Rubber molded article

Abstract

The main purpose of the present invention is to provide a rubber molded article that has a layer of a non-fluorine-based resin film on the surface, and that has preferable gas barrier properties and electron beam resistance and exhibits preferable moldability during production.　Provided is a rubber molded article that includes a layer of a non-fluorine-based resin film. The non-fluorine-based resin film before being laminated exhibits a ratio (TD / MD) of 0.80-1.20 regarding the elongation in the TD-direction with respect to the elongation in the MD-direction. Furthermore, the elongation in the MD-direction may be 150-450% and the elongation in the TD-direction may be 150-450% in the non-fluorine-based resin film before being laminated.

Description

Rubber molded products

[0001] This technology relates to molded rubber products.

[0002] Traditionally, rubber has been considered superior as a sealing material for containers or devices used in pharmaceutical and medical applications due to its airtight properties. Historically, natural rubber was widely used, while synthetic rubber is more common today. However, when rubber used in containers or devices comes into contact with chemicals (which may be liquids, solids, gases, or combinations thereof), problems specific to rubber can occur, such as the leaching of rubber components. For this reason, rubber molded products containing a fluororesin film layer and rubber material, in which a chemically inert fluororesin film is used on part or all of the surface of the rubber molded product, are widely available on the market.

[0003] For example, Patent Document 1 discloses a composite rubber molded body for pharmaceuticals in which a fluororesin film is laminated to the surface, wherein on the surface of the composite rubber molded body, the proportion of fluorine is 40% or more of the total 100% of the three elements carbon, oxygen, and fluorine, or the fluorine / carbon element ratio (F / C) is 0.8 or more, and the b* in the L*a*b* color system is 2.0 or less.

[0004] Japanese Patent Publication No. 2018-201671, Japanese Patent Publication No. 2014-131874, Japanese Patent Publication No. 61-272134

[0005] M. Doumeng et al., Polymer Testing, 93 (2021), Article 106878, 2021:1-10A.WL Chen et al., Journal of Composite Materials, Vol. 27, No.9, 1993:862-885H.Liu et al., Royal Society open science 5: 171775, 25 April 2018.

[0006] Furthermore, during the manufacturing of rubber molded products, the resin film layer may tear or peel, resulting in poor moldability during production. In recent years, when sterilized rubber molded products are distributed to the market, electron beam sterilization is sometimes used instead of high-pressure steam sterilization to sterilize them after sealing them in packaging containers. Therefore, there is a demand for rubber molded products that can withstand electron beam sterilization. The inventors of this invention have attempted to provide a rubber molded product that has good gas barrier properties and electron beam resistance, as well as good moldability during production, even when a non-fluorine-based resin film is used on the surface of the rubber molded product.

[0007] Therefore, the main objective of this technology is to provide a rubber molded product that has good gas barrier properties and electron beam resistance, as well as good moldability during manufacturing.

[0008] As a result of diligent research, the inventors of the present invention have discovered that by using a non-fluorine resin film having specific conditions and providing it as a non-fluorine resin film layer on the surface of a rubber molded product, it is possible to provide a rubber molded product that has good gas barrier properties and electron beam resistance, as well as good moldability during manufacturing, and have thus completed the present invention.

[0009] This technology can provide a rubber molded product comprising a non-fluorinated resin film layer, wherein the ratio of the elongation in the TD direction to the elongation in the MD direction (TD / MD) of the non-fluorinated resin film before lamination is 0.80 or more and 1.20 or less. Furthermore, the elongation in the MD direction of the non-fluorinated resin film before lamination may be 150% or more and 450% or less, and the elongation in the TD direction may be 150% or more and 450% or less. Also, the tensile strength in the MD direction of the non-fluorinated resin film before lamination may be 60 MPa or more and 160 MPa or less, and the tensile strength in the TD direction may be 60 MPa or more and 160 MPa or less, and / or the ratio of the tensile strength in the TD direction to the tensile strength in the MD direction (TD / MD) may be 0.80 or more and 1.00 or less. Furthermore, the non-fluorinated resin may be one or more selected from polyaryletherketone resin and polyamide resin. Furthermore, the rubber may be selected from butyl rubber and chlorinated butyl rubber.

[0010] This figure shows a side cross-section of a rubber molded product according to one embodiment of this technology, but this technology is not limited thereto. The chart shows the measurement results (XRD patterns) of the low-crystallinity PAEK resin (PEEK resin) film shown in the upper section and the low-crystallinity PA resin (PACM-12 resin) film shown in the lower section, as measured by an X-ray diffractometer (vertical axis: intensity (counts), horizontal axis: diffraction angle (2θ (°))). The low-crystallinity PAEK resin (PEEK resin) film (Shin-Etsu Sepla Film) used in the [Examples] is shown. （Ｒ） This chart shows the measurement results (DSC curve) of a low-crystallinity type PEEK resin film (Shin-Etsu Sepla Film) using a differential scanning calorimeter (vertical axis: heat flow (mW), horizontal axis: temperature (°C)). （Ｒ） This chart shows the measurement results (DSC curve) obtained by a differential scanning calorimeter (vertical axis: heat flow (mW), horizontal axis: temperature (°C)).

[0011] The following describes preferred embodiments for carrying out the present invention. Note that the embodiments described below are merely examples of typical embodiments of the present invention, and this should not be interpreted as narrowing the scope of the present invention.

[0012] The present invention will be described in the following order: 1. Rubber molded product relating to this technology 1-1. Rubber substrate 1-2. Film layer 1-2-1. Non-fluorinated resin film layer 1-3. Non-fluorinated resin film before molding (raw material film) 1-3-1. Elongation (strain) of raw material film 1-3-1-1. Elongation of PAEK resin film 1-3-1-2. Elongation of PA resin film 1-3-2. Tensile strength of raw material film 1-3-2-1. Tensile strength of PAEK resin film 1-3-2-2. Tensile strength of PA resin film 1-3-3. Oxygen permeability coefficient of raw material film 1-3-4. Crystallinity of raw material film 1-3-4-1. Calculation of degree of crystallinity and determination of crystallinity using XRD method 1-3-4-2. Calculation of crystallization energy or degree of crystallinity and determination of crystallinity using DSC method 1-3-5. 1-3-6. Elution resistance of raw material film 1-4. Electron beam resistance of raw material film 2. Application of rubber molded products related to this technology 2. Method of manufacturing rubber molded products 2-1. Compression molding to mold the lower and upper parts of the rubber molded product in stages

[0013] 1. Rubber molded products related to this technology

[0014] This technology can provide a rubber molded article containing a non-fluorinated resin film layer, and it is preferable that the rubber molded article contains at least a non-fluorinated resin film layer and a rubber substrate. Furthermore, this technology may also provide a rubber molded article containing a film layer having at least one non-fluorinated resin film layer having specific conditions, and the film layer may consist of multiple layers. The non-fluorinated resin film layer having specific conditions is preferably the surface layer of the film layer. Furthermore, the non-fluorinated resin film layer having specific conditions is preferably provided on the surface of the rubber molded article, and there may be one or more other film layers in between, or other chemical layers. The surface of the non-fluorinated resin film layer having specific conditions (the surface on the rubber substrate side) is preferably provided so as to be in close contact with the surface of the rubber substrate.

[0015] The non-fluorinated resin film used in molding the aforementioned rubber molded product is preferably a non-fluorinated resin film having specific conditions. Note that "molding" in "molding the aforementioned rubber molded product" may be replaced with "manufacturing" or "coating." The specific conditions are preferably one or more selected from conditions relating to elongation in the MD direction and / or TD direction, conditions relating to tensile strength in the MD direction and / or TD direction, conditions relating to crystallinity, etc. This makes it possible to provide a rubber molded product with better moldability during manufacturing and better gas barrier properties and electron beam resistance of the manufactured rubber molded product.

[0016] The present technology may appropriately adopt the following configurations: [1] A preferred embodiment of the present technology is a rubber molded product comprising a non-fluorinated resin film layer, wherein the ratio of the elongation in the TD direction to the elongation in the MD direction (TD / MD) of the non-fluorinated resin film used for molding is 0.80 or more and 1.20 or less. A more preferred embodiment of [1] may further incorporate the configuration described in [2] below, and / or the configuration described in [3] below, and / or the configuration described in [4] below, and / or the configuration described in [5] below. [2] A preferred embodiment of the present technology is a rubber molded product comprising a non-fluorinated resin film layer, wherein the elongation in the MD direction of the non-fluorinated resin film used for molding is 150% or more and 450% or less, and the elongation in the TD direction is 150% or more and 450% or less. In a more preferred embodiment of [2], the configuration described in [1] above, and / or the configuration described in [3] below, and / or the configuration described in [4] below, and / or the configuration described in [5] below may be further incorporated.

[0017] [3] A preferred embodiment of the present technology is a rubber molded product comprising a non-fluorinated resin film layer, wherein the tensile strength in the MD direction of the non-fluorinated resin film used for molding is 60 MPa or more and 160 MPa or less, and the tensile strength in the TD direction is 60 MPa or more and 160 MPa or less. A more preferred embodiment of [3] may further incorporate the configuration described in [1] above, and / or the configuration described in [2] above, and / or the configuration described in [4] below, and / or the configuration described in [5] below. [4] A preferred embodiment of the present technology is a rubber molded product comprising a non-fluorinated resin film layer, wherein the ratio of the tensile strength in the TD direction to the tensile strength in the MD direction used for molding (TD / MD) is 0.80 or more and 1.00 or less. In a more preferred embodiment of [4], the configuration described in [1] above, and / or the configuration described in [2] above, and / or the configuration described in [3] above, and / or the configuration described in [5] below may be further incorporated.

