JP2007002155A - Resin composition and its molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which is excellent in transparency, moisture resistance, stiffness, chemical resistance, heat resistance, and sanitary properties, also is excellent in impact resistance and moldability, and can be suitably used for medical applications which require sterilizability and elution characteristics, as well as for such application as optical components. <P>SOLUTION: The resin composition comprises a component (A) which is an amorphous cycloolefin-based polymer having glass transision temperature of ≥130°C and a component (B) which is a block copolymer expressed in general formula [(A-B)<SB>n</SB>] and/or [(A-B)<SB>n</SB>-A], wherein A is a copolymer block of a vinyl aromatic hydrocarbon, B is a copolymer block of a vinyl aromatic hydrocarbon, which may be hydrogenated, and a conjugated diene, and n is an integer of 1-5. The resin composition can be also used for medical applications such as for a liquid medicine where the use of conventional moldings has been limited because of various kinds of problems associated. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin composition and a molded body thereof. Specifically, a resin that has excellent impact resistance and molding processability without losing the characteristics of an amorphous cyclic olefin polymer that excels in transparency, heat resistance, rigidity, moisture resistance, chemical resistance, hygiene, etc. The present invention relates to a composition and a molded body thereof.

  The cyclic olefin polymer is a general term for polymers containing alicyclic hydrocarbon groups in the molecule. As the polymer, an addition polymer of an α-olefin and a cyclic olefin and a ring-opening homopolymer of the cyclic olefin are known. Each of these polymers has a cyclic olefin as a polymerization constitutional unit, and not only has excellent solvent resistance and water resistance derived from polyolefin, but also has high transparency, heat resistance and moisture resistance, and gas permeability. Is also low. As the transparent plastic, polycarbonate, acrylic resin, etc. are typical, and are widely used together with cyclic olefin polymers, but there are unsolved problems in terms of hygiene, elution resistance, etc., especially in medical applications.

  Conventionally, medical molded products that have been mainly used for glass containers have problems in handling safety (breakage, etc.) and hygiene in repeated use. Disposal containers made of polypropylene or polyethylene are currently used instead of glass. Then it is mainstream. Furthermore, in recent years, a “prefilled method” in which a chemical solution is filled and stored for various purposes such as simplification of work and prevention of human error has been proposed and commercialized. However, currently used molded products such as polypropylene are difficult to store for long periods of time due to problems such as oxygen and humidity (moisture) permeability, and are difficult to see due to lack of transparency. The problem has also occurred.

  These problems can be improved by using a cyclic olefin polymer. However, amorphous polyolefin resins have low impact resistance, low fluidity and low moldability, which makes it difficult not only to handle but also difficult to mold complex molded bodies. It has occurred.

  These problems can be improved to some extent, for example, by changing the copolymerization ratio of the cyclic olefin and the α-olefin or changing the structure of the cyclic olefin polymer itself. However, the improved method by changing the copolymerization ratio reduces the glass transition temperature and heat resistance, and the method of changing the structure of the cyclic olefin polymer itself has a sufficient level of improvement in impact resistance. It can not be said. In addition, these methods have a problem in molding processability due to insufficient fluidity of the resin, and also have difficulty in mold release after injection molding.

  As other methods, a method of blending a polyolefin or ethylene rubber-like polymer with a cyclic olefin polymer (see Patent Document 1), a random copolymer of a conjugated diene-vinyl aromatic compound with a cyclic olefin polymer. Many methods using polymer alloy techniques such as a method of blending (see Patent Document 2) and a method of blending an aromatic vinyl compound-isobutylene block copolymer with a cyclic olefin polymer (see Patent Document 3) have been reported. ing.

According to the methods shown in the above documents, although improvement in impact resistance and molding processability is recognized, transparency is impaired, and a large amount of blending is required to obtain impact resistance, which is necessary for medical use. There are various problems such as heat resistance and gas permeability that cannot be ensured.
JP-A-6-136245 JP-A-6-316652 JP-A-9-124854

  The present invention has been made in view of the above circumstances, and features of an amorphous polyolefin resin (cyclic olefin polymer) excellent in transparency, moisture resistance, rigidity, chemical resistance, heat resistance, hygiene, and the like. An object of the present invention is to provide a resin composition excellent in impact resistance and molding processability, and a molded article thereof without impairing the properties.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by blending an amorphous cyclic olefin polymer with a styrene thermoplastic elastomer having a specific structure. Is completed.

