JP2019010889A - Resin laminate - Google Patents

Abstract

To provide a resin laminate capable of enhancing adhesiveness of a fluorine resin layer.SOLUTION: The above described problem is solved by a resin laminate having an adhesive resin layer on one surface of a fluorine resin layer, in which the fluorine resin layer is formed by an electron beam collapsible fluorine resin, the electron beam collapsible fluorine resin is polytetrafluoroethylene or polychlorotrifluoroethylene, the adhesive resin layer contains an electrolytic dissociation radiation curable resin, and does not contain polymerizable initiator or a residue thereof.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin laminate having a fluororesin layer.

Fluoropolymers have excellent properties such as heat resistance, insulation, flame resistance, weather resistance, moisture proofing, and antifouling properties. Taking advantage of these properties, corrosion resistant materials, lining materials, insulating materials, coating materials, gas barriers Use of a fluororesin film as a material is being promoted.
However, the fluororesin film has difficulty in adhesion due to its water and oil repellency, and even if the fluororesin film is bonded to other members, the fluororesin film easily peels off. Yes. For this reason, examination about the improvement of the adhesiveness of a fluororesin film is performed.

  As a method for improving the adhesiveness of the fluororesin film, for example, there is a method of modifying the surface of the fluororesin film using a metal sodium-containing surface modifier. This is a method of forming a functional group on the surface of the fluororesin film using the reducing power of metallic sodium. Since the surface free energy is increased by the functional group, the adhesiveness of the fluororesin film is improved.

  As another surface modification method, there is a physical method in which the surface of the fluororesin film is subjected to corona discharge treatment, plasma treatment, vacuum plasma treatment or the like to form a rough surface and the adhesion area is increased by increasing the adhesion area. . In particular, as disclosed in Patent Document 1, a method of etching by subjecting the surface of a fluororesin film to sputtering or ion plating in the presence of an inert gas such as argon gas under high vacuum is a corona discharge treatment. It is said that a higher effect of improving adhesiveness can be obtained.

  In addition to the above-described method, for example, in Patent Document 2, a material mainly composed of an ultraviolet-absorbing acrylic resin and a cationic polymer is applied on a fluororesin film, and the coating layer is cured to form a coating layer. Thus, a method for improving the adhesion of the fluororesin film to the coating layer is disclosed. Patent Document 3 discloses a method for improving the adhesion of a fluoride-containing thin film layer by forming a thin film layer by vacuum-depositing a fluoride of silicon oxide and an alkaline earth metal on a plastic film. Yes.

JP-A-5-043721 JP-A-7-214732 Japanese Patent Application Laid-Open No. 8-224955

However, the above-described surface treatment method does not sufficiently improve the adhesiveness of the fluororesin film, and even if the initial adhesive strength between the fluororesin film and other members is improved, the adhesion of the fluororesin film over time There is a problem that the property is lowered and peeling occurs.
In addition, depending on the type of fluororesin, there is a problem that it is difficult to improve adhesiveness by the above-described method. For example, among the fluororesins, polytetrafluoroethylene (hereinafter sometimes abbreviated as PTFE) has characteristics that it has higher chemical resistance and a lower dynamic friction coefficient than other fluororesins, and polychlorotriethylene. Fluoroethylene (hereinafter sometimes abbreviated as PCTFE) has the characteristics of higher gas barrier properties and better transparency and moisture resistance than other fluororesins, so these fluororesins were used. Films and sheets are expected to be used further as industrial and medical materials. However, PTFE and PCTFE are particularly poor in adhesiveness, and for films formed from these fluororesins, the adhesiveness cannot be sufficiently improved even if the conventional method described above is used.

  This invention is made | formed in view of the said subject, and it aims at providing the manufacturing method of a resin laminated body which can improve the adhesiveness of a fluororesin layer, and a resin laminated body.

  In order to solve the above-mentioned problems, the present invention provides a method for producing a resin laminate having an adhesive resin layer on one surface of a fluororesin layer, wherein the electron beam curable resin is disposed on the one surface of the fluororesin layer. An application step of applying the composition, and irradiating an electron beam from the surface side of the fluororesin layer on which the electron beam curable resin composition is applied to cure the electron beam curable resin composition to form the adhesive resin And an irradiation step of forming a layer. A method for producing a resin laminate is provided.

  According to the present invention, in the irradiation step, the adhesive resin layer is formed by curing the electron beam curable resin composition by irradiating the fluororesin layer with an electron beam through the coating layer of the electron beam curable resin composition. At the same time, reactive species such as radicals are generated in the fluororesin layer, and the above reactive species react with the polymerizable functional group in the electron beam curable resin composition, whereby the fluororesin layer and the adhesive resin Crosslinks are formed between the layers. Thereby, the interlayer adhesive strength between an adhesive resin layer and a fluororesin layer can be improved.

  In the said invention, it is preferable that the said fluororesin layer is what was formed of polytetrafluoroethylene or polychlorotrifluoroethylene. When PTFE or PCTFE is irradiated with an electron beam, the cleavage of the molecular chain is promoted by the reactive species generated in the molecule, and a crosslink is formed by the reaction between the molecular chain cleavage portion and the ionizing radiation curable resin. This is because the interlayer adhesive strength between the fluororesin layer and the adhesive resin layer can be further improved.

  In the case of the said invention, it is preferable that the irradiation dose of the electron beam irradiated by the said irradiation process exists in the range of 5MGy or more and less than 20MGy. While suppressing excessive electron beam irradiation to the fluororesin layer, it is possible to promote the breaking of the molecular chain in the molecule of the fluororesin, and the interlayer adhesion between the fluororesin layer formed by PTFE or PCTFE and the adhesive resin layer This is because the strength can be further improved.

  In the said invention, it is preferable to have a functional layer formation process which forms a functional layer on the said adhesive resin layer after the said irradiation process. This is because the adhesion of the fluororesin layer to the functional layer can be improved, and a desired function can be added to the resin laminate according to the type of the functional layer.

  The present invention is a resin laminate having an adhesive resin layer on one surface of the fluororesin layer, wherein the fluororesin layer is formed of polytetrafluoroethylene or polychlorotrifluoroethylene, The adhesive resin layer includes an ionizing radiation curable resin.

