JP6950247B2 - Laminated film, rubber molded product using it, and their manufacturing method - Google Patents

Description

The present invention relates to a laminated film, a rubber molded body using the laminated film, and a method for producing the same. More specifically, the present invention is a laminated film having an adhesive layer for adhering to a rubber member and a fluororesin film. , And a rubber molded body in which the laminated film and the rubber member are adhered to each other. The rubber molded body has excellent slipperiness on the surface of the rubber member, that is, has low sliding resistance and is also excellent in solvent resistance.

It is known that various rubber products such as syringe stoppers and pharmaceutical vial stoppers are coated with an appropriate resin film on the surface of the rubber member in order to improve the slipperiness and solvent resistance. As such a resin film, a fluorine-based resin film whose surface has been modified by plasma etching treatment, sputter etching treatment, chemical treatment, or the like so as to enhance the adhesiveness to the rubber member (hereinafter, also referred to as adhesion) is used. There are (Patent Documents 1 and 2).
However, even if the surface of the fluorine-based resin film is etched, the improvement of the adhesiveness with the rubber member is insufficient. Therefore, a fluorine-based resin film exhibiting stronger adhesiveness is desired. Further, when the above-mentioned treatment method is used, there is a problem that the film is colored when the treatment strength is increased in order to improve the adhesiveness.

As a method for solving the above problem, a method of laminating a thin film layer formed by graft-polymerizing an acrylic monomer on the surface of a fluororesin film is known, but there is a risk that the monomer component forming the thin film layer may elute. Yes, the application is limited. (Patent Document 3)

Further, there is known a method of laminating an adhesive layer made of an organic silicon compound using plasma CVD on the surface of a fluororesin film so that a monomer component does not elute. By having a methyl group and an ethyl group derived from the organic silicon compound, the adhesiveness between the surface layer of the adhesive layer and the rubber member is exhibited. However, even if this method is used, the adhesiveness with the rubber member may be insufficient. (Patent Document 4)

Japanese Unexamined Patent Publication No. 2000-129015 Japanese Unexamined Patent Publication No. 2002-177390 Japanese Unexamined Patent Publication No. 2012-23038 Japanese Unexamined Patent Publication No. 2013-107961

An object of the present invention is to solve the above problems and provide a laminated film having excellent adhesiveness to a rubber member, a rubber molded product using the same, and a method for producing the same.

As a result of various studies, the present inventor has a laminated film having an adhesive layer for adhering a rubber member by heat-bonding means on at least one surface of a fluororesin film, and the adhesive layer is an organic silicon compound. A vapor deposition film formed on the fluororesin film by a plasma vapor phase chemical vapor deposition method (hereinafter, also referred to as “plasma CVD method”) using a gas composition for vapor deposition containing the above, and further, the vapor deposition film is exposed. It has been found that a laminated film characterized in that an oxidation-treated surface is formed on the surface by oxygen plasma treatment using oxygen gas achieves the above object.

The present invention is characterized by the following points.
1. 1. A laminated film having a fluororesin film and an adhesive layer, the adhesive layer can be adhered to a rubber member by heat-bonding means, and the adhesive layer is at least one of the fluororesin films. The adhesive layer is exposed on the surface and laminated, and the adhesive layer is further oxygenated on a vapor deposition film formed on the fluororesin film by a plasma vapor phase chemical vapor deposition method using a gas composition for vapor deposition containing an organic silicon compound. A laminated film characterized in that an oxidation-treated surface subjected to plasma treatment is formed, and the contact angle of water on the surface of the adhesive layer is 1 ° or more and 35 ° or less.
2. A rubber molded product having a structure in which the laminated film according to 1 and the rubber member are bonded to each other via the adhesive layer of the laminated film.
3. 3. 2. The rubber molded body according to 2 above, wherein the rubber molded body is a product in which the surface of the adhesive layer of the laminated film and the rubber member are overlapped, molded, and heat-bonded. ..
4. The rubber molded body according to 2 or 3 above, wherein the rubber member is one or more selected from the group consisting of a rubber composition, a rubber composition uncured product, and a rubber composition cured product.
5. The rubber molded product according to 2 or 3 above, wherein the rubber member is a rubber composition or a rubber composition uncured product.
6. The rubber molded product according to any one of 2 to 5, wherein the rubber molded product is further subjected to a post-hardening treatment.
7. The rubber molded product according to any one of 2 to 6 above, wherein the rubber molded product is a syringe plug.
8. The rubber molded product according to any one of 2 to 6 above, wherein the rubber molded product is a stopper for a pharmaceutical vial.
9. The method for producing a laminated film according to 1 above, wherein the production method includes the following steps 1 and 2, and the steps 1 and 2 are continuously performed without being exposed to the outside air. A method for manufacturing a laminated film.
Step 1) A step of forming an adhesive layer made of a thin-film deposition film by a plasma vapor phase chemical vapor deposition method using a gas composition for vapor deposition containing an organic silicon compound on a fluororesin film.
Step 2) A step of forming an oxidation-treated surface on the exposed surface of the vapor-deposited film by oxygen plasma treatment using oxygen gas.
10. The method for manufacturing a rubber molded product according to any one of the above 2 to 8, wherein the laminated film is manufactured by the manufacturing method according to the above 7, and the rubber molded body is the adhesion of the laminated film. A method for producing a rubber molded body, wherein the surface of the layer and the rubber member are overlapped and molded and heat-bonded.
11. The method for producing a rubber molded product according to the above 10, further comprising a post-hardening treatment of the rubber molded product.