[0018] [5] A preferred embodiment of the present technology is a rubber molded product comprising a non-fluorine resin film layer, wherein the non-fluorine resin film used for molding is low-crystallinity. In a more preferred embodiment of [5], the configuration described in [1] above, and / or the configuration described in [2] above, and / or the configuration described in [3] above, and / or the configuration described in [4] above may be further incorporated.

[0019] [6] The non-fluorinated resin is one or more selected from polyaryletherketone resin and polyamide resin, as described in any one of [1] to [5] above. [7] The rubber is one or two selected from butyl rubber and chlorinated butyl rubber, as described in any one of [1] to [6] above. [8] Use of a non-fluorinated resin film in a rubber molded product or a method of use thereof. The non-fluorinated resin film is preferably the non-fluorinated resin film described in any one of [1] to [7] above. [9] A non-fluorinated resin film or its use for manufacturing or using in manufacturing a rubber molded product. More preferably a non-fluorinated resin film and rubber. The non-fluorinated resin film or rubber is preferably the non-fluorinated resin film described in any one of [1] to [7] above.

[10] A non-fluorinated resin film for use in a rubber molded product or for use in manufacturing a rubber molded product. More preferably, non-fluorinated resin film and rubber. The non-fluorinated resin film or rubber is preferably the non-fluorinated resin film or rubber described in any one of [1] to [7] above.

[11] A method for manufacturing a rubber molded product using a non-fluorinated resin film. The manufacturing method preferably uses a non-fluorinated resin film and rubber. The non-fluorinated resin film or rubber is preferably the non-fluorinated resin film or rubber described in any one of [1] to [7] above.

[12] The manufacturing method according to

[11] above, comprising processing the non-fluorinated resin film and rubber using a mold.

[13] The manufacturing method according to

[11] or

[12] above, comprising processing the non-fluorinated resin film and rubber using compression molding.

[14] It is preferable that any one of the rubber molded articles described in [1] to

[13] has the non-fluorine resin film arranged on the surface of the rubber molded article as a layer, directly or indirectly covering the bare surface of the rubber substrate (for example, part or all of the leg portion or top portion).

[15] It is preferable that any one of the rubber molded articles described in [1] to

[14] is used for pharmaceuticals, medicine, or medical purposes.The rubber molded product is preferably used as one or more types selected from sealing materials, rubber stoppers, gaskets, nozzle caps, cylinder caps, inner plugs, etc.

[0020] 1-1. Rubber base material

[0021] The material used for the rubber substrate in this technology is not particularly limited, but is preferably rubber and a thermoplastic elastomer, of which rubber is preferred, and more preferably synthetic rubber. The thermoplastic elastomer is not particularly limited, but is preferably one that has properties intermediate with rubber, and examples include olefin-based, styrene-based, vinyl chloride-based, urethane-based, polyester-based, polyamide-based, fluorine-based, polybutadiene-based, polyisobutylene-based, silicone-based, and ethylene-vinyl acetate-based resins, and one or more selected from these can be used, and it is preferable to use a non-fluorine-based resin. The rubber is not particularly limited, but examples include synthetic rubbers such as butyl rubber, halogenated butyl rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, nitrile rubber, and isobutylene rubber, natural rubber, etc., EPDM, rubber materials mainly composed of components such as polybutadiene and polyisobutylene (including thermoplastic elastomers), and some thermoplastic elastomer-based compounds can be used.

[0022] Suitable examples of rubber used in the rubber substrate include, for example, butyl rubber, halogenated butyl rubber, butadiene rubber, and isoprene rubber, and one or more selected from these can be used. Among these, it is preferable to use one or more selected from butyl rubber and halogenated butyl rubber for the rubber substrate from the viewpoint of moldability, low permeability, and electron beam resistance. The halogenated (e.g., fluorinated, chlorinated, brominated, etc.) butyl rubber is not particularly limited, but chlorinated butyl rubber is preferred.

[0023] The three-dimensional shape of the rubber substrate is not particularly limited as long as it is a three-dimensional shape that can be applied as a sealing material for containers or devices. Examples include a roughly disc shape, a roughly cylindrical shape, a combination of a roughly cone and a roughly cylindrical shape, and it may have concave and / or convex shapes, and may have multiple circumferential grooves on its sides, like a gasket.

[0024] 1-2. Film layer

[0025] The film layer is preferably provided on part or all of the surface of the rubber molded product. The surface of the rubber molded product is preferably the part of the rubber molded product that can be exposed to the outside. Furthermore, the film layer is preferably placed on the raw surface (also referred to as the surface) of the rubber substrate provided on the rubber molded product, and may be in close contact with the raw surface of the rubber substrate.

[0026] The film layer preferably has at least a non-fluorinated resin film layer, and the film layer may be a single layer consisting only of a non-fluorinated resin film layer. The film layer may also have a multilayer structure having another layer different from the non-fluorinated resin film layer. The other layer may be, for example, a layer using the same or different material as the material used in the non-fluorinated resin film layer. Examples of non-fluorinated resin films described later include polyolefin (also called polyalkene) films such as polyethylene and polypropylene; and polyester films such as polybutylene terephthalate (PBT).

[0027] The thickness of the film layer is not particularly limited, but may be, for example, 2 μm or more, preferably 5 μm or more, and more preferably 10 μm or more. Also, the thickness of the film layer is not particularly limited, but may be, for example, 5 to 300 μm, preferably 10 to 200 μm, and more preferably 10 to 150 μm.

[0028] 1-2-1. Non-fluorine resin film layer

[0029] The non-fluorine resin film layer used in the present technology is preferably provided on a part or all of the surface of the rubber molded product. The non-fluorine resin film layer is preferably a part that can be exposed to the outside. When the film layer has a multilayer structure, the non-fluorine resin film layer is preferably the outermost layer of the film layer. Further, the non-fluorine resin film layer is preferably configured to be provided on the surface that comes into contact with the chemical.

[0030] For example, when the rubber molded product 100 is a rubber stopper, a rubber molded product 100 including a film layer 2 disposed on the surface of the leg portion 10 of the rubber base material 1 as shown in FIG. 1 can be cited as an example. Appropriately, the film layer 2 may be disposed on the surface of one or more rubber base materials selected from the surface of the leg portion 10, the surface of the flange portion 20, the upper surface 31 of the top portion 30, the side surface 32 of the top portion 30, etc. Further, each surface may appropriately have a film layer on all or a part of that surface. As examples other than the above, for example, a rubber molded product having a non-fluorine resin film layer on the upper surface 31 of the top portion 30; a rubber molded product having a non-fluorine resin film layer on the entire surface of the rubber base material 1 such as the upper surface 31 and the side surface 32 of the top portion 30, the surface of the flange portion 20, and the surface of the leg portion 10; a rubber molded product having a non-fluorine resin film layer on the surface of the leg portion 10 and the surface of the flange portion 20; a rubber molded product having a non-fluorine resin film layer on a part of the surface of the leg portion 10; etc. can be cited, but it is not particularly limited thereto. Note that a part of the rubber molded product 100 does not necessarily have the non-fluorine resin film layer 2 disposed on the deburred portion where deburring has been performed. For example, there may be a portion without a film layer at the lower end portion of the side surface 32.

[0031] The non-fluorinated resin film layer used in this technology preferably does not contain fluorine. The non-fluorinated resin film layer is preferably a film that can be formed from a non-fluorinated resin. Such non-fluorinated resins are not particularly limited, but examples include polyaryletherketone resins (PAEK resins) and polyamide resins (PA resins), and one or more selected from these can be used. Among these, PAEK resins (preferably PEEK resins) and / or PA resins (preferably PACM resins) are preferred. The non-fluorinated resin preferably has certain conditions (e.g., elongation, tensile strength, crystallinity) described later.

[0032] In PAEK resin (preferably PEEK resin), the melting point (intermediate melting temperature: °C) is not particularly limited, but for example, it can be 325 to 345 °C, preferably 330 to 340 °C, and more preferably 335 to 339 °C. The glass transition temperature (glass transition start temperature: °C) is not particularly limited, but for example, it can be 135 to 155 °C, preferably 140 to 150 °C, and more preferably 141 to 145 °C. In PA resin (preferably PACM resin), the melting point (intermediate melting temperature: °C) is not particularly limited, but for example, it can be 240 to 250 °C, preferably 243 to 248 °C. The glass transition temperature (glass transition start temperature: °C) is not particularly limited, but for example, it can be 120 to 140 °C, preferably 125 to 135 °C, and more preferably 128 to 133 °C.

[0033] The PAEK resin used in the present technology is not particularly limited, and examples include those composed of an aromatic hydrocarbon group, an ether group, and a carbonyl group [—C(═O)—]. A more suitable PAEK resin preferably contains a repeating unit composed of an arylene group [—Ar—], an ether group [—O—], and a ketone group [—C(═O)—]. A suitable “—Ar—” (divalent aromatic hydrocarbon ring group) is preferably a phenylene group (e.g., p-phenylene group) or a biphenylene group (e.g., 4,4′-biphenylene group), and more preferably a phenylene group (disubstituted benzene ring group). The suitable “—Ar—” may have a substituent or may not have a substituent. The PAEK resin may be obtained by a known production method or a commercially available product may be used.