  According to the present invention, since the adhesive resin layer containing the ionizing radiation curable resin is formed on the fluororesin layer formed by PTFE or PCTFE, the interlayer adhesive strength between the adhesive resin layer and the fluororesin layer is And the peeling of the fluororesin layer can be prevented.

  In the said invention, it is preferable that the interlayer adhesive strength of the said fluororesin layer and the said adhesive resin layer is 200 gf / cm or more. This is because peeling hardly occurs between the fluororesin layer and the adhesive resin layer.

  In the said invention, it is preferable to have a functional layer on the said adhesive resin layer. This is because the adhesiveness of the fluororesin layer to the functional layer is improved, and a desired function can be added to the resin laminate according to the type of the functional layer.

  In this invention, there exists an effect that it is possible to improve the adhesiveness of a fluororesin layer.

It is process drawing which shows an example of the manufacturing method of the resin laminated body of this invention. It is a schematic sectional drawing which shows the other example of the resin laminated body in this invention. It is a schematic sectional drawing which shows an example of the resin laminated body of this invention.

  Hereinafter, the method for producing a resin laminate and the resin laminate of the present invention will be described in detail.

A. First, a method for producing a resin laminate of the present invention will be described. The method for producing a resin laminate of the present invention is a method for producing a resin laminate having an adhesive resin layer on one surface of a fluororesin layer, and the electron beam curable resin composition on the one surface of the fluororesin layer. An application step of applying an object, and irradiation of an electron beam from the surface of the fluororesin layer on which the electron beam curable resin composition is applied to cure the electron beam curable resin composition, thereby the adhesive resin layer And an irradiation step for forming the structure.

The manufacturing method of the resin laminated body of this invention is demonstrated with reference to figures. FIG. 1 is a process diagram showing an example of a method for producing a resin laminate of the present invention.
First, the fluororesin layer 1 is prepared (FIG. 1A), and the electron beam curable resin composition 2A is applied to one surface of the fluororesin layer 1 (FIG. 1B). Subsequently, the electron beam X is irradiated from the surface of the fluororesin layer 1 on which the electron beam curable resin composition 2A is applied (FIG. 1 (c)), and the electron beam curable resin composition on the fluororesin layer 1 is irradiated. 2A is cured to form the adhesive resin layer 2 (FIG. 1 (d)). At this time, when the electron beam X reaches the fluororesin layer 1, the adhesive resin layer 2 is formed, and at the same time, a cross-linking bond is formed between the fluororesin layer 1 and the adhesive resin layer 2. A resin laminate 10 is obtained.
1B is an application process, and FIGS. 1C and 1D are irradiation processes.

According to the present invention, in the irradiation step, the electron beam is irradiated onto the fluororesin layer through the coating layer of the electron beam curable resin composition, whereby the adhesive resin layer by the curing of the electron beam curable resin composition. Simultaneously with the formation of, it is possible to improve the adhesion of the fluororesin layer to the adhesive resin layer.
That is, when the electron beam curable resin composition applied to the surface of the fluororesin layer is cured by irradiation with an electron beam, the fluororesin layer is also irradiated with an electron beam, so that radicals or the like are contained in the molecule of the fluororesin. Reactive species are generated. At this time, at the interface between the fluororesin layer and the coating layer of the electron beam curable resin composition, a cross-linking bond is formed by the reaction between the reactive species and the polymerizable functional group contained in the electron beam curable resin composition. . Thereby, the interlayer adhesive strength between the fluororesin layer and the adhesive resin layer is improved, and the adhesiveness of the fluororesin layer can be improved.

In addition, as a method for improving the adhesiveness of the fluororesin layer, a method of forming a pressure-sensitive adhesive layer on the fluororesin layer is also assumed. However, in order to obtain a desired interlayer adhesion strength between the fluororesin layer and the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer needs to be thick. When the film thickness is increased, the end surface is likely to be tacked, which may cause defects in processing and products. In particular, when a fluororesin having poor adhesion is used as the fluororesin layer, it is necessary to further increase the thickness of the pressure-sensitive adhesive layer in order to improve the interlayer adhesive strength, and thus the above-described problems are likely to occur.
On the other hand, according to the present invention, the cross-linking formed between the fluororesin layer and the adhesive resin layer makes it possible to obtain a desired interlayer adhesive strength even when the thickness of the adhesive resin layer is small. Have. Also, for the reasons described later, it is possible to improve the adhesiveness of the fluororesin layer by reducing the thickness of the adhesive resin layer even for the fluororesin layer having poor adhesiveness such as PTFE and PCTFE. The obtained resin laminate has a feature that the above-described problems are hardly caused.

  Hereinafter, each process of the manufacturing method of the resin laminated body of this invention is demonstrated.

1. Application Step The application step of the present invention is a step of applying the electron beam curable resin composition to one surface of the fluororesin layer.

(1) Fluororesin layer As the fluororesin layer in the present invention, it exhibits surface slipperiness, insulation, gas barrier property, chemical resistance and other various properties suitable for the use of the resin laminate obtained by the present invention. If it is. Examples of such a fluororesin layer include polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA) made of a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, and a copolymer of tetrafluoroethylene and hexafluoropropylene. Polymer (FEP), copolymer of tetrafluoroethylene, perfluoroalkyl vinyl ether and hexafluoropropylene (EPE), copolymer of tetrafluoroethylene and ethylene or propylene (ETFE), polychlorotrifluoroethylene (PCTFE) ), A copolymer of ethylene and chlorotrifluoroethylene (ECTFE), perfluoroethylenepropylene copolymer (PFEP), vinylidene fluoride resin (PVDF), vinyl fluoride resin ( One or films formed from more fluorine resin VF) or the like, can be used sheets.

In particular, in the present invention, the fluororesin layer is formed of a fluororesin in which molecular chain scission is preferentially generated over intramolecular crosslinkage due to reactive species generated in the molecule of the fluororesin by electron beam irradiation. It is preferable that it is a layer formed from an electron beam-disintegrating fluororesin. The reason is as follows.
As a result of intensive studies on the adhesiveness between the fluororesin layer and the resin adhesive layer by the electron beam irradiation, the present inventors have found that an electron beam collapsible fluororesin has an electron beam from the application side of the electron beam curable resin composition. In addition to crosslinking by reactive species generated in the fluororesin, it has been found that cross-linking is also formed by reaction between the molecular chain breakage and the electron beam curable resin. For this reason, by using a fluororesin layer formed from an electron beam collapsible fluororesin, many cross-linking bonds are formed between the adhesive resin layer and the interlayer adhesive strength can be further improved. Because there is.
Examples of the electron beam collapsible fluororesin include PTFE, PCTFE, PFA, and PFEP. Among them, in the present invention, it is preferable that the fluororesin layer is formed of PTFE or PCTFE. This is because PTFE or PCTFE is electron beam collapsible and is particularly inferior in adhesiveness among fluororesins, so that the effect of using the production method of the present invention can be further enhanced.

