JP5888161B2 - Resin composition, and film and container comprising the resin composition - Google Patents

Description

  The present invention is well balanced in transparency, optical properties, flexibility, mechanical properties, moldability, heat resistance, gas barrier properties, low hygroscopicity, and chemical non-adsorption properties, and in particular, in transparency, gas barrier properties, flexibility, etc. The present invention relates to an excellent resin composition, and a film and a container made of the resin composition.

  Resin compositions used as molding materials for various products are required to have excellent balance in transparency, optical properties, flexibility, mechanical properties, moldability, heat resistance, gas barrier properties, low hygroscopicity, and non-adsorption of chemicals In particular, containers used for medical, food, and other applications, and molding materials for protective films of various products, transparency and content for checking container contents and film-attached articles It is required to have excellent gas barrier properties such as water vapor impermeability for protecting articles and film-attached articles from the external environment. Further, in order to provide a product with excellent durability by preventing breakage during use, impact resistance is also an important required characteristic.

  Patent Document 1 discloses a block comprising an amorphous polyolefin resin (A) and an aromatic vinyl compound polymer block and an isobutylene polymer block as a resin composition excellent in impact resistance, transparency and gas barrier properties. Addition copolymer (A) containing copolymer (B), wherein amorphous polyolefin resin (A) comprises both monomers of ethylene and cyclic olefin, or both of them and α-olefin. A-1) or a hydrogenated product (A-2) of a ring-opening polymer of a cyclic olefin, and the weight ratio of (A) / (B) is in the range of 95/5 to 50/50. The resin composition characterized by being inside is disclosed.

JP-A-9-124854

According to the study by the present inventors, although the resin composition described in Patent Document 1 is described as being excellent in impact resistance, transparency, and gas barrier properties, transparency and gas barrier properties (non-water vapor) (Transparency) is not yet sufficient, and in particular, the transparency and gas barrier properties that are inherently excellent in amorphous polyolefin resin are impaired as the block copolymer (B) in Patent Document 1 is added. The problem was found that the trend was large.

  The present invention is well balanced in transparency, optical properties, flexibility, mechanical properties, moldability, heat resistance, gas barrier properties, low hygroscopicity, and chemical non-adsorption properties, and in particular, in transparency, gas barrier properties, flexibility, etc. It is an object of the present invention to provide an excellent resin composition, and a film and a container made of the resin composition.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have hydrogenated the aromatic vinyl compound polymer block of the block copolymer (B) of the resin composition of Patent Document 1 to obtain a hydrogenated block copolymer. It has been found that good transparency and gas barrier properties can be obtained by combining, and the above-described problems can be solved, and the present invention has been completed.

  That is, the gist of the present invention is the following [1] to [9].

[1] A resin composition comprising the following component (X) and component (Y).
Component (X): Hydrogenated block copolymer having hydrogenated vinyl aromatic polymer block A and block B of polymer mainly composed of isobutylene Component (Y): Copolymer of ethylene and cyclic olefin (y1 ) And a hydrogenated product (y2) of a ring-opened polymer of a cyclic olefin

[2] The resin composition according to [1], wherein the component (X) has a weight average molecular weight of 10,000 or more and 200,000 or less.

[3] The resin composition according to [1] or [2], wherein the component (X) has two or more hydrogenated vinyl aromatic polymer blocks A.

[4] The resin composition according to any one of [1] to [3], wherein the hydrogenated vinyl aromatic polymer block A is a hydrogenated polystyrene block obtained by hydrogenating an aromatic ring.

[5] The resin composition according to any one of [1] to [4], wherein the hydrogenation rate of the aromatic ring of the vinyl hydride aromatic polymer block A is 50 mol% or more.

[6] Any one of [1] to [5], wherein the block B of the polymer mainly containing isobutylene contains 70% by weight or more of isobutylene as a monomer component. Resin composition.

[7] The content of the component (X) is 5 to 90% by weight and the content of the component (Y) is 95 to 10% by weight, according to any one of [1] to [6] The resin composition as described.

[8] A film comprising the resin composition according to any one of [1] to [7].

[9] A container comprising the resin composition according to any one of [1] to [7].

  The resin composition of the present invention has an excellent balance of transparency, optical properties, flexibility, mechanical properties, moldability, heat resistance, gas barrier properties, low hygroscopicity, and non-adsorbing properties for chemicals, and in particular, transparency and gas barrier. Because of its excellent properties and flexibility, it can be used in a wide range of applications as molding materials for various containers, films, and other products.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In addition, in this invention, when expressing by putting a numerical value or a physical-property value before and behind using "-", it shall use as what includes the value before and behind.

The resin composition of the present invention comprises the following component (X) and component (Y).
Component (X): Hydrogenated block copolymer (hereinafter referred to as “hydrogenated block copolymer (X)”) having a hydrogenated vinyl aromatic polymer block A and a block B of a polymer mainly composed of isobutylene May be referred to.)
Component (Y): Amorphous polyolefin selected from copolymer (y1) of ethylene and cyclic olefin, and hydrogenated product (y2) of ring-opened polymer of cyclic olefin (hereinafter referred to as “amorphous polyolefin (Y)”) May be referred to.)

  The hydrogenated block copolymer (X) of the component (X) used in the present invention is transparent, optical properties, flexibility, mechanical properties, moldability, heat resistance, gas barrier properties, low hygroscopicity, and chemical non-adsorbing properties. In addition, it is excellent in balance, and is particularly flexible and excellent in moldability such as film moldability, and also has excellent gas barrier properties. This hydrogenated block copolymer (X) also has good compatibility with the amorphous polyolefin (Y) of the component (Y), and is non-functional as a resin composition with the amorphous polyolefin (Y). Crystalline polyolefin (Y) does not impair the original impact resistance, and since hydrogenated block copolymer (X) and amorphous polyolefin (Y) have similar refractive indexes, transparency is improved. An excellent resin composition can be obtained. Therefore, according to the present invention, it is possible to provide a resin composition that is flexible and excellent in moldability and excellent in impact resistance, transparency, and gas barrier properties.