[0034] As a more suitable PAEK resin, for example, resins containing a repeating unit represented by any of the following formulas (a1) to (a5) can be mentioned, but are not limited thereto. [—Ar—O—Ar—C(═O)—] (a1) [—Ar—O—Ar—C(═O)—Ar—C(═O)—] (a2) [—Ar—O—Ar—O—Ar—C(═O)—] (a3) [—Ar—O—Ar—C(═O)—Ar—O—Ar—C(═O)—Ar—C(═O)—] (a4) [—Ar—O—Ar—O—Ar—C(═O)—Ar—C(═O)—] (a5) (In the formula, Ar represents a divalent aromatic hydrocarbon ring group which may have a substituent)

[0035] The divalent aromatic hydrocarbon ring group represented by Ar is not particularly limited, but examples include phenylene groups (o-, m-, or p-phenylene groups, etc.), naphthylene groups, and other arylene groups having 6 to 10 carbon atoms, biarylene groups such as biphenylene groups (2,2'-biphenylene groups, 3,3'-biphenylene groups, 4,4'-biphenylene groups, etc.) (each arylene group has 6 to 10 carbon atoms), and terarylene groups such as o-, m-, or p-terphenylene groups (each arylene group has 6 to 10 carbon atoms). The aromatic hydrocarbon ring group may have substituents, such as halogen atoms, alkyl groups (such as linear or branched C1-C4 alkyl groups like methyl groups), haloalkyl groups, hydroxyl groups, alkoxy groups (such as linear or branched C1-C4 alkoxy groups like methoxy groups), mercapto groups, alkylthio groups, carboxyl groups, sulfo groups, amino groups, N-substituted amino groups, and cyano groups. The aromatic hydrocarbon ring group may have one or more of these substituents as appropriate.

[0036] In addition, in the repeating units (a1) to (a5), the types of Ar may be the same or different from each other. Preferred Ars are phenylene groups (e.g., p-phenylene groups) and biphenylene groups (e.g., 4,4'-biphenylene groups), and more preferably phenylene groups (disubstituted benzene ring groups).

[0037] The PAEK resin used in this technology is not particularly limited, but examples include polyether ketone (PEK), polyether ether ketone (PEEK), polyether ether ketone ketone (PEEKK), polyether ketone ketone (PEKK), polyether ketone ether ketone ketone (PEKEKK), polyether ether ketone ether ketone (PEEK), polyether ether ether ketone (PEEK), and polyether diphenyl ether ketone (PEDEK), and one or more of these can be used.

[0038] The PEEK resin used in this technology is not particularly limited, but examples include the polymer compound shown in Chemical Formula 1 below. The PEEK resin may be obtained by known manufacturing methods, or a commercially available product may be used.

[0039]

[0040] The PA resin used in this technology is not particularly limited, but examples include polyamides whose constituent units are a reaction product of bis(para-aminocyclohexyl)methane (PACM) and a linear alkylenedicarboxylic acid having X carbon atoms, and PACM resin is preferred. Examples of PACM resins include the polymer compound shown in the following chemical formula 2, where l in the following chemical formula 2 can be 12, 14, 16, 18, 20, or 8 to 22. In one embodiment, the PA resin preferably contains a polyamide (when l is 12) whose constituent units are a reaction product of PACM and a linear dicarboxylic acid (dodecanediic acid) having 12 carbon atoms (poly(bis-4,4'-dicyclohexylmethane)n-dodecanediamide), as shown in the following chemical formula (2). PA resin, PACM resin, and PACM-12 resin may be obtained by known manufacturing methods, or commercially available products may be used.

[0041]

[0042] This technology can provide a rubber molded product having a non-fluorinated resin film layer on its surface, obtained using a non-fluorinated resin film and rubber material having specific conditions. The rubber molded product may also be configured such that the rubber substrate is coated with a non-fluorinated resin film. The rubber molded product has good gas barrier properties and electron beam resistance, and also has good moldability during manufacturing. The specific conditions may be the physical properties or characteristics of the raw material film before molding, or the physical properties or characteristics of the film layer after molding, and compression molding is preferred for molding. Examples of specific conditions include the physical properties or characteristics of the raw material film used for the non-fluorinated resin film layer. Examples of specific conditions for the raw material film include elongation, tensile strength, crystallinity, oxygen permeability coefficient, electron beam resistance, and elution resistance, and one or more of these can be selected.

[0043] 1-3. Non-fluorinated resin film before molding (raw material film)

[0044] The raw material film used in this technology is preferably a non-fluorinated resin having a specific thickness. The thickness of the non-fluorinated resin film before molding (hereinafter referred to as the raw material film) is not particularly limited, but a suitable lower limit is preferably 2 μm or more, more preferably 5 μm or more, even more preferably 10 μm or more, more preferably 20 μm or more, more preferably 30 μm or more, and more preferably 40 μm or more. A suitable upper limit is preferably 250 μm or less, more preferably 200 μm or less, and even more preferably 150 μm or less. For example, the thickness of the raw material film is preferably 30 μm or more and 150 μm or less.

[0045] 1-3-1. Elongation (strain) of the raw material film

[0046] The raw material film used in this technology is preferably a film having a specific elongation. The elongation (also called strain) in the MD direction (direction of resin flow) of the raw material film used in this technology is not particularly limited, but a suitable lower limit is preferably 110% or more, more preferably 120% or more, even more preferably 130% or more, more preferably 140% or more, more preferably 150% or more, more preferably 160% or more, more preferably 170% or more, and more preferably 180% or more. A suitable upper limit is preferably 500% or less, more preferably 480% or less, even more preferably 450% or less, more preferably 430% or less, more preferably 410% or less, more preferably 400% or less, more preferably 380% or less, more preferably 350% or less, more preferably 330% or less, more preferably 300% or less, and more preferably 280% or less. For example, the elongation in the MD direction is preferably 140% to 500% and more preferably 150% to 450% from the viewpoint of improving the moldability of the rubber molded product according to this technology.

[0047] The elongation in the TD direction (direction perpendicular to the MD direction) of the raw material film is not particularly limited, but a suitable lower limit is preferably 110% or more, more preferably 120% or more, even more preferably 130% or more, more preferably 140% or more, even more preferably 150% or more, and more preferably 160% or more. A suitable upper limit is preferably 500% or less, more preferably 480% or less, even more preferably 450% or less, more preferably 430% or less, more preferably 410% or less, more preferably 400% or less, more preferably 380% or less, more preferably 350% or less, more preferably 330% or less, more preferably 300% or less, and more preferably 280% or less. For example, from the viewpoint of improving the moldability of the rubber molded product according to this technology, the elongation in the TD direction is preferably 140% to 500%, more preferably 150% to 450%.

[0048] The ratio of the elongation in the TD direction to the elongation in the MD direction (TD / MD) of the raw material film is not particularly limited, but a suitable lower limit is preferably 0.70 or more, more preferably 0.75 or more, and even more preferably 0.80 or more, and a suitable upper limit is preferably 1.30 or less, more preferably 1.25 or less, and even more preferably 1.20 or less. For example, from the viewpoint of improving the moldability of the rubber molded product according to this technology, the ratio of the elongation in the TD direction to the elongation in the MD direction is preferably 0.75 or more and 1.30 or less, and more preferably 0.80 or more and 1.20 or less.

[0049] The elongation (%) of the raw material film is measured in accordance with JIS K 7127:1999. Elongation refers to the elongation rate when the test specimen (100%) breaks. A dumbbell-shaped No. 5 test specimen made from the raw material film is used as the test specimen. The elongation of the raw material film is the value measured at a predetermined tensile speed.

[0050] 1-3-1-1. Elongation of PAEK resin film

[0051] The raw material film used in this technology is preferably a PAEK resin (preferably PEEK resin) film having a specific elongation. The specific elongation of the PAEK resin (preferably PEEK resin) film may be a combination of the elongation in the MD direction, the elongation in the TD direction, the (TD / MD) ratio, or a suitable upper or lower limit, as described in "Elongation (strain) of the raw material film" above.

[0052] The elongation in the MD direction of a PAEK resin (preferably PEEK resin) film is not particularly limited, but a preferred lower limit is preferably 130% or more, more preferably 140% or more, and even more preferably 150% or more. A preferred upper limit is preferably 370% or less, more preferably 360% or less, and even more preferably 350% or less. For example, the elongation in the MD direction of a PAEK resin (preferably PEEK resin) film is preferably 140% to 360%, and more preferably 150% to 350%.

[0053] The elongation in the TD direction of a PAEK resin (preferably PEEK resin) film is not particularly limited, but a preferred lower limit is preferably 130% or more, more preferably 140% or more, and even more preferably 150% or more. A preferred upper limit is preferably 370% or less, more preferably 360% or less, and even more preferably 350% or less. For example, the elongation in the TD direction of a PAEK resin (preferably PEEK resin) film is preferably 140% to 360%, and more preferably 150% to 350%.

[0054] The ratio of the elongation in the TD direction to the elongation in the MD direction (TD / MD) of a PAEK resin (preferably PEEK resin) film is not particularly limited, but a preferred lower limit is preferably 0.70 or more, more preferably 0.75 or more, and even more preferably 0.80 or more, and a preferred upper limit is preferably 1.30 or less, more preferably 1.25 or less, and even more preferably 1.20 or less. For example, the ratio of the elongation in the TD direction to the elongation in the MD direction of a PAEK resin (preferably PEEK resin) film is preferably 0.75 or more and 1.25 or less, and more preferably 0.80 or more and 1.20 or less.

[0055] 1-3-1-2. Elongation of PA resin film

[0056] The raw material film used in this technology has a specific elongation. The specific elongation of the PA resin (preferably PACM resin) film may be a combination of the elongation in the MD direction, the elongation in the TD direction, the suitable upper or lower limits regarding the (TD / MD) ratio, or any combination thereof, as described in "Elongation (strain) of the raw material film" above.

[0057] The elongation in the MD direction of a PA resin (preferably PACM resin) film is not particularly limited, but a preferred lower limit is preferably 130% or more, more preferably 140% or more, and even more preferably 150% or more. A preferred upper limit is preferably 500% or less, more preferably 480% or less, and even more preferably 450% or less. For example, the elongation in the MD direction of a PA resin (preferably PACM resin) film is preferably 140% to 480%, and more preferably 150% to 450%.

