CN114026027A - Fluororesin coating and method for producing same - Google Patents

Fluororesin coating and method for producing same Download PDF

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Publication number
CN114026027A
CN114026027A CN202080044242.4A CN202080044242A CN114026027A CN 114026027 A CN114026027 A CN 114026027A CN 202080044242 A CN202080044242 A CN 202080044242A CN 114026027 A CN114026027 A CN 114026027A
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China
Prior art keywords
fluororesin
film
atoms
substrate
cover according
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CN202080044242.4A
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Chinese (zh)
Inventor
加贺谷浩之
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DIC Corp
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DIC Corp
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D41/00—Caps, e.g. crown caps or crown seals, i.e. members having parts arranged for engagement with the external periphery of a neck or wall defining a pouring opening or discharge aperture; Protective cap-like covers for closure members, e.g. decorative covers of metal foil or paper
    • B65D41/02—Caps or cap-like covers without lines of weakness, tearing strips, tags, or like opening or removal devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
    • B32B3/14—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a face layer formed of separate pieces of material which are juxtaposed side-by-side
    • B32B3/16—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a face layer formed of separate pieces of material which are juxtaposed side-by-side secured to a flexible backing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D55/00—Accessories for container closures not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/12—Organic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

Providing: for example, a water-and oil-repellent fluororesin coating which is easily assembled as an adhesive or heat-sealing treatment used for packaging. A fluororesin cover having an uneven fluororesin cover containing fluorine, carbon and oxygen on a substrate made of a fibrous material, the shortest distance of the uncovered portion being 5nm to 10 [ mu ] m, and the coverage per unit area being 10 to 80%, and a method for producing the fluororesin cover, comprising: providing a non-uniform distribution of carbonyl groups, hydroxyl groups, or aluminum atoms, silicon atoms, copper atoms, or nitrogen atoms on the surface of a base material composed of a fibrous material; and a step of providing a fluororesin film on the uneven distribution.

Description

Fluororesin coating and method for producing same
Technical Field
The present invention relates to a water-and oil-repellent article having a surface showing water-and oil-repellency.
Background
Conventionally, as a method for imparting water-and oil-repellency, a method using a compound having a fluorine group such as a perfluoroalkyl group, a fluorine group, or a perfluoroalkoxy group has been known. These fluorine-containing compounds have very low surface free energy and therefore have water repellency, oil repellency, chemical resistance, mold release property, stain resistance, lubricity, and the like. These properties are widely used for water-and oil-repellent agents, lubricants for magnetic recording media, mold release agents, and the like.
As a method for forming a surface having water-and oil-repellency on a substrate by using a compound having a fluorine group, a vapor deposition method is known (for example, see patent documents 1 and 2), whereby a uniform film having a thickness of about several nm to 1 μm is formed. However, this method has a problem that, when a water-and oil-repellent substrate is applied to a packaging material because a uniform film is formed over the entire surface of the substrate, the substrate cannot be bonded with an adhesive or a heat-sealing treatment used for packaging a package, for example, and the packaging of the package becomes difficult. In addition, in the case of a substrate having no heat sealing performance, such as paper, cellulose fiber, carbon fiber forming inorganic fiber, metal fiber, etc., the gas adsorption property, conductivity, etc., of the fiber itself are deteriorated.
On the other hand, as a method of imparting water-and oil-repellency, a method of imparting a fine uneven structure to a surface to show water-and oil-repellency (Lotus effect) on the surface is known, and for example, there are known: a water repellent structure having a concavo-convex structure (a structure in which a plurality of projecting convex portions are regularly arranged, a structure in which a plurality of linear convex portions are arranged in parallel to each other, or a structure in which lattice-shaped convex portions are arranged) formed by photolithography and isotropic wet etching on a substrate (see patent document 3); a water-and oil-repellent article having a plurality of independent recesses on a surface thereof, wherein the ratio (A/B) of the width A of the recess at a position 1/2 of the depth D of the recess to the width B of a portion other than the recess at the same position is 3 or more (see, for example, patent document 4); and the like.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 11-116278
Patent document 2: japanese patent laid-open publication No. 2011-230466
Patent document 3: japanese patent laid-open No. 2000-203035
Patent document 4: japanese patent laid-open No. 2014-177072
Disclosure of Invention
Problems to be solved by the invention
The problem to be solved by the present invention is to provide: for example, a water-and oil-repellent fluororesin coating which is easily assembled as an adhesive or heat-sealing treatment used for packaging.
Or providing: for example, a fluororesin coating having water-and oil-repellency and retaining appropriate gas-adsorbing ability and gas-transmitting ability as a material for packaging materials and building material assembly.
Or providing: for example, a fluororesin coating having water and oil repellency while retaining appropriate conductivity as a material to be assembled into a filter or the like.
