JP2000265019A - Vinylated cyclic hydrocarbon resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which can give a product improved in impact strength without detriment to transparency, high heat resistance, etc., by including a vinylated cyclic hydrocarbon resin with a block copolymer containing a triblock chain in a specified ratio. SOLUTION: This composition comprises 60-99 wt.% vinylated cyclic hydrocarbon resin comprising a vinylated cyclic hydrocarbon polymer comprising at least one type of repeating units represented by formulae I to III or mixture thereof and 40-1 wt.% block copolymer containing a triblock chain represented by the formula: A-B-A in the polymer chain. In the formulae, R1 to R42 are each H or a 1-4C alkyl; A is a polymer block based on a hydrogenated vinylaromatic hydrocarbon and having a number-average molecular weight of 10,000-200,000; B is a polymer block based on a conjugated diene compound and having a number-average molecular weight of 20,000-500,000; at least 90 mol% of the entire olefinic unsaturations and at least 80 mol% of the aromatic rings have been hydrogenated; and the content of the conjugated diene compound and a hydrogenation product thereof is 50-90 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition containing a vinylated cyclic hydrocarbon 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.

[0005] The vinylated cyclic hydrocarbon resin according to the present invention,
Particularly, polyvinylcyclohexane-based resins have been known for a long time. For example, Japanese Patent Publication No. 45-11425 discloses polyvinylcyclohexane (same as polystyrene with ring hydrogenation) and vinylcyclohexane-alkyl-substituted polyethylene block copolymer (including the aromatic ring of vinyl aromatic hydrocarbon-conjugated diene compound block copolymer). In the specification, it is described that a homopolymer of vinylcyclohexane is already known at the time of filing the application.

US Pat. No. 3,333,024 relates to block polymers, compositions thereof and methods for their preparation. Specifically, styrene-isoprene-
A polymer containing a vinylcyclohexane chain obtained by hydrogenation including an aromatic ring of a styrene triblock copolymer (hereinafter abbreviated as “ring hydrogenation”) is disclosed. Among them, it has been reported that a ring hydrogenated block copolymer having a low bound styrene content of about 20% by weight has rubber-like properties.

Further, 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. High vinylcyclohexane content copolymers are rigid, optically clear plastics that are useful for making injection molded parts, extruded films, pipes, fibers, and the like. It is also disclosed that the copolymer having a low vinylcyclohexane content is rubbery and is useful for applications such as wire coating, packaging materials, films, fibers, extruded products and molded products.

As described above, the vinylated cyclic hydrocarbon resin of the component (a) and the block copolymer of the component (b) constituting the vinylated cyclic hydrocarbon resin composition of the present invention are both known as substances. The general performance as a resin material is also known. Furthermore, these vinylated cyclic hydrocarbon resins are a kind of amorphous olefin resin, and the following features can be expected as a natural consequence. That is, since it has a saturated structure, it has excellent weather resistance. In general, there is no residual aromatic monomer which is pointed out to be harmful, and it is excellent in safety and hygiene such as endocrine problems caused by eluates. Since it does not contain foreign atoms such as halogens, there is no problem of harmful gas generation during incineration, and it is environmentally friendly. Because it is an olefin-based polymer, it can be expected to those skilled in the art that it has excellent optical performance such as small birefringence due to polarization and also has excellent electrical characteristics such as high-frequency insulation. Performance.

However, although the vinylated cyclic hydrocarbon resin has the above-mentioned excellent characteristics, the homopolymer generally has a drawback that strength properties, particularly impact resistance, are remarkably poor. Mixing with other polymers has been proposed to improve this.

Japanese Patent Application Laid-Open No. 05-271482 relates to a resin composition of a polyvinylcyclohexane-based resin and a crystalline polyolefin such as polypropylene. A polyolefin resin composition having excellent heat resistance, rigidity and hardness and low molding shrinkage has been proposed. However, this type of composition is a fatal drawback depending on the use in that the transparency, which is a great feature of the polyvinylcyclohexane-based polymer, is significantly reduced.

