Laminate

Abstract

The present invention relates to a laminate having a structure in which a fluororesin layer and a vinyl chloride resin layer are laminated with an adhesive layer in between, and provides a new laminate in which the composition of the adhesive layer can be improved to increase the delamination strength between the fluororesin layer and the vinyl chloride resin layer. [Solution] The laminate comprises a fluororesin layer with fluororesin as the main component resin, an adhesive layer, and a vinyl chloride resin layer with vinyl chloride resin as the main component resin, wherein the adhesive layer contains polyglycidyl methacrylate (PGMA), and the PGMA content is 20 to 60% by mass relative to 100% by mass of the resin constituting the adhesive layer.

Description

Technical Field

[0005] , , , ,

[0004] ,

[0001] The present invention relates to a laminate including a fluororesin layer having a fluororesin as a main component resin and a vinyl chloride resin layer having a vinyl chloride resin as a main component resin.

Background Art

[0002] The vinyl chloride resin contains chlorine in its molecule, so it not only has excellent flame retardancy, but also can add various additives in large amounts. Therefore, over a wide range, it can improve mechanical properties, heat resistance, moldability, and weather resistance. Due to such characteristics, the molded products of vinyl chloride resin compositions, especially rigid vinyl chloride resin compositions, are used as interior and exterior materials for transportation equipment such as aircraft, ships, and vehicles; interior and exterior materials for buildings; daily necessities such as furniture and office supplies; housing materials for home appliances and electronic devices; parts of semiconductor devices, building materials such as rain gutters, industrial members such as plates, and pipe materials such as pipes. On the other hand, soft vinyl chloride resins have been widely used as packaging materials such as films and sheets, coating materials such as shrink tubes, surface decoration materials for home appliances, furniture, doors, and fixtures, wall materials for houses and stores, daily sundries, and medical members.

[0003] On the other hand, fluororesins are excellent in heat resistance, chemical resistance, solvent resistance, weather resistance, and electrical insulation, etc., so they are used in various fields such as automobiles and OA equipment.

[0004] Conventionally, as a member having both the characteristics of vinyl chloride resin such as mechanical properties and flame retardancy and the characteristics of fluororesin such as heat resistance and chemical resistance, a laminate having a structure formed by laminating a fluororesin layer and a vinyl chloride resin layer has been developed. However, since the adhesion between vinyl chloride resin and fluororesin is low, there has been a problem that the fluororesin layer and the vinyl chloride resin layer are likely to peel off.

[0005] To improve the adhesion between the fluororesin layer and the vinyl chloride resin layer, for example, Patent Documents 1 and 2 propose improving the composition of the fluororesin layer and the vinyl chloride resin layer to enhance adhesion. Furthermore, Patent Document 3 discloses a configuration in which a fluororesin layer and a vinyl chloride resin layer are laminated with an adhesive layer in between, wherein the adhesive layer is made of acrylic resin, for example, rubber-modified acrylic resin, and Patent Document 4 discloses that silica is included in the adhesive layer. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2010-58438 [Patent Document 2] Japanese Patent Publication No. 2017-13314 [Patent Document 3] Japanese Patent Application Publication No. 11-005279 [Patent Document 4] Japanese Patent Publication No. 2008-18680 [Overview of the project] [Problems that the invention aims to solve]

[0007] The present invention relates to a laminate comprising a fluororesin layer and a vinyl chloride resin layer laminated with an adhesive layer in between, and aims to provide a new laminate in which the interlayer peel strength between the fluororesin layer and the vinyl chloride resin layer can be increased by improving the composition of the adhesive layer. [Means for solving the problem]

[0008] To solve these problems, the present invention proposes a laminate in the following embodiment.

[0009] [1] A first aspect of the present invention is a laminate comprising a fluororesin layer having fluororesin as the main component resin, an adhesive layer, and a vinyl chloride resin layer having vinyl chloride resin as the main component resin, The adhesive layer is a laminate containing polyglycidyl methacrylate (PGMA), with the PGMA content being 20 to 60% by mass relative to 100% by mass of the resin constituting the adhesive layer.

[0010] [2] A second aspect of the present invention is a laminate in which, in the first aspect, the adhesive layer contains, in addition to PGMA, at least one of a fluororesin which is the main component resin of the fluororesin layer and a vinyl chloride resin which is the main component resin of the vinyl chloride resin layer.