That is, the gist of the present invention resides in a resin composition containing the following components (A) and (B).
(A) Amorphous cyclic olefin polymer having a glass transition temperature of 130 ° C. or higher
(B) A block copolymer represented by the general formula [(AB) _n ] and / or [(AB) _n -A] (wherein A represents a polymer block of vinyl aromatic hydrocarbon). B represents a copolymer block of vinyl aromatic hydrocarbon and conjugated diene which may be hydrogenated, and n is an integer of 1 to 5.)

Moreover, the other summary of this invention exists in the molded object obtained by shape | molding the resin composition containing the following component (a) and (b).
(A) Amorphous cyclic olefin polymer having a glass transition temperature of 130 ° C. or higher
(B) A block copolymer represented by the general formula [(AB) _n ] and / or [(AB) _n -A] (wherein A represents a polymer block of vinyl aromatic hydrocarbon). B represents a copolymer block of vinyl aromatic hydrocarbon and conjugated diene which may be hydrogenated, and n is an integer of 1 to 5.)

In addition, another gist of the present invention is to provide the following resin composition containing component (a) and component (b) in which the content of component (a) is less than 50% by mass, and pellets of component (a). Dry blending, if necessary, further melt-kneading to produce a resin composition having a component (b) content of 95-50% by mass and a component (b) content of 5-50% by mass Exist.
(A) Amorphous cyclic olefin polymer having a glass transition temperature of 130 ° C. or higher
(B) A block copolymer represented by the general formula [(AB) _n ] and / or [(AB) _n -A] (wherein A represents a polymer block of vinyl aromatic hydrocarbon). B represents a copolymer block of vinyl aromatic hydrocarbon and conjugated diene which may be hydrogenated, and n is an integer of 1 to 5.)

  According to the present invention, a resin composition excellent in impact resistance and molding processability as well as transparency, moisture resistance, rigidity, chemical resistance, heat resistance and hygiene can be obtained. This resin composition can be suitably used not only for medical applications requiring sterilization resistance and elution characteristics, but also for optical parts. In particular, the conventional medical molded body has remarkable value in the medical field such that it can be used for applications such as chemical liquid types, containers, and container lids that have been limited by various problems.

1. Component (a) Amorphous Cyclic Olefin Polymer with a Glass Transition Temperature of 130 ° C. or More Component (A) constituting the resin composition as a raw material of the molded article of the present invention is a component of the cyclic olefin. It is a polymer, has a cyclic structure in the side chain, has an amorphous property in which a melting point by a differential scanning calorimeter (DSC) measurement is not substantially observed, and has a glass transition temperature of 130 ° C. or higher. Refers to things. Specific examples include addition homopolymers of cyclic olefins, addition copolymers of cyclic olefins and α-olefins, and ring-opening (homo) polymers of cyclic olefins. A part or all of the main chain of the ring-opening polymer may be hydrogenated.

Cycloolefins for the production of addition (homo) polymers include bicyclo (2.2.1) -2-heptene, 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-methyl tetracyclo (4.4.0.1 ^2,5 .1 ^7,10) -3- dodecene, 8 , 9-dimethyl-tetracyclo (4.4.0.1 ^2,5 .1 ^7,10) -3- but dodecene and the like as an example, not limited thereto. Examples of cyclic olefins include DCPD (dicyclopentadiene), Diels-Alder adduct of CPD (cyclopentadiene) and olefin. These cyclic olefins can be used alone or in combination of several kinds.

  Copolymerization components for the production of addition copolymers include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, etc. Examples thereof include 2 to 20 α-olefins. These α-olefins are usually used in an amount of 50 to 90 mol%, preferably 50 to 70 mol%, based on the cyclic olefin. When the copolymerization amount of α-olefin is too large, crystallinity of the resulting addition copolymer may appear.

