JP2019043134A - Non-adhesive sheet - Google Patents

Abstract

To have satisfactory peel strength between a fluororesin layer and a base material layer and sustain an effect by the fluorine layer, in a laminate of the fluororesin layer and the base material layer.SOLUTION: There are provided: a non-adhesive sheet that is a laminate formed by joining a resin sheet containing polytetrafluoroethylene as a resin component and a base material sheet, where a peel strength of the resin sheet and the base material sheet is 3 N/mm or more; and a method for producing a non-adhesive member of installing the non-adhesive sheet onto a surface of a member and covering at least a part of the member with the non-adhesive sheet; and a surface modification method of the member.SELECTED DRAWING: None

Description

  The present invention relates to a non-adhesive sheet. The present invention also relates to various devices or tools provided with the non-adhesive sheet, and vehicles equipped with the devices or tools.

  For example, in the case of transporting raw materials and the like, hoppers, buckets, vehicle loading platforms and the like (hereinafter referred to as "hoppers and the like") provided in the transport machine Raw materials and the like may adhere to the surface of the hopper and the like while the feeding operation is repeated, and the like. If such a raw material or the like adheres to the hopper, the raw material or the like becomes difficult to be discharged from the discharge port of the hopper, and it may be necessary to forcibly deliver the raw material or the like by a machine or the like. If raw materials etc. adhere to a bucket or a vehicle loading platform, since raw materials etc. accumulate, work efficiency may fall. In addition, buckets of construction machines may have sticking excavates attached to their surfaces during repeated drilling operations.

  In addition, for example, in various devices or tools for snowfall applications and vehicles equipped with the devices or tools (hereinafter sometimes referred to as “snow devices etc.”), snow removal devices, snow removal tools when removing snowfall When snow adheres to the surface of a member constituting the side in contact with snow, such as a car body, the amount of adhesion increases with the continuation of the snow removal operation, and the efficiency of the snow removal operation decreases. In these snow removal vehicles and general vehicles, if the vehicle travels with snow or ice, the fuel efficiency may deteriorate, or snow or ice lumps may fall during traveling, damaging the vehicle body and the like. In addition, it is necessary to remove the lump regularly to suppress the damage.

  As measures to remedy these problems, the surface of the material such as the hopper, the surface of the member that contacts the excavated object, etc., or the surface of the member that constitutes the snowfall area of snow or ice is coated with a fluorine resin or covered with a fluorine resin layer. And the like have been proposed (patent documents 1 to 4).

  Moreover, various techniques regarding the laminated body which provided the fluorine-type resin layer in the surface of the base material are proposed (patent documents 5-7).

Japanese Utility Model Publication No. 63-22865 Japanese Utility Model Publication No. 52-44601 JP 10-181417 A JP 2008-57275 A Japanese Patent No. 5884358 Patent No. 4244286 Patent No. 6149739 gazette

For example, although the invention described in Patent Documents 1 to 4 can be applied to the hopper, bucket, vehicle bed, etc., various devices or tools for snow use, or vehicles equipped with these, certain effects can be obtained. There is room for improvement. The hoppers and the like and the snowfall devices and the like are required to be durable because they are used continuously or continuously. Fluororesins, particularly polytetrafluoroethylene (hereinafter referred to as PTFE), have high non-adhesiveness, so that adhesion of raw materials etc. can be suppressed, but bonding with a member constituting a hopper etc. or a snow sliding device etc. is generally difficult It is. Also, PTFE
Since the coating of the above is easy to wear, it needs to have a certain mechanical strength and be able to ensure a certain thickness. That is, it is required that the coating or the like of the fluorine resin does not easily peel off and the effect can be sustained. Furthermore, since the coating process requires large-scale equipment, there has been a problem that these apparatuses or tools have to be brought in to the factory where the coating process can be performed.

  Patent Document 1 discloses a hopper for a tacking machine in which a thick deep drawn container made of polytetrafluoroethylene resin (PTFE) is attached to a main body. However, it is a silicone adhesive that is used for sticking, and in view of the non-stickiness of the tetrafluoroethylene resin, the peel strength is generally low and there is a possibility that the molded container may be easily peeled off from the main body high. In addition, it is considered that the manufacturing cost is high for the deep draw formed container made of tetrafluoroethylene resin described in Patent Document 1. Patent Document 2 discloses a bucket apparatus in which an adhesion preventing member is provided at a corner of a bucket body, and a non-adhesive lining made of polytetrafluoroethylene or the like is adhered to the surface of the adhesion preventing member by adhesion or fusion. Although the specific bonding method and lining thickness are not disclosed, the bonding strength is unknown. Patent Document 3 discloses a loading platform structure of a vehicle with a slope loading platform in which a plate made of fluorocarbon resin is attached to a loading floor made of aluminum or the like, but using rivets or screws for attachment of both. There is no disclosure. Moreover, in such a deposition method, the peel strength of the portion not fixed by the rivet or the like is 0 N / mm, and there is a possibility that the portion may be easily broken in the vicinity of the portion fixed by the rivet and the other portion. Although the front work tool of the snow removal work machine by which the work surface was coated with fluorine is disclosed by patent document 4, it does not disclose about the specific coating method, and the continuity of the intensity | strength and effect is unknown. .

  Further, Patent Document 5 discloses a method for producing a laminate having a step of laminating a resin sheet made of modified PTFE and a metal layer and performing heat pressing. However, joining undenatured PTFE to a metal layer is not disclosed. Further, the bonding strength between the resin sheet made of modified PTFE and the metal layer is about 20 N / 3 inch, which is not sufficient. Patent Document 6 discloses a laminate in which a fluorine resin film layer and a metal plate are laminated via a specific ethylene copolymer composition layer. However, in the examples, the adhesive strength with a film of ethylene tetrafluoroethylene copolymer which is less non-tacky than PTFE is at most about 2 N / mm (converted value) in the 180 ° C. peel test, which is sufficient. It can not be said. Patent Document 7 discloses a laminate in which a specific primer layer and a top coat layer made of a fluorine resin are laminated in this order on the surface of a substrate. However, it is not disclosed that the topcoat layer is a sheet, and there is a limit in increasing the thickness of the topcoat layer and maintaining its effect as a hopper or the like and a snow-sliding application.

  As described above, Patent Documents 1 to 4 disclose that in a non-adhesive sheet for hoppers, buckets, vehicle loading platforms or sliding snow, forming a fluorocarbon resin layer such as PTFE on the surface of a base material However, the peel strength of the two is not considered at all or there is room for improvement. Moreover, although the laminated body which provided the fluorine resin layer in the base-material surface is disclosed by patent documents 5-7, in the invention of patent documents 5 and 6, peel strength is still insufficient again, and patent documents In the invention described in 7, there is a limit to sustaining the effect of the top coat layer made of fluorocarbon resin.