[0058] The elongation in the TD direction of a PA resin (preferably PACM resin) film is not particularly limited, but a preferred lower limit is preferably 130% or more, more preferably 140% or more, and even more preferably 150% or more. A preferred upper limit is preferably 500% or less, more preferably 480% or less, and even more preferably 450% or less. For example, the elongation in the TD direction of a PA resin (preferably PACM resin) film is preferably 140% to 480%, and more preferably 150% to 450%.

[0059] The ratio of the elongation in the TD direction to the elongation in the MD direction (TD / MD) of a PA resin (preferably PACM resin) film is not particularly limited, but a preferred lower limit is preferably 0.70 or more, more preferably 0.75 or more, and even more preferably 0.80 or more, and a preferred upper limit is preferably 1.30 or less, more preferably 1.25 or less, and even more preferably 1.20 or less. For example, the ratio of the elongation in the TD direction to the elongation in the MD direction of a PA resin (preferably PACM resin) film is preferably 0.75 or more and 1.25 or less, and more preferably 0.80 or more and 1.20 or less.

[0060] 1-3-2. Tensile strength of raw material film

[0061] The tensile strength in the MD direction of the raw material film used in this technology is not particularly limited, but a preferred lower limit is preferably 40 MPa or more, more preferably 50 MPa or more, more preferably 60 MPa or more, and even more preferably 70 MPa or more. A preferred upper limit is preferably 200 MPa or less, more preferably 190 MPa or less, even more preferably 180 MPa or less, even more preferably 170 MPa or less, and even more preferably 160 MPa or less. For example, from the viewpoint of improving the moldability of the rubber molded product according to this technology, the tensile strength in the MD direction is preferably 50 MPa or more and 170 MPa or less, and more preferably 60 MPa or more and 160 MPa or less.

[0062] The tensile strength in the TD direction of the raw material film used in this technology is not particularly limited, but a preferred lower limit is preferably 40 MPa or more, more preferably 50 MPa or more, more preferably 60 MPa or more, and even more preferably 70 MPa or more. A preferred upper limit is preferably 200 MPa or less, more preferably 190 MPa or less, even more preferably 180 MPa or less, even more preferably 170 MPa or less, even more preferably 160 MPa or less, and even more preferably 150 MPa or less. For example, from the viewpoint of improving the moldability of the rubber molded product according to this technology, the tensile strength in the TD direction is preferably 50 MPa or more and 170 MPa or less, and more preferably 60 MPa or more and 160 MPa or less.

[0063] The ratio of the tensile strength in the TD direction to the tensile strength in the MD direction (TD / MD) of the raw film is not particularly limited, but a preferred lower limit is preferably 0.70 or more, more preferably 0.75 or more, and even more preferably 0.80 or more, and a preferred upper limit is preferably 1.10 or less, more preferably 1.05 or less, and even more preferably 1.00 or less. For example, from the viewpoint of improving the moldability of the rubber molded product according to this technology, the ratio of the tensile strength in the TD direction to the tensile strength in the MD direction (TD / MD) is preferably 0.75 or more and 1.05 or less, and more preferably 0.80 or more and 1.00 or less.

[0064] The tensile strength (MPa) of the raw material film was measured using the same measurement method as the elongation of the raw material film described above, and the tensile strength at which the test specimen broke was calculated.

[0065] 1-3-2-1. Tensile strength of PAEK resin film

[0066] The raw material film used in this technology is preferably a PAEK resin (preferably PEEK resin) film having a specific tensile strength. The specific tensile strength of the PAEK resin (preferably PEEK resin) film may be a combination of the suitable upper or lower limits for the tensile strength in the MD direction, the tensile strength in the TD direction, and the tensile strength (TD / MD) ratio, as described in "Tensile Strength of Raw Material Film" above.

[0067] The tensile strength in the MD direction of a PAEK resin (preferably PEEK resin) film is not particularly limited, but a preferred lower limit is preferably 70 MPa or more, more preferably 80 MPa or more, even more preferably 90 MPa or more, even more preferably 100 MPa or more, even more preferably 110 MPa or more, and even more preferably 120 MPa or more. A preferred upper limit is preferably 180 MPa or less, even more preferably 170 MPa or less, and even more preferably 160 MPa or less. For example, the tensile strength in the MD direction of a PAEK resin (preferably PEEK resin) film is preferably 110 MPa or more and 170 MPa or less, and more preferably 100 MPa or more and 160 MPa or less.

[0068] The tensile strength in the TD direction of a PAEK resin (preferably PEEK resin) film is not particularly limited, but a preferred lower limit is preferably 70 MPa or more, more preferably 80 MPa or more, even more preferably 90 MPa or more, more preferably 100 MPa or more, more preferably 110 MPa or more, even more preferably 100 MPa or more, even more preferably 110 MPa or more, and even more preferably 120 MPa or more. A preferred upper limit is preferably 180 MPa or less, more preferably 170 MPa or less, and even more preferably 160 MPa or less. For example, the tensile strength in the TD direction of a PAEK resin (preferably PEEK resin) film is preferably 110 MPa or more and 170 MPa or less, and more preferably 100 MPa or more and 160 MPa or less.

[0069] The ratio of the tensile strength in the TD direction to the tensile strength in the MD direction (TD / MD) is not particularly limited, but a preferred lower limit is preferably 0.70 or more, more preferably 0.75 or more, and even more preferably 0.80 or more, and a preferred upper limit is preferably 1.10 or less, more preferably 1.05 or less, and even more preferably 1.00 or less. For example, the ratio of the tensile strength in the TD direction to the tensile strength in the MD direction (TD / MD) is preferably 0.75 or more and 1.05 or less, and more preferably 0.80 or more and 1.00 or less.

[0070] 1-3-2-2. Tensile strength of PA resin film

[0071] The raw material film used in this technology is preferably a PA resin (preferably PACM resin) film having a specific tensile strength. The specific tensile strength of the PA resin (preferably PACM resin) film may be a combination of the following, as described in "Tensile Strength of Raw Material Film" above: suitable upper or lower limits for the tensile strength in the MD direction, the tensile strength in the TD direction, and the tensile strength (TD / MD) ratio.

[0072] The tensile strength in the MD direction of a PA resin (preferably PACM resin) film is not particularly limited, but a preferred lower limit is preferably 30 MPa or more, more preferably 40 MPa or more, even more preferably 50 MPa or more, and even more preferably 60 MPa or more. A preferred upper limit is preferably 120 MPa or less, more preferably 110 MPa or less, and even more preferably 100 MPa or less. For example, the tensile strength in the MD direction of a PA resin (preferably PACM resin) film is preferably 40 MPa or more and 110 MPa or less, and more preferably 50 MPa or more and 100 MPa or less.

[0073] The tensile strength in the TD direction of a PA resin (preferably PACM resin) film is not particularly limited, but a preferred lower limit is preferably 30 MPa or more, more preferably 40 MPa or more, even more preferably 50 MPa or more, and even more preferably 60 MPa or more. A preferred upper limit is preferably 120 MPa or less, more preferably 110 MPa or less, even more preferably 100 MPa or less, and even more preferably 90 MPa or less. For example, the tensile strength in the TD direction of a PA resin (preferably PACM resin) film is preferably 40 MPa or more and 110 MPa or less, and more preferably 50 MPa or more and 100 MPa or less.

[0074] The ratio of the tensile strength in the TD direction to the tensile strength in the MD direction (TD / MD) of a PA resin (preferably PACM resin) film is not particularly limited, but a preferred lower limit is preferably 0.70 or more, more preferably 0.75 or more, and even more preferably 0.80 or more, and a preferred upper limit is preferably 1.10 or less, more preferably 1.05 or less, and even more preferably 1.00 or less. For example, the ratio of the tensile strength in the TD direction to the tensile strength in the MD direction (TD / MD) of a PA resin (preferably PACM resin) film is preferably 0.75 or more and 1.05 or less, and more preferably 0.80 or more and 1.00 or less.

[0075] 1-3-3. Oxygen permeability coefficient of raw material film

[0076] The raw material film used in this technology preferably has a specific oxygen permeability coefficient. The oxygen permeability coefficient of the raw material film at 23 ± 2°C is not particularly limited. However, from the perspective of improving the gas barrier properties of the rubber molded product according to this technology, it is preferable that the oxygen permeability coefficient is lower, preferably 2.00×10 －１６ mol·m / (m ２ ·s·Pa) or less, more preferably 1.00×10 －１７ mol·m / (m ２ ·s·Pa) or less, still more preferably 8.50×10 －１７ mol·m / (m ２ ·s·Pa) or less, even more preferably 7.00×10 －１７ mol·m / (m ２ ·s·Pa) or less.

[0077] The oxygen permeability coefficient (mol·m / (m ２ ·s·Pa)) of the raw material film at 23 ± 2°C is measured in accordance with JIS K 7126-1:2006.

[0078] 1-3-4. Crystallinity of the raw material film

[0079] The raw material film used in this technology is preferably a resin film having a specific crystallinity. The crystallinity of the raw material film is preferably not highly crystalline. That is, the crystallinity of the raw material film is preferably low crystalline and may be amorphous. In this specification, low crystallinity can also include microcrystallinity.

[0080] In this technology, for the measurement of the crystallinity and the determination of the crystallinity of the raw material film, it is preferable to use the X-ray diffraction method (XRD method) and / or the differential scanning calorimetry method (DSC method). These methods can be performed using known measurement methods or known measuring devices.

[0081] 1-3-4-1. Calculation of crystallinity and determination of crystallinity using the XRD method

[0082] In the XRD method, the crystallinity can be calculated from the chart of the raw material film obtained using an X-ray diffractometer. Based on the calculated crystallinity, it is preferable to determine the crystallinity of the raw material film.