Cyclic olefins for the production of ring-opening (homo) polymers include bicyclo (2.2.1) -2-heptene, 5-methylbicyclo (2.2.1) -2-heptene, 5,6-dimethylbicyclo (2.2 .1) -2-heptene, 5-carboxymethyl-bicyclo (2.2.1) -2-heptene, dicyclopentadiene, 2,3-dihydro-dicyclopentadiene, tetracyclo (4.4.0.1 ^{2, 5} .1 ^7,10) 3-dodecene, 8-methyl tetracyclo (4.4.0.1 ^2,5 .1 ^7,10) -3- dodecene, 8-ethyl-tetracyclo (4.4.0.1 ^2,5 .1 ^7,10) -3- dodecene , 8-carboxymethyl tetracyclododecene (4.4.0.1 ^2,5 .1 ^7,10) -3- dodecene, 8-methyl-8-carboxymethyl tetracyclododecene (4.4.0.1 ^2,5 .1 ^7,10) -3 -Dodecene is an example, but not limited to this.

Various known methods can be employed as the production method by addition polymerization. For example, polymerization can be performed using a Ziegler catalyst or a metallocene catalyst. More specifically, a copolymer component such as a cyclic olefin and ethylene is combined with a promoter such as a soluble vanadium compound, a soluble titanium compound, a soluble zirconium compound, and an organoaluminum compound in a hydrocarbon solvent such as cyclohexane. The polymerization can be carried out at a temperature range of -50 to 100 ° C., usually at a pressure range of 0 to 50 kg / cm ² .

Various known methods can also be adopted as a production method by ring-opening polymerization. For example, in a catalyst system containing a cyclic olefin as a transition metal compound or an organometallic compound such as a platinum group metal compound and an organoaluminum compound, if necessary, in the presence of an additive such as an aliphatic or aromatic tertiary amine. , the temperature range of usually -20 to 100 ° C., usually can be polymerized at a pressure range of 0~50kg / cm ^2. Furthermore, the hydrogenation reaction after polymerization can also be carried out in the presence of a known hydrogenation catalyst.

  If the manufacturing method of the cyclic olefin polymer demonstrated above is illustrated by reaction formula, it will be as FIG. (1) shows a method for producing an addition copolymer, and (2) shows a method for producing a ring-opening homopolymer.

  The cyclic olefin polymer obtained as described above needs to have a glass transition temperature of 130 ° C. or higher, preferably 135 ° C. or higher, from the viewpoint of heat resistance as the resin composition of the present invention. . In order to obtain a good thermoplastic material, the glass transition temperature is preferably 250 ° C. or lower, particularly 230 ° C. or lower. The glass transition temperature can be controlled by appropriately selecting the structure of the cyclic olefin, the polymerization method, the copolymer substance, the copolymerization ratio, and the like. The glass transition temperature was measured according to JIS K7191.

  Moreover, the cyclic olefin polymer obtained needs to be amorphous. Here, the term “amorphous” means that substantially no melting point is observed by differential scanning calorimetry (DSC) measurement. A crystalline polymer having a substantially melting point cannot be used in the present invention because of poor transparency. As for the cyclic olefin-based polymer, those obtained under normal polymerization conditions are generally non-crystalline unless the copolymerization monomer other than the cyclic olefin monomer is excessively large. The DSC measurement is performed according to JIS K7121.

Commercially available products of the above amorphous cyclic olefin polymers include “Apel 6015” manufactured by Mitsui Chemicals, “Zeonex 480” “Zeonor” manufactured by Nippon Zeon, “Arton” manufactured by JSR, “ Topas "and the like. In the present invention, those having a glass transition temperature of 130 ° C. or higher may be selected from these commercially available products.
(B) A block copolymer represented by the general formula [(AB) _n ] and / or [(AB) _n -A] (wherein A represents a polymer block of vinyl aromatic hydrocarbon). B represents a copolymer block of vinyl aromatic hydrocarbon and conjugated diene which may be hydrogenated, and n is an integer of 1 to 5.)
The component (b) comprises a vinyl aromatic hydrocarbon polymer block (A) and a vinyl aromatic hydrocarbon / conjugated diene copolymer block (B). The polymer block (A) constitutes a hard segment, and the copolymer block (B) constitutes a soft segment. Typically, a block copolymer having a copolymer structure represented by A-B or A-B-A, in which a double bond of a conjugated diene may be partially or completely hydrogenated. It is a coalescence.

