Resin composition and film made therefrom

Abstract

To provide a resin composition which keeps high transparency and is formed of cyclic polyolefin and an ethylenic polymer.SOLUTION: A resin composition contains: 5-95 wt.% of cyclic polyolefin (A) having a glass transition temperature of 125°C or higher and a refractive index according to JIS K 7142 of 1.52 to 1.54; and 5-95 wt.% of an ethylenic polymer (B) having a long chain branch having 6 or more carbon atoms which has a refractive index according to JIS K 7142 of 1.52 to 1.53, and has a ratio (Mw / MN) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) in molecular weight measurement by gel permeation chromatography of 2-7.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to resin compositions and films made therefrom. More specifically, it relates to resin compositions and films made therefrom that are suitable for medical films or components used in intravenous fluids and food packaging, and for food films or components. [Background technology]

[0002] Medical films or components used to package liquid medicines, blood, etc., and food films used to package food products require transparency to allow visual confirmation of the presence or absence of foreign matter, as well as the ability to prevent the dissipation of active ingredients in the liquid or contents.

[0003] Conventionally, polyolefin resins and cyclic polyolefin resins have been used for medical and food films that meet these performance requirements. However, because cyclic polyolefin resins have a glass transition temperature above room temperature, films made solely of cyclic polyolefins have limitations in terms of impact resistance, such as cracking under impact.

[0004] Therefore, various resin compositions have been developed by blending cyclic polyolefins, which are the material for films, with linear polyolefins such as polyethylene and polypropylene, styrene block copolymers, isobutylene copolymers, etc., and medical films using resin compositions consisting of cyclic polyolefins and linear polyolefins, etc., have been proposed (see, for example, Patent Documents 1 to 6).

[0005] However, films made from resin compositions of cyclic polyolefin resin and polyethylene-based resin have drawbacks such as reduced transparency. Similarly, films made from resin compositions of cyclic polyolefin resin and polypropylene have drawbacks such as reduced impact resistance at low temperatures. On the other hand, films made from resin compositions of cyclic polyolefin resin and styrene block copolymer or isobutylene copolymer have drawbacks such as increased film costs. Therefore, the development of a resin that improves the impact resistance of cyclic polyolefin resin has been desired.

[0006] Furthermore, in recent years, multi-chamber containers that allow for the separate storage of multiple components and the mixing of these components within the container immediately before use have been widely used in the field of medical containers. In such multi-chamber containers, it is important to provide easy-peel sealing properties with a wide heat-seal temperature range that allows for the formation of easily peelable seals to isolate adjacent storage compartments.

[0007] Multilayer films have been proposed to provide easy-peel sealing properties. These multilayer films are designed to satisfy various physical properties such as easy-peel sealing, transparency, and heat resistance to heat sterilization.

[0008] As an example of such a multilayer film and a container using the same, Patent Document 2 proposes a medical multi-chamber container in which a composition containing a cyclic polyolefin and a linear polyolefin is used as the sealant layer.

[0009] Patent Document 3 proposes a chemical solution bag that uses a sealant layer made of a composition consisting of two types of linear low-density polyethylene with different densities.

[0010] Patent Document 4 proposes a drug container that uses a composition consisting of linear polyethylene and propylene homopolymer as a sealant layer.

[0011] However, films made from resin compositions of cyclic polyolefin resin and polyethylene-based resin have drawbacks such as reduced transparency. Furthermore, films made from resin compositions of cyclic polyolefin resin and vinyl aromatic hydrocarbon polymers, styrene block copolymers, or isobutylene copolymers have drawbacks such as increased film costs. On the other hand, films made from resin compositions of two types of linear low-density polyethylene with different densities have drawbacks such as insufficient heat resistance to heat sterilization. Additionally, films made from resin compositions of linear polyethylene and propylene homopolymer have drawbacks such as insufficient transparency.

[0012] As a material having easy peelability and having impact resistance and transparency, Patent Documents 5 and 6 propose a resin composition comprising a cyclic polyolefin and a specific ethylene-based polymer.

Prior Art Documents

Patent Documents

[0013]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Summary of the Invention

Problems to be Solved by the Invention

[0014] The resin compositions proposed in Patent Documents 5 and 6 have effects in terms of easy peelability, impact resistance, and transparency and were capable of being developed for food packaging films and the like, but there was a need to improve the stability of chemical solutions in the medical field.

[0015] Therefore, an object of the present invention is to provide a resin composition and a film made therefrom that maintain high transparency as a further improvement of medical or food films made of cyclic polyolefin resins.

[0016] Furthermore, in products using medical or food films, heat treatments such as sterilization and cooking are performed, and an object is to provide a resin composition and a film made therefrom in which chemical solutions, cooking liquids, and contained components (hereinafter sometimes referred to as active ingredients) are stably retained even after the heat treatment.

[0017] Furthermore, an object of the present invention is to provide a resin composition having the easily peelable sealability required for the inner layer of a multilayer film, a film made from the resin composition, and a film in which the resin composition is used as the sealant layer of a multilayer film. [Means for solving the problem]

[0018] As a result of diligent research, the inventors of the present invention discovered that a resin composition containing a specific cyclic polyolefin resin and a specific polyethylene-based resin in specific amounts can solve the above problems, and thus completed the present invention.

[0019] In other words, the various embodiments of the present invention are as follows [1] to

[16] . [1] A resin composition comprising 5 to 95% by weight of a cyclic polyolefin (A) having a glass transition temperature of 125°C or higher and a refractive index of 1.52 to 1.54 according to JIS K7142, and 5 to 95% by weight of an ethylene polymer (B) having a refractive index of 1.52 to 1.53 according to JIS K7142, a ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (Mw / Mn) in the range of 2 to 7 as measured by molecular weight measurement by gel permeation chromatography, and having 0.15 or more long-chain branches with 6 or more carbon atoms per 1,000 carbon atoms of the main chain in fractions with Mn of 100,000 or more after molecular weight fractionation. [2]Cyclic polyolefin (A) has a melt mass flow rate of 10-30 g / 10 min measured at 260°C and 21.18 N in accordance with ASTM D1238, (ii) a melt mass flow rate of 10-60 g / 10 min measured at 280°C and 21.2 N in accordance with ISO 1133, or (iii) a melt volume flow rate of 10-60 cm³ measured at 230°C and 21.18 N in accordance with ISO 1133. 3 The resin composition according to [1], which satisfies at least one of the following conditions: / 10min, wherein the ethylene polymer (B) conforms to JIS K 6922-1 and has a melt mass flow rate of 0.1 to 15 g / 10 min measured at 190°C and a load of 21.18 N. [3] The resin composition according to [1] or [2], wherein the cyclic polyolefin (A) is a polymer containing the unit shown in the following structural formula (1).

[0020] [ka]

[0021] (In formula (1) above, Ra and Rb may be the same or different, and each represents a hydrogen atom or an organic group. Ra and Rb may be bonded to each other to form a ring. m is an integer of 1 or more, and n is an integer of 0 or more.) [4] The resin composition according to any one of [1] to [3], wherein the cyclic polyolefin (A) is a polymer containing 30 mol% or more of the unit shown in the following structural formula (3).

[0022] [ka]

[0023] [5] The resin composition according to [4], wherein the cyclic polyolefin (A) is a polypolymer containing 20 mol% or more of the unit shown in the following structural formula (4).

[0024] [ka]

[0025] [6] The resin composition according to [5], wherein the cyclic polyolefin (A) is a polypolymer containing 10 mol% or more of the unit shown in the following structural formula (5).