The laminated film of the present invention is formed by a plasma CVD method using a vapor deposition gas composition (hereinafter, also referred to as “raw material gas”) containing an organic silicon compound as an adhesive layer with a rubber member on at least one surface. It has an adhesive layer that is a thin-film vapor deposition film, and an oxidation-treated surface is further formed on the exposed outermost surface of the adhesive layer by oxygen plasma treatment.

The vapor-deposited film is formed by forming a plasma-generated raw material gas into a thin film on a fluororesin film, and has a hydrocarbon group mainly composed of carbon, silicon, and oxygen, and is dense and flexible. It is a continuously vapor-deposited thin film rich in water.
The exposed outermost surface of the vapor deposition film is oxidized by oxygen plasma treatment using oxygen gas, and has oxygen-containing functional groups such as hydroxyl groups, carboxyl groups, aldehyde groups, and ketone groups.

By providing an oxidation-treated surface containing such a hydrocarbon group, a hydroxyl group, a carboxyl group, an aldehyde group, and a ketone group on the surface of the adhesive surface of the fluororesin film, a methyl group and an ethyl group derived from an organic silicon compound can be obtained. Since the hydrocarbon group exhibiting high adhesiveness and the hydroxyl group, carboxyl group, aldehyde group, and ketone group exhibiting even higher adhesiveness are exposed, the laminated film of the present invention exhibits high adhesiveness to the rubber member.
Further, since this vapor-deposited film forms a surface chemical bond with the fluorine-based resin film and adheres extremely strongly, delamination with the fluorine-based resin film is unlikely to occur.

Further, according to the vapor deposition by the plasma CVD method of the present invention, the adhesive layer is efficiently formed in a short time by not coloring the fluororesin film, generating eluates, and further promoting the oxidation of the surface. Therefore, the laminated film of the present invention also has an advantage of being excellent in productivity.

It is the schematic sectional drawing which shows an example about the layer structure of the laminated film of this invention. It is the schematic sectional drawing which shows an example about the layer structure of the laminated film of this invention. It is a schematic cross-sectional view which shows an example about the layer structure of the rubber molded article of this invention. It is a schematic cross-sectional view which shows an example about the layer structure of the rubber molded article of this invention. It is a schematic block diagram which shows the outline of an example of a plasma CVD apparatus.

The present invention will be described in detail below.
As the resin name used in the present invention, those commonly used in the industry are used. Further, in the present invention, the density was measured according to JIS K7112.

<I> Layer Structure of Laminated Film and Rubber Molded Body of the Present Invention FIGS. 1 and 2 are schematic cross-sectional views showing an example of each layer structure of the laminated film and the rubber molded body of the present invention.

The laminated film of the present invention shown in FIG. 1 is composed of a fluororesin film 10 and a thin-film film of silicon oxide formed on one surface of the film by a plasma CVD method using an organic silicon compound as a vapor-deposited monomer material. The adhesive layer 20 has an oxidation-treated surface 30 obtained by oxidizing the adhesive layer 20.

The laminated film of the present invention shown in FIG. 2 is an adhesive layer composed of a fluororesin film 10 and a thin-film film of silicon oxide formed on both sides of the film 10 by a plasma CVD method using an organic silicon compound as a vapor-deposited monomer material. It has an oxidation-treated surface 30 obtained by oxidizing the 20 and the adhesive layer 20.

The rubber molded body of the present invention shown in FIG. 3 has a structure in which a laminated film composed of a fluororesin film 10, an adhesive layer 20, and an oxidation-treated surface 30 is laminated on one side of a rubber member 40 by heat pressure bonding.

The rubber molded body of the present invention shown in FIG. 4 has a structure in which a laminated film composed of a fluororesin film 10, an adhesive layer 20, and an oxidation-treated surface 30 is laminated on both sides of a rubber member 40 by heat pressure bonding.

What is important is that a vapor-deposited film of a silicon oxide formed from an organic silicon compound is formed between the fluorine-based resin film 10 and the rubber member 40 by a plasma CVD method, and further oxidized to form an oxidation-treated surface 30. By forming the above, the adhesiveness between the fluororesin film 10 and the rubber member 40 is significantly improved.