On the other hand, the strength performance is maintained while maintaining the resin performance including transparency of the vinylated cyclic hydrocarbon resin,
In particular, proposals for improving impact resistance have been known for a long time.

For example, Japanese Patent Publication No. 45-11425 mentioned above relates to a polymer composition (blend) of a vinylcyclohexane-alkyl-substituted polyethylene block copolymer obtained by cyclohydrogenating polyvinylcyclohexane and a styrene-based block polymer. is there. It is disclosed that this composition has better impact resistance than a polyvinylcyclohexane homopolymer. However, the specific disclosure is limited to a diblock copolymer of vinylcyclohexane-alkyl-substituted polyethylene, and there is no disclosure of a triblock copolymer according to the present application. Moreover, in this technique, it is necessary to increase the content of the alkyl-substituted polyethylene segment in order to effectively improve the impact resistance. In this case, the heat resistance (HDT) or the flexural modulus of the resin is significantly reduced. It is clear from the embodiment.

[0013] In recent years, several similar techniques with limited applications have been proposed. Japanese Patent Application Laid-Open No. 01-294721 relates to a substrate material for an optical disk, and relates to the use of a vinylcyclohexane-based block copolymer obtained by ring-hydrogenating a styrene-based block copolymer for an optical disk substrate. The use of a ring hydrogenated styrene-butadiene-styrene triblock copolymer as a vinylcyclohexane-based block polymer is also disclosed. However, the disclosed block polymer is a ring hydrogenated product of a block copolymer containing 60 to 90% by weight of a segment mainly composed of a styrene monomer, and is limited to use of the block polymer alone.

JP-A-03-115349 relates to a hydrogenated (hydrogenated) vinyl aromatic hydrocarbon polymer composition and an optical disk substrate, and (a) a vinyl aromatic hydrocarbon-conjugated diene diblock copolymer. A composition comprising a ring hydrogenated product and (b) a ring hydrogenated product of a vinyl aromatic hydrocarbon polymer is disclosed. However, the specific disclosure is limited to diblock copolymers, and discloses a composition using a hydrogenated product of a triblock copolymer such as vinyl aromatic hydrocarbon-conjugated diene-vinyl aromatic hydrocarbon. There is no.

JP-A-04-288360 relates to a hydrogenated vinyl aromatic hydrocarbon polymer composition and an optical disk substrate, and (a) a cyclic hydrogenated vinyl aromatic hydrocarbon-
The present invention relates to a composition comprising a conjugated diene block copolymer and (b) a ring-hydrogenated vinyl aromatic hydrocarbon. However, the content of the conjugated diene polymer segment of the component (a) is limited to 1 to 50% by weight, and the hydrogenation rate of all double bonds and aromatic rings is limited to 60 to 80 mol%. However, specific disclosure is limited to diblock copolymers, and there is no disclosure of a composition using a ring hydrogenated triblock copolymer.

As described above, vinylated cyclic hydrocarbon resin,
In particular, it is known to use a vinylcyclohexane-based resin and a ring-hydrogenated vinyl aromatic hydrocarbon-conjugated diene (both di and tri) block polymers as resin materials, respectively. Further, a resin composition comprising a ring hydrogenated product of a vinylcyclohexane resin and a vinyl aromatic hydrocarbon-conjugated diene block polymer is basically known, and generally, while maintaining the transparency of the vinylcyclohexane resin,
Strength performance, especially impact resistance, can be improved.

However, in order to sufficiently improve the impact resistance of this type of resin composition, it is necessary to introduce a certain amount or more of a hydrogenated conjugated diene block having rubber properties. For this reason, ring-hydrogenated vinyl aromatic hydrocarbons
It is thought that a large amount of the conjugated diene block polymer is mixed, but in this case, there is a problem that the elastic modulus of the resin, particularly the high-temperature elastic modulus as indicated by HDT or the like, is remarkably reduced.