[0011] [3] A third aspect of the present invention is a laminate in which, in the first aspect, the adhesive layer contains, in addition to PGMA, a fluororesin which is the main component resin of the fluororesin layer and a vinyl chloride resin which is the main component resin of the vinyl chloride resin layer.

[0012] [4] A fourth aspect of the present invention is a laminate comprising a fluororesin layer / adhesive layer / vinyl chloride resin layer / adhesive layer / fluororesin layer laminate in any one of the first to third aspects, wherein the thickness of each layer is symmetrical in the thickness direction.

[0013] [5] A fifth aspect of the present invention is a laminate in any one of the first to fourth aspects, wherein the fluororesin is at least one of polytetrafluoroethylene (PTFE), tetrafluoroethylene-ethylene-hexafluoropropylene copolymer (EFEP), and polyvinylidene fluoride (PVDF). [6] A sixth aspect of the present invention is a laminate in which, in any one of the first to fifth embodiments, the polyvinyl chloride resin is a post-chlorinated polyvinyl chloride resin with a chlorination rate of 60 to 72%. [Effects of the Invention]

[0014] The present invention relates to a laminate having a structure in which a fluororesin layer and a vinyl chloride resin layer are laminated via an adhesive layer, and by containing polyglycidyl methacrylate (PGMA) in the adhesive layer and limiting the content ratio of PGMA to a predetermined range, the interlayer peeling strength between the fluororesin layer and the vinyl chloride resin layer can be increased.

Brief Description of Drawings

[0015] [Figure 1] It is a schematic explanatory view of the measurement method of the interlayer shear peeling strength carried out in the examples. [Figure 2] It is a schematic explanatory view of the measurement method of the tensile strength carried out in the examples.

Modes for Carrying Out the Invention

[0016] Hereinafter, an example of an embodiment of the present invention will be described. However, the present invention is not limited to the embodiments described below.

[0017] <The laminate of the present invention> A laminate according to an example of an embodiment of the present invention (also referred to as "the laminate of the present invention") is a laminate including a fluororesin layer having a fluororesin as a main component resin, an adhesive layer, and a vinyl chloride resin layer having a vinyl chloride resin as a main component resin. In the present invention, "resin" means a polymer, that is, a polymer.

[0018] <Fluororesin layer> The fluororesin layer is preferably a layer having a fluororesin as a main component resin. That is, it is preferable that the fluororesin is the resin having the highest mass ratio among the resins constituting the fluororesin layer. The content of the fluororesin in the fluororesin layer is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more with respect to the total mass of the fluororesin layer. Note that the fluororesin layer may be a layer made of fluororesin, and the content of the fluororesin may be 100% by mass with respect to the total mass of the fluororesin layer.

[0019] (Fluororesin) Examples of the fluororesin, which is the main component resin of the fluororesin layer, include polytetrafluoroethylene (PTFE), and melt fluororesins capable of melt molding, such as tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether (EPA), tetrafluoroethylene-ethylene copolymer (ETFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene-ethylene copolymer (ECTFE), tetrafluoroethylene-ethylene-hexafluoropropylene copolymer (EFEP), polytetrafluorodioxole copolymer, vinylidene fluoride (VdF), and the like. Among these, PTFE, EFEP, and PVDF are particularly preferable. That is, from the viewpoint of heat resistance, PTFE is preferable. Further, since the melting point is close to that of vinyl chloride resin, EFEP and PVDF are preferable from the viewpoint of easy processing.

[0020] (Other components) The fluororesin layer may contain a resin other than the fluororesin as necessary. Examples of the resin other than the fluororesin include vinylidene chloride resin, ethylene-vinyl alcohol copolymer, and the like. However, the resin is not limited thereto.

[0021] Further, the fluororesin layer may contain various additives. Examples of additives include heat stabilizers, antioxidants, UV absorbers, light stabilizers, nucleating agents, antibacterial / antifungal agents, antistatic agents, and lubricants. These may be used individually or in combination of two or more. However, the additives are not limited to these.

[0022] (Thickness) The thickness of the fluororesin layer is not particularly limited. However, from the viewpoint of chemical resistance and heat resistance, it is preferably 2 mm or more, more preferably 3 mm or more, and even more preferably 4 mm or more. On the other hand, from the viewpoint of weight reduction, it is preferably 10 mm or less, more preferably 9 mm or less, and even more preferably 8 mm or less.