These fibers are often permeable to water and oil, but they have water-and oil-repellency, and thus the fluororesin coating can provide a surface that is not permeable to water and oil.
Means for solving the problems
The inventors of the present invention found that: the fluororesin coating body is provided on a substrate made of a fibrous material, wherein the fluororesin coating body comprises an uneven fluororesin coating film containing fluorine, carbon and oxygen, and wherein the fluororesin coating body has a specific range of the shortest distance of an uncovered portion and the coverage rate per unit area.
When a thin film is formed by a vapor deposition method, the form of the thin film on a substrate changes depending on the conditions under which particles such as a substrate, a thin film material, temperature, a vapor deposition rate, a degree of vacuum (pressure), and residual gas are incident on the substrate.
In general, the growth of a vapor deposition film is often of a nuclear growth type, and vapor generated from an evaporation source collides with a substrate, and is partially reflected and partially adsorbed. The adsorbed species undergo surface diffusion at the substrate surface, causing two-dimensional collisions of the species with each other to form clusters, or re-evaporation. The clusters repeat collision and release with the surface diffusing substance, but become stable nuclei if they exceed a certain amount. The stable nuclei grow by collision with a surface diffusion substance or an incident substance, and merge with adjacent stable nuclei to finally become a continuous film. In this case, the stable nuclei initially exist in island-like dispersed form, the stable nuclei grow and merge with each other, the number of junctions thereof increases, uneven islands are formed, the area of the stable nuclei in island form increases, the islands change from a form in which the islands are dispersed on the surface of the sea-like substrate to a sea-like form, and a large number of pores forming pits are present in the uneven film in the film based on the stable nuclei in sea form. In general, the vapor deposited film is further grown to form a continuous film with almost no holes on the pits or to such an extent that extremely small pinholes remain, thereby completing the vapor deposited film.
The inventors of the present invention found that: a fluororesin coating having a coating rate of 10 to 80%, that is, a fluororesin coating having about 20 to 90% of the exposed portion of the surface of a substrate, is formed on a substrate made of a fibrous material in a state in which a large number of crater-like pores are present in an uneven film of a film formed of uneven island-like stable nuclei and sea-like stable nuclei, whereby water repellency and oil repellency can be achieved even in the form of a thin film.
That is, the present invention provides a fluororesin cover having an uneven fluororesin cover film containing fluorine, carbon and oxygen on a substrate made of a fibrous material, wherein the shortest distance of the uncovered portion is 5nm to 10 μm, and the coverage per unit area is 10 to 80%.
The present invention also provides the fluororesin cover as described above, wherein the fluororesin cover has a thickness of 1nm to 200 nm.
The present invention also provides the fluororesin cover as described above, wherein the contact angle of water is 90 ° or more.
The present invention also provides the fluororesin cover as described above, wherein the static contact angle of n-hexadecane is 60 ° or more.
The present invention also provides the fluororesin cover as described above, wherein the fibrous substrate is a substrate made of cellulose, hydrophobically modified cellulose, natural rock, glass, quartz, carbon fiber, or activated carbon fiber.
The present invention also provides the fluororesin cover as described above, wherein the fibrous base material is paper, nonwoven fabric, or woven fabric.
The present invention also provides the fluororesin cover described above, wherein the fibrous substrate has an uneven distribution of carbonyl groups, hydroxyl groups, amino groups, or aluminum atoms, silicon atoms, copper atoms, nickel atoms, or nitrogen atoms on the surface thereof, and the fluororesin film is present in the uneven distribution.
Further, the present invention provides a method for producing a fluororesin cover, comprising the steps of: providing a non-uniform distribution of carbonyl groups, hydroxyl groups, or aluminum atoms, silicon atoms, copper atoms, or nitrogen atoms on the surface of a base material composed of a fibrous material; and a step of providing a fluororesin film on the uneven distribution.
The present invention also provides the above-described method for producing a fluororesin cover, wherein the uneven distribution is provided by corona treatment, plasma treatment, laser treatment, ITRO treatment, or sputtering treatment.
The present invention also provides the above-described method for producing a fluororesin cover, wherein the step of providing a fluororesin film is performed by a chemical vapor deposition method (CVD method), a physical vapor deposition method (PVD method), or a sputtering method.
ADVANTAGEOUS EFFECTS OF INVENTION
In the fluororesin coating body of the present invention, since the coverage per unit area of the substrate made of a fibrous material is 10 to 80%, that is, the exposed portion of the surface of the substrate is about 20 to 90%, the water repellency and oil repellency of the coating fluororesin and both the adhesiveness to an adhesive and the heat-sealability, which are characteristics of the substrate itself, can be exhibited, and therefore, for example, the coating body can be easily assembled as an adhesive used for packaging or a heat-sealing treatment.