  Examples of the compound constituting the vinyl aromatic hydrocarbon polymer block (A) include styrene, α-methylstyrene, o-, m-, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene and vinyl. Anthracene and the like can be mentioned, among which styrene is preferable. They can also be used as a mixture.

  The vinyl aromatic hydrocarbon constituting the copolymer block (B) of the copolymer of vinyl aromatic hydrocarbon and conjugated diene is the same as the compound constituting the polymer block (A). On the other hand, examples of the conjugated diene compound constituting the copolymer block (B) include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like. Among them, butadiene, Isoprene or a mixture of both butadiene / isoprene is preferred.

  The vinyl aromatic hydrocarbon-conjugated diene copolymer block (B) constitutes a soft segment and is a random copolymer from the viewpoint of increasing the flexibility of the composition and reducing the resilience. Preferably there is.

  In the present invention, the block copolymer comprising a polymer block (A) -copolymer block (B) or a polymer block (A) -copolymer block (B) -polymer block (A) The lower limit of the content of (A) is usually 3% by mass, preferably 4% by mass, more preferably 5% by mass with respect to the total amount of (A) and (B). 70% by mass, preferably 50% by mass, and more preferably 30% by mass. The content of (A) is preferably at least the above lower limit from the viewpoint of mechanical strength and heat resistance as the composition, and is preferably at most the above upper limit in terms of flexibility.

  When the copolymer block (B) is used after hydrogenation, the hydrogenation rate is usually 30% or more, preferably 50% or more, particularly 90% or more. From the viewpoint of improving the weather resistance and heat resistance of the composition, the hydrogenation rate is preferably at least the above lower limit.

  The molecular weight of the component (b) of the present invention is preferably 50,000 to 500,000 as a polystyrene-reduced weight average molecular weight measured by gel permeation chromatography (GPC), and 70,000 to 300,000. Are particularly preferred. The weight average molecular weight of the thermoplastic elastomer composition is preferably not less than the above lower limit from the viewpoint of mechanical strength, and is preferably not more than the above upper limit from the viewpoint of scratchability and moldability. The molecular weight can be usually measured using a liquid chromatograph or a chromatograph dedicated to SEC (size exclusion chromatograph). The measurement conditions are not particularly specified, but as an example, chloroform as a solvent, flow rate 0.5 mL / min, normal temperature, measurement concentration 0.1 mass%, injection volume 20 μL, for example, Tosoh TSK gelsuper HM It can be measured using a column such as -M. As a detection method, a normal method such as UV detection or RI detection can be employed. In the case of UV detection, since the detection ratio varies depending on the content of vinyl aromatic hydrocarbon, correction is required each time. In the case of RI detection, such correction is unnecessary and is convenient. The calculation method is generally used polystyrene conversion.

  In the present invention, the vinyl aromatic hydrocarbon polymer block (A) -vinyl aromatic hydrocarbon and conjugated diene copolymer block (B) block copolymer of conjugated diene in the block copolymer, vinyl aromatic The structure of the hydrocarbon polymer block was determined by measuring the nuclear magnetic resonance spectrum (NMR). C. Randall, J. et al. Polym. Sci. Polym. Phs. Ed. , Vol. 13, 901 (1975), and obtained by assigning a signal.

  As a manufacturing method of the block copolymer used in the present invention, any manufacturing method may be used as long as the above structure and physical properties can be obtained. For example, it can be obtained by performing block polymerization in an inert solvent using a lithium catalyst or the like by the method described in Japanese Patent Publication No. 40-23798. The hydrogenation treatment of these block copolymers is described in, for example, JP-B-42-8704, JP-B-43-6636, JP-A-59-133203, and JP-A-60-79005. The process described can be carried out in the presence of a hydrogenation catalyst in an inert solvent.

  An example of the reaction sequence for forming the block may be obtained by first polymerizing styrene or a derivative thereof alone, then copolymerizing styrene and a conjugated diene, and coupling them with a coupling agent. Alternatively, styrene and a conjugated diene can be polymerized using a dilithium compound as an initiator, and then styrene or a derivative thereof can be sequentially polymerized.