<II> Fluorine-based resin film The base film that constitutes the laminated film of the present invention is fluorine-based because it exhibits low sliding resistance, that is, good surface slipperiness and low reactivity with various chemicals. Resin film is used.
As the fluororesin film, any one that exhibits surface slipperiness, low reactivity, and various other properties suitable for the use of the laminated film and that can withstand the vapor deposition conditions of the plasma CVD method is used. can do.

Examples of such a fluororesin film include polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA) made of a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, and tetrafluoroethylene and hexafluoropropylene copolymer (PFA). FEP), tetrafluoroethylene and perfluoroalkyl vinyl ether and hexafluoropropylene copolymer (EPE), tetrafluoroethylene and ethylene or propylene copolymer (ETFE), polychlorotrifluoroethylene resin (PCTFE), ethylene and chlorotrifluoroethylene A film composed of one or more fluororesins such as a copolymer (ECTFE), a vinylidene fluoride resin (PVDF), or a vinyl fluoride resin (PVF) can be used.

In the present invention, when used for medical supplies such as a stopper for a syringe and a stopper for a pharmaceutical vial, a vinyl fluoride resin (PVF) or a copolymer of tetrafluoroethylene and ethylene or propylene (in particular, is used. A fluororesin film made of ETFE) is preferable from the viewpoints of excellent slidability, low reactivity with various chemicals and solvents, heat resistance, durability, adhesion to a vapor-deposited film, and the like.

In the present invention, the fluororesin film may be produced by any manufacturing method as long as it has surface slipperiness and low reactivity suitable for each application. For example, an extrusion method, a cast molding method, or T. A method of forming a film using a film forming method such as a die method, a cutting method, or an inflation method, a method of forming a multi-layer coextruded film using two or more types of fluororesins, and two types of film formation. The above fluororesin is used and mixed before forming a film to form a film, and if necessary, for example, a tenter method, a tubular method, or the like is used. A film formed by stretching in the axial or biaxial direction can be used.

In the present invention, the film thickness of the fluororesin film is preferably 12 to 300 μm, more preferably 50 to 150 μm. If it is thinner than the above range, it becomes difficult to manufacture and handle it, and if it is thicker than the above range, the rigidity of the fluororesin film becomes high, the rigidity of the rubber molded body also becomes high, and the rubber elasticity is impaired, which is not preferable. Also, the thicker it is, the more expensive it becomes, which is not preferable.

When one or more of the above-mentioned fluororesins are used and the film is formed, for example, film processability, heat resistance, light resistance, weather resistance, mechanical properties, dimensional stability, antioxidant property, slippage Various plastic compounding agents and additives can be added for the purpose of improving and modifying the properties, releasability, flame retardancy, antifungal property, electrical properties, etc. , From a very small amount to several tens of percent of the total amount of the fluororesin depending on the reducing agent or the like, it can be arbitrarily added according to the purpose.

Further, an epoxy-based silane coupling agent may be added in order to improve the adhesiveness, and a blocking inhibitor may be added in order to prevent blocking of the film or the like. The amount of these additions is preferably about 0.1% by weight to 10% by weight.

In the present invention, the surface of the fluororesin film may be further provided with a desired surface treatment layer in advance, if necessary, in order to improve the adhesiveness between the fluororesin film and the vapor-deposited film. ..
As the surface treatment, for example, a treatment such as a corona discharge treatment, an ozone treatment, a glow discharge treatment, or an oxidation treatment using a chemical or the like can be used.

Further, as a method for improving the adhesiveness, for example, a primer coating agent layer, an undercoating agent layer, an anchor coating agent layer, an adhesive layer, a vapor deposition anchor coating agent layer, or the like is previously applied to the surface of the fluororesin film. It can also be arbitrarily formed to form a surface treatment layer. Examples of the pretreatment coating agent layer include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, and polyolefins such as polyethylene and polypropylene. A resin composition containing a based resin, a copolymer thereof, a modified resin, a cellulose-based resin, or the like as the main component of the vehicle can be used.

Further, in the above, as a method for forming the coating agent-based surface treatment layer, for example, a coating agent such as a solvent type, an aqueous type, or an emulsion type is used, and a roll coating method, a gravure roll coating method, a kiss coating method, or the like is used. It can be coated by using a coating method, and the coating time may be after film formation of the film, as a post-step after biaxial stretching treatment, film formation, in-line treatment of biaxial stretching treatment, or the like. Can be carried out at.

<III> Adhesive layer In the laminated film of the present invention, the adhesive layer for adhering to a rubber member by heat-bonding means has _{three CHs existing on the surface layer when the surface layer of the adhesive layer is activated by low-pressure plasma treatment or the like.} And from the C ₂ H ₅ groups, hydrogen atoms are released and carbon radicals are generated. In addition, the methyl group and the ethyl group derived from the organic silicon compound are separated from each other to generate a silicon radical. After that, these radicals are combined with oxygen in the atmosphere, and hydrogen atoms supplied in the atmosphere or from the film substrate or the like form oxygen-containing functional groups such as hydroxyl groups, carboxyl groups, aldehyde groups, and ketone groups. ing.

