JPH1086282A - Ethylene propylene rubber film composite body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the workability of incorporation into various devices or parts as well as the separating strength between layers of both films by a method wherein an ethylene propylene rubber film is laminated at least on one side of a base film and separating strength between the layers of both films is specified. SOLUTION: The terpolymer of ethylene, propylene and dien (EPDM) is blended with peroxide compound, carbon black or the like to knead and resolve it into toluene while the methacrylate ester of multivalent alcohol is added into an obtained rubber solution and is mixed. The EPDM rubber solution is applied on a PET film, on which an adhesive property improvement agent is laminated, and is dried while a cover sheet is superposed on the surface of the EPDM rubber film to bond by pressure, then, electronic beam is projected against the obtained laminated body from the side of the substrate film and, further, the electronic beam is projected from the side of the EPDM rubber film after separating a cover sheet. Thus, a separating strength between the substrate film layer and the rubber film layer is increased to 4N/20mm or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ethylene-propylene-based rubber film composite, and more particularly, to a laminate of an ethylene-propylene-based rubber film and a substrate film, which has excellent delamination strength and seals in various fields. An object of the present invention is to provide an ethylene propylene rubber film composite which can be used as a material or a cushion material.

[0002]

2. Description of the Related Art An ethylene propylene rubber film is
Due to its excellent cushioning properties, it is used as a sealing material and a cushioning material in a wide range of industrial fields. However, ethylene propylene rubber films have poor adhesiveness to other materials, and when incorporating ethylene propylene rubber films into equipment and parts, practical adhesive strength cannot be obtained with inexpensive general-purpose adhesives. Expensive adhesive had to be used. In addition, since the ethylene-propylene rubber film is flexible, it has disadvantages such as inferior workability in assembling work. As means for solving such a problem, it is known that the adhesiveness is better than that of an ethylene propylene rubber film, and that a composite with a base film that can be bonded with a low-cost general-purpose adhesive is used. Although the ethylene propylene rubber film is reinforced by the base film, the workability at the time of assembling work is improved, but the adhesion between the ethylene propylene rubber film and the base film is poor, so that it has not been put to practical use.

[0003] Silicone rubber is a rubber having poor adhesion like ethylene-propylene rubber, and as a means for improving the adhesiveness of this silicone rubber to other materials,
Compounding allyl glycidyl ether and glycidyl acrylate with silicone rubber (JP-A-54-1627)
No. 51), and the addition of an organosiloxane such as hexavinyldisiloxane or dimethyltetravinyldisiloxane (see JP-A-3-111452).
It has been proposed to mix an alkenyl carbonate group-containing compound and / or a mercaptoacetate group-containing compound (see JP-A-8-120177). However, even if these methods are applied to an ethylene propylene rubber film, There is no effect of improving the adhesiveness, which is not practical.

[0004]

SUMMARY OF THE INVENTION The present invention comprises a laminate of an ethylene propylene rubber film and a base film, and can be bonded with an inexpensive general-purpose adhesive when incorporated into various devices and parts. Another object of the present invention is to provide an ethylene-propylene-based rubber film composite which has good workability at the time of assembling work and has excellent peel strength between the ethylene-propylene-based rubber film and the base film.

[0005]

According to the present invention, there is provided an ethylene-propylene rubber film composite comprising an ethylene-propylene rubber film laminated on at least one surface of a base film. An ethylene propylene rubber film composite, characterized in that the propylene rubber film and the base film have an interlayer peel strength of 4 N / 20 mm or more.

The ethylene-propylene rubber composite of the present invention can improve the adhesiveness of the ethylene-propylene rubber itself by blending the ethylene-propylene rubber with an adhesion improver, as described later. Laminating a layer made of a compound (easy-adhesive component) that improves the adhesiveness on the surface, or treating the surface of the film with an actinic ray such as corona discharge, and then unvulcanized ethylene-propylene rubber By laminating the film and the base film and subjecting them to a cross-linking treatment, the film is manufactured so that the above-mentioned delamination strength is 4 N / 20 mm or more, preferably 6 N / 20 mm or more, particularly 8 N / 20 mm or more.

[0007] This ethylene propylene rubber film composite has high interlayer peel strength between the ethylene propylene rubber and the base film and is 4 N / 20 mm or more, so that the ethylene propylene rubber film and the base film are easily separated. It can be handled as a single film when incorporating this complex into any device, and by providing a base film with good adhesiveness, the base film surface can be bonded with an inexpensive general-purpose adhesive And can be easily attached to a desired portion of the device. And, due to the presence of the base film, the workability at the time of assembling is better than that of the ethylene propylene rubber film alone. Therefore, it can be effectively used as a sealing material or a cushioning material by utilizing the good cushioning properties of the ethylene propylene rubber film.

