.0 to 2.0. The number average molecular weight of each polymer block in the block copolymer of the present invention is not necessarily limited.
３０300,000, and B block is 8000 to 90
It is preferable that the number of C blocks is in the range of 1,000 to 300,000. Also, the content of each polymer block in the block copolymer of the present invention is not necessarily limited, but the content of the A block in the state before hydrogenation is based on the block copolymer before hydrogenation. The amount (sum of the contents before hydrogenation when the block copolymer contains a plurality of A blocks in the block copolymer) is in the range of 5 to 60% by weight, The amount (the sum of the contents of a plurality of B blocks when the block copolymer is contained) is in the range of 30 to 90% by weight, and the content of the C block (in the block copolymer). When a plurality of C-blocks are contained, the sum of the contents is preferably in the range of 5 to 40% by weight.

The method for producing the block copolymer of the present invention is not necessarily limited. For example, according to a known anionic polymerization method, A block before hydrogenation,
A block copolymer of the present invention can be obtained by producing a precursor block copolymer by sequentially forming predetermined polymer blocks such as a B block and a C block, and then performing a hydrogenation reaction.

In the polymerization reaction for obtaining the above precursor block copolymer, conditions usually used for anionic polymerization can be adopted. Usually, the polymerization temperature is -100
℃ ~ +100 ℃, the polymerization time is 0.01 ~
Within the range of 200 hours. The polymerization atmosphere is preferably under an inert gas such as dry argon or nitrogen. The polymerization initiator in the above-described anionic polymerization is not necessarily limited, but an initiator capable of normally performing anionic polymerization of butadiene can be appropriately selected and used. Examples of the initiator include alkali metals such as sodium metal and lithium metal; and organic alkali metal compounds such as methyl lithium, ethyl lithium, n-butyl lithium and s-butyl lithium. In the above-described anionic polymerization, a solvent that can be used in ordinary anionic polymerization can be appropriately selected and used. Therefore, in a series of polymerizations for forming the A block, the B block and the C block before hydrogenation, respectively, a polymer block capable of satisfying the above-mentioned conditions regarding the 1,2 bond amount and the glass transition point in each block. In order to obtain the compound, the solvent may be appropriately exchanged during the polymerization, or an additive, a solvent and the like may be added.

Hereinafter, a method for producing a precursor block copolymer by a polymerization method in which A block, B block and C block before hydrogenation are formed in this order will be described as an example.

The solvent used in the polymerization for forming the A block precursor before hydrogenation may be any solvent as long as it can control the amount of 1,2 bonds of butadiene to less than 20%. It is a hydrocarbon solvent. Examples of the hydrocarbon solvent include hexane, cyclohexane,
Methylcyclohexane, benzene, toluene and the like can be mentioned. In addition, the 1,2 bond amount of butadiene is 20
%, A mixture of solvents may be used or a solvent to which an additive or the like is added may be used.

Suitable conditions such as a solvent and an additive in the polymerization for forming the B block or its precursor block differ depending on the monomer to be used. Therefore, appropriate conditions are selected according to the type of the monomer. Good to do. For example,
When a block of polyisoprene is formed as the B block, the polymerization can be carried out by directly adding isoprene to the reaction system after the completion of the polymerization reaction for forming the A block precursor. 1,2 bond amount is 2
When a polybutadiene block of 0% or more is formed, ethers such as diethyl ether, anisole, and tetrahydrofuran are added to the reaction system after the completion of the polymerization reaction for forming the A block precursor; triethylamine;
By adding a predetermined amount of a polar compound represented by amines such as N, N, N ', N'-tetramethylethylenediamine, and then adding butadiene, a 20%
It is possible to form a polybutadiene block having the above 1,2 bond amount. Forming a polymer block mainly composed of a methacrylate unit and / or an acrylate unit typified by a block of polylauryl methacrylate or a block of n-butyl polyacrylate, and having a glass transition point of 20 ° C. or lower. When the polymerization is performed, for example, after the polymerization reaction for forming the A block precursor is completed, for example, 1,1-diphenylethylene is added into the polymerization system, and the polymerization system is cooled to a temperature of about −80 ° C.
A method of adding a polar solvent such as tetrahydrofuran from which impurities have been sufficiently removed, and then adding a monomer mainly composed of a predetermined methacrylate and / or acrylate to start a polymerization reaction; A block precursor formation After the completion of the polymerization reaction, a method of adding an organoaluminum compound to the reaction system, and then adding a monomer mainly containing a predetermined methacrylate and / or acrylate to start the polymerization reaction, It is possible to form a target B block or a precursor thereof.

As the solvent used in the polymerization for forming the C block, methacrylic acid ester and / or
Or among monomers mainly composed of acrylic acid esters,
Any material can be used as long as it can polymerize a type that forms a polymer chain having a glass transition point higher than 20 ° C. For example, after the polymerization for forming the B block is completed,
A method in which a polar solvent such as tetrahydrofuran, from which impurities have been sufficiently removed, is added to the reaction system, and then a predetermined monomer is added to start the polymerization reaction; It is possible to form a target C block by a method of adding an aluminum compound and then adding a predetermined monomer to start a polymerization reaction.