In addition, in the fluororesin coating body of the present invention, since about 20 to 90% of the exposed portion of the surface of the base material made of a fibrous material is present, both water-and oil-repellency and appropriate gas adsorption ability can be exhibited as a material for building material assembly, for example.
In the fluororesin coating body of the present invention, the exposed portion of the surface of the base material made of a fibrous material is present in an amount of about 20 to 90%, and therefore, for example, as a member for avoiding static electricity, both water-and oil-repellency and appropriate conductivity can be exhibited.
As the pretreatment method of the base material, pretreatment by corona discharge treatment, laser treatment, argon plasma etching, oxygen plasma modification, or sputtering can be performed to change the uniformity or unevenness of the surface. Further, the adhesion between the fluororesin coating layer as a post-treatment and the substrate can also be improved by rendering the substrate surface super-hydrophilic by the ITRO treatment.
By these surface pretreatments, water repellency and oil repellency can be achieved even in the form of a film.
Compared with a continuous film, the fluororesin cover body of the invention which can realize water repellency and oil repellency by virtue of the film has advantages in material cost and film preparation speed compared with a continuous film fluororesin cover body. By performing the surface pretreatment, the film can be further made thinner, which is more advantageous. Further, by utilizing the characteristics of the substrate itself, for example, a heat-sealable fluororesin film body can be obtained.
Further, since the surface pretreatment is performed by sputtering or the like to form a macroscopically uniform and microscopically non-uniform sparse element distribution surface, the number of stable nuclei at the beginning of the vapor deposition increases, and a state of a non-uniform film can be efficiently formed.
Detailed Description
(definition of terms)
In the present invention, "water repellency" means: water repellency properties, "oil repellency" refers to: oil repellent properties.
(nonuniform resin film containing fluorine, carbon and oxygen)
The uneven resin film containing fluorine, carbon, and oxygen used in the present invention is specifically a resin film having a compound containing a perfluoroalkyl group, a fluoro group, a perfluoroalkoxy group, or the like. Examples of the fluorine compound containing a perfluoroalkoxy group and the like (hereinafter referred to as a fluorine compound) include perfluoroalkanes such as tetrafluoromethane, perfluoroethane, perfluoropropane, perfluorobutane, perfluoropentane and perfluorohexane, perfluoroolefins such as hexafluoropropylene, perfluoro (4-methyl-2-pentene), perfluoro (2-methyl-2-pentene) and perfluoro-1-hexene, and fluorine compounds represented by the following general formula (1).
F(CF2)n-Y (1)
(in the formula (1), n is desirably 1 to 10, but n may be 10 or more and Y is a substituent group containing no fluorine atom.)
Examples of Y include a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a substituent such as a halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom. The alkyl group is more preferably an alkyl group having 1 to 4 carbon atoms, and the alkenyl group is preferably an alkenyl group having 2 to 4 carbon atoms. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, and various butenyl groups. In addition, an unsaturated hydrocarbon group or an iodine group which is likely to generate an active material such as ions or radicals may be contained.
Among the fluorine compounds represented by the formula (1), fluorine compounds having 10 or less carbon atoms are preferable. Specific examples of the fluorine compound having 10 or less carbon atoms include 1H-perfluoroalkanes such as 1H-perfluoropentane and 1H-perfluorohexane, perfluoroalkylethylenes such as perfluorobutylethylene and perfluorohexylethylene, perfluorobutyl iodide, perfluorohexyl iodide, 1-chlorotridecylfluoropentane, 1-chlorotridecylohexane, 1-bromotridecafluoropentane, and 1-bromotridecafluorohexane.
Among them, n is preferably 3 to 6 from the viewpoint of good water and oil repellency.
In the fluorine compound represented by the formula (1), the substituent represented by Y is more preferably 1 atom selected from the group consisting of a hydrogen atom, a carbon atom, a chlorine atom, a bromine atom and an iodine atom, or a compound formed of a carbon atom and 1 or more atoms selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom and an iodine atom. The compound having a carbon atom and 1 or more atoms selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom and an iodine atom is preferably a hydrocarbon group, an unsaturated hydrocarbon group is preferable, and an alkenyl group is more preferable.
Examples of suitable fluorine compounds include perfluorobutylethylene, perfluorohexylethylene, and perfluorohexyliodide.
(method of producing nonuniform resin film containing fluorine, carbon and oxygen)
Examples of the uneven resin film containing fluorine, carbon and oxygen include a method of forming a coating on a substrate made of a fibrous material using the above-mentioned fluorine compound (Wet method), a physical vapor (mists in the original text) vapor deposition method (PVD method), a chemical vapor deposition method (CVD method), a sputtering method (sputtering method), and the like. Among them, the PVD method, the CVD method, and the sputtering method improve adhesion to a base material by plasma assistance, and may change film quality.