[0023] <Vinyl chloride resin layer> The vinyl chloride resin layer is preferably a layer whose main component is vinyl chloride resin. In other words, it is preferable that vinyl chloride resin has the highest mass proportion among the resins constituting the vinyl chloride resin layer. The content of vinyl chloride resin in the vinyl chloride resin layer is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the vinyl chloride resin layer. The vinyl chloride resin layer may be a layer made of vinyl chloride resin, and the content of vinyl chloride resin may be 100% by mass of the total mass of the vinyl chloride resin layer.

[0024] (Vinyl chloride resin) The vinyl chloride resin is not particularly limited and may be any conventionally known vinyl chloride resin, for example, vinyl chloride homopolymer; copolymer of vinyl chloride monomer and monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer; graft copolymer obtained by graft copolymerizing vinyl chloride with a (co)polymer other than vinyl chloride; post-chlorinated vinyl chloride resin, etc. These may be used alone or in combination of two or more. In particular, from the viewpoint of heat resistance, it is preferable to use post-chlorinated polyvinyl chloride resin (CPVC), which will be described later.

[0025] Examples of monomers having unsaturated bonds that can copolymerize with the vinyl chloride monomer include vinyl fatty acid vinyl esters such as vinyl acetate and vinyl propionate; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate; α-olefins such as ethylene, propylene, and styrene; alkyl vinyl ethers such as vinyl methyl ether and vinyl butyl ether; and vinyl compounds such as unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride, or their acid anhydrides. Additionally, allyl compounds such as allyl chloride, allyl alcohol, allyl ethyl ether, allyl-2-hydroxyethyl ether, allyl glycidyl ether, and metharyl glycidyl ether can be used. These may be used individually or in combination of two or more types.

[0026] Specific examples of vinyl chloride copolymers include vinyl chloride-vinyl acetate copolymer, vinyl chloride-(meth)acrylic acid copolymer, vinyl chloride-methyl (meth)acrylate copolymer, vinyl chloride-(meth)acrylate copolymer, vinyl chloride-ethyl (meth)acrylate copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylonitrile copolymer, and vinyl chloride-various vinyl ether copolymers, which are copolymers of vinyl chloride with other monomers copolymerizable with vinyl chloride.

[0027] The average degree of polymerization of the polyvinyl chloride resin is preferably 300 to 5000, more preferably 500 or more or 4000 or less, and more preferably 700 or more or 3000 or less, from the viewpoint of ensuring good mechanical properties and processability of the resulting molded article.

[0028] (Post-chlorinated polyvinyl chloride resin) The aforementioned post-chlorinated vinyl resin (CPVC) is produced by adding chlorine to polyvinyl chloride resin (PVC), and has the characteristics of having a higher softening temperature and heat resistance that is 20 to 30°C higher than that of PVC.

[0029] From the viewpoint of maintaining impact resistance and melt fluidity, the post-chlorinated polyvinyl chloride resin is preferably one in which the average degree of polymerization of the polyvinyl chloride resin before chlorination is 500 to 1400.

[0030] The chlorination rate (average chlorine content) of the post-chlorinated polyvinyl chloride resin is preferably 60% or more, more preferably 62% or more, and even more preferably 64% or more, from the viewpoint of maintaining fluidity and moldability.

[0031] (Other ingredients) The vinyl chloride resin layer may contain resins other than vinyl chloride resin as needed. Examples of resins other than vinyl chloride resin include vinylidene chloride resin and ethylene-vinyl alcohol copolymer, but are not limited to these.

[0032] The polyvinyl chloride resin layer may contain various additives in addition to the polyvinyl chloride resin, as needed. Examples of additives include heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, nucleating agents, antibacterial and antifungal agents, antistatic agents, and lubricants. These may be used individually or in combination of two or more. However, the additives are not limited to these.

[0033] (Thickness) The thickness of the polyvinyl chloride resin layer is not particularly limited. However, from the viewpoint of mechanical strength, it is preferably 4 mm or more, more preferably 5 mm or more, and even more preferably 6 mm or more. On the other hand, from the viewpoint of weight reduction, it is preferably 10 mm or less, more preferably 9 mm or less, and even more preferably 8 mm or less.