Further, when considering the use of a ring-hydrogenated vinyl aromatic hydrocarbon-conjugated diene block polymer as a resin material, the bond content of the vinyl aromatic hydrocarbon is usually 50%.
It was limited to about weight% or more. If it is less than 50% by weight, the copolymer will show rubber-like properties, and it is not suitable for use as a resin material. For this reason, there has been no idea that a triblock polymer of a cyclic hydrogenated aromatic hydrocarbon-conjugated diene having properties as a thermoplastic elastomer is mixed in a small amount with a vinylcyclohexane resin.

Further, a composition of a vinylcyclohexane resin and a commercially available styrene-based thermoplastic elastomer, for example, a styrene-ethylene / butylene-styrene-based triblock polymer can also be considered. But,
As a result of the study by the present inventors, although some improvement in impact strength is observed even in these methods, various resin properties, such as transparency and bending strength, are remarkably reduced because of the poor miscibility between polymers. It turned out that there was a problem.

[0020]

The problems to be solved by the present invention are the transparency, rigidity (elastic modulus), high heat resistance, chemical resistance, and electrical insulation which are the excellent characteristics of the vinylated cyclic hydrocarbon resin. While maintaining the properties, moisture permeability, safety and health, etc.,
It is intended to improve the strength properties, particularly the impact strength, which is a disadvantage.

[0021]

Means for Solving the Problems The present inventors have conducted intensive studies on the improvement of the strength characteristics, particularly impact resistance, of a vinylated cyclic hydrocarbon resin, and have achieved the present invention. The present invention relates to a ring of a block polymer containing a triblock chain of a vinyl aromatic hydrocarbon-conjugated diene-vinyl aromatic hydrocarbon rubber-like, that is, a hydrogenated conjugated diene block having 50% by weight or more of a vinylated cyclic hydrocarbon resin. By mixing a small amount of a hydrogenated product, particularly a block polymer having a hydrogenated conjugated diene having a constant molecular weight, the inventors have found that strength characteristics, particularly impact resistance, can be remarkably improved, and the present invention has been achieved. The present invention relates to (a) a block copolymer containing 60 to 99% by weight of a vinylated cyclic hydrocarbon resin and (b) a block copolymer containing at least a triblock chain represented by the general formula ABA in a polymer chain. (Wherein A is mainly composed of hydrogenated vinyl aromatic hydrocarbon and has a number average molecular weight of 10,000 to 200,000). Of a polymer block, in each A is the same structure, the .B which may be a different structure and composed mainly of a conjugated diene compound is hydrogenated, the number-average molecular weight of 20,00
It is a polymer block in the range of 0 to 500,0000.
90 mol% or more of all the olefinically unsaturated bonds and 80 mol% or more of the aromatic ring of the block copolymer are hydrogenated, and the content of the conjugated diene compound and its hydrogenated product is 50 to 90% by weight. Range. ).

The vinylated cyclic hydrocarbon resin as the component (a) used in the resin composition of the present invention may be one of the repeating units represented by the following general formula 1, general formula 2 or general formula 3, or It is a vinylated cyclic hydrocarbon polymer composed of two or more kinds, or a mixture of these polymers.

[0023]

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[0024]

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[0025]

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The above general formulas 1, 2 and 3
In the formula, R1 to R42 represent a hydrogen atom or a carbon atom having 1 to 4
R4 to R12, R16 to R2
6, R30 to R42 represent an alkyl group directly adjacent to a carbon atom forming a ring, and may form a double bond.

The vinylated cyclic hydrocarbon-based monomer used to obtain the vinylated cyclic hydrocarbon-based polymer of the present invention includes vinylcyclopentane-based monomers such as vinylcyclopentane and isopropenylcyclopentane. Vinylated five-membered hydrocarbon-based monomers such as vinylcyclopentene-based monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene styrene, α-methylstyrene, 4-methylstyrene,
Styrene monomers such as 2-methylstyrene and 4-phenylstyrene, vinylcyclohexane monomers such as vinylcyclohexane and 3-methylisopropenylcyclohexane, 4-vinylcyclohexene, 4-isopropenylcyclohexene, and 1-methyl- 4-vinylcyclohexene, 1-methyl-4-isopropenylcyclohexene,
2-methyl-4-vinylcyclohexene, 2-methyl-
Vinylcyclohexene monomers such as 4-isopropenylcyclohexene, and vinylated 6-membered hydrocarbon monomers such as terpene monomers such as d-terpene, 1-terpene and diterpene vinylcycloheptane, isopropenylcycloheptane and the like And vinylcycloheptene monomers such as 4-vinylcycloheptene and 4-isopropenylcycloheptene. Among them, a six-membered ring hydrocarbon monomer is preferred. Particularly preferred is styrene.

