JP2000273265A - Cyclolefinic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which has the improved strength characteristics, especially improved impact-resistant strength, of a cycloolefinic polymer resin. SOLUTION: This resin composition comprises (a) 1-99 wt.% of a cycloolefin polymer resin and (b) 99-1 wt.% of a block copolymer which contains at least a triblock chain represented by the general formula: A-B-A in the polymer chain, (A groups are each a polymer block which consists mainly of a hydrogenated vinyl aromatic compound and has a number-average mol.wt. of 10,000-200,000, and the structures of the A groups may be the same or different each other; B is a polymer block which consists mainly of a hydrogenated conjugated diene and has a number-average mol.wt. of 5,000-50,000; >=90 mol.% of the whole olefinic unsaturated bonds of the block copolymer and >=80 mol.% of the aromatic rings are hydrogenated; the total content of the conjugated diene and its hydrogenated product is 5-90 wt.%).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition containing a cycloolefin polymer resin. Specifically, resin materials for medical equipment that do not alter the encapsulated or contacting chemicals, electrical insulating resin materials with excellent electrical insulation, especially high-frequency characteristics, electronic component processing resin materials with excellent heat resistance and chemical resistance, and transparent materials The present invention relates to an optical material that takes advantage of low birefringence.

[0002]

2. Description of the Related Art In recent years, in order to prevent secondary infection with viruses due to repeated use, medical device materials have been increasingly replaced with disposable materials. For example, injections and the like have conventionally been used by inhaling with an sterilized syringe from the ampoule at the time of injection, but recently, prefilled syringes in which the injection has been previously inhaled into the syringe are distributed and used. Later syringes were discarded instead of being reused. In medical drug containers, some degree of transparency is required so that the contents can be easily viewed. Therefore, glass, polyethylene, polypropylene, polyvinyl chloride and the like have been conventionally used. However, glass cannot be incinerated, is easily broken, and is dangerous. In addition, polyethylene and polypropylene have high moisture and gas permeability, and there is a problem of deterioration of drugs depending on the contents. In addition, polyvinyl chloride tends to elute a plasticizer and a monomer, has a problem of deterioration depending on the contents, and also has a problem of generation of chlorine-based harmful gas upon incineration.

[0003] As an electrical insulating material, polyolefin resins such as polyvinyl chloride, polyethylene, and polystyrene have been widely used. These have excellent electrical characteristics such as high insulation resistance, high dielectric breakdown voltage, and low dielectric constant, and also have features such as low water absorption and excellent chemical resistance. However, there is a problem that the heat resistance, particularly the rigidity under high temperature, is insufficient, and it cannot be used under severe conditions. Polystyrene also has problems such as low high-frequency insulation and poor arc resistance and tracking resistance. Polyethylene terephthalate is an electrical insulating material having both excellent electrical properties, mechanical strength, transparency and the like, but has problems such as high water absorption and easy hydrolysis by hot water or alkali.

[0004] Metals such as brass and fluorine resins such as polypropylene, polytetrafluoroethylene and perfluoroalkoxy fluororesin are used in equipment for processing electronic parts such as silicone wear carriers. However, metal objects are heavy and have poor resistance to acids used for processing electronic components. Polypropylene and perfluoroalkoxy fluororesin are inferior in dimensional accuracy at the time of molding, and polytetrafluoroethylene cannot be injection-molded, and have problems such as inferior productivity because shaving is required.

The cycloolefin polymer resin according to the present invention is a polymer having a cycloparaffin ring in the main chain.
Cycloolefin polymer resins of this kind are already known. For example, JP-A-06-136035 discloses a resin composition containing a hydrogenated norbornene-based polymer. Japanese Patent Application Laid-Open No. 09-296028 discloses a polymer obtained by subjecting two kinds of norbornene monomers to ring-opening polymerization and then hydrogenating. JP-A-09-324082 discloses a resin composition containing a hydrogenated product of a ring-opening polymer of phenyl-norbornenes and an ethylene-cyclic olefin copolymer. JP-A-06-1360
57 is a hydrogenated cyclopentadiene resin. Special edition 08-8
No. 10596, a hydrogenated product of a ring-opened polymer of a specific norbornene monomer. JP-A-04-359027 discloses a hydride of a dicyclopentadiene ring-opening polymer.