[0026] [ka]

[0027] [7] The resin composition according to [5] or [6], wherein the cyclic polyolefin (A) is a multipolymer containing 50 mol% or more of its stereoisomer, the endo form, and less than 50 mol% of its exo form, as units represented by the structural formula (4) above. [8] The ethylene polymer (B) has a density of 930-960 kg / m³ as measured by the density gradient pipe method in accordance with JIS K6922-1. 3 A resin composition according to any one of [1] to [7], which is an ethylene polymer. [9] The resin composition according to any one of [1] to [8], wherein the ethylene polymer (B) exhibits two peaks in molecular weight measurement by gel permeation chromatography.

[10] A resin composition according to any one of [1] to [9], wherein cyclic polyolefin (A) is 50 to 90% by weight and ethylene polymer (B) is 10 to 50% by weight.

[11] A resin composition according to any one of [1] to

[10] , further comprising 20 to 300 parts by weight of high-density polyethylene (C) having 0.14 or fewer long-chain branches with 6 or more carbon atoms per 1,000 carbon atoms of the main chain in fractions of which the Mn after molecular weight fractionation is 100,000 or more.

[12] High-density polyethylene (C) has a density of 940-970 kg / m³ as measured by the density gradient pipe method in accordance with JIS K6922-1. 3 The resin composition described in

[11] , wherein the melt mass flow rate measured at 190°C and a load of 21.18N in accordance with JIS K 6922-1 is 0.1 to 15 g / 10 min.

[13] The resin composition according to

[11] or

[12] , wherein the high-density polyethylene (C) has a Mw / Mn ratio of 2.0 to 3.5 and a Mn ratio of 25,000 or more.

[14] A resin composition according to any one of

[11] to

[13] , comprising 20 to 60 parts by weight of high-density polyethylene (C) per 100 parts by weight of a total of cyclic polyolefin resin (A) and ethylene polymer (B). A film comprising the resin composition described in any of

[15] [1] to

[14] . A film containing the film described in

[16]

[15] as a sealant layer. [Effects of the Invention]

[0028] A resin composition according to one aspect of the present invention can maintain high transparency, and when made into a film, it can maintain high transparency and exhibit the ability to stably retain lipid-soluble vitamins, which are active ingredients. Furthermore, a film according to one aspect of the present invention can exhibit easy peel-off sealability even after sterilization. [Brief explanation of the drawing]

[0029] [Figure 1] This figure shows the relationship between seal strength and sealing temperature after sterilizing the heat-sealed samples in the example at 121°C for 20 minutes and measuring the seal strength. [Modes for carrying out the invention]

[0030] The present invention will be described in detail below.

[0031] A resin composition according to one aspect of the present invention contains 5 to 95% by weight of a cyclic polyolefin (A) having a glass transition temperature of 125°C or higher and a refractive index of 1.52 to 1.54 according to JIS K7142, and 5 to 95% by weight of an ethylene polymer (B) having a refractive index of 1.52 to 1.53 according to JIS K7142, a ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (Mw / Mn) in the range of 2 to 7 as measured by molecular weight measurement by gel permeation chromatography, and having 0.15 or more long-chain branches with 6 or more carbon atoms per 1,000 carbon atoms in the fraction with Mn of 100,000 or more when molecular weight fractionated.

[0032] Cyclic polyolefin (A) is a cyclic polyolefin having a glass transition temperature of 125°C or higher and a refractive index of 1.52 to 1.54 in accordance with JIS K7142, and contains a cyclic olefin component as a polymerization component, and is a polyolefin resin containing a cyclic olefin component in the main chain, and is not particularly limited as long as it is a cyclic polyolefin having a glass transition temperature of 125°C or higher and a refractive index of 1.52 to 1.54 in accordance with JIS K7142. Here, if the cyclic polyolefin has a glass transition temperature of less than 125°C, the resulting resin composition will have poor heat resistance, and problems are likely to arise in maintaining the content of active ingredients during sterilization treatment when used in containers, etc. Also, if the cyclic polyolefin has a refractive index outside the range of 1.52 to 1.54, problems are likely to arise in the transparency of the resulting composition. Examples of cyclic polyolefins include polymers having units shown in the following structural formula (1) (hereinafter sometimes referred to as "polymer (1)") and / or copolymers having units shown in the following structural formula (2) (hereinafter sometimes referred to as "polymer (2)"). Using polymer (1) is particularly preferable because it is less likely to cause appearance defects when the film is formed. However, even when using polymer (2), appearance defects can be prevented by setting the film formation conditions, such as molding temperature, screw rotation speed, and screw design, to appropriate conditions, so this does not preclude the use of polymer (2).

[0033] [ka]

[0034] [ka]

[0035] (In formula (1) above, Ra and Rb may be the same or different, and each represents a hydrogen atom or an organic group, and Ra and Rb may be bonded to each other to form a ring. n is an integer of 0 or more.)

[0036] In formula (2) above, Rc and Rd may be the same or different, and each represents a hydrogen atom or an organic group. Rc and Rd may be bonded to each other to form a ring. n is a non-negative integer. The organic groups Ra, Rb, Rc, and Rd mentioned above include hydrocarbon residues having 1 to 8 carbon atoms, or polar groups such as halogens, esters, nitriles, and pyridyls.

[0037] Polymer (1) is a hydrogenated ring-opening metathesis polymer of an unsaturated cyclic olefin monomer. Examples of the unsaturated cyclic olefin monomer include monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclooctene, and cyclododecene, and their derivatives having substituents, as well as substituted and unsubstituted bicyclic or tricyclic or more polycyclic cyclic olefin monomers having a norbornene ring (hereinafter sometimes referred to as norbornene monomers). From the viewpoint of suitability for manufacturing and suitability for contents, norbornene monomers are preferably used.

[0038] On the other hand, polymer (2) is a copolymer of ethylene and an unsaturated cyclic olefin monomer.

[0039] The unsaturated cyclic olefin monomers constituting polymer (1) and polymer (2) are preferably the norbornene-based monomers mentioned above. More specifically, the norbornene-based monomers include, for example, norbornene, norbornadiene, methylnorbornene, dimethylnorbornene, ethylnorbornene, chlorinated norbornene, chloromethylnorbornene, trimethylsilylnorbornene, phenylnorbornene, cyanonorbornene, dicyanonorbornene, methoxycarbonylnorbornene, and pyridylnorbornene. Examples include bicyclic cycloolefins such as nadic anhydride and nadic acid imide; tricyclic cycloolefins such as dicyclopentadiene, dihydrodicyclopentadiene and their alkyl, alkenyl, alkylidene, and aryl substituted derivatives; tetracyclic cycloolefins such as dimethanohexahydronaphthalene, dimethanooctahydronaphthalene and their alkyl, alkenyl, alkylidene, and aryl substituted derivatives; pentacyclic cycloolefins such as tricyclopentadiene; and hexacyclic cycloolefins such as hexacycloheptadecene. It is also possible to use compounds containing norbornene rings, such as dinorbornene, compounds in which two norbornene rings are linked by a hydrocarbon chain or ester group, and alkyl and aryl substituted derivatives thereof.

[0040] The method for producing polymer (1) is not particularly limited, and various known production methods can be employed. Polymer (1) can be produced, for example, by ring-opening polymerization of the above-mentioned unsaturated cyclic olefin monomer, preferably norbornene-based monomer, and then hydrogenating the olefinic unsaturated bond portion of the resulting polymer. This ring-opening polymerization can be carried out, for example, by polymerizing the unsaturated cyclic olefin monomer in a catalyst system containing a transition metal compound or a platinum group metal compound and an organometallic compound such as an organoaluminum compound, in the presence of additives such as an aliphatic or aromatic tertiary amine as needed, at a temperature in the range of -20 to 100°C and at a rate of 0.01 to 50 kg / cm³. 2 This can be carried out at a pressure within the range of G. Furthermore, this hydrogenation can be carried out in the presence of a conventional hydrogenation catalyst.