  Therefore, an object of the present invention is to make the peel strength between the fluorocarbon resin layer and the base material layer good in the laminate of the fluorocarbon resin layer and the base material layer, and to make the effect of the fluorocarbon resin layer sustainable.

As a result of intensive investigations conducted by the present inventor, a resin sheet whose resin component is PTFE is used as the fluorine resin layer, and a base material sheet is used as the base material layer, so that the peel strength of both may be a predetermined value or more. By joining, it discovers that the above-mentioned subject is solvable, and came to complete this invention. The gist of the present invention is as follows.

  The first of the present invention is a laminate in which a resin sheet having a resin component of polytetrafluoroethylene and a substrate sheet are joined, and the peel strength between the resin sheet and the substrate sheet is 3 N / mm or more. It relates to a non-adhesive sheet. In the embodiment of the non-adhesive sheet, the thickness of the resin sheet may be 0.5 mm or more. Moreover, when a non-adhesive sheet is installed in the surface of a predetermined member, the fixing | fixed part for fixing to the member may be formed in the base material sheet. In addition, the resin sheet and the base sheet may be bonded via an adhesive, and in this case, the adhesive may be an adhesive fluorine-containing copolymer.

  The second of the present invention relates to a hopper provided so that the resin sheet side of the above-mentioned non-adhesive sheet becomes a sliding face.

  The third of the present invention relates to a vehicle equipped with a snow removal device or a snow removal tool, provided such that the resin sheet side of the non-adhesive sheet described above is the snow-covered side.

  A fourth aspect of the present invention is a method for producing a resin sheet having a thickness of 0.5 mm or more among the above-mentioned non-adhesive sheets, wherein a resin sheet having a thickness of 0.5 mm or more formed in advance, and a substrate The present invention relates to a method for producing a non-adhesive sheet, including the step of bonding a sheet with a peel strength of 3 N / mm or more.

  The fifth of the present invention is non-adhesiveness with non-adhesiveness on the surface, in which the above-mentioned non-adhesive sheet is placed on the surface of the member according to the shape to cover at least a part of the surface. The present invention relates to a method of manufacturing a member. In the embodiment of the manufacturing method, the base sheet of the non-adhesive sheet can be fixed to the member to cover at least a part of the surface of the member. In this case, the fixing of the base sheet to the member may be at least one selected from welding, bonding with an adhesive, and physical bonding.

  According to a sixth aspect of the present invention, a non-adhesive sheet as described above is disposed on the surface of a member in accordance with the shape thereof to cover at least a part of the surface and to impart non-adhesiveness to the surface. The present invention relates to a surface modification method. In the embodiment of the surface modification method, the base sheet of the non-adhesive sheet can be fixed to the member to cover at least a part of the surface of the member. In this case, the fixing of the base sheet to the member may be at least one selected from welding, bonding with an adhesive, and physical bonding.

  According to the present invention, a non-adhesive sheet having good peel strength between the resin sheet having a resin component of PTFE and the base sheet and good retention of the adhesive strength of the resin sheet based on PTFE. Can be provided. Therefore, the non-adhesive sheet is suitable for, for example, a hopper, a snow removal device, or a vehicle provided with a snow removal tool.

  Hereinafter, embodiments of the present invention will be described.

  In the embodiment of the present invention, the non-adhesive sheet is a laminate in which a resin sheet whose resin component is PTFE and a base sheet are joined. And the peeling strength of the joined resin sheet and a base material sheet is 3 N / mm or more. In the following, unless otherwise specified, a resin sheet in which the resin component is PTFE is referred to as a PTFE sheet. In the following, unless stated otherwise, although non-adhesive sheets for hoppers, buckets, vehicle loading platforms or snow slides are mainly described, they can be applied to other various uses as described later.

  As described above, since the peel strength between the PTFE sheet and the base sheet is equal to or greater than the predetermined value, the PTFE sheet is used, for example, for a hopper, a bucket, a vehicle bed or a sliding snow, etc. Are well bonded to the substrate sheet. Further, as described later, for example, since it is possible to bend the non-adhesive sheet without peeling off the PTFE sheet from the base sheet, depending on the constituent material of the base sheet, desired sites for various uses It is possible to process according to the shape of and install. Moreover, since lamination is performed using a PTFE sheet formed in advance, it is possible to increase the thickness as compared with the case where the powder of PTFE is sintered on the surface of the base sheet as described in, for example, Patent Document 7 It is. In addition, the PTFE sheet is superior in mechanical strength to the coating. Therefore, it is possible to maintain the effect by the PTFE sheet better than such conventional techniques. Furthermore, non-adhesiveness can be easily imparted to the sliding surface simply by installing the non-adhesive sheet on the sliding surface of the hopper or the like or the snow-covered member according to the shape. Therefore, for example, installation of a non-adhesive sheet on an existing machine or the like is easy, and when the non-adhesiveness decreases after long-term use, the non-adhesive sheet is replaced to change the original non-adhesive on the sliding surface. It can be easily given.

  The PTFE sheet is molded using PTFE as a resin component.

  PTFE exhibits excellent chemical resistance, shows no dissolution or swelling with almost all chemicals, and exhibits excellent stability only by being attacked by molten metal sodium or high temperature high concentration fluorine gas. It has excellent heat resistance, a melting point of about 327 ° C., a continuous use temperature of about 260 ° C., which is extremely high in organic materials, and mechanical strength hardly decreases even when left at 250 ° C. for a long time. Furthermore, its surface properties show excellent hydrophobicity, oleophobicity and non-stickiness.

  As described above, PTFE is excellent in chemical resistance and heat resistance and is high in hydrophobicity, oleophobicity and non-adhesiveness. Therefore, for example, PTFE sheets are used as raw materials in applications such as hoppers and applications such as snowfalls, By being provided on the surface in contact with snow and ice, the PTFE sheet becomes a sliding surface, and their slidability becomes good, and the adhering matter on the sliding surface falls etc. Adhesion to the moving surface, survival can be suppressed.

  The PTFE sheet is previously formed into a sheet shape. Since PTFE only gels upon heating and does not exhibit fluidity, it is not easy for general injection molding and extrusion molding. Therefore, it is formed by, for example, a sintering method or a paste extrusion method. Known methods can be adopted as these methods. In the sintering method, for example, a powder of PTFE is placed in a mold and pressurized, and firing is performed at a temperature equal to or higher than the melting point of PTFE. If necessary, it may be transferred to another mold immediately after being in the form of a clear gel and subjected to secondary forming. Further, after molding, machining may be performed to obtain a desired shape. In the paste extrusion method, an organic solvent or the like is added to the PTFE powder to make it into a paste, and after it is made into a sheet by a calender, the solvent is volatilized and then firing is performed. As a method other than the sintering method and the paste extrusion method, for example, a cylindrical or prismatic molded body is cut into a sheet, or a suspension of PTFE is cast on a flat surface and then sintered to form a sheet. Methods etc.

