Rubber molded products

Abstract

The main objective is to provide a rubber molded product having a non-fluorine-based resin film layer on its surface, which exhibits good gas barrier properties and electron beam resistance, as well as good moldability during manufacturing. The present invention provides a rubber molded product comprising a non-fluorinated resin film layer, wherein the ratio of elongation in the TD direction to 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.

Description

[Technical Field]

[0001] This technology relates to molded rubber products. [Background technology]

[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. In the past, natural rubber was widely used, while currently synthetic rubber is more common. Furthermore, when rubber used in containers or utensils comes into contact with chemicals (which may be liquids, solids, gases, or combinations thereof), problems specific to rubber may 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. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2018-201671 [Patent Document 2] Japanese Patent Publication No. 2014-131874 [Patent Document 3] Japanese Patent Application Publication No. 61-272134 [Non-patent literature]

[0005] [Non-Patent Document 1] M. Doumeng et al., Polymer Testing, 93 (2021), Article 106878, 2021:1-10 [Non-Patent Document 2] AWL Chen et al., Journal of Composite Materials, Vol. 27, No.9, 1993:862-885 [Non-Patent Document 3] H. Liu et al., Royal Society open science 5: 171775, 25 April 2018. [Overview of the project] [Problems that the invention aims to solve]

[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. [Means for solving the problem]

[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] The present technology can provide a rubber molded product including a non-fluorine-based resin film layer, wherein the ratio (TD / MD) of the elongation in the TD direction to the elongation in the MD direction in the non-fluorine-based resin film before lamination is 0.80 or more and 1.20 or less. Moreover, the elongation in the MD direction in the non-fluorine-based 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. Moreover, the tensile strength in the MD direction in the non-fluorine-based resin film before lamination may be 60 MPa or more and 160 MPa or less, the tensile strength in the TD direction may be 60 MPa or more and 160 MPa or less, and / or the ratio (TD / MD) of the tensile strength in the TD direction to the tensile strength in the MD direction may be 0.80 or more and 1.00 or less. Moreover, the non-fluorine-based resin may be one or more selected from polyaryl ether ketone resin and polyamide resin. Also, the rubber may be selected from butyl rubber and chlorinated butyl rubber.

Brief Description of Drawings

[0010] [Figure 1] It is a figure showing a side cross-section of a rubber molded product according to an embodiment of the present technology, but the present technology is not limited thereto. [Figure 2] A chart diagram (vertical axis: intensity (counts), horizontal axis: diffraction angle (2θ(°))) showing the measurement results (XRD pattern) by an X-ray diffractometer of the low-crystalline PAEK resin (PEEK resin) film shown in the upper row and the low-crystalline PA resin (PACM-12 resin) film shown in the lower row used in [Examples]. [Figure 3] A chart diagram (vertical axis: heat flow (mW), horizontal axis: temperature (°C)) showing the measurement results (DSC curve) by a differential scanning calorimeter of the low-crystalline PAEK resin (PEEK resin) film (Shin-Etsu Sepla Film(R) low-crystalline type) used in [Examples]. [Figure 4]This chart (vertical axis: heat flow (mW), horizontal axis: temperature (°C)) shows the measurement results (DSC curve) of the highly crystalline PAEK resin (PEEK resin) film (Shin-Etsu Sepla Film(R)) used in the [Examples] using a differential scanning calorimeter. [Modes for carrying out the invention]

[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 products related to this technology 1-1. Rubber base material 1-2. Film layer 1-2-1. Non-fluorine resin film layer 1-3. Non-fluorinated resin film before molding (raw material film) 1-3-1. Elongation (strain) of the 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 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 the DSC method. 1-3-5. Leaching resistance of raw material film 1-3-6. Electron beam resistance of raw material films 1-4. Application of rubber molded products related to this technology 2. Method for manufacturing rubber molded products 2-1. Compression molding, a method for gradually molding the lower and upper parts of a rubber molded product.