[0083] The degree of crystallinity using the XRD method is calculated by substituting the area of ​​a predetermined diffraction peak and the area of ​​the amorphous region into the following equation (Equation 1). The predetermined diffraction peak is the diffraction peak originating from the crystals of the raw material film, and the area of ​​the predetermined diffraction peak is the sum of the areas of the diffraction peaks originating from the crystals of the raw material film. The area of ​​the amorphous region is the area of ​​the peaks originating from the amorphous (amorphous) material of the raw material film.

[0084]

[0085] The raw material film used in this technology is preferably a resin film having a specific range of crystallinity determined by XRD. The degree of crystallinity of the raw material film calculated using XRD is not particularly limited, but a suitable upper limit is preferably 30% or less, more preferably 25% or less, even more preferably 20% or less, 10% or less, 5% or less, or 3% or less. Alternatively, it is preferable that no diffraction peaks are detected.

[0086] The raw material film used in this technology is preferably one or two selected from PAEK resin (preferably PEEK resin) film and PA resin (preferably PACM resin) film having a specific range of crystallinity determined by the XRD method. The specific range of crystallinity calculated by the XRD method for the PAEK resin (preferably PEEK resin) film or the PA resin (preferably PACM resin) film may be the degree of crystallinity described in "Degree of Crystallinity of Raw Material Film Calculated Using the XRD Method" above, as appropriate.

[0087] The degree of crystallinity of a PAEK resin (preferably PEEK resin) film calculated using the XRD method is not particularly limited, but a preferred upper limit is preferably 30% or less, more preferably 25% or less, even more preferably 20% or less, 10% or less, 5% or less, or 3% or less. Alternatively, it is preferable that no diffraction peaks are detected in the PAEK resin (preferably PEEK resin) film. In this specification, a PAEK resin (preferably PEEK resin) film having the above degree of crystallinity, or a PAEK resin (preferably PEEK resin) film in which no diffraction peaks are detected, is determined to be a low-crystallinity PAEK resin (preferably PEEK resin) film.

[0088] The degree of crystallinity of a PA resin (preferably PACM resin) film calculated using the XRD method is not particularly limited, but a suitable upper limit may be preferably 20% or less, more preferably 18% or less, and even more preferably 15% or less, 10% or less, or 5% or less. Alternatively, it is preferable that no diffraction peaks are detected in the PA resin (preferably PACM resin) film. In this specification, a PA resin (preferably PACM resin) film having the above degree of crystallinity, or a PA resin (preferably PACM resin) film in which no diffraction peaks are detected, is determined to be a low-crystallinity PA resin (preferably PACM resin) film.

[0089] 1-3-4-2. Calculation of crystallization energy or degree of crystallinity and determination of crystallinity using the DSC method.

[0090] In the DSC method, the crystallization energy or degree of crystallinity can be calculated from a chart of the raw material film obtained using a differential scanning calorimeter. It is preferable to determine the crystallinity of the raw material film based on the calculated crystallization energy or degree of crystallinity.

[0091] The crystallization energy using the DSC method is calculated by determining the area of ​​the exothermic peak originating from the crystallization of the raw material film, and then dividing this area by the weight of the sample (raw material film).

[0092] The degree of crystallinity using the DSC method is calculated by substituting the crystallization energy mentioned above, as well as the melting energy and the melting energy of a perfect crystal, into the following equation (Equation 2). The melting energy is calculated by determining the area of ​​the melting peak originating from the melting of the raw material film and dividing the calculated area by the weight of the sample (raw material film). Normally, the melting energy is a negative value, but when calculating the degree of crystallinity, the absolute value of the melting energy is used. The melting energy of a perfect crystal can be cited, for example, from Non-Patent Document 1 (M. Doumeng et al., Polymer Testing, 93 (2021), Article 106878, 2021:1-10).

[0093]

[0094] The raw material film used in this technology is preferably a PAEK resin (preferably PEEK resin) film having a specific range of crystallinity determined by the DSC method. The crystallization energy of the PAEK resin (preferably PEEK resin) film calculated using the DSC method is not particularly limited, but a suitable lower limit is preferably 1 J / g or more, more preferably 3 J / g or more, even more preferably 5 J / g or more, more preferably 8 J / g or more, more preferably 10 J / g or more, more preferably 13 J / g or more, 15 J / g or more, 18 J / g or more, or 20 J / g or more, and a suitable upper limit is at least less than or equal to the melting energy of the PEEK resin film.

[0095] The degree of crystallinity of a PAEK resin (preferably PEEK resin) film calculated using the DSC method is not particularly limited, but a suitable upper limit is preferably 25% or less, more preferably 20% or less, even more preferably 15% or less, 13% or less, 8% or less, 5% or less, or 3% or less. In this specification, a PAEK resin (preferably PEEK resin) film having the above-mentioned crystallinity energy or degree of crystallinity is determined to be a low-crystallinity PAEK resin (preferably PEEK resin) film. In this specification, a PAEK resin (preferably PEEK resin) film having a crystallinity energy less than 1 J / g, or a PAEK resin (preferably PEEK resin) film for which crystallinity energy cannot be calculated (no exothermic peak is detected) is determined to be a high-crystallinity PAEK resin (preferably PEEK resin) film.

[0096] 1-3-5. Leaching Resistance of Raw Material Film The raw material film used in this technology is preferably a resin film having specific elution resistance. If a rubber molded product exhibits excellent elution resistance, it can be determined that the raw material film used is a film having specific elution resistance. The raw material film and the rubber molded product formed using the rubber material can be used as samples to perform an evaluation based on a general elution test (18th edition of the Japanese Pharmacopoeia, First Supplement, 7.03 Test Method for Rubber Stoppers for Infusions, 3. Leaching Test). Evaluation items include, for example, one or more selected from pH value, ultraviolet absorption spectrum, transmittance, potassium permanganate reducing substance, foaming, and properties (the test solution is colorless and clear, and no foreign matter is visible to the naked eye). The more items there are, the better from the viewpoint of evaluating elution resistance. Of these, it is preferable to include at least the pH value as an evaluation item from the viewpoint of elution resistance. Then, using the sample, if it conforms to the standards specified in each evaluation item described above (18th Revised Japanese Pharmacopoeia, First Supplement, 7.03 Test Method for Rubber Stoppers for Infusions, 3. Leaching Test), it can be judged as passing, and if it does not conform, it can be judged as failing. Those judged as passing can be said to have elution resistance. Furthermore, it is preferable that the rubber molded product laminated with a non-fluorine resin film and the raw material film used therein have a relatively good evaluation when compared with the evaluation of the rubber molded product laminated with ETFE. In this case, it is desirable to use the same materials (rubber material) and manufacturing method as the raw material film.

[0097] 1-3-6. Electron beam resistance of raw material film. The raw material film used in this technology is preferably a resin film having a specific electron beam resistance. If a rubber molded product has excellent electron beam resistance, it can be determined that the raw material film used at that time is a film having a specific electron beam resistance.

[0098] Using raw material films and rubber molded products formed from rubber materials as samples, the electron beam-irradiated samples can be evaluated based on a general elution test (18th Revised Japanese Pharmacopoeia, First Supplement 7.03, Test Method for Rubber Stoppers for Infusions, 3. Leaching Test). If the electron beam resistance of the rubber molded product is excellent, it can be determined that the raw material film used is a film with specific electron beam resistance. As evaluation items, the evaluation items listed in "1-3-5. Leaching Resistance of Raw Material Films" above can be appropriately adopted, and one or more of these may be selected. The more items there are, the more preferable it is from the viewpoint of electron beam resistance evaluation, and it is preferable to include at least the pH value as an evaluation item from the viewpoint of electron beam resistance. Then, using the electron beam-irradiated sample, if it conforms to the standards specified in each evaluation item described above (18th Revised Japanese Pharmacopoeia, First Supplement 7.03, Test Method for Rubber Stoppers for Infusions, 3. Leaching Test), it can be judged as passing, and if it does not conform, it can be judged as failing. Furthermore, even if the electron beam-irradiated sample is judged to conform to the standard, if the evaluation results of the electron beam-irradiated sample are compared with the evaluation results of the unirradiated sample and the evaluation results of the electron beam-irradiated sample are worse, it can be determined that the sample (in other words, the raw material film) has deteriorated due to electron beam irradiation. When evaluating the unirradiated sample, the evaluation can be carried out in the same manner as the evaluation items described above, except that the electron beam-irradiated sample is replaced with the unirradiated sample. Regarding electron beam resistance, for relative evaluation by comparison with the evaluation of rubber molded products laminated with ETFE, the content of the relative evaluation described in "1-3-5. Leaching Resistance of Raw Material Film" above may be appropriately adopted, and rubber molded products and raw material films used therein that have a good relative evaluation are preferred.

[0099] 1-4. Application of rubber molded products related to this technology

[0100] The rubber molded articles relating to this technology are not particularly limited, but are preferably used as sealing materials for containers or devices, and more preferably as sealing materials for containers or devices used in pharmaceutical and medical applications. The rubber molded articles are preferably applied as sealing materials for containers or devices that come into contact with chemicals. The situations in which chemicals come into contact with the articles are not particularly limited, but include use and storage. The chemicals may be liquids, solids, gases, or combinations of one or more selected from these (e.g., a liquid layer and a gas layer, a solid layer and a gas layer). Furthermore, the rubber molded articles are preferably applied to seal containers for storing pharmaceuticals and other drugs. The rubber molded articles relating to this technology are not particularly limited, but include, for example, rubber stoppers for sealing containers and gaskets provided at the tip of a plunger in a syringe to prevent leakage. Furthermore, examples of rubber molded articles include rubber stoppers, gaskets, nozzle caps, cylinder caps, and inner stoppers, and one or more of these can be used. Furthermore, the film layer included in the rubber molded product preferably directly or indirectly covers the bare surface of the rubber substrate (part or all of the legs or top surface) and is positioned on the surface of the rubber molded product.