[0034] From the viewpoint of mechanical strength, the thickness of the polyvinyl chloride resin layer is preferably 100% or more of the thickness of the fluororesin layer, more preferably 120% or more, and even more preferably 140% or more. On the other hand, from the viewpoint of weight reduction, the thickness is preferably 300% or less of the thickness of the fluororesin layer, more preferably 250% or less, and even more preferably 200% or less.

[0035] <Adhesive layer> From the viewpoint of lamination press molding with the vinyl chloride resin layer, the adhesive layer preferably contains polyglycidyl methacrylate (PGMA).

[0036] From the viewpoint of adhesion, the PGMA preferably has a glycidyl group content of 80 to 99% by mass, more preferably 85% or more by mass or 98% or less by mass, and more preferably 90% or more by mass or 97% or less by mass. Furthermore, from the viewpoint of adhesion, the PGMA preferably has an epoxy equivalent of 140 to 190 g / eq., more preferably 145 g / eq. or more, and even more preferably 150 g / eq. or more.

[0037] From the viewpoint of adhesion, the PGMA content is preferably 20% by mass or more relative to 100% by mass of the resin constituting the adhesive layer, more preferably 25% by mass or more, and more preferably 30% by mass or more. On the other hand, from the viewpoint of adhesion, it is preferably 60% by mass or less relative to 100% by mass of the resin constituting the adhesive layer, more preferably 55% by mass or less, and more preferably 50% by mass or less.

[0038] The components other than PGMA contained in the adhesive layer are not particularly limited. Examples include organic siloxanes, polyurethanes, epoxy resins, acrylic resins other than PGMA, vinyl alcohol, polyesters, polyester polyurethanes, polyether polyurethanes, and polyisocyanates.

[0039] In particular, the adhesive layer preferably contains at least one of fluororesin and vinyl chloride resin in addition to PGMA in order to enhance the adhesion of the fluororesin layer or vinyl chloride resin layer, and among these, it is preferable that it contains at least one of fluororesin, which is the main component resin of the fluororesin layer, and vinyl chloride resin, which is the main component resin of the vinyl chloride resin layer. Furthermore, in order to improve the adhesion between the fluororesin layer and the vinyl chloride resin layer, the adhesive layer preferably contains both fluororesin and vinyl chloride resin in addition to PGMA, and more preferably contains both fluororesin, which is the main component resin of the fluororesin layer, and vinyl chloride resin, which is the main component resin of the vinyl chloride resin layer.

[0040] When the adhesive layer contains PGMA and fluororesin, the fluororesin content in the adhesive layer is preferably 40 to 60% by mass, more preferably 42% or more by mass or 58% or less by mass, and more preferably 44% or more by mass or 56% or less by mass. When the adhesive layer contains PGMA and vinyl chloride resin, the content of vinyl chloride resin in the adhesive layer is preferably 40 to 60% by mass, more preferably 42% or more by mass or 58% or less by mass, and more preferably 44% or more by mass or 56% or less by mass.

[0041] (Thickness) The thickness of the adhesive layer is not particularly limited. However, from the viewpoint of adhesion and handling, it is preferably 0.01 mm or more, more preferably 0.02 mm or more, and even more preferably 0.03 mm or more. On the other hand, from the viewpoint of mechanical properties, it is preferably 0.2 mm or less, more preferably 0.15 mm or less, and even more preferably 0.1 mm or less.

[0042] <Layered structure> The laminate of the present invention may include other layers as long as it comprises the fluororesin layer, the adhesive layer, and the vinyl chloride resin layer. For example, in a configuration in which the fluororesin layer, the adhesive layer, and the vinyl chloride resin layer are laminated in this order, other layers may be provided at one or more locations among the following: between the fluororesin layer and the adhesive layer, between the adhesive layer and the vinyl chloride resin layer, on the outside of the fluororesin layer, and on the outside of the vinyl chloride resin layer.

[0043] The laminate of the present invention may have a three-layer structure consisting of a fluororesin layer / adhesive layer / vinyl chloride resin, or a four-layer structure consisting of a fluororesin layer / adhesive layer / vinyl chloride resin / adhesive layer / fluororesin layer, or vinyl chloride resin / adhesive layer / fluororesin layer / adhesive layer / vinyl chloride resin. It may also be a laminate consisting of more than that number of layers. Among these, from the viewpoint of preventing warping, a fluororesin layer / adhesive layer / vinyl chloride resin / adhesive layer / fluororesin layer is preferred. In this specification, when "fluororesin layer / adhesive layer / vinyl chloride resin" is indicated, it refers to a laminated structure in which a fluororesin layer, an adhesive layer, and vinyl chloride resin are laminated in that order.