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

[0014] This technology can provide a rubber molded product containing a non-fluorinated resin film layer, and it is preferable that the rubber molded product contains at least a non-fluorinated resin film layer and a rubber substrate. Furthermore, this technology may also provide a rubber molded product 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 product, 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] This technology can employ the following configurations as appropriate. [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. In a more preferred embodiment of [1], 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 may be further incorporated. [2] A preferred embodiment of the present technology is a rubber molded product comprising a non-fluorinated resin film layer, wherein the non-fluorinated resin film used for molding has an elongation in the MD direction of 150% or more and 450% or less, and an elongation in the TD direction of 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. In a more preferred embodiment of [3], 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 may be further incorporated. [4] A preferred embodiment of the present technology is a rubber molded product comprising a non-fluorine 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 this 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 rubber molded article according to any one of [1] to [5] above, wherein the non-fluorinated resin is one or more selected from polyaryletherketone resin and polyamide resin. [7] The rubber molded article according to any one of [1] to [6] above, wherein the rubber is one or two selected from butyl rubber and chlorinated butyl rubber. [8] Use or method of use of a non-fluorine resin film in a rubber molded product. Preferably, the non-fluorine resin film is the non-fluorine resin film described in any one of [1] to [7] above. [9] A non-fluorinated resin film or the use thereof for manufacturing or for 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 or in the manufacture of rubber molded products. More preferably, 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.

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

[12] The manufacturing method according to

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

[13] The manufacturing method according to

[11] or

[12] , comprising processing the non-fluorine resin film and the 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 surface portion).

[15] Preferably, one of the rubber molded articles described in [1] to

[14] above is used for pharmaceuticals, medicines, or medical purposes. The rubber molded article is preferably used as one or more types selected from sealing materials, rubber stoppers, gaskets, nozzle caps, cylinder caps, inner stoppers, 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 is preferably rubber, 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 aforementioned 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, as well as natural rubber; rubber materials mainly composed of EPDM, polybutadiene, polyisobutylene (including thermoplastic elastomers), and some thermoplastic elastomer-based compounds.

[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-fluorinated resin film layer used in this technology is preferably provided on part or all of the surface of the rubber molded product. The non-fluorinated resin film layer is preferably on a part that can be exposed to the outside. If the film layer has a multilayer structure, the non-fluorinated resin film layer is preferably the outermost layer of the film layer. Furthermore, the non-fluorinated resin film layer is preferably configured to be provided on a surface that comes into contact with chemicals.

[0030] For example, if the rubber molded product 100 is a rubber stopper, an example is the rubber molded product 100 which includes a film layer 2 placed on the surface of the leg portion 10 of the rubber base material 1, as shown in Figure 1. The film layer 2 may be appropriately placed on the surface of one or more types of rubber base materials selected from the surface of the leg portion 10, the surface of the lower part of the cap 20, the upper surface 31 of the top portion 30, the side surface 32 of the top portion 30, etc. Furthermore, each surface may have a film layer on all or part of its surface as appropriate. Other examples include, for instance, a rubber molded product having a non-fluorine resin film layer on the upper surface 31 of the top surface 30; a rubber molded product having a non-fluorine resin film layer on the entire surface of the rubber substrate 1, such as the upper surface 31 of the top surface 30, the side surface 32 of the top surface 30, the surface of the lower part of the cap 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 lower part of the cap 20; a rubber molded product having a non-fluorine resin film layer on a part of the surface of the leg portion 10; and the product is not particularly limited to these. In addition, a non-fluorine resin film layer 2 may not be placed on the deburred portion of the rubber molded product 100, and for example, there may be a part without a film layer at the lower end of the side surface 32.

[0031] The non-fluorinated resin film layer used in this technology is preferably fluorine-free. 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 is preferably said to have certain conditions (e.g., elongation, tensile strength, crystallinity) as 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. Furthermore, in PA resin (preferably PACM resin), the melting point (intermediate melting temperature: °C) is not particularly limited, but can be, for example, 240 to 250 °C, preferably 243 to 248 °C, and the glass transition temperature (glass transition start temperature: °C) is not particularly limited, but can be, for example, 120 to 140 °C, preferably 125 to 135 °C, more preferably 128 to 133 °C.

[0033] The PAEK resin used in this technology is not particularly limited, but examples include those composed of aromatic hydrocarbon groups, ether groups, and carbonyl groups [-C(=O)-]. More preferable PAEK resins are those that contain repeating units composed of arylene groups [-Ar-], ether groups [-O-], and ketone groups [-C(=O)-]. Preferred "-Ar-" (divalent aromatic hydrocarbon ring group) is a phenylene group (e.g., p-phenylene group), a biphenylene group (e.g., 4,4'-biphenylene group), and more preferably a phenylene group (disubstituted benzene ring group). The preferred "-Ar-" may or may not have substituents. The PAEK resin may be obtained by known manufacturing methods, or a commercially available product may be used.

[0034] Examples of more suitable PAEK resins include, but are not limited to, resins containing repeating units represented by any of the following formulas (a1) to (a5). [-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) (Note that in the formula, Ar represents a divalent aromatic hydrocarbon ring group which may have substituents.)

