JP2012139884A - Laminated body and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated body which is obtained by adhering a polyacrylonitrile resin film to a polyester resin film by the use of no adhesive agent, which prevents the leaking of foreign substances and residual solvent and the like, and exhibits excellent oxygen-impermeability, chemical resistance, aroma retention property and strength.SOLUTION: A covalent bond is formed between atoms in a polyacrylonitrile resin film and atoms in a polyester resin film, in at least a portion of the polyacrylonitrile resin film and the polyester resin film. The polyacrylonitrile resin film is adhered to the polyester resin film with no adhesive agent.

Description

  The present invention relates to a laminate, and more particularly, to a laminate in which a polyacrylonitrile resin film and a polyester resin film are bonded without using an adhesive and a method for producing the same.

  A package in which a film or the like is processed into a bag shape is used. In such a package, a multifunctional film in which various materials are laminated is used as a film to be used in order to develop a desired function depending on the contents to be filled. As such a multifunctional film, a laminated film in which a polyester resin film having high strength and excellent gas barrier properties is laminated on a polyacrylonitrile resin film excellent in oxygen impermeability, chemical resistance, and fragrance retention is known. .

  The package is generally performed by processing a long film, but in order to process it into a bag shape, the end portions of the films are overlapped and bonded. As a method of bonding films, a laminate resin (adhesive) is applied to the ends of the films to be bonded, and the films are pressed and sealed, or the two films are overlapped and heated at the ends. In general, a so-called heat sealing process is performed to add and fuse. In addition, the laminated film that is the material of the package is also laminated with two or more kinds of films by melt extrusion, or two or more kinds of films are laminated via a laminating resin like a polyolefin film laminated with aluminum foil. Lamination is performed.

  However, in the case of a package made by bonding films made of different materials through a laminate resin, the laminate resin component may gradually elute or volatilize in the package, and the contents may be altered. In the medical field where cleanliness is important, contamination of the contents by the laminate resin may be a problem. In addition, the laminate resin itself may deteriorate due to long-term use of the package, and particularly in exterior applications that are used outdoors, the weather resistance of the laminated package may become a problem. In addition, in the laminating technique using an adhesive, since a resin component diluted in a solvent is generally applied, the solvent remains after laminating to form a final product such as a package. There was a case.

  By the way, surface modification of a material using radiation or an electron beam has been conventionally performed. For example, Japanese Patent Application Laid-Open No. 2003-119293 (Patent Document 1) proposes that a crosslinked composite fluororesin can be obtained by irradiating the fluororesin with radiation. In Journal of Photopolymer Science and Technology Vol.19, No. 1 (2006), pp123-127 (Non-patent Document 1), a polytetrafluoroethylene film and a polyimide film are laminated and an electron beam ( In the following, it has been proposed to bond each other by irradiating EB. In Material Transactions Vol.50, No.7 (2009), pp1859-1863 (Non-patent Document 2), the surface of the polycarbonate resin is covered with a nylon film, and an electron beam (hereinafter abbreviated as EB) may be applied from above. A technique for adhering a nylon film to a polycarbonate resin surface has been proposed. Furthermore, the Journal of the Japan Institute of Metals, Vol. 72, No. 7 (2008), pp 526-531 (Non-patent Document 3) can be bonded to each other by irradiating EB from a nylon film placed on silicone rubber. Is described.

JP 2003-119293 A

Journal of Photopolymer Science and Technology Vol.19, No. 1 (2006), pp123-127 Material Transactions Vol.50, No. 7 (2009), pp1859-1863 Journal of the Japan Institute of Metals, Vol. 72, No. 7 (2008), pp 526-531

  In the manufacture of a laminate in which a polyacrylonitrile resin film and a polyester resin film are laminated, the present inventors use a laminate resin or the like by irradiating the polyacrylonitrile resin film and / or the polyester resin film with an electron beam. And found that both films can be firmly bonded. The present invention is based on this finding.