When it is desired to obtain a block copolymer having another polymer block in addition to the A block, B block and C block, the other copolymer block is required at a predetermined stage in the above-mentioned multi-stage anionic polymerization. A polymerization step for forming a polymer block may be added. After completion of the above series of anionic polymerization, 1,2
-Dibromoethane, bis (bromomethyl) benzene, 4
The polymers may be coupled with each other by adding a coupling agent such as silicon chloride or tin chloride to the reaction system.

A block and B block before hydrogenation (or B block before hydrogenation) thus obtained
By hydrogenating a precursor block copolymer containing C and C blocks and converting 80% or more of the carbon-carbon unsaturated bonds in the A block before the hydrogenation into carbon-carbon saturated bonds, the present invention Can be obtained. When the precursor block copolymer has a carbon-carbon unsaturated bond even in the B block before hydrogenation, in the hydrogenation, 80% or more of the carbon-carbon unsaturated bond is carbon-carbon saturated. Preferably, it is converted into a bond.

The above-mentioned hydrogenation reaction is not necessarily limited, but may be carried out, for example, by catalytic hydrogenation of a precursor block copolymer in a solvent in the presence of a hydrogenation catalyst in accordance with a known method. Can be. As a solvent used for the hydrogenation reaction, a solvent inert to the hydrogenation reaction, such as hexane, cyclohexane, and toluene, is preferable. Examples of usable catalysts include, for example, supported catalysts in which metals such as Pt, Pd, Ru, Rh, and Ni are supported on a carrier such as carbon, alumina, and diatomaceous earth; heterogeneous catalysts such as Raney nickel; Ziegler-based catalysts that are combined with an organic aluminum compound, an organic lithium compound, and the like are included. Although other reaction conditions are not necessarily limited, the hydrogen pressure is from normal pressure to 200 kg / c.
in the range of m ^2, the range of room temperature to 250 DEG ° C., in the range of 0.1 to 200 hours and the reaction time is usually adopted as the reaction temperature.

The method of obtaining the block copolymer from the obtained reaction mixture after the above hydrogenation reaction is not necessarily limited. For example, the reaction mixture containing the block copolymer may be mixed with a poor mixture such as methanol. The block copolymer of the present invention can be obtained by coagulating by contacting with a solvent, taking out the coagulated product, pre-drying it, and drying it under heating or reduced pressure.

Since the block copolymer of the present invention has thermoplasticity, it can be used in various molding methods such as injection molding and extrusion molding, and has various shapes such as sheet, hose, box and ball shapes. It can be molded into molded articles. The obtained molded product not only has the properties of vulcanized rubber such as flexibility and rubber elasticity (elastomeric), but also has excellent weather resistance and solvent resistance, and further has good adhesion to polar polymers, paintability, Because of its excellent heat resistance, automotive parts, sporting goods,
It is particularly advantageously used for applications such as light electrical parts, electric wires and cables, and civil engineering materials. The block copolymer of the present invention utilizes the fact that it has good adhesion to polar polymers such as polymethyl methacrylate (PMMA), ABS resin, polycarbonate, etc. It can be used in the form of a laminate or composite composed of coalescing.

The characteristics of the block copolymer of the present invention, such as flexibility, affinity for polar polymers, affinity for non-polar polymers, heat resistance, weather resistance, and solvent resistance, are the characteristics of the block copolymer of the present invention. It is also effective in a polymer composition containing a copolymer and at least one other polymer. That is, the block copolymer of the present invention functions as a modifier (for example, a softness-imparting agent, a polarity-imparting agent, and the like) with respect to other polymers, and is used in combination with other plural kinds of polymers. On the other hand, it functions as a compatibilizer. Furthermore, the block copolymers of the present invention are susceptible to modification by other polymers.

Preferred polymers for constituting the polymer composition in combination with the block copolymer of the present invention include polyethylene, ethylene-α-olefin copolymer (eg, ethylene-1-octene copolymer), Non-polar polymers represented by olefin polymers such as polypropylene; acrylic polymers such as polymethyl methacrylate (PMMA); vinyl chloride polymers such as polyvinyl chloride; vinylidene fluoride such as polyvinylidene fluoride Polar polymers represented by acrylonitrile-styrene copolymers such as ABS resins and AS resins; and maleic anhydride-styrene copolymers. For example, since the block copolymer of the present invention has good compatibility with polar polymers, by forming a composition in combination with PMMA, a soft material having excellent properties derived from PMMA such as transparency can be obtained. Material can be obtained. The block copolymer of the present invention functions as a compatibilizer in a polymer composition containing the block copolymer, at least one other polar polymer, and at least one nonpolar polymer. Can be.
Preferred embodiments for making the block copolymer of the present invention function as a compatibilizer include a block copolymer, a polymer composition containing another acrylic polymer and an olefin polymer, and the like. .

In a polymer composition containing the block copolymer of the present invention and at least one other polymer,
The blending ratio of the block copolymer is not necessarily limited, but generally, (weight of the block copolymer)
The ratio of (/ the weight of the other polymer (the sum of the weights of the polymers when there are a plurality thereof)) is in the range of 1/99 to 97/3. Of these, if the purpose is to mainly utilize the properties of the block copolymer of the present invention and to impart the properties of other polymers to it, generally, (block copolymer)
/ (Other polymer) in a weight ratio of 50/50 to 95 /
It is preferably within the range of 5. When the block copolymer of the present invention is used as a modifier for another polymer,
Generally, the weight ratio of (block copolymer) / (other polymer) should be within the range of 5/95 to 50/50, while taking advantage of the basic properties of the other polymer. It is preferable from the viewpoint of effectively exhibiting properties such as softness derived from the block copolymer of the present invention. When the block copolymer of the present invention is used as a compatibilizing agent for a plurality of other polymers, generally, (weight of block copolymer) / (weight of all other polymers) Weight)
It is preferable that it is in the range of 99 to 40/60 in order to efficiently exhibit the compatibility improving effect derived from the block copolymer of the present invention while utilizing the basic properties of each of the other polymers. . The polymer composition containing the block copolymer of the present invention and another polymer can be easily produced by a method such as kneading both under melting conditions.