  The thickness of the PTFE sheet can be set in consideration of each application. From the viewpoint of continuously obtaining various effects such as abrasion resistance and durability by the above-mentioned PTFE, 0.3 mm or more is preferable, 0.5 mm or more is more preferable, 1 mm or more is more preferable, and 3 mm or more is particularly preferable.

  The resin component of the PTFE sheet is PTFE, but other additives may be added in addition to the resin component. As an additive, a coloring agent, a reinforcing material, a lubricity imparting material etc. are mentioned, for example.

  As a material which comprises a substrate sheet, it can be suitably selected, for example according to each use of a hopper etc., a snow-sliding application, etc. Examples of such a material include metals such as iron, steel, aluminum, copper, gold and silver, ceramic, glass, synthetic resin, natural resin, wood, paper, diamond and the like. The steel may be an alloy of iron containing 2.0% or less of carbon and other elements, and examples thereof include stainless steel and the like. Synthetic resins include fiber reinforced resins such as carbon fiber reinforced resins and glass fiber reinforced resins. Among them, stainless steel, aluminum and iron are preferable in view of corrosion resistance, weight and versatility.

  The thickness of the substrate sheet can be set in consideration of the respective applications and constituent materials. As described later, when using a non-adhesive sheet by bending or the like, the thickness can be determined according to the characteristics of the constituent material of the base sheet. When the constituent material is metal, for example, it can be 0.1 to 5.0 mm.

  The base sheet is provided with a fixing portion for fixing the non-adhesive sheet to, for example, the surface of a member constituting a hopper, a bucket, a vehicle loading platform or the like, or a member constituting a snowfall location. It may be done. By forming the fixing portion, the non-adhesive sheet can be easily fixed in a short time to a hopper or the like or a member constituting a snow-covered place without coating treatment or the like. Therefore, for example, a sliding surface or the like to which non-adhesiveness is imparted to a machine provided with an existing hopper or the like, a snow removal device and a snow removal tool having members constituting existing snow locations, a machine equipped with these, The surface of the member can be easily formed in a short time. That is, for example, the hopper, the bucket, the vehicle bed, etc., and the members that constitute the snow-covered area are often relatively large members, so they are difficult to carry, but by adopting the configuration described above, It is possible to install easily in a short time regardless of the location without using a large-scale coating equipment. As such a fixing portion, for example, a through hole for fixing to a hopper or a member constituting a snow spot with a bolt, a nut, a rivet or the like, a female screw hole screwed with an external screw, a hopper or the like Such as a clip for holding a predetermined part such as a member constituting a part, a hopper, etc., a projection receiving member engaged with and engaged with a projection provided on a predetermined part such as a member constituting a snow covered part, a hopper A fitting structure or the like which is fitted and fixed in a recess provided in a predetermined part such as a member constituting a snow cover, a permanent magnet fixed to a substrate sheet, an electromagnet or a magnetic body (these are various members and bases The material sheet is selected depending on whether or not it is a magnetic body, and those employed in physical bonding such as various members and non-adhesive sheets are fixed by the interaction between the magnet and the magnetic body. Such a fixing portion can be provided at one or two or more places depending on the application and the like. The installation position of the fixing portion can also be determined according to the application and the like. Moreover, these various fixing | fixed parts may be combined and employ | adopted.

  Thus, although a fixing | fixed part may be provided in a base material sheet, when the material which comprises a base material sheet can be welded, a non-adhesive sheet can be a hopper etc. or a snowfall location by welding a base material sheet. You may fix to the member etc. which comprise these. In this case, it is preferable to select the shape of the substrate sheet in consideration of the fixing site or to control the output of the welding apparatus so that the PTFE sheet is not excessively heated. In addition, an adhesive may be used to fix the non-adhesive sheet to a hopper or the like, or a member or the like that constitutes a snowfall location. As described above, a welded portion (welded surface) of the non-adhesive sheet or an adhesive surface coated with an adhesive may be used as the joint portion.

  The peel strength between the PTFE sheet and the base sheet is 3 N / mm or more. There is no particular upper limit to the peel strength, as it is generally better. Such peel strength can be measured, for example, by the peel strength test of the adhesive tape-adhesive sheet test method. The test conditions at that time can be performed according to JIS Z 0237. In the present invention, the peel strength is a value obtained by dividing the measured value by the width of the test piece.

There is no particular limitation on the method of bonding the PTFE sheet and the base sheet so as to have such peel strength, for example, a method of surface-treating the bonding surface of both sheets and then crimping the both, via an adhesive The method of joining etc. are mentioned. As the adhesive, it is preferable to use one having affinity to both the base sheet and the PTFE sheet. By using such an adhesive, surface treatment of both sheets can be omitted. Moreover, it is preferable that the whole joining surface of the PTFE sheet is joined to the base sheet.

  As described above, the PTFE sheet has excellent non-stickiness and tends to be difficult to bond, so it is preferable to select an adhesive having good affinity to PTFE. As such an adhesive, an adhesive fluorine-containing copolymer can be illustrated. Examples of the adhesive fluorine-containing copolymer include those described in Japanese Patent No. 4424246, Japanese Patent No. 536539, and Japanese Patent No. 5263269. These adhesive fluorine-containing copolymers are shown below.

  The adhesive fluorine-containing copolymer has a repeating unit (a) based on tetrafluoroethylene (hereinafter referred to as TFE) and / or chlorotrifluoroethylene (hereinafter referred to as CTFE), and a dicarboxylic acid anhydride group and The repeating unit (b) and other monomers based on a cyclic hydrocarbon monomer having a polymerizable unsaturated group in the ring (but excluding the monomer when overlapping with repeating units (a) and (b)) And the repeating unit (c).