(physical vapor deposition method (PVD method)
The PVD method is as follows: a method in which tetrafluoroethylene is heated by various heat sources to generate vapor, and the vapor is deposited as droplets or crystals on the surface of a substrate kept at a lower temperature. Even in the batch method in which the entire processing surface is processed at once, a method in which the substrate or the reaction tank is moved to continuously process the apparatus and continuously process different processing surfaces may be used.
The vapor deposition process in the present invention can be carried out under any atmosphere of pressure, normal pressure, reduced pressure, vacuum state, oscillation thereof, atmosphere, and inert gas. By forming a reduced pressure or vacuum state, the evaporation rate can be improved and the evaporation temperature can be lowered, and deposition of evaporated material can be promoted by pressurization. Further, although oxidation of polytetrafluoroethylene or a carrier can be suppressed by forming a vacuum or an inert atmosphere, the present invention can perform a low-temperature treatment at a temperature lower than the thermal decomposition temperature, and therefore, an atmospheric atmosphere can be used in terms of cost.
In the present invention, a preferable adhesion state can be obtained according to the purpose by adjusting the deposition conditions of the fluorine compound. As the deposition conditions, the pressure in the deposition chamber and the time of contact of the fluorine compound vapor with the surface of the substrate are important, and by controlling this time, the unevenness of the fluorine resin coating such as the coating rate and the shortest distance of the uncovered portion can be controlled.
(sputtering method)
As the sputtering method, RF magnetron sputtering is suitable. Sputtering is desirably carried out under reduced pressure of, for example, 1X 10-4Pa or less, and introducing an inert gas (e.g., argon gas). A target to be a raw material of a thin film is disposed in a processing space so as to face a substrate. A permanent magnet is disposed on the rear surface side of the target. The magnetic field binds the spiral orbit of the electrons to generate high-density plasma, thereby performing sputtering. The ionization of the inert gas is promoted, and the ions collide with the target to generate fine particles serving as a raw material of the thin film. At this time, the fine particles having obtained energy are accelerated at a high speed and fly out from the target, and a film is formed on the substrate.
In the case of a target of a water repellent material, for example, polytetrafluoroethylene (of PTFE), pellets obtained by compressing PTFE particles and molding, or a sheet of PTFE can be used as the target.
The high-frequency power for performing RF magnetron sputtering is not particularly limited, and can be adjusted from the viewpoint of achieving an appropriate film formation rate. In addition, it is desirable to control the temperature of the substrate during film formation from room temperature to about 100 ℃.
(chemical vapor deposition method (CVD method)
The CVD method is: a film-forming method in which 1 or more compound gases formed of elements constituting a thin film material and a carrier gas (a reactive gas containing a fluorine compound in the present invention) are supplied onto a substrate to be processed, and a desired thin film is formed by a chemical reaction in a gas phase or on the surface of the substrate. The film can be formed without high temperature. Further, the plasma CVD method is usually performed under reduced pressure, but an atmospheric pressure plasma CVD method may be used.
As CVD methods, there are known: plasma-assisted CVD for generating plasma, thermal CVD for heating a reaction vessel, optical CVD for irradiating light (laser, ultraviolet, etc.), and the like, and in the present invention, the following plasma-assisted CVD is preferably employed: the reactive gas is converted into plasma under the condition of discharge dissociation, and the deposition matter excited in the plasma is deposited on the surface of the processed substrate, so that the fluorine-containing organic film is formed. The plasma-assisted CVD method can form a film at a lower temperature than the thermal CVD method or the like. In addition, a diluent gas may be mixed into the plasma reaction gas in order to control the reactivity of the fluorine compound and improve the operability. As the diluent gas, a rare gas or a hydrocarbon-based gas can be used, and examples thereof include argon, helium, xenon, and the like. Examples of the hydrocarbon-based gas include hydrocarbons having 1 to 3 carbon atoms such as methane, ethylene, and acetylene. Among them, argon, methane or ethylene gas is preferably used. These diluent gases may be used alone or in combination of 2 or more.
The amount of diluent gas used is generally 0 to 95 wt% relative to the total amount of plasma reactive gas components.
In the present invention, if the CVD method, particularly the plasma-assisted CVD method is used, the fluororesin film can be formed without being exposed to a high-temperature environment, and the material for the substrate is not limited to a material having high heat resistance, and therefore, a wide selection range of materials is preferable. In addition, the CVD method is preferable because the fluororesin film can be formed on a material having a fibrous surface so that the surface can be covered even if the shape of the material for forming the fluororesin film is three-dimensionally complicated.
(method for producing uneven fluororesin coating film)
In order to produce the fluororesin coating body of the present invention in which the uncoated portion has a shortest distance of 5nm to 10 μm and a coverage per unit area of 10 to 80% by using the PVD method, the CVD method, or the sputtering method, conditions under which the substrate and particles such as temperature, deposition rate, vacuum degree (pressure), residual gas are incident on the substrate can be appropriately controlled.