Alternatively, the oxygen radicals generated in the atmosphere by the low-pressure oxygen plasma treatment cause _{the abstraction of hydrogen atoms from the CH 3} groups and C ₂ H ₅ groups on the surface layer of the adhesive layer and the addition reaction of oxygen, which are further supplied from the film substrate. Oxygen-containing functional groups such as hydroxyl groups, carboxyl groups, aldehyde groups, and ketone groups are formed by the hydrogen atoms.
It is considered that the surface layer in which these functional groups are present has an improved adhesiveness due to a significant improvement in affinity and reactivity with the rubber material.

The vapor deposition film uses an organic silicon compound monomer containing a methyl group directly bonded to a Si atom as a vapor deposition material, and uses a vapor deposition gas composition containing a monomer gas for vapor deposition and, in some cases, an oxygen supply gas. The film was formed by the CVD method.
Further, there are several CVD methods such as thermal CVD method and optical CVD method, but it is preferable to adopt a plasma CVD method that enables low-temperature film formation and is less likely to cause coloring of the fluororesin film. The film forming conditions in the plasma CVD method will be described later.

_{The amount of CH 3} and C ₂ H ₅ present on the surface of the adhesive layer can be adjusted by changing the ratio of the vapor deposition monomer gas to the oxygen supply gas in the vapor deposition gas composition at the time of film formation. can.
The film thickness of the adhesive layer is preferably 5 nm or more and 200 nm, more preferably 10 nm or more and 100 nm or less, particularly preferably 20 nm or more and 60 nm or less, and most preferably 30 nm or more and 50 nm or less. If it is thinner than the above range,
The adhesive layer tends to be less likely to exist as a continuous film, the fluorine atoms of the fluorine-based resin film are more likely to be exposed on the surface, and the adhesiveness to rubber tends to be impaired. On the other hand, if it is thicker than the above range, it is not preferable from the viewpoint of productivity, the rigidity of the adhesive layer is increased, and cracks and the like are likely to occur in the adhesive layer.
The thickness of the adhesive layer can be measured using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Co., Ltd.

In order to form a thin-film vapor-deposited film to be the adhesive layer of the present invention, for example, a film to be vapor-deposited (fluorine-based resin film) 10 is introduced into a vacuum chamber. Then, a vapor deposition gas composition containing an organic silicon compound-based vapor deposition monomer gas and, in some cases, an oxygen supply gas is introduced into the vacuum chamber at a constant ratio, and an adhesive layer is formed on the surface by a plasma CVD method. ..

Examples of the organic silicon compound used for forming the adhesive layer _{include organic silicon compounds containing CH 3} directly bonded to the silicon (Si) atom, for example, hexamethyldisiloxane (HMDSO), tetramethyldisiloxane (TMDSO), and octame. Chilicyclotetrasiloxane, methylsilane, dimethylsilane, therimethylsilane, tetramethylsilane, ethylsilane and the like are preferably used.

The other organic silicon compound may be any material as long as it is an organic compound, has an appropriate vapor pressure at room temperature, and can carry out the plasma CVD method. Therefore, an organic silicon film (adhesive layer) containing at least one of _{CH 3} and C ₂ H ₅ is formed by a plasma CVD method using a material having a functional group having 3 or more carbon atoms, such as C ₃ H _8. It is theoretically possible to manufacture it. However, in reality, it is difficult to form an organic silicon film because the vapor pressure of these materials is very low.

When forming the adhesive layer according to the present embodiment, it is particularly preferable to use HMDSO, TMDSO, or octamethylcyclotetrasiloxane among the organic silicon compounds. These siloxane materials are _{stable in the vapor-deposited film because the three} CH groups that exhibit adhesiveness are directly bonded to the Si atom, not via the Si—O bond or OC bond, which are easily broken. This is because it becomes easy to be taken in.

In the present invention, for example, oxygen gas is used as the oxygen supply gas. Instead of oxygen gas, it is also possible to use such ozone or laughing gas (N ₂ O gas), in terms of film formation efficiency and cost, it is preferred to use the oxygen gas.

Further, in the vapor deposition gas composition, the gas (carrier gas) for efficiently introducing the vapor deposition monomer gas into the vacuum chamber and the gas for the purpose of generating or enhancing the plasma are enhanced. It may be introduced or may be carried out as needed.

The most common plasma CVD method is a method in which an electric field of 13.56 MHz is applied between the parallel plate electrodes. That is, the pressure is maintained at a constant pressure by introducing the vapor deposition gas composition into the vacuum chamber, and between the flat plate electrode installed in the vacuum chamber and the ground electrode installed parallel to the flat plate electrode. An RF AC voltage of 56 MHz is applied.