[0044] From the viewpoint of preventing warping, it is preferable that the thickness of each layer of the laminate of the present invention is symmetrical in the thickness direction. That is, it is preferable that the laminate has a structure in which layers of the same thickness are sequentially laminated from the center or the central layer on both sides in the thickness direction. As an example, one can be cited which has a laminate structure of fluororesin layer / adhesive layer / vinyl chloride resin layer / adhesive layer / fluororesin layer, in which the thickness of each layer is symmetrical in the thickness direction.

[0045] The thickness of the laminate of the present invention is preferably 6 mm or more from the viewpoint of mechanical strength and chemical resistance, more preferably 8 mm or more, and more preferably 10 mm or more. On the other hand, from the viewpoint of lightweightness, it is preferably 20 mm or less, more preferably 19 mm or less, and more preferably 18 mm or less.

[0046] <Possible physical properties of the laminated material of the present invention> The laminate of the present invention may have the following physical properties.

[0047] (Interlaminar shear delamination strength) The laminate of the present invention preferably has an interlayer shear peel strength of 200 N or more between the fluororesin layer and the vinyl chloride resin layer, more preferably 210 N or more, and more preferably 220 N or more. The interlaminar shear peel strength in this case is the peel strength when the bonding area is 20 mm wide and 12 mm long, in accordance with JIS K 6850. In the laminate of the present invention, in order to adjust the interlayer shear peel strength between the fluororesin layer and the vinyl chloride resin layer to the above range, it is preferable to form the adhesive layer as described above.

[0048] (Tensile strength) The laminate of the present invention preferably has a tensile strength of 30 MPa or more, more preferably 31 MPa or more, and more preferably 32 MPa or more. The tensile strength in this case was measured by preparing a strip-shaped test specimen with a width of 10 mm, a thickness of 8 mm (3 mm fluororesin layer, 5 mm polyvinyl chloride resin layer), and a length of 110 mm. The specimen was pulled with a load at a constant speed, and the force required to break was divided by the cross-sectional area to determine the fracture stress. To adjust the tensile strength of the laminate of the present invention to the above range, the composition and thickness of each layer, the fluororesin layer, the adhesive layer, and the polyvinyl chloride resin layer, should be adjusted.

[0049] <Explanation of terms, etc.> In this invention, the term "film" includes "sheets," and the term "sheet" includes "film." In this invention, when "α~β" (where α and β are arbitrary numbers) is written, unless otherwise specified, it means "α or greater and β or less," and also includes the meaning of "preferably greater than α" or "preferably less than β." Furthermore, when written as "α or greater" or "α ≤" (where α is any number), unless otherwise specified, it includes the meaning of "preferably greater than α," and when written as "β or less" or "≤β" (where β is any number), unless otherwise specified, it also includes the meaning of "preferably less than β." [Examples]

[0050] The following describes an example of an embodiment of the present invention. However, the present invention is not limited to the embodiment described below.

[0051] <Example 1> (Formation of adhesive layer sheet) Metabrene P1901 (PGMA) and BASF Bondfaster 7B (GMA-VA copolymer) were mixed in a ratio of 50 wt% / 50 wt% and kneaded in a Laboplast mill at 190°C for 10 minutes. The resulting mixture was then sandwiched between upper and lower press plates and hot-pressed at 190°C for 15 minutes to obtain a 0.1 mm thick sheet for adhesive layer formation. • Metabrene P1901 (PGMA): Glycidyl group content 95-98% by mass, epoxy equivalent 170 g / eq. BASF Bondfaster 7B (GMA-VA copolymer): 12 wt% glycidyl methacrylate (GMA), 5 wt% vinyl acetate (VA) (catalog value)

[0052] (Fabrication of laminates) A laminate was fabricated using the above-mentioned adhesive layer-forming sheet and the following materials. • PTFE plate: PTFE sheet manufactured by Yodogawa Hutech Co., Ltd., made of PTFE, 3mm thick • Heat-resistant PVC plate: Mitsubishi Chemical Infratec's "Hishiplate 101 Series Heat-Resistant Grade," made of post-chlorinated polyvinyl chloride resin (CPVC) (average degree of polymerization 700, chlorination rate (average chlorine content) 67%), 5mm thick.