Specifically, as described above, since the growth of the vapor deposition thin film is often formed by a nucleus growth type, specifically, the island-shaped stable nuclei are increased in area, and the islands are changed to a sea shape so that the islands are dispersed and present on the surface of the sea-shaped substrate, and the coating can be completed at a stage where a heterogeneous film of a film based on the sea-shaped stable nuclei is formed in which a large number of pit-shaped pores are present.
(pretreatment of substrate surface)
In the present invention, the surface of the base material is subjected to pretreatment such as corona discharge treatment, laser treatment, argon plasma etching, oxygen plasma modification, nitrogen plasma modification, sputtering, etc., in advance, whereby the uniformity and unevenness of the surface can be further controlled. Further, the adhesion between the fluororesin layer as a post-treatment and the substrate can also be improved by rendering the substrate surface super-hydrophilic by the ITRO treatment.
By these treatments, a non-uniform distribution of carbonyl groups, hydroxyl groups, or aluminum atoms, silicon atoms, copper atoms, or nitrogen atoms can be provided on the surface of the substrate.
The carbonyl group may be provided by corona discharge treatment, laser treatment, or oxygen plasma modification treatment. The hydroxyl group may be provided by corona discharge treatment, laser treatment, or oxygen plasma modification treatment. In addition, the amino group may be provided by ITRO treatment using an aminosilane-containing compound. Further, the aluminum atoms can be obtained by sputtering, PVD, or CVD. Aluminum atoms can also be obtained by argon plasma etching of a film obtained by sputtering, PVD, or CVD.
In addition, the silicon atoms may be set by a sputtering process, a PVD process, a CVD process, or an ITRO process. In addition, the copper atoms may be provided by sputtering, PVD, CVD. In addition, the nickel atoms may be provided by sputtering, PVD, CVD. The nitrogen atoms may be provided by a nitrogen plasma modification treatment.
(shortest distance of portion not covered by Property)
In the fluororesin coating body of the present invention thus obtained, the shortest distance of the uncovered portion is 5nm to 10 μm. Among the shortest distances, 20nm to 5 μm are preferable. The method for measuring the shortest distance can be applied to, for example: a method of obtaining a cross-sectional enlarged photograph corresponding to a plan view by sequentially comparing them with each other using an Atomic Force Microscope (AFM) or a Scanning Electron Microscope (SEM); various methods such as a method of obtaining an enlarged plan view picture by image processing, but in the present invention, the method of obtaining an enlarged plan view picture by image processing is used. At this time, the shortest distance of the uncovered portion of the surface of the fibrous materials of the substrate was measured, and the distance between the fibrous materials was not measured.
(coverage per unit area of the Property)
In the fluororesin coating body of the present invention, the coverage per unit area is 10 to 80%. Among the coverage, 25 to 60% is preferable. The coverage is determined by image processing of a top-view magnified photograph using, for example, an Atomic Force Microscope (AFM) or a Scanning Electron Microscope (SEM).
(thickness of film)
In the fluororesin cover of the present invention, the thickness of the fluororesin cover is 1nm to 200 nm. The film thickness ratio is preferably 5nm to 50 nm. The film thickness is determined by image processing of a cross-sectional enlarged photograph using, for example, an Atomic Force Microscope (AFM) or a Scanning Electron Microscope (SEM).
(contact Angle of Property)
The fluororesin coating of the present invention preferably has a contact angle of 90 ° or more. Specifically, the static contact angle of pure water on the film surface is preferably 95 ° or more by θ/2 method from the viewpoint of excellent water repellency, and the static contact angle of n-hexadecane on the film surface is preferably 60 ° or more by θ/2 method from the viewpoint of excellent oil repellency.
The properties of the fluororesin cover of the present invention are based on the inherent properties of fluorine atoms. The atomic radius and polarizability of fluorine atoms are small, and the electronegativity is highest among all elements. Further, carbon-fluorine bonds have a large binding energy, and therefore, excellent heat resistance, weather resistance, and chemical resistance can be achieved, and since the polarizability is small, the intermolecular aggregation force is small, and a low surface free energy surface can be formed.
(substrate)
The substrate forming the fluororesin coating film of the present invention is composed of a fibrous material. In the present invention, the base material made of a fibrous material means: having a fibrous material as a main component, may contain: and other materials necessary for processing into a shape capable of using the fibrous material as a substrate, that is, a film, a thin film or a sheet.
The substrate made of a fibrous material may be appropriately selected depending on the application, and is not particularly limited. Examples of the fibrous material include cellulose, hydrophobically modified cellulose, natural rock, glass, plastic fiber, carbon fiber, activated carbon fiber, and metal fiber.