[0006] These cycloolefin polymers have excellent electrical properties such as high insulation resistance, high dielectric breakdown voltage and low dielectric constant, and generally also have excellent water absorption, chemical resistance and heat resistance. . Further, it has a feature of being excellent in optical properties such as transparency and low birefringence.

[0007] However, although these polymers have the above-mentioned excellent characteristics, there is a problem that they are inferior in strength characteristics, particularly impact resistance.

On the other hand, proposals have already been made to improve the impact resistance of cycloolefin resins. For example,
It is already known that the strength characteristics, particularly the impact resistance, can be improved to some extent by mixing a small amount of a rubbery polymer with a cycloolefin resin. As an example of this type of technology, JP-A-03-0725558 discloses a composition of a ring-opened polymer of a norbornene-based monomer and a rubbery polymer. Japanese Patent Application Laid-Open No. 03-281563 discloses a technique such as a composition of a hydrogenated polymer of a norbornene derivative containing a polar substituent and a rubbery polymer. With these technologies, high insulation resistance, a feature of cycloolefin polymer resin,
While maintaining the electrical characteristics such as high dielectric breakdown voltage and low dielectric constant, and the characteristics such as low water absorption and chemical resistance, it is possible to improve a certain degree of strength characteristics, particularly impact resistance. However, there is a problem that heat resistance generally indicated by high-temperature rigidity is reduced. Further, there is also a problem that optical characteristics, particularly transparency, which is one of the great features of the cycloolefin polymer resin, are significantly reduced.

On the other hand, Japanese Patent Application Laid-Open No. 09-118812
Japanese Patent Application Laid-Open Publication No. H11-157,086 discloses a composition comprising norbornene and a styrene-ethylene-propylene block copolymer, and slightly improves light transmittance while achieving the same effect of improving strength characteristics. However, even though it is an improvement, it is far from being transparent as described in the specification to have a pearl luster.

The triblock copolymer (b) used in the resin composition of the present invention is already known.
For example, U.S. Pat. No. 3,333,024 relates to block copolymers, compositions thereof and methods for their production. Specifically, it discloses a polymer containing a vinylcyclohexane chain obtained by hydrogenation (hereinafter abbreviated as "ring hydrogenation") including an aromatic ring of a styrene-isoprene-styrene triblock copolymer.

Furthermore, Japanese Patent Publication No. 53-11556 relates to a method for producing a ring water additive of a vinyl aromatic hydrocarbon-conjugated diene block copolymer. According to the description in the specification, the properties of the obtained vinylcyclohexane-based polymer differ depending on the contained vinylcyclohexane content. It is disclosed that the copolymer having a high vinylcyclohexane content is a hard and optically transparent plastic, and the copolymer having a low vinylcyclohexane content is a rubbery polymer.

As described above, the cycloolefin polymer resin (a) and the block copolymer (b) constituting the cycloolefin resin composition of the present invention are both known as substances, General performance is also known. However, a resin composition containing both components (a) and (b) has not been known hitherto.

[0013]

The problems to be solved by the present invention are the transparency, high rigidity (high elastic modulus), high heat resistance, chemical resistance, and electrical properties of the cycloolefin polymer resin. An object of the present invention is to improve strength characteristics, particularly, impact resistance, which are disadvantages, while maintaining insulation, low moisture permeability, safety and hygiene, and the like.

[0014]

Means for Solving the Problems The present inventors have made intensive studies on the improvement of the strength characteristics, especially impact resistance, of a cycloolefin resin, and have achieved the present invention. The present invention relates to a block copolymer containing a vinyl aromatic hydrocarbon-conjugated diene-vinyl aromatic hydrocarbon triblock chain in which a hydrogenated conjugated diene block is contained in a cycloolefin polymer resin in a range of 5 to 90% by weight. By mixing a small amount of a ring hydrogenated product, in particular, a block copolymer having a hydrogenated conjugated diene having a constant molecular weight, it has been found that strength properties, particularly impact resistance, can be significantly improved, and the present invention has been achieved. That is, the present invention provides, as set forth in the claims, (a) 1 to 99% by weight of a cycloolefin polymer resin and (b) at least a triene represented by a general formula of ABA in a polymer chain. Block copolymer containing block chain
A resin composition comprising 99 to 1% by weight (wherein A is a polymer block mainly composed of hydrogenated vinyl aromatic hydrocarbon and having a number average molecular weight of 10,000 to 200,000; May have the same structure or different structures, and B is mainly composed of a hydrogenated conjugated diene compound and has a number average molecular weight of 5,000.
-500,0000 polymer blocks. 90 mol% or more of all olefinically unsaturated bonds and 80 mol% or more of aromatic rings of the block copolymer are hydrogenated, and the content of the conjugated diene compound and its hydrogenated product is 5 to 90% by weight. Range. The cycloolefin resin as the component (a) used in the resin composition of the present invention is a cycloolefin polymer composed of a repeating unit represented by the following general formula (1).