[0041] The polymer (1) may be a polymer containing multiple units of different structures, as long as they are the units shown in structural formula (1) above. Furthermore, among the units shown in structural formula (1), it is preferable to include the unit shown in structural formula (3) below, as it results in amorphous, colorless, and transparent polymer due to the introduction of bulky substituents. More specifically, it is preferable to have a polymer containing 30 mol% or more of the unit shown in structural formula (3) below in the molecule. Moreover, a multi-component copolymer containing 30 mol% or more of the unit shown in structural formula (3) below and 20 mol% or more of the unit shown in structural formula (4) below in the molecule is preferable, and in particular, it is preferable to have a multi-component copolymer containing 10 mol% or more of the unit shown in structural formula (5) below, which increases the glass transition temperature due to the introduction of even bulkier substituents than those in structural formula (3) below. Furthermore, when the unit shown in structural formula (4) below is included, endo isomers and exo isomers exist as stereoisomers. In this case, the heat resistance is excellent and deformation at high temperatures can be reduced, so it is preferable that the composition ratio of endo-exo isomers be 50 mol% or more, preferably 70 mol% or more, and more preferably 80 mol% or more for the endo type in a multicomponent copolymer.

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] On the other hand, the ratio of ethylene residue units and unsaturated cyclic olefin monomer residue units, particularly norbornene-based monomer residue units, as units constituting polymer (2) is preferably in the range of 80 / 20 to 30 / 70 as the molar ratio of ethylene residue units to unsaturated cyclic olefin monomer residue units. Within this range, the fewer ethylene residue units there are, the higher the glass transition temperature of polymer (2) tends to be, resulting in superior heat resistance. Conversely, within this range, the more ethylene residue units there are, the better the moldability of polymer (2) tends to be, and the better the toughness tends to be.

[0046] The method for producing polymer (2) is not particularly limited, and various known production methods can be employed. Polymer (2) can be produced, for example, by copolymerizing ethylene and unsaturated cyclic olefin monomers, particularly norbornene-based monomers, in the liquid phase. This copolymerization in the liquid phase can be carried out, for example, in the presence of a catalyst consisting of a soluble vanadium compound and an organoaluminum compound, in a hydrocarbon solvent such as cyclohexane, at a temperature in the range of -50 to 100°C, and at a rate of 0.01 to 50 kg / cm³. 2 It can be performed at pressures within the range of G.

[0047] Cyclic polyolefin (A) is suitable for the following applications from the viewpoint of moldability and toughness: (i) 10-30 g / 10 min in MFR according to ASTM D1238 (260°C, 21.18 N), (ii) 10-60 g / 10 min in MFR according to ISO 1133 (280°C, 21.2 N), or (iii) 10-60 cm in MVR according to ISO 1133 (230°C, 21.18 N). 3 It is preferable that one or more of the following conditions be met: / 10min.

[0048] Such cyclic polyolefins (A) are available commercially, and examples of polymers (1) include the trade names "Zeonex®" and "Zeonor®" manufactured by Nippon Zeon Co., Ltd., and the trade name "ARTON®" manufactured by JSR Corporation.

[0049] Examples of polymers (2) include "APPEL®" manufactured by Mitsui Chemicals, Inc. and "TOPAS®" manufactured by TOPAS Advanced Polymers.

[0050] In the present invention, as the cyclic polyolefin (A), only one type of polymer (1) may be used, or two or more types may be used in combination. Alternatively, only one type of polymer (2) may be used, or two or more types may be used in combination. Furthermore, one or more types of polymer (1) and one or more types of polymer (2) may be used in combination.

[0051] As the cyclic polyolefin (A), polymer (1) is preferred because it allows for a wide range of setting conditions for film formation and is less prone to appearance defects. Among cyclic polyolefins (A) that contain the units shown in structural formula (1), polymers containing 30 mol% or more of the units shown in structural formula (3) are preferred because they allow for a high glass transition temperature. In particular, multi-component copolymers containing 30 mol% or more of the units shown in structural formula (3) and 20 mol% or more of the units shown in structural formula (4) are preferred, and even more preferably multi-component copolymers containing 30 mol% or more of the units shown in structural formula (3), 20 mol% or more of the units shown in structural formula (4), and 10 mol% or more of the units shown in structural formula (5) are preferred. Furthermore, among cyclic polyolefins (A) represented by structure (4), polymers containing 50 mol% or more of endo-type and less than 50 mol% of exo-type are preferred because they have excellent heat resistance and allow for reduced deformation at high temperatures.

[0052] The ethylene polymer (B) constituting the resin composition according to one aspect of the present invention has a refractive index of 1.52 to 1.53 in accordance with JIS K7142, a ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (Mw / Mn) in molecular weight measurement by gel permeation chromatography in the range of 2 to 7, and is an ethylene polymer having 0.15 or more long-chain branches with 6 or more carbon atoms per 1,000 carbon atoms of the main chain in fractions with Mn of 100,000 or more when molecular weight fractionation is performed, such as an ethylene homopolymer or an ethylene-α-olefin copolymer. Such ethylene polymers include, for example, low-pressure ethylene polymers that can be obtained by polymerization of ethylene using a metallocene catalyst or copolymerization with a copolymer. More specifically, they can be obtained by methods described in Japanese Patent Publication No. 2012-126862, 2012-126863, 2012-158654, 2012-158656, 2013-28703, etc. However, if the refractive index falls outside the range of 1.52 to 1.53 or if it is not an ethylene polymer, the resulting composition is likely to have problems with transparency. Also, if the Mw / Mn ratio exceeds 7, the resulting composition will have poor heat resistance.

[0053] The ethylene-based polymer (B) is chosen because the resulting resin composition has high melt tension and excellent moldability when formed into a film. It is characterized by having a long-chain branching number of 6 or more carbon atoms in fractions with a Mn content of 100,000 or more obtained by molecular weight fractionation, with 0.15 or more long-chain branchings per 1,000 carbon atoms in the main chain.

[0054] The ethylene polymer (B) is preferable because the resulting resin composition has excellent moldability for forming films, laminates, and the like. Therefore, according to JIS K6922-1, the MFR measured at 190°C and a load of 21.18N is preferably 0.1 to 15 g / 10 min, particularly preferably 0.5 to 10.0 g / 10 min, and even more preferably 1.0 to 5.0 g / 10 min.

[0055] The ethylene-based polymer (B) preferably has a density in the range of 930 to 960 kg / m 3 in accordance with JIS K6922-1, more preferably 935 to 955 kg / m 3 and even more preferably 940 to 950 kg / m 3 in order to obtain a resin composition with particularly excellent heat resistance and transparency.

[0056] The ethylene-based polymer (B) preferably exhibits two peaks in the molecular weight measurement by GPC in order to obtain a particularly excellent transparency. The peak top molecular weight (Mp) is obtained by dividing the molecular weight distribution curve obtained by GPC measurement into two peaks by the method described below, evaluating the top molecular weights of the high molecular weight side peak and the low molecular weight side peak, and when the difference is 100,000 or more, it is regarded as having two Mp. When it is less than 100,000, the top molecular weight of the actually measured molecular weight distribution curve is regarded as one Mp.

[0057] The molecular weight distribution curve was divided as follows. For the LogM of the molecular weight distribution curve in which the weight ratio is plotted against LogM, which is the logarithm of the molecular weight, obtained by GPC measurement, two logarithmic distribution curves with a standard deviation of 0.30 and an arbitrary average value (the molecular weight at the peak top position) are added together at an arbitrary ratio to create a synthetic curve. Furthermore, the average value and ratio are determined so that the sum of the squared deviations of the weight ratios for the same molecular weight (M) value between the actually measured molecular weight distribution curve and the synthetic curve becomes the minimum value. The minimum value of the sum of the squared deviations was set to 0.5% or less with respect to the sum of the squared deviations when the ratio of each peak was all 0. When the average value and ratio that give the minimum value of the sum of the squared deviations are obtained, the molecular weight at the peak top of each logarithmic distribution curve obtained by dividing into two logarithmic normal distribution curves was taken as Mp.

