JPWO2014141817A1 - Solvent container and solvent storage method - Google Patents

Abstract

To provide a solvent container having excellent solvent barrier properties and to provide a method for storing a solvent using the solvent container. The present invention provides a container for a solvent comprising a resin composition containing a cyclic olefin-based resin having a glass transition point of more than 100 ° C. and not more than 180 ° C., and high-density polyethylene. The present invention also relates to a method for storing a solvent in a solvent container comprising a resin composition comprising high-density polyethylene and a cyclic olefin-based resin having a glass transition point of more than 100 ° C. and not more than 180 ° C. Provides a method for preserving a solvent in which the difference between the solubility parameter of the solvent and the solubility parameter of the cyclic olefin resin is 0.5 Jl / 2 / cm3 / 2 or more and 16 Jl / 2 / cm3 / 2 or less.

Description

  The present invention relates to a solvent container and a solvent storage method.

  Polyethylene resin is widely used as a material for containers and the like because it has excellent mechanical strength and is inexpensive. However, when a container obtained from polyethylene resin is used for filling and storage of a solvent, the solvent resistance of the container is sufficient, but the storage stability (solvent barrier property) of the solvent may not be sufficient. For this reason, there are problems such that the solvent permeates the container, and when the solvent is a mixture, the component concentration in the solvent changes.

  For example, Patent Document 1 discloses a barrier layer mainly composed of a cyclic olefin resin and a seal layer mainly composed of a polyethylene resin for the purpose of obtaining a liquid storage container having excellent drug storage stability. There is disclosed a liquid container made of a multilayer film comprising:

International Publication No. 2008-001496 Pamphlet

  However, conventional containers obtained from polyethylene resin, such as the container described in Patent Document 1, may not have sufficient solvent barrier properties.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a solvent container having excellent solvent barrier properties and to provide a method for storing a solvent using the solvent container.

  The inventors of the present invention provide a solvent container and a solvent barrier property obtained from a resin composition containing high-density polyethylene and a cyclic olefin-based resin having a glass transition point of more than 100 ° C. and 180 ° C. or less. The superior point was found and the present invention was completed. Specifically, the present invention provides the following.

  (1) A solvent container comprising a resin composition comprising a cyclic olefin-based resin having a glass transition point of more than 100 ° C and 180 ° C or less and high-density polyethylene.

(2) The difference between the solubility parameter of the solvent and the solubility parameter of the cyclic olefin-based resin is 0.5 J ^1/2 / cm ^3/2 or more and 16 J ^1/2 / cm ^3/2 or less (1) The solvent container as described.

  (3) The mass ratio of the cyclic olefin resin and the high density polyethylene (cyclic olefin resin / high density polyethylene) in the resin composition is 10/90 to 90/10 (however, 10/90 and 90 / 10).) The solvent container according to (1) or (2).

  (4) The solvent container according to any one of (1) to (3), wherein the solvent is any one of butyl acetate, ethyl acetate, methyl ethyl ketone, and acetone.

(5) A method for storing a solvent by a solvent container comprising a resin composition comprising high-density polyethylene and a cyclic olefin resin having a glass transition point of more than 100 ° C. and 180 ° C. or less,
The solvent is storage method of the solvent the difference between the solubility parameter of the solubility parameter and the cyclic olefin-based resin of the solvent is less than ^0.5J l ^/ 2 / ^{cm 3/2} or more ^16J l ^/ 2 / ^{cm 3/2} .

  ADVANTAGE OF THE INVENTION According to this invention, the container for solvents which is excellent in solvent barrier property, and the preservation | save method of the solvent by this container for solvents are provided.

  Hereinafter, embodiments of the present invention will be described. In addition, this invention is not limited to the following embodiment.

  The solvent container of the present invention (hereinafter also simply referred to as “container”) comprises a resin composition comprising a cyclic olefin resin having a glass transition point of more than 100 ° C. and not more than 180 ° C., and high-density polyethylene. Hereinafter, each component will be described.