[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 with 6 to 10 carbon atoms, biarylene groups (2,2'-biphenylene groups, 3,3'-biphenylene groups, 4,4'-biphenylene groups, etc.) (each arialene group has 6 to 10 carbon atoms), and terarylene groups (o-, m-, or p-terphenylene groups) (each arialene 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 polyetherketone (PEK), polyetheretherketone (PEEK), polyetheretherketoneketone (PEEKK), polyetherketoneketone (PEKK), polyetherketoneetherketoneketone (PEKEKK), polyetheretherketoneetherketone (PEEKEK), polyetheretheretherketone (PEEEK), and polyetherdiphenyletherketone (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] [ka]

[0040] The PA resin used in this technology is not particularly limited, but examples include polyamides whose constituent units are the 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 the reaction product of PACM and a linear dicarboxylic acid (dodecanediic acid) having 12 carbon atoms (poly(bis-4,4'-dicyclohexylmethane)n-dodecanediamide) in the polymer compound 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] [ka]

[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 referred to as strain) in the MD direction (the direction in which the resin flows) 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, elongation in the TD direction, and suitable upper or lower limits regarding the (TD / MD) ratio, 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 suitable lower limit is preferably 130% or more, more preferably 140% or more, and even more preferably 150% or more. A suitable 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 suitable lower limit is preferably 130% or more, more preferably 140% or more, and even more preferably 150% or more. A suitable 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 appropriately adopted and combined from the elongation in the MD direction, the elongation in the TD direction, the suitable upper or lower limit values ​​for 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 the PA resin (preferably PACM resin) film is not particularly limited, but a suitable lower limit is preferably 130% or more, more preferably 140% or more, and even more preferably 150% or more, and a suitable 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%, 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 suitable 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 suitable upper limit is preferably 200 MPa or less, more preferably 190 MPa or less, even more preferably 180 MPa or less, 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 suitable 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 suitable 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 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 1.10 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 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, more preferably 100 MPa or more, more preferably 110 MPa or more, and 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 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 suitable 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 suitable 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 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.

[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 transmission coefficient. The oxygen transmission coefficient of the raw material film at 23 ± 2 °C is not particularly limited, but from the perspective of improving the gas barrier properties of the rubber molded product according to this technology, a lower oxygen transmission coefficient is preferred, 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, more preferably 7.00×10 -17 mol·m / (m 2 ·s·Pa) or less.

[0077] The oxygen transmission 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. [[ID=2〕6]]

[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 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), and these methods can be carried out using known measurement methods or known measurement apparatuses.

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

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

[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 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 film. The area of ​​the amorphous region is the area of ​​the peaks originating from the amorphous (amorphous) material of the raw film.

[0084]

number

[0085] The raw material film used in this technology is preferably a resin film having a specific range of crystallinity determined by the XRD method. The degree of crystallinity of the raw material film calculated using the XRD method 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, which may be used 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 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 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 Literature 1 (M. Doumeng et al., Polymer Testing, 93 (2021), Article 106878, 2021:1-10).

[0093]

number

[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 a 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, and 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 at that time is a film having specific elution resistance. Rubber molded products formed using raw material films and rubber materials can be used as samples and evaluated based on the general elution test (18th edition of the Japanese Pharmacopoeia, First Supplement, 7.03 Test Methods for Rubber Stoppers for Infusions, 3. Leaching Test). The evaluation items may include one or more selected from, for example, pH value, ultraviolet absorption spectrum, transmittance, potassium permanganate reducing agent, foaming, and properties (the test solution is colorless and clear, and no foreign matter is visible to the naked eye). A larger number of items is preferable 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; otherwise, it can be judged as failing. Those judged as passing can be considered to have elution resistance. Furthermore, it is preferable that the rubber molded product laminated with a non-fluorine-based resin film and the raw material film used therein perform relatively well when compared to 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 films The raw material film used in this technology is preferably a resin film having specific electron beam resistance. If a rubber molded product exhibits excellent electron beam resistance, it can be determined that the raw material film used is a film having specific electron beam resistance.