[0058] The ethylene-based polymer (B) preferably has a number average molecular weight (Mn) measured by GPC of 15,000 or more, more preferably 15,000 to 100,000, and particularly preferably 15,000 to 50,000. When Mn is 15,000 or more, the strength of the obtained film increases.

[0059] Furthermore, since the ethylene polymer (B) has a low extrusion load during molding and produces a resin composition with a good appearance (surface texture) of the resulting film, it is preferable that the proportion of fractions with a molecular weight of 100,000 or more obtained by molecular weight fractionation is less than 40% of the total ethylene polymer (B).

[0060] The resin composition of the present invention contains 5 to 95% by weight of the cyclic polyolefin (A) and 5 to 95% by weight of the ethylene polymer (B). It is preferable that the composition contains 50 to 90% by weight of the cyclic polyolefin (A) and 10 to 50% by weight of the ethylene polymer (B) to obtain a resin composition with particularly excellent stability of the chemical solution. Here, if the amount of cyclic polyolefin (A) is less than 5% by weight, the resulting composition will have poor heat resistance. On the other hand, if it exceeds 95% by weight, the impact resistance will be poor. The above-mentioned content of cyclic polyolefin (A) and ethylene polymer (B) indicates the ratio when their total is considered to be 100% by weight.

[0061] A resin composition according to one aspect of the present invention has high heat resistance, such as not deforming when heated when used as a container, and maintains transparency. Therefore, it is preferable that the resin composition further contains high-density polyethylene (C) in which the fraction with a molecular weight of Mn of 100,000 or more has 0.14 or fewer long-chain branches per 1,000 carbon atoms in the main chain. The high-density polyethylene (C) can be any type, for example, an ethylene homopolymer or a copolymer of ethylene and α-olefin. It is preferable that the composition contains 20 to 300 parts by weight, particularly 20 to 60 parts by weight, of high-density polyethylene (C) per 100 parts by weight of the total of the cyclic polyolefin and the ethylene-based polymer. In particular, a resin composition that results in a low load on the extruder during molding and excellent moldability is preferred, and therefore, in accordance with JIS K6922-1, the melt mass flow rate (hereinafter referred to as MFR), measured at 190°C and a load of 21.18N, is preferably 0.1 to 15 g / 10 min, especially 0.5 to 10.0 g / 10 min, and even more preferably 0 to 5.0 g / 10 min.

[0062] Furthermore, this high-density polyethylene (C) is a resin composition that exhibits high heat resistance, such as preventing deformation of the container during heat treatment, and also minimizes the reduction in transparency, thus having a density of 940-970 kg / m³ in accordance with JIS K6922-1. 3 It is preferable that the load be 945-970 kg / m³. 3 Furthermore, 950-965 kg / m 3 It is preferable that the following conditions are met. Furthermore, since moldability issues such as film vibration during molding are less likely to occur and the resulting resin composition has excellent transparency, it is preferable that the Mw / Mn ratio is in the range of 2.0 to 3.5, and that the Mn ratio is 25,000 or higher.

[0063] The high-density polyethylene (C) may be a commercially available product, for example, Nipolon Hard 5700, 8500, 8022, etc. (product names) manufactured by Tosoh Corporation, or Nipotec 06S81H, YK47, etc. (product names) manufactured by Tosoh Corporation.

[0064] Furthermore, the high-density polyethylene (C) related to the present invention can be produced by manufacturing methods such as the slurry method, solution method, or gas phase method. When producing the high-density polyethylene (C), a Ziegler catalyst consisting of a solid catalyst component containing magnesium and titanium and an organoaluminum compound, a metallocene catalyst consisting of an organotransition metal compound containing a cyclopentadienyl derivative and a compound that reacts with it to form an ionic complex and / or an organometallic compound, a vanadium-based catalyst, etc. can be used, and it can be produced by homopolymerizing ethylene or copolymerizing ethylene and α-olefin using the catalyst. The α-olefin can be any α-olefin generally referred to as such, and is preferably an α-olefin having 3 to 12 carbon atoms, such as propylene, butene-1, hexene-1, octen-1, or 4-methyl-1-pentene. Examples of copolymers of ethylene and α-olefins include ethylene-hexene-1 copolymer, ethylene-butene-1 copolymer, and ethylene-octen-1 copolymer.

[0065] A resin composition according to one aspect of the present invention can be obtained by mixing the aforementioned cyclic polyolefin (A), ethylene polymer (B), and optionally high-density polyethylene (C) using conventionally known methods, such as a Henschel mixer, V-blender, ribbon blender, tumbler blender, etc., or by further melt-kneading the mixture obtained by such methods using a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, etc., in which case it can be obtained as granules such as pellets.

[0066] In a resin composition according to one aspect of the present invention, commonly used known additives, such as antioxidants, neutralizing agents, antistatic agents, lubricants, antiblocking agents, antifogging agents, organic or inorganic pigments, ultraviolet absorbers, dispersants, etc., may be appropriately and as needed, provided that they do not significantly impair the effects of the present invention. The method of incorporating the above additives into the resin composition according to the present invention is not particularly limited, but examples include adding them directly in the pellet granulation process after polymerization, or preparing a high-concentration masterbatch in advance and dry-blending it during molding.

[0067] Furthermore, in one embodiment of the present invention, the resin composition may also be used in combination with other thermoplastic resins such as high-pressure low-density polyethylene, ethylene-propylene copolymer rubber, and poly-1-butene, within a range that does not impair the effects of the present invention.

[0068] One aspect of the present invention is a resin composition that is particularly suitable as a film, a constituent layer of a laminated film, or especially a sealant layer (hereinafter referred to as "film, etc.") for containers and packaging materials that have excellent impact resistance, transparency, and heat resistance. The thickness of the film, etc. is not particularly limited and can be determined as needed. For example, it can be 3 to 5000 μm, preferably 5 to 2000 μm, and especially when used for medical or food purposes, it can be 10 to 500 μm, preferably 20 to 300 μm.

[0069] There are no particular restrictions on the manufacturing method of films, etc., and common methods include extrusion molding, blow molding, injection molding, calendering, press molding, and inflation molding.

[0070] Furthermore, the films can be used in a wide range of medical applications, such as intravenous fluid films, blood films, and even intravenous fluid containers, blood containers, and pharmaceutical containers. They can also be used in a wide range of food-related applications, such as retort container films and shrink films. [Examples]

[0071] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. A. Resin The properties of the resins used in the examples and comparative examples were evaluated by the following method.

[0072] <Molecular weight, molecular weight distribution> Weight-average molecular weight (Mw), number-average molecular weight (Mn), the ratio of weight-average molecular weight to number-average molecular weight (Mw / Mn), and peak-top molecular weight (Mp) were measured by GPC. A GPC instrument (HLC-8121GPC / HT, manufactured by Tosoh Corporation) and a column (TSKgel GMHhr-H(20)HT, manufactured by Tosoh Corporation) were used. The column temperature was set to 140°C, and 1,2,4-trichlorobenzene was used as the eluent. The sample was prepared at a concentration of 1.0 mg / ml, and 0.3 ml was injected for measurement. The molecular weight calibration curve was calibrated using polystyrene samples with known molecular weights. Mw and Mn were determined as linear polyethylene equivalents.

[0073] <Molecular weight fractionation> For molecular weight fractionation, a glass bead-packed column (diameter: 21 mm, length: 60 cm) was used, with the column temperature set to 130°C. A 1 g sample solution was dissolved in 30 mL of xylene and injected. Next, a 5 / 5 xylene / 2-ethoxyethanol solution was used as the developing solvent, and the distillate was removed. Then, xylene was used as the developing solvent, and the remaining components in the column were distilled to obtain a polymer solution. Five times the volume of methanol was added to the obtained polymer solution to precipitate the polymer, and the solution was filtered and dried to recover components with a manganese content of 100,000 or more.