The polymer composition containing the block copolymer of the present invention and another polymer can be subjected to various molding methods such as injection molding, extrusion molding, and the like. And molded articles of various shapes such as a ball shape. The obtained molded product is particularly advantageously used for applications such as automobile parts, sports goods, weak electric parts, electric wires and cables, and civil engineering materials.

[0052]

The present invention will be specifically described below with reference to examples.
Note that the present invention is not limited by these examples.

The polymers obtained in Examples and Comparative Examples were analyzed by the following methods (1) and (2).

(1) Measurement of 1,2 bond amount in butadiene-based polymer block before hydrogenation A sample was taken from the reaction mixture after the predetermined polymerization step was completed, and the solvent was sufficiently removed from the sample under reduced pressure. The obtained residue was dissolved in deuterated chloroform and subjected to nuclear magnetic resonance absorption measurement. With respect to the obtained signal, the integral ratio of the peak around 5.0 ppm derived from the 1,2 bond in the polybutadiene and the peak around 5.4 ppm derived from the 1,4 bond was determined. The amount was determined.

(2) Determination of Crystallinity in Polymer Block and Measurement of Glass Transition Point
After vacuum drying at 0 ° C for 20 hours, it was subjected to compression molding at 220 ° C. Using the obtained test piece, -150 ° C to +250
Differential scanning calorimetry was performed at a temperature rising rate of 10 ° C./min in a temperature range of 10 ° C. At that time, when a change in specific heat due to the glass transition of the polymer block in the polymer is observed,
The temperature was determined as the glass transition point (Tg) of the polymer block. When an endothermic peak due to melting of the polymer block was observed, the polymer block was determined to have crystallinity.

Reference Example 1 [Production example of triblock copolymer of (1,2 bond low content polybutadiene)-(1,2 bond high content polybutadiene)-(polymethyl methacrylate)] During the liter autoclave,
After charging 270 g of degassed and dehydrated methylcyclohexane and 0.108 g of s-butyllithium (hereinafter abbreviated as “s-BuLi”), 10.5 g of 1,3-butadiene was added, and the mixture was heated to 40 ° C. The temperature was raised and polymerization was carried out for 3 hours. Next, a part of the produced polymer was sampled and analyzed. The analysis was performed by gel permeation chromatography (hereinafter abbreviated as "GPC") and nuclear magnetic resonance absorption measurement (hereinafter abbreviated as "NMR").
The number average molecular weight (hereinafter abbreviated as “Mn”), the ratio of weight average molecular weight / number average molecular weight (hereinafter abbreviated as “Mw / Mn”), and the 1,2 bond amount were determined. As a result, Mn = 6200, Mw / Mn = 1.0
It was found that polybutadiene having a low 1,2 bond content of 4,1,2 bonds = 6% was formed. After the above polymerization, 1.4 g of degassed and dehydrated tetrahydrofuran was added to the polymerization system, and then 49 g of 1,3-butadiene was added to the system and polymerization was performed at 40 ° C. for 3 hours. Next, sampling is performed, and the second formed by GPC and NMR.
A block analysis was performed. As a result, it was found that a polybutadiene block having a high 1,2 bond content with Mn = 28900, Mw / Mn = 1.09, and 1,2 bond content = 59% was formed as the second block. In the obtained polymerization system,
Degassed and dehydrated 1,1-diphenylethylene 0.6
g was added and the polymerization system was cooled to 0 ° C. Degas there,
310 g of dehydrated tetrahydrofuran was added and reacted for 1 hour with stirring. Next, the polymerization system was cooled to -80 ° C, and 10.5 g of methyl methacrylate was added, and polymerization was performed for 3 hours. Thereafter, 0.8 g of methanol was added into the polymerization system to terminate the polymerization.

After the termination of the polymerization, a small sample of the polymer was collected and analyzed by GPC and NMR. As a result, as the third block, Mn = 6200, Mw / Mn = 1.18
It was found that a polymethyl methacrylate block was formed. Finally, Mn = 42200, M
It was confirmed that a triblock copolymer of (1,2 bond low content polybutadiene)-(1,2 bond high content polybutadiene)-(polymethyl methacrylate) with w / Mn = 1.18 was formed. The polymer solution thus obtained was poured into 8000 g of methanol to coagulate the polymer, and the coagulated product was recovered and dried at 30 ° C. for 20 hours under vacuum to obtain the triblock copolymer. 65 g of the combined product were obtained.