  The fluororesin layer may have an arbitrary layer on the surface for improving adhesiveness. As an arbitrary layer, a primer coating agent layer, an undercoat agent layer, an anchor coating agent layer, a vapor deposition anchor coating agent layer, etc. are mentioned, for example. These arbitrary layers are preferably formed on one surface of the fluororesin layer.

The film thickness of the fluororesin layer is not particularly limited as long as the physical properties of the fluororesin can be exhibited. For example, the thickness is preferably in the range of 10 μm to 300 μm, and more preferably in the range of 30 μm to 150 μm. It is because the resin laminated body obtained by this invention may not fully show the characteristic of a fluororesin when the film thickness of a fluororesin layer is smaller than the said range. In addition, depending on the type of fluororesin, the fluororesin layer deteriorates due to electron beam irradiation, and physical properties such as heat resistance, insulation, flame resistance, weather resistance, and moisture resistance are assumed from the fluororesin used. It is because it may fall rather than. On the other hand, if it is larger than the above range, the production cost increases because the amount of the fluororesin used increases.
The film thickness of the fluororesin layer can be measured, for example, with a Digimatic micrometer manufactured by Mitutoyo Corporation.

  It does not specifically limit as a manufacturing method of a fluororesin layer, A well-known method can be used. For example, a method using a film forming method such as an extrusion method, a cast molding method, a T-die method, a cutting (skive) method, an inflation method or the like, a method for forming a film by multilayer coextrusion using two or more kinds of fluororesins, Examples thereof include a method of forming a film using a mixture of at least one kind of fluororesin. If necessary, the fluororesin layer produced by the above-described method may be stretched uniaxially or biaxially by a tenter method, a tubular method, or the like.

(2) Electron beam curable resin composition The electron beam curable resin composition used in this step is cured by electron beam irradiation to form an adhesive resin layer. / Or a monomer having a cationic polymerizable bond, a polymer having a low degree of polymerization, and a reactive polymer are appropriately mixed.

As the electron beam curable resin, commonly used ones can be used. Among them, the adhesive resin layer obtained by curing by electron beam irradiation has the same elasticity and elongation characteristics as the fluororesin layer. It is preferable. Moreover, when a functional layer is further formed on the adhesive resin layer as will be described later, it is preferable that the adhesiveness and followability with the functional layer are good.
As such an electron beam curable resin, a monomer, a dimer, an oligomer and a polymer having a polymerizable functional group that directly undergoes a reaction such as polymerization or dimerization when irradiated with an electron beam can be used. For example, radically polymerizable monomers and oligomers having an ethylenically unsaturated bond such as an acryl group, a vinyl group, and an allyl group can be exemplified.

  As the polymerizable monomer, a (meth) acrylate-based monomer having a radical polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate is preferable. Here, “(meth) acrylate” means “acrylate or methacrylate”, and other similar ones have the same meaning. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified diphosphate ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylo Propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ( Acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Is mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.

  In the present invention, together with the above polyfunctional (meth) acrylate, a monofunctional (meth) acrylate can be used in combination as long as the object of the present invention is not impaired for the purpose of reducing the viscosity. Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, and N-acryloylmorpholine. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Examples of the polymerizable oligomer include oligomers having a radical polymerizable unsaturated group in the molecule, such as epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. Can be mentioned. Here, the epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. . Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Polyester (meth) acrylate-based oligomers are obtained by esterifying the hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polyvalent carboxylic acids and polyhydric alcohols with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding alkylene oxide to carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Moreover, the polymer which has an ethylenically unsaturated bond can also be used as electron beam curable resin. In the above polymer, an intermediate polymer is synthesized by radical (co) polymerizing a monomer or oligomer having a polar group capable of causing an addition or condensation reaction with an ethylenically unsaturated bond in one molecule, and then ethylenically in one molecule. It is obtained by reacting a compound having a functional group capable of reacting with the polar group of the intermediate polymer together with the unsaturated bond. Monomers or oligomers having such radically polymerizable groups and polar groups include epoxy (meth) acrylates, glycidyl (meth) acrylates, glycerol mono (meth) acrylates, glycerol di (meth) acrylates, 2- Hydroxyethyl (meth) acrylate and its caprolactone-modified product, 2-hydroxypropyl (meth) acrylate and its caprolactone-modified product, phosphoric acid (meth) acrylates, polyethylene glycol (meth) acrylates, polypropylene glycol (meth) acrylates, Examples thereof include (meth) acrylates, succinic acid acrylates, and acrylamides of polyethylene glycol-polypropylene glycol copolymers. The compound used to introduce an ethylenically unsaturated bond pendant structure into the intermediate polymer can react with the polar group of the intermediate polymer from monomers or oligomers having a polar group together with the ethylenically unsaturated bond. Anything can be selected and used.

  In particular, in the present invention, it is preferable to use a polyfunctional urethane acrylate compound (oligomer) having a polyester polyol as a main raw material as the electron beam curable resin. This is because the above-mentioned urethane acrylate compound is crosslinked with a fluororesin at a plurality of locations and has a high tensile elongation that flexibly follows the subsequent heat / working stretching stress.

The electron beam curable resin composition may contain any additive depending on the physical properties of the resulting adhesive resin layer. Optional additives include, for example, weather resistance improvers such as light stabilizers and heat stabilizers, antifoaming agents, leveling agents, thixotropic agents, plasticizers, surfactants, antistatic agents, antioxidants, An ultraviolet absorber, an infrared absorber, a pigment | dye, an extender, a light-diffusion agent, a coupling agent etc. can be mentioned.
In addition, since it hardens | cures by electron beam irradiation, a polymerization initiator is not contained in the electron beam curable resin composition in this invention.