[0074] <Long chain branching> The number of long-chain branches was measured by 13C-NMR using a JEOL Ltd. JNM-GSX400 nuclear magnetic resonance spectrometer to determine the number of branches with hexyl groups or more. The solvent used was benzene-d6 / orthodichlorobenzene (volume ratio 30 / 70). The number of branches per 1000 methylene carbon atoms in the main chain (chemical shift: 30 ppm) was determined from the average values ​​of the α-carbon (34.6 ppm) and β-carbon (27.3 ppm) peaks.

[0075] <density> The density was measured using the density gradient pipe method in accordance with JIS K6922-1.

[0076] <mfr> MFR was measured in accordance with JIS K6922-1.

[0077] <Fusion Tension> For measuring melt tension, the sample was prepared by adding heat-resistant stabilizers (Chiba Specialty Chemicals, Irganox 1010™; 1,500 ppm, Irgaphos 168™; 1,500 ppm) to the sample and kneading it for 30 minutes at 190°C and 30 rpm under a nitrogen stream using an internal mixer (Toyo Seiki Seisakusho, product name Laboplastmill).

[0078] The melt tension was measured using a capillary viscometer with a barrel diameter of 9.55 mm (Toyo Seiki Seisakusho, product name: Capillograph), with a die measuring 8 mm in length and 2.095 mm in diameter mounted at an inlet angle of 90°. The temperature was set to 160°C, the piston descent speed to 10 mm / min, and the stretch ratio to 47. The load required for pull-up (mN) was defined as the melt tension. If the maximum stretch ratio was less than 47, the load required for pull-up at the highest stretch ratio without fracture (mN) was defined as the melt tension.

[0079] <Structural analysis> Among the examples, the primary structure of some cyclic polyolefins was analyzed by nuclear magnetic resonance spectroscopy (hereinafter sometimes simply referred to as "NMR"). For proton NMR (hereinafter sometimes simply referred to as "¹H NMR") measurements, a BRUKER AVANCE III HD500 nuclear magnetic resonance spectrometer was used, with the observed nucleus set to ¹H (500.1 MHz), the number of integrations set to 128, the solvent set to toluene-d8, the concentration set to 2% (w / v), and the temperature set to 100°C. For carbon-13 NMR (hereinafter sometimes simply referred to as "¹³C NMR") measurements, a BRUKER AVANCE III HD500 nuclear magnetic resonance spectrometer was used, with the observed nucleus set to ¹³C (125.8 MHz), the number of integrations set to 1,024, the solvent set to toluene-d8, the concentration set to 10% (w / v), and the temperature set to 100°C, and the measurement mode set to reverse gated decoupling. Furthermore, for detailed structural analysis, we also utilized two-dimensional NMR (hereinafter sometimes simply referred to as "2D NMR") heteronuclear single-quantum correlation spectroscopy (hereinafter sometimes simply referred to as "HSQC"), heteronuclear multi-quantum correlation spectroscopy (hereinafter sometimes simply referred to as "HMBC"), and total correlation spectroscopy (hereinafter sometimes simply referred to as "TOCSY"). For 2D NMR, we used a BRUKER AVANCE III HD500 nuclear magnetic resonance spectrometer, with the observed nucleus set to 1H (500.1 MHz) or 13C (125.8 MHz), the solvent to toluene-d8, the concentration to 10% (w / v), and the temperature to 100°C. The number of integration cycles was 8 for HSQC, 16 for HMBC, and 16 for HSQC-TOCSY.

[0080] <Refractive index> The refractive index was measured in accordance with JIS K7142 (Method A) using a multi-wavelength Abbe refractometer (ATAGO Corporation, model DR-M2) with an interference filter to measure the refractive index at a reference wavelength of 589 nm. The measurement room temperature was set to 23°C. The measurement film samples used had dimensions of 5-8 mm in width, 20-40 mm in length, and approximately 100 μm in thickness. 1-bromonaphthalene was used as the intermediate solution. The measurement film was prepared by compressing resin pellets in a compression molding machine AWFA.50 (Shinto Metal Industries Co., Ltd.) with the heating temperature set to an arbitrary temperature between 180 and 230°C and the heating pressure 10 kgf / cm². 2 After heating and compressing for 10 minutes, the cooling temperature was set to 30°C and the cooling pressure to 10 kgf / cm². 2 The material was solidified after a cooling time of 4 minutes to form a 100 μm thick film, which was then used.

[0081] In the examples and comparative examples, resins manufactured by the following methods and commercially available products were used. (1) Cyclic polyolefins The following commercially available products were used.

[0082] (A)-1: Manufactured by Nippon Zeon Co., Ltd. (Product name) Zeonex 690R ([MFR (ISO 1133 (280℃, 21.2N))] = 17g / 10min, [Glass transition temperature (JIS K7121)] = 136℃) (A)-2: Manufactured by Nippon Zeon Co., Ltd. (Product name) Zeonor 1430R ([MFR (ISO 1133 (280℃, 21.2N))] = 30g / 10min, [Glass transition temperature (JIS K7121)] = 133℃) (A)-3: Manufactured by Nippon Zeon Co., Ltd. (Product name) Zeonor 1020R ([MFR (ISO 1133 (280℃, 21.2N))] = 20g / 10min, [Glass transition temperature (JIS K7121)] = 102℃) (A)-4: TOPAS Advanced Polymers (Product Name) TOP AS 6013F-04 ([MVR(ISO 1133 (230℃, 21.18N))]=12cm 2 / 10 min, [glass transition temperature (ISO 11357-1, -2, -3)] = 138°C) (A)-5: TOPAS Advanced Polymers (Product Name) TOP AS 8007F-04 ([MVR(ISO 1133 (230℃, 21.18N))]=12cm 2 / 10 min, [glass transition temperature (ISO 11357-1, -2, -3)] = 78°C) (A)-6: Mitsui Chemicals, Inc. (Product name) Apel APL6013T ([MFR (ASTM D1238 (260℃, 21.18N))] = 15g / 10min, [Glass transition temperature (Mitsui Chemicals method)] = 125℃) Table 1 shows the mole percentages of structural units contained in (A)-1 and (A)-3.

[0083] [Table 1]

[0084] Table 2 shows the refractive indices of cyclic polyolefins (A)-1 to (A)-6.

[0085] [Table 2]

[0086] (2) Ethylene polymer Products obtained by the following manufacturing methods or commercially available products were used.

[0087] (B)-1: Obtained by the following manufacturing method. [Preparation of polymerization catalyst] After purging a 300 mL flask with nitrogen, dimethylhexacosylamine (Me2N(C)) with a median diameter of 14 μm was added. 26 H 53 25.0 g of modified synthetic hectorite and 108 mL of hexane were added, then 0.4406 g of dimethylsilylene (cyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride and 142 mL of 20% triisobutylaluminum were added, and the mixture was washed five times with hexane to obtain a polymerization catalyst suspension (solid weight: 12.0% by weight). [(B)-1 Manufacturing] In a 2 L autoclave, 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added, along with 75 mg (equivalent to 9.0 mg of solids) of the catalyst suspension obtained in [Preparation of Polymerization Catalyst]. After heating to 80°C, 8.3 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied to maintain a partial pressure of 0.85 MPa (hydrogen concentration in the ethylene / hydrogen mixed gas: 850 ppm). After 90 minutes, 58.5 g of low-pressure ethylene-based polymer was obtained.