The catalyst used for the polymerization of the vinylated cyclic hydrocarbon resin is not particularly limited.
Cationic polymerization catalysts, Ziegler catalysts, Kaminsky catalysts and the like can be used. Alternatively, radical polymerization or thermal radical polymerization using a radical initiator can be used. Generally, the polymerization is from -100 to 200C, more usually from 0 to 150.
Performed in the range of ° C.

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 vinylated cyclic hydrocarbon polymer needs to be hydrogenated after polymerization depending on the polymer structure. For example, when the polymer has an olefin bond or an aromatic ring, it is preferable that the polymer is substantially completely saturated by hydrogenation in the presence of a hydrogenation catalyst having the hydrogenation ability of the unsaturated bond of such a polymer. In this case, the hydrogenation rate is 80 mol% or more, preferably 90 mol% or more, and particularly preferably 9 mol% or more.
5 mol% or more.

The hydrogenation catalyst used here 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 preferred weight average molecular weight of the vinylated cyclic hydrocarbon resin is in the range of 10,000 to 1,000,000, more preferably in the range of 50,000 to 500,000, and particularly preferably in the range of 80,000 to 300,000. . 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 vinylated cyclic hydrocarbon resin is preferably 80 ° C. or higher, more preferably 10 ° C.
The temperature is 0 ° C or higher, particularly preferably 120 ° C or higher. If the glass transition temperature of the vinylated cyclic hydrocarbon 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 (4) to (8).

(AB) n-A (4) (AB) m (5) B- (AB) m (6) ｛(AB) n｝ mX (7) ｛B -(AB) n @ m-X (8) (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-
20,000 to 50 of the number average molecular weight of the B block chain
It is in the range of 0000, and each B may have the same structure or different structures. X is a polyfunctional coupling agent.

N is an integer of 1 or more, and m is an integer of 2 or more. 9 of all olefinically unsaturated bonds in the block copolymer
At least 0 mol% and at least 80 mol% of the aromatic rings are hydrogenated, and the content of the conjugated diene compound and its hydrogenated product must be in the range of 50 to 90% by weight. 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, a homopolymer of B, Alternatively, it may contain a part of an AB diblock copolymer or the like. Even in this case, the block copolymer containing a triblock chain has at least 5
Unless it is contained in an amount of 0% by weight, preferably 70% by weight or more, more preferably 90% by weight or more, the effect intended by the present application, that is, the effect of improving strength properties such as impact resistance, is not sufficiently exhibited.

These block copolymers contain vinyl aromatic hydrocarbon-based monomers and conjugated diene-based monomers sequentially 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 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. Further, a small amount of a vinyl aromatic hydrocarbon or another monomer copolymerizable with another conjugated diene compound 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 resulting 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%. A low hydrogenation rate is not preferred because it causes a decrease in miscibility with the vinylated cyclic hydrocarbon resin and a decrease in the thermal stability of the resin composition.

The hydrogenation reaction can be obtained by hydrogenation in the presence of a hydrogenation catalyst having the ability to hydrogenate the aromatic ring of the block copolymer. Specifically, it can be performed by the same method as the above-described method for hydrogenating a vinylated cyclic hydrocarbon 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 50% by weight. It is preferably in the range of 20 to 45% by weight, particularly preferably 30 to 40% by weight. If the content of the ring-hydrogenated vinyl aromatic hydrocarbon block in the block copolymer is too high, the phase separation of the vinylated cyclic hydrocarbon-based resin composition as a morphology does not proceed effectively, The improvement effect is not sufficiently exhibited. Also, if the content of the hydrogenated conjugated diene block is too high, the miscibility of the vinylated cyclic hydrocarbon resin and the block copolymer is significantly reduced, and various physical properties of the resin composition, such as transparency and bending strength. Is undesirably reduced.