The electron beam curable resin composition preferably does not contain a low molecular material. When the resin laminate obtained by the present invention is used as a food material or medical material containing food or medicine, a low molecular material may be eluted from the adhesive resin layer, and the safety of the inclusion may be impaired. Because.
Here, the low molecular weight material refers to unreacted monomers and oligomers, various solvents, photodegradable radical generating materials such as ultraviolet polymerization initiators, plasticizers such as phthalates, additives, and the like. Refers to a material having 1000 or less.

  In the present invention, “the electron beam curable resin composition does not contain a low molecular material” means that it does not substantially contain a low molecular material, and is excluded when a low molecular material as an impurity is contained. And Specifically, “the electron beam curable resin composition does not contain a low molecular material” means that the ratio of the low molecular material contained in the total amount of the electron beam curable resin composition is 0.5% by mass. Hereinafter, it is preferably 0.05% by mass or less.

(3) Coating method In this step, the method for coating the electron beam curable resin composition on one surface of the fluororesin layer is not particularly limited as long as a coating layer having a desired film thickness can be formed. However, it is appropriately selected according to the material of the electron beam curable resin composition. Examples of the coating method include spin coating, casting, dipping, bar coating, blade coating, roll coating, gravure coating, reverse roll coating, comma coating, flexographic printing, and spray coating. There are known methods.
In addition, the said electron beam curable resin composition is apply | coated directly on a fluororesin layer using the above-mentioned method, without using a solvent.

  The thickness of the coating layer formed in this step is preferably such that the electron beam irradiated in the irradiation step can reach the fluororesin layer, such as the electron beam irradiation conditions and the electron beam attenuation tendency. Depending on the case, it is suitably selected, but for example, it is preferably in the range of 2 μm to 50 μm, and more preferably in the range of 5 μm to 25 μm. If the thickness of the coating layer is larger than the above range, the energy of the electron beam is sufficiently attenuated during the transmission of the coating layer, and the electron beam cannot reach or reach the fluororesin layer. This is because energy is small and a cross-linking bond may not be formed between the coating layer and the fluororesin layer. On the other hand, if the thickness of the coating layer is smaller than the above range, the function as the adhesive layer may not be achieved.

2. Irradiation step The irradiation step in the present invention is performed by irradiating an electron beam from the surface side of the fluororesin layer on which the electron beam curable resin composition is applied, and curing the electron beam curable resin composition. It is a process of forming a layer.

  As an irradiation condition of the electron beam used in this step, the fluorine resin layer can be irradiated with an electron beam via the coating layer of the electron beam curable resin composition, and the fluorine resin layer and the electron beam curable resin can be irradiated. The conditions may be any as long as they can form a cross-linking bond with the coating layer of the composition, and can be set as appropriate depending on the type of the electron beam curable resin composition, the film thickness of the coating layer, and the like.

  The electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type should be used. Can do.

The irradiation dose of the electron beam is such an amount that sufficient crosslinking can be obtained in the coating layer of the electron beam curable resin composition, and the fluorine resin layer can be irradiated with an electron beam. Any amount that can form a cross-linked bond at the interface with the coating layer may be used, and the amount can be appropriately set according to the thickness of the coating layer and the type of the fluororesin. Specifically, the irradiation dose of the electron beam is preferably 5 MGy or more and less than 20 MGy, and particularly preferably in the range of 9 MGy to 16 MGy.
By setting the electron beam irradiation dose within the above range, it is possible to form a cross-linked bond between the fluororesin layer and the adhesive resin layer while suppressing excessive electron beam irradiation to the fluororesin layer. is there. In addition, when the fluororesin layer is formed from an electron beam-disintegrating fluororesin, the irradiation dose is used to promote the cleavage of molecular chains by reactive species in the molecule of the fluororesin. Crosslinks can be formed by the reaction between the chain breaks and the polymerizable functional groups contained in the electron beam curable resin composition, and the interlayer adhesion strength between the adhesive resin layer and the fluororesin layer can be further improved. Because it becomes.
In addition, if the electron beam irradiation dose is smaller than the above range, the number of reactive active species generated in the fluorine resin molecule is reduced, the molecular chain breakage is not promoted in the electron beam collapsing fluorine resin, etc. For the reason, the proportion of cross-linking formed between the fluororesin layer and the adhesive resin layer decreases, and the interlayer adhesion strength may not be sufficiently obtained. On the other hand, if the irradiation dose of the electron beam is larger than the above range, a high-energy electron beam is irradiated to the fluororesin layer, and deterioration may occur depending on the type of the fluororesin.

The acceleration voltage at the time of electron beam irradiation is about the thickness of the coating layer of the electron beam curable resin composition, the penetration depth of the electron beam in the fluororesin layer, the electron beam curable resin composition and the fluororesin. It can be set as appropriate according to the type.
Here, the higher the acceleration voltage is, the more the electron beam transmission capability increases. Therefore, the irradiated electron beam passes through the coating layer of the electron beam curable resin composition, and enters the interface between the coating layer and the fluororesin layer. It is preferable to set the acceleration voltage so that the attenuation rate of the electron beam when it reaches 5% or more and 60% or less. Specifically, the acceleration voltage is preferably in the range of 50 kV to 400 kV, and more preferably in the range of 100 kV to 250 kV. As a result, the electron beam is transmitted through the fluororesin layer, and reactive species can be generated in the molecule of the fluororesin. In the case where the fluororesin layer is made of an electron beam collapsible fluororesin, This is because the cleavage of the molecular chain by the reactive species in the molecule of the fluororesin can be promoted.

  Note that the number of electron beam irradiations may be one or more. When the electron beam is irradiated a plurality of times, it is only necessary that the total irradiation dose of the irradiated electron beam falls within the above-mentioned specified range.

The oxygen concentration in the electron beam irradiation environment is preferably 100 ppm or less. This is because irradiation with an electron beam in the presence of oxygen generates ozone, which may adversely affect the apparatus and the environment.
In order to set the oxygen concentration to 100 ppm or less, electron beam irradiation may be performed 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, 100 ppm or less can be achieved.

  In this step, the electron beam is irradiated from the surface side of the fluororesin layer on which the electron beam curable resin composition is applied. When an electron beam is irradiated from the side of the fluororesin layer on which the electron beam curable resin composition is not applied, a high-energy electron beam is irradiated to the fluororesin layer, and deterioration occurs depending on the type of fluororesin. There is a case.