(Cyclic olefin resin)
The cyclic olefin-based resin in the present invention has a glass transition point (hereinafter also referred to as “Tg”) of more than 100 ° C. and 180 ° C. or less. This temperature is higher than the glass transition point (for example, Tg = 30 ° C. or more and 100 ° C. or less) of the cyclic olefin resin conventionally used as a component of the container. However, as a result of the study by the present inventors, a container obtained from a resin composition containing a cyclic olefin resin having a glass transition point of more than 100 ° C. and 180 ° C. or less and high-density polyethylene is filled in the container, etc. Regardless of the type of solvent used, it was found that white turbidity and deformation were suppressed, and the solvent resistance was excellent. Further, the container is suppressed in the mass loss of the solvent filled in the container over time, and is excellent in the storage stability of the solvent (also referred to as “solvent barrier property”).

  The reason why the Tg of the cyclic olefin-based resin affects the solvent resistance and solvent barrier property of the container is not clear, but may be caused by the following action. In other words, the Tg of the cyclic olefin resin can vary depending on, for example, the type of monomer unit constituting the cyclic olefin resin, but the type of monomer unit also affects the molecular motion of the cyclic olefin resin. As a result, it is presumed to affect the permeability of the solvent into the container.

  The Tg of the cyclic olefin resin in the present invention is preferably 105 ° C. or higher and 180 ° C. or lower, more preferably 110 ° C. or higher and 180 ° C. or lower. A higher Tg is preferable in that the solvent barrier property of the container is maintained at a high level and the solvent resistance is improved, so that the effects of the present invention are easily obtained. However, if the Tg of the cyclic olefin-based resin exceeds 180 ° C, the resulting container may have low impact resistance. Therefore, the Tg of the cyclic olefin-based resin is preferably 180 ° C or lower.

  The Tg of the cyclic olefin-based resin is specified by measuring under a temperature increase rate of 10 ° C./min according to JIS K7121. When two or more kinds of cyclic olefin resins are used, the Tg of the cyclic olefin resin is specified as a weighted average of each cyclic olefin resin.

  The cyclic olefin resin in the present invention is not particularly limited as long as Tg is in the above range and the polymer or copolymer includes a structural unit derived from the cyclic olefin in the main chain. A cyclic olefin resin may be used individually by 1 type, or may be used in combination of 2 or more type. Examples of the cyclic olefin-based resin include an addition polymer of a cyclic olefin or a hydrogenated product thereof, an addition copolymer of a cyclic olefin and an α-olefin, or a hydrogenated product thereof.

（式中、Ｒ^１〜Ｒ^１２は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、及び炭化水素基からなる群より選ばれるものであり、Ｒ^９とＲ^１０、Ｒ^１１とＲ^１２は、一体化して２価の炭化水素基を形成してもよく、Ｒ^９又はＲ^１０と、Ｒ^１１又はＲ^１２とは、互いに環を形成していてもよい。また、ｎは、０又は正の整数を示し、ｎが２以上の場合には、Ｒ^５〜Ｒ^８は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよい。）The said cyclic olefin is not specifically limited, For example, the cyclic olefin shown by the following general formula (I) is mentioned.

(In the formula, R ^{1 to} R ¹² may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R ⁹ and R ¹⁰ , R ¹¹ and R ¹² may be integrated to form a divalent hydrocarbon group, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other, and n is 0 Alternatively, it represents a positive integer, and when n is 2 or more, R ^{5 to} R ⁸ may be the same or different in each repeating unit.

R ^{1 to} R ¹² in the general formula (I) may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.

Specific examples of R ^{1 to} R ⁸ include hydrogen atom; halogen atom such as fluorine atom, chlorine atom and bromine atom; alkyl group such as methyl group, ethyl group, propyl group and butyl group. May be different from each other, may be partially different, or all may be the same.

Specific examples of R ^{9 to} R ¹² include, for example, hydrogen atom; halogen atom such as fluorine atom, chlorine atom, bromine atom; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl Group, alkyl group such as stearyl group; cycloalkyl group such as cyclohexyl group; substituted or unsubstituted aromatic hydrocarbon group such as phenyl group, tolyl group, ethylphenyl group, isopropylphenyl group, naphthyl group, anthryl group; Groups, phenethyl groups, and other aralkyl groups in which an alkyl group is substituted with an aryl group. These may be different, may be partially different, or may be all the same. Good.