[Component (X)]
The hydrogenated block copolymer (X) of the component (X) contained in the resin composition of the present invention is a hydrogen having a hydrogenated vinyl aromatic polymer block A and a polymer block B mainly composed of isobutylene. Block copolymer. The hydrogenated block copolymer (X) preferably has two or more hydrogenated vinyl aromatic polymer blocks A and a block B of a polymer mainly composed of isobutylene. That is, the hydrogenated block copolymer (X) is preferably a hydrogenated block copolymer having two or more blocks A and at least one block B. The weight average molecular weight is preferably 10,000 or more and 200,000 or less.

  The vinyl aromatics of the monomer before hydrogenation constituting the hydrogenated vinyl aromatic polymer block A of the hydrogenated block copolymer (X) include benzene ring, naphthalene ring, anthracene ring, fluorene ring, Examples include those in which a vinyl group is bonded to an aromatic ring such as a phenanthrene ring, and a substituent other than a vinyl group may be bonded to the aromatic ring. Specifically, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5- t-butyl-2-methylstyrene, 4-monochlorostyrene, 4-chloromethylstyrene, 4-hydroxymethylstyrene, 4-t-butoxystyrene, dichlorostyrene, 4-monofluorostyrene, 4-phenylstyrene, vinylnaphthalene, Vinyl anthracene and the like, and styrene, α-methylstyrene, 4-methylstyrene, 4-t-butylstyrene, 4-chloromethylstyrene, vinylnaphthalene are preferably used, and styrene, α-methylstyrene, 4-methyl Styrene and 4-t-butylstyrene are preferred Are, most preferably styrene is used. These vinyl aromatics may be used individually by 1 type, and may use 2 or more types together. In particular, the hydrogenated vinyl aromatic polymer block A is preferably a hydrogenated polystyrene block obtained by hydrogenating an aromatic ring.

  The hydrogenated vinyl aromatic polymer block A is usually a block composed only of vinyl aromatics hydrogenated as a monomer, but within a range not impairing the object of the present invention, for example, Monomer components other than vinyl aromatics may be contained in a proportion of 50% by weight or less of the total weight of the hydrogenated vinyl aromatic polymer block A.

  On the other hand, the block B of the polymer mainly composed of isobutylene is composed of isobutylene as a monomer component, 50% by weight or more of the total weight of the block B of the polymer mainly composed of isobutylene, preferably 55% by weight or more. Is 60% by weight or more, more preferably 70% by weight or more, and particularly preferably 80 to 100% by weight. In the above range, other monomers may be copolymerized. By including isobutylene as a monomer component in the above range in the block B of the polymer mainly composed of isobutylene, transparency, optical properties, flexibility, mechanical properties, gas barrier properties, low moisture absorption, non-chemical absorption Thus, an excellent hydrogenated block copolymer (X) with a good balance can be obtained. When the block B of the polymer mainly composed of isobutylene contains other monomer components other than isobutylene, the other monomer is not particularly limited as long as it is a monomer that can be cationically polymerized with isobutylene. , One or more of the above-mentioned vinyl aromatics, aliphatic olefins, dienes, vinyl ethers, β-pinene and the like.

The hydrogenated block copolymer (X) preferably has two or more segments A (hydrogenated vinyl aromatic polymer block A) and one or more segments B (polymer block B mainly composed of isobutylene). Depending on the combination, those having a structure such as A- (BA) _n , (A-B) _m , B-A- (BA) _n -B may be mentioned (where n is 1). Among these, m represents an integer of 2 or more), and among these, A- (BA) _n , particularly those having a structure of ABA are preferable.

  However, the hydrogenated block copolymer (X) has one segment A (hydrogenated vinyl aromatic polymer block A) and one segment B (polymer block mainly composed of isobutylene), that is, AB may be sufficient.

  The molecular structure of the hydrogenated block copolymer (X) may be any of linear, branched, radial, or any combination thereof.

  The content of the hydrogenated vinyl aromatic polymer block A in the hydrogenated block copolymer (X) is preferably 5% by weight or more, more preferably 10% by weight or more, and further preferably 15% by weight or more. On the other hand, it is preferably 95% by weight or less, more preferably 80% by weight or less, still more preferably 60% by weight or less, and particularly preferably 40% by weight or less. When the content of the hydrogenated vinyl aromatic polymer block A in the hydrogenated block copolymer (X) is not more than the above upper limit value, the flexibility and elasticity become favorable, and the impact resistance tends to be excellent. On the other hand, the heat resistance tends to be good when it is at least the above lower limit.

The hydrogenated block copolymer (X) only needs to have a hydrogenated vinyl aromatic polymer block A and a polymer block B mainly composed of isobutylene. You may have other polymer or copolymer block C other than the block B of the polymer which has A and isobutylene as a main component. In this case, as the other block C, for example, in the block B of a polymer mainly composed of isobutylene, a polymer or copolymer block having an isobutylene content of less than 50% by weight, aliphatic olefins, diene And a polymer or copolymer block composed of one kind or two or more kinds of vinyl ethers, vinyl ethers and β-pinene.
However, if the content of the other block C in the hydrogenated block copolymer (X) is too large, it contains a hydrogenated vinyl aromatic polymer block A and a block B of a polymer mainly composed of isobutylene. Since the effect of the hydrogenated block copolymer (X) due to the above tends to decrease, when the hydrogenated block copolymer (X) contains another block C, the content thereof is the hydrogenated block copolymer. It is preferably 40% by weight or less, particularly preferably 20% by weight or less, based on the total weight of (X).