[0008] The ethylene-propylene rubber used in the present invention is not particularly limited, and may be a binary copolymer EPM of ethylene and propylene, or a terpolymer EPDM of ethylene, propylene and diene. It may be a mixture. EPM or EPDM above
Can be used, and the ethylene content thereof is preferably 30 to 80% by weight.
Examples of M include those using ethylidene norbornene, dicyclopentadiene, and 1,4-hexadiene as diene monomers.

It is preferable that the ethylene-propylene rubber is blended with an adhesion improver for improving the adhesion of the rubber itself, as described in claim 2. As described in, is preferably a compound containing a functional group active against a radical reaction,
Acrylic acid derivatives, methacrylic acid derivatives, allyl derivatives and the like are exemplified, but as described in claim 4, methacrylic acid esters of polyhydric alcohols are particularly preferred.

The above-mentioned methacrylic acid ester of a polyhydric alcohol is an ester compound obtained by esterifying two or more alcoholic hydroxyl groups of a polyhydric alcohol having two or more alcoholic hydroxyl groups with methacrylic acid, such as ethylene glycol dimethacrylate, 1,3 butanediol dimethacrylate, 1,4 butanediol dimethacrylate, 1,6 hexanediol dimethacrylate, neopentyl glycol dimethacrylate, 2,2'bis (4
-Methacryloxydiethoxyphenyl) pron, glycene dimethacrylate, glycentri methacrylate, trimethylolpropane trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, tetramethylolmethane dimethacrylate,
Examples thereof include tetramethylol methane trimethacrylate and tetramethylol tetramethacrylate, and a compound containing three or more methacrylic esters is particularly preferable.
In addition, any one of the above compounds may be used alone, or two or more of them may be used in combination.

The compounding amount of the methacrylic acid ester is 3 to 30 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the ethylene propylene rubber component.
When the amount is less than 3 parts by weight, the adhesive strength with the base film becomes insufficient. On the other hand, when the amount exceeds 30 parts by weight, the effect of improving the adhesive strength reaches saturation, and the physical properties of the ethylene propylene rubber are reduced. descend. The methacrylic acid ester serves as an adhesion improver for the ethylene propylene rubber composition, and if necessary, a reinforcing filler, a pigment, a dye, an antioxidant, an antioxidant, a mold release. Agents, flame retardants, thixotropic agents, filler dispersants, co-crosslinking agents, and the like.

The substrate film used in the present invention is not particularly limited, and may be any film that is superior in adhesiveness to ethylene propylene-based rubber and has more rigidity. For example,
Polyester films, polyamide films, polyphenylene sulfide films, polyimide films, polyetheretherketone films, polysulfone films, and the like can be mentioned. The polyester film according to claim 5 has comprehensive properties such as heat resistance, dimensional stability, and economy. It is particularly preferable in terms of the best force.

The polyester film can be arbitrarily used as long as it contains polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate or the like as a main component. As this polyester film,
An easily-adhesive polyester film obtained by treating the surface with an actinic ray or laminating a compound (easily-adhesive component) for improving the adhesiveness on the surface of the polyester film can be used. The compounding amount of the adhesion improver in the ethylene propylene rubber film can be reduced. That is, the delamination strength of the ethylene propylene-based rubber film and the polyester film (base film) is 4 N / 20 mm by a combination of the above-described actinic ray treatment, selection of the easily-adhesive polyester film, and the amount of the above-mentioned adhesiveness improver. As described above, it is preferably set to 6 N / 20 mm or more, and particularly preferably set to 8 N / 20 mm or more.

Examples of the treatment method using the actinic ray include corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, flame treatment and the like, and the easy-adhesion component of the easily-adhesive film is the polyester described in claim 6. Preferred are polyurethane-based, polyurethane-based, polyacryl-based polymers, or mixtures thereof. The method of laminating the easily adhesive layer may be a so-called in-line method of laminating at the time of film formation or a so-called off-line method of laminating on a formed film. Further, the surface of the easy-adhesion layer of the film on which the easy-adhesion layer is laminated can be treated with the above-mentioned actinic ray.

In the present invention, a peroxide compound or a silicone rubber is added to the ethylene propylene rubber in order to promote the manifestation of the effect of improving the adhesiveness by the adhesiveness improving agent. Can be blended. By the addition of these compounds, the delamination strength between the ethylene propylene rubber film and the base film is further improved.