For example, a glow discharge plasma is generated by applying a power of 300 W, and a vapor deposition film made of an organic silicon film can be formed by chemically reacting the vapor deposition gas composition by using the plasma flow. Is. The film to be vapor-deposited (fluorine-based resin film) for forming the thin-film deposition film is usually installed on the surface of the ground electrode, but may be installed on the flat plate electrode side to which the RF voltage is applied.

In the present embodiment, instead of applying the RF AC voltage of 13.56 MHz, it is possible to apply a lower frequency (40 kHz, 50 kHz, etc.) or a higher frequency (2.45 GHz, etc.). Is. Further, a DC voltage may be applied. Instead of the flat plate electrode, it is also possible to use a hollow cathode electrode that generates a plasma flow by blowing out gas, or to generate inductive plasma from an external coil. It is also possible to increase the plasma density by using a magnetic field or by using an ECR resonance phenomenon (a phenomenon in which electrons in a plasma are cyclotron resonated by appropriately adjusting an electric field and a magnetic field).

The film formation conditions of the plasma CVD method include various parameters such as input power, gas flow rate, film formation pressure, electrode-to-electrode distance, and film formation time, and these are used so as to obtain a vapor-deposited film showing a desired contact angle. Parameters can be adjusted as appropriate.

In particular, when the input power is large, the reaction with the fluororesin film is likely to occur, so that the effect of surface modification is large and the adhesiveness with the rubber member is high. However, if it is too large, heat will be applied to deform the fluororesin film, and heat will be applied non-uniformly to cause unevenness in the vapor-deposited film, so care must be taken. In the present invention, it is preferable to carry out the film formation with an input power of 20 to 500 W, more preferably 50 to 300 W.

In the present invention, an adhesive layer is formed on the surface of the fluororesin film by the plasma CVD method while controlling the flow rate ratio of the monomer gas for vapor deposition and the oxygen supply gas within a certain range.
The film forming apparatus by the plasma CVD method used in the manufacturing method of the present invention is not limited to the above-mentioned batch type parallel plate type plasma CVD apparatus, but in the chamber as shown in FIG. It is preferable that the roll film forming machine or the like forms a vapor deposition film while transporting the raw material of the fluororesin film onto the coating drum.

<IV> Formation of Oxidized Surface As a method for improving the adhesion of the adhesive layer, treatment with an electron beam, corona treatment, atmospheric pressure plasma treatment, low pressure plasma treatment and the like can be mentioned. Corona treatment, atmospheric pressure plasma treatment, low pressure plasma treatment and the like are preferable from the viewpoint of productivity, and oxygen plasma treatment under low pressure is particularly preferable from the viewpoint of ease of controlling the plasma atmosphere.

As the low-pressure plasma processing, an ICP type plasma processing device, a parallel plate type plasma processing device, a roll-to-roll type plasma processing device, or the like can be used.
The low-pressure plasma treatment conditions include various parameters such as input power, gas flow rate, film formation pressure, distance between electrodes, and treatment time, and these parameters are appropriately set so as to obtain a vapor-deposited film showing a desired contact angle. Can be prepared in.

It is preferable that the step of forming the oxidation-treated surface is continuous with the step of forming the vapor-deposited film without being exposed to the outside air.
Specifically, in FIG. 5, the fluororesin film is transported from the film storage roll a1, a vapor-deposited film is formed, and after being stored in the film storage roll a2, the gas type is switched and the transfer is reversed. Examples thereof include a method in which the fluororesin film on which the vapor-deposited film has been formed is conveyed from the film storage roll a2 to form an oxidation-treated surface so that the film is stored in the film storage roll a1.

Further, the thin-film deposition film formation and the oxidation-treated surface formation may be carried out on individual treatment lines without being exposed to the outside air. For example, individual treatment lines may be installed in the same tank, or each treatment line may be installed in a separate tank so that they can be connected so as not to be exposed to the outside air.

When the surface layer portion of the vapor-deposited film is activated by low-pressure plasma treatment or the like, hydrogen atoms are separated from _{CH 3} groups and C ₂ H _{5 groups existing in the surface layer portion, and carbon radicals are generated.} In addition, the methyl group and the ethyl group derived from the organic silicon compound are separated from each other to generate a silicon radical. After that, these radicals are combined with oxygen in the atmosphere, and hydrogen atoms supplied in the atmosphere or from the film substrate or the like form oxygen-containing functional groups such as hydroxyl groups, carboxyl groups, aldehyde groups, and ketone groups. ing.