  As a manufacturing method of hydrogenated block copolymer (X), as long as said structure is obtained, what kind of manufacturing method may be used. For example, the aromatic ring of the vinyl aromatic block copolymer obtained by cationic polymerization in an organic solvent using a Lewis acid catalyst or the like is hydrogenated by the method described in JP-A-11-100420. Can be obtained.

  The hydrogenation method and reaction mode of the aromatic ring of the vinyl aromatic block copolymer are not particularly limited and may be carried out according to a known method, but the hydrogenation rate can be increased, and the polymer chain scission can be performed. A hydrogenation process with little reaction is preferred. Examples of such a preferable hydrogenation method include a method using a catalyst containing at least one metal selected from nickel, cobalt, iron, titanium, rhodium, palladium, platinum, ruthenium, rhenium and the like. As the hydrogenation catalyst, either a heterogeneous catalyst or a homogeneous catalyst can be used, and the hydrogenation reaction is preferably performed in an organic solvent.

  The heterogeneous catalyst can be used in the form of a metal or a metal compound or supported on a suitable carrier. Examples of the carrier include activated carbon, silica, alumina, calcium carbonate, titania, magnesia, zirconia, diatomaceous earth, silicon carbide, calcium fluoride and the like. These may be used alone or in combination of two or more. The supported amount of the catalyst component is usually 0.1% by weight or more, preferably 1% by weight or more, and usually 60% by weight or less, preferably 50% by weight or less based on the total amount of the catalyst component and the carrier.

  As homogeneous catalysts, catalysts combining metal compounds such as nickel, cobalt, titanium or iron and organometallic compounds such as organoaluminum and organolithium; rhodium, palladium, ruthenium, rhenium, titanium, zirconium, hafnium, etc. An organometallic complex of the above can be used.

  As said metal compound, the acetylacetone salt of each metal, a naphthenate, a cyclopentadienyl compound, a cyclopentadienyl dichloro compound, etc. are used. As the organic aluminum, alkyl aluminum such as triethylaluminum and triisobutylaluminum; alkylaluminum halide such as diethylaluminum chloride and ethylaluminum dichloride; alkylaluminum hydride such as diisobutylaluminum hydride and the like are used.

  Examples of the organometallic complex include γ-dichloro-π-benzene complex, dichloro-tris (triphenylphosphine) complex, hydrido-chloro-tris (triphenylphosphine) complex of the above metals.

  These hydrogenation catalysts can be used alone or in combination of two or more. The amount of the hydrogenation catalyst used is usually 0.001 parts by weight or more, preferably 0.005 parts by weight or more, more preferably 0.01 parts by weight, based on 100 parts by weight of the vinyl aromatic block copolymer. It is at least 50 parts by weight, preferably at most 30 parts by weight, more preferably at most 15 parts by weight.

  The hydrogenation reaction is carried out at a pressure of 5 to 25 MPa at a temperature of 100 to 200 ° C., as a solvent, a saturated hydrocarbon solvent such as cyclohexane, methylcyclohexane, n-octane, decalin, tetralin, naphtha, or an ether such as tetrahydrofuran. It is preferable to use a system solvent. Although there is no restriction | limiting in particular in the usage-amount of a solvent, Usually, it is 100 to 1000 weight part with respect to 100 weight part of vinyl aromatic type block copolymers.

The hydrogenation rate of the aromatic ring of the vinyl aromatic block copolymer is preferably 50 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more. When the hydrogenation rate is not less than the above lower limit, the transparency, heat resistance, and moldability are excellent. The hydrogenation rate of the aromatic ring is calculated from, for example, the integrated value of the peak derived from an aliphatic group near 0.5 to 2.5 ppm and the peak derived from an aromatic ring near 6.0 to 8.0 ppm by ¹ H-NMR. be able to.

  The method for recovering the hydrogenated block copolymer after completion of the hydrogenation reaction is not particularly limited. The recovery method is usually a steam coagulation method in which the hydrogenated catalyst residue is removed by a method such as filtration or centrifugation, and then the solvent is removed from the solution in which the hydrogenated block copolymer is dissolved by steam stripping, heating under reduced pressure. Direct solvent removal method to remove solvent under, hydrogenated block copolymer by pouring solution into poor solvent of hydrogenated block copolymer such as methanol, ethanol, isopropyl alcohol, water, acetone, methyl ethyl ketone, ethyl acetate A known method such as a coagulation method for precipitating and solidifying can be employed.

  The hydrogenated block copolymer (X) has a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, preferably 10,000 or more, more preferably 30000. More preferably, it is 50000 or more, on the other hand, preferably 200000 or less, more preferably 150,000 or less, and further preferably 130,000 or less. When Mw of the hydrogenated block copolymer (X) is not less than the above lower limit value, the resulting molded article tends to have good mechanical strength, heat resistance and moldability, and is not more than the above upper limit value. As a result, the melt viscosity during processing tends to decrease, and the moldability tends to be good.

  The molecular weight distribution of the hydrogenated block copolymer (X) can be appropriately selected depending on the purpose of use, but the ratio (Mw / Mn) between the polystyrene-equivalent Mw and the number average molecular weight (Mn) measured by the GPC. And is preferably 4 or less, more preferably 3 or less, and particularly preferably 2 or less. It is preferable for Mw / Mn to be equal to or lower than the above upper limit value because a molded article having excellent moldability, heat resistance, transparency, and the like can be easily obtained.