2. Blending ratio of each component The blending ratio of the components (A) and (B) is preferably in the range of (A) / (B) = 95/5 to 50/50. That is, it is preferable that content of component (a) and (b) is 95-50 mass% and component (b) is 5-50 mass% with respect to the total amount of both. The above upper limit is preferable in terms of the effect of improving impact resistance, and the above lower limit is preferable in terms of heat resistance and rigidity.

3. Additional components In addition to the above components, the resin composition that is a raw material of the molded article of the present invention includes other optional compounding components depending on the purpose within a range that is compatible with the use of the present invention and does not impair the effect. Can be blended. Optional components include, for example, softeners, fillers, antioxidants, heat stabilizers, light stabilizers, UV absorbers, neutralizers, lubricants, antifogging agents, antiblocking agents, slip agents, dispersants, and coloring. Agents, flame retardants, antistatic agents, conductivity-imparting agents, metal deactivators, molecular weight modifiers, antibacterial agents, antifungal agents, fluorescent brighteners and other additives, thermoplastic resins other than the above essential components Further, elastomers and fillers other than the above essential components can be mentioned, and any of these can be used alone or in combination.

  The blending amount of these optional components is not particularly limited as long as the excellent effects of the present invention are not significantly impaired. However, in the case of a resin or elastomer component, the content in the entire resin composition is usually 40 masses. % Or less, particularly 10% by mass or less, and more preferably 5% by mass or less. In various function-imparting agents, the content is preferably 2% by mass or less, particularly 1% by mass or less.

4). Compounding method The compounding method for obtaining the resin composition as the raw material of the molded article of the present invention includes a commonly used melting method, solution method, suspension dispersion method, and the like, and is not particularly limited. Practically, the melt kneading method is preferable. For melt-kneading, a Henschel mixer, ribbon blender, V-type blender, etc. are used to uniformly mix, and then a usual kneader such as a Banbury mixer, kneader, roll, uniaxial or biaxial multiaxial kneading extruder is used. A method of kneading can be exemplified.

  The melt kneading temperature of each component may be a temperature that exceeds the melting point of the component to be used and becomes a molten state, but it is preferably 280 ° C. or less in consideration of resin degradation and the like. In addition, in order to avoid discoloration and the like, it is preferable to employ a method that further reduces oxidation of the resin in melt-kneading as much as possible, such as injecting an inert gas from the feed portion or making a vacuum using a pump or the like.

  Furthermore, the kneading order and method of each component are not particularly limited, and a method of kneading the compounded materials at once, a part of which is kneaded, and then the remaining components including the additional compounded material are kneaded. It may be a method.

5. Molding method The obtained resin composition is formed by, for example, injection molding, extrusion molding, inflation molding, T-die film molding, laminate molding, blow molding, hollow molding, compression molding, calendar molding, and the like. It can be directly molded by the method. Also, a method of obtaining a molded body by a method such as vacuum forming from a sheet formed by extrusion molding or the like can be adopted, but it is mainly suitable for injection molding.

  It is also possible to perform insert injection molding, two-color injection molding, etc. with other resins such as polyolefin resins such as polyethylene and polypropylene, and to form laminated films and sheets in T-die molding and laminate molding methods. .

  In the case of performing various molding processes such as injection molding, the resin composition of component (a) (b), which contains a relatively small amount (less than 50% by mass) of component (b), is added to component (b). A dry blend of single pellets can be used. Thereby, content of the component (I) (B) in a resin composition can be easily controlled to a desired value. That is, this is an embodiment in which the pellet of component (a) alone is used as a master batch.

6). Physical Properties of Molded Body The molded body of the present invention is excellent in heat resistance, and the heat distortion temperature measured according to JIS-K7191 (measurement under a 0.45 MPa load) is usually 120 ° C. or higher.

  The molded article of the present invention is excellent in transparency, and the haze (degree) measured in accordance with JIS-K7105 is usually 20% or less, preferably 15% or less, and particularly preferably 10 % Or less. Similarly, the total light transmittance (measured using an integrating sphere type light transmittance measuring device with a 2 mm thick injection-molded plate) is usually 80% or more, preferably 85% or more, particularly preferably. Is 90% or more.

Further, the molded article of the present invention is excellent in impact resistance, and the Izod impact strength (using a molded piece with a mold notch) measured in accordance with JIS-K7110 is usually ² kJ / m ² or more, preferably and a 3 kJ / m ² or more and 6 kJ / m ² or more particularly preferred.