Alternatively, the oxygen radicals generated in the atmosphere by the low-pressure oxygen plasma treatment cause _{the abstraction of hydrogen atoms from the CH 3} groups and C ₂ H ₅ groups on the surface layer of the vapor deposition film and the addition reaction of oxygen, which are further supplied from the film substrate. Oxygen-containing functional groups such as hydroxyl groups, carboxyl groups, aldehyde groups, and ketone groups are formed by the hydrogen atoms.

It is considered that the surface layer in which these functional groups are present has an improved adhesiveness due to a significant improvement in affinity and reactivity with the rubber material.
The affinity with the rubber material depending on the amount of these functional groups present can be expressed by the contact angle of water on the surface layer of the adhesive layer. The contact angle of water is preferably 1 ° or more and less than 40 °, and more preferably 1 ° or more and 35 ° or less. If it is larger than the above range, the affinity with the rubber material is low, the adhesive strength is weakened, and peeling is likely to occur.

<V> Heat crimping with a rubber member In the present invention, the rubber member is a general term for a rubber composition, a rubber composition uncured product, a rubber composition cured product, and the like.
The rubber composition refers to a composition in which the raw materials constituting the rubber composition are blended, mixed, kneaded, and heat-kneaded as necessary, and the curing reaction rate is not necessarily zero and is given in the manufacturing process. It has an extent of reaction according to the normal heat history and the like.
Further, the rubber composition can be molded into a rubber composition having an arbitrary shape such as a plate shape, a sheet shape, or a rubber stopper shape by a known molding method.

In the rubber composition, the curing reaction may proceed to some extent within the range of having fluidity that can be molded in the molding die, and the degree of progress of the curing reaction is appropriately set by those skilled in the art. can do.
The cured rubber composition is one in which the curing reaction has proceeded to a target level normally enabled by the rubber composition, and the curing reaction rate is not necessarily 100%.
A rubber composition uncured product is one in which the rubber composition has undergone a curing reaction to some extent, but has not progressed to a target level that is normally possible, and is in a state before and after gelation and molding. Refers to those with a low curing level, etc., although they have been cured. Also called a rubber composition semi-cured product.
The post-curing treatment is a treatment in which the rubber composition is molded and cured, taken out, and then the curing reaction is further advanced by further heating or the like, if necessary.
The rubber molded body refers to a product in which a laminated film and a rubber member are adhered to each other.

By adhering the laminated film of the present invention to a rubber member, it is possible to obtain a rubber molded body of the present invention having excellent slipperiness and solvent resistance on the surface while maintaining the elasticity of the rubber member.
Here, by superimposing the surfaces of the adhesive layer of the laminated film of the present invention so as to face the rubber member and heat-pressing, extremely strong adhesion between the laminated film and the rubber member is achieved.

As the raw material rubber for the rubber member used in the present invention, any rubber can be used depending on the intended use. For example, any synthetic rubber or natural rubber can be used as a main raw material. Examples of synthetic rubber include butyl rubber such as butyl rubber, chlorinated butyl rubber, brominated butyl rubber, and divinylbenzene copolymerized butyl rubber, isoprene rubber, isoprene-isoprene rubber, butadiene rubber, styrene butadiene rubber, ethylene propylene rubber, and nitrile rubber. Can be mentioned.

In particular, when producing a rubber molded body for medical use, for example, a rubber molded body for a syringe, a stopper for a pharmaceutical vial, an inner lid of a medicine bottle, etc., good gas impermeableness, ozone resistance, aging resistance, etc. Chlorinated butyl rubber or brominated butyl rubber can be preferably used because it retains electrical properties, chemical resistance, and the like, and exhibits excellent heat resistance and adhesiveness to metals.
For example, a composite rubber sheet in which the slipperiness and chemical resistance of one side are improved by superimposing the surface of the adhesive layer of the laminated film of the present invention on one side or both sides of a rubber sheet made of a rubber composition and heat-pressing. Can be. Further, this composite rubber sheet can be punched into an arbitrary shape to produce various processed products such as syringe stoppers and pharmaceutical vial stoppers.

Further, the present invention is obtained by superimposing a molded product obtained by heat-molding a rubber sheet made of a rubber composition into a desired shape with the surface of an adhesive layer of the laminated film of the present invention and heat-pressing laminating. A rubber molded body may be manufactured.
Further, after superimposing the surface of the adhesive layer of the laminated film of the present invention on one side or both sides of the rubber sheet made of the rubber composition, it is placed in an arbitrary molding die and heat-pressed and laminated at the same time as heat molding. If necessary, it can be post-cured to obtain a rubber molded product having a desired shape.

Examples of the curing agent or curing accelerator that promotes the above curing include sulfur powder, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and other sulfur, sulfur chloride, sulfur dichloride, high molecular weight polysulfide, morpholine disulfide, and the like. Examples thereof include sulfur compounds such as alkylphenol disulfide, tetramethylthiuram disulfide and selenium dimethyldithiocarbamate, organic peroxides such as dicumyl peroxide, polyamines and oximes, and two or more of these may be used in combination.
Examples of the rubber molded product include, but are not limited to, the composite rubber sheet, various medical rubber products, for example, a syringe stopper, and a pharmaceutical vial stopper.