[0088] The obtained low-pressure ethylene polymer had an MFR of 4.0 g / 10 min and a density of 941 kg / m³. 3 The results were as follows: The number-average molecular weight was 21,200, and the weight-average molecular weight was 74,000, with peaks observed at molecular weights of 41,500 and 217,100. Furthermore, the number of long-chain branches in the fractions with Mn 100,000 or more after molecular weight fractionation was 0.18 per 1,000 carbon atoms in the main chain. The proportion of fractions with Mn 100,000 or more after molecular weight fractionation was 14.8% by weight of the total polymer. The melt tension was 49 mN. The evaluation results are shown in Table 3.

[0089] (B)-2: Obtained by the following manufacturing method. [Preparation of polymerization catalyst] After purging a 300 mL flask with nitrogen, 25.0 g of dimethylhebenylamine-modified synthetic hectorite with a median diameter of 15 μm and 108 mL of hexane were added. Then, 0.4406 g of dimethylsilylene (cyclopentadienyl)(2,4,7-trimethylindenyl) zirconium dichloride and 142 mL of 20% triisobutylaluminum were added, and the mixture was stirred at 60°C for 3 hours. After washing five times with hexane, a polymerization catalyst suspension was obtained (solid weight: 12.4% by weight). [(B)-2 Manufacturing] In a 2 L autoclave, 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added, along with 52 mg (equivalent to 6.4 mg of solids) of the polymerization catalyst suspension obtained in [Preparation of Polymerization Catalyst]. After heating to 70°C, 17.6 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied to maintain a partial pressure of 0.80 MPa (hydrogen concentration in the ethylene / hydrogen mixed gas: 590 ppm). After 90 minutes, the pressure was removed, the slurry was filtered off, and dried to obtain 61.8 g of low-pressure ethylene-based polymer.

[0090] The obtained low-pressure ethylene polymer had an MFR of 1.6 g / 10 min and a density of 930 kg / m³. 3 The results were as follows: The number-average molecular weight was 17,600, and the weight-average molecular weight was 86,700, with peaks observed at molecular weights of 30,500 and 155,300. Furthermore, the number of long-chain branches in the Mn fractions above 100,000 after molecular weight fractionation was 0.27 per 1,000 carbon atoms in the main chain. The proportion of the Mn fractions above 100,000 after molecular weight fractionation was 20.1% by weight of the total polymer. The melt tension was 75 mN. The evaluation results are shown in Table 3.

[0091] (B)-3: Obtained by the following manufacturing method. [(B)-3 Manufacturing] In a 2 L autoclave, 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum, and 70 mg of the polymerization catalyst suspension used in B-2 (equivalent to 8.4 mg of solids) were added. After heating to 80°C, 2.4 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied to maintain a partial pressure of 0.90 MPa (hydrogen concentration in the ethylene / hydrogen mixed gas: 720 ppm). After 90 minutes, the pressure was removed, the slurry was filtered off, and dried to obtain 63.0 g of low-pressure ethylene-based polymer.

[0092] The obtained low-pressure ethylene polymer had a molecular weight (MFR) of 11.5 g / 10 min and a density of 954 kg / m³. 3 The results were as follows: The number-average molecular weight was 16,200, and the weight-average molecular weight was 58,400, with peaks observed at molecular weights of 28,200 and 181,000. Furthermore, the number of long-chain branches in the fractions with Mn 100,000 or more after molecular weight fractionation was 0.16 per 1,000 carbon atoms in the main chain. The proportion of fractions with Mn 100,000 or more after molecular weight fractionation was 6.8% by weight of the total polymer. The melt tension was 38 mN. The evaluation results are shown in Table 3.

[0093] (B)-4: Obtained by the following manufacturing method. [(B)-4 Manufacturing] In a 2 L autoclave, 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum, and 74 mg (equivalent to 8.3 mg of solids) of the polymerization catalyst suspension used in B-2 were added. After heating to 65°C, 17.5 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied to maintain a partial pressure of 0.75 MPa (hydrogen concentration in the ethylene / hydrogen mixed gas: 570 ppm). After 90 minutes, the pressure was removed, the slurry was filtered off, and dried to obtain 51.5 g of low-pressure ethylene-based polymer.

[0094] The obtained low-pressure ethylene polymer had an MFR of 0.8 g / 10 min and a density of 928 kg / m³. 3 The results were as follows: The number-average molecular weight was 17,900, and the weight-average molecular weight was 99,300, with peaks observed at molecular weights of 28,100 and 229,100. Furthermore, the number of long-chain branches in the fractions with Mn 100,000 or more after molecular weight fractionation was 0.26 per 1,000 carbon atoms in the main chain. The proportion of fractions with Mn 100,000 or more after molecular weight fractionation was 25.4% by weight of the total polymer. The melt tension was 90 mN. The evaluation results are shown in Table 3.

[0095] (B)-5: Obtained by the following manufacturing method. [(B)-5 Manufacturing] In a 2 L autoclave, 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum, and 90 mg of the polymerization catalyst suspension used in B-2 (equivalent to 10.4 mg of solids) were added. After heating to 65°C, 17.5 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied to maintain a partial pressure of 0.75 MPa (hydrogen concentration in the ethylene / hydrogen mixed gas: 550 ppm). After 90 minutes, the pressure was removed, the slurry was filtered off, and dried to obtain 61.4 g of low-pressure ethylene-based polymer.

[0096] The obtained low-pressure ethylene polymer had an MFR of 0.08 g / 10 min and a density of 926 kg / m³. 3 The results were as follows: The number-average molecular weight was 21,900, and the weight-average molecular weight was 127,000, with peaks observed at molecular weights of 31,300 and 247,800. Furthermore, the number of long-chain branches in the fractions with Mn 100,000 or more after molecular weight fractionation was 0.32 per 1,000 carbon atoms in the main chain. The proportion of fractions with Mn 100,000 or more after molecular weight fractionation was 36.9% by weight of the total polymer. The melt tension was 140 mN. The evaluation results are shown in Table 3.

[0097] (B)-6: Obtained by the following manufacturing method. [Preparation of polymerization catalyst] After purging a 300 mL flask equipped with a thermometer and reflux tubing with nitrogen, 25.0 g of dimethylbehenialuminine-modified synthetic hectorite with a median diameter of 15 μm was suspended in 165 mL of hexane. 0.3485 g of dimethylsilanediylbis(cyclopentadienyl)zirconium dichloride and 85 mL of hexane solution of triethylaluminum (1.18 M) were added, and the mixture was washed twice with 200 mL of hexane solution of 1% triisobutylaluminum. The supernatant after washing was removed, and the total volume was increased to 250 mL with hexane solution of 5% triisobutylaluminum. Next, a solution prepared by adding 5 ml of a hexane solution (0.71 M) of 20% triisobutylaluminum to a hexane solution of 0.1165 g of diphenylmethylene (1-cyclopentadienyl)(2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride was added. After washing twice with 200 ml of hexane, 200 ml of hexane was added to obtain a polymerization catalyst suspension (solid weight: 12.0% by weight). [(B)-6 Manufacturing] Add 1.2L of hexane and 1 / 20% triisobutylaluminum to a 2L autoclave. 0.0 mL of the polymerization catalyst suspension obtained in [Preparation of Polymerization Catalyst] was added to 125 mg (equivalent to 15.0 mg of solids), the temperature was raised to 85°C, 2.4 g of 1-butene was added, and ethylene was continuously supplied to maintain a partial pressure of 0.90 MPa. After 90 minutes, the pressure was removed, the slurry was filtered off, and dried to obtain 45.0 g of low-pressure ethylene polymer.