Examples of the cellulose include natural cellulose having a fiber diameter of 15 to 50 μm and cellulose nanofibers obtained by loosening the natural cellulose to a fiber diameter of 4 to 20 nm. Further, modified celluloses such as carboxymethyl cellulose (CMC) obtained by substituting a part of the hydroxyl groups of cellulose with carboxymethyl groups, Ethyl Cellulose (EC) obtained by substituting with ether groups, and Methyl Cellulose (MC) obtained by substituting with methyl ether groups may be mentioned.
Examples of the hydrophobically modified cellulose include a hydrophobically modified cellulose nanofiber having a fiber diameter of about 3 to 10nm, which is obtained by subjecting cellulose to TEMPO (2,2,6, 6-tetramethylpiperidine-1-oxyl) catalytic oxidation and then to a slight defibration treatment.
Examples of the natural rock include basalt, quartz, and other natural rocks, and examples thereof include: rock wool and slag wool which enable the rock to form fibrous materials; the quartz is formed into artificial mineral fibers such as fiber-like quartz wool with a fiber diameter of about 2 to 10 μm.
Examples of the glass include: forming glass into fiber-like glass wool with the fiber diameter of about 2-10 mu m; the quartz is formed into a fibrous quartz wool having a fiber diameter of about 2 to 10 μm.
Examples of the plastic fibers include: plastic fibers are produced by processing polyester resins such as polyethylene terephthalate and polyethylene naphthalate, olefin resins such as polyethylene, polypropylene and polymethylpentene, acrylic resins, polyurethane resins, polyether sulfone, polycarbonate, polysulfone, polyphenylene sulfide, polyamide, polyimide, polyether ketone, acrylonitrile polymer, acrylonitrile copolymer, methacrylonitrile polymer, methacrylonitrile copolymer, cycloolefin polymer and cycloolefin copolymer into fibers having a fiber diameter of about 5nm to 100 μm.
Examples of the carbon fibers include: and a fibrous material having a fiber diameter of about 2 to 10 μm obtained by carbonizing acrylic fiber or PITCH (a by-product mainly composed of hydrocarbons in the production of petroleum, coal tar, and the like), and is called carbon fiber.
Examples of the activated carbon fibers include: an activated carbon fiber having a fiber diameter of about 2 to 40 μm and having surface adsorption performance is obtained by increasing the surface area of the fiber through an activation step of oxidizing an acrylic fiber, PITCH, or cellulose fiber by heat treatment or the like to develop the pore structure of the fiber.
Examples of the metal fibers include: a metal fiber having a fiber diameter of about 10 to 200 μm, which is made of stainless steel, copper, brass, titanium, aluminum, or the like.
These fibers can be processed into a film, a film or a sheet by a known method and used as a substrate. In the present invention, the base material made of a fibrous material after processing is preferably paper, nonwoven fabric, or woven fabric. Moreover, it may be a roll-up; bending the steel sheet without bending the steel sheet as in the case of being wound up, but with a load applied thereto; the bending is not at all. The substrate may be a container-shaped article obtained by processing a substrate made of each fibrous material. The thickness of the base material made of the fibrous material is not particularly limited and may be suitably selected depending on the application, and is usually 10 μm to 200 mm.
The structure of the base material made of a fibrous material used in the present invention is not limited to the structure formed of a single layer, and may be a structure in which a plurality of layers are laminated. In the case of a configuration in which a plurality of layers are stacked, layers having the same composition may be stacked, or a plurality of layers having different compositions may be stacked.
Examples
Next, the present invention will be specifically described with reference to examples and comparative examples. In the examples, "part" and "%" are based on mass unless otherwise specified.
(use base)
As the base material, paper for cups (made of cellulose), plain white high-quality paper (made of cellulose), carbon fiber felt (made of carbon fiber), activated carbon fiber, plastic nonwoven fabric (made of plastic fiber), glass cloth (made of glass), rock wool paper (made of basalt), titanium fiber sheet (made of metallic titanium) were used.