  In the adhesive fluorine-containing copolymer, the repeating unit (a) is 50 to 99.89% by mole based on the total molar amount of the repeating unit (a), the repeating unit (b) and the repeating unit (c), The repeating unit (b) is 0.01 to 5 mol%, and the repeating unit (c) is 0.1 to 49.99 mol%. The repeating unit (a) is preferably 50 to 99.47 mol%, the repeating unit (b) is 0.03 to 3 mol%, and the repeating unit (c) is preferably 0.5 to 49.97 mol%, more preferably Is 50 to 98.95 mol% of the repeating unit (a), 0.05 to 2 mol% of the repeating unit (b), and 1 to 49.95 mol% of the repeating unit (c). When the mole percentage of the repeating unit (a), the repeating unit (b) and the repeating unit (c) is in this range, the adhesive fluorine-containing copolymer is excellent in heat resistance and chemical resistance. Furthermore, when the molar percentage of the repeating unit (b) is in this range, the adhesive fluorine-containing copolymer is a substrate sheet and a PTFE sheet of constituent materials such as thermoplastic resins other than the adhesive fluorine-containing copolymer. Excellent adhesion to When the molar percentage of the repeating unit (c) is in this range, the adhesive fluorine-containing copolymer is excellent in moldability and mechanical properties such as stress crack resistance.

  The “cyclic hydrocarbon monomer having a dicarboxylic acid anhydride group and having a polymerizable unsaturated group in the ring” (hereinafter simply referred to simply as “cyclic hydrocarbon monomer”) has one or more 5-membered rings or 6 It is a cyclic hydrocarbon comprising a member ring, and further a polymerizable compound having a dicarboxylic acid anhydride group and an endocyclic polymerizable unsaturated group. The cyclic hydrocarbon is preferably a cyclic hydrocarbon having one or more bridged polycyclic hydrocarbons. That is, a cyclic hydrocarbon comprising a bridged polycyclic hydrocarbon, a cyclic hydrocarbon formed by condensation of two or more of the bridged polycyclic hydrocarbon, or a cyclic hydrocarbon formed by condensation of a bridged polycyclic hydrocarbon and another cyclic hydrocarbon Is preferred. Further, this cyclic hydrocarbon monomer has one or more endocyclic polymerizable unsaturated groups, that is, polymerizable unsaturated groups present between carbon atoms constituting the hydrocarbon ring. The cyclic hydrocarbon monomer further has a dicarboxylic acid anhydride group (-CO-O-CO-), and the dicarboxylic acid anhydride group may be bonded to two carbon atoms constituting the hydrocarbon ring, It may be bonded to the other two carbon atoms. Preferably, the dicarboxylic acid anhydride group is a carbon atom constituting the ring of the cyclic hydrocarbon and is bonded to two adjacent carbon atoms. Furthermore, in place of a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, or another substituent may be bonded to a carbon atom constituting a ring of a cyclic hydrocarbon.

  As the specific example, it is represented by Formula (1)-(8). Here, R in the formulas (2) and (5) to (8) is a lower alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a halogen atom selected from a bromine atom and an iodine atom, and the lower The hydrogen atom in an alkyl group shows the halogenated alkyl group substituted by the halogen atom.

  As the above-mentioned cyclic hydrocarbon monomer, 5-norbornene-2,3-dicarboxylic acid anhydride (hereinafter referred to as NAH) represented by the formula (1), preferably a table of the formulas (3) and (4) The cyclic hydrocarbon monomer which is an acid anhydride, and the cyclic hydrocarbon monomer whose substituent R is a methyl group in the formulas (2) and (5) to (8). More preferably, it is NAH.

As other monomers, vinyl fluoride, vinylidene fluoride (hereinafter referred to as VdF), CTFE (except when used as a repeating unit (a)), trifluoroethylene, hexafluoropropylene (hereinafter referred to as, HFP.), CF ₂ CCFOR ^{f 1} (where R ^f 1 is a perfluoroalkyl group having 1 to 10 carbon atoms and optionally containing an oxygen atom between carbon atoms), CF ₂ CCFOR ^f ₂ SO ₂ X ¹ (R ^f2 is a perfluoroalkylene group having 1 to 10 carbon atoms and may contain an oxygen atom between carbon atoms, X ¹ is a halogen atom or a hydroxyl group), CF ₂ CCFOR ^f ₂ CO ₂ X ² (wherein R ^f2 is the same as above) the same, ^{X 2} is an alkyl group having 1 to 3 carbon hydrogen atom or a _{C.), CF 2 = CF (} CF 2) p OCF = CF 2 ( wherein, p 1 or ^{_{2.), CH 2 = CX}} 3 (CF 2) q X 4 ( wherein, ^{X 3} and ^{X 4} are each independently a hydrogen atom or a fluorine atom, q is 2 to 10 integers.), Perfluoro ( 2-methylene-4-methyl-1,3-dioxolane), olefins having 2 to 4 carbon atoms such as ethylene, propylene and isobutene, vinyl esters such as vinyl acetate, and vinyl ethers such as ethyl vinyl ether and cyclohexyl vinyl ether. The other monomers may be used alone or in combination of two or more.

As a specific example of CF ₂ = CFOR ^{f 1} , for example, CF ₂ = CFOCF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₂ CF ₃ , CF ₂ = CFO (CF _{2 8} F etc. may be mentioned. _Preferably, a _{CF 2 = CFOCF 2 CF 2 CF} 3.

^{_{CH 2 = CX 3 (CF 2}} ) Examples of q ^{X 4} may, for _{example, CH 2 = CH (CF 2} ) 2 F, CH 2 = CH (CF 2) 3 F, CH 2 = CH (CF 2) ₄ F, CH ₂ CFCF (CF ₂ ) ₃ H, CH ₂ CFCF (CF ₂ ) ₄ H, and the like. Preferably, CH ₂ CHCH (CF ₂ ) ₄ F or CH ₂ CHCH (CF ₂ ) ₂ F.

Other monomers, preferably, VdF, HFP, CTFE (excluding, however, the case where they are used as a repeating unit ^{_{(a).), CF 2}} = CFOR f1, CH 2 = CX 3 (CF 2) q X 4 At least one member selected from the group consisting of ethylene, propylene and vinyl acetate, more preferably HFP, CTFE (except when used as a repeating unit (a)), CF ₂ = CFOR ^{f 1} , It is at least one selected from the group consisting of ethylene and CH ₂ = CX ³ (CF ₂ ) _q X ⁴ . Most preferably, HFP or CF ₂ = CFOR ^f1 . _As the CF 2 = CFOR ^f1, preferably ^{R f1} is perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 2 to 4 carbon atoms, perfluoropropyl group is most preferred.

Specific examples of the adhesive fluorine-containing copolymer include, for example, TFE / CF ₂ CCFOCF ₂ CF ₂ CF ₃ / NAH copolymer, TFE / HFP / NAH copolymer, TFE / CF ₂ CCFOCF ₂ CF ₂ CF ₃ / HFP / NAH copolymer, TFE / VdF / NAH copolymer, TFE / CH ₂ CHCH (CF ₂ ) ₄ F / NAH / ethylene copolymer, TFE / CH ₂ CHCH (CF ₂ ) ₂ F / NAH / ethylene copolymer, CTFE / CH ₂ CHCH (CF ₂ ) ₄ F / NAH / ethylene copolymer, CTFE / CH ₂ CHCH (CF ₂ ) ₂ F / NAH / ethylene copolymer, CTFE / CH ₂ CHCH (CF ₂ ) ₂ F / NAH / ethylene copolymer and the like.