The adhesive resin layer formed in this step is formed by curing the coating layer of the electron beam curable resin composition, and the adhesive force is appropriately determined according to the use of the resin laminate obtained by the present invention. Can be designed.
About the film thickness of an adhesive resin layer, it is the same as that of the coating layer of the electron beam curable resin composition mentioned above.

3. Optional process In the present invention, after the adhesive resin layer is formed on one surface of the fluororesin layer by the application process and the irradiation process, the application process is similarly applied to the surface of the fluororesin layer on which the adhesive resin layer is not formed. And an irradiation step may be performed. Thereby, as illustrated in FIG. 2, a resin laminate having the adhesive resin layer 2 on both surfaces of the fluororesin layer 1 can be formed.

  In addition to the above-described steps, the present invention can have any step as necessary. Hereinafter, the optional steps assumed in the present invention will be described.

(1) Functional layer formation process It is preferable that this invention has a functional layer formation process which forms a functional layer on the said adhesive resin layer after the said irradiation process. Adhesion, compounding, and simultaneous molding with the functional layer can improve the adhesion of the fluororesin layer to the functional layer, and add a desired function to the resin laminate obtained according to the type of the functional layer. Because it can.

Here, the functional layer is not particularly limited as long as it can impart a desired function to the resin laminate obtained by the present invention, and is appropriately designed according to the material of the functional layer. Examples of the desired function include self-supporting property, moldability, adhesion imparting function, thermoplasticity, and stretchability.
In addition, an adhesive provision function means the function which further improves the adhesiveness of the whole resin laminated body obtained by this invention by providing the functional layer which shows stronger adhesiveness than an adhesive resin layer.
Examples of the functional layer capable of imparting these functions include a thermoplastic resin layer, a rubber base material layer, paper, metal, graphite fiber, and ceramic.

  The thickness of the functional layer is not particularly limited as long as it is a size that can exhibit a desired function, and can be appropriately designed according to the type of the functional layer.

  Hereinafter, among the functional layers, the thermoplastic resin layer and the rubber base layer will be described.

(A) Thermoplastic resin layer The thermoplastic resin layer may be any layer as long as it can provide the above-described desired function, and may or may not have transparency.
It does not specifically limit as a material of a thermoplastic resin layer, According to the function to provide, it selects suitably. For example, polyolefin resin, vinyl chloride resin, (meth) acrylic resin, polyurethane resin, polyester resin, polyamide resin, (meth) acrylic ester-olefin copolymer resin, vinyl chloride resin, ethylene-vinyl acetate copolymer resin ( EVA resin), ionomer resin, olefin-α olefin copolymer resin, and the like can be used. These can be used alone or in combination of two or more.

  The method for forming the thermoplastic resin layer is not particularly limited as long as it can be formed on the adhesive resin layer. For example, an extrusion method in which a thermoplastic resin is extruded and coated on the adhesive resin layer, an adhesive resin layer and a support are used. Examples thereof include a sandwich laminate method in which a molten thermoplastic resin is allowed to flow between layers with the base material layer to form a thermoplastic resin.

(B) Rubber base material layer The rubber base material layer may be any material as long as it can provide the above-mentioned desired functions. For example, any synthetic rubber or natural rubber is used as a main raw material, and this is necessary. Accordingly, a rubber resin composition obtained by kneading an arbitrary compounding agent may be molded into an arbitrary shape such as a sheet shape or a rubber plug shape by a known molding method.

  Examples of the synthetic rubber used as the main raw material of the rubber base layer include butyl rubbers such as butyl rubber, chlorinated butyl rubber, brominated butyl rubber, and divinylbenzene copolymer butyl rubber, isoprene rubber, isoprene-isobutylene rubber, butadiene rubber, and styrene. Examples thereof include resins such as butadiene rubber, ethylene propylene rubber, nitrile rubber, and silicon rubber.

  The method for forming the rubber base material layer on the adhesive resin layer is not particularly limited. For example, the rubber base material layer is overlaid on the adhesive resin layer formed on one surface of the fluororesin layer, and is heat-pressed. A method is mentioned. Also, an unvulcanized rubber sheet is used as the rubber base layer, and the rubber base layer is overlaid on the adhesive resin layer formed on one side of the fluororesin layer and placed in the mold for vulcanization molding. At the same time, a method of laminating by thermocompression bonding can be mentioned. The resin laminate obtained at this time may be a layered product provided with a rubber base layer, or a molded product in which the surface of the rubber molded product is coated with a fluororesin layer via an adhesive resin layer. There may be.

  The vulcanization conditions, thermocompression bonding conditions, etc. in this step can be appropriately set according to the type and vulcanization state of the rubber base layer to be used, the melting point of the fluorocarbon film, the thickness, etc. The conditions disclosed in JP2013-107961A can be used.

(2) Surface treatment process It is preferable that this invention has a surface treatment process which makes the surface of the said fluororesin layer rough before the said application | coating process. By making the surface of the fluororesin layer rough, the contact area with the electron beam curable resin composition increases, and more crosslinks can be formed between the fluororesin layer and the adhesive resin layer. This is because the interlayer adhesive strength can be further improved.

The surface treatment method in this step is not particularly limited as long as the surface of the fluororesin layer can be roughened to make it rough, but in the method using a metallic sodium-containing surface modifier, fluorine is used. Since the discoloration and transparency of the resin layer may decrease, it is preferable that the surface treatment does not cause the discoloration or transparency of the fluororesin layer.
Such a surface treatment method may be physical treatment or mechanical treatment, and can be appropriately selected. Examples of the physical treatment include corona discharge treatment, plasma treatment, vacuum plasma treatment, ozone treatment, ultraviolet treatment, electron beam irradiation, flame treatment, and sputtering. Moreover, as a mechanical process, a rubbing process etc. are mentioned, for example.

  The surface roughness of the fluororesin layer after the surface treatment is not particularly limited, and can be appropriately designed according to the type of fluororesin, adhesiveness, and the like.

4). Resin Laminate The resin laminate obtained by the present invention has an adhesive resin layer on one surface of the fluororesin layer.
The resin laminate preferably has a high interlayer adhesive strength between the fluororesin layer and the adhesive resin layer, specifically 200 gf / cm or more, more preferably 300 gf / cm or more, and particularly preferably 400 gf / cm or more. This is because if the interlayer adhesive strength between the fluororesin layer and the adhesive resin layer is smaller than the above range, peeling easily occurs between the fluororesin layer and the adhesive resin layer.
In addition, the said interlayer adhesive strength is a value measured according to JIS-K-6854-3 1999 (T-type peeling test method), and using Tensilon (Orientec company make tensile tester RTA-250), it is standard. The average value of the peel strength at a position 30 mm long in the length direction of the test piece where the T-type peel strength is stabilized from the peeling start side end of the test piece while being loaded with 20% by a load cell. Interlayer adhesion strength.