Specific examples of the case where R ⁹ and R ¹⁰ or R ¹¹ and R ¹² are integrated to form a divalent hydrocarbon group include, for example, alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group. Can be mentioned.

When R ⁹ or R ¹⁰ and R ¹¹ or R ¹² form a ring with each other, the formed ring may be monocyclic or polycyclic, or may be a polycyclic ring having a bridge. , A ring having a double bond, or a ring composed of a combination of these rings may be used. Moreover, these rings may have a substituent such as a methyl group.

Specific examples of the cyclic olefin represented by the general formula (I) include those disclosed in JP-A-2007-302722.
A cyclic olefin may be used individually by 1 type, or may be used in combination of 2 or more type.

The α-olefin is not particularly limited, and examples thereof include α-olefins having 2 to 20 carbon atoms, and specific examples include those disclosed in Japanese Patent Application Laid-Open No. 2007-302722.
The α-olefin may be used alone or in combination of two or more.

  The cyclic olefin-based resin may contain a structural unit derived from an unsaturated monomer other than the cyclic olefin and the α-olefin, if necessary, as long as the object of the present invention is not impaired. Such an unsaturated monomer is not particularly limited, and examples thereof include a hydrocarbon monomer containing two or more carbon-carbon double bonds in one molecule. Specific examples of such hydrocarbon monomers include those disclosed in Japanese Patent Application Laid-Open No. 2007-302722.

  Examples of the unsaturated monomer include unsaturated compounds having a polar group. That is, the cyclic olefin-based resin is obtained by grafting and / or copolymerizing an unsaturated compound having a polar group in the polymer or copolymer containing a structural unit derived from a cyclic olefin in the main chain. May be. Examples of the polar group include a carboxyl group, an acid anhydride group, an epoxy group, an amide group, an ester group, and a hydroxyl group. Examples of the unsaturated compound having a polar group include (meth) acrylic acid and maleic acid. Acid, maleic anhydride, itaconic anhydride, glycidyl (meth) acrylate, alkyl (meth) acrylate (1 to 10 carbon atoms) ester, alkyl maleate (1 to 10 carbon atoms) ester, (meth) acrylamide, Examples include (meth) acrylic acid-2-hydroxyethyl.

(Solubility parameter of cyclic olefin resin)
Since the container of the present invention contains a cyclic olefin resin having a glass transition point of more than 100 ° C. and 180 ° C. or less as its component, unexpectedly, the container is filled with a solvent having a solubility parameter close to that of the cyclic olefin resin. Even so, the solvent resistance of the container is unlikely to be impaired.

  The solubility parameter (hereinafter also referred to as “SP value”) is a numerical value that is a measure of the solubility of the polymer (high-density polyethylene, cyclic olefin resin, etc.) in the solvent and the compatibility between the polymer and the solvent. . The smaller the difference between the SP value of the polymer and the SP value of the solvent, the higher the solubility and compatibility of the polymer in the solvent. In other words, normally, when a solvent having a solubility parameter close to that of an amorphous cyclic olefin resin is filled into a container containing the cyclic olefin resin as a component, the solvent is expected to erode the container, resulting in cloudiness of the container. However, the effect of the present invention that the solvent resistance of the container is hardly impaired even when such a solvent is filled is unexpected.

The solubility parameter (δ) of the polymer or solvent is calculated by the following equation. In the formula, “ΔH” is the heat of molar evaporation (unit: J / mol), “V” is the molar volume (unit: cm ³ ), “R” = 8.314 J / mol · K (gas constant) , “T” represents temperature (unit: K), respectively.