  150-320 degreeC is preferable and, as for melting | fusing point of an adhesive fluorine-containing copolymer, 200-310 degreeC is more preferable. The melting point can be adjusted by appropriately selecting the content ratio of the repeating unit (a), the repeating unit (b) and the repeating unit (c) within the above range.

  An adhesive fluorine-containing fluorine-containing copolymer having an adhesive functional group such as an ester group, a carbonate group, a hydroxyl group, a carboxyl group, a carbonyl fluoride group or an acid anhydride residue as a polymer terminal group of the adhesive fluorine-containing copolymer It is preferable because it is excellent in adhesion to a substrate sheet of a constituent material such as a thermoplastic resin other than a copolymer and a PTFE sheet. The polymer terminal group having the adhesive functional group can be introduced by appropriately selecting a radical polymerization initiator, a chain transfer agent, and the like at the time of production of the adhesive fluorocopolymer.

The adhesive fluorine-containing copolymer can have a volumetric flow rate (hereinafter referred to as Q value) of 0.1 to 1000 mm ³ / sec. The Q value is an index that represents the melt flowability of the adhesive fluorine-containing copolymer, and is an index of the molecular weight. The larger the Q value, the lower the molecular weight, and the smaller the Q value, the higher the molecular weight. Q value is adhesion when extruded into an orifice with a diameter of 2.1 mm and a length of 8 mm under a load of 7 kg at a temperature 50 ° C. higher than the melting point of the adhesive fluorine-containing copolymer using a flow tester made by Shimadzu Corporation Rate of the fluorocarbon copolymer. When the Q value is too small, extrusion molding becomes difficult, and when it is too large, the mechanical strength of the adhesive fluorocopolymer decreases. Q values of the adhesive fluorocopolymer is preferably from 5 to 500 mm ³ / sec, 10 to 200 mm ³ / sec is more preferable.

  The method for producing the adhesive fluorine-containing copolymer is not particularly limited, and a radical polymerization method using a radical polymerization initiator is used. As a polymerization method, bulk polymerization, solution polymerization using an organic solvent such as fluorohydrocarbon, chlorohydrocarbon, fluorochlorohydrocarbon, alcohol, hydrocarbon and the like, an aqueous medium and, if necessary, an appropriate organic solvent are used. Suspension polymerization, emulsion polymerization using an aqueous medium and an emulsifying agent, and solution polymerization is particularly preferable.

As a radical polymerization initiator, the radical polymerization initiator whose temperature whose half life is 10 hours is 0 degreeC-100 degreeC is preferable. More preferably, it is 20-90 ° C. Specific examples thereof include azo compounds such as azobisisobutyronitrile, non-fluorinated diacyl peroxides such as isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, lauroyl peroxide and the like, diisopropyl peroxydicarbonate, di-n-propyl Peroxydicarbonates such as peroxydicarbonate, tert-butylperoxypivalate, tert-butylperoxyisobutyrate, peroxyesters such as tert-butylperoxyacetate, (Z (CF ₂ ) _r COO) ₂ (where Z is Fluorine-containing diacyl peroxides such as a compound represented by a hydrogen atom, a fluorine atom or a chlorine atom, and r is an integer of 1 to 10), potassium persulfate, sodium persulfate, ammonium persulfate and the like Peroxides and the like.

  When controlling the Q value of the adhesive fluorine-containing copolymer, it is also preferable to use a chain transfer agent. Examples of chain transfer agents include alcohols such as methanol and ethanol, chlorofluorohydrocarbons such as 1,3-dichloro-1,1,2,2,3-pentafluoropropane and 1,1-dichloro-1-fluoroethane, Examples thereof include hydrocarbons such as pentane, hexane and cyclohexane. As a chain transfer agent for introducing an adhesive functional group to the polymer terminal of the adhesive fluorine-containing copolymer, acetic acid, acetic anhydride, methyl acetate, ethylene glycol, propylene glycol and the like can be mentioned.

  The polymerization conditions of the adhesive fluorine-containing copolymer are not particularly limited, and the polymerization temperature is preferably 0 to 100 ° C, and more preferably 20 to 90 ° C. The polymerization pressure is preferably 0.1 to 10 MPa, and more preferably 0.5 to 3 MPa. The polymerization time is preferably 1 to 30 hours.

  The concentration of the cyclic hydrocarbon monomer in the polymerization is preferably 0.01 to 5 mol%, more preferably 0.1 to 3 mol%, and most preferably 0.1 to 1 mol% with respect to the total monomers. When the concentration of the cyclic hydrocarbon monomer is too high, the polymerization rate tends to decrease. When it is in the above range, the polymerization rate at the time of production does not decrease, and the fluorine-containing copolymer is excellent in adhesiveness. During the polymerization, as the cyclic hydrocarbon monomer is consumed in the polymerization, it is preferable to continuously or intermittently supply the consumed amount into the polymerization tank to maintain the concentration of the cyclic hydrocarbon monomer in this range.

  The adhesive fluorine-containing copolymer obtained by the production method as described above can be obtained in the form of pellets, powder or other according to a conventional method. Since the adhesive fluorine-containing copolymer is excellent in moldability, it can be injection-molded or extrusion-molded and can be molded into a desired shape. In addition, since the above-mentioned adhesive fluorine copolymer is excellent in flexibility, a sheet molded product using them as an adhesive suppresses peeling of the laminated sheet even if bending or drawing is performed. it can.

  The adhesive fluorine-containing copolymer can be produced as described above, but a commercially available product can be used. For example, EA-2000 manufactured by Asahi Glass Co., Ltd., etc. may be mentioned.

  The form of the adhesive is not particularly limited, and examples thereof include powder, paste, liquid, sheet and the like. When the adhesive is the above-mentioned adhesive fluorine-containing copolymer, a molded article of a sheet can be used.

  When an adhesive is used, the thickness of the adhesive is preferably 5 to 100 μm, and more preferably 25 to 100 μm, from the viewpoint of securing a predetermined peel strength or more, depending on the type.