The peroxide compound may be either an acyl compound or an alkyl compound, such as benzoyl peroxide, monochlorobenzoyl peroxide,
4-dichlorobenzoyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5bis (t
-Butylperoxy) hexane, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-bis-t-butylperoxy-3,3,5
-Trimethylcyclohexane, di-t-butyl peroxide, t-butyl cumyl peroxide and the like.

The amount of the peroxide compound is 0.05 to 10 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the ethylene propylene rubber component.
8 parts by weight are preferred. If the amount is less than 0.05 part by weight, the effect of improving the adhesiveness is not promoted. If the amount exceeds 10 parts by weight, the above-mentioned effect is saturated and the physical properties of the rubber film are reduced.

The silicone rubber used in the present invention is an organopolysiloxane represented by an average unit formula: RaSiO _{(4-a) / 2} . In the above formula, R is a substituted or unsubstituted monovalent hydrocarbon group, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a vinyl group, an allyl group, and butenyl. Group, pentenyl group, alkenyl group such as hexenyl group, phenyl group, tolyl group, xylyl group, aryl group such as naphthyl group, cyclopentyl group, cycloalkyl group such as cyclohexyl group,
Benzyl group, aralkyl group such as phenethyl group, halogenated alkyl group such as 3-chloropropyl group, 3,3,3-trifluoropropyl group, and the like, preferably methyl group, vinyl group, phenyl group, 3, 3,3-trifluoropropyl group. In the above formula, a is 1.9 to 2.
A number in the range of 1. The silicone rubber component is represented by the above average unit formula. Specific siloxane units constituting the silicone rubber component include, for example, R ₃ SiO _1/2 unit, R
₂ (HO) SiO _{2 1/2} unit, R ₂ SiO _2/2 unit, RS
_{io3 / 2} units and _{io4 / 2} units.

The main component of the silicone rubber component is R ₂ Si
O _2/2 unit and R ₃ SiO _1/2 unit or R ₂ (HO)
It is a linear polymer essentially containing SiO _1/2 units, and optionally a small amount of RSio _3/2 units and / or R ₃ S
It can have a partially branched structure by containing _{iO1 / 2} units. Also, as part of the silicone rubber component, R ₃ Si
A resinous polymer composed of O _1/2 units and _{SiO 4/2} units can be blended. As described above, the silicone rubber component may be a mixture of two or more polymers.
When the composition is an addition reaction-curable silicone rubber composition, at least two Rs in the organopolysiloxane represented by the above average unit formula must be alkenyl groups.

The molecular structure of the silicone rubber component is not particularly limited, and may be, for example, linear, partially branched linear, branched, or resinous. , A linear polymer, or a mixture mainly composed of a linear polymer. Such silicone rubber components include, for example, dimethylpolysiloxane having trimethylsiloxy groups at both ends of molecular chains, methylvinylpolysiloxane having trimethylsiloxy groups at both ends of molecular chains, methylphenylpolysiloxane having trimethylsiloxy groups at both ends of molecular chains, and methylphenylpolysiloxane. Trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer at both ends of chain, trimethylsiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer at both ends of molecular chain, dimethylsiloxane / methyl-blocked trimethylsiloxy group at both ends of molecular chain 3,3-trifluoropropyl) siloxane copolymer, molecular chain terminal trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, molecular chain terminal dimethyl Nylsiloxy group-blocked dimethylpolysiloxane, molecular chain terminal dimethylvinylsiloxy group-blocked methylvinylpolysiloxane, molecular chain terminal dimethylvinylsiloxy group-blocked methylphenylpolysiloxane, molecular chain terminal dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane Copolymer, dimethylvinylsiloxy-group-blocked dimethylsiloxane / methylphenylsiloxane copolymer with both ends of molecular chain, dimethylsiloxane-methyl (3,3,3-trifluoropropyl) siloxane-copolymer with both ends of molecular chain dimethylvinylsiloxy-group Coupling, dimethylvinylsiloxy group-blocked dimethylsiloxane at both ends of molecular chain
Methyl vinyl siloxane / methyl phenyl siloxane copolymer, dimethyl polysiloxane with silanol groups at both ends of molecular chain, methyl vinyl polysiloxane with silanol groups at both ends of molecular chain, methyl phenyl polysiloxane with silanol groups at both ends of molecular chain, both ends of molecular chain Silanol group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain-terminated silanol group-terminated dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain-terminated silanol group-blocked dimethylsiloxane / methyl (3,3
3-trifluoropropyl) siloxane copolymer, dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer with silanol groups at both ends of molecular chain, dimethylpolysiloxane with trimethoxysiloxy groups at both ends of molecular chain, tris at both ends of molecular chain Methoxysiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain terminal trimethoxysiloxy group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain terminal trimethoxysiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methyl Phenylsiloxane copolymer, organopolysiloxane copolymer comprising R ₃ SiO _1/2 units and _{SiO 2/2} units, R ₂ SiO
Organopolysiloxane copolymers consisting of _2/2 units and RSi O _3/2 units, R ₃ Si O _1/2 units and R ₂ Si O _2/2
And organopolysiloxane copolymers consisting of RSiO _3/2 units and a mixture of two or more of these. The viscosity of the silicone rubber component at 25 ° C.
Although not particularly limited, practically, it is preferably 100 centistokes or more, and particularly preferably 1,000 centistokes or more.