  Therefore, an object of the present invention is a laminate in which a polyacrylonitrile resin film and a polyester resin film are bonded without using an adhesive, and foreign matter and residual solvent are not leached, and oxygen-impermeable is not used. It is to provide a laminate having excellent properties, chemical resistance, fragrance retention, and strength.

The laminate according to the present invention is a laminate in which a polyacrylonitrile resin film and a polyester resin film are laminated,
In at least a part of the polyacrylonitrile resin film and the polyester resin film, a covalent bond is formed between an atom in the polyacrylonitrile resin film and an atom in the polyester resin film, and the polyacrylonitrile resin film And the said polyester resin film is adhere | attached without an adhesive agent.

Further, as an aspect of the present invention, an oxygen atom or a hydroxyl group is covalently bonded to an atom in the polyacrylonitrile resin film and the polyester resin film, and the oxygen atom and / or hydroxyl group in the polyacrylonitrile resin film and the polyester resin It is preferable that a hydrogen bond is formed between an oxygen atom or a hydroxyl group in the film.

  Moreover, as an aspect of the present invention, the polyester resin film is preferably polyethylene terephthalate.

Moreover, the production method as another aspect of the present invention is a method for producing a laminate in which a polyacrylonitrile resin film and a polyester resin film are laminated,
At least one surface of the polyacrylonitrile resin film and / or the polyester resin film is irradiated with an electron beam,
The polyacrylonitrile resin film surface and / or the polyester resin film surface irradiated with the electron beam are superposed and bonded together.

  Moreover, as an aspect of the present invention, it is preferable to perform electron beam irradiation before and / or after the polyacrylonitrile resin film and the polyester resin film are superimposed.

  Moreover, as another aspect of the present invention, the bonding is preferably performed by applying pressure, and the bonding is preferably performed by heating.

  According to the present invention, in a laminate in which a polyacrylonitrile resin film and a polyester resin film are laminated, atoms in the polyacrylonitrile resin film and carbon atoms in the polyester resin film are shared directly or via oxygen atoms. Since the bond is formed, a laminated body in which the polyacrylonitrile resin film and the polyester resin film are firmly bonded can be obtained even if they are not bonded via an adhesive. As a result, it is possible to realize a laminate that does not exude foreign matter, residual solvent, and the like and is excellent in oxygen impermeability, chemical resistance, aroma retention, and strength.

It is the schematic sectional drawing which showed one Embodiment of the laminated body of this invention. It is the schematic cross section which expanded the interface (adhesion surface) of the laminated body. It is the schematic diagram which showed one Embodiment of the manufacturing method of the laminated body by this invention. It is the schematic schematic diagram which expanded a part of manufacturing process. It is the schematic diagram which showed another embodiment of the manufacturing method of the laminated body by this invention. It is the schematic diagram which showed another embodiment of the manufacturing method of the laminated body by this invention. It is the schematic diagram which showed another embodiment of the manufacturing method of the laminated body by this invention.

  Hereinafter, the laminated body by this invention is demonstrated, referring drawings. The laminate according to the present invention has a structure in which a polyacrylonitrile resin film 1 is laminated on at least one surface of a polyester resin film 2 without an adhesive as shown in FIG.