  The shape of the non-adhesive sheet is not particularly limited, and examples thereof include flat plates, curved plates, and tubes. Further, for example, it is possible to form in advance a shape suitable for various applications such as a hopper and a member constituting a snowfall location and directly use it as a component for each application, and use for a hopper etc. It is also possible to make it the shape which can be installed on the surface of the existing members in contact with snow, ice, such as raw materials, for the purpose of use. Such a shape may be formed by forming the substrate sheet into a desired shape and subjecting it to heat and pressure treatment, or by subjecting a flat non-adhesive sheet to bending or cutting. it can. The hopper and the like and the members and the like constituting the snowfall location may have various shapes according to the request of the customer, so when processing is performed according to the shape, a flat plate may be used. Since the non-adhesive sheet has a peeling strength equal to or higher than a predetermined value, peeling of the PTFE sheet and the base sheet can be suppressed even if bending or drawing processing is performed.

  The method of manufacturing the non-adhesive sheet includes the step of bonding the pre-formed PTFE sheet and the base sheet such that the peel strength between them is 3 N / mm or more. It is as follows when the case where an adhesive agent is used is demonstrated.

  First, a PTFE sheet is formed. Then, an adhesive is disposed between the desired base sheet and the PTFE sheet, and if necessary, surface treatment, heating and pressing of both sheets are performed so that both sheets have a predetermined peel strength. A bonded laminate is obtained. The thickness of the PTFE sheet is preferably 0.5 mm or more.

  When the above-mentioned adhesive fluorine-containing copolymer is used as an adhesive, various forms such as powder, pellet, sheet and the like can be used, but from the viewpoint of control of peeling strength, it is preferable to use a sheet. . The thickness of the sheet is preferably 5 to 100 μm, and more preferably 25 to 100 μm, from the viewpoint of adhesion stability and cost. In addition, as described above, the adhesive fluorine-containing copolymer has a good affinity to the PTFE sheet, so the surface treatment of the PTFE sheet is unnecessary. In addition, since the affinity to metals and organic substances is also good, when the material of the substrate sheet is those, surface treatment is unnecessary. Moreover, it is preferable to heat to the temperature more than the melting | fusing point of PTFE, Preferably, it is 330-400 degreeC, It is more preferable to perform a pressurization process in the state heated at such temperature. The pressure treatment is preferably 0.1 to 10 MPa.

  The non-adhesive sheet described above is provided, for example, on a surface (also referred to as a sliding surface) in contact with raw materials, etc., snow, ice, etc. of a hopper, a bucket, a vehicle loading platform, etc. . Thereby, non-adhesiveness can be provided to each surface (sliding surface). Alternatively, it is possible to manufacture a non-adhesive member in which non-adhesiveness is imparted to the surface (sliding surface) of various members such as a hopper and the like and members forming snowfall places and the like by an adhesive sheet. More specifically, the non-adhesive sheet described above is installed on the surface of various members in accordance with the shape thereof, and at least a part of the surface is covered, for example, the surface that becomes the sliding surface of various members The non-adhesive member to which the non-adhesiveness was provided can be newly manufactured. Alternatively, for example, the surface of various existing members can be rendered non-tacky to modify the surface. At that time, for fixing the non-adhesive sheet to the various members, it is preferable to fix the base sheet of the non-adhesive sheet to the various members. Also, this fixing can be at least one selected from welding, bonding with an adhesive, and physical bonding. Physical bonding can be performed, for example, through the above-described fixing portion provided on the base sheet.

The hopper constitutes an input part for raw materials such as a kneader, a container for mixing and kneading the raw materials of the kneader, and the like (see, for example, Patent Document 1). And the above-mentioned non-adhesive sheet is installed in the part which the raw material contacts of the injection | throwing-in part or a container, and it becomes a sliding surface which a PTFE sheet | seat contacts with a raw material.

  As a raw material to be introduced into the hopper, it is effective for adhesive materials, for example, foods such as butter, salmon, flesh, meat, fish and vegetables, inorganic substances such as sand and iron oxide, pellets and powders of resin, etc. Can be mentioned. PTFE is particularly suitable for food hoppers because it is highly safe for the human body. In addition, since the adhesive fluorine-containing copolymer described above is also highly safe, when it is used as an adhesive, the safety is further improved.

  For the installation of the non-adhesive sheet for hoppers into the hopper, for example, at least a part of the sliding surface by pre- or post-installing the non-adhesive sheet according to the shape on the sliding surface of the hopper which is a member Preferably, it is carried out by coating the whole. In this way, it is possible to modify the sliding surface of the hopper, which is the production or member of the non-adhesive hopper. The hopper generally has a conical, pyramidal, bowl-like shape, etc., and has a shape that tapers downward in the vertical direction. Therefore, for example, in the case of a pyramidal shape, a plurality of strip-like flat non-adhesive sheets are arranged in a tapered manner on the sliding surface of the hopper, and the entire sliding surface is covered without gaps to form a base sheet. The fixing portion can fix the entire sliding surface of the hopper by fixing to the hopper. The shape of each of the plurality of strip-shaped flat plates can be adjusted appropriately in accordance with the pyramidal shape. In the case of a cone, instead of a flat plate, it may be a curved plate subjected to a bending process in the minor axis direction. In the case of the bowl shape, it is preferable to use a curved plate which has been subjected to a bending process in the short axis direction and the long axis direction. Also, for example, the hopper can be manufactured or the sliding surface thereof can be modified by forming the hopper directly so that the PTFE sheet is a sliding surface, using a non-adhesive sheet of substantially the same shape. In this case, it is a matter of course to adjust the non-adhesive sheet so as to have mechanical strength suitable for hopper application.

  A bucket is a container which is provided in construction machines, such as bulldozers and shovels, for loading and transporting excavated materials such as clay and raw materials (see, for example, Patent Document 2). And the above-mentioned non-adhesive sheet is installed in the part which the excavated thing and raw materials of a bucket contact, so that it may become a sliding face which a PTFE sheet contacts with an excavated thing etc. The non-adhesive sheet may be disposed on the entire part in contact with the excavated object or the like, or may be disposed only on a part of the part, for example, the part where the excavated object or the like easily adheres and deposits.

  For the installation of the non-adhesive sheet for bucket on the bucket, for example, at least a part of the sliding surface of the non-adhesive sheet according to the shape is previously or subsequently installed on the sliding surface of the bucket which is a member It is done by coating. This makes it possible to manufacture the non-tacky bucket and modify the sliding surface of the bucket, which is a member. The bucket generally has a structure formed by one curved portion having a substantially U-shaped cross section and flat plate portions provided at both ends in the longitudinal direction. Therefore, for example, when providing a non-adhesive sheet in the curved portion, one non-adhesive sheet in a flat plate may be bent to be installed so as to cover the entire sliding surface of the curved portion of the bucket. The flat plate and / or the non-adhesive sheet of the curved plate may be used to cover all or a part of the sliding surface of the curved portion. For the two flat plate parts of the bucket, place one or more flat non-adhesive sheets on each flat plate part so as to cover all or a part of the sliding surface of the flat plate part of the bucket Can. Moreover, fixation of the non-adhesive sheet to a bucket can be fixed by the above-mentioned fixing | fixed part provided in the base material sheet. Also, for example, by using a non-adhesive sheet having substantially the same shape and forming the sliding surface of the bucket directly so that the PTFE sheet is a sliding surface, the bucket is manufactured or the sliding surface is reformed be able to. In this case, it goes without saying that the non-adhesive sheet is adjusted to have a mechanical strength suitable for a bucket application.