  The lower limit value of the melt flow rate (MFR) at 230 ° C. (nozzle diameter 2 mm) of the hydrogenated block copolymer (X) is usually 0.01 g / min or more, preferably 0.1 g / min or more, more preferably 0.5 g / min or more, most preferably 1 g / min or more, and the upper limit of the MFR is usually 500 g / min or less, preferably 200 g / min or less, more preferably 100 g / min or less, most preferably 50 g / min. It is as follows. When the MFR is equal to or higher than the lower limit, the viscosity is suitable for molding and manufacturing, and the manufacturing is easy. When the MFR is equal to or lower than the upper limit, the moldability during processing is good and the mechanical properties of the product are sufficient. It becomes.

[Component (Y)]
The component (Y) contained in the resin composition of the present invention comprises a copolymer (y1) of ethylene and a cyclic olefin (hereinafter sometimes referred to as “copolymer (y1)”), and the opening of the cyclic olefin. Amorphous selected from hydrogenated ring polymer (y2) (hereinafter sometimes referred to as “hydrogenated ring-opened polymer (y2)”) (ie, substantially no melting point is observed by DSC measurement) (Y) having a property). The copolymer (y1) is not limited to a copolymer composed of ethylene and a cyclic olefin, but may be a copolymer of ethylene, a cyclic olefin, and an olefin other than ethylene.

  The number average molecular weight or intrinsic viscosity number of the amorphous polyolefin (Y) is not particularly limited and can be suitably selected according to the purpose and the like. In general, the number average molecular weight is 10,000. It is preferable that it is in the range of ˜500000 or the intrinsic viscosity number measured in decalin at 135 ° C. is in the range of 0.01 to 20 dL / g. From the viewpoint of moldability, the number average molecular weight or intrinsic viscosity of the amorphous polyolefin (Y) is preferably not more than the above upper limit, and more preferably not less than the above lower limit from the toughness.

  Preferable specific examples of the amorphous polyolefin (Y) include, for example, a polymer having a repeating unit represented by the following formula (1) and a polymer having a repeating unit represented by the following formula (2). However, the amorphous polyolefin (Y) used in the present invention is not limited to the following.

<Copolymer (y1)>
Examples of the cyclic olefin of the ethylene copolymerization component in the copolymer (y1) include norbornene, bicyclo [2.2.1] -2-heptene, and 5-methylbicyclo [2.2.1] -2-heptene. 5,6-dimethylbicyclo [2.2.1] -2-heptene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-dimethyltetracyclo [4.4.0.1 ^2,5 . Norbornenes such as ^{17, 10} ] -3-dodecene. These cyclic olefins may further have a substituent such as an alkyl group, a polar group such as halogen, ester, nitrile, and pyridyl. These cyclic olefins may be used alone or in combination of two or more. Among them, norbornene and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene is preferred.

  When the copolymer (y1) contains an olefin other than ethylene as the copolymer component, examples of the olefin include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, C3-C20 alpha olefins, such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, etc. are mentioned. These olefins may be used alone or in combination of two or more.

  The ratio of ethylene and cyclic olefin as a monomer component contained in the copolymer (y1) is, as a molar ratio of ethylene / cyclic olefin, ethylene / cyclic olefin = 80/20 to 30/70. preferable. In this range, the smaller the amount of ethylene, the higher the glass transition temperature of the copolymer (y1) and the better the heat resistance. The larger the amount in this range, the better the moldability of the copolymer (y1). In addition, the toughness tends to be excellent.

  When the copolymer (y1) contains an olefin other than ethylene as the monomer component, the ratio of the olefin other than ethylene is the same as that of ethylene in order to maintain the properties as a copolymer of ethylene and cyclic olefin. On the other hand, it is preferably 50 mol% or less, particularly preferably 30 mol% or less.

The manufacturing method of such a copolymer (y1) is not specifically limited, A well-known various manufacturing method is employable. The copolymer (y1) can be produced, for example, by copolymerizing ethylene and a cyclic olefin, or an olefin other than ethylene used as necessary, in a liquid phase. The copolymerization in the liquid phase is performed, for example, at a temperature in the range of −50 ° C. to 100 ° C. in a hydrocarbon solvent such as cyclohexane in the presence of a catalyst composed of a soluble vanadium compound and an organoaluminum compound, 0 to 50 kg. / Cm ² G can be carried out at a pressure in the range.

  For example, the copolymer (y1) is preferably a polymer having a repeating unit represented by the following formula (1).

In the above formula (1), R ¹ and R ² may be the same or different and each represents a hydrogen atom, a hydrocarbon residue, or a polar group such as halogen, ester, nitrile, pyridyl or the like. R ¹ and R ² may be bonded to each other to form a ring. a is an integer of 1 or more, b is an integer of 0 or more, and c is an integer of 1 or more.

  The copolymer (y1) is available as a commercial product. Specific examples thereof include a trade name “Apel (registered trademark)” manufactured by Mitsui Chemicals, Inc., and a trade name “Topas (registered trademark)” of Polyplastics Co., Ltd. ) "And the like.

<Hydrogenated ring-opening polymer (y2)>
Examples of the cyclic olefin constituting the hydrogenated ring-opening polymer (y2) include bicyclo [2.2.1] -2-heptene, 5-methylbicyclo [2.2.1] -2-heptene, 5, 6-dimethylbicyclo [2.2.1] -2-heptene, 5-carboxymethylbicyclo [2.2.1] -2-heptene, cyclopentadiene, dicyclopentadiene, 2,3-dihydrodicyclopentadiene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 . And norbornenes such as ^{17, 10} ] -3-dodecene. These cyclic olefins may further have a substituent such as an alkyl group, a polar group such as halogen, ester, nitrile, and pyridyl. These cyclic olefins may be used alone or in combination of two or more.