Moreover, it is preferable that the resin laminated body obtained by this invention does not contain a low molecular material substantially. The reason and details of the low molecular weight material are the same as the contents described in the above-mentioned section of “1. Application step (2) Electron beam curable resin composition”, and thus the description thereof is omitted here. In addition to the materials listed in the section of “1. Application step (2) Electron beam curable resin composition”, low molecular weight materials include uncured reactive materials in the adhesive resin layer, and undecomposed materials in the fluororesin layer. Reaction materials and the like are also included.
Here, the resin laminate does not substantially contain a low molecular material. Specifically, the elution amount of the low molecular material eluted from 1 cm ^{2 of} the adhesive resin layer is 5 mg / cm ² or less, preferably 0. .5 mg / cm ² or less.
In addition, the elution amount of the low molecular weight material is measured by a plastic food container, a pharmaceutical container, and a medical instrument elution test method (Japanese Pharmacopoeia plastic drug container test method).

The resin laminate obtained by the present invention may have an adhesive resin layer 2 on one side of the fluororesin layer 1 as shown in FIG. 1 (d), and the fluororesin layer 1 as shown in FIG. The adhesive resin layer 2 may be formed on both sides.
In addition, the arbitrary layer formed on the adhesive resin layer may be a single layer or a plurality of arbitrary layers may be laminated.

B. Next, the resin laminate of the present invention will be described. The resin laminate of the present invention is a resin laminate having an adhesive resin layer on one surface of a fluororesin layer, wherein the fluororesin layer is formed of PTFE or PCTFE, and the adhesive resin layer is It comprises an ionizing radiation curable resin.

  The resin laminate of the present invention will be described with reference to the drawings. FIG. 3 is a schematic cross-sectional view showing an example of the resin laminate of the present invention. The resin laminate 10 has an adhesive resin layer 2 containing an ionizing radiation curable resin on one surface of a fluororesin layer 1 formed by PTFE or PCTFE.

  According to the present invention, since the adhesive resin layer containing the ionizing radiation curable resin is formed on the fluororesin layer formed by PTFE or PCTFE, the interlayer adhesive strength between the adhesive resin layer and the fluororesin layer is high. And the peeling of the fluororesin layer can be prevented.

  Hereinafter, each structure of the resin laminated body of this invention is demonstrated.

1. Fluorine resin layer The fluorine resin layer in the present invention is formed of PTFE or PCTFE.
The other details of the fluororesin layer are the same as those described in the section “A. Method for producing resin laminate”, and thus the description thereof is omitted here.

2. Adhesive Resin Layer The adhesive resin layer in the present invention is provided on one surface of the fluororesin layer and contains an ionizing radiation curable resin.
In the present invention, the ionizing radiation curable resin contained in the adhesive resin layer is not particularly limited as long as the interlayer adhesive strength between the adhesive resin layer and the fluororesin layer is within the range described later. Examples thereof include curable resins. Among these, an electron beam curable resin is preferable.
The composition of the electron beam curable resin and other details of the adhesive resin layer are the same as those described in the section “A. Method for producing resin laminate”, and thus the description thereof is omitted here. .

3. Arbitrary Layer The resin laminate of the present invention may have a functional layer on the adhesive resin layer. The reason why it is preferable to have a functional layer on the adhesive resin layer and the details of the functional layer are the same as the contents described in the section of “A. Method for producing resin laminate”, and thus the description thereof is omitted here. To do.

4). Others In the present invention, the interlayer adhesive strength between the fluororesin layer and the adhesive resin layer is preferably 200 gf / cm or more. The reason and the like are the same as those described in the section “A. Manufacturing Method of Resin Laminate”, and thus the description thereof is omitted here.
In addition, when the interlayer adhesive strength of the adhesive resin layer formed of an electron beam curable resin and the fluororesin layer formed of PTFE or PCTFE is within the above range, the resin laminate of the present invention is “A. It can be inferred that it is formed by the production method described in the section “Production Method of Laminate”.

  Since the other details regarding the resin laminate of the present invention are the same as the contents described in the above-mentioned section “A. Method for producing resin laminate”, description thereof is omitted here.

  Although it does not specifically limit as a use of the resin laminated body of this invention, According to the physical property which a fluororesin layer shows, it can use as industrial material, food material, and medical material. Specifically, the resin laminate of the present invention suppresses deterioration of packaging materials for foods and drinks, medicines, electronic members, various rubber products such as syringe stoppers and medicine vial stoppers, and display elements of displays. Therefore, it can be used as a peripheral member such as a sealing material. Further, the resin laminate of the present invention can be used as an ID tag sealing material that requires chemical resistance and heat resistance such as dry cleaning, a heat dissipation and heat resistance plate, a fan, a chiller board, a pipe, a shaft, and a bearing. .

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  The following examples illustrate the present invention in more detail.

[Examples 1-1 to 1-4]
(Coating process)
An electron beam curable resin composition D having the following composition was applied to one side of a fluororesin layer A (PTFE Skype film, 50 μm thick, manufactured by Nichias) so as to have a thickness of 15 g / m ² .

<Electron beam curable resin composition D>
・ Violet UV-3200B (curing with isophorone diisocyanate, polyester polyol and 3-methyl-1,5-pentamethylene diol, adipic acid and isophthalic acid, and residual isocyanate mainly composed of 2-hydroxyethyl acrylate 2 to 3 functional urethane acrylate reactants sometimes having flexibility. (Manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) ... 80 parts by mass / acryloylmorpholine ... 20 parts by mass

(Irradiation process)
Using an electron beam irradiation apparatus, an electron beam is irradiated from the application surface side of the electron beam curable resin composition D under any of the irradiation conditions A to D shown in Table 1, and the electron beam curable resin composition D is irradiated. The coating layer was cured to form an adhesive resin layer, and resin laminates 1-1 to 1-4 were obtained.