  The vehicle carrier is provided on a dump truck or the like. It is a container which puts and transports excavated things and materials, such as clay, (for example, refer to patent documents 3.). And the above-mentioned non-adhesive sheet is installed in the part which the excavated thing and raw materials of a vehicle loading platform contact, so that a PTFE sheet may come in contact with an excavated thing etc. Such a vehicle loading platform is suitable for use as an inclined loading platform, since an excavated object or the like is slid out from the vehicle loading platform. In addition, since the non-adhesive sheet is formed by joining the PTFE sheet and the base sheet to the vehicle bed, even if the vehicle bed is loaded with a large amount of excavated objects etc., damage to the PTFE sheet is suppressed. can do.

  For the installation of the non-adhesive sheet for vehicle loading platform on the vehicle loading platform, for example, a non-adhesive sheet conforming to the shape is previously or subsequently installed on the sliding surface of the vehicle loading platform which is a member. It is carried out by covering a part, preferably the whole. Then, the non-adhesive sheet described above is installed at a portion of the vehicle bed, in which the excavated object and the like come in contact, with the PTFE sheet as a sliding surface in contact with the excavated object and the like. Thus, it is possible to modify the sliding surface of the vehicle bed, which is a manufacturing or member of the vehicle bed, to which non-adhesiveness is imparted. In general, the vehicle bed has a shape in which the upper surface of the rectangular upper side is open. That is, it has one substantially rectangular bottom portion and four substantially rectangular side portions. Therefore, for example, one or more flat non-adhesive sheets are arranged without gaps in the bottom and side portions of the vehicle bed respectively to cover the sliding surfaces of the bottom and side portions of the vehicle bed. It can be installed. Moreover, fixation of the non-adhesive sheet to a vehicle loading platform can be fixed by the above-mentioned fixing | fixed part provided in the base material sheet. In addition, for example, by using a non-adhesive sheet having substantially the same shape, the sliding surface of the vehicle bed is directly formed so that the PTFE sheet is the sliding surface, thereby manufacturing the vehicle bed or modifying the sliding surface. Can be quality. In this case, it is a matter of course to adjust the non-adhesive sheet so as to have mechanical strength suitable for a vehicle loading platform application.

  A snow removal device or a snow removal tool (including a snow plow of a general train) included in a road or railway vehicle, or a vehicle such as a road or railway vehicle, which constitutes a snow deposition site Body / windows / lights, aircraft, ships, machines for agriculture such as tractors, wall materials for buildings, roofing materials, traffic lights, mountain climbing tools such as eisins, and the like. However, when a non-adhesive sheet is applied to these, it is possible to impart antifouling property from the function of the PTFE sheet in addition to the snow-slide property. For example, in ships, it is possible to impart an adhesion preventing effect to aquatic organisms such as shellfish and algae.

  Among these, for example, a snow removal device or snow removal tool is provided on a snow removal vehicle for roads or railways, a leading vehicle of a general train, etc., and contacts snow on roads or tracks, snowfall, ice, etc. (For example, about the snow removal vehicle for roads, refer patent document 4). In snow removal trains for railroads, for example, members such as snowboards of Russell cars, wings of McGrey cars and Jordan cars, rotors of rotary cars, etc. may be mentioned. Road snow removal vehicles include members such as snow removal trucks and snow removal dozers, front plows (blades) or buckets, snow removal graders blades, rotary snow removal vehicle rotors, and the like. In addition, as a snow deposition site of the snow removal vehicle, a snow removal device, a vehicle body (body) other than the snow removal tool, and the like may be included.

  The non-adhesive sheet described above is installed on the surface of the member constituting the snow contact area as described above, but the sliding surface of the PTFE sheet is in contact with snow or the like.

For the installation of the non-adhesive sheet for snowfall on a member (also referred to as a snow cover member) constituting a snow cover area, for example, a non-adhesive sheet conforming to the shape on the sliding surface of the member constituting a snow cover area It is performed by covering the sliding surface by installing in advance or after. In this way, it is possible to perform the manufacturing of the snow-covered member that is provided with non-adhesiveness and that constitutes the snow-covered part or the modification of the sliding surface of the snow-covered member that constitutes the snow-covered part. At that time, depending on the shape, one or more flat or curved non-adhesive sheets can be used. When two or more non-adhesive sheets are used, they are preferably arranged without gaps. In addition, the curved plate may be previously formed into a curved shape, or may be a flat plate subjected to bending. The non-adhesive sheet can be fixed to the member which comprises a snow covered location by the fixing | fixed part provided in the base material sheet. Also, for example, a snow covering member to which non-adhesiveness is imparted by forming the sliding surface of the snow covering member directly so that the PTFE sheet is a sliding surface using a non-adhesive sheet of substantially the same shape. The sliding surface of the snow-covered member can be modified. In this case, it goes without saying that the non-adhesive sheet is adjusted to have a mechanical strength suitable for the application of the snow-covered member.