The syringe stopper and the pharmaceutical vial stopper having the laminated film of the present invention exhibit good slipperiness and chemical resistance while maintaining excellent sealing property.

In the present invention, the heat pressure bonding, heat molding, and post-hardening treatment of the laminated film and the rubber member can be performed by a conventionally known method. Further, various conditions at that time can be appropriately set by those skilled in the art according to the compounding composition of the rubber composition to be used, the state of progress of curing, the melting point of the fluororesin film, the thickness, and the like.
For example, when the cured rubber composition, which is a rubber member, obtained by molding and curing the rubber composition and the laminated film of the present invention are bonded to each other, the temperature is 150 to 250 ° C., the pressure is 0.1 to 20 Pa, and the time is It is preferable to heat-press in 10 to 300 seconds.

When the rubber composition or the uncured rubber composition is bonded to the laminated film of the present invention, it is heat-molded and heat-pressed at a temperature of 150 to 250 ° C., a pressure of 0.1 to 20 Pa, and a time of 10 to 600 seconds. It is preferable to do so.

In the rubber molded body composed of the laminated film and the rubber member of the present invention, for example, a composite rubber sheet, a syringe stopper and a pharmaceutical vial stopper, the rubber member and the laminated film are firmly adhered to each other, so that the rubber member is on the rubber member. The laminated film does not peel off and float or whiten.
The rubber molded body composed of the laminated film and the rubber member of the present invention exhibits particularly excellent adhesiveness when the rubber member is an uncured rubber composition or a rubber composition uncured product. This is because, when the rubber member is an uncured rubber composition or a rubber composition uncured product, there are many functional groups having high affinity or reactivity with various functional groups on the oxidation-treated surface on the laminated film side. It is presumed that it exists.

Next, the present invention will be specifically described with reference to examples.
[Example 1]
(Formation of thin-film deposition film on fluororesin film)
A 100 μm-thick fluororesin film (ETFE, manufactured by Daikin Industries, Ltd., untreated surface) is used and stored in the film storage roll a1 in the chamber b of the roll-to-roll type CVD apparatus (FIG. 5). , Connected to the film storage roll a2 via the transport roll c and the main roll d. Next, the pressure inside the chamber of the plasma processing apparatus was reduced to 0.001 Pa.
Next, HMDSO was prepared as an organic silicon compound and vaporized by a vaporizer e heated to 40 ° C. while controlling the flow rate to obtain a monomer gas for vapor deposition, which was supplied to the chamber at a flow rate of 100 sccm (gas state). Further, oxygen gas f was supplied to the chamber at a flow rate of 1500 sccm.

Next, the distance between the main drum d and the magnet electrode g is 50 mm, and plasma is generated by applying 700 W, 13.56 MHz of power between the main drum d and the magnet electrode g, and the inside of the chamber at the time of film formation is formed. The film was formed while being transported at a film transport speed of 2.0 m / min while maintaining the pressure of 3 Pa, and was stored in the film storage roll a2. The fluororesin film during the treatment was water-cooled and kept at room temperature.

(Formation of oxidation-treated surface on thin-film deposition film)
Next, the inside of the chamber of the plasma processing apparatus was reduced to 0.001 Pa, and the monomer gas for vapor deposition was not supplied to 0 sccm, and then the oxygen gas f was supplied to the chamber at a flow rate of 1500 sccm.
Then, the distance between the main drum d and the magnet electrode g is 50 mm, and plasma is generated by applying 700 W, 13.56 MHz of electric power between the main drum and the magnet electrode, and the pressure in the chamber at the time of film formation is reduced. It was kept at 8 Pa.
Then, the fluororesin film having the vapor-deposited film formed stored in the film storage roll a2 is directed toward the film storage roll a1 via the transport roll c and the main roll d at a film transport speed of 4.2 m / min. Oxidation treatment was performed while transporting, an oxidation-treated surface was formed, an adhesive layer was completed, and a laminated film was produced.
The thickness of the adhesive layer was 43 nm.
The contact angle of water was measured with respect to the obtained laminated film. The results are shown in Table 1.

(Adhesion treatment between fluorine-based resin film and rubber member)
The surface of the adhesive layer of the obtained laminated film was superposed on an uncured rubber composition sheet (Essobutyl manufactured by Exxon Chemical Co., Ltd., thickness 1 mm), and a precision press machine manufactured by Tester Sangyo Co., Ltd. was used at 170 ° C. Heat pressure bonding and curing were performed at 5 MPa for 600 seconds to obtain a composite rubber sheet, which is a rubber molded product of the present invention.
A peeling test was performed using the obtained composite rubber sheet. The results are shown in Table 1.