[0053] The above PTFE plate, the above adhesive layer forming sheet, and the above heat-resistant PVC plate were stacked in that order, and this laminate was sandwiched between upper and lower press plates and heat-pressed at 190°C for 20 minutes at a pressure of 3 MPa to produce a laminate (sample).

[0054] (Measurement of shear peel strength) In accordance with JIS K 6850, the above laminate (sample) was cut to a width of 20 mm, and as shown in Figure 1, the PTFE plate (fluororesin layer 1) and the heat-resistant PVC plate (vinyl chloride resin layer 2) were cut to prepare test specimens so that the bonding length L between the PTFE plate and the heat-resistant PVC plate was 12 mm. These test specimens were inserted into the gripping section 10 of a tensile testing machine together with the backing plates 11, 11, and a tensile test was performed at a speed of 10 mm / min to measure the maximum strength (tensile shear peel strength). The test was conducted in a laboratory environment of 23°C and 50% humidity.

[0055] (Tensile test) The above laminate (sample) was cut to a width of 10 mm to prepare test specimens. As shown in Figure 2, the test specimen was inserted into the gripping section of a tensile testing machine and set up. A tensile test was performed at a speed of 50 mm / min and a chuck distance of 60 mm, and the tensile strength was measured. The test was conducted in a laboratory environment of 23°C and 50% humidity.

[0056] <Example 2> (Formation of adhesive layer sheet) The crushed heat-resistant PVC plate described below and Metabren P1901 (PGMA) were mixed in a ratio of 50 wt% / 50 wt%. The mixture was kneaded at 190°C for 5 minutes in a Toyo Seiki Lab Plast Mill mixer. The resulting mixture was then sandwiched between upper and lower press plates and hot-pressed at 190°C for 15 minutes to obtain a 0.1 mm thick sheet, which was used to form an adhesive layer.

[0057] (Fabrication of laminates) A laminate was fabricated using the above-mentioned adhesive layer-forming sheet and the following materials. • EFEP plate: Made of tetrafluoroethylene-ethylene-hexafluoropropylene copolymer (EFEP), 3mm thick. • Heat-resistant PVC plate: Mitsubishi Chemical Infratec's "Hishiplate 101 Series Heat-Resistant Grade," made of post-chlorinated polyvinyl chloride resin (CPVC) (average degree of polymerization 700, chlorination rate (average chlorine content) 67%), 5mm thick.

[0058] The above EFEP plate, the above adhesive layer forming sheet, and the above heat-resistant PVC plate were stacked in that order, and this laminate was sandwiched between upper and lower press plates and hot-pressed at 190°C for 20 minutes at a pressure of 3 MPa to produce a laminate (sample).

[0059] The obtained laminate (sample) was subjected to shear peel strength measurement and tensile testing in the same manner as in Example 1.

[0060] <Example 3> (Formation of adhesive layer sheet) The pulverized PVDF plate and Metabren P1901 (PGMA) were mixed in a 50 wt% / 50 wt% ratio and kneaded at 190°C for 5 minutes in a Toyo Seiki Lab Plast Mill mixer. The resulting mixture was then sandwiched between upper and lower press plates and hot-pressed at 190°C for 15 minutes to obtain a 0.1 mm thick sheet for adhesive layer formation.

[0061] (Fabrication of laminates) A laminate was fabricated using the above-mentioned adhesive layer-forming sheet and the following materials. • Heat-resistant PVC plate: Mitsubishi Chemical Infratec's "Hishiplate 101 Series Heat-Resistant Grade," made of post-chlorinated polyvinyl chloride resin (CPVC) (average degree of polymerization 700, chlorination rate (average chlorine content) 67%), 5mm thick. • PVDF plate: Made of polyvinylidene fluoride (PVDF), 3mm thick

[0062] The above PVDF plate, the above adhesive layer forming sheet, and the above heat-resistant PVC plate were stacked in that order, and this laminate was sandwiched between upper and lower press plates and heat-pressed at 190°C for 20 minutes at a pressure of 3 MPa to produce a laminate (sample).

[0063] The obtained laminate (sample) was subjected to shear peel strength measurement and tensile testing in the same manner as in Example 1.