The production method of the hydrogenated ring-opening polymer (y2) is not particularly limited, and various known production methods can be employed. The hydrogenated ring-opening polymer (y2) can be produced, for example, by subjecting a cyclic olefin to ring-opening polymerization and then hydrogenating the olefinically unsaturated bond portion of the produced polymer. The ring-opening polymerization may be carried out by using, for example, a cyclic olefin, a transition metal compound or a platinum group metal compound and an organometallic compound such as an organoaluminum compound, and an aliphatic or aromatic tertiary amine as necessary. In the presence of the additive, a temperature in the range of −20 ° C. to 100 ° C. and a pressure in the range of 0 to 50 kg / cm ² G can be performed. The hydrogenation can be carried out in the presence of a normal hydrogenation catalyst.

The hydrogenated ring-opening polymer (y2) is preferably a polymer having a repeating unit represented by the following formula (2), for example.

In the above formula (2), R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, a hydrocarbon residue, or a polar group such as halogen, ester, nitrile or pyridyl. R ³ and R ⁴ may be bonded to each other to form a ring. e is an integer of 1 or more, and d is 0 or an integer of 1 or more. The hydrogenated ring-opened polymer (y2) may include a plurality of different structures among the structures represented by the above formula (2). Among those represented by the above formula (2), those represented by the following formula (3) are preferably included, and more specifically those represented by the following formula (3) in the molecule. It is preferable that 30 mol% or more is contained.

  The hydrogenated ring-opening polymer (y2) is available as a commercial product. Specific examples thereof include hydrogenated polymers manufactured by Nippon Zeon Co., Ltd., trade names “Zeonor (registered trademark)”, manufactured by JSR Corporation. Product name “ARTON (registered trademark)”.

[Content Ratio of Component (X) and Component (Y)]
In the resin composition of the present invention, the content ratio of the hydrogenated block copolymer (X) of component (X) and the amorphous polyolefin (Y) of component (Y) is the same as that of the hydrogenated block copolymer of component (X). The blend (X) is preferably 5 to 90% by weight, and the amorphous polyolefin (Y) of the component (Y) is preferably 95 to 10% by weight. When the content ratio of component (X) is not less than the above lower limit value, the balance between flexibility, transparency, and gas barrier properties due to blending of component (X) tends to be good, and the content ratio of component (X) Is less than the above upper limit value, the effect of improving the gas barrier property by blending the component (Y) tends to be good, and from the viewpoint of making this effect better, the more preferable content ratio is the component ( X) is 5 to 80% by weight, component (Y) is 95 to 20% by weight, particularly preferably component (X) is 10 to 60% by weight and component (Y) is 90 to 40% by weight.

  The resin composition of the present invention may contain only one kind of the hydrogenated block copolymer (X) as the component (X), and the constituent components and compositions of the block A and the block B described above. Two or more kinds of hydrogenated block copolymers (X) having different weight average molecular weights or aromatic ring hydrogenation rates may be contained. Similarly, the component (Y) may contain only one type of the copolymer (y1) or the hydrogenated ring-opened polymer (y2), and two or more different types such as the copolymerization component and the copolymerization composition may be included. Two or more types of the copolymer (y1) and the hydrogenated ring-opened polymer (y2) may be contained. Moreover, the 1 type (s) or 2 or more types of copolymer (y1) and the 1 type (s) or 2 or more types of hydrogenated ring-opening polymer (y2) may be contained.

[Other ingredients]
The resin composition of this invention should just contain component (X) and component (Y), and may contain other resin components other than these components, various additives, etc. as needed.

  Other resin components that may be contained in the resin composition of the present invention include ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / acrylic acid ester copolymer, Ethylene / α-olefin copolymer such as ethylene / methacrylic acid ester copolymer, polyolefin resin such as polyethylene, polypropylene, polybutene-1 resin, polyphenylene ether resin, polyamide resin such as nylon 6 and nylon 66, aramid Resins, aromatic polyester resins such as polyethylene terephthalate and polybutylene terephthalate, aliphatic polyester resins such as polylactic acid, polybutylene succinate and polycaprolactone, polycarbonate resins, polyarylate resins, modified polyphenylene oxide trees , Polysulfone resins, polyphenylene sulfide resins, polyether sulfone resins, polyether ketone resins, polyether ether ketone resins, polyimide resins, polyoxymethylene homopolymers, polyoxymethylene copolymers, and other polyoxymethylene resins, polymethyl methacrylate resins Resins, silicon-containing soft polymers such as dimethylpolysiloxane, diphenylpolysiloxane, dihydroxypolysiloxane, vinyl aromatic polymers such as polystyrene, ethylene / propylene copolymer rubber (EPM), ethylene / propylene / nonconjugated diene copolymer rubber (EPDM), ethylene elastomer such as ethylene / butene copolymer rubber (EBM), ethylene / propylene / butene copolymer rubber, styrene-butadiene-styrene block copolymer, Styrene elastomer such as styrene-isoprene-styrene block copolymer, styrene-ethylene / butylene-styrene block copolymer, styrene-ethylene / propylene-styrene block copolymer, polybutadiene, vinyl hydride aromatic polymer, hydrogen And other hydrogenated vinyl aromatic block copolymers including cyclostyrene / butadiene or styrene / isoprene block copolymers, cycloolefin polymers, cycloolefin copolymers, etc. (however, among the above resin components, Excluding those contained in components (X) and (Y)). These may be used alone or in combination of two or more.

  Among these, it is excellent in the balance of transparency, heat resistance, gas barrier property, and non-adsorbing property for chemicals, so that it is possible to use hydrogenated vinyl aromatic polymers, hydrogenated vinyl aromatic block copolymers, cycloolefin polymers, cycloolefin copolymers. Polymers and polyolefin resins are preferred, and vinyl hydride aromatic polymers are particularly preferred.