[0098] Using raw material films and rubber molded products formed from rubber materials as samples, samples irradiated with electron beams can be evaluated based on a general elution test (18th edition of the Japanese Pharmacopoeia, First Supplement, 7.03 Test Methods for Rubber Stoppers for Infusions, 3. Leaching Test). If the rubber molded product exhibits excellent electron beam resistance, 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. Elution Resistance of Raw Material Film" 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 of these, it is preferable to include 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; otherwise, it can be judged as failing. Furthermore, even if the electron beam-irradiated sample is judged to conform to the standards, 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 judged that the sample (in other words, the raw material film) has deteriorated due to electron beam irradiation. When evaluating the unirradiated sample, the procedure is the same as for each evaluation item test described above, except that the electron beam-irradiated sample is replaced with the unirradiated sample. Furthermore, regarding electron beam resistance, for relative evaluation in comparison with the evaluation of rubber molded products laminated with ETFE, the content of the relative evaluation described in "1-3-5. Elution Resistance of Raw Material Film" above may be appropriately adopted, and rubber molded products and raw material films used therein that have good relative evaluations 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 the articles come into contact with chemicals 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 (such as 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 products relating to this technology are not particularly limited, but examples include 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 products 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 products The rubber molded articles relating to this technology can be manufactured by known manufacturing methods using a raw material film and raw rubber (rubber material). Known manufacturing methods are not particularly limited, but examples include methods of coating the raw rubber with a raw material film, and methods of coating (applying, etc.) the raw rubber with the resin material of the film. The raw rubber (rubber material) may also be in the form of a sheet. To improve 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 the 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 surface-treat the raw material film. The surface treatment method is not particularly limited, but one or more known methods selected from, for example, chemical treatment, corona discharge, and 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. In this technology, known rubber mold molding methods can be used. Examples of rubber mold molding include direct pressure molding (compression molding) and injection molding (transfer molding), and one or more of these can be used, 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. [Examples]

[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 PAEK resin (material name: Shin-Etsu Sepla Film). (R) Low-crystallinity type (manufactured by Shin-Etsu Polymer Co., Ltd., film thickness 50 μm) was used. The rubber molded product of Test Example 2 (Example 2) contains a film of low-crystallinity PEEK resin, a type of PAEK 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) contains a film of low-crystallinity PEEK resin, a type of PAEK resin (material name [Superior (TM) [UT HT-type] (manufactured by Mitsubishi Chemical Group Corporation, film thickness 100 μm) was used. The rubber molded product of Test Example 4 (Example 4) contains a low-crystallinity PA resin film (material name [Diamilon]). (TM) [MF] (Mitsubishi Chemical Group Corporation, film thickness 100 μm) was used. The rubber molded product in Test Example 5 (Comparative Example 1) contains a film of highly crystalline PEEK resin, a type of PAEK resin (material name [EXPEEK]). (R) A film manufactured by Kurabo, with a film thickness of 50 μm, was used. The rubber molded product of Test Example 6 (Comparative Example 2) contains a film of highly crystalline PEEK resin, a type of PAEK resin (Material name: Shin-Etsu Sepla Film). (R) [High-crystallinity type] (manufactured by Shin-Etsu Polymer Co., Ltd., film thickness 100 μm) was used. Test Example 7 (Reference Example 1) used a highly crystalline ETFE (ethylene tetrafluoroethylene) film (film thickness 100 μm) manufactured by Nitto Denko Corporation. For the rubber molded products in Test Examples 1 to 7, 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 the rubber material.

[0110] The elongation and tensile strength of each film used in these test examples 1 to 7 are shown in Table 4 below.

[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, while Test Example ○-2 and "-2" refer to rubber molded products using chlorinated butyl rubber. The rubber molded product was molded on a prototype scale using the method described in "2-1. Compression molding for gradually molding the lower and upper parts of the rubber molded product" above. In the prototype scale, the final rubber molded product was a rubber stopper for vials (diameter 19.05 mm, height 8.00 mm) with legs attached to the bottom of a disc shape, as shown in Figure 1. The mold had 8 x 8 holes, and 64 pieces were produced in one batch. The manufacturing conditions for the first and second molds were as follows: heating temperature 130°C to 180°C and clamping pressure 20 kg / cm². 2 ~120 kg / cm 2 The heating temperature and the time for applying the clamping pressure were 5 to 20 minutes. In this way, the rubber molded products of Test Example 1-1 and Test Example 1-2 were obtained. The rubber molded products in Test Examples 2 to 7 were obtained in the same manner, except that the raw material film was changed. The resulting rubber molded product was a rubber stopper for vial bottles, 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 for 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 90% or higher can be considered excellent.