  In the laminate according to the present invention, a covalent bond is formed between an atom in the polyacrylonitrile resin film and an atom in the polyester resin film on at least a part of the adhesion surface of the polyacrylonitrile resin film 1 and the polyester resin film 2. Thus, the polyacrylonitrile resin film 1 and the polyester resin film 2 are firmly bonded. Normally, even if a polyester resin film is laminated on the surface of a polyacrylonitrile resin film, hydrogen bonds and covalent bonds are not formed between the two, so it is not possible to bond the two without using an adhesive or heat sealing. . In the present invention, as will be described later, the surface of the polyacrylonitrile resin film 1 and / or the polyester resin film 2 is irradiated with an electron beam to generate radicals, and as shown in FIG. A covalent bond is formed between the atom of the polyester resin film 2 and the atom on the surface of the polyester resin film 2, or the atom on the surface of the polyacrylonitrile resin film 1 and the atom on the surface of the polyester resin film 2 are covalently bonded through an oxygen atom. By forming the film, the polyacrylonitrile resin film 1 and the polyester resin film 2 are firmly bonded without using an adhesive. In addition, radicals generated by electron beam irradiation and oxygen in the air are bonded to each other so that OH groups may be present on the surface of the polyacrylonitrile resin film 1 and / or the polyester resin film 2, and in that case, polyacrylonitrile is present. The OH group on the resin film 1 side and the OH group on the polyester resin film 2 side may form a hydrogen bond in some cases. The generation of radicals by electron beam irradiation is confirmed by identifying the free radical species existing in the film after electron beam irradiation using an electron spin resonance apparatus (hereinafter also referred to as ESR). be able to.

  The fact that a covalent bond is formed between atoms between the polyacrylonitrile resin film and the polyester resin film means that an X-ray photoelectron analyzer (hereinafter also referred to as XPS) or a Fourier transform infrared spectrometer (hereinafter referred to as FTIR). This can also be confirmed. For example, before bonding a polyacrylonitrile resin film and a polyester resin film, the surface state of each film is measured by XPS to confirm what atoms exist on the surface of each material before bonding. Then, both are bonded by electron beam irradiation to form a laminate, and then the laminate is forcibly separated to separate it into a polyacrylonitrile resin film and a polyester resin film, and the surface state of both is again measured by XPS. Check what atoms are present. As a result, atoms derived from the polyacrylonitrile resin film (that is, N atoms) are present on the polyester resin film side, or N atoms are not present on the polyacrylonitrile resin film side and are covered with atoms derived from the polyester resin film. It can be confirmed whether or not a covalent bond is formed between both films. Moreover, you may confirm whether covalent bonds, such as a CN bond, exist on the surface of the polyester resin film after peeling using FTIR.

  Moreover, since the laminated body which adhere | attached the polyacrylonitrile resin film 1 and the polyester resin film 2 by electron beam irradiation has formed not only the above-mentioned covalent bond but a hydrogen bond as shown in FIG. Even if it is not used at all, a laminate that does not peel off can be obtained. The presence of hydrogen bonds can be confirmed by immersing the laminate in water or an alcohol solution and confirming the presence or absence of peeling. When the polyacrylonitrile resin film and the polyester resin film are bonded only by hydrogen bonds, when the laminate is immersed in water or an alcohol solution, the hydrogen bond formed between the two is broken and water or alcohol is lost. Since hydrogen bonds with hydrogen atoms or oxygen atoms are reformed, the adhesive force is lost and both films are peeled off. Therefore, it can be confirmed whether the adhesion is due to a covalent bond and a hydrogen bond or only due to a hydrogen bond.

  Hereinafter, the polyester resin film and the polyacrylonitrile resin film constituting the laminate according to the present invention will be described.

<Polyester resin film>
As the polyester resin film constituting the laminate of the present invention, a film made of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, etc. can be used, among these, A film made of polyethylene terephthalate, which is a versatile film, can be preferably used. Further, it may be a polyester laminated film in which the surface to be bonded to the polyacrylonitrile resin film is polyester. Although the thickness of a film can be suitably determined according to a use application, it is about 10-300 micrometers in general.

  Various conventionally known additives such as a light stabilizer, an ultraviolet absorber, an antioxidant, a filler, a lubricant and the like can be appropriately added to the polyester resin film as necessary. Conventionally known light stabilizers and ultraviolet absorbers can be used. For example, phenol-based, phosphorus-based, hindered amine-based light absorbers, benzotriazole-based, benzophenone-based, and salicylic acid ester-based ultraviolet absorbers are used. it can.