[0064] <Comparative Example 1> (Formation of adhesive layer sheet) The crushed heat-resistant PVC plate described below and Metabren P1901 (PGMA) were mixed in a ratio of 90 wt% / 10 wt%, kneaded at 190°C for 5 minutes in a Toyo Seiki Lab Plast Mill mixer, and the resulting mixture was placed between upper and lower press plates and hot-pressed at 190°C for 15 minutes to obtain a 0.1 mm thick sheet, which was used to obtain a sheet for forming an adhesive layer.

[0065] (Fabrication of laminates) A laminate was fabricated using the above-mentioned adhesive layer-forming sheet and the following materials. • EFEP plate: Made of tetrafluoroethylene-ethylene-hexafluoropropylene copolymer (EFEP), 3mm thick. • Heat-resistant PVC plate: Mitsubishi Chemical Infratec's "Hishiplate 101 Series Heat-Resistant Grade," made of post-chlorinated polyvinyl chloride resin (CPVC) (average degree of polymerization 700, chlorination rate (average chlorine content) 67%), 5mm thick.

[0066] The above EFEP plate, the above adhesive layer forming sheet, and the above heat-resistant PVC plate were stacked in that order, and this laminate was sandwiched between upper and lower press plates and hot-pressed at 190°C for 20 minutes at a pressure of 3 MPa to produce a laminate (sample).

[0067] The obtained laminate (sample) was subjected to shear peel strength measurement in the same manner as in Example 1.

[0068] <Comparative Example 2> The pulverized PVDF plate and Metabrene P1901 (PGMA) were mixed in a ratio of 90 wt% / 10 wt%, kneaded at 190°C for 5 minutes in a Toyo Seiki Lab Plast Mill mixer, and the resulting mixture was placed between upper and lower press plates and hot-pressed at 190°C for 15 minutes to obtain a 0.1 mm thick sheet for adhesive layer formation.

[0069] (Fabrication of laminates) A laminate was fabricated using the above-mentioned adhesive layer-forming sheet and the following materials. • Heat-resistant PVC plate: Mitsubishi Chemical Infratec's "Hishiplate 101 Series Heat-Resistant Grade," made of post-chlorinated polyvinyl chloride resin (CPVC) (average degree of polymerization 700, chlorination rate (average chlorine content) 67%), 5mm thick. • PVDF plate: Made of polyvinylidene fluoride (PVDF), 3mm thick

[0070] The above PVDF plate, the above adhesive layer forming sheet, and the above heat-resistant PVC plate were stacked in that order, and this laminate was sandwiched between upper and lower press plates and heat-pressed at 190°C for 20 minutes at a pressure of 3 MPa to produce a laminate (sample).

[0071] The obtained laminate (sample) was subjected to shear peel strength measurement in the same manner as in Example 1.

[0072] <Comparative Example 3> (Formation of adhesive layer sheet) The BASF BONDFAST E (E-GMA) shown below was placed between upper and lower press plates and hot-pressed at 190°C for 15 minutes to obtain a 0.1 mm thick sheet for adhesive layer formation. • BASF Bondfaster E (E-GMA): Ethylene-glycidyl methacrylate copolymer, glycidyl methacrylate (GMA) 12 wt%

[0073] (Fabrication of laminates) A laminate was fabricated using the above-mentioned adhesive layer-forming sheet and the following materials. • PTFE plate: PTFE sheet manufactured by Yodogawa Hutech Co., Ltd., made of PTFE, 3mm thick • Heat-resistant PVC plate: Mitsubishi Chemical Infratec's "Hishiplate 101 Series Heat-Resistant Grade," made of post-chlorinated polyvinyl chloride resin (CPVC) (average degree of polymerization 700, chlorination rate (average chlorine content) 67%), 5mm thick.

[0074] The above PTFE plate, the above adhesive layer forming sheet, and the above heat-resistant PVC plate were stacked in that order, and this laminate was sandwiched between upper and lower press plates and heat-pressed at 190°C for 20 minutes at a pressure of 3 MPa to produce a laminate (sample).

[0075] The obtained laminate (sample) was subjected to shear peel strength measurement in the same manner as in Example 1.