7). Fields of Use The resin composition of the present invention and the molded product thereof are excellent in transparency, heat resistance, gas permeability, hygiene, etc., and not only improve molding processability in medical syringes and various containers, but also autoclaves. It can be used for sterilization, and it can also be used for pre-filled chemicals that are stored after injection. It is also suitable for optical parts.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. The raw materials and physical property evaluation methods used in the following examples and comparative examples are shown below.

1. Raw material component (I): Cyclic olefin polymer component I-1; “Apel 6015T” manufactured by Mitsui Chemicals, Inc. Glass transition temperature 145 ° C., MFR 7 g / 10 min (260 ° C., load 21 N).
B-2: “ZEONEX 480” manufactured by Nippon Zeon Co., Ltd. Glass transition temperature 139 ° C., MFR 20 g / 10 min (280 ° C., load 21 N).
I-3; "Appel 6509" manufactured by Mitsui Chemicals, Inc. Glass transition temperature 80 ° C., MFR 30 g / 10 min (260 ° C., load 21 N).

Component (b): Styrene elastomer component Row 1; Hydrogenated triblock copolymer consisting of styrene polymer block-styrene / butadiene random copolymer block-styrene polymer block (total styrene content: 60% by mass) Styrene polymer block content: 45% by mass, hydrogenation rate: 99%, weight average molecular weight: 162,000, 1,2-vinyl bond content of butadiene: 60%)
B-2: Hydrogenated triblock copolymer consisting of styrene polymer block-styrene / butadiene random copolymer block-styrene polymer block (total styrene content: 39% by mass, styrene polymer block content: (19% by mass, hydrogenation rate: 99%, weight average molecular weight: 127,000, 1,2-vinyl bond content of butadiene: 35%)

Component (C): Resin component C-1 used for others; “Dynalon 1322P” manufactured by JSR Corporation. Hydrogenated product of styrene / butadiene random copolymer.
C-2: “Dynalon 4600P” manufactured by JSR Corporation. Hydrogenated product of a triblock copolymer composed of styrene-butadiene-butadiene (the terminal butadiene block is a complete 1,4 bond, and thus has a chemical structure similar to that of crystalline polyethylene after hydrogenation).
C-3: “Septon 2104” manufactured by Kuraray Co., Ltd. Hydrogenated product of styrene-isoprene-styrene triblock copolymer.
C-4: A homopropylene polymer having an MFR of 20 g / 10 min (230 ° C., 21 N) and a flexural modulus of 1500 MPa.

2. Physical property evaluation method (1) Melt flow rate (MFR)
Using pellets of the resin composition obtained by melt-kneading, measurement was performed under the conditions of 230 ° C. and a load of 49 N in accordance with JIS-K7210.
(2) Bending elastic modulus Injected using an in-line screw type injection molding machine (“IS130” manufactured by Toshiba Machine Co., Ltd.) using JIS family molds under conditions of an injection pressure of 50 MPa, a cylinder temperature of 240 ° C., and a mold temperature of 40 ° C. It measured based on JIS-K7171 (1993) using the various molded products shape | molded.
(3) Tensile property It measured based on JIS-K7161 using the injection molded product similar to the above.
(4) Izod impact strength It measured based on JIS-K7110 using the injection molded product similar to the above. As the molded product, a molded piece with a mold notch was used.
(5) Thermal deformation temperature Using the same injection molded product as described above, it was measured at a load of 0.45 MPa in accordance with JIS-K7191.
(6) Light transmittance and haze Based on JIS-K7105, it measured on the injection molding board of thickness 2mm using the integrating sphere type light transmittance measuring apparatus.
(7) Water vapor permeability A film having a thickness of 0.50 ± 0.05 mm was molded at a press molding temperature of 220 ° C. using a hydraulic electric press molding machine. Using this film, measurement was performed at a test temperature of 40 ° C. and 90% RH using a measuring apparatus “PERMATRAN W200 manufactured by Motan Control Co., Ltd.” in accordance with JIS-K7129B method.
(8) Oxygen permeability Based on the JIS-K7126B method, the oxygen permeability was measured at a test temperature of 23 ° C. using a measuring device “manufactured by MOCON, OXTRAN 10 / 50A”.
(9) Carbon dioxide permeability Using the same film as described above, measurement was performed at a test temperature of 23 ° C. using a measuring apparatus “manufactured by Toyo Seiki Co., Ltd., differential pressure type gas permeation tester” in accordance with JIS-K7126A method.