[0015]

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In the general formula (1), h is 0, 1 or 2, i is an integer of 2 to 4, and h + i is 3 or 4. R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen, a hydroxyl group, an alkoxy group, a cyano group, an amide group, an imide group, a silyl group or an alcohol ester group of a carboxylic acid, and each R has the same structure However, a different structure may be used. When R is an alkyl group, R may combine with another R to form a bicyclo ring. j is an integer of 1 or more; k is 0 or 1
In the above integers, j and k indicate the composition ratio of both segments.

Specific examples of the cycloolefin-based polymer include a norbornene-based polymer or a hydrogenated product thereof,
Examples include hydrogenated products of norbornadiene-based polymers, ring-opened polymers of cycloolefins, and hydrogenated products of ring-opened polymers of cyclopentadiene and cyclohexadiene. Preferred examples are a hydrogenated product of a ring-opening polymer of a norbornene-based polymer and a hydrogenated product of a non-ring-opened polymer of 1,3-cyclohexadiene.

A reaction formula for synthesizing the norbornene-based polymer and examples of preferred substituents of the norbornene monomer constituting the polymer are shown in Chemical Reaction Formulas (2) and (3).

[0019]

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[0020]

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As shown in the above formula, a cycloolefin polymer resin is obtained by subjecting a norbornene-based monomer to ring-opening polymerization and hydrogenation. The norbornene-based monomer used in the present invention is, for example, norbornene, 2-norbornene, 5-methyl-2-norbornene, 5,5-
Dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methoxycarbonyl-2-
Norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5
-Phenyl-2-norbornene, 5-phenyl-5-methyl-norbornene and the like.

The monomer used may contain the above norbornene-based monomer alone, a mixture of two or more of the norbornene-based monomers, or a small amount of other copolymerizable monomers. Specific examples of preferred other copolymerizable monomers are cyclopentene, cyclohexene, cycloheptene,
Cyclic olefins such as cyclooctene; These cycloolefin-based monomers are ring-opened to form a linear bonded chain, which generally lowers the heat resistance of the resin.
Therefore, at least 50% by weight, preferably 70% by weight, particularly preferably 90% by weight, of the monomers forming the ring structure
If not included, the performance as a resin having high heat resistance as the object of the present invention is undesirably reduced.

As the polymerization catalyst used for the ring-opening polymerization, a tungsten, molybdenum, or chromium-based catalyst usually called a metathesis polymerization catalyst can be preferably used, and the polymerization is carried out in a solution system.

A preferred synthetic reaction formula of the cyclohexadiene polymer used in the present invention is shown in chemical reaction formula (4).

[0025]

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In the formula, p and q each represent 0 or an integer of 1 or more, and p + q represents the degree of polymerization.

These cycloolefin polymer resins are obtained by anionic polymerization of 1,3 cyclohexadiene in a hydrocarbon solvent using, for example, an organolithium initiator, followed by hydrogenation.

The polymerization catalyst used for synthesizing the cycloolefin polymer resin is not necessarily limited to the above. It can be selected from known anionic polymerization catalysts, cationic polymerization catalysts, Ziegler catalysts, Kaminsky catalysts and the like suitable for the polymerization of each monomer. Alternatively, radical polymerization or thermal radical polymerization using a radical initiator can be preferably used depending on the monomer. Generally, the polymerization is carried out at a temperature in the range of -100 to 200C, more usually 0 to 150C.

Usually, polymerization of the monomer is carried out using a solvent. Examples of the solvent include aromatic solvents such as benzene, toluene, and xylene; aliphatic solvents such as pentane, hexane, heptane, octane, cyclopentane, cyclohexane, and methylcyclohexane; methyl chloride, methylene chloride, 1,2-dichloroethane; And halogenated hydrocarbon solvents such as 1,1,1-trichloroethane and 1,1,2-trichloroethylene.