[0076] <Comparative Example 4> Except for replacing BASF's BONDFAST E (E-GMA) in Comparative Example 3 with BASF's BONDFAST 7M, adhesive layer-forming sheets and laminates were prepared in the same manner as in Comparative Example 3, and shear peel strength measurements were performed. • BASF Bondfaster 7M: GMA-MA copolymer (methyl methacrylate), 6 wt% glycidyl methacrylate (GMA), 27 wt% methyl acrylate (MA)

[0077] <Comparative Example 5> (Formation of adhesive layer sheet) Except for mixing Metabrene P1901 (PGMA) and BASF BondfAST 7B (GMA-VA copolymer) in a ratio of 75 wt% / 25 wt%, a sheet for forming an adhesive layer and a laminate were prepared in the same manner as in Example 1, and the shear peel strength was measured.

[0078] [Table 1]

[0079] (Consideration) Based on the results of the above examples and comparative examples, as well as the test results conducted by the inventors to date, it has been found that, with respect to a laminate comprising a fluororesin layer, an adhesive layer, and a vinyl chloride resin layer, the peel strength between the fluororesin layer and the vinyl chloride resin layer can be increased by including PGMA in the adhesive layer and setting the PGMA content ratio to 20-60% by mass relative to 100% by mass of the resin constituting the adhesive layer. Furthermore, it was found that by including fluororesin, particularly fluororesin which is the main component resin of the fluororesin layer, and / or vinyl chloride resin, particularly vinyl chloride resin which is the main component resin of the vinyl chloride layer, in the adhesive layer along with PGMA, the delamination strength between the fluororesin layer and the vinyl chloride resin layer can be further increased.

[0080] <Example 4> Using the PVDF plate used in Example 3, the adhesive layer forming sheet described above, and the PVDF plate, a laminate (sample) was prepared as follows. The above PVDF plate, adhesive layer forming sheet, heat-resistant PVC plate, adhesive layer forming sheet, and PVDF plate were stacked in that order, and this laminate was sandwiched between upper and lower press plates and hot-pressed at 190°C for 20 minutes at a pressure of 3 MPa to produce a laminate (sample).

[0081] <Warpage Measurement> The laminates (samples) prepared in Examples 3 and 4 were placed on a flat surface, and one end was fixed to the surface. The distance between the other end and the surface was measured and judged according to the following criteria. Passing: Less than 2mm Fail: 2mm or more

[0082] As a result, the laminate (sample) prepared in Example 4 passed the test, but the laminate (sample) prepared in Example 3 failed. From this, it was found that, from the viewpoint of preventing warping, it is preferable for the thickness of each layer to be symmetrical in the thickness direction, that is, for the laminated structure to be such that layers of the same thickness are sequentially stacked on both sides in the thickness direction from the center or the central layer. [Explanation of Symbols]

[0083] 1. Fluororesin layer 2. Polyvinyl chloride resin layer 3 Adhesive layer L Bonding length 10. Grip section of tensile testing machine 11 backing plate

Claims

1. A laminate comprising a fluororesin layer with fluororesin as the main component resin, an adhesive layer, and a vinyl chloride resin layer with vinyl chloride resin as the main component resin, A laminate in which the adhesive layer contains polyglycidyl methacrylate (PGMA), and the PGMA content is 20 to 60% by mass relative to 100% by mass of the resin constituting the adhesive layer.

2. The laminate according to claim 1, wherein the adhesive layer contains, in addition to PGMA, at least one of the fluororesin which is the main component resin of the fluororesin layer and the vinyl chloride resin which is the main component resin of the vinyl chloride resin layer.

3. The laminate according to claim 1, wherein the adhesive layer contains, in addition to PGMA, both a fluororesin which is the main component resin of the fluororesin layer and a vinyl chloride resin which is the main component resin of the vinyl chloride resin layer.

4. The laminate according to claim 1, comprising a laminated structure of fluororesin layer / adhesive layer / vinyl chloride resin layer / adhesive layer / fluororesin layer, wherein the thickness of each layer is symmetrical in the thickness direction.

5. The laminate according to claim 1, wherein the fluororesin is at least one of polytetrafluoroethylene (PTFE), tetrafluoroethylene-ethylene-hexafluoropropylene copolymer (EFEP), and polyvinylidene fluoride (PVDF).

6. The laminate according to claim 1, wherein the vinyl chloride resin is a post-chlorinated vinyl chloride resin with a chlorination rate of 60 to 72%.

Images