[0113] In Test Examples 1-1 to 4-1 and Test Example 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 the rubber molded products of Test Examples 1-2 to 4-2 and Test Example 7-2, which used chlorinated butyl rubber as the rubber material, the number of acceptable products was 100% of the total, and the moldability evaluation for these products was satisfactory and excellent. On the other hand, in all of the rubber molded products of Test Examples 5-2 to 6-2, tearing or peeling of the film layer was observed, so the moldability evaluation for these products was deemed unsatisfactory.

[0114] Therefore, the PAEK resin (preferably PEEK resin) films in Test Examples 1-3 and the PA resin (preferably PACM resin) film in 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 in 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 1-3 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] [Table 1]

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

[0118] <Oxygen permeability test> For each test example, the raw material film was subjected to an oxygen permeability test at 23±2°C. The oxygen permeability test was measured 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 values ​​were below (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 are 7.37 × 10⁻⁶. -17 , 1.16 × 10 -16 , 3.95×10 -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 articles (rubber base material: butyl rubber, chlorinated butyl rubber) obtained in Test Examples 1, 4, and 7 were evaluated based on the elution test (18th Edition of the Japanese Pharmacopoeia, First Supplement, 7.03 Test Methods for Rubber Stoppers for Infusions, 3. Leaching Test). In Test Example ○-1, the rubber molded article used butyl rubber, and in Test Example ○-2, the rubber molded article used chlorinated butyl rubber. The evaluation items included pH value, ultraviolet absorption spectrum, transmittance, potassium permanganate reducing agent, foaming, and properties (the test solution was colorless and clear, and no foreign matter was visible to the naked eye).

[0120] <<pH value evaluation in elution testing>> After washing the rubber stopper with water, let it dry at room temperature. The 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, then heat in an autoclaver at 121°C for 1 hour. 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 solution is prepared using only water, in the same manner as described 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 the pH value standard, the closer it is to 0.0, the better the result, and the closer it is to 1.0, the worse the result.

[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, the rubber molded articles in Test Examples 1, 4, and 7 were judged to 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 articles.

[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 rubber molded product was irradiated with an electron beam using the electron accelerator Rhodetron TT200 (manufactured by IBA Corporation), with the beam energy set to 10 MeV, and the target dose at the surface was 50 kGy. The electron beam-irradiated rubber molded products were evaluated based on "The 18th Revised Japanese Pharmacopoeia, First Supplement, 7.03 Test Methods for Rubber Stoppers for Infusions, 3. Leaching Test." Specifically, the electron beam-irradiated rubber molded products were used to perform tests on pH value, ultraviolet absorption spectrum, transmittance, potassium permanganate reducing agent, foaming, and properties (the test solution was colorless and clear, and no foreign matter was observed with the naked eye), and these were evaluated. Where necessary, unirradiated rubber molded products (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] [Table 2]

[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 the elution 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, if at least the pH value evaluation item is passed, it was determined that the electron beam resistance is good.

[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 crystallinity of resin films using the XRD method>

[0132] For the measurement and calculation of crystallinity in the XRD method, an X-ray diffractometer (PANalytical, X'pert PRO MPD) and the XRD analysis software attached to the X-ray diffractometer were used. The XRD analysis software may be an XRD analysis tool. The XRD analysis software can perform XRD measurement and derive measurement results, detect and calculate diffraction peaks, their areas, amorphous regions, and their areas necessary for calculating crystallinity from the measurement results, and calculate the crystallinity of each resin film considering these calculated areas. Note that the analysis software or analysis tool used in this technology can also perform automatic analysis that automatically executes calculations and analysis from measurement results to crystallinity using a processor such as a CPU built into a computer or server and a memory such as ROM. In this case, automatic analysis was performed.

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

[0134] The crystallinity was calculated by substituting the areas of the diffraction peaks and the amorphous region into the above (Equation 1). More specifically, it was calculated by the following (Equation 3). Here, as shown in Non-Patent Document 3 (H. Liu et al., Royal Society open science 5: 171775, 25 April 2018.), for the detection of diffraction peaks derived from PEEK resin, diffraction peaks from the (110) plane, (111) plane, (200) plane, and (211) plane were used as standards.

[0135]

number

[0136] Figure 2 is a chart showing the measurement results obtained using the aforementioned 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 Document 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 PEEK resin in Non-Patent Document 3 are 18.8° ((110) plane), 20.7° ((111) plane), 22.9° ((200) plane), and 28.9° ((211) plane), indicating a crystallinity of 40.9-45.3% for PEEK.