<Polyacrylonitrile resin film>
The polyacrylonitrile resin film used in the laminate of the present invention has performances excellent in oxygen impermeability, chemical resistance, fragrance retention and the like. The polyacrylonitrile resin may be not only an acrylonitrile homopolymer but also a copolymer obtained by copolymerizing one or more compounds copolymerizable with acrylonitrile. Such a compound is not particularly limited, and examples thereof include rubber components such as nitrile rubber (NBR), acrylic acid esters such as methyl acrylate and ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Examples include methacrylic acid esters, haloolefins such as vinyl chloride, vinyl fluoride, and vinylidene chloride, vinylamides such as acrylamide and vinylpyrrolidone, vinyl aromatic compounds such as styrene, vinyl carboxylic acids, and vinyl sulfonic acids. The proportion of the compound to be copolymerized is preferably 30 mol% or less, and more preferably 15 mol% or less.

  In the present invention, the thickness of the laminated polyacrylonitrile resin film is approximately 20 to 300 μm.

  The laminate obtained by laminating and bonding the polyacrylonitrile resin film and the polyester resin film as described above does not exude foreign matter or residual solvent even when using the laminate, and is oxygen non-permeable, It also has excellent chemical resistance, fragrance retention and heat sealability. Therefore, it can be suitably used for a package used in the medical field, for example, a syringe package bag or a package for filling and packaging a powder or granular pharmaceutical product, not to mention the food field.

<Method for producing laminate>
Next, a method for producing the laminate as described above will be described with reference to the drawings. First, the polyacrylonitrile resin film 1 and the polyester resin film 2 described above are prepared (FIG. 3 (1)), and either or both of the two films are irradiated with an electron beam (FIG. 3). (2)). As a result, as shown in FIG. 3 (3), the polyacrylonitrile resin film 1 and the polyester resin film 2 are bonded only to the portion irradiated with the electron beam.

  In the present invention, it is preferable to press the stacked films 1 and 2 using a roller 6 or the like as shown in FIG. 4 immediately after irradiating the film with an electron beam. Since the surfaces of the films 1 and 2 are uneven at a micro level as shown in FIG. 4, even if the films are overlapped, they are not completely adhered to each other, and the contact area at the contact interface between the two films is small. In this invention, since the contact area in the adhesion surface of both films increases by pressing the films 1 and 2 with the roller 6 etc. immediately after irradiating an electron beam, adhesiveness improves.

  After the polyacrylonitrile resin film 1 and the polyester resin film 2 are overlaid, when pressing both the films 1 and 2, it is preferable to press both the films 1 and 2 while heating. By pressing while heating, the flexibility of the polyacrylonitrile resin film 1 and the polyester resin film 2 is improved, and the contact area at the interface (adhesion surface) between the polyacrylonitrile resin film 1 and the polyester resin film 2 is further increased. Therefore, the adhesion is further improved. The heating temperature may be any temperature at which the film can be thermally deformed, although it depends on the type of film to be used. For example, the heating can be performed at a temperature higher than the glass transition temperature of the resin constituting the film. For example, when a polyethylene terephthalate (PET) film is used as the polyester resin film, the heating temperature is 80 to 180 ° C, preferably 100 to 160 ° C. If the heating temperature is too high, the generated radicals are deactivated, and a strong bond cannot be realized. The pressing force (contact pressure) may be increased, and the heating temperature can be lowered by increasing the contact pressure.

  In order to overlap and press the polyacrylonitrile resin film 1 and the polyester resin film 2, the heat roller 6 or the like can be suitably used as described above. In addition, as shown in FIG. 4, the support roller 7 may be placed at a position facing the heat roller 6 so that the superposed film can be pressed between the heat roller 6 and the support roller 7. . In this way, by placing the support roller 7 at a position facing the heat roller 6, the contact between the laminate (the laminate of the film 1 and the film 2) and the heat roller 6 is brought close to the line contact, and the heat roller 6. It is possible to minimize the deformation that occurs in the laminated body due to the heat from the.