[Examples 1-5 to 1-8]
Resin laminate 1-5 in the same manner as in Examples 1-1 to 1-4 except that instead of the electron beam curable resin composition D, an electron beam curable resin composition E having the following composition was used. ˜1-8 was obtained.

<Electron beam curable resin composition E>
・ Violet UV-3200B (curing with isophorone diisocyanate, polyester polyol and 3-methyl-1,5-pentamethylene diol, adipic acid and isophthalic acid, and residual isocyanate mainly composed of 2-hydroxyethyl acrylate 2 to 3 functional urethane acrylate reactants sometimes having flexibility. (Manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) ... 70 parts by mass · Acrylylmorpholine ... 30 parts by mass

[Examples 1-9 to 1-12]
Resin laminate 1-9 in the same manner as in Examples 1-1 to 1-4 except that the electron beam curable resin composition F having the following composition was used instead of the electron beam curable resin composition D. ˜1-12 was obtained.

<Electron beam curable resin composition F>
・ Violet UV-3200B (curing with isophorone diisocyanate, polyester polyol and 3-methyl-1,5-pentamethylene diol, adipic acid and isophthalic acid, and residual isocyanate mainly composed of 2-hydroxyethyl acrylate 2 to 3 functional urethane acrylate reactants sometimes having flexibility. (Manufactured by Nippon Synthetic Chemical Co., Ltd.) ... 80 parts by mass · Phenoxyethyl acrylate ... 20 parts by mass

[Examples 2-1 to 2-4]
Resin laminate in the same manner as in Examples 1-1 to 1-4 except that the fluororesin layer B (PTFE cast film, thickness 43 μm, manufactured by Chukoh Chemical Industry Co., Ltd.) was used instead of the fluororesin layer A. 2-1 to 2-4 were obtained.

[Examples 2-5 to 2-8]
Resin laminates 2-5 to 2-8 were prepared in the same manner as in Examples 2-1 to 2-4 except that the electron beam curable resin composition E was used instead of the electron beam curable resin composition D. Obtained.

[Examples 2-9 to 2-12]
Resin laminates 2-9 to 2-12 were prepared in the same manner as in Examples 2-1 to 2-4 except that the electron beam curable resin composition F was used instead of the electron beam curable resin composition D. Obtained.

[Examples 3-1 to 3-4]
Resin laminate 3- in the same manner as in Examples 1-1 to 1-4 except that fluororesin layer C (PCTFE cast film, thickness 50 μm, manufactured by Daikin) was used instead of fluororesin layer A. 1-3-4 were obtained.

[Examples 3-5 to 3-8]
Resin laminates 3-5 to 3-8 were prepared in the same manner as in Examples 3-1 to 3-4 except that the electron beam curable resin composition E was used instead of the electron beam curable resin composition D. Obtained.

[Examples 3-9 to 3-12]
Resin laminates 3-9 to 3-12 were prepared in the same manner as in Examples 3-1 to 3-4 except that the electron beam curable resin composition F was used instead of the electron beam curable resin composition D. Obtained.

[Examples 4-1 to 4-4]
(Surface treatment process)
Prior to the coating step, one side of the fluororesin layer A was depressurized to 10 ⁻⁵ Torr using a 13.56 MHz vacuum plasma apparatus and etched for 30 seconds in an argon gas atmosphere.

  Resin laminates 4-1 to 4-4 were obtained in the same manner as in Examples 1-1 to 1-4 except that the electron beam curable resin composition D was applied to the etched surface of the fluororesin layer A.

[Examples 4-5 to 4-8]
Resin laminates 4-5 to 4-8 were obtained in the same manner as in Examples 1-5 to 1-8, except that the surface treatment step was performed in the same manner as in Examples 4-1 to 4-4.

[Examples 4-9 to 4-12]
Resin laminates 4-9 to 4-12 were obtained in the same manner as in Examples 1-9 to 1-12 except that the surface treatment step was performed in the same manner as in Examples 4-1 to 4-4.

[Examples 5-1 to 5-4]
Prior to the coating process, the surface treatment process was performed on one side of the fluororesin layer B under the same conditions as in Examples 4-1 to 4-4. Thus, resin laminates 5-1 to 5-4 were obtained.

[Examples 5-5 to 5-8]
Resin laminates 5-5 to 5-8 were obtained in the same manner as in Examples 2-5 to 2-8, except that the surface treatment step was performed in the same manner as in Examples 5-1 to 5-4.

[Examples 5-9 to 5-12]
Resin laminates 5-9 to 5-12 were obtained in the same manner as in Examples 2-9 to 2-12, except that the surface treatment step was performed in the same manner as in Examples 5-1 to 5-4.

[Examples 6-1 to 6-4]
Prior to the coating process, the surface treatment process was performed on one side of the fluororesin layer C under the same conditions as in Examples 4-1 to 4-4. Thus, resin laminates 6-1 to 6-4 were obtained.

[Examples 6-5 to 6-8]
Resin laminates 6-5 to 6-8 were obtained in the same manner as in Examples 3-5 to 3-8, except that the surface treatment step was performed in the same manner as in Examples 6-1 to 6-4.

[Examples 6-9 to 6-12]
Resin laminates 6-9 to 6-12 were obtained in the same manner as in Examples 3-9 to 3-12, except that the surface treatment step was performed in the same manner as in Examples 6-1 to 6-4.

[Comparative Example 1-1]
(Surface treatment process)
Prior to the coating step, one side of the fluororesin layer A was depressurized to 10 ⁻⁵ Torr using a 13.56 MHz vacuum plasma apparatus and etched for 30 seconds in an argon gas atmosphere.

(Coating process)
An ultraviolet curable resin composition G is prepared by sufficiently dispersing and dissolving 4 parts by mass of a photopolymerization initiator (Irgacure 184 Ciba Specialty Chemicals Co., Ltd.) in the electron beam curable resin composition D. It apply | coated so that it might become a thickness of 15 g / m < ² > on the etching surface of the resin layer A. FIG.

(Curing process)
Using an ultraviolet irradiation device, an ultraviolet ray is irradiated from the coated surface side under an output of 80 W / cm, under a high pressure mercury UV lamp at an integrated light amount of 800 mJ / cm ₂ , and the coated layer of the ultraviolet curable resin composition G is cured and bonded. A resin layer was formed to obtain a resin laminate 7-1.