The cycloolefin polymer needs to be hydrogenated after polymerization depending on the polymer structure. For example, when the obtained polymer has an olefin bond or an aromatic ring, hydrogenation is carried out to substantially complete saturation in the presence of a hydrogenation catalyst having a hydrogenation ability for the unsaturated bond of such a polymer. It is necessary. In this case, the hydrogenation rate is at least 80 mol%, preferably at least 90 mol%, particularly preferably at least 95 mol%.

The hydrogenation catalyst used here is not particularly limited. Examples thereof include metals such as nickel, cobalt, titanium, ruthenium, rhodium, platinum, and palladium, or oxides, salts, and complexes thereof, and those supported on activated carbon, diatomaceous earth, alumina, silica, and the like. Among them, Raney nickel, Raney cobalt, stabilized nickel and rhodium, ruthenium, platinum carbon, alumina, and silica-supported catalysts are particularly preferable in terms of catalytic activity.

The hydrogenation reaction is generally carried out at normal pressure to 250 kg.
/ Cm ² , at a temperature of 50 to 200 ° C., as a solvent, a saturated hydrocarbon solvent such as cyclohexane, methylcyclohexane, n-octane, decalin, tetralin, or naphtha;
Alternatively, the reaction is performed using an ether-based solvent such as THF. When a hydrogenation reaction is performed, the reactivity can be increased by adding a small amount of an alcohol or an ether compound. The amount of the alcohol or ether used for such purpose is 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the solvent.

The preferred molecular weight of the cycloolefin polymer resin is 0.1 to 20 dl /, expressed as the intrinsic viscosity [η].
g, more preferably 0.2 to 10 dl / g, particularly preferably 0.5 to 5 dl / g. If the molecular weight is too low, the strength of the resin composition will be extremely low, and if the molecular weight is too high, the moldability will be significantly reduced, which is not preferable.

The glass transition temperature of the cycloolefin polymer resin is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher. When the glass transition temperature of the cycloolefin polymer resin is low,
The heat resistance of the resin composition is lowered, which is not preferable.

The component (b) used in the resin composition of the present invention is a block copolymer containing at least a triblock chain represented by the general formula ABA in the polymer chain. That is, at least A in the block copolymer chain
It is a block copolymer having a block of -BA, and B may be composed of a plurality of B blocks via a coupling agent. More specific block structures are represented by the following general formulas (5) to (9).

(AB) nA (5) (AB) m (6) B- (AB) m (7) ｛(AB) n｝ mX (8) ｛B -(AB) n @ m-X (9) (wherein A is a polymer block mainly composed of a ring-hydrogenated vinyl aromatic hydrocarbon and having a number average molecular weight of 10,000 to 200,000. And each A may have the same structure or a different structure, and each B is a polymer block mainly composed of a hydrogenated conjugated diene compound. The block chain structure of -B is
It does not mean that it is divided by another polymer block, but it is considered to correspond to one B block in the block molecular weight specification of the present application. That is, the B block and especially BX-
5,000 to 500, the number average molecular weight of the B block chain
0000, and each B may have the same structure or different structures. X is a polyfunctional coupling agent. n is 1 or more and m is an integer of 2 or more.
90 mol% or more of all olefinically unsaturated bonds and 80 mol% or more of aromatic rings of the block copolymer are hydrogenated, and the content of the conjugated diene compound and its hydrogenated product is 5 to 90% by weight. Must be in range. In addition, the block copolymer containing a triblock chain of the component (b) of the resin composition of the present invention is an incomplete block that does not fall under the above-mentioned block structure specification, for example, a homopolymer of A, B
Or a part of an AB diblock copolymer or the like. Even in this case, at least 50% by weight of the block copolymer containing a triblock chain,
Preferably 70% by weight or more, more preferably 90% by weight
If not included, the effect aimed at by the present application, that is, the effect of improving strength characteristics such as impact resistance, is not sufficiently exhibited.

These block copolymers contain vinyl aromatic hydrocarbon-based monomers and conjugated diene-based monomers in order by a living anion polymerization method and then contain an aromatic ring by a hydrogenation reaction. Obtained by substantially completely unsaturated unsaturated bonds.