  FIG. 5 is a schematic view showing another embodiment of the manufacturing method according to the present invention. In the process of superposing and bonding the polyacrylonitrile resin film 1 and the polyester resin film 2, both the films 1 and 2 are guided to the electron beam irradiation position 3 by the guide rollers, respectively, and both the films 1 and 2 are irradiated. The process of pressing both films 1 and 2 with the heat roller 6 is continuously performed later. Each film 1, 2 may be supplied in roll form.

  When irradiating each film 1 and 2 with the electron beam 4 from the electron beam irradiation apparatus 3, it is preferable to irradiate the electron beam 4 from the film side with smaller thickness. Since the electron beam has the property that its transmission power increases as the acceleration voltage increases, depending on the thickness of the film, the electron beam may reach the other film when irradiated with the electron beam from one of the film sides. May not arrive. In that case, the electron beam can reach the deep part of the other film by increasing the acceleration voltage of the electron beam, but unnecessary irradiation is performed on the film itself as the electron beam energy increases. It will deteriorate. Therefore, when a thick film and a thin film are laminated and bonded, it is preferable to irradiate an electron beam from the thin film side without increasing the electron beam energy so much. For example, when the thickness of the polyacrylonitrile resin film is 25 μm or less and the thickness of the polyester resin film is 50 μm or more, the electron beam is irradiated from the polyacrylonitrile resin film side. By adopting such an electron beam irradiation method, deterioration of the film can be minimized.

  When the films 1 and 2 to be overlapped are both thick, another electron is placed at a position facing the electron beam irradiation device 3 so that an electron beam can be irradiated from both film sides as shown in FIG. A line irradiation device 3 ′ may be provided. According to this aspect, since the irradiation energy of an electron beam can be adjusted according to the thickness of a film, both films can be adhere | attached, without deteriorating a film.

  FIG. 6 is a schematic view showing an embodiment of another manufacturing method according to the present invention. In this embodiment, the electron beam irradiation is performed before the polyacrylonitrile resin film 1 and the polyester resin film 2 are overlapped. First, a pair of supplied films (polyacrylonitrile resin film 1 and polyester resin film 2) are applied to film 1 (2) by electron beam irradiation device 3 (3 ′) before both films 1 and 2 are superimposed. ) Is irradiated with an electron beam 4 (4 ′). In the embodiment shown in FIG. 5, both the films 1 and 2 are overlapped so that the surfaces opposite to the electron beam irradiation side of the films 1 and 2 face each other, whereas in the embodiment shown in FIG. The difference is that the two films 1 and 2 are overlapped so that the surfaces of the two films 1 and 2 on the electron beam irradiation side face each other. Thus, by superimposing the other film 2 on the surface of the film 1 irradiated with the electron beam, the irradiation energy of the electron beam can be made smaller regardless of the thickness of the film. As a result, the film Degradation due to electron beam irradiation can be further reduced.

  Also in the embodiment shown in FIG. 6, a pair of electron beam irradiation devices 3 and 3 ′ are provided, and each of the polyacrylonitrile resin film 1 and the polyester resin film 2 is provided as in the embodiment shown in FIG. 5. Electron beams 4 and 4 'may be irradiated. By these combinations, the deterioration of the film can be further reduced and the adhesive strength can be improved.

  FIG. 7 is a schematic view showing another embodiment of the manufacturing method according to the present invention. In this embodiment, the polyacrylonitrile resin film 1 and the polyester resin film 2 are overlapped and pressed by the heat roller 6 and then irradiated with an electron beam. First, the pair of supplied materials 1 and 2 are led to a guide roller and overlapped. Subsequently, both the films 1 and 2 are pressed by the heat roller 6 and the support roller 7, and heating is performed by the heat roller 6. Thereafter, the electron beam irradiation device 3 irradiates the surface of the polyacrylonitrile resin film 1 and the polyester resin film 2 with the electron beam 4 so that the bonding of the two is continued. Also in the embodiment shown in FIG. 7, a pair of electron beam irradiation devices 3 and 3 ′ are provided, and the electron beams 4 and 4 are respectively applied to both materials 1 and 2 in the same manner as the embodiment shown in FIGS. 5 and 6. 4 'may be irradiated. By these combinations, the deterioration of the film can be further reduced and the adhesive strength can be improved.