The content of the hydrogenated conjugated diene segment relative to the entire vinylated cyclic hydrocarbon resin composition of the present invention is preferably 1 to 30% by weight, more preferably 2 to 20% by weight, and particularly preferably 3 to 20% by weight. In the range of 10 to 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 20,000 to 500,000, preferably in the range of 40,000 to 300,000, especially Preferably it is in the range of 80,000 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 vinylated cyclic hydrocarbon resin and the block copolymer is significantly reduced, and various physical properties of the resin composition such as transparency and strength are reduced. Is not preferred.

The number average molecular weight of the ring-hydrogenated vinyl aromatic hydrocarbon polymer block, that is, the A block is from 10,000 to 2
00,000, preferably 14,000 to 100,000
0, particularly preferably in the range of 20,000 to 50,000. When the molecular weight of the cyclic hydrogenated vinyl aromatic hydrocarbon block is low, the miscibility of the vinylated cyclic hydrocarbon resin and the block copolymer is significantly reduced, and various physical properties of the resin composition, such as transparency and bending strength, are reduced. Is not preferred. 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 vinylated cyclic hydrocarbon resin composition of the present invention comprises (a) 60 to 99% by weight of the vinylated cyclic hydrocarbon resin and (b) at least ABA in the polymer chain.
Of a block copolymer having a triblock chain represented by the general formula: The preferred composition of component (b) is 30 to 3% by weight, more preferably 20 to 5% by weight, and the remaining polymer component is (a) a vinylated cyclic hydrocarbon 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 for mixing the above-mentioned polymer components is not particularly limited. Usually, a method in which the above-mentioned vinylated cyclic hydrocarbon resin as the polymer component (a) and the block copolymer as the component (b) are melt-mixed with a kneader such as an extruder, a plast mill, or a Banbury mixer is used. it can. However, it is also possible for both polymer components to be polymerized in parallel in the same reactor during the polymer production stage. 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) propionatemethane, 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.

[0060]

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) Molecular weight measurement: The molecular weights of the vinylated cyclic hydrocarbon resin and the block copolymer were measured by gel permeation chromatography (GPC) using TH
The measurement was performed using F as a solvent.

(2) Analysis of Composition Ratio of Binder Monomer in Block Copolymer The block copolymer before hydrogenation was analyzed from proton NMR. Alternatively, it can be calculated and confirmed from the monomer composition charged during polymerization and the addition ratio thereof.

(3) Analysis of Number Average Molecular Weight of Polymer Block In a complete block copolymer containing no random copolymerized portion, it is calculated from the composition ratio of the bonding monomer constituting each block and the molecular weight of the entire block copolymer. did.

(4) Measurement of Hydrogenation Rate Analysis was performed based on the proton NMR spectrum.

Resin Production Example-1: A small amount of T
A styrene monomer was homopolymerized in a cyclohexane solvent containing HF (tetrahydrofuran) using n-butyllithium as a polymerization initiator. After the polymerization, a small amount of methanol was added to stop the growth terminal. Thereafter, hydrogenation was performed using a palladium catalyst to obtain a vinylated cyclic hydrocarbon resin.

As a result of the analysis, the weight average molecular weight was 124,000,
The hydrogenation rate was 99.5 mol%.

Resin Production Example-2: A small amount of T
Styrene-butadiene-styrene was sequentially polymerized using cyclohexane containing HF as a solvent and n-butyllithium as a polymerization initiator to obtain a substantially contaminant-free block polymer. 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 the cyclic hydrogenated and unhydrogenated styrene 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 A, B, A
They are 165,000, 611,000 and 1.65,000, respectively.

The conjugated diene portion was almost completely hydrogenated, and the hydrogenation ratio 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 portion was almost completely hydrogenated, and the hydrogenation ratio of the styrene portion was 99.6%.