The amount of the silicone rubber is preferably 5 to 100 parts by weight, particularly preferably 10 to 70 parts by weight, per 100 parts by weight of the ethylene propylene rubber. The above amount is 5
If the amount is less than the weight part, the improvement of the adhesion improving effect is not promoted,
On the other hand, if it exceeds 100 parts by weight, the above-mentioned accelerating effect reaches saturation and is not economical. The heat resistance of the ethylene propylene rubber is also improved by blending the silicone rubber.

Further, instead of blending the silicone rubber with the ethylene propylene rubber, an adhesion improver is blended as an intermediate layer between the base film and the ethylene propylene rubber film. The interlayer peel strength between the base film and the ethylene propylene rubber film can be improved by interposing a layer of the silicone rubber composition. In this case, the same silicone rubber as described above can be used, and the same adhesion improver as that used in the above-mentioned ethylene propylene rubber film can be used. The amount of the adhesion improver to silicone rubber is preferably 0.5 to 30 parts by weight, particularly preferably 1 to 20 parts by weight, based on 100 parts by weight of silicone rubber in the case of the methacrylic acid ester.
If the amount is less than 0.5 part by weight, the adhesive strength to the substrate film becomes insufficient, and if it exceeds 30 parts by weight, the strength is saturated, which is economically disadvantageous.

When the above-mentioned layer of the silicone rubber composition is used as an intermediate layer, the adhesion to the base film can be further increased by blending the peroxide with the silicone rubber. In this case, even if the above-mentioned adhesion improver (methacrylic acid ester of polyhydric alcohol) or the adhesion improvement accelerator (peroxide and silicone rubber) is not blended with the ethylene propylene rubber film, it is practical. Although a proper delamination strength can be obtained, the composition is not limited. Also,
The thickness of the intermediate layer is preferably 0.0005 to 0.05 mm.

The method of compounding the above-mentioned adhesiveness improving agent and other compounding agents with ethylene propylene rubber or silicone rubber is not particularly limited. For example, when a rubber compound is produced, two rolls, a Banbury mixer, a dough mixer (kneader) ) May be carried out using a rubber kneading machine, or when the above rubber is dissolved in a solvent and a film is formed by a casting method, the rubber compound is dissolved in a solvent to prepare a solution, or It may be a method of adding and blending in the prepared solution.

In the present invention, the method of laminating the ethylene propylene rubber film on the base film is optional. For example, a solution obtained by dissolving the ethylene propylene rubber composition in a solvent is applied to the surface of the base film and dried. A thin film of ethylene propylene rubber by extruding an ethylene propylene rubber composition on the surface of a base film under high pressure to form a thin film of ethylene propylene rubber. The method of forming the intermediate layer is also not particularly limited, and for example, an ethylene propylene rubber layer and an intermediate layer may be simultaneously laminated on a base film with a multilayer die,
You may laminate | stack an intermediate | middle layer first on a base material film, and then laminate | stack an ethylene propylene-type rubber | gum. In addition, the thickness composition ratio of the ethylene propylene rubber film and the base film in the present invention can be arbitrarily set according to the use of the composite.

The crosslinking method is not particularly limited. For example, a peroxide compound is blended in the ethylene propylene rubber composition, and after laminating by the above method, the laminate may be cross-linked by heat treatment, and ultraviolet rays, electron beams, active rays such as γ rays may be used. Irradiation may be used for crosslinking. In addition, addition of various auxiliaries during these crosslinking treatments is not limited at all.