[0101] 2. Method for Manufacturing Rubber Molded Articles The rubber molded articles according to this technology can be manufactured by known manufacturing methods using a raw material film and raw material rubber (rubber material). Known manufacturing methods are not particularly limited, but examples include a method of coating the raw material rubber with a raw material film; a method of coating (applying, etc.) the raw material rubber with the resin raw material of the film. The raw material rubber (rubber material) may also be in the form of a sheet. To improve the adhesion between the raw material film and the rubber substrate, surface treatment may be applied to the surface of the raw material film and / or rubber substrate before molding. The surface to be surface-treated is preferably the surface in contact with the raw material film and the rubber substrate, and it is preferable to surface-treat either one or both, and more preferably the raw material film. The surface treatment method is not particularly limited, but for example, one or more known methods selected from chemical treatment methods, corona discharge methods, etching methods such as sputtering and plasma treatment can be used. Of these, etching methods such as sputtering and plasma treatment are preferred from the viewpoint of avoiding discoloration of the treated surface, simplifying equipment, and product control. This technology can utilize known rubber mold molding methods, such as direct pressure molding (compression molding) and injection molding (transfer molding), of which one or more can be selected, with compression molding being preferred. This technology provides a method for manufacturing rubber molded products by processing raw material film and raw material rubber using a mold, and compression molding may be performed by applying pressure and heat for a predetermined time during processing.

[0102] The manufacturing of rubber molded articles using this technology, in which a raw material film is directly or indirectly coated onto the raw surface of a rubber substrate, can utilize known compression molding. Known compression molding methods include, for example, compression molding in which the lower part (sometimes referred to as the leg portion) and upper part (sometimes referred to as the top surface portion) of a rubber molded article are molded simultaneously, or compression molding in which the lower part and upper part of a rubber molded article are molded in stages. An example of compression molding in which the lower part and upper part of a rubber molded article are molded simultaneously is the compression molding disclosed in Patent Document 2 (Japanese Patent Application Publication No. 2014-131874).

[0103] 2-1. Compression molding, a method for gradually molding the lower and upper parts of a rubber molded product.

[0104] This technology can provide a compression molding method for molding the lower and upper parts of a rubber molded product in stages. An example of such compression molding is the compression molding disclosed in Patent Document 3 (Japanese Patent Publication No. 61-272134).

[0105] In this compression molding process, a first mold is used to form the lower part of the rubber molded product. The raw material film and the sheet-like rubber material that forms the rubber base are pressurized and heated, thereby forming a primary molded product in which only the lower part of the rubber molded product is formed. The manufacturing conditions using the first mold are not particularly limited, but may be appropriately changed depending on the type of raw material film and rubber material. The heating temperature is preferably, for example, 130°C to 180°C. The clamping pressure is, for example, 20 kg / cm². ２ ~120 kg / cm ２ It is preferable that this is the case. The heating temperature and the time for applying the clamping pressure are preferably, for example, 5 to 20 minutes.

[0106] Next, the rubber molded product can be formed by pressurizing and heating the first molded product (lower part) and the rubber material using a second mold for forming the upper part of the rubber molded product. The manufacturing conditions using the second mold at this time are not particularly limited, but may be appropriately changed depending on the type of first molded product and rubber material. The heating temperature is preferably, for example, 130°C to 180°C. The clamping pressure is, for example, 20 kg / cm². ２ ~120 kg / cm ２ It is preferable that this is the case. The heating temperature and the time for applying the clamping pressure are preferably, for example, 5 to 20 minutes.

[0107] In the compression molding process described above, the film layer is placed only at the bottom of the rubber substrate in the molded rubber product. However, the film layer can be placed at both the bottom and top of the rubber substrate as needed. That is, if necessary, the primary molded product, the raw rubber (rubber material), and the raw film can be placed before the pressurization and heating using the second mold.

[0108] The present invention will be described in more detail below based on examples. These examples are representative examples of the present invention, and the scope of the present invention is not limited to these examples.

[0109] <Test Examples 1-7> The rubber molded product of Test Example 1 (Example 1) contains a film of low-crystallinity PEEK resin, a type of PEEK resin (material name: Shin-Etsu Sepla Film). （Ｒ） Low-crystallinity type; manufactured by Shin-Etsu Polymer Co., Ltd., film thickness 50 μm) was used for the rubber molded product in Test Example 2 (Example 2). A film of low-crystallinity PEEK resin, a type of PEEK resin (material name [Superior （ＴＭ） [UT αHN-type]; manufactured by Mitsubishi Chemical Group Corporation, film thickness 100 μm) was used. The rubber molded product of Test Example 3 (Example 3) used a film of low-crystallinity PEEK resin, which is a type of PEEK resin (material name [Superior （ＴＭ） [UT HT-type]; manufactured by Mitsubishi Chemical Group Corporation, film thickness 100 μm) was used. The rubber molded product in Test Example 4 (Example 4) used a low-crystallinity PA resin film (material name [Diamilon]).（ＴＭ） [MF]; manufactured by Mitsubishi Chemical Group Corporation, film thickness 100 μm) was used. The rubber molded product of Test Example 5 (Comparative Example 1) used a film of highly crystalline PEEK resin, a type of PEEK resin (material name [EXPEEK]). （Ｒ） ]; Kurabo Corporation, film thickness 50 μm) was used for the rubber molded product in Test Example 6 (Comparative Example 2). A film of highly crystalline PEEK resin, a type of PEEK resin (material name [Shin-Etsu Sepla Film]) was used. （Ｒ） High-crystallinity type; manufactured by Shin-Etsu Polymer Co., Ltd., film thickness 100 μm) was used. In Test Example 7 (Reference Example 1), a high-crystallinity ETFE (ethylene tetrafluoroethylene) film (film thickness 100 μm) manufactured by Nitto Denko Corporation was used. Butyl rubber (D713 (without film coating): manufactured by Daikyo Seiko Co., Ltd.) and chlorinated butyl rubber (D21-7S (without film coating): manufactured by Daikyo Seiko Co., Ltd.) were used as rubber materials for the rubber molded products in Test Examples 1 to 7.

[0110] The elongation and tensile strength of each film used in these test examples 1 to 7 are shown in Table 4, which will be described later.

[0111] <Moldability Test> A rubber molded product was manufactured by applying the raw material film of Test Example 1 to the film layer. In Test Example 1-1, butyl rubber was used as the rubber material, and in Test Example 1-2, chlorinated butyl rubber was used. Unless otherwise specified, Test Example ○-1 and "-1" refer to rubber molded products using butyl rubber, and Test Example ○-2 and "-2" refer to rubber molded products using chlorinated butyl rubber. The rubber molded product was molded on a prototype scale by the method described in "2-1. Compression molding for stepwise molding of the lower and upper parts of the rubber molded product" above. On the prototype scale, a first mold and a second mold were used so that the final rubber molded product would be a rubber stopper for a vial bottle with legs attached to the disc-shaped lower part as shown in Figure 1 (diameter 19.05 mm, height 8.00 mm). The holes in this mold were 8 x 8, and 64 pieces were obtained in one production run. Regarding the manufacturing conditions when using the first and second molds, the heating temperature was 130°C to 180°C, and the clamping pressure was 20 kg / cm². ２~120 kg / cm ２ The heating temperature and clamping pressure were applied for 5 to 20 minutes. In this way, the rubber molded product of Test Example 1-1 and the rubber molded product of Test Example 1-2 were obtained. The rubber molded products of Test Examples 2 to 7 were obtained in the same manner, except that the raw material film was changed. The obtained rubber molded product was a rubber stopper for a vial bottle with legs attached to the bottom of a disc shape, as shown in Figure 1. This rubber molded product had a diameter of 19.05 mm and a height of 8.00 mm. Furthermore, the desired rubber molded products of Test Examples 2 to 7 were obtained in the same manner as in Test Example 1, except that the raw material film was changed.

[0112] Using a prototype scale, the molded rubber products were visually inspected for any tears or peeling of the film layer. While a higher number of acceptable products relative to the total is desirable, a rate of 80% or higher can be considered good, and a rate of 90% or higher can be considered excellent.

[0113] In Test Examples 1-1 to 4-1 and 7-1, which used butyl rubber as the rubber material, no tearing or peeling of the film layer was observed, and the number of acceptable products was 100% of the total, with at least 80% being acceptable. Therefore, the moldability evaluation for these products was satisfactory and excellent. On the other hand, in Test Examples 5-1 to 6-1, tearing or peeling of the film layer was observed in all of the rubber molded products, so the moldability evaluation for these products was unsatisfactory. Similarly, in Test Examples 1-2 to 4-2 and 7-2, which used chlorinated butyl rubber as the rubber material, 100% of the number of acceptable products was observed, and the moldability evaluation for these products was satisfactory and excellent. On the other hand, in Test Examples 5-2 to 6-2, tearing or peeling of the film layer was observed in all of the rubber molded products, so the moldability evaluation for these products was unsatisfactory.

[0114] Therefore, the PAEK resin (preferably PEEK resin) films of Test Examples 1-3 and the PA resin (preferably PACM resin) film of Test Example 4 were judged to be films with excellent moldability when obtaining rubber molded products. On the other hand, the highly crystalline PEEK resins of Test Examples 5-6 were judged to be films with poor moldability when obtaining rubber molded products.

[0115] Furthermore, the PAEK resin (preferably PEEK resin) films of Test Examples 1 to 3 and the PA resin (preferably PACM resin) film of Test Example 4 can be surface-treated by an etching method using plasma treatment, thereby further improving the adhesion between the rubber substrate and the resin film. By bringing the surface-treated film resin surface into contact with the surface of the rubber substrate, a rubber molded product can be obtained by the compression molding described above.