Resin Production Example-4: 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 is 0.82 million for each of A, B and A,
The styrene content was 75.40,000 and 0.82,000, and the hydrogenated and unhydrogenated styrene content was 18% by weight.

The conjugated diene portion was almost completely hydrogenated, and the hydrogenation ratio of the styrene portion was 99.0%.

Resin Production Example-5: Using the same base polymer before hydrogenation as polymerized in Resin Production Example-2, hydrogenation was performed using a titanium catalyst to selectively hydrogenate the conjugated diene segment. 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%. A, B and A have a number molecular weight of 1.58, 5.87 and 1.58, respectively, and a cyclic hydrogenated and unhydrogenated styrene content of 35% by weight.

Resin Production Example-6 A polystyrene resin was obtained in the same manner as in Resin Production Example-1, except that no hydrogenation reaction was performed. As a result of the analysis, the weight average molecular weight was 119,000.

Resin Production Example-7 Under a nitrogen atmosphere, cyclohexane containing a small amount of THF was used as a solvent, n-butyllithium was used as a polymerization initiator, and styrene-butadiene was polymerized sequentially. After the polymerization was completed, trichloromethylsilane was converted to n-butyl. 0.9 equivalents were added to lithium. The obtained block copolymer had a composition of 83% by weight of a polymer having an (AB ′) 3-X structure, 13% by weight of a block copolymer having an (AB ′) 2-X structure, and 4% by weight. Met. Thereafter, hydrogenation was performed using a palladium catalyst to obtain a cyclic hydrogenated block copolymer. There was almost no change in the molecular weight distribution and molecular weight before and after the hydrogenation reaction.

As a result of analysis, the number average molecular weight of the (AB ′) 3-X block copolymer was 114,000. The 1,2-bond content of the butadiene moiety was 45 mol%. As a result of proton NMR analysis, the weight composition ratio of each block verified from the charged monomer composition is A: B = 35: 65.
Therefore, the number average molecular weight of each block is 1.330, 49,800 (B 'is 2.470,000) for A, B, and A, respectively.
330,000. The relationship between B and B 'is described above. The hydrogenation ratio of the conjugated diene portion was almost completely hydrogenated, and the hydrogenation ratio of the styrene portion was 99.0%.

Resin Production Example-8 Under a nitrogen atmosphere, a mixed monomer composed of 80% by weight of styrene and 20% by weight of α-methylstyrene was suspended in water using AIBN (azobisisobutyronitrile) as an initiator. Polymerized. After polymerization, the polymer was dried, further dissolved in cyclohexane, and hydrogenated in the same manner as in Resin Production Example 1.

As a result of analysis, the weight average molecular weight was 114,000,
The hydrogenation rate was 97 mol%.

Resin Production Example-9 A block polymer was obtained by sequentially polymerizing styrene-butadiene in a nitrogen atmosphere using cyclohexane containing a small amount of THF as a solvent and n-butyllithium as a polymerization initiator. Thereafter, a small amount of methanol was added to stop the growth terminal, and hydrogenation was performed using a palladium catalyst to obtain an AB diblock copolymer.

As a result of the analysis, the number average molecular weight of the block copolymer was 106,000. The bonding mode of the butadiene moiety was 1,2-bond content of 43 mol%. Proton NM
The weight composition ratio of each block verified from the R analysis result and the charged monomer composition is A: B = 13: 87. Therefore, the number average molecular weight of each block is 1.
40,000, 920,000, ring hydrogenated and unhydrogenated styrene content 8
It was 6.8% by weight.

The conjugated diene part was almost completely hydrogenated, and the hydrogenation ratio of the styrene part was 98.6%.

Examples 1-4 and Comparative Examples 1-3 The cyclic hydrogenated polystyrene resin obtained in Resin Production Example-1 (VC
H: polyvinylcyclohexane) and the ring-hydrogenated SBS triblock copolymer (SBS) obtained in Resin Production Example 2 in a weight composition ratio shown in Table 1 by using a Labo Plastomill,
A test piece was prepared by compression molding, and the physical properties were evaluated. Table 1 shows the evaluation results.