  Examples of the vinyl aromatics constituting the above-mentioned hydrogenated vinyl aromatic polymer and vinyl hydrogenated aromatic block copolymer include styrene, α-methylstyrene, 2-methylstyrene, 3-methyl. Styrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, 4-monochlorostyrene, dichlorostyrene, 4-mono Fluorostyrene, 4-phenylstyrene vinyl naphthalene, vinyl anthracene and the like can be mentioned. Among them, styrene, α-methylstyrene and 4-methylstyrene are preferably used. These vinyl aromatics may be used individually by 1 type, and may use 2 or more types together.

  However, in order to effectively obtain the effect of the present invention by using the component (X) and the component (Y), these other resin components should be 30% by weight or less as the content in the resin composition. Is preferable, and it is more preferable to set it as 15 weight% or less.

  Additives include antioxidants, heat stabilizers, light stabilizers, UV absorbers, fillers such as fillers, neutralizers, lubricants, antifogging agents, antiblocking agents, slip agents, dispersants, colorants, Flame retardants, antistatic agents, conductivity-imparting agents, cross-linking agents, cross-linking aids, metal deactivators, molecular weight regulators, antibacterial agents, antifungal agents, fluorescent whitening agents, organic diffusing agents and inorganic diffusing agents And the like.

[Method for Producing Resin Composition]
The resin composition of the present invention can be produced, for example, by a method of mechanically melting and kneading the above components. Examples of the melt kneader that can be used here include a single-screw extruder, a twin-screw extruder, a Brabender, a Banbury mixer, a kneader blender, and a roll mill. The lower limit of the kneading temperature is usually 100 ° C. or higher, preferably 145 ° C. or higher, more preferably 160 ° C. or higher. The upper limit of the kneading temperature is usually 350 ° C., preferably 300 ° C., more preferably 250 ° C. When kneading, each component may be kneaded all at once, or a multistage division kneading method may be used in which any component is kneaded and then the other remaining components are added and kneaded.

[Method for Molding Resin Composition]
Examples of the resin composition of the present invention include injection molding (insert molding method, two-color molding method, sandwich molding method, gas injection molding method, etc.), extrusion molding method, inflation molding method, T-die film molding method, laminate molding method, It can be processed into various molded articles by molding methods such as blow molding, hollow molding, compression molding, and calendar molding. There is no restriction | limiting in particular in the shape of a molded object, A sheet | seat, a film, plate shape, particle shape, a lump body, a fiber, a rod shape, a porous body, a foam etc. are mentioned, Preferably it is a sheet | seat, a film, and plate shape. Further, the formed film can be uniaxially or biaxially stretched. Examples of the stretching method include a roll method, a tenter method, and a tubular method. Furthermore, surface treatments such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment and the like which are usually used industrially can also be applied.

[Usage]
Although the use of the molded object formed by shape | molding the resin composition of this invention is not specifically limited, The following uses can be mentioned as an example. That is, coating materials such as electric wires, cords, wire harnesses, insulation sheets, OA equipment displays and touch panels, membrane switches, photo covers, relay parts, coil bobbins, IC sockets, fuse cases, camera pressure plates, etc. FDD collet, floppy hub, optical disk substrate in optical components field, optical disk pickup lens, optical lens, LCD substrate, PDP substrate, television screen for projection TV, retardation film, fog lamp lens, illumination switch lens, sensor switch lens, fullnel Lens, protective glasses, projection lens, camera lens, sunglasses, light guide plate, camera strobe reflector, LED reflector, headlamp lens for automobile parts, window Car lamp lens, tail lamp lens, resin window glass, meter cover, outer panel, door handle, rear panel, wheel cap, visor, roof rail, sunroof, instrument panel, panels, control cable covering material, air bag cover, mud guard, bumper, Various malls such as boots, air hoses, lamp packings, gaskets, window moldings, site shields, weather strips, glass run channels, grommets, vibration control and sound insulation materials, joint materials in the field of building materials, handrails, windows, table edge materials, Sashes, bathtubs, window frames, signboards, lighting covers, water tanks, stair lumbar boards, carports, highway sound insulation walls, multi-wall sheets, steel wire coverings, lighting lamp globes, switch breakers, protective covers for machine tools, industrial deep drawing vacuum Shaped containers, pump housings, home appliances, various packings in the field of weak electricity, grips, belts, rubber feet, rollers, protectors, suction cups, refrigerators, gaskets, switches, connector covers, game machine covers, pachinko machines, OA Housing, notebook PC housing, HDD head tray, instrument window, transparent housing, roller with OA gear, switch case slider, gas cock knob, clock frame, clock train wheel inset, amber cap, various rolls for OA equipment Tubular molded products such as hoses and tubes, atypical extrusions, leather-like articles, articulating tools, soft tactile dolls, pen grips, straps, suckers, watches, umbrella bones, cosmetic cases, toothbrush patterns, etc. General miscellaneous goods, containers such as houseware, tupperware, cable ties, braces Various types of bottles such as infusion bottles, food bottles, water bottles, cosmetics bottles, and other personal care bottles, medical components, catheters, syringes, syringe gaskets, drip tubes, tubes, ports, caps, rubber stoppers, diamonds Examples include risers, blood connectors, dentures, disposable containers, and the like, and can also be applied to applications using foam molding.
Among the above, the tube is particularly suitable for a medical tube that can prevent the adsorption of medicinal components, and the multilayer tube is most suitable for its inner layer material or intermediate layer material.