[0098] The obtained low-pressure ethylene polymer had a molecular weight (MFR) of 4.4 g / 10 min and a density of 951 kg / m³. 3 The results were as follows: The number-average molecular weight was 9100, the weight-average molecular weight was 77100, and peaks were observed at molecular weights of 10400 and 168400. Furthermore, the number of long-chain branches contained in the fractions with Mn of 100,000 or more after molecular weight fractionation was 0.24 per 1000 carbon atoms in the main chain. In addition, the proportion of fractions with Mn of 100,000 or more after molecular weight fractionation was 15.7% by weight of the total polymer. The melt tension was 210 mN. The evaluation results are shown in Table 3. (S)-1: The following commercially available products were used.

[0099] Tosoh Corporation, (product name) Petrocene 219 (MFR = 3.0g / 10 min, density = 934 kg / m³) 3 The results of the basic characteristic evaluation of (S)-1 are shown in Table 3.

[0100] [Table 3]

[0101] (3) High-density polyethylene Products obtained by the following manufacturing methods or commercially available products were used. (C)-1: Obtained by the following manufacturing method. [Preparation of modified clay] Dimethyl behenylamine is dissolved in a mixed solvent of 4.8 L of deionized water and 3.2 L of ethanol. C 22 H 45 Add 354g of (CH3)2N and 83.3mL of 37% hydrochloric acid, then add dimethyl ester. A henylamine hydrochloride solution was prepared. 1,000 g of synthetic hectorite was added to this solution. The mixture was stirred overnight, and the resulting reaction solution was filtered. The solid was then thoroughly washed with water. The solid was dried. As a result, 1,180g of organically modified clay was obtained. The liquid content measured with an infrared moisture meter was 0.8 The result was %. Next, this organically modified clay was crushed to adjust the average particle size to 6.0 μm. [Preparation of polymerization catalyst] In a 5L flask, add dimethylbehenylamine (C) with an average particle size of 6.0 μm. 22 H 45 450 g of (CH3)2N) modified synthetic hectorite and 1.4 kg of hexane were added, followed by 1.78 kg (1.8 mol) of a 20 wt% triisobutylaluminum solution in hexane and 7.32 g (18 mmol) of bis(n-butyl-cyclopentadienyl) zirconium dichloride. Next, 1.78 kg (0.09 mol) of a 1 wt% triisobutylaluminum solution in hexane was added, and the mixture was re-diluted with hexane to a total volume of 4.5 L to prepare the polymerization catalyst. [(C)-1 Manufacturing] A polymerization reactor with a capacity of 300 L was continuously supplied with hexane at a rate of 135 kg / hour, ethylene at a rate of 20.0 kg / hour, butene-1 at a rate of 0.3 kg / hour, hydrogen at a rate of 5 NL / hour, and the polymerization catalyst obtained in the section on [Preparation of Polymerization Catalyst]. In addition, triisobutylaluminum was continuously supplied as a co-catalyst to maintain a concentration of 0.93 mmol / kg hexane in the liquid. The polymerization temperature was controlled to 85°C. The resulting high-density polyethylene ((C)-1) had an MFR of 1.0 g / 10 min and a density of 952 kg / m³. 3 The results of the basic characteristic evaluation of (C)-1 are shown in Table 4.

[0102] (C)-2: Obtained by the following manufacturing method. [Preparation of modified clay] Modified clay was prepared using the same method as in (C)-1. [Preparation of polymerization catalyst] A polymerization catalyst was prepared using the same method as in (C)-1. [(C)-2 Manufacturing] A polymerization reactor with a capacity of 300 L was continuously supplied with hexane at a rate of 135 kg / hour, ethylene at a rate of 20.0 kg / hour, butene-1 at a rate of 0.4 kg / hour, hydrogen at a rate of 8 NL / hour, and the polymerization catalyst obtained in the section on [Preparation of Polymerization Catalyst]. In addition, triisobutylaluminum was continuously supplied as a co-catalyst to maintain a concentration of 0.93 mmol / kg hexane in the solution. The polymerization temperature was controlled to 85°C. The resulting high-density polyethylene ((C)-2) had an MFR of 3.0 g / 10 min and a density of 945 kg / m³. 3 The results of the basic characteristic evaluation of (C)-2 are shown in Table 4.

[0103] [Table 4]

[0104] (4) Linear low-density polyethylene The following commercially available products were used.

[0105] (Q)-1: Tosoh Corporation (Product name) Nipolon-Z HF213K (MFR=2.0g / 10min, Density=905kg / m³) 3 (Refractive index = 1.51) Examples 1 to 14, Comparative Examples 1 to 13 Using the resin compositions shown in Tables 5 and 6, films and medical containers were manufactured and evaluated using the following methods. The results are shown in Tables 7 to 9.

[0106] [Table 5]

[0107] [Table 6]

[0108] <Production of films and medical containers> A three-layer film with a width of 135 mm and a thickness of 250 μm was manufactured using a water-cooled three-layer co-extrusion inflation molding machine (manufactured by Placo Co., Ltd.) with cylinder temperatures of 180°C for the outer and intermediate layers, 230°C or 260°C for the inner layer, a water bath temperature of 15°C, and a take-up speed of 6 m / min. The thickness of each layer was set to outer / intermediate / inner = 20 μm / 210 μm / 20 μm. At this time, the resin composition according to the present invention was used for the inner layer, and linear low-density polyethylene (product name) Nipolon-P FY12 (MFR = 1.5 g / 10 min, density = 916 kg / m³) manufactured by Tosoh Corporation was used for the intermediate layer. 3 ), the outer layer is made of high-density polyethylene manufactured by Tosoh Corporation (product name) Nipolon-P FY13 (MFR = 1.1g / 10 min, density = 950kg / m³) 3 Next, a 200 mm long sample was cut from the three-layer film, one end was heat-sealed to form a bag, 300 ml of ultrapure water was filled in, a headspace of 50 ml was left, and the bag was heat-sealed to create a medical container for sterilization. <Sterilization> The above medical containers were sterilized using a high-temperature, high-pressure cooking and sterilization device (manufactured by Hisaka Works, Ltd.) at a temperature of 121°C for 20 minutes. <Evaluation of film properties> The film characteristics were evaluated using the following method. The results are shown in Tables 7 to 14.

[0109] <Transparency> Test specimens measuring 10 mm wide x 50 mm long were cut from the above three-layer film and the medical container after sterilization. The light transmittance at a wavelength of 450 nm in pure water was measured using a UV-Vis spectrophotometer (JASCO Corporation, model V-530). A container with good transparency was considered to have maintained a light transmittance of 70% or more after sterilization.

[0110] <Stability testing of fat-soluble vitamins> To evaluate the adsorption inhibition performance of the above three-layer film for fat-soluble vitamins, experiments were conducted using tocopherol acetate as the fat-soluble vitamin.

[0111] Two three-layer films were stacked and heat-sealed on three sides using an impulse sealing machine so that the dimensions of the area in contact with the filling liquid were 50 mm vertically and 50 mm horizontally. Then, 12 ml of Santen Pharmaceutical Co., Ltd.'s Sante 40 Plus, which contains 500 ppm tocopherol acetate, was filled and sealed by heat sealing. After sterilization at 121°C for 20 minutes using a high-temperature, high-pressure cooking and sterilization device (manufactured by Hisaka Works, Ltd.), two Ageless (product number: ZP-202) and two Ageless Eye (product number: LS loose (with thread)) manufactured by Mitsubishi Gas Chemical Co., Ltd. were enclosed in a Laminated Zip Flat Bag AL type (product number: AL-G) manufactured by Seisan Nippon Co., Ltd. The product was then stored in an environment of 25°C, 60% RH or 40°C, 75% RH. The tocopherol acetate concentration in the container was measured by high-performance liquid chromatography at the start of storage (initial), 1 month, and 3 months later, and the percentage of the concentration relative to the concentration at the time of filling was determined as the remaining concentration. A container in which the tocopherol acetate concentration was maintained at 70% or higher at the start of storage (initial) was considered to have good stability, and a container in which the tocopherol acetate concentration was maintained at 75% or higher was considered to have particularly good stability. In addition, a container in which the decrease in tocopherol acetate concentration was less than 10% compared to the start of storage (initial) after 1 month to 3 months from the start of storage was considered to have good storage stability.