Paper for cups: DCK 200g/m2(paper made by king)
Pure white high-quality paper: はまゆう 40g/m2(Jizhou paper)
Carbon fiber felt GF-20-7FH (manufactured by Nippon Carbon)
Activated carbon fiber: KF paper 110g/m2(Dongyang spinning)
Nonwoven (polyester/polyamide): WC001 (made by Japan Vilene)
Nonwoven (polyethylene): tyvek 1443R (DuPont system)
Glass cloth: EGW110 TH-153110 g/m2(manufactured by Central glass fiber)
Rock cotton paper: RW300 (made from Bachuan paper)
Titanium fiber sheet: 1.4mm sheet based on titanium 50 μm fiber (manufactured by Nikko Techno)
(plasma CVD method)
As the plasma CVD apparatus, a plasma CVD apparatus based on PED-401 (manufactured by Anelva) was used. In this apparatus, the gas supply portion can be improved so as to be supplied from a plurality of positions. A substrate is placed in a vacuum chamber of a plasma CVD apparatus and is provided on a lower electrode. The temperature of the lower electrode was set to 22 ℃. After the chamber was closed and the pressure was reduced to 0.4Pa, perfluorohexylethylene (Daikin Industries, Ltd., product No. F-1620) as a fluorine compound (monomer material) was supplied into the vacuum chamber using argon (Ar) as a carrier gas. At this time, the flow rate of Ar gas was set to 30 sccm. After the exhaust gas amount was adjusted to 50Pa, the film formation was performed with the discharge power set at 54W. The film forming time was set to 10 seconds to 10 minutes, and the fluororesin coatings of examples and comparative examples were obtained.
In the case of performing the oxygen plasma treatment, the apparatus was used to perform the treatment for 1 minute under the same flow rate, vacuum, and discharge conditions in oxygen gas, instead of Ar gas.
(sputtering method)
A magnetron sputtering apparatus (model EB1100, manufactured by Canon Anelva) was used as the sputtering apparatus.
Here, a PTFE target was used as a target, and argon gas or argon gas and oxygen gas were used as process gases, and a PTFE deposited layer was formed by DC sputtering. The power of the sputtering power supply is set to be 5.0W/cm2The film formation pressure was set to 0.4 Pa. When oxygen is used, the oxygen partial pressure is 10%. The deposition time was controlled to be about 10 seconds to 40 minutes, and the film thickness of the example was obtained.
When this apparatus is used as a pretreatment, the treatment is carried out in a very short time of 0.5 to 5 seconds using Ni, Cu, or SiOx targets as targets.
(PVD method)
As a PVD deposition apparatus, a PTFE target put in a crucible was charged into a vacuum deposition apparatus (ULVAC techon manufactured by ltd.) capable of EB heating and resistance heating, and vacuum was evacuated to a vacuum degree: 3.0X 10-3Pa, the film forming speed can be determined by the crystal oscillator
Figure BDA0003414606630000131
Range of (1)The inner film is heated. The film forming time was 1 second to 10 minutes, and the fluororesin covers of examples and comparative examples were obtained.
(pretreatment of substrate surface)
As a method for pretreating the surface of the base material, corona treatment or ITRO treatment was performed.
(Corona treatment)
The treatment was carried out using TEC-4AX (thermo electric.
(ITRO treatment)
The method is a method of treating a silicon compound film constituting a very thin film on the surface of a substrate by flame treatment, and depends on ITRO company. The OPP film (FOR 25 μm, manufactured by Dimura Cork.) was treated under the same conditions so that the treated surface became a super-hydrophilic film with a surface energy of >70 mN/m.
(method of measuring shortest distance, coverage and film thickness of uncovered portion (uncovered portion))
The shortest distance of the portion of the obtained fluororesin coating not covered was measured by the following method.
(1) The fluorine resin was detected by an Atomic Force Microscope (AFM) or a Scanning Electron Microscope (SEM).
(2) Then, the shortest distance of the uncovered portion is detected. As a method for obtaining the shortest distance, the shortest distance is obtained by image processing of a top-view enlarged photograph.
(3) The coverage is obtained by image processing of a top-view enlarged photograph.
(4) The film thickness was obtained by image processing of a cross-sectional enlarged photograph.
(measurement of contact Angle)
On the surface of the obtained fluororesin film, about 2. mu.l of pure water or n-hexadecane as an evaluation liquid was placed, and the angle (contact angle) formed between the water droplet and the film surface was measured by a contact angle meter (CA-X, manufactured by Kyowa Kagaku Co., Ltd.).
(measurement of volume resistivity)
The volume resistivity was measured by a four-terminal measurement method using Loresta GX manufactured by Mitsubishi Chemical Analytich.
(measurement of Water vapor Transmission Rate)
The water vapor permeability was measured by a conductivity method "ISO-15106-3" using a water vapor permeability measuring apparatus 7012 manufactured by Illinois Inc. under an atmosphere of 40 ℃ and 90% RH. The measurement area is 5cm2。
(measurement of moisture adsorption quantity)
The humidity of the apparatus was adjusted for 24 hours at a constant temperature and humidity of 23 ℃ and a relative humidity of 65% RH, and then the rate of change in weight after leaving at a constant temperature and humidity of 40 ℃ and a relative humidity of 90% RH for 24 hours was measured.
(measurement of Cobb value)
As an index of water resistance of paper, the water absorption was measured by a water absorption Tester (Garley Cobb sizing ratio measuring machine, Tester industry) according to JIS P8140 (1998) by the Cobb method. The measurement conditions were 20 ℃ room temperature, and the contact time with water at water temperature was 1 minute.