The above-mentioned ethylene-propylene-based rubber film composite may be required to have various surface roughness depending on the purpose of use. For example, in a cushioning rubber tape to be mounted on a drive table of a compact disc, it is necessary to set an appropriate surface roughness in order to balance the grip and detachability of the compact disc. As a means for controlling the surface roughness of the ethylene propylene rubber film for such a purpose, a cover sheet made of a film or a cloth having a different surface roughness is superimposed on the surface of the uncrosslinked ethylene propylene rubber film to form a cover sheet. A method of transferring a surface morphology to an ethylene propylene rubber film is known. For example,
As a means to give fine irregularities to the surface of a general rubber sheet, the basis weight using a polyester film or vinyl chloride film subjected to matting or embossing, or a filament fabric such as nylon taffeta or polyester taffeta for the cover sheet is widely used. Is being done.

The above-mentioned cover sheet is superimposed on the surface of the ethylene-propylene rubber sheet at the time of cross-linking, and is peeled off after the cross-linking. When an adhesiveness improving agent that improves the delamination strength is blended, the peel strength of the ethylene propylene-based rubber sheet and the cover sheet is also improved, even if the cover sheet is to be peeled off after crosslinking. However, if the cover sheet was peeled off before the crosslinking treatment, there was a problem that the rubber of the ethylene propylene rubber film was chipped and adhered to the cover sheet.

In the present invention, when the surface roughness of the ethylene propylene rubber film is controlled by the cover sheet, the following method can be employed to improve the peelability of the cover sheet. That is, as the cover sheet, a material having low adhesion to ethylene propylene rubber, for example, a film made of poly-4-methylpentene-1 or an ethylene / methyl methacrylate copolymer can be used. Further, the ethylene propylene rubber film can be multi-layered, and the compounding amount of the adhesion improver can be reduced on the cover sheet side than on the base film side. When crosslinking is performed by an electron beam crosslinking method, the irradiation conditions are optimized by, for example, performing electron beam irradiation from the substrate film side.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiment 1 0.05 to 10 parts by weight of a peroxide compound is added to 100 parts by weight of EPDM (ethylene content: 30 to 80%),
It is compounded with carbon black, a plasticizer and other usual compounding agents, kneaded by a conventional method, dissolved in toluene, and a methacrylic acid ester of a polyhydric alcohol is added to the obtained rubber solution in an amount of 3 parts per 100 parts by weight of EPDM rubber. Add ~ 30 parts by weight and stir. The obtained EPDM rubber solution was coated with a polyester-based adhesion improver with a thickness of 0.003 to
The composite is coated on a 0.25 mm polyester film (substrate film) so that the total thickness after drying is 0.03 to 0.5 mm, dried, and a cover sheet is placed on the surface of the EPDM rubber film and pressed. The obtained laminate is irradiated with an electron beam of 0.5 to 6 Mrad from the substrate film side to perform pre-crosslinking, and after the cover sheet is peeled off, the EPD
Post-crosslinking is performed by irradiating 5 to 50 Mrad of electron beam from the M rubber film side to complete the crosslinking, and a total thickness of 0.03 to 0.5 mm in which the surface shape of the cover sheet is transferred to the surface.
To obtain an ethylene-propylene-based rubber film composite.

In this embodiment, since the crosslinking is carried out by electron beam irradiation, a composite having a uniform thickness can be economically produced. In addition, since the pre-crosslinking by low-energy electron beam irradiation is performed from the base film side, the cover sheet can be smoothly peeled off, and post-crosslinking by high-energy electron beam irradiation from the rubber film side is performed after this peeling. The crosslinking of the rubber film can be completed. Thus, the obtained EPDM rubber film composite can be easily adhered to desired equipment with a commercially available general-purpose adhesive by using the surface of the base film as an adhesive surface.
Since the delamination strength between the PDM rubber film and the base film is strong, it is practical because it is not peeled off from this interface by an external force. For example, when using a double-sided pressure-sensitive adhesive tape that is widely used when bonding an EPDM rubber film to equipment, since the above-mentioned delamination strength is strong, when an external force is applied, delamination does not occur between layers, and a double-sided pressure-sensitive adhesive tape is used. Peeling occurs at the bonded portion due to Moreover, since it is a composite comprising an EPDM rubber film and a base film, and has a higher rigidity than an EPDM rubber film alone, it is excellent in workability when incorporated into an arbitrary device. Therefore, the EPDM rubber film can be used as a sealing material or a cushioning material by fully utilizing the excellent cushioning property.

Embodiment 2 An EPDM rubber film composite is produced in the same manner as in Embodiment 1 except that the compounding of the peroxide compound in Embodiment 1 is omitted. EP in the obtained composite
Although the delamination strength between the DM rubber film and the base film is slightly lower than that of the first embodiment, it is 4 N / 20 mm or more, so that the composite can be used without any trouble similarly to the first embodiment.