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[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 abbreviation in the table 1) VCH content: polyvinylcyclohexane weight content (% by weight) 2) SBS content: ring-hydrogenated styrene in the resin composition -Weight content of butadiene-styrene triblock copolymer (% by weight) 3) Rubber content: weight content of hydrogenated and unhydrogenated butadiene blocks in the cyclic hydrogenated styrene / butadiene block polymer in the resin composition. 4) Bd chain length: Number average chain length of butadiene block (same as 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 D25
6 Notched (kg · cm / cm) 8) Transparency: Judgment of transparency by visual observation ：: Excellent transparency equivalent to polystyrene ×: Translucent white turbidity and poor transparency.

Example 5 80% by weight of the cyclic hydrogenated polystyrene resin obtained in Resin Production Example 1 and 20% by weight of the (A-B) 3-X type cyclic hydrogenated block copolymer obtained in Resin Synthesis Example 7 Was mixed in a lab plast mill and compression molded to prepare a test piece, and the physical properties were evaluated. Table 2 shows the evaluation results.

Example 6 Ring-Hydrogenated Styrene-α-Methylstyrene Copolymer Resin Obtained in Resin Preparation Example 8 and Ring-Hydrogenated SB- Obtained in Resin Preparation Example 3
Using S-triblock copolymer (SBS), the procedure was the same as in Example 3. Table 2 shows the evaluation results.

Example 7 Laboplast was prepared by combining 84% by weight of the cyclic hydrogenated polystyrene resin obtained in Resin Synthesis Example 1 and 16% by weight of the cyclic hydrogenated SBS triblock copolymer obtained in Resin Preparation Example-4. Mix in a mill,
A test piece was prepared by compression molding, and the physical properties were evaluated. Table 2 shows the evaluation results.

Comparative Example 4 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 5 A test piece was prepared by compression molding the ring-hydrogenated SB diblock copolymer obtained in Resin Production Example-9.
Table 2 shows the results of the evaluation of the physical properties.

Comparative Example 6 A-A obtained by hydrogenating only the butadiene portion obtained in Resin Production Example-5
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.

Comparative Example 7 The polystyrene resin obtained in Resin Production Example-6 was replaced with cyclic hydrogenated polystyrene and evaluated in the same manner as in Example 3. Table 2 shows the evaluation results.

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[Table 2]

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Industrial Applicability The vinylated cyclic hydrocarbon resin composition of the present invention is excellent in transparency, high heat resistance, chemical resistance, electrical insulation, and low moisture permeability, which are excellent characteristics of the vinylated cyclic hydrocarbon resin. While maintaining excellent performances such as the above, the strength characteristics, particularly the impact strength, which is a defect, are remarkably improved.

Continued on front page F-term (reference) 4J002 BB171 BC031 BC081 BC091 BK001 BL021 BP012 GB01 GP00 GQ00 GQ01 4J026 HA06 HA26 HB14 HB15 HB16 HB26 HC06 HC26 HE02 HE05

Claims (3)

[Claims] 1. A block copolymer 40 comprising (a) 60 to 99% by weight of a vinylated cyclic hydrocarbon resin and (b) a polymer chain containing at least a triblock chain represented by the general formula ABA in the polymer chain. (Wherein A is a polymer block mainly composed of hydrogenated vinyl aromatic hydrocarbons and having a number average molecular weight in the range of 10,000 to 200,000, and each A is B may be the same or different, and B is mainly composed of a hydrogenated conjugated diene compound and has a number average molecular weight of 20,000.
It is a polymer block in the range of 0 to 500,0000.
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 50 to 90% by weight. Range. ) 2. The resin composition according to claim 1, wherein the content of the component (b) is in the range of 20% by weight to 1% by weight. 3. A polymer block comprising 1,3-butadiene in which the B block constituting the copolymer (b) is a hydrogenated 1,3-butadiene having a 1,2-bond content of 2
The resin composition according to claim 1, wherein the content is 0 mol% to 60 mol%.