Example 1 [Production example of triblock copolymer of (hydrogenated polybutadiene with a low content of 1,2 bonds)-(hydrogenated polybutadiene with a high content of 1,2 bonds)-(polymethyl methacrylate)] Was replaced with nitrogen in a 1 liter autoclave,
55 g of the block copolymer obtained in Reference Example 1 was degassed,
It was dissolved in 520 g of dehydrated toluene. Nickel octylate / triisobutylaluminum = 1 /
3.2 g of a hydrogenation catalyst consisting of 3 (molar ratio) was added, and 8
After the temperature was raised to 0 ° C., hydrogen gas was supplied into the system until the pressure reached 10 kg / cm ^2, and the reaction was carried out for 10 hours under the conditions.
Next, 8 g of 30% by weight aqueous hydrogen peroxide and 8.6 citric acid were used.
The hydrogenation reaction was stopped by adding g. Thereafter, the polymer solution is washed twice with 800 g of distilled water each time, and the obtained polymer solution is poured into 8000 g of methanol to coagulate the polymer, the coagulated product is collected, and vacuum drying is performed at 60 ° C. for 20 hours. 50 g of a polymer was obtained.

When the obtained polymer was measured by NMR, it was confirmed that 97% of the unsaturated bonds contained in the original polybutadiene portion were hydrogenated and converted to saturated bonds. When analyzed by GPC and NMR, the 1,2-bond low content polybutadiene hydride block was 15% by weight, the 1,2-bond high content polybutadiene hydride block was 70% by weight, and the polymethyl methacrylate block was 15% by weight. %, Mn = 4250
0, it was confirmed that a polymer having Mw / Mn = 1.18 was obtained. From these facts, it was found that a triblock copolymer of (1,2 bond low content polybutadiene hydrogenated)-(1,2 bond high content polybutadiene hydrogenated)-(polymethyl methacrylate) was obtained. did. Also,
As a result of differential scanning calorimetry of the obtained triblock copolymer, the change in specific heat due to the glass transition of the 1,2-bond high-content polybutadiene hydride block at -70 ° C was 1
At 10 ° C, an endothermic peak due to crystal melting of the 1,2-bond low content polybutadiene hydride block was observed, and at 120 ° C, a change in specific heat due to glass transition of the polymethyl methacrylate block was observed. The analysis results of the obtained triblock copolymer are summarized in Table 1 below.

Reference Example 2 [Production example of triblock copolymer of (1,2 bond low content polybutadiene)-(polyisoprene)-(polymethyl methacrylate)] In a 1-liter autoclave in which the inside was replaced with nitrogen,
After charging 270 g of degassed and dehydrated methylcyclohexane and 0.072 g of s-BuLi, 1,3-
7 g of butadiene was added, the temperature was raised to 40 ° C., and polymerization was performed for 3 hours. Next, a part of the produced polymer was sampled and analyzed by GPC and NMR. As a result, Mn = 62.
It was found that a 1,2-bond low polybutadiene having a Mw / Mn of 1.08 and a 1,2-bond content of 6% was formed. After the above polymerization, 56 g of isoprene was added into the system, and polymerization was performed at 40 ° C. for 3 hours. Next, sampling was performed and analyzed by GPC and NMR. As a result, Mn = 49500 and Mw / Mn = 1.
It was found that 05 polyisoprene blocks had formed. In the obtained polymerization system, degassed and dehydrated 1,1
-0.4 g of diphenylethylene was added, and the polymerization system was cooled to 0 ° C.
Cooled down. 310 g of degassed and dehydrated tetrahydrofuran was added thereto, and the mixture was reacted for 1 hour with stirring. Next, the polymerization system was cooled to -80 ° C, 7 g of methyl methacrylate was added, and polymerization was performed for 3 hours. Then 0.5
g of methanol was added to the polymerization system to terminate the polymerization.

At the end of the polymerization, a small amount of the polymer was collected,
As a result of analysis by C and NMR, as a third block,
It was found that a polymethyl methacrylate block having Mn = 6200 and Mw / Mn = 1.18 was formed.
Further, finally, Mn = 62000, Mw / Mn = 1.
It was confirmed that 18 triblock copolymers of (1,2 bond low content polybutadiene)-(polyisoprene)-(polymethyl methacrylate) were obtained. The polymer solution thus obtained was poured into 8000 g of methanol to coagulate the polymer, and the coagulated product was recovered.
By performing vacuum drying at 30 ° C. for 20 hours, 65 g of the above triblock copolymer was obtained.

Example 2 [(1,2-bond low content polybutadiene hydrogenated product)-(polyisoprene hydrogenated product)-
Production Example of Triblock Copolymer of (Poly (methyl methacrylate)) In a 1 liter autoclave in which the inside is replaced with nitrogen,
55 g of the block copolymer obtained in Reference Example 2 was degassed,
It was dissolved in 520 g of dehydrated toluene. Nickel octylate / triisobutylaluminum = 1 /
2.8 g of a hydrogenation catalyst consisting of 3 (molar ratio)
After the temperature was raised to 0 ° C., hydrogen gas was supplied into the system until the pressure reached 10 kg / cm ^2, and the reaction was carried out under these conditions for 14 hours.
Next, 7 g of 30% by weight aqueous hydrogen peroxide and 7.4 parts of citric acid were added.
The hydrogenation reaction was stopped by adding g. Thereafter, washing is performed twice with 800 g of distilled water each time, and the obtained polymer solution is poured into 8000 g of methanol to coagulate the polymer, the coagulated product is collected, and vacuum drying is performed at 60 ° C. for 20 hours. 50 g of a polymer was obtained.