For example, the container of the present invention has a difference (hereinafter also referred to as “ΔSP”) between the solubility parameter of the solvent filled in the container and the solubility parameter of the cyclic olefin resin in the resin composition constituting the container. Even if it is small, the cloudiness and deformation of the container are suppressed, and the solvent resistance can be excellent. For example, many commonly used solvents have an SP value of 25 J ^1/2 / cm ^3/2 or less. In that case, the upper limit value of ΔSP can be equal to or less than 16 J ^1/2 / cm ^3/2 . A characteristic of the container of the present invention is that the container has high solvent resistance even when ΔSP is lower than 16 J ^{l / 2} / cm ^3/2 or less. For example, ΔSP is 10 J ^{l / 2} / cm ^3/2. Even if it is below (for example, 5 J ^{l / 2} / cm ^3/2 or less, ³ J ^{l / 2} / cm ^3/2 or less, 1 J ^{l / 2} / cm ^3/2 or less, etc.), good solvent resistance is exhibited. In the present invention, even when ΔSP is low as described above, the cloudiness and deformation of the container can be suppressed unexpectedly. The lower limit value of ΔSP is not particularly limited, but as the value is larger, the cloudiness and deformation of the container are suppressed, and the solvent resistance is easily improved. For example, 0.5 J ^1/2 / cm ^3/2 or more, preferably 0. It may be 7J ^{l / 2} / cm ^3/2 or more.

  Note that the SP values of the cyclic olefin-based resin and the high-density polyethylene are substantially the same (7.8 to 7.9). Therefore, in the present invention, “SP value of cyclic olefin resin” is synonymous with “SP value of cyclic olefin resin and high density polyethylene”.

The solvent filled in the container of the present invention may be composed of a single component or a plurality of components. When the solvent is a mixed solution composed of a plurality of components (for example, component 1 and component 2), the SP value (δ ₁₂ ) of the mixed solution is calculated by the following equation. In the formula, “X ₁ ” represents the molar ratio of component 1, “δ ₁ ” represents the SP value of component 1, and “δ ₂ ” represents the SP value of component 2.

(High density polyethylene)
As the high-density polyethylene (hereinafter also referred to as “HDPE”) in the present invention, those usually used as components of containers can be used. For example, it may be either linear or branched HDPE. Further, the density of HDPE may be 0.935 g / cm ³ or more and 0.965 g / cm ³ or less. The melt index (MI) of HDPE may be a value measured in accordance with JIS K 7120 (190 ° C.) of 0.2 g / 10 min or more and 40 g / 10 min or less.

  HDPE is a material that has many crystal components and can provide a container having excellent solvent barrier properties and solvent resistance compared to other polyethylenes (such as linear low density polyethylene (LLDPE)). However, according to the present invention, a container having remarkably excellent solvent barrier properties and solvent resistance, which cannot be obtained by using HDPE alone, can be obtained.

(Resin composition)
The mass ratio of the cyclic olefin resin and HDPE in the resin composition in the present invention (cyclic olefin resin / HDPE) is not particularly limited as long as these two components are contained in the resin composition, but 10/90 to 90 / 10 (however, including 10/90 and 90/10), preferably 10/90 to 40/60 (however, including 10/90 and 40/60) may be used.

  Further, the total amount of the cyclic olefin resin and HDPE in the resin composition may be 50% by mass or more and 100% by mass or less, preferably 80% by mass or more and 100% by mass or less. The total amount of the cyclic olefin resin and HDPE in the resin composition being 100% by mass indicates that the container of the present invention is composed of the cyclic olefin resin and HDPE.

  The resin composition in the present invention includes conventionally known components such as other resins (linear low density polyethylene, etc.), colorants, stabilizers, mold release agents and the like within a range not impairing the effects of the present invention. It may be. The compounding quantity in the resin composition of these components can be suitably adjusted according to the effect to be acquired.

  The method for producing a resin composition in the present invention is not particularly limited as long as the above components constituting the resin composition can be uniformly mixed, and conventionally known methods for producing resin compositions can be appropriately used. For example, after melt-kneading and extruding each component using a melt-kneading apparatus such as a single-screw or twin-screw extruder, the resulting resin composition is processed into a desired form such as powder, flakes, pellets, etc. Is mentioned.

(Solvent container)
The solvent container of the present invention can be obtained by molding the above resin composition. As a method for molding the container, a commonly used method can be used, and examples thereof include an extrusion blow molding method, an injection blow molding method, an injection stretch blow molding method, an injection molding method, and a vacuum molding method.

  The molding conditions of the container of the present invention are not particularly limited, and are appropriately set according to the shape of the container to be obtained. However, since the container of the present invention contains a cyclic olefin resin having a Tg higher than usual as a component, the molding temperature is higher than usual, for example, 190 ° C. or higher and 300 ° C. or lower, preferably 220 ° C. or higher and 250 ° C. or lower. You may shape | mold.