[0116]

[0117] <Elongation Test and Tensile Strength Test> Elongation tests and tensile strength tests were performed on the raw film used in each test example. The elongation tests and tensile strength tests were measured in accordance with JIS K 7127:1999. The elongation tests and tensile strength tests were measured under a tensile speed of 500 mm / min.

[0118] <Oxygen Permeability Test> The raw material films used in each test example were subjected to oxygen permeability tests at 23±2°C. The oxygen permeability tests were performed in accordance with JIS K 7126-1:2006. The oxygen permeability coefficient of the raw material film at 23±2°C was 2.00 × 10⁻¹⁰. －１６ mol・m / (m) ２ The gas barrier properties of the rubber molded product were judged to be good when the value was less than or equal to s・Pa. The oxygen permeability coefficients of the PAEK resin (preferably PEEK resin) film in Test Example 1, the PA resin (preferably PACM resin) film in Test Example 4, and the ETFE resin film in Test Example 7 were 7.37 × 10⁻¹⁰. －１７ , 1.16 × 10 －１６ , 3.95 x 10 －１６ Furthermore, the oxygen permeability coefficient was below the above standard, and in both cases, we considered the gas barrier properties of the rubber molded product to be good.

[0119] <Leaching Test> The rubber molded products (rubber base material: butyl rubber, chlorinated butyl rubber) obtained in Test Examples 1, 4, and 7 were evaluated based on the leaching test (18th Edition of the Japanese Pharmacopoeia, First Supplement, 7.03 Test Method for Rubber Stoppers for Infusions, 3. Leaching Test). In the case of Test Example ○-1, the rubber molded product was made using butyl rubber, and in the case of Test Example ○-2, the rubber molded product was made using chlorinated butyl rubber. The evaluation items included pH value, ultraviolet absorption spectrum, transmittance, potassium permanganate reducing substance, foaming, and properties (the test solution was colorless and clear, and no foreign matter was observed with the naked eye).

[0120] <<pH value evaluation in the elution test>> After washing the rubber stopper with water, dry it at room temperature. Surface area is approximately 150 cm². ２ Take a number of samples such that the sample size is 1 cm, place these rubber stopper samples in a hard glass container, and ２ Add water to make a total volume of 2 mL per container, properly stopper the container, and heat it in an autoclaver at 121°C for 1 hour. Then, remove the hard glass container and let it stand at room temperature. Immediately remove the rubber stopper, and this liquid will be used as the test solution. Separately, a blank test solution (blank) is prepared using only water, in the same manner as above, except that a rubber stopper sample is not used.

[0121] The following tests are performed on the test solution and blank solution. Take 20 mL each of the test solution (sample) and blank solution, add 1 mL of a solution made by dissolving 1.0 g of potassium chloride in water to each, and measure the pH of both solutions. If the pH difference between these two solutions is 1.0 or less, the pH value standard is considered to be met. Even if the pH difference between the two solutions is within the range of compliance with the pH value standard, the closer the pH difference between the two solutions is to 0.0, the better the result is, and the closer it is to 1.0, the worse the result is.

[0122] Test Examples 1 (Example 1), 4 (Example 4), and 7 (Reference Example 1) (these rubber substrates: butyl rubber and chlorinated butyl rubber) all passed all evaluation items of these <elution tests> (pH value, ultraviolet absorption spectrum, transmittance, potassium permanganate reducing substance, foaming, and properties). Regarding the pH value evaluation in Test Examples 1, 4, and 7, there was almost no difference in pH between the two solutions, and the pH value evaluation was very good. Therefore, it was determined that the rubber molded products of Test Examples 1, 4, and 7 have elution resistance. From this, it was determined that PAEK resin (preferably PEEK resin) film and PA resin (preferably PACM resin) film are resins that have excellent elution resistance for use in rubber molded products.

[0123] <Electron Beam Resistance Test> The electron beam-irradiated rubber molded products used in the electron beam resistance test were obtained by irradiating the rubber molded products obtained in Test Examples 1, 4, and 7 with electron beams. To obtain the electron beam-irradiated rubber molded products, the electron beam was irradiated using the electron accelerator Rhodetron TT200 (manufactured by IBA) with a beam energy set to 10 MeV, and the target dose at the surface was 50 kGy. This electron beam-irradiated rubber molded product was evaluated based on "18th Edition Japanese Pharmacopoeia, First Supplement 7.03 Test Methods for Rubber Stoppers for Infusions 3. Leaching Test". Specifically, the electron beam-irradiated rubber molded product was used to perform tests on pH value, ultraviolet absorption spectrum, transmittance, potassium permanganate reducing substance, foaming, and properties (test solution was colorless and clear, no foreign matter was observed with the naked eye), and these were evaluated. Where necessary, rubber molded products without electron beam irradiation (the rubber molded products obtained in Test Examples 1, 4, and 7) were prepared as controls, and the same test items were performed. The results are shown in Table 2 below.

[0124]

[0125] In the case of pH value evaluation in the electron beam resistance test, the procedure was carried out in the same manner as described in <<pH Value Evaluation in Leaching Test>> above, except that the "rubber stopper" was replaced with the "electron beam irradiated rubber stopper". The pH difference between the test solution (electron beam irradiated rubber stopper) and the blank solution (water) was confirmed and evaluated. If the difference in pH value between the test solution of the electron beam irradiated rubber stopper and the blank solution was 1.0 or less, the rubber molded product and the resin film used therein were deemed to be compliant (pass) in the electron beam resistance test.

[0126] Using rubber molded products without electron beam irradiation, the pH difference between the test solution (rubber stopper without electron beam irradiation) and the blank solution (water) was confirmed in the same manner. The results of the pH difference between the test solution (rubber stopper with electron beam irradiation) and the blank solution (water) were compared with the results of the pH difference between the test solution (rubber stopper without electron beam irradiation) and the blank solution (water). Although the results were deemed acceptable (passing), it was determined that the larger these pH differences were, the worse the pH difference was due to electron beam irradiation, and the lower the electron beam resistance.

[0127] The above evaluations of electron beam resistance were performed on the rubber molded articles of Test Example 1 (Example 1), Test Example 4 (Example 4), and Test Example 7 (Reference Example 1). The rubber molded articles of Test Example 1-2 (chlorinated butyl rubber), Test Example 4-1 (butyl rubber), and Test Example 4-2 (chlorinated butyl rubber) all conformed to the specified standards for all evaluation items and passed. On the other hand, for the rubber molded articles (2 types) of Reference Example 1 (ETFE), the pH value evaluation was unfavorable for the butyl rubber substrate and "favorable (but worsened)" for the chlorinated butyl rubber substrate.

[0128] In the pH evaluation of electron beam resistance in Test Examples 1 and 4, there was almost no difference in pH between the two solutions, and the pH evaluation was very good. However, in the pH evaluation of electron beam resistance in Test Example 7, the difference in pH between the sample solution with electron beam irradiation and the blank solution was high at approximately 0.8, although it was within the acceptable range. In the case of the blank solution without electron beam irradiation, there was almost no difference in pH between the two solutions. Therefore, the pH evaluation of electron beam resistance in Test Example 7 was "acceptable (deteriorated)".

[0129] Furthermore, the rubber molded articles of Test Example 1 (PAEK resin (preferably PEEK resin)) and Test Example 4 (PA resin (preferably PACM resin)) were found to be superior in terms of pH value evaluation when compared with the results of each evaluation item of the rubber molded article of Reference Example (ETFE). For this reason, it was determined that electron beam resistance was good if at least the pH value evaluation item was passed.

[0130] Based on the above, it was determined that rubber molded products using PAEK resin (preferably PEEK resin) film and rubber molded products using PA resin (preferably PACM resin) film had excellent electron beam resistance. Therefore, it was determined that PAEK resin (preferably PEEK resin) film and PA resin (preferably PACM resin) film are resins with excellent electron beam resistance for use in rubber molded products.

[0131] <Calculation of the degree of crystallinity of resin film using the XRD method>

[0132] The crystallinity was measured and calculated using the XRD method with an X-ray diffractometer (PANlytical, X'pert PRO MPD) and the XRD analysis software attached to the XRD diffractometer. The XRD analysis software may also be an XRD analysis tool. The XRD analysis software is capable of performing XRD measurements and deriving measurement results, detecting and calculating diffraction peaks and their areas, amorphous regions and their areas, etc., necessary for calculating the crystallinity from the measurement results, and calculating the crystallinity of each resin film considering these calculated areas. The analysis software or analysis tool used in this technology can also perform automated analysis, which automatically executes the calculation and analysis from measurement results to crystallinity using a processor such as a CPU and memory such as ROM built into a computer or server, and in this case, automated analysis was performed.

[0133] Measurement conditions: Target: Cu anode Divergence slit: 1 / 4° Divergence prevention slit: 1°, 5.5 mm Scanning range (2θ): 5-50° Scan step time: 100 sec Scan step width: 0.0334°

[0134] The degree of crystallinity was calculated by substituting the area of ​​the diffraction peak and the area of ​​the amorphous region into the above-mentioned (Equation 1). More specifically, it was calculated using the following (Equation 3). Here, as shown in Non-Patent Literature 3 (H. Liu et al., Royal Society Open Science 5: 171775, 25 April 2018), diffraction peaks originating from the (110) plane, (111) plane, (200) plane, and (211) plane were used as standard for detecting diffraction peaks originating from the PEEK resin.

[0135]

[0136] Figure 2 is a chart showing the measurement results obtained using the X-ray diffractometer: the upper panel shows the low-crystallinity PEEK resin film of Test Example 3 (Example 3), and the lower panel shows the PA resin film (PACM-12 resin film) of Test Example 4 (Example 4).