When the obtained polymer was measured by NMR, it was found that 99% of the unsaturated bonds contained in the polybutadiene block and 90% of the unsaturated bonds contained in the polyisoprene block were each hydrogenated to form a saturated bond. The conversion was confirmed. GPC and NMR
Analysis showed that the 1,2-bond low content polybutadiene hydride block occupied 10% by weight, the polyisoprene hydride block 80% by weight, the polymethyl methacrylate block 10% by weight, Mn = 63500, Mw
It was confirmed that a polymer having /Mn=1.18 was obtained. From these, (1,2 bond low content polybutadiene hydrogenated product)-(polyisoprene hydrogenated product)-
It was found that a triblock copolymer of (polymethyl methacrylate) was obtained. Further, as a result of differential scanning calorimetry of the obtained triblock polymer, a change in specific heat due to the glass transition of the polyisoprene hydride block at -65 ° C was observed. An endothermic peak due to crystal melting of the product block and a change in specific heat due to the glass transition of the polymethyl methacrylate block at 120 ° C. were observed. The analysis results of the obtained triblock copolymer are summarized in Table 1 below.

Example 3 A polymerization reaction, separation of a precursor block copolymer, and a hydrogenation reaction were carried out in the same manner as in Reference Example 1 and Example 1 except that the amounts of the polymerization initiator and the monomers charged were changed. And by performing each operation of separation of the block copolymer,
(1,2-bond low content polybutadiene hydrogenated product)
(1,2 bond high content polybutadiene hydrogenated product)-(polymethyl methacrylate) triblock copolymer was obtained. The analysis results of the obtained triblock copolymer are shown in Table 1 below.

Example 4 A polymerization reaction, separation of a precursor block copolymer, and a hydrogenation reaction were performed in the same manner as in Reference Example 2 and Example 2 except that the amounts of the polymerization initiator and the monomers charged were changed. And by performing each operation of separation of the block copolymer,
(1,2 bond low content polybutadiene hydrogenated product)-(polyisoprene hydrogenated product)-(polymethyl methacrylate) triblock copolymer was obtained. The analysis results of the obtained triblock copolymer are shown in Table 1 below.

[0066]

[Table 1]

COMPARATIVE EXAMPLE 1 Triblock copolymerization of ((1,2 bond low content polybutadiene hydrogenated product)-(1,2 bond high content polybutadiene hydrogenated product)-(1,2 bond low content polybutadiene hydrogenated product) Production Example of Coalescence] In a 1 liter autoclave in which the inside is replaced with nitrogen,
270 g of degassed and dehydrated cyclohexane and s-
After charging 0.108 g of BuLi, 10.5 g of 1,3-butadiene was added, the temperature was raised to 40 ° C., and polymerization was performed for 3 hours. Next, a part of the produced polymer was sampled and analyzed by GPC and NMR.
It was found that a polybutadiene having a low 1,2 bond content of Mw / Mn = 1.04 and a 1,2 bond content of 6% was formed. After the above polymerization, 1.4 g of degassed and dehydrated tetrahydrofuran was added to the system, and then 24.5 g of 1,3-butadiene was added and polymerization was performed at 40 ° C. for 3 hours. Next, sampling was performed and analyzed by GPC and NMR. As a result, Mn = 14500 and M
It was found that a 1,2-bond high polybutadiene block having w / Mn = 1.08 and 1,2 bond content = 59% was formed. In the obtained polymerization system, 1, degassed sufficiently
The polymer was coupled by adding 0.32 g of 2-dibromoethane, heating to 50 ° C., and reacting for 4 hours. Thereafter, 0.8 g of methanol was added into the polymerization system to terminate the polymerization. After stopping the polymerization, a small amount of the polymer was collected and analyzed by GPC and NMR. As a result, finally, (1,2) having Mn = 42200 and Mw / Mn = 1.13 was obtained.
2-bond low polybutadiene)-(1,2-bond high polybutadiene)-(1,2-bond low polybutadiene)
It was confirmed that the triblock copolymer was obtained.
The polymer was recovered by the same operation as in Reference Example 1, and
By performing a hydrogenation reaction in the same manner as described above, (1,2 bond low content polybutadiene hydrogenated product)-(1,2 bond high content polybutadiene hydrogenated product)-(1,2 bond low content polybutadiene hydrogenated product) ) Was obtained. As a result of differential scanning calorimetry of the obtained polymer,
At −70 ° C., the change in specific heat due to the glass transition of the 1,2-bond high-content polybutadiene hydrogenated portion, and at 110 ° C., the endothermic peak due to the crystal melting of the 1,2-bond low-content polybutadiene hydrogenated portion, respectively. Observed.