[Comparative Example 1-2]
In place of the ultraviolet curable resin composition G, 4 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) is sufficiently dispersed and dissolved in the electron beam curable resin composition E. Except having used the ultraviolet curable resin composition H which was used, it carried out similarly to the comparative example 1-1, and obtained the resin laminated body 7-2.

[Comparative Example 1-3]
In place of the ultraviolet curable resin composition G, 4 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) is sufficiently dispersed and dissolved in the electron beam curable resin composition F. A resin laminate 7-3 was obtained in the same manner as in Comparative Example 1-1 except that the ultraviolet curable resin composition I was used.

[Comparative Example 2-1]
Except having used the fluororesin layer B instead of the fluororesin layer A, the resin laminated body 8-1 was obtained like the comparative example 1-1.

[Comparative Example 2-2]
Except having used the fluororesin layer B instead of the fluororesin layer A, the resin laminated body 8-2 was obtained like the comparative example 1-2.

[Comparative Example 2-3]
A resin laminate 8-3 was obtained in the same manner as in Comparative Example 1-3 except that the fluororesin layer B was used instead of the fluororesin layer A.

[Comparative Example 3-1]
Except having used the fluororesin layer C instead of the fluororesin layer A, the resin laminated body 9-1 was obtained like the comparative example 1-1.

[Comparative Example 3-2]
Except having used the fluororesin layer C instead of the fluororesin layer A, the resin laminated body 9-2 was obtained like the comparative example 1-2.

[Comparative Example 3-3]
Except having used the fluororesin layer C instead of the fluororesin layer A, the resin laminated body 9-3 was obtained like the comparative example 1-3.

[Evaluation 1]
The resin laminates of Examples and Comparative Examples were cut into strips having a width of 15 mm, and a sample was reinforced by sticking a gum tape on the adhesive resin layer. About each sample, the T-type peeling test was done and the measured T-type peeling strength was made into the interlayer adhesive strength of a fluororesin layer and an adhesive resin layer. The T-type peel test is conducted in accordance with JIS-K-6854-3 1999 (T-type peel test method) using Tensilon (Orientec Tensile Tester RTA-250) with a standard load cell weighing 20%. Peeling was performed at a speed of 100 mm / min. For the peel strength, the average value of the strength at the position where the T-type peel strength is stabilized from the end of the sample located on the peel start side of the sample (position at 30 mm in the length direction from the end of the sample) was recorded.
Table 2 shows the evaluation results for Example 1 (1-1 to 1-12), Example 2 (2-1 to 2-12), and Example 3 (3-1 to 3-12). 4 (4-1 to 4-12), Example 5 (5-1 to 5-12), and Example 6 (6-1 to 6-12) are evaluated in Table 3, and Comparative Example 1 ( Table 4 shows the evaluation results for 1-1 to 1-3), Comparative Example 2 (2-1 to 2-3), and Comparative Example 3 (3-1 to 3-3).

  From Tables 2 to 4, for each of Comparative Examples 1 to 3 in which a resin laminate was formed by irradiation with ultraviolet rays, the surface treatment of the fluororesin layer was carried out with the adhesive resin layer and the fluororesin layer. Interlayer adhesion strength showed a low value compared with each Example of Examples 1-6 which formed the resin laminated body by electron beam irradiation.

[Example 7-1]
On the adhesive resin layer of the resin laminate 1-3, an olefin-based adhesive resin (Modic P596 manufactured by Mitsubishi Chemical Corporation) is extruded to form a thermoplastic resin layer, and unstretched PP is formed on the thermoplastic resin layer. A film (ZK99S manufactured by Toray Industries, Inc.) was bonded to obtain a resin laminate 10-1.

[Example 7-2]
A resin laminate 10-2 was obtained in the same manner as in Example 7-1 except that the resin laminate 1-11 was used instead of the resin laminate 1-3.

[Example 8-1]
On the adhesive resin layer of the resin laminate 2-3, an olefin-based adhesive resin (Modic P596 manufactured by Mitsubishi Chemical Corporation) is extruded to form a thermoplastic resin layer, and unstretched PP is formed on the thermoplastic resin layer. A film (ZK99S manufactured by Toray Industries, Inc.) was bonded to obtain a resin laminate 10-3.

[Example 8-2]
A resin laminate 10-4 was obtained in the same manner as in Example 8-1 except that the resin laminate 2-11 was used instead of the resin laminate 2-3.

[Comparative Example 4]
A thermoplastic resin layer is formed by extruding an olefin-based adhesive resin (Modic P596, manufactured by Mitsubishi Chemical Corporation) onto the etched surface of the fluororesin layer A that has been etched on one side under the same conditions as the surface treatment step performed in Example 4. Then, an unstretched PP film (ZK99S manufactured by Toray Industries, Inc.) was bonded onto the thermoplastic resin layer to obtain a resin laminate 10-5.

[Comparative Example 5]
A thermoplastic resin layer is formed in the same manner as in Comparative Example 4 on the etched surface of the fluororesin layer B that has been etched on one side under the same conditions as the surface treatment step performed in Example 5. A stretched PP film (ZK99S manufactured by Toray Industries, Inc.) was bonded to obtain a resin laminate 10-6.

[Evaluation 2]
In the resin laminates obtained in Examples 7-1 to 7-2 and Examples 8-1 to 8-2, each layer of the fluororesin layer, the adhesive resin layer, the thermosetting resin layer, and the unstretched PP film No peeling occurred in. On the other hand, in the resin laminates obtained in Comparative Examples 4 to 5, peeling occurred between the fluororesin layer and the thermoplastic resin layer.

DESCRIPTION OF SYMBOLS 1 ... Fluorine resin layer 2 ... Adhesive resin layer 2A ... Electron beam curable resin composition 10 ... Resin laminated body

Claims (3)

A resin laminate having an adhesive resin layer on one surface of the fluororesin layer,
The fluororesin layer is formed of an electron beam collapsible fluororesin, and the electron beam collapsible fluororesin is polytetrafluoroethylene or polychlorotrifluoroethylene,
The adhesive resin layer includes an ionizing radiation curable resin, and does not include a polymerizable initiator or a residue thereof.   The resin laminate according to claim 1, wherein an interlayer adhesive strength between the fluororesin layer and the adhesive resin layer is 200 gf / cm or more.   The resin laminate according to claim 1, further comprising a functional layer on the adhesive resin layer.

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