[Examples 1 to 5]
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl) is added to 100 parts by mass of the total amount of components (A) to (C) blended in the blending amounts (parts by mass) shown in Table 1. -4′-hydroxyphenyl) propionate] 0.1 parts by mass of methane (manufactured by Ciba Specialty Chemicals, “Irganox 1010”) was added, and 230 using a twin screw extruder with L / D of 33 and cylinder diameter of 44 mm. The mixture was melt kneaded at a temperature of 0 ° C., extruded from a die into a strand shape, and cut to obtain pellets of a resin composition. The obtained pellets were evaluated by the various methods described above. The evaluation results are shown in Table 1.

[Comparative Examples 1 to 10]
Pellets were obtained and evaluated in the same manner as in the above examples with respect to 100 parts by mass of the total amount of components (I) to (C) blended in the blending amounts (parts by mass) shown in Table 2. The evaluation results are shown in Table 2.

From Tables 1 and 2, the following is clear.
(1) According to the examples of the present invention, the light transmittance of 85% or more is achieved, and the Izod impact strength is at least 6 kJ / m ² or more.
(2) As can be seen from Comparative Examples 1 to 3, although the light transmittance is excellent when the cyclic olefin polymer is used alone, it is inferior in Izod impact strength.
(3) As can be seen from Comparative Examples 4 to 10, in a composition obtained by adding a hydrogenated product of a block copolymer other than the present invention to a cyclic olefin polymer, or in homopolypropylene, transparency (HAZE) and Any of light transmittance, Izod impact strength, or heat distortion temperature is poor.

An example of a production reaction of the cyclic olefin polymer used in the present invention will be shown.

Explanation of symbols

1: Addition copolymer 2: Ring-opening homopolymer (including hydrogenation)
R ₁ , R ₂ , R ₃ : hydrogen or hydrocarbon group l, m, n: degree of polymerization (number of repeating units)

Claims (8)

A resin composition containing the following components (A) and (B).
(A) Amorphous cyclic olefin polymer having a glass transition temperature of 130 ° C. or higher
(B) A block copolymer represented by the general formula [(AB) _n ] and / or [(AB) _n -A] (wherein A represents a polymer block of vinyl aromatic hydrocarbon). B represents a copolymer block of vinyl aromatic hydrocarbon and conjugated diene which may be hydrogenated, and n is an integer of 1 to 5.)   The resin composition according to claim 1, wherein the copolymer block B of vinyl aromatic hydrocarbon and conjugated diene is a hydrogenated product of a copolymer block of styrene and butadiene.   The content of component (a) and (b) is 95 to 50% by mass of component (b) and 5 to 50% by mass of component (b) with respect to the total amount of both. Resin composition.   The molded object obtained by shape | molding the resin composition of any one of Claims 1-3. The heat distortion temperature of the molded body is 120 ° C or higher, the light transmittance of a flat molded body having a thickness of 2 mm is 80% or higher, and the Izod impact strength is ² kJ / m ² or higher. 4. The molded product according to 4.   The molded body according to claim 4 or 5, wherein the molded body is a container or a container lid.   The molded body according to any one of claims 4 to 6, which relates to a medical molded body. The following resin composition containing components (a) and (b) having a content of component (a) of less than 50% by mass is dry-blended with the component (a) pellets and further melted if necessary. A method of kneading to produce a resin composition having a component (A) content of 95 to 50% by mass and a component (B) content of 5 to 50% by mass.
(A) Amorphous cyclic olefin polymer having a glass transition temperature of 130 ° C. or higher
(B) A block copolymer represented by the general formula [(AB) _n ] and / or [(AB) _n -A] (wherein A represents a polymer block of vinyl aromatic hydrocarbon). B represents a copolymer block of vinyl aromatic hydrocarbon and conjugated diene which may be hydrogenated, and n is an integer of 1 to 5.)

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