A is a polymer block mainly composed of a ring-hydrogenated vinyl aromatic hydrocarbon. Examples of the vinyl aromatic hydrocarbon monomer include, for example, styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, p-
tert-butylstyrene, 4-phenylstyrene, p-
One or two of methoxystyrene, vinylnaphthalene, etc.
Species or more. A particularly typical example is styrene. Further, other monomers copolymerizable with the above-mentioned vinyl aromatic hydrocarbon may be contained as long as the properties of the vinyl aromatic hydrocarbon polymerization block are not lost.

B is a polymer block mainly composed of a hydrogenated conjugated diene compound. Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene,
One or more of 1,3-hexadiene and the like can be mentioned. In particular, 1,3-butadiene and isoprene are common. Also, a small amount of a vinyl aromatic hydrocarbon, or other monomers copolymerizable with other conjugated diene compounds,
It may be contained as long as the properties of the conjugated diene polymer block are not lost.

The blocks A and B are preferably complete blocks, but the boundaries between the blocks A and B may be randomly copolymerized and may have a tapered structure whose composition gradually changes. .

These monomers are polymerized by a known method called a living anion polymerization method. For example, JP-B-36-19286, JP-B-43-141979,
The method described in JP-B-49-36957 can be used. Specifically, for example, it can be carried out as a solution polymerization in bulk or in a hydrocarbon solvent using an organolithium compound as an initiator. Especially in hydrocarbon solvents such as hexane, pentane and cyclohexane, diethyl ether,
It can be easily obtained by mixing an ether compound such as tetrahydrofuran and a tertiary amine compound such as triethylamine and tetramethylethylenediamine as necessary, controlling the bonding mode of the conjugated diene compound, and polymerizing. If necessary, after completion of the polymerization, the block copolymer having a branched or radial structure may be formed using a known polyfunctional coupling agent such as a halogenated hydrocarbon, an ester compound, an epoxy compound, or silicon tetrachloride as a terminal coupling agent. A polymer can be obtained.

The obtained block copolymer is subjected to a hydrogenation reaction after polymerization, so that all olefinically unsaturated bonds are 9
It must be hydrogenated at 0 mol% or more. It is preferably at least 95 mol%, more preferably at least 97%. Further, the aromatic ring needs to be hydrogenated by 80 mol% or more. It is preferably at least 90 mol%, more preferably at least 95 mol%. If the hydrogenation rate is low, the miscibility with the cycloolefin polymer resin and the thermal stability of the resin composition decrease, which is not preferable.

The hydrogenation reaction can be obtained by hydrogenation in the presence of a hydrogenation catalyst capable of hydrogenating the aromatic ring of the block copolymer. Specifically, it can be performed by the same method as the above-described method for hydrogenating a cycloolefin polymer resin.

That is, the polymer can be obtained by hydrogenation in the presence of a hydrogenation catalyst having a hydrogenation ability for the aromatic ring of the polymer. The hydrogenation catalyst used is not particularly limited. Examples thereof include metals such as nickel, cobalt, ruthenium, rhodium, platinum and palladium, or oxides, salts and complexes thereof, and those supported on activated carbon, diatomaceous earth, alumina and silica. Among them, Raney nickel, Raney cobalt, stabilized nickel and rhodium, ruthenium, platinum carbon, alumina, and silica-supported catalysts are particularly preferable in terms of catalytic activity.

The hydrogenation reaction is generally carried out at normal pressure to 250 kg.
/ Cm ² , at a temperature of 50 to 200 ° C., as a solvent, a saturated hydrocarbon solvent such as cyclohexane, methylcyclohexane, n-octane, decalin, tetralin, or naphtha;
Alternatively, the reaction is performed using an ether-based solvent such as THF. When a hydrogenation reaction is performed, the reactivity can be increased by adding a small amount of an alcohol or an ether compound. The amount of the alcohol or ether used for such purpose is 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the solvent.