(measurement of seal Strength)
The resulting fluororesin cover was subjected to surface sealing by a heat-sealing bar having a width of 10mm × a length of 400mm, and wire sealing by a heat-sealing bar having a width of 1mm × a length of 400mm, and knurling by knurling, a knurling process was performed at a pitch of 0.51 mm. (Heat-sealing conditions: 5 seconds at 200 ℃ C., 0.2MPa)
After cooling the obtained heat-sealed product to room temperature, the laminate strength was measured at a peel rate of 200 mm/min in a 180 ° peel test by a method according to JIS K6854.
The composition and properties of the production method of the fluororesin coating are shown in the table.
Note that the abbreviations in the tables are as follows.
Ar: argon gas
N2: nitrogen gas
O2: oxygen gas
PE-CVD: plasma assisted CVD method
Constitution and properties of a method for producing a fluororesin coating by (plasma CVD method)
[ Table 1]
Figure BDA0003414606630000161
[ Table 2]
Figure BDA0003414606630000171
Constitution and properties of a method for producing a fluororesin coating by (sputtering)
[ Table 3]
Figure BDA0003414606630000181
Constitution and Properties of method for producing fluororesin coating by (PVD method)
[ Table 4]
Figure BDA0003414606630000182
Constitution and properties of a method for producing a fluororesin coating using a pretreated substrate
[ Table 5]
Figure BDA0003414606630000191
Measurement of sealing Strength of fluororesin-coated nonwoven Fabric (polyethylene)
[ Table 6]
Figure BDA0003414606630000192
As a result, the fluororesin coating obtained in the examples obtained a seal strength which was practically free from problems in the line seal and the knurling seal.
Measurement of Water vapor Transmission Rate, Water vapor adsorption amount by Water vapor, Cobb value of fluorine-coated paper for cups
[ Table 7]
Figure BDA0003414606630000201
As a result, the fluororesin coating obtained in the examples can achieve both water resistance (Cobb value) and sufficient water vapor transmission rate, which are practically free from problems, and sufficient water vapor adsorption capacity (water adsorption amount over a long period of time).
Determination of volume resistivity of fluorine-coated titanium fiber sheet
[ Table 8]
TABLE 8 Base material Volume resistivity (four-terminal measurement) Ω · m
Comparative example 9 Titanium fiber sheet 0.8×10-6Ω·m
Example 9 Titanium fiber sheet 1.6×10-5Ω·m
Comparative example 11 Titanium fiber sheet 3×102Ω·m
As a result, the fluororesin coating obtained in example can realize a volume resistivity close to that of the exposed metal fibers of comparative example 9.

Claims (10)

1. A fluororesin coating comprising a fibrous substrate and an uneven fluororesin coating containing fluorine, carbon and oxygen, characterized in that the shortest distance of the uncovered portion is 5nm to 10 [ mu ] m and the coverage per unit area is 10 to 80%.
2. The fluororesin cover according to claim 1, wherein the fluororesin cover film has a thickness of 1 to 200 nm.
3. The fluororesin cover according to claim 1 or2, wherein a contact angle of water is 90 ° or more.
4. The fluororesin cover according to any one of claims 1 to 3, wherein a static contact angle of n-hexadecane is 60 ° or more.
5. The fluororesin cover according to any one of claims 1 to 4, wherein the substrate made of a fibrous material is a substrate made of cellulose, hydrophobically modified cellulose, natural rock, glass, plastic fiber, carbon fiber, activated carbon fiber, or metal fiber.
6. The fluororesin cover according to any one of claims 1 to 5, wherein the base material made of a fibrous material is paper, nonwoven fabric, or woven fabric.
7. The fluororesin cover according to any one of claims 1 to 6, wherein the fibrous substrate has a non-uniform distribution of carbonyl groups, hydroxyl groups, amino groups, or aluminum atoms, silicon atoms, copper atoms, nickel atoms, or nitrogen atoms on the surface thereof, and the non-uniform distribution has a fluororesin film thereon.
8. A method for producing a fluororesin coating, comprising the steps of: providing a non-uniform distribution of carbonyl groups, hydroxyl groups, or aluminum atoms, silicon atoms, copper atoms, or nitrogen atoms on the surface of a base material composed of a fibrous material; and a step of providing a fluororesin film on the uneven distribution.
9. The method for producing a fluororesin cover according to claim 8, wherein the uneven distribution is set by corona treatment, plasma treatment, laser treatment, ITRO treatment, or sputtering treatment.
10. The method of producing a fluororesin cover according to claim 8 or 9, wherein the step of providing a fluororesin film is performed by a chemical vapor deposition method (CVD method), a physical vapor deposition method (PVD method), or a sputtering method.
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