Comparative Example 2 [Production Example of Triblock Copolymer of (Polystyrene)-(Polyisoprene Hydrogenated Product)-(Polystyrene)] In a 1-liter autoclave in which the inside was replaced with nitrogen,
270 g of degassed and dehydrated cyclohexane and s-
After charging 0.108 g of BuLi, styrene 10.
5 g was added, the temperature was raised to 40 ° C., and polymerization was performed for 3 hours.
Next, a part of the produced polymer was sampled and analyzed by GPC and NMR. As a result, Mn = 6200, Mw / M
It was found that polystyrene with n = 1.04 was formed. After the above polymerization, 49 g of isoprene was added to the system, and 4
Polymerization was carried out at 0 ° C. for 3 hours. Next, sample
As a result of analysis by GPC and NMR, it was found that a polyisoprene block having Mn = 29000 and Mw / Mn = 1.08 was formed as the second block. 10.5 g of styrene was added to the obtained polymerization reaction system,
Polymerization was carried out for hours. Thereafter, 0.8 g of methanol was added into the polymerization system to terminate the polymerization. After the polymerization was stopped, a small amount of the polymer was collected and analyzed by GPC and NMR.
Finally, it was confirmed that a triblock copolymer of (polystyrene)-(polyisoprene)-(polystyrene) having Mn = 42200 and Mw / Mn = 1.13 was obtained. The polymer was recovered by the same operation as in Reference Example 1, and a hydrogenation reaction was carried out in the same operation as in Example 1 to obtain a triblock copolymer of (polystyrene)-(hydrogenated polyisoprene)-(polystyrene). Coalescence was obtained. As a result of differential scanning calorimetry of the obtained polymer, a change in specific heat due to a glass transition of a polyisoprene hydrogenated portion at -65 ° C and a change in specific heat due to a glass transition of a polystyrene portion at 100 ° C were respectively obtained. Observed.

Evaluation Test Examples Various evaluation tests were performed on the polymers obtained in the above Examples and Comparative Examples by the following methods.

(1) Tensile test After drying a polymer sample at 60 ° C. for 20 hours,
It was subjected to compression molding at 0 ° C. A dumbbell No. 3 described in JIS standard “Vulcanized rubber physical test method” (JIS K6301) was punched out from the sheet-like sample thus manufactured. Using this dumbbell, a tensile speed of 50
A tensile test was performed under the condition of 0 mm / min, and the breaking strength and elongation were measured.

(2) Weather Resistance Test A polymer sample was dried at 60 ° C. for 20 hours.
It was subjected to compression molding at 0 ° C. 5 cm from the obtained sheet
A 5 cm sample piece was cut out and subjected to a weathering test for 500 hours in a xenon weather meter. Before and after the weather resistance test, the hue of each sample piece was visually observed.

(3) Solvent resistance test 0.1 g of a polymer sample piece was immersed in 10 ml of a test solvent (hexane, cyclohexane and toluene) and allowed to stand at room temperature overnight. A solvent test was performed. The state of the sample piece after the test was visually observed. When neither swelling nor dissolution was observed, it was judged as “insoluble”, when partly swelling was observed, “partially swelling”, and when completely dissolved, it was judged as “easy soluble”.

(4) Test for Adhesion to Polar Resin A polymer sample was dried at 60 ° C. for 20 hours.
It was subjected to compression molding at 0 ° C. 10cm from the obtained sheet
A sample piece of × 5 cm was cut out. On the other hand, test polar resins (PMMA, ABS and polycarbonate (P
C)) was subjected to injection molding to prepare an adherend (flat plate) of 10 cm × 5 cm. An adhesion test is performed by subjecting the sample piece and the adherend to compression molding under the conditions of 210 ° C. and 20 kgf / cm ² for 2 minutes in a state where the sample piece and the adherend are superimposed on each other so as to be in close contact with each other at a 5 cm × 5 cm portion. Was done.
After the test, it was determined whether or not both were adhered. The results of the various evaluation tests are shown in Table 2 below.

[0074]

[Table 2]

From Table 2 above, the block copolymers of the present invention obtained in Examples 1 to 4 show that the styrene obtained in Comparative Example 2 has high breaking strength and high elongation in a tensile test. It can be seen that it has excellent mechanical properties close to SEPS which is a thermoplastic elastomer. Furthermore, the block copolymer of the present invention had no hue change in a weather resistance test, obtained a result of "insoluble" or "partially swelled" in a solvent resistance test, and adhered to a polar resin in an adhesion test. From the results, it can be seen that they are excellent also in weather resistance, solvent resistance and adhesiveness to polar resins. On the other hand, in the styrene-based thermoplastic elastomer of Comparative Example 2 other than the present invention, a hue change occurs in a weather resistance test, and a result of "partially swelling" or "easily soluble" is obtained in a solvent resistance test,
Since it did not adhere to the polar resin in the adhesiveness test, it is understood that the weather resistance, the solvent resistance and the adhesiveness to the polar resin were inferior. In addition, obtained in Comparative Example 1,
The hydrogenated product of the block copolymer other than the present invention having two 1,2-bond low polybutadiene blocks and one 1,2-bond high polybutadiene block did not adhere to the polar resin in the adhesion test. This indicates that the adhesiveness to the polar resin is inferior.

Examples 5 and 6 [Block copolymer and P
Composition with MMA] The same block copolymer as obtained in Example 3 and polymethyl methacrylate (HR-L manufactured by Kuraray Co., Ltd.) in a weight ratio of 70:30 (Example 5) or 50: These were used at a weight ratio of 50 (Example 6), and these were used in a Brabender-type melt-kneading apparatus (Laboplast Mill; manufactured by Toyo Seiki Seisakusho).
The mixture was melt-kneaded at a temperature of 230 ° C. under a screw rotation speed of 100 rpm for 10 minutes. The appearance (color, transparency) of the obtained polymer composition was visually evaluated, the surface hardness (JIS A hardness) was measured at 25 ° C., and the compression set was defined in JIS K6301. It measured according to the method (compression conditions: 70 degreeC, 22 hours). The results obtained are shown in Table 3 below.