[0137] As shown in the upper part of Figure 2, when the PEEK resin film of Test Example 3 was measured using the X-ray diffractometer described above, no diffraction peaks originating from crystals were observed, and therefore the degree of crystallinity could not be calculated.

[0138] Furthermore, diffraction peaks originating from PEEK resin can be found in Non-Patent Literature 3 (H. Liu et al., Royal Society Open Science 5: 171775, 25 April 2018). As can be seen from "3.4. Microstructure characterization," "Figure 7," and "Table 3," the diffraction peaks originating from the crystals of the PEEK resin in Non-Patent Literature 3 are 18.8° ((110) plane), 20.7° ((111) plane), 22.9° ((200) plane), and 28.9° ((211) plane), indicating a crystallinity of PEEK of 40.9–45.3%.

[0139] Based on this, we concluded that the PEEK resin film in Test Example 3 clearly has a crystallinity of 30% or less, and is a low-crystallinity resin film in which no diffraction peaks originating from crystals were detected. This result is consistent with the properties of the product, as the resin film in Test Example 3 was purchased as a low-crystallinity PEEK resin.

[0140] As shown in the lower part of Figure 2, when the PA resin film (PACM-12 resin film) of Test Example 4 was measured using the aforementioned X-ray diffractometer, no diffraction peaks originating from individual crystals of the PA resin (PACM-12 resin) were detected, and the degree of crystallinity could not be detected. From this, it was concluded that the PA resin film of Test Example 4 is a low-crystallinity resin film with a crystallinity of 30% or less, or in which no diffraction peaks originating from crystals were detected. This result is consistent with the properties of the product, as the resin film of Test Example 4 was purchased as a low-crystallinity PA resin. Furthermore, for diffraction peaks originating from PA resin (PACM-12 resin), refer to Non-Patent Literature 2 (AWL Chen et al., Journal of Composite Materials, Vol. 27, No.9, 1993:862-885). In Non-Patent Literature 2, the diffraction peaks originating from the PACM-12 resin crystals consist of four peaks within the diffraction angle range of 14° to 22°. Of these, the diffraction angle of one diffraction peak is 17.4° and its vicinity, and the diffraction angle of another diffraction peak is 19.2° and its vicinity.

[0141] <Measurement of melting point and glass transition temperature>

[0142] The melting point (intermediate melting temperature) and glass transition temperature (glass transition onset temperature) were measured using a differential scanning calorimeter (Rigaku Corporation, DSCVesta; analysis tool: Thermo plus EVO2 system). For the measurements, the measurement atmosphere was 50 mL / min of nitrogen gas, the reference material was an aluminum pan, and the heating rate was 10°C / min. The measurement range was PEEK: 30°C to 380°C, PA: 30°C to 290°C. Analysis was performed on the peaks observed during the first heating process, determining the melting point and glass transition temperature.

[0143] <Calculation of crystallization energy and degree of crystallinity of resin film using the DSC method>

[0144] To calculate the crystallization energy and degree of crystallinity using the DSC method, a differential scanning calorimeter (Rigaku Corporation, DSCVesta; analysis tool: Thermo plus EVO2 system) was used. For the measurements, the measurement atmosphere was 50 mL / min of nitrogen gas, the reference material was an aluminum pan, the temperature range was 30°C to 380°C, and the heating rate was 10°C / min. Analysis was performed on the peak observed during the first heating process.

[0145] In the DSC method, crystallization energy and degree of crystallinity were determined using a differential scanning calorimeter and the DSC analysis tool attached to the differential scanning calorimeter. The DSC analysis tool may also be DSC analysis software. The DSC analysis tool can measure and derive the measurement results of the DSC, detect and calculate the crystallization energy or melting energy necessary for calculating the degree of crystallinity from the measurement results, and calculate the degree of crystallinity of each resin film considering these factors. The analysis software can also perform automated analysis, which automatically performs the calculation and analysis from the measurement results to the degree of crystallinity using a processor such as a CPU and memory such as ROM built into a computer or server. In this case, the crystallization energy was calculated by the automated analysis software performing data processing based on the baseline, after the start and end points of the baseline of the exothermic peak originating from crystallization were determined by the operator, so it was performed as a semi-automated analysis.

[0146] More specifically, the crystallization energy was calculated by having the automated analysis software perform data processing based on the baseline, after which the start and end points of the baseline of the exothermic peak originating from crystallization were determined by the operator. The melting energy was calculated in the same manner as the crystallization energy, after which the analysis software performed data processing based on the baseline, after which the start and end points of the baseline of the melting peak originating from melting were determined by the operator. The degree of crystallinity was calculated by substituting the calculated crystallization energy and melting energy into equation (2) described above. More specifically, it was calculated using the following equation (4).

[0147]

[0148] Figure 3 is a chart showing the measurement results (DSC curve) of the PEEK resin film of Test Example 1, measured using a differential scanning calorimeter. As shown in Figure 3, the chart for the PEEK resin film of Test Example 1 shows an exothermic peak (peak around 175°C) originating from crystallization and a melting peak (peak around 337°C) originating from melting.

[0149] Except for changing the resin film, the cold crystallization energy, melting energy, and crystallinity of each low-crystallinity PEEK resin film in Test Example 2 and Test Example 3 were calculated using a differential scanning calorimeter and analysis tools, in the same manner as in Test Example 1. The calculation results for the crystallization energy and crystallinity of the resin films of Test Examples 1 to 3 by the DSC method are shown in Table 3. The values ​​in Table 3 are the average values ​​of three measurements taken for each low-crystallinity PEEK resin film.

[0150]

[0151] Figure 4 shows an example of a chart of the highly crystalline PEEK resin of Test Example 6 (Comparative Example 2), measured using a differential scanning calorimeter. As shown in Figure 4, no exothermic peaks originating from crystallization were observed in the chart of this highly crystalline PEEK resin.

[0152] <Results>

[0153] Table 4 shows the results for each of the above-mentioned test examples 1 to 7. In Table 4, "electron beam resistance" and "elution resistance" both refer to the "electron beam resistance" and "elution resistance" when evaluated by pH value. In Table 4, "Excellent" for electron beam resistance (pH value evaluation) means that at least one of the butyl rubber or chlorinated butyl rubber meets the pH value evaluation for electron beam resistance, and there is almost no difference in pH between the respective sample solution and the blank solution. Furthermore, "Good" for electron beam resistance (pH value evaluation) means that the pH value evaluation for electron beam resistance meets the requirements, but there is a large difference in the evaluation results between those with and without electron beam resistance. In test example 7, when chlorinated butyl was used, the pH value evaluation with electron beam irradiation deteriorated to about 0.8. In this case, when the difference in electron beam resistance (pH value evaluation) was 0.5, 0.6, or 0.7 or more, it was judged to be good and to meet the requirements, and when there was almost no difference, such as 0 or 0.1 or less, it was judged to be excellent.

[0154]

[0155] <Discussion> Based on the above results, when a resin film having a ratio of elongation in the TD direction to elongation in the MD direction (TD / MD) of 0.80 or more and 1.20 or less was used as the film layer of a rubber molded product, the resulting rubber molded product had good moldability (passed). For such a resin film, it was preferable that the elongation in the MD direction of the resin film was 150% or more and 450% or less, and the elongation in the TD direction was 150% or more and 450% or less. Furthermore, for such a resin film, it was preferable that the tensile strength in the MD direction of the resin film was 60 MPa or more and 160 MPa or less, and the tensile strength in the TD direction was 60 MPa or more and 160 MPa or less, and that the ratio of the tensile strength in the TD direction to the tensile strength in the MD direction (TD / MD) was 0.80 or more and 1.00 or less. The rubber molded product obtained using a non-fluorine resin film having the above-mentioned specific elongation and / or specific tensile strength also exhibited excellent gas barrier properties and electron beam resistance.

[0156] Furthermore, the results above indicate that a low-crystallinity resin film was preferable as a raw material. The rubber molded products obtained using the non-fluorinated resin film with the aforementioned specific crystallinity exhibited excellent gas barrier properties and electron beam resistance.

[0157] Furthermore, based on the above results, it was preferable that the resin film used be one or more types selected from PAEK resin (preferably PEEK resin) and PA resin (preferably PACM resin). It was also preferable that the rubber material used be one or two types selected from butyl rubber and chlorinated butyl rubber.

[0158] In this specification, the upper limit (less than or equal to) and lower limit (greater than or equal to) of each numerical range (~) can be arbitrarily combined as desired. In numerical ranges described stepwise in this specification, the upper limit or lower limit of a numerical range in one step may be replaced with the upper limit or lower limit of a numerical range in another step. Unless otherwise specified, the examples in this specification may be used individually or in combination of two or more examples selected from the examples.

Claims

1. A rubber molded product comprising a non-fluorinated resin film layer, wherein the ratio of the elongation in the TD direction to the elongation in the MD direction (TD / MD) of the non-fluorinated resin film before molding is 0.80 or more and 1.20 or less.

2. The rubber molded article according to claim 1, wherein the non-fluorine resin film before molding has an elongation of 150% or more and 450% or less in the MD direction and an elongation of 150% or more and 450% or less in the TD direction.

3. The rubber molded article according to claim 1 or 2, wherein the tensile strength in the MD direction of the non-fluorinated resin film before molding is 60 MPa or more and 160 MPa or less, the tensile strength in the TD direction is 60 MPa or more and 160 MPa or less, and / or the ratio of the tensile strength in the TD direction to the tensile strength in the MD direction (TD / MD) is 0.80 or more and 1.00 or less.

4. The rubber molded article according to claim 1 or claim 2, wherein the non-fluorinated resin is one or more selected from polyaryletherketone resin and polyamide resin.

5. The rubber molded article according to claim 1 or 2, wherein the rubber is one or two selected from butyl rubber and chlorinated butyl rubber.

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