The content of the hydrogenated vinyl aromatic hydrocarbon block in such a block copolymer is 10 to 95% by weight. It is preferably in the range of 10 to 50% by weight, particularly preferably 20 to 45% by weight. If the content of the ring-hydrogenated vinyl aromatic hydrocarbon block in the block copolymer is too high, the effect of improving the impact resistance may be due to the fact that the phase separation of the cycloolefin resin composition as a morphology does not proceed effectively. Not sufficiently expressed. When the content of the hydrogenated conjugated diene block is too high, the miscibility of the cycloolefin polymer resin and the block copolymer is significantly reduced, and various physical properties of the resin composition, such as transparency and bending strength, are reduced. It is not preferable because it decreases.

Further, the content of the hydrogenated conjugated diene segment in the whole cycloolefin resin composition of the present invention is 0.5 to 50% by weight, preferably 1 to 30% by weight.
More preferably, 2 to 20% by weight, particularly preferably 3 to 20% by weight.
It is in the range of 10% by weight. If the content of the hydrogenated conjugated diene polymer segment in the resin composition is too large, the heat resistance and rigidity of the resin composition decrease, which is not preferable. Conversely, if the content of the conjugated diene polymer segment is too small, the effect of improving impact resistance cannot be sufficiently exhibited, which is not preferable.

The number average molecular weight of the hydrogenated conjugated diene polymer block, ie, the B block and the BB block, is in the range of 5,000 to 500,000, preferably 2
In the range of from 000 to 300,000, particularly preferably 5
The range is from 0.00 to 200,000. If the weight average molecular weight of the hydrogenated conjugated diene polymer block is too low, the effect of improving impact resistance is not sufficiently exhibited, which is not preferable.
If the content of the hydrogenated conjugated diene polymer is too high, the miscibility of the cycloolefin polymer resin and the block copolymer is significantly reduced, and various physical properties of the resin composition such as transparency and strength are reduced. Not preferred.

The number average molecular weight of the ring-hydrogenated vinyl aromatic hydrocarbon polymer block, that is, the A block, is 10,000 to 2
00,000, preferably 14,000 to 100,000
0, particularly preferably in the range of 20,000 to 50,000. If the molecular weight of the cyclic hydrogenated vinyl aromatic hydrocarbon block is low, the miscibility of the cycloolefin polymer resin and the block copolymer is significantly reduced, and various physical properties of the resin composition,
For example, transparency and bending strength are undesirably reduced. If the molecular weight is too high, the impact resistance is undesirably reduced.

The bonding mode of the conjugated diene segment is not particularly limited. However, it is preferred that the polymer block comprising these segments after hydrogenation exhibits rubber-like properties. That is, it is preferable not to crystallize or vitrify at room temperature. Therefore, when the conjugated diene is 1,3-butadiene, the 1,2-bond content is 10 mol% or less.
The range is 90 mol%, more preferably 20 mol% to 60 mol%, and still more preferably 30 mol% to 50 mol%. If the 1,2-bonded chain is lower than this, remarkable crystallinity appears, and the effect of improving impact resistance is undesirably reduced.

The cycloolefin resin composition of the present invention comprises (a) 1 to 99% by weight of a cycloolefin polymer resin and (b) a triblock chain represented by at least ABA in the polymer chain. -Containing block copolymer 9
9 to 1% by weight. The preferred composition of the component (b) is 4
The range is from 0 to 1% by weight, more preferably from 30 to 3% by weight, particularly preferably from 20 to 5% by weight, and the remaining polymer component is (a) a cycloolefin polymer resin.

If the content of the block copolymer (b) is higher than this, the modulus of elasticity, particularly the modulus of elasticity at high temperatures, is undesirably reduced. On the other hand, if the content of the block copolymer is lower than this, strength properties, particularly impact resistance, are undesirably reduced.

The method of mixing the above-mentioned polymer components is not particularly limited. Usually, a method in which the above-mentioned cycloolefin polymer resin of the polymer component (a) and the block copolymer of the component (b) are melt-mixed by a kneading machine such as an extruder, a plastmill, or a Banbury mixer can be used. . Alternatively, they may be mixed in a solution state after polymerization or hydrogenation separately.

In the resin composition of the present invention, known resin additives not specified in the present invention may be added. For example, known effects can be achieved by adding inorganic or organic fillers, pigments, dyes, stabilizers, ultraviolet absorbers, plasticizers, flame retardants, lubricants, and the like. The timing and method for mixing these resin additives with the resin composition of the present invention are not particularly limited. It can be mixed at the solution stage at the time of polymerization production, or can be mixed at the time of mixing resin components or at the time of molding.