  The pressure-sensitive adhesive sheet as described above is applicable to various uses other than the hopper, the bucket, the vehicle bed, and the members constituting the snow cover. And various functions (low friction, antifouling property, non-adhesiveness, heat resistance, chemical resistance, insulation etc.) based on a PTFE sheet can be easily given. The application examples of the pressure-sensitive adhesive sheet are further exemplified as follows, but the invention is not limited thereto and can be applied to the surface of various members which are required to provide various functions based on PTFE sheet. . (A) By applying to the inner wall surface in contact with the raw material of the kneading machine, etc., the screw, the inner wall surface in contact with the raw material of the stirrer, etc. . (A) By applying to the surface of a member (belt or the like) constituting a portion in contact with the article or the like in a conveyor for transporting the article or the like, adhesion of the article can be prevented and contamination by the article or the like can be prevented. . In addition, even when the article exhibits a high temperature, the heat resistance of the PTFE sheet is applicable. (C) By applying to the inner surface of the pipe, it is possible to prevent the adhesion of the passing material passing through the inside of the pipe and to prevent the contamination due to the passing material. In addition, since heat resistance and chemical resistance can be imparted, it is possible to pass high temperature substances, acids, alkalis and the like as passables. Examples of the pipe include a general water channel, a supply pipe for raw materials in a factory, a weir and the like. (D) By applying the present invention to a crushing blade or cutting blade of a crusher or a cutting machine, or an inner wall surface containing a crush object of a crusher or an object to be crushed, adhesion of a processing object or a processed material can be prevented. . In addition, it is possible to suppress the influence of the heat generated at the time of the treatment and the heat of the treatment object and the like. (O) By applying to the surface of a heating appliance such as a rice cooker or a rice cooker, it is possible to prevent adhesion of the object to be heated on the surface and prevent soiling. Moreover, the influence of the heat at the time of heating can be suppressed. The object to be heated may have various chemicals in order to have chemical resistance. (F) It is also possible to apply to packing etc. of the part which a medical fluid, such as a battery, contacts. Good packing performance can be imparted by the chemical resistance and the antifouling property of the PTFE sheet. (K) By using as a washer, insulation can be provided. (G) It can also be applied to the surface in contact with at least the chemical solution of the chemical solution sensor. The chemical resistance of the PTFE sheet makes it possible to apply the chemical solution sensor to various chemical solutions, and the antifouling property of the same sheet prevents adhesion of the chemical solution and facilitates maintenance and management of the chemical solution sensor. Can.

  The non-adhesive sheet described above may be installed on the surface of a hopper or the like, or a member constituting a snow-covered area, for example, and after the effect of the PTFE sheet is reduced, it may be easily regenerated by replacing the non-adhesive sheet. It is possible.

  Hereinafter, based on an example, a detailed embodiment is described.

Example 1
PTFE sheet (manufactured by Starlight Industries, product name # 31000, length 100 mm, width 16 mm, thickness 0.5 mm), base material sheet made of iron (length 100 mm, width 16 mm, thickness 1.0 mm), adhesive Use a sheet of adhesive fluorine-containing copolymer (manufactured by Asahi Glass Co., Ltd., EA-2000, length 30 mm, width 16 mm, thickness 0.05 mm) to match the PTFE sheet with the iron sheet in the length and width direction As shown in FIG. 6A, the adhesive was placed at one end between the two, and placed in a press (a bench test press manufactured by Tester Sangyo Co., Ltd.). The mold temperature was set to 360 ° C., heated and pressurized at 3 MPa for 200 seconds, and then cooled to obtain a non-adhesive sheet in which the PTFE sheet and the base sheet were joined. The obtained non-adhesive sheet was used for the peeling test.

(Examples 2 to 4)
A non-adhesive sheet was obtained in the same manner as in Example 1 except that a sheet of the material shown in Table 1 was used instead of the iron sheet. In Table 1, "SUS" is a sheet of stainless steel of SUS304 of JIS G4304, "aluminum" is a sheet of aluminum of alloy symbol A5052 of JIS H4000, and "copper" is an alloy of JIS H3100. It means that a copper sheet of symbol C1100 is used. The dimensions of the substrate sheet were the same as in Example 1.

(Comparative example 1)
Cellophane tape using a cellophane tape (made by Nichiban Co., Ltd., Cellotape (registered trademark) No. 405 (for industrial use), width 10 mm) and using the same stainless steel sheet as in Example 2 as a substrate sheet Were attached to a stainless steel sheet to prepare a laminate of cellophane tape and a stainless steel sheet. The resulting laminate was used for the peel test. In Table 1, the column of the resin sheet was shown as "cellophane".

(Comparative example 2)
As a resin sheet, a PFA tape (made by Chuko Kasei Kogyo Co., Ltd., Chuko Flow adhesive tape, AFA-113A, width 25 mm) is used, and as a base sheet, a stainless steel sheet made of the same stainless steel as in Example 2 is used. It was stuck to a stainless steel sheet to prepare a laminate of PFA tape and stainless steel sheet. The resulting laminate was used for the peel test. In Table 1, the column of the resin sheet was shown as "PFA."

(Evaluation)
<Peeling test>
The 180-degree peel strength was measured using an autograph (AG-20 kNXPLUS, manufactured by Shimadzu Corporation) using the non-adhesive sheet and the laminate obtained in Examples and Comparative Examples. As a test condition, a tensile speed was set to 20 mm / min, and an average value obtained four times was taken as a peel strength. The results are shown in Table 1.

From Table 1, in the example, since the peel strength is 3 N / mm or more, the pre-formed PTFE sheet and the base sheet are joined well, and for example, they are used for applications such as hoppers and sliding snow etc. However, it can be expected that the effect of PTFE can be sustained more than before.

Claims (13)

  The non-adhesive sheet which is a laminated body in which the resin sheet whose resin component is a polytetrafluoroethylene, and a base material sheet were joined, and the peeling strength of a resin sheet and a base material sheet is 3 N / mm or more.   The non-adhesive sheet according to claim 1, wherein the resin sheet and the base sheet are joined via an adhesive.   The non-adhesive sheet according to claim 1 or 2, wherein the thickness of the resin sheet is 0.5 mm or more.   The non-adhesive sheet according to any one of claims 1 to 3, which is a non-adhesive sheet placed on the surface of a member, and a fixing portion for fixing to the member is formed on the base sheet.   The non-adhesive sheet according to any one of claims 1 to 4, wherein the adhesive is an adhesive fluorocopolymer.   The hopper provided so that the resin sheet side of the non-adhesive sheet in any one of Claims 1-5 might become a sliding face.   The vehicle provided with the snow removal apparatus or the snow removal tool provided so that the resin sheet side of the non-adhesive sheet in any one of Claims 1-5 might turn to a snow-covered side. It is a manufacturing method of the non-adhesive sheet of Claim 3.
A method for producing a non-adhesive sheet, comprising the step of bonding a resin sheet having a thickness of 0.5 mm or more and a base sheet to a peel strength of 3 N / mm or more.   The non-adhesive sheet according to any one of claims 1 to 5 is disposed on the surface of the member according to the shape to cover at least a part of the surface, and the non-adhesive surface is imparted with non-stickiness. A method of manufacturing an adhesive member.   The manufacturing method of the non-adhesive member of Claim 9 which fixes the base material sheet of the said non-adhesive sheet to the said member, and coat | covers at least one part of the surface of a member.   The method for producing a non-tacky member according to claim 10, wherein the fixing of the base sheet to the member is at least one selected from welding, bonding with an adhesive, and physical bonding.   The non-adhesive sheet according to any one of claims 1 to 5 is placed on the surface of a member in accordance with the shape to cover at least a part of the surface and to impart non-adhesiveness to the surface. Method of surface modification of members. The method according to claim 12, wherein the base sheet of the non-adhesive sheet is fixed to the member to cover at least a part of the surface of the member.