  The container of the present invention is for a solvent. In the present invention, the phrase “for a solvent” means that the container is used for the purpose of filling, storing, storing, preserving, sealing, etc. the inside of the container.

  The solvent in the present invention refers to all liquids, and characteristics such as presence / absence of polarity and boiling point are not particularly limited. The container of the present invention is resistant to solvent even if it is filled with an organic solvent (butyl acetate, ethyl acetate, methyl ethyl ketone, acetone, isopropanol, ethanol, methanol, etc.), which is known to cause white turbidity and deformation of the polyethylene container. And excellent solvent barrier properties. Examples of other solvents include water. Among the above solvents, the container of the present invention exhibits solvent resistance and excellent solvent barrier properties even when filled with butyl acetate, ethyl acetate, methyl ethyl ketone, or acetone, which easily penetrates a polyethylene container.

  The container of the present invention can suitably store a substance containing a solvent (liquid) as a component. Examples of the substance include a substance composed only of a liquid, a substance containing a liquid, and a solid and / or a gas. Specific examples of the substance containing a solvent as a component include drugs, reagents, foods, beverages, cosmetics, shampoos, detergents, paints, and the like.

  The container of the present invention is excellent in solvent resistance and solvent barrier properties. The solvent resistance of the container is specified by visually evaluating the appearance of the container after filling the container with the solvent and storing it at 40 ° C. for 30 days. If the cloudiness or deformation of the container is suppressed during visual evaluation, it can be determined that the container has high solvent resistance.

Moreover, the solvent barrier property of a container is specified by calculating the mass decreasing rate of the solvent in a container after filling a solvent in a container and preserve | saving for 30 days at 40 degreeC. The mass reduction rate of the solvent is calculated based on the following formula. If the mass reduction rate is less than 0.1% by mass, it can be determined that the solvent barrier property of the container is high.
Mass reduction ratio (%) = (initial total mass of solvent−total mass after storage of solvent) / initial total mass of solvent Total mass of solvent = mass of container + solvent

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

[Example: Examination of drop impact resistance, solvent resistance and solvent barrier property of container of the present invention]
A resin composition made of polyethylene and / or a cyclic olefin-based resin (Tg = 78 ° C., 110 ° C., 135 ° C. or 142 ° C.) at a ratio shown in Tables 1 and 2 is molded by injection blow molding, and a container (internal volume) 40 ml, wall thickness 1 mm). Hereinafter, “%” in the table represents mass%.

The conditions for injection blow molding are as follows.
Processing temperature 240 ℃
Injection mold temperature 60 ℃
Blow mold temperature 60 ℃

Abbreviations in Tables 1 and 2 correspond to the following compounds, respectively.
HDPE: high density polyethylene, trade name “Novatec HY540”, Nippon Polyethylene Corporation LLDPE: linear short chain branched polyethylene, trade name “EvolueSP2320”, Prime Polymer Co., Ltd. COCTg78: Cyclic olefin resin (Tg = 78 ° C. ), Trade name “TOPAS 8007S-04”, TOPAS ADVANCED POLYMERS COCTg110: cyclic olefin resin (Tg = 110 ° C.), trade name “TOPAS7010F-600”, TOPAS ADVANCED POLYMERS COCTg135: cyclic olefin resin (Tg = 135 ° C), trade name “TOPAS5013S-04”, TOPAS ADVANCED POLYMERS COCTg142: Cyclic olefin resin ( g = 142 ℃), the trade name of "TOPAS6013M-07", TOPAS ADVANCED POLYMERS, Inc.