  Although the usage in the field of the film and sheet of the molded product formed by molding the resin composition of the present invention is not particularly limited, the following usage can be given as an example. That is, stretch film for packaging, wrap film for business use or household use, pallet stretch film, stretch label, shrink film, shrink label, film for sealant, film for retort, sealant film for retort, aroma retaining heat seal film, A- PET sealant, frozen food containers and lids, cap seals, heat-sealing films, heat-bonding films, heat-sealing films, bag-in-box sealant films, retort pouches, standing pouches, spout pouches, laminated tubes, heavy bags , Food packaging such as fiber wrapping film, miscellaneous goods packaging field, house film, multi-film agricultural film field, infusion bag, high-calorie infusion and peritoneal dialysis (CAPD), antibiotic kit bag, etc. , Drainage bags for peritoneal dialysis, blood bags, urine bags, surgical bags, ice pillows, ampoule cases, medical film and sheet fields such as PTP packaging, civil engineering impermeable sheets, waterproofing materials, mats, joint materials, Building materials related fields such as flooring, roofing, decorative film, skin film, wallpaper, leather, ceiling material, trunk room lining, interior skin material, vibration control sheet, sound insulation sheet, etc., display cover, battery case, mouse Pads, mobile phone cases, IC card holders, floppy disk cases, CD-ROM cases, etc., weak electric fields, toothbrush cases, puff cases, cosmetic cases, eye drops and other pharmaceutical cases, tissue cases, face packs, etc. toiletries or sanitary fields, for stationery Film / sheet, clear file, pencil case, notebook cover Desk mats, keyboard covers, book covers, office supplies related fields such as binders, furniture leather, beach ball toys, umbrellas, raincoats, tablecloths, blister packages, bath lids, towel cases, fancy cases, General household use such as tag cases, pouches, amulet bags, insurance card covers, passbook cases, passport cases, knife cases, etc., miscellaneous goods field, retroreflective sheets, synthetic paper, and the like. In addition, as a pressure-sensitive adhesive composition, or as a film / sheet field in which a pressure-sensitive adhesive is applied to a substrate to impart adhesiveness, carrier tape, pressure-sensitive adhesive tape, marking film, semiconductor or glass dicing film, surface protective film, Steel plate / plywood protective film, automotive protective film, adhesive tape for packaging / bundling, office / house adhesive tape, bonding adhesive tape, coating masking adhesive tape, surface protective adhesive tape, sealing adhesive tape, anti-corrosion / waterproof Adhesive tape for electrical insulation, adhesive tape for electrical insulation, adhesive tape for electronic equipment, adhesive film, adhesive tape for medical and sanitary materials such as base material film, identification and decoration adhesive tape, display tape, packaging tape, surgical tape, For example, an adhesive tape for labels.

  Although the use in the field | area of a fiber and a nonwoven fabric of the molded object formed by shape | molding the resin composition of this invention is not specifically limited, The following uses can be mentioned as an example. That is, by making non-woven fabric by continuous spinning, continuous crimped yarn, short fibers, monofilaments, flat yarn, melt blow method, spunbond method, sanitary materials such as disposable diapers, surgical clothes, medical supplies such as gloves, Applications include inner gloves, carpets, linings, and ropes. Further, canvases, tent materials, hoods, flexible containers, leisure sheets, tarpaulins, etc. by laminating these woven fabrics, monofilaments, flat yarns, slit tapes and the like with films / sheets.

[the film]
The resin composition of the present invention is particularly useful as a film molding material among the various uses described above because of its excellent impact resistance, transparency and gas barrier properties.

The film of the present invention formed by molding the resin composition of the present invention may be a single-layer film made of the resin composition of the present invention, or two or more layers formed by coextrusion with other resin compositions. It may be a laminated film.
Such a film is useful as a raw film for processing and forming into a container to be described later, or as a protective film for a display surface of an electronic device, a mobile phone, a smartphone or the like. The visibility of the display surface is not impaired, and because of its excellent impact resistance and gas barrier properties, the device has an excellent protective effect.

[container]
The resin composition of the present invention is particularly useful as a molding material for containers among the above-mentioned various applications due to its excellent impact resistance, transparency and gas barrier properties, and its contents can be easily confirmed by its excellent transparency. In addition, its excellent impact resistance and gas barrier properties stabilize the contents by preventing deterioration of the contents and composition changes due to external stress, permeation from the outside air, or dissipation of the contents. Can be saved. In particular, in the case of a liquid contact member of a pharmaceutical container such as a prefilled syringe, an ampule or an infusion bag, and further a laminate composed of multiple layers, it is most suitable as an inner layer material or an intermediate layer material.

  EXAMPLES Hereinafter, although this invention is demonstrated still in detail using an Example, this invention is not limited by a following example, unless the summary is exceeded. In addition, various production conditions and evaluation result values in the following examples have meanings as preferred values of the upper limit or the lower limit in the embodiment of the present invention, and the preferred range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

In the following, various physical properties were measured according to the following methods.
(1) Molecular weight:
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the hydrogenated block copolymer or block copolymer are measured by gel permeation chromatography (GPC) and calculated in terms of standard polystyrene under the following conditions. It was.
Apparatus: Waters 2690 manufactured by Nippon Waters Co., Ltd.
Detector (RI detection): Waters 2410 manufactured by Nippon Waters Co., Ltd.
Column: Shodex KF-604, KF-603, manufactured by Showa Denko KK
Three each of KF-602.50 were connected in series.
Solvent: Tetrahydrofuran Flow rate: 0.7 mL / min
Temperature: 40 ° C

(2) Hydrogenation rate:
The hydrogenation rate (mol%) of the aromatic ring of the hydrogenated block copolymer was calculated by measuring a ¹ H-NMR spectrum.