[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 FIG. 2, when the PA resin film (PACM-12 resin film) of Test Example 4 was measured using the X-ray diffractometer, diffraction peaks derived from each crystal of the PA resin (PACM-12 resin) were not detected, and the crystallinity could not be detected. From this, it was considered that the PA resin film of Test Example 4 was a low-crystalline resin film with a crystallinity of 30% or less or from which diffraction peaks derived from crystals were not detected. This result is consistent with the properties of the product since the resin film of Test Example 4 was purchased as a low-crystalline PA resin. Regarding the diffraction peaks derived from the PA resin (PACM-12 resin), reference can be made to Non-Patent Document 2 (A.W.L. Chen et al., Journal of Composite Materials, Vol. 27, No.9, 1993:862-885). The diffraction peaks derived from the crystals of the PACM-12 resin in this Non-Patent Document 2 are four peaks within the diffraction angle range of 14° to 22°, and the diffraction angle of one of the diffraction peaks 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 (midpoint 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). In the measurement, the measurement atmosphere was nitrogen gas at 50 mL / min, the reference substance was an aluminum pan, and the heating rate was 10 °C / min. The measurement range was from 30 °C to 380 °C for PEEK and from 30 °C to 290 °C for PA. The analysis was performed on the peaks observed in the first heating process, and the melting point and glass transition temperature were used.

[0143] <Calculation of Crystallization Energy and Crystallinity of Resin Film Using DSC Method>

[0144] A differential scanning calorimeter (DSCVesta, Rigaku Corporation; analysis tool: Thermo plus EVO2 system) was used to calculate the crystallization energy and degree of crystallinity using the DSC method. For the measurements, the measurement atmosphere was nitrogen gas at 50 mL / min, 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] Crystallization energy and degree of crystallinity in the DSC method 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 DSCs and derive measurement results, detect and calculate crystallization energy or melting energy necessary for calculating the degree of crystallinity from these measurement results, and calculate the degree of crystallinity of each resin film, taking these factors into consideration. The analysis software can also perform automated analysis, using a processor such as a CPU and memory such as ROM built into a computer or server to automatically perform calculations and analysis from measurement results to the degree of crystallinity. In this case, the start and end points of the baseline of the exothermic peak originating from crystallization were determined by the operator, and then the automated analysis software performed data processing based on this baseline to calculate the crystallization energy, thus the analysis was performed using a semi-automated method.

[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, by having the analysis software perform 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]

number

[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 originating from crystallization (peak near 175°C) and a melting peak originating from melting (peak near 337°C).

[0149] Except for changing the resin film, the cold crystallization energy, melting energy, and degree of 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. Table 3 shows the results of the DSC method calculations for the crystallization energy and degree of crystallinity of the resin films in Test Examples 1-3. The values ​​in Table 3 are the average values ​​obtained from three measurements of each low-crystallinity PEEK resin film.

[0150] [Table 3]

[0151] Figure 4 shows an example of a chart for 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 for this highly crystalline PEEK resin.

[0152] <Result>

[0153] The results for each of the above-mentioned test examples 1 to 7 are shown in Table 4. Note that in Table 4, "electron beam resistance" and "elution resistance" both refer to "electron beam resistance" and "elution resistance" as 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 criteria 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 criteria for electron beam resistance meet the criteria, 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 higher, it was judged to be good and met the criteria, and when there was almost no difference, such as 0 or 0.1 or lower, it was judged to be excellent.

[0154] [Table 4]

[0155] <Consideration> Based on the above results, using a resin film with 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 as the film layer of a rubber molded product resulted in good moldability (acceptable) of the obtained rubber molded product. For such resin films, 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 resin films, 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. Furthermore, the rubber molded articles obtained using the 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.

Claims

1. A rubber molded product having a polyamide resin layer, which is a non-fluorine resin film layer, provided on part or all of the surface, 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. The aforementioned rubber molded product.

2. The rubber molded article according to claim 1, wherein the non-fluorine resin film before molding has an elongation in the MD direction of 150% or more and 400% or less, and an elongation in the TD direction of 150% or more and 400% or less.

3. The rubber molded article according to Claim 2, wherein the tensile strength in the MD direction of the non-fluorine resin film before molding is 70 MPa or more and 160 MPa or less, and the tensile strength in the TD direction is 70 MPa or more and 160 MPa or less.

4. 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 70 MPa or more and 160 MPa or less, the tensile strength in the TD direction is 70 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.

5. A rubber molded product having a polyaryletherketone resin layer, which is a non-fluorine resin film layer, provided on part or all of the surface, 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. The aforementioned rubber molded product.

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

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