[Examples 2 to 3 and Comparative Examples 1 to 3]
Except for changing the flow rate of oxygen gas f during oxygen plasma treatment to the conditions shown in Table 1, the same operation as in Example 1 was performed to form a vapor-deposited film and an oxidation-treated surface to complete and laminate an adhesive layer. A film was made, then a composite rubber sheet was made and evaluated in the same manner. The results are shown in Table 1.

[Measurement of adhesive layer thickness]
The thickness of the adhesive layer was measured using a fluorescent X-ray analyzer RIX2000 manufactured by Rigaku Co., Ltd.

[Evaluation of adhesiveness]
(Contact angle)
In order to evaluate the adhesiveness of the surface of the laminated film adhesive layer, the contact angle of water was measured at 20 ° C. and 50% RH using a contact angle tester (Kyowa Interface Science Co., Ltd. fully automatic contact angle meter Drop Master 700). Measured under conditions.
(Peeling test)
In order to examine the adhesiveness between the laminated film and the rubber member, a peeling test was performed according to JISK 6404-5. Specifically, using test pieces cut out from each composite rubber sheet to a width of 15 mm, they were manually pulled at a peeling angle of 180 ° to attempt peeling. The judgment criteria are as follows.
◯: The test piece was stretched by tension, and then the film and the rubber member did not peel off until it broke. Δ: The test piece stretched and the film and the rubber member peeled off before breaking. The film and rubber member peeled off

[Result Summary]
The laminated films of Examples 1 to 3 showed a low value of water contact angle of 35 ° or less. Further, in the composite rubber sheet using these laminated films, the laminated film and the rubber member showed strong adhesion.
On the other hand, the laminated films of Comparative Examples 1 to 3 showed a high value in which the contact angle of water exceeded 35 °. Further, in the composite rubber sheet using these films, the adhesion between the film and the rubber member was weak, and the film was peeled off from the rubber member.

10 Fluorine-based resin film 20 Adhesive layer 30 Oxidation-treated surface 40 Rubber members a1, a2 Film storage roll b Chamber c Conveyance roll d Main roll e Vaporizer f Oxygen gas g Magnet electrode h Material gas piping i Discharge power supply j Exhaust pump

Claims (12)

A laminated film having a fluorine-based resin film, an adhesive layer made of a vapor-deposited film formed on the fluorine-based resin film, and an oxidation-treated surface formed on the adhesive layer .
The vapor-deposited film is mainly composed of carbon, silicon and oxygen.
An oxidation-treated surface on which the adhesive layer is oxidized is formed on the exposed outermost surface of the vapor-deposited film .
The oxidation-treated surface contains an oxygen-containing functional group and contains an oxygen-containing functional group.
Of the oxidized surface, the contact angle of water, characterized in that 1 ° or more and 35 ° or less, the laminated film. The laminated film according to claim 1, wherein the oxygen-containing functional group is any one of a hydroxyl group, a carboxyl group, an aldehyde group, and a ketone group. A rubber molded body having a structure in which the laminated film according to claim 1 or 2 and a rubber member are bonded to each other via the adhesive layer of the laminated film. The rubber molding is, the surface of the adhesive layer of the laminated film, the rubber member, characterized in that it is one that is molded and pressed under heating by the superimposed, rubber molding according to claim 3 body. The rubber molded body according to claim 3 or 4 , wherein the rubber member is one or more selected from the group consisting of a rubber composition, a rubber composition uncured product, and a rubber composition cured product. The rubber molded product according to claim 3 or 4 , wherein the rubber member is a rubber composition or a rubber composition uncured product. The rubber molded product according to any one of claims 3 to 6 , wherein the rubber molded product is further subjected to a post-hardening treatment. The rubber molded product according to any one of claims 3 to 7 , wherein the rubber molded product is a syringe plug. The rubber molded product according to any one of claims 3 to 7 , wherein the rubber molded product is a stopper for a pharmaceutical vial. The method for producing a laminated film according to claim 1 or 2.
The manufacturing method includes the following steps 1 and 2.
Steps 1 and 2 are methods for producing a laminated film, which are continuously performed without being exposed to the outside air.
Step 1) A step of forming an adhesive layer made of a vapor-deposited film by a plasma vapor phase chemical vapor deposition method using a gas composition for vapor deposition containing an organic silicon compound on a fluororesin film.
Step 2) A step of forming an oxidation-treated surface by subjecting the exposed surface of the vapor-deposited film to an oxygen plasma treatment using oxygen gas. The method for producing a rubber molded product according to any one of claims 3 to 9.
The laminated film is manufactured by the manufacturing method according to claim 10.
The rubber molded body is a method for producing a rubber molded body, wherein the surface of the adhesive layer of the laminated film and the rubber member are overlapped and molded and heat-pressed. The method for producing a rubber molded product according to claim 11 , wherein the rubber molded product is post-hardened.

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