Examples of the stabilizer include a hindered phenol stabilizer, a sulfur stabilizer, a phosphorus stabilizer and the like. The combination use of a hindered phenol-based stabilizer and a phosphorus-based stabilizer is particularly preferred from the viewpoint of improving heat resistance and deterioration.

Specific examples of the hindered phenol stabilizer usable in the present invention include tetrakis [methylene-3].
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate methane, 3,9-bis [1,1,-
Dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspro [5,5]
Undecane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl-s-triazine-2,
4,6- (1H, 3H, 5H) -trione, 1,3,5
-Trimethyl-2,4,6-tris (3,5-di-t-
Butyl-4-hydroxybenzyl) benzene and the like.

Specific examples of the phosphorus-based stabilizer include tetrakis (2,4-di-t-butylphenyl) -4,
4'-bisphenylenephosphonite, bis (2,6-
Di-butyl-4-methylphenyl) pentaerythritol-di-phosphite.

The preferred amount of the stabilizer is 0.001 to 1 part by weight per 100 parts by weight of the resin component. In addition, even with a stabilizer, the resin composition of the present invention has a certain level of stability, and the stabilizer may be preferable depending on the use.

[0059]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, various polymer structures in the following Examples and Comparative Examples were measured by the following methods.

(1) Measurement of intrinsic viscosity [η]: Measured in toluene at 25 ° C.

(2) Measurement of molecular weight: The molecular weights of the cycloolefin polymer resin and the block copolymer were determined by gel permeation chromatography (GPC).
The measurement was performed using HF as a solvent.

(3) Analysis of composition ratio of bonded monomer in block copolymer: Proton N of block copolymer before hydrogenation
Analyzed from MR. Alternatively, it can also be calculated and confirmed from the monomer composition charged during polymerization and the addition ratio thereof.

(4) Number-average molecular weight analysis of polymer block: In the case of a complete block copolymer containing no random copolymerized portion, the number-average molecular weight analysis is based on the composition ratio of the bonding monomer constituting each block and the molecular weight of the entire block copolymer. Calculated.

(5) Measurement of hydrogenation rate: proton NMR
Analysis was based on the spectrum.

Resin Production Example-1 Tungsten hexachloride, an organoaluminum-based polymerization initiator and a norbornene monomer were subjected to ring-opening polymerization in a toluene solvent under a nitrogen atmosphere. After the polymerization, a small amount of methanol was added to stop the growth terminal. Then, after the solvent was volatilized and removed, it was dissolved again in cyclohexane and hydrogenated using a palladium catalyst to obtain a cycloolefin polymer resin. As a result of the analysis, the intrinsic viscosity [η] was 1.1 and the hydrogenation rate was almost 100%.

Resin Production Example-2: A small amount of T under a nitrogen atmosphere
Styrene-butadiene-styrene was sequentially polymerized using cyclohexane containing HF as a solvent and n-butyllithium as a polymerization initiator to obtain a block copolymer having substantially no contamination. Thereafter, a small amount of methanol was added to stop the growth terminal, and hydrogenation was performed using a palladium catalyst to obtain an ABA triblock copolymer. There was substantially no change in molecular weight distribution and molecular weight before and after the hydrogenation reaction.

As a result of the analysis, the number average molecular weight of the block copolymer was 94,000, and the styrene content of cyclic hydrogenated and unhydrogenated was 35.
% By weight. The 1,2-bond content of the butadiene moiety was 45 mol%. The weight composition ratio of each block verified from the proton NMR analysis results and the charged monomer composition is A: B: A = 17.5: 65: 17.5. Therefore, the number average molecular weight of each block is 165,000, 611,000, and 1.65,000, respectively, for A, B, and A. The conjugated diene portion was almost completely hydrogenated, and the hydrogenation rate of the styrene portion was 99.2%.

Resin Production Example-3: A triblock copolymer was obtained in the same manner as in Resin Production Example-2. The molecular weight of the block was varied by changing the monomer charge. The number average molecular weight of each block was 423,000 for A, B and A, respectively.
The styrene content was 1.336, 4.23 million, and the content of ring-hydrogenated and unhydrogenated styrene was 86% by weight. The conjugated diene part is almost completely hydrogenated, and the hydrogenation rate of the styrene part is 9
It was 9.6%.