(3) Haze and total light transmittance A film having a thickness of 0.1 mm was formed, and the total light transmittance and diffuse transmittance were measured on this film based on JIS K7105, and the haze was calculated by the following formula. . A smaller haze value and a larger total light transmittance are evaluated to be excellent in transparency.
[Haze] = [[diffuse transmittance] / [total light transmittance]] × 100

(4) Tensile modulus Based on JIS K7113, a film test piece having a length of 400 mm, a width of 10 mm, and a thickness of 0.1 mm was prepared so that the horizontal direction was the measurement direction, and an autograph AG-1000 manufactured by Shimadzu Corporation was used. The tensile modulus was measured under the conditions of a temperature of 23 ° C. and a tensile speed of 1 mm / min. The tensile modulus is an index of flexibility, and the smaller the tensile modulus, the better the flexibility.

(5) Water vapor permeability The water vapor permeability (g / m ² · 24 h) was determined by an infrared sensor method based on JIS K7129 B method (MOCON method) using a film having a thickness of 0.1 mm. The smaller the value of water vapor permeability, the better the gas barrier property.

[Example 1]
<Production of hydrogenated block copolymer (hydrogenation of block copolymer)>
In a stainless steel autoclave equipped with a stirrer, a solution comprising 25 parts by weight of a styrene-isobutylene-styrene block copolymer having a polystyrene block content of 30% by weight, Mw = 111000 and Mn = 82100, and 75 parts by weight of tetrahydrofuran; Then, 4 parts by weight of 5% by weight palladium on activated carbon catalyst was added and mixed as a hydrogenation catalyst. The inside of the reactor was replaced with hydrogen gas, and hydrogen gas was supplied while stirring the solution, and a hydrogenation reaction was performed at a temperature of 170 ° C. and a pressure of 10 MPa for 4.5 hours.

  After completion of the hydrogenation reaction, the reaction solution was diluted with 100 parts by weight of tetrahydrofuran, and the solution was filtered to remove the hydrogenation catalyst. The filtrate was poured into 1200 parts by weight of methanol with stirring, and the precipitated hydrogenated block copolymer was separated by filtration and dried by a vacuum dryer.

  The hydrogenated block copolymer thus obtained was represented by the following formula, the weight average molecular weight (Mw) was 103000, and the number average molecular weight (Mn) was 78200 (Mw / Mn = 1.3). . The hydrogenation rate was 97%. In Table 1, the obtained hydrogenated block copolymer was described as “(X-1)”.

<Film molding of resin composition>
15 parts by weight of the hydrogenated block copolymer obtained above and a polymer having a repeating unit represented by the formula (2) (R ³ and R ⁴ form a cyclopentyl ring structure, and d is 0. The repeating unit of the formula (2) corresponds to a hydrogenated product of a ring-opening polymer of dicyclopentadiene represented by the formula (3)), and represented by the formula (3) A compound containing 85 mol% of a hydrogenated product of a ring-opening polymer of dicyclopentadiene (“Zeonor (registered trademark) 1020R” manufactured by Nippon Zeon Co., Ltd. (MFR 2.0 g / min (230 ° C., 21.2 N))) A twin screw extruder KZW15 (screw diameter 15 mmφ, biaxial in the same direction L / D = 45) with a weight of 85 parts by weight and a coat hanger type die with a width of 150 mm and a lip opening of 0.8 mm made by Technobel Then, the film was extruded at a set temperature of 260 ° C. at a rotation speed of 500 rpm, and a film having a thickness of 0.1 mm was obtained by taking it out with a 150 mmφ cooling roll at a roll temperature of 10 ° C. and a line speed of 5 m / min. "Trademark) 1020R" is represented as "(Y-1)" in Table-1.

<Evaluation>
The obtained films (3) to (5) were evaluated and the results are shown in Table-1.

[Comparative Example 1]
In Example 1, the resin composition was prepared and film-formed in the same manner except that the styrene-isobutylene-styrene block copolymer was melt-kneaded with "Zeonor (registered trademark) 1020R" without being hydrogenated. The evaluation results are shown in Table 1. In Table 1, an unhydrogenated styrene-isobutylene-styrene block copolymer is represented as “(Z-1)”.

From Table 1, it can be seen that the resin composition of the present invention is excellent in transparency and gas barrier properties.
In contrast, Comparative Example 1 using a block copolymer that was not hydrogenated was inferior in transparency and gas barrier properties as compared to Example 1.

Claims (9)

The resin composition containing the following component (X) and component (Y).
Component (X): Hydrogenated block copolymer having hydrogenated vinyl aromatic polymer block A and block B of polymer mainly composed of isobutylene Component (Y): Copolymer of ethylene and cyclic olefin (y1 ) And a hydrogenated product (y2) of a ring-opened polymer of a cyclic olefin   The resin composition according to claim 1, wherein the component (X) has a weight average molecular weight of 10,000 or more and 200,000 or less.   The resin composition according to claim 1 or 2, wherein the component (X) has two or more hydrogenated vinyl aromatic polymer blocks A.   The resin composition according to any one of claims 1 to 3, wherein the vinyl hydride aromatic polymer block A is a hydrogenated polystyrene block obtained by hydrogenating an aromatic ring.   The resin composition according to any one of claims 1 to 4, wherein a hydrogenation rate of the aromatic ring of the hydrogenated vinyl aromatic polymer block A is 50 mol% or more.   The resin composition according to any one of claims 1 to 5, wherein the block B of the polymer mainly composed of isobutylene contains 70% by weight or more of isobutylene as a monomer component. object.   The resin according to any one of claims 1 to 6, wherein the content of the component (X) is 5 to 90% by weight and the content of the component (Y) is 95 to 10% by weight. Composition.   The film which consists of a resin composition of any one of Claims 1 thru | or 7.   A container comprising the resin composition according to any one of claims 1 to 7.