(Examination of drop impact)
After putting 40 ml of water into each container, the container was dropped from 1.5 m height onto concrete, and the drop impact property of each container was evaluated according to the following criteria. The results are shown in Table 1.
○: not cracked ×: easy to break or break

(Examination of solvent resistance)
Fill each container (bottle shape) with the solvent (40 ml) shown in Table 1, place a plate (thickness 1 mm) made of the same material as the container on the mouth of the container, heat the plate with an iron, The container mouth was thermally welded. Then, it preserve | saved at 40 degreeC for 30 days.
After storage, the appearance of each container was visually evaluated according to the following criteria. The results are shown in Table 1. In the following, “MEK” is an abbreviation for methyl ethyl ketone. Hereinafter, “ΔSP” in the table indicates the difference between the SP value of various solvents and the SP value of the cyclic olefin resin.
○: No change ×: Cloudiness and / or deformation

(Examination of solvent barrier properties)
Each container was filled with the solvent (40 ml) shown in Table 2 and stored at 40 ° C. for 30 days.
After storage, the mass reduction rate of the solvent in each container was calculated based on the following formula. The results are shown in Table 2.
Mass reduction rate (%) = (initial total mass of solvent−total mass after storage of solvent) / initial total mass of solvent Total mass of solvent = container + mass of solvent ◎: mass reduction rate is less than 0.1% by mass A: Mass reduction rate is 0.1% by mass or more and less than 0.5% by mass X: Mass reduction rate is 0.5% by mass or more

  As shown in Table 1, a container obtained from a resin composition containing a cyclic olefin resin having a Tg of 110 ° C. or higher and HDPE not only has good drop impact properties, but also has white turbidity and / or deformation. It is suppressed and has high resistance to various solvents.

  As shown in Table 2, a container obtained from a resin composition containing a cyclic olefin resin having a Tg of 110 ° C. or higher and HDPE has a low mass reduction rate and a high solvent barrier property against various solvents.

[Reference Example: Effect of Difference between SP Value of Various Solvents and SP Value of Cyclic Olefin Resin on Appearance of Container]
A resin composition consisting only of a cyclic olefin resin (Tg = 78 ° C. or 142 ° C.) was molded by injection blow molding to produce a container (internal volume 40 ml, wall thickness 1 mm). Each container was filled with chemicals (40 ml) shown in Table 3 and stored at 40 ° C. or 20 ° C. for 30 days. After storage, the appearance of each container was visually evaluated. The results are shown in Table 3. In the table, the unit of “ΔSP” is J ^1/2 / cm ^3/2 .

The abbreviations in Table 3 correspond to the following compounds, respectively. The number in parentheses immediately after the abbreviation is the storage temperature of the container filled with the solvent.
COCTg78: Cyclic olefin resin (Tg = 78 ° C.), trade name “TOPAS8007S-04”, manufactured by TOPAS ADVANCED POLYMERS COCTg142: Cyclic olefin resin (Tg = 142 ° C.), trade names “TOPAS 6013M-07”, TOPAS ADVANCED POLYMERS Made by company

  As shown in Table 3, the container obtained from only the cyclic olefin-based resin composition having a Tg of 142 ° C. is suppressed in white turbidity, deformation, etc., is maintained in transparency, has high resistance to various solvents, In particular, the resistance to butyl acetate was high. However, a container obtained only from a cyclic olefin resin composition having a Tg of 142 ° C. has low drop impact properties (data not shown), and is considered unsuitable for practical use.

Claims (5)

  A container for a solvent comprising a resin composition comprising a cyclic olefin-based resin having a glass transition point of more than 100 ° C and 180 ° C or less and high-density polyethylene. 2. The solvent according to claim 1, wherein a difference between the solubility parameter of the solvent and the solubility parameter of the cyclic olefin resin is 0.5 J ^{l / 2} / cm ^3/2 or more and 16 J ^{l / 2} / cm ^3/2 or less. container.   The mass ratio of the cyclic olefin-based resin and the high-density polyethylene (cyclic olefin-based resin / high-density polyethylene) in the resin composition is 10/90 to 90/10 (however, 10/90 and 90/10 are included) The solvent container according to claim 1 or 2.   The solvent container according to any one of claims 1 to 3, wherein the solvent is any one of butyl acetate, ethyl acetate, methyl ethyl ketone, and acetone. A method for storing a solvent in a solvent container comprising a resin composition comprising high-density polyethylene and a cyclic olefin resin having a glass transition point of more than 100 ° C. and 180 ° C. or less,
The solvent is a method for storing a solvent, wherein a difference between a solubility parameter of the solvent and a solubility parameter of the cyclic olefin resin is 0.5 J ^{l / 2} / cm ^3/2 or more and 16 J ^{l / 2} / cm ^3/2 or less. .