Resin Production Example-4: A conjugated diene segment was selectively hydrogenated by hydrogenation using a titanium catalyst using the same base polymer before hydrogenation as polymerized in Resin Production Example-2. . The hydrogenation rate of the conjugated diene part of the obtained polymer was 98%, and the hydrogenation rate of the styrene part was almost 0%. The number molecular weight of each of A, B and A is 1.
58, 5.87, 1.58, cyclic hydrogenated and unhydrogenated styrene content 35% by weight.

Examples 1 to 4 and Comparative Examples 1 and 2 The cycloolefin polymer resin (P
CO) and the cyclic hydrogenated SBS triblock copolymer (SBS) obtained in Resin Production Example-2 at a weight composition ratio shown in Table 1,
A test piece was prepared by mixing with a Labo Plastomill and compression molding, and the physical properties were evaluated. Table 1 shows the evaluation results.

[0071]

[Table 1]

Note * 1) Since it is rubbery or extremely soft at room temperature, its elastic modulus is extremely small and measurement is difficult.
Is less than 80 ° C. Note * 2) No break occurred Description of abbreviations in table 1) PCO content: weight content of cycloolefin polymer resin (% by weight) 2) SBS content: in resin composition Weight content of cyclic hydrogenated styrene-butadiene-styrene triblock copolymer (% by weight) 3) Rubber content: resin composition of hydrogenated and unhydrogenated butadiene block in cyclic hydrogenated styrene / butadiene block polymer 4) Bd chain length: number average chain length of butadiene blocks as described above (10,000) 5) Elastic modulus: flexural modulus ASTM D790 (kg /
cm ²⁾ 6) HDT: heat distortion temperature ASTM D648, load 1
8.6 kg / cm ² (° C) 7) Impact strength: Izod impact strength ASTM D256
Notched (kg · cm / cm) 8) Transparency: Judgment of transparency by visual observation ：: Excellent transparency equivalent to polystyrene ×: Translucent white turbidity and poor transparency.

Comparative Example 3 A test piece was prepared by compression molding the ring-hydrogenated SBS triblock copolymer obtained in Resin Synthesis Example-3, and the physical properties were evaluated. Table 2 shows the evaluation results.

Comparative Example 4 A-A wherein only the butadiene portion obtained in Resin Production Example-4 was hydrogenated.
The evaluation was performed in the same manner as in Example 3 except that the BA triblock copolymer was replaced with a cyclic hydrogenated triblock copolymer. Table 2 shows the evaluation results.

[0075]

[Table 2]

[0076]

The cycloolefin resin composition of the present invention has excellent characteristics such as transparency, high heat resistance, chemical resistance, electrical insulation, and low moisture permeability, which are excellent characteristics of the cycloolefin polymer resin. While maintaining performance, strength characteristics that are disadvantages,
In particular, the impact strength is remarkably improved.

Claims (5)

[Claims] (1) (a) a cycloolefin polymer resin 1
-99% by weight and (b) at least A-
A resin composition comprising 99 to 1% by weight of a block copolymer containing a triblock chain represented by the general formula of B-A (wherein A is mainly composed of hydrogenated vinyl aromatic hydrocarbon, and has a number average molecular weight of A is a polymer block in the range of 10,000 to 200,000, and each A may have the same structure or a different structure, and B has a hydrogenated conjugated diene compound as a main component and has a number average molecular weight. 5,000
-500,0000 polymer blocks. 90 mol% or more of all olefinically unsaturated bonds and 80 mol% or more of aromatic rings of the block copolymer are hydrogenated, and the content of the conjugated diene compound and its hydrogenated product is 5 to 90% by weight. Range. ) 2. The resin composition according to claim 1, wherein the cycloolefin polymer resin is a hydrogenated product of a polymer of a norbornene-based monomer. 3. The resin composition according to claim 1, wherein the cycloolefin resin is a hydrogenated product of a non-ring-opening polymer of cyclohexadiene. 4. The composition according to claim 1, wherein the content of the hydrogenated conjugated diene segment which is the B block of the block copolymer is in the range of 0.5 to 50% by weight based on the whole composition. 4. The cycloolefin resin composition according to claim 1. 5. A polymer block comprising a 1,3-butadiene in which the B block constituting the copolymer of the component (b) is hydrogenated and having a 1,2-bond content of 10 mol. %.