Embodiment 3 In place of the peroxide compound in Embodiment 1, silicone rubber is used in an amount of 5 to 100 parts by weight of EPDM rubber.
An EPDM rubber film composite is produced in the same manner as in Embodiment 1, except that 100 parts by weight are blended. The delamination strength between the EPDM rubber film and the base film in the obtained composite is further improved as compared with Embodiment 1, and can be used in the same manner as the composite of Embodiment 1.

Embodiment 4 The compounding of the peroxide compound and the methacrylic acid ester of the polyhydric alcohol in Embodiment 1 is omitted,
Instead, a silicone rubber solution prepared in the same manner as the EPDM rubber solution shown in Embodiment 1 (provided that the blending amount of the polyhydric alcohol methacrylate with respect to 100 parts by weight of the silicone rubber is 0.5 to 30 parts by weight) ) Is dried and applied on the same polyester film as in Embodiment 1 so that the thickness becomes 0.0005 to 0.05 mm, and then an EPDM rubber layer is laminated in the same manner as in Embodiment 1, followed by crosslinking. By performing the treatment, an EPDM rubber film composite is obtained. This composite has the same high peel strength between the EPDM rubber film and the base film as in the first embodiment, and can be used in the same manner as in the first embodiment.

[0035]

The present invention will be described below in detail with reference to examples. In the following description, "parts" indicates parts by weight.

Example 1 EPDM (34% ethylene content, "EP21" manufactured by Nippon Synthetic Rubber Co., Ltd.) was used as a rubber, and zinc salt of 2-mercaptobenzimidazole ("Nocrack" manufactured by Ouchi Shinko Chemical Co., Ltd.) was used as an antioxidant A. MBZ ") and 4,4- (α, α-dimethylbenzyl) diphenylamine (" Nocrack CD "manufactured by Ouchi Shinko Chemical Co., Ltd.) as anti-aging agent B, respectively, and kneaded in a conventional manner with the composition shown in Table 1 below. did.

Table 1 EPDM 100.0 parts Polyethylene glycol (molecular weight 4000) 2.5 parts Stearic acid 0.5 parts Antioxidant A 1.5 parts Antioxidant B 0.7 parts Phenol formaldehyde resin 2.0 parts MAF Carbon 30.0 parts FT carbon 40.0 parts Polybutene 15.0 parts N, N'-m phenylenedimaleimide 1.5 parts 2,5-dimethyl-2,5-di (t-butylperoxy) hexane 5. 0 copies

The above kneaded rubber was formed into a sheet having a thickness of 3 mm. The unvulcanized rubber sheet was cut into 1 cm square pieces, weighed so that the weight ratio to toluene was 30%, and put into a stirrer with a vacuum defoaming device together with toluene, and the atmospheric pressure was applied. After stirring for 15 hours under a low temperature and dissolving the strips in toluene, trimethylolpropane trimethacrylate was added to the solution in an amount of 12 parts with respect to 100 parts of EPDM rubber. The defoaming device was driven, and the mixture was further stirred under vacuum at a gauge pressure of -750 mmHg for 20 minutes to defoam.

Next, the EP obtained by the dissolution and defoaming described above is used.
A DM rubber solution is supplied to a roll coater, and a polyester-based adhesion improver (polyester comprising terephthalic acid, isophthalic acid, sodium salt of 3-sulfoisophthalic acid, ethylene glycol, diethylene glycol and neopentyl glycol) is laminated on both sides. After drying, the coated polyethylene terephthalate film having a thickness of 0.038 mm was coated so as to have a thickness of 0.20 mm, then introduced into an oven, dried at 80 ° C., and poly-4-methylpentene was added to the surface of the EPDM rubber. A matted film ("Opulan X-60YMT4" manufactured by Mitsui Petrochemical Co., Ltd.) having a thickness of 0.035 mm made of the copolymer of No. 1 is laminated so that the matted surface faces the EPDM rubber surface, and a pressure of 5 kgf is applied using a pressure roll. / Cm while continuously laminating,
The obtained laminate was further continuously introduced into an electron beam irradiation device, and 200 mm from the polyethylene terephthalate film side.
KV, pre-crosslinking is performed by irradiating an electron beam with an energy of 3 Mrad.
A composite comprising a rubber film and a polyester film was obtained. Then, the composite was further introduced into an electron beam irradiation apparatus, and 200 KV, 30 Mra was applied from the EPDM rubber film side.
d) Post-crosslinking by electron beam irradiation
A 4 mm composite was obtained and wound into a roll.

Comparative Example 1 Comparative Example 1 was carried out in the same manner as in Example 1 except that the addition of trimethylolpropane trimethacrylate was omitted.
EPDM rubber film composite was produced.