[0112] The reason for using Sante 40 Plus as the filling solution is as follows: When the container was filled with an aqueous solution of tocopherol acetate dissolved in ultrapure water using a surfactant such as polysorbate or polyoxyethylene hydrogenated castor oil, and the aforementioned prescribed treatments such as sterilization were performed, the tocopherol acetate concentration was maintained at 95% or higher after sterilization, regardless of the type of container and surfactant. This is thought to be because the tocopherol acetate is dissolved in water surrounded by surfactant micelles, thus preventing contact between the tocopherol acetate and the film. In order to bring the tocopherol acetate into contact with the film, it is thought that adding a compound with a structure that disrupts the micelle structure, specifically a compound in which hydrophilic functional groups such as hydroxyl groups, sulfonyl groups, or amino groups are bonded to both ends of a hydrophobic part such as an alkyl chain, is effective. Examples of such compounds include taurine, epsilon-aminocaproic acid, benzalkonium chloride, panthenol, pyridoxine hydrochloride, and thiamine hydrochloride. Therefore, in the present invention, Sante 40 Plus, which contains tocopherol acetate, the surfactant polyoxyethylene hydrogenated castor oil, and the compounds taurine and epsilon-aminocaproic acid, was used as the filler solution.

[0113] <Exterior> After sterilization, the film surface was visually evaluated for wrinkles, deformation, and fusion between inner layers. A score of 4 was given for no wrinkles or deformation, 3 for slight wrinkles or deformation, 2 for significant wrinkles or deformation, and 1 for fusion between inner layers.

[0114] <Seal stability after sterilization> The shape of the seal area after sterilization was visually evaluated. ○: No change in the shape of the sealing surface. △: Part of the seal surface is peeling off (e.g., reduction in seal width) ×: The seal surface peels off (the seal width disappears), causing leakage of the internal fluid. <Seal strength after sterilization> The heat-sealed portion was cut into strips 15 mm wide perpendicular to the sealing direction, and peeled at a speed of 200 mm / min at a 180° angle. The maximum value obtained during peeling was defined as the peel strength. (The test was conducted with n=5, and the average value was calculated.) A post-sterilization seal strength of 35 N / 15 mm or higher was considered an indicator of sufficient sealing performance to prevent peeling of the heat-sealed portion around the container periphery.

[0115] <Sealing temperature range after sterilization> The above-mentioned inflation film (cylindrical shape), in which the inner layers, i.e., the sealant layers, face each other, is sealed at a pressure of 2 kg / cm². 2 Samples were prepared by heat-sealing a sample with a sealing time of 2 seconds and varying the sealing temperature in increments of 1-2°C. Next, each sample was sterilized at 121°C for 20 minutes, and the sealing strength was measured using the method described in the <Seal Strength> section above. A graph (heat seal curve) showing the relationship between sealing strength and sealing temperature, as shown in Figure 1, was created. Using this graph, the sealing temperature range for which the sealing strength was 5-20 N / 15 mm was calculated. A sealing temperature range of 6°C or higher was considered a guideline for obtaining stable peelability with minimal fluctuation in the sealing strength of the easily peelable seal.

[0116] [Table 7]

[0117] [Table 8]

[0118] [Table 9]

[0119] [Table 10]

[0120] [Table 11]

[0121] Table 12

[0122] Table 13

[0123] Table 14 < / mfr>

Claims

1. A resin composition comprising 5 to 95% by weight of a cyclic polyolefin (A) having a glass transition temperature of 125°C or higher and a refractive index of 1.52 to 1.54 according to JIS K7142, and 5 to 95% by weight of an ethylene polymer (B) having a refractive index of 1.52 to 1.53 according to JIS K7142, a ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (Mw / Mn) in the range of 2 to 7 as measured by molecular weight measurement by gel permeation chromatography, and having 0.15 or more long-chain branches with 6 or more carbon atoms per 1,000 carbon atoms of the main chain in fractions with Mn of 100,000 or more when molecular weight fractionated, wherein the cyclic polyolefin (A) is a multi-component copolymer containing 30 mol% or more of the unit shown in the following structural formula (3) and 20 mol% or more of the unit shown in the following structural formula (4). 【Chemistry 1】 【Chemistry 2】

2. For cyclic polyolefin (A), (i) a melt mass flow rate of 10–30 g / 10 min measured at 260°C and 21.18 N in accordance with ASTM D1238, (ii) a melt mass flow rate of 10–60 g / 10 min measured at 280°C and 21.2 N in accordance with ISO 1133, or (iii) a melt volume flow rate of 10–60 cm³ measured at 230°C and 21.18 N in accordance with ISO 1133. ３ The resin composition according to claim 1, which satisfies at least one of the following conditions: / 10min, wherein the ethylene polymer (B) conforms to JIS K 6922-1 and has a melt mass flow rate of 0.1 to 15 g / 10 min measured at 190°C and a load of 21.18 N.

3. The resin composition according to claim 1 or 2, wherein the cyclic polyolefin (A) is a polymer containing the unit shown in the following structural formula (1). 【Transformation 3】 (In formula (1) above, Ra and Rb may be the same or different, and represent a hydrogen atom or an organic group. Ra and Rb may be bonded to each other to form a ring. m is an integer of 1 or more, and n is an integer of 0 or more.)

4. The resin composition according to any one of claims 1 to 3, wherein the cyclic polyolefin (A) is a polypolymer containing 10 mol% or more of the unit shown in the following structural formula (5). 【Chemistry 4】

5. The resin composition according to any one of claims 1 to 4, wherein the cyclic polyolefin (A) is a polypolymer containing 50 mol% or more of its stereoisomer, the endo form, and less than 50 mol% of its exo form, as units represented by the above structural formula (4).

6. The ethylene polymer (B) has a density of 930–960 kg / m³ as measured by the density gradient tube method in accordance with JIS K6922-1. ３ A resin composition according to any one of claims 1 to 5, wherein the polymer is an ethylene-based polymer.

7. The resin composition according to any one of claims 1 to 6, wherein the ethylene polymer (B) exhibits two peaks in molecular weight measurement by gel permeation chromatography.

8. The resin composition according to any one of claims 1 to 7, wherein cyclic polyolefin (A) is 50 to 90% by weight and ethylene polymer (B) is 10 to 50% by weight.

9. The resin composition according to any one of claims 1 to 8, further comprising 20 to 300 parts by weight of high-density polyethylene (C) having 0.14 or fewer long-chain branches with 6 or more carbon atoms per 1,000 carbon atoms of the main chain in fractions with a total of 100 parts by weight of a cyclic polyolefin resin (A) and an ethylene-based polymer (B).

10. High-density polyethylene (C) has a density of 940-970 kg / m³ as measured by the density gradient pipe method in accordance with JIS K6922-1. ３ The resin composition according to claim 9, wherein the melt mass flow rate measured at 190°C and a load of 21.18 N in accordance with JIS K 6922-1 is 0.1 to 15 g / 10 min.

11. The resin composition according to claim 9 or 10, wherein the high-density polyethylene (C) has a Mw / Mn ratio of 2.0 to 3.5 and a Mn value of 25,000 or more.

12. A resin composition according to any one of claims 9 to 11, comprising 20 to 60 parts by weight of high-density polyethylene (C) per 100 parts by weight of a total of cyclic polyolefin resin (A) and ethylene polymer (B).

13. A film comprising the resin composition according to any one of claims 1 to 12.

14. A film comprising the film described in claim 13 as a sealant layer.

Images