COMPARATIVE EXAMPLE 3 [Composition of Block Copolymer and PMMA] In Example 6, the same block copolymer as that obtained in Example 3 was used instead of the same block copolymer obtained in Example 3. A polymer composition was prepared and evaluated in the same manner except that a block copolymer was used. The results obtained are shown in Table 3 below.

[0078]

[Table 3]

In Table 3, the evaluation results of the same block copolymer alone obtained in Example 3 are also shown for reference.

From the results shown in Table 3 above, the polymer compositions according to the present invention obtained in Examples 5 and 6, respectively, showed that the copolymers between the block copolymer of the present invention and polymethyl methacrylate (PMMA) It has good transparency reflecting good affinity (compatibility), has softness evaluated by surface hardness, and has excellent heat resistance evaluated by compression set. On the other hand, the polymer composition obtained in Comparative Example 3, which is different from the present invention in that it contains another block copolymer instead of the block copolymer of the present invention, is inferior in transparency and heat resistance. You can see that.

Comparative Example 4 [Production Example of Diblock Copolymer of (1,2 Bond Low Content Polybutadiene Hydrogenate)-(Polymethyl Methacrylate)] In Reference Example 1, the first polymerization step (1,2 The toluene used instead of methylcyclohexane as the solvent for the polymerization in the step of forming the polybutadiene having a low content of bonded
(I.e., a step of forming a 1,2-bond high content polybutadiene block) is omitted (that is, after the first polymerization step,
The polymerization operation and the separation operation are performed in the same manner except that the process directly proceeds to the third polymerization step (the step of forming a polymethyl methacrylate block), and the amounts of the polymerization initiator and the monomers charged are changed. Thus, a diblock copolymer of (1,2-bond low content polybutadiene)-(polymethyl methacrylate) was obtained. For the polybutadiene block of the obtained diblock copolymer, Mn = 2200
0, Mw / Mn = 1.09, 1,2 bond amount = 7%. The polymethyl methacrylate block had Mn = 23000 and Mw / Mn = 1.18. In Example 1, a hydrogenation reaction operation and a separation operation were carried out in the same manner except that the diblock copolymer obtained above was used to obtain (1,2 bond low content polybutadiene hydrogenated product)-(poly A diblock copolymer of methyl methacrylate) was obtained. By this hydrogenation reaction, it was confirmed that 98% of the unsaturated bonds contained in the polybutadiene portion before hydrogenation were hydrogenated and converted to saturated bonds. When analyzed by GPC and NMR, the diblock copolymer finally obtained showed that the 1,2-bond low content polybutadiene hydride block accounted for 52% by weight and the polymethyl methacrylate block accounted for 48% by weight.
It was confirmed that the polymer had Mn = 49000 and Mw / Mn = 1.12. Also, as a result of differential scanning calorimetry of the finally obtained diblock copolymer,
An endothermic peak due to crystal melting of the two-bond low-content polybutadiene hydride block and a change in specific heat at 120 ° C. due to a glass transition of the polymethyl methacrylate block were observed.

Examples 7 and 8 [Composition of ethylene-1-octene copolymer / PMMA / block copolymer] The same block copolymer as obtained in Example 3 and polymethyl methacrylate (manufactured by Kuraray's HR-L) and an ethylene-1-octene copolymer (Engage 8200, manufactured by Dupont Dow Elastomer Co., Ltd.)
These were used at a weight ratio of 33 (Example 7) or at a weight ratio of 15:25:60 (Example 8), and these were used in a Brabender-type melt-kneading apparatus (Laboplast Mill; manufactured by Toyo Seiki Seisakusho)
The mixture was melt-kneaded at a temperature of 230 ° C. under a screw rotation speed of 100 rpm for 10 minutes. The appearance (color, transparency) of the obtained polymer composition was visually evaluated, the breaking strength and the elongation were measured by a method according to the tensile test, and the surface hardness (JIS A hardness) was 25 ° C. The compression set was measured in accordance with the method (compression conditions: 70 ° C., 22 hours) specified in JIS K6301. The results obtained are shown in Table 4 below. The polymer composition obtained in Example 7 was compression-molded to a thickness of 1 mm and a width of 5 mm.
Was prepared and the dynamic viscoelastic behavior was measured under the conditions of a distance between tensile jigs of 30 mm and a frequency of 11 Hz. As a measuring device, "D" manufactured by Rheology Co., Ltd.
VE-V4 FT Rheospectral "was used. FIG. 1 shows a correlation diagram between the storage elastic modulus (E ′) and the temperature obtained by the measurement.

Comparative Example 5 [Composition of Ethylene-1-octene Copolymer / PMMA] In Example 7, polymethyl methacrylate (HR-L manufactured by Kuraray Co., Ltd.) and ethylene-1-octene copolymer (DuPont) Dow Elastomer: Engage 82
00) was used in the same manner as above except that the weight ratio was 50:50, and various evaluations were performed on the obtained polymer composition. The obtained evaluation results are shown in Table 4 below.