Example 2 In Example 1, 2,5-dimethyl-2,5-di (t
An EPDM rubber film composite of Example 2 was produced in the same manner as in Example 1 except that the blending of -butylperoxy) hexane was omitted.

Example 3 In Example 1, a polyester film which had been subjected to corona treatment was used, and the corona treated surface was EPDM.
An EPDM rubber film composite of Example 3 was produced in the same manner as in Example 1 except that the EPDM rubber film composite was laminated on a rubber film.

Example 4 In Example 1, 2,5-dimethyl-2,5-di (t
-Butyl peroxy) hexane instead of a commercially available high-strength silicone rubber compound ("KE" manufactured by Shin-Etsu Chemical Co., Ltd.)
555-U ”) was added in the same manner as in Example 1 except that 30 parts of EPD rubber was mixed with 100 parts of EPDM rubber.
An M rubber film composite was produced.

Comparative Example 2 Comparative Example 2 was carried out in the same manner as in Example 1 except that the addition of trimethylolpropane trimethacrylate in Example 4 was omitted.
EPDM rubber film composite was produced.

Example 5 The EPDM rubber film composite of Example 5 was prepared in the same manner as in Example 1 except that the kneaded rubber having the composition shown in Table 2 below was used and the addition of trimethylolpropane trimethacrylate was changed to 6 parts. Manufactured.

Table 2 EPDM (“Sprene 301A” manufactured by Sumitomo Chemical Co., Ltd.) 100.0 parts Polyethylene glycol (molecular weight 4000) 2.5 parts Stearic acid 0.6 parts Antioxidant A 1.5 parts Antioxidant B 0. 7 parts Phenol formaldehyde resin 2.0 parts MAF carbon 30.0 parts FT carbon 40.0 parts Polybutene 15.0 parts 2,5-dimethyl-2,5-di (t-butylperoxy) hexane 3.0 parts Silicone 15.0 parts of rubber compound ("KE575U" manufactured by Shin-Etsu Chemical Co., Ltd.)

Comparative Example 3 An EPDM rubber film composite of Comparative Example 3 was produced in the same manner as in Example 5, except that the addition of trimethylolpropane trimethacrylate of Example 5 was omitted.

Example 6 Example 1 was repeated except that the blending of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and trimethylolpropane trimethacrylate was stopped.
An EPDM rubber solution was prepared in the same manner as described above. As a silicone rubber compound, a commercially available high-strength silicone rubber compound ("KE555-Shin-Etsu Chemical Co., Ltd.")
U ") and a commercially available silicone rubber compound for general molding (" KE958-U "manufactured by Shin-Etsu Chemical Co., Ltd.):
40 weight ratio, using two rolls, 100-2
The mixture was kneaded at 00 ° C. to form a rubber sheet having a thickness of 3 mm. This unvulcanized rubber sheet is cut into 1 cm square pieces, weighed so that the weight ratio to toluene is 23%, and put into a stirrer with a vacuum defoaming device together with toluene, and the atmospheric pressure is reduced. After stirring for 15 hours under a low pressure to dissolve the strips in toluene, trimethylolpropane trimethacrylate was added to the solution in an amount of 10 parts per 100 parts of silicone rubber.
Parts and uniformly stirred, and then the vacuum defoaming device was driven, and the vacuum was further reduced to 20 g under a vacuum of -750 mmHg.
Stirred for minutes and degassed.

The obtained two rubber solutions were supplied to a roll coater equipped with two coater heads, and a silicone rubber solution and EPDM were applied to the surface of the polyester film.
The EPDM of Example 6 was applied in the same manner as in Example 1 except that the rubber solution was applied in order and the thickness after drying was 0.01 mm for the silicone rubber layer and 0.19 mm for the EPDM rubber layer.
A rubber film composite was manufactured.

The peel strength between the rubber film and the polyester film in the composites of the above Examples and Comparative Examples was measured by a T-type peeling method according to JIS K6854.
The results are shown in Table 3 below. However, “real” in the table indicates an example, and “ratio” indicates a comparative example.