  The irradiation energy of the electron beam needs to be appropriately adjusted according to the film thickness and the like as described above. In the present invention, the electron beam is irradiated in an irradiation energy range of about 20 to 750 kV, preferably 25 to 400 kV, and more preferably about 30 to 300 kV. However, the irradiation energy is preferably lower, and 40 to 200 kV. Can do. Thus, by setting it as low irradiation energy, not only deterioration of a film can be suppressed, but since radical generation | occurrence | production of a film surface occurs more efficiently, stronger bond can be implement | achieved. The absorbed dose of the electron beam is 10 to 800 kGy, preferably 25 to 600 kGy.

  As such an electron beam irradiation apparatus, conventionally known ones can be used. For example, a curtain type electron irradiation apparatus (LB1023, manufactured by I. Electron Beam Co., Ltd.) or a line irradiation type low energy electron beam irradiation apparatus (EB-ENGINE). , Manufactured by Hamamatsu Photonics Co., Ltd.) can be preferably used.

  When irradiating with an electron beam, the oxygen concentration is preferably 100 ppm or less. This is because irradiation with an electron beam in the presence of oxygen generates ozone and may adversely affect the environment. In order to reduce the oxygen concentration to 100 ppm or less, the film may be irradiated with an electron beam in a vacuum or in an inert gas atmosphere such as nitrogen or argon. For example, by filling the electron beam irradiation apparatus with nitrogen, A concentration of 100 ppm or less can be achieved.

  The laminate obtained by laminating the polyacrylonitrile resin film and the polyester resin film obtained by the above-described adhesion method can realize an adhesive strength equal to or higher than that obtained by using a conventional laminate resin. In addition, since no laminate resin or the like is used, foreign matter, residual solvent, and the like do not ooze out when the laminate is used, and light shielding properties and gas non-permeability are excellent.

<Preparation of polyacrylonitrile resin film and polyester resin film>
A 30 μm-thick polyacrylonitrile resin film (Hitron BX, manufactured by Tamapoly) was prepared as a polyacrylonitrile resin film, and the following two types of films were prepared as polyester resin films.
A: Polyester resin film with a thickness of 12 μm (Embret, manufactured by Unitika Ltd.)
B: Vapor deposition polyester resin film having a thickness of 12 μm (Tech Barrier TXR, manufactured by Mitsubishi Chemical Corporation)

Example 1
<Production of laminate>
Samples obtained by cutting each of the above-mentioned two types of films into a size of 150 mm × 75 mm were prepared, and an electron beam irradiation apparatus (line irradiation type low energy electron beam irradiation apparatus EES-L-DP01, manufactured by Hamamatsu Photonics Co., Ltd.) It was placed side by side on the sample stage. At this time, in order to provide a portion where the sample is not irradiated with the electron beam, masking is performed on one end portion of both samples of about 5 to 10 mm.

Next, after purging with nitrogen gas so that the oxygen concentration in the chamber of the electron irradiation apparatus becomes 100 ppm or less, the surface of the sample was irradiated with an electron beam under the following electron beam irradiation conditions.
Voltage: 40 kV
Absorbed dose: 200kGy
In-device oxygen concentration: 100 ppm or less

  After irradiating the electron beam, the sample was taken out from the apparatus and immediately laminated so that the electron beam irradiation surface sides of both films were opposed to each other, and both films were bonded by a thermal laminating method to obtain a laminate.