Comparative Example 6 [Composition of ethylene-1-octene copolymer / PMMA / block copolymer] In Example 7, the same diblock copolymer and polymethacrylic acid as those obtained in Comparative Example 4 were used. Methyl (HR-L manufactured by Kuraray Co., Ltd.) and ethylene-1-octene copolymer (manufactured by Dupont Dow Elastomers: Engage 82)
00) was used in the same manner as above except that the weight ratio was 8:25:67, and various evaluations and dynamic viscoelastic behavior measurements were performed on the obtained polymer composition. The obtained evaluation results are shown in Table 4 below. FIG. 2 shows a correlation diagram between the storage elastic modulus (E ′) and the temperature obtained by the dynamic viscoelastic behavior measurement.

Comparative Example 7 [Composition of ethylene-1-octene copolymer / PMMA / block copolymer] In Example 7, the same triblock copolymer and polymethacrylic acid as those obtained in Comparative Example 2 were used. Methyl (HR-L manufactured by Kuraray Co., Ltd.) and ethylene-1-octene copolymer (manufactured by Dupont Dow Elastomers: Engage 82)
00) was used in the same manner as above except that the weight ratio was 15:25:60, and various evaluations were performed on the obtained polymer composition. Table 4 below shows the obtained evaluation results.
Shown in

[0086]

[Table 4]

From the results shown in Table 4 above, ethylene-
1-octene copolymer (metallocene TPE) and P
In the polymer composition other than the present invention obtained in Comparative Example 5 containing only two components of MMA, the transparency evaluated by appearance,
Examples comprising the block copolymer of the present invention in addition to these two components, while the tensile properties evaluated by breaking strength and the heat resistance evaluated by compression set are insufficient. It can be seen that in the polymer composition of the present invention obtained in 7, the transparency, tensile properties and heat resistance are significantly improved. This result suggests that the compatibility between the metallocene-based TPE and PMMA was improved by the incorporation of the block copolymer of the present invention. Also, from Table 4 above,
The polymer composition of the present invention obtained in Example 8 was also used in Example 7
As in the polymer composition of the present invention obtained in the above, it is found that the polymer composition has excellent properties in transparency, tensile properties, heat resistance and the like. On the other hand, in the polymer compositions obtained in Comparative Examples 6 and 7, which are different from the present invention in that they contain another block copolymer instead of the block copolymer of the present invention, the polymer of Example 7 was used. It can be seen that, despite having the same surface hardness as the composition, the tensile properties evaluated by the breaking strength and the heat resistance evaluated by the compression set are insufficient.

Further, from the graph (FIG. 1) showing the temperature dependence of the storage elastic modulus (E ') of the polymer composition according to the present invention obtained in Example 7, it can be seen from FIG.
It can be seen that the storage modulus is maintained up to this point. On the other hand, the storage modulus (E ′) of the polymer composition obtained in Comparative Example 6, which is different from the present invention in that the block copolymer of the present invention contains another block copolymer instead of the block copolymer of the present invention. From the graph showing the temperature dependence (FIG. 2), a decrease in the storage elastic modulus is observed at a temperature of about 50 ° C. under elevated temperature conditions.
These facts suggest that the block copolymer of the present invention and the polymer composition containing the block copolymer have high heat resistance.

[0089]

According to the present invention, it has good elastomeric properties, excellent weather resistance, solvent resistance and heat resistance, and good affinity for each of a polar polymer and a non-polar polymer. A block copolymer having the same is provided. In the polymer composition containing the block copolymer of the present invention and another polymer, the above-mentioned features of the block copolymer are effectively exhibited.

[Brief description of the drawings]

FIG. 1 is a graph showing the temperature dependence of the storage elastic modulus (E ′) of the polymer composition according to the present invention obtained in Example 7.

FIG. 2 is a graph showing the temperature dependence of the storage elastic modulus (E ′) of the polymer composition obtained in Comparative Example 6 other than the present invention.

Continued on the front page (72) Inventor Kazunari Ishiura 41 Miyukigaoka, Tsukuba, Ibaraki Pref.

Claims (7)

[Claims] 1. A block copolymer comprising at least one of the following polymer blocks A, at least one of the following polymer blocks B and at least one of the following polymer blocks C in the main chain: A: a polymer block in which 80% or more of the unsaturated bonds of a butadiene-based polymer block having a 1,2 bond amount of less than 20% are hydrogenated and having crystallinity; B: a glass transition of 20 ° C or less C: a polymer block mainly composed of methacrylate or acrylate units and having a glass transition point higher than 20 ° C. 2. At least a portion of the main chain, wherein at least one polymer block B is located between at least one polymer block A and at least one polymer block C. 2. The block copolymer according to 1. [3] [A]-[B]-[C] wherein [A] represents a polymer block A, and [B] represents a polymer Represents a block B, [C] represents a polymer block C, and a solid line (-) represents that the polymer blocks at both ends are directly connected to each other by a chemical bond or are connected via a partial structure derived from a coupling agent. The block copolymer according to claim 2, which has a structure represented by the following formula: 4. A polymer composition comprising the block copolymer according to claim 1 and at least one other polymer. 5. The block copolymer according to claim 1, wherein the polymer is an olefin polymer, an acrylic polymer, a vinyl chloride polymer, a vinylidene fluoride polymer, or maleic anhydride. A polymer composition containing at least one polymer selected from the group consisting of a styrene copolymer and an acrylonitrile-styrene copolymer. 6. A polymer composition comprising the block copolymer according to claim 1, another polar polymer and a non-polar polymer. 7. A polymer composition comprising the block copolymer according to claim 1, another acrylic polymer and an olefin polymer.