Table 3 Actual 1 Ratio 1 Actual 2 Actual 3 Actual 4 Ratio 2 Actual 5 Ratio 3 Actual 6 Peel strength (N / 20 mm) 12 0.7 8 7 14 0.5 14 0.8 14

As shown in Table 3 above, Examples 1 to 6
Has a large delamination strength between an EPDM rubber film and a polyester film (base film).
Samples Nos. 4, 5, and 6 had a large delamination strength to the extent that the EPDM rubber film was broken during the measurement. Therefore, when the polyester film surface is used as the bonding surface, the EPDM rubber film composite of this example can be bonded to the equipment using a general-purpose adhesive, and the interlaminar peel strength between the EPDM rubber film and the polyester film can be reduced. 4N /
Since it was 20 mm or more, it was excellent in practicability without peeling between the two layers due to external force. For example, when the polyester film side was adhered to an arbitrary device with a double-sided adhesive tape, even if an attempt was made to peel the EPDM rubber film, the peeling did not occur between the polyester film and the adhesive film, but occurred at the bonded portion with the double-sided adhesive tape. Further, since the above-mentioned composite is stiffer than the EPDM rubber film alone, it is easy to handle when incorporated into an apparatus or a part, and has excellent workability.

On the other hand, Comparative Examples 1, 2 and 3 correspond to Examples 1, 4 and 5, respectively.
Omitting the trimethylolpropane methacrylate, and the above peel strengths of 0.7 N / 20 mm, 0.5 N / 20 mm and 0.8 N / 20 mm, the EPDM rubber film is easily peeled from the polyester film, and the Was inferior.

[0054]

As described above, the first aspect of the present invention provides
Since it is a composite of an ethylene propylene rubber film and a base film, if the base film surface is incorporated into the device as an adhesive surface, it is an inexpensive general-purpose adhesive that cannot be used with a single ethylene propylene rubber film because of its weak adhesion. The agent can be used, and is stiffer than a single ethylene propylene rubber film, so that the workability of the assembling work is improved. Furthermore, the delamination strength between the ethylene propylene rubber film and the polyester film is 4
Since it is N / 20 mm or more, delamination does not occur due to external force and can be suitably used as a sealing material or a cushioning material in a wide field.

According to the second aspect of the present invention, the adhesiveness of the ethylene propylene rubber film itself can be improved. According to the third aspect of the present invention, the above-mentioned improvement in adhesiveness can be performed by a radical reaction. According to the invention described in claim 4, the above-mentioned improvement in adhesiveness can be effectively performed by blending a methacrylic acid ester of a polyhydric alcohol with an ethylene propylene rubber film.

According to the fifth aspect of the invention, the adhesion, heat resistance and dimensional stability of the ethylene-propylene rubber film composite are further improved. According to the invention of claim 6, when a polyester film is used as the base film, the adhesiveness to the ethylene propylene rubber film can be improved by processing the polyester film. According to the seventh and eighth aspects of the present invention, the effect of improving the adhesiveness of the rubber film itself is further promoted.

According to the ninth aspect of the present invention,
Since the intermediate layer is made of a silicone rubber composition in which an adhesion improver is blended between the base film and the ethylene propylene rubber film, the adhesion between the base film and the ethylene propylene rubber film is improved. Can be

Claims (9)

[Claims] In an ethylene propylene rubber film composite obtained by laminating an ethylene propylene rubber film on at least one surface of a base film, the ethylene propylene rubber film and the base film have a delamination strength of 4 N / 20 mm. An ethylene propylene rubber film composite characterized by the above. 2. The ethylene-propylene rubber film composite according to claim 1, wherein the ethylene-propylene rubber film comprises a composition containing an adhesion improver. 3. The ethylene-propylene-based rubber film composite according to claim 2, wherein the adhesion improver is a compound containing a functional group active against a radical reaction. 4. A compound containing a functional group active to a radical reaction is a methacrylic acid ester of a polyhydric alcohol, and the compounding amount of the methacrylic acid ester is 3 to 30 parts by weight per 100 parts by weight of the ethylene propylene rubber. The ethylene propylene rubber film composite according to claim 3, which is: 5. The ethylene-propylene rubber film composite according to claim 1, wherein the base film is a polyester film. 6. The ethylene-propylene rubber film composite according to claim 5, wherein the polyester film is surface-modified with a polyester-based polymer, a polyurethane-based polymer, a polyacryl-based polymer or a mixture thereof. 7. The ethylene according to any one of claims 1 to 6, wherein the ethylene propylene rubber film comprises a composition in which 0.05 to 10 parts by weight of a peroxide compound is blended with respect to 100 parts by weight of the ethylene propylene rubber. Propylene rubber film composite. 8. The ethylene propylene rubber according to claim 1, wherein the ethylene propylene rubber film comprises a composition in which 5 to 100 parts by weight of a silicone rubber is blended with respect to 100 parts by weight of the ethylene propylene rubber. Film composite. 9. A layer of a silicone rubber composition containing an adhesion improver as an intermediate layer between a base film and an ethylene propylene rubber film.
8. The ethylene-propylene-based rubber film composite according to any one of 7.