Examples 2-4
A laminate was obtained in the same manner as in Example 1 except that the resin films used were combinations shown in Table 1 below, and the electron beam irradiation conditions and adhesive conditions shown in Table 1 were used. In addition, when irradiating the electron beam to the vapor deposition polyester resin film B, it arrange | positioned on the sample stand so that an electron beam may be irradiated not to a vapor deposition surface but to the polyester resin side.

Comparative Example 1
A laminate was obtained in the same manner as in Example 1 except that electron irradiation was not performed. However, the obtained laminate was not bonded to the polyacrylonitrile resin film and the polyester resin film.

Comparative Example 2
A laminate was obtained in the same manner as in Example 3 except that the electron irradiation was not performed. However, the obtained laminate was not bonded to the polyacrylonitrile resin film and the polyester resin film.

Comparative Example 3
A laminate was obtained by a dry laminating method in which the two types of resin films used in Example 1 were bonded together via a two-component curable aromatic ester adhesive (Takelac A-3, manufactured by Mitsui Chemicals, Inc.).

<Evaluation of adhesive strength of laminate>
The obtained laminate was cut into a strip shape with a width of 15 mm, and a 90 ° peel test was performed at a rate of 50 mm / min using a tensile tester (Tensilon Universal Material Tester RTC-1310A, manufactured by ORIENTEC). went. As described above, in the laminate of Comparative Example 1, the polyacrylonitrile resin film and the resin film were not adhered, and the adhesive strength of the laminate could not be measured. The evaluation results were as shown in Table 1 below.

  In addition, in order to indirectly check whether the adhesion of the laminates of Examples 1 to 3 is due to a covalent bond, the obtained laminate was stored in water, and then the adhesive strength of the laminate in the same manner as described above. Was measured. The evaluation results were as shown in Table 1 below.

  As is clear from the evaluation results in Table 1, the laminates of Examples 1 to 4 have the same adhesive strength as that measured in air even after storage in water. From this result, it can be seen that in the laminates of Examples 1 to 4, the polyacrylonitrile resin film and the polyester resin film are not bonded only by hydrogen bonds or intermolecular forces. Therefore, although indirectly, it can be inferred that a covalent bond is formed between the atoms in the polyacrylonitrile resin film and the atoms in the polyester resin film, which is the same as the conventional laminate laminated with an adhesive. It has the adhesive strength.

DESCRIPTION OF SYMBOLS 1 Polyacrylonitrile resin film 2 Polyester resin film 3, 3 'Electron beam irradiation apparatus 4, 4' Electron beam 5 Film base material contact interface 6 Heat roller 7 Support roller

Claims (7)

A laminate in which a polyacrylonitrile resin film and a polyester resin film are laminated,
In at least a part of the polyacrylonitrile resin film and the polyester resin film, a covalent bond is formed between an atom in the polyacrylonitrile resin film and an atom in the polyester resin film, and the polyacrylonitrile resin film And the said polyester resin film is adhere | attached without using an adhesive agent, The laminated body characterized by the above-mentioned.   An oxygen atom or a hydroxyl group is covalently bonded to an atom in the polyacrylonitrile resin film and the polyester resin film, an oxygen atom and / or a hydroxyl group in the polyacrylonitrile resin film, and an oxygen atom or a hydroxyl group in the polyester resin film The laminated body of Claim 1 in which the hydrogen bond is formed between.   The laminate according to claim 1 or 2, wherein the polyester resin film is a polyethylene terephthalate film. A method for producing a laminate in which a polyacrylonitrile resin film and a polyester resin film according to any one of claims 1 to 3 are laminated,
At least one surface of the polyacrylonitrile resin film and / or the polyester resin film is irradiated with an electron beam,
A method comprising superposing and bonding the polyacrylonitrile resin film surface and / or the polyester resin film surface irradiated with the electron beam.   The method according to claim 4, wherein the electron beam irradiation is performed before and / or after superposing the polyacrylonitrile resin film and the polyester resin film.   The method according to claim 4 or 5, wherein the adhesion is performed under pressure.   The method according to claim 4, wherein the bonding is performed by heating.

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