Classifications

• • 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
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
  • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
  • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers

Definitions

• the present invention relates to a film formation substrate.
• a substrate on which a film has been formed is obtained by applying an initiator to the substrate in advance, supplying a monomer for polymerization, and allowing the substrate to adsorb the polymer as a polymer (Patent Document 1).
• an object of the present invention is to provide a novel film-formed substrate in which a high-density film is formed on at least part of the metal surface existing on the substrate.
• a film containing a compound having structural units derived from an adsorption group and a monomer is formed on at least a portion of a metal surface present on a substrate, A deposition substrate, wherein the metal has a specific gravity of 19.30 g/cm 3 or less.
• the adsorptive group is one selected from the group consisting of an SH group, a phosphoric acid group, a phosphonic acid group, a carboxylic acid group, an isocyanate group, an unsaturated hydrocarbon group, a halogenated alkyl group, and an amino group.
• Structural units derived from the above monomers are one or more structural units selected from structural units derived from (meth)acrylic acid esters and structural units derived from aromatic group-containing monomers.
• a film containing a compound having structural units derived from an adsorptive group and a monomer is formed on at least a portion of the metal surface present on the substrate,
• a method for producing a film-formed substrate comprising the step of forming a film of a composition containing a polymer having an adsorptive group on at least a portion of a metal surface present on the substrate.
• the deposition substrate of the present disclosure is obtained by forming a high-density film on at least a portion of the metal surface present on the substrate, and the formation of such a high-density film specifically modifies the physical properties of the surface. Is possible. Therefore, the film-forming substrate of the present disclosure can be applied to various fields such as the construction field, the automobile field, the electrical/electronic field, and the medical field.
• the substrate of the present disclosure may contain metal (hereinafter sometimes referred to as a metal-containing substrate).
• the metal-containing substrate includes substrates made of only metal and substrates made of metal and materials other than metal. Materials other than metals are not particularly limited, and examples thereof include resins. If the substrate contains metal, it is preferred to have the metal on at least part of the surface of the substrate.
• Substrates in the present disclosure include, but are not limited to, metal strips, metallized films, semiconductor wafers, printed circuit boards, metallized films, and the like.
• the shape and thickness of the substrate in the present disclosure are not particularly limited, but the thickness of the substrate is preferably 0.5 to 5 mm, more preferably 1 to 2 mm, in the case of a plate such as a printed circuit board. preferable.
• the thickness is preferably 10 to 250 ⁇ m, more preferably 20 to 200 ⁇ m.
• the metal species contained in the substrate of the present disclosure is not particularly limited. Metal elements of Groups 6 to 12 are preferred, metal elements of Groups 6 and 8 to 11 are more preferred, and metal elements of Groups 6, 8 and 11 are even more preferred. It is a metal element of Groups 9 and 11, particularly preferably molybdenum, ruthenium, tungsten, cobalt, silver and copper, most preferably copper and cobalt. One kind of metal species may be contained, but two or more kinds may be contained.
• the density of the substrate of the present disclosure is not particularly limited, but is preferably 1 g/cm 3 to 30 g/cm 3 , more preferably 3 g/cm 3 to 20 g/cm 3 , still more preferably 10 g/cm 3 . ⁇ 19.3 g/cm 3 .
• the content of the metal contained in the metal-containing substrate of the present disclosure is preferably 0.000001 to 100 parts by mass, more preferably 0.00001 to 99 parts by mass with respect to 100 parts by mass of the metal-containing substrate. parts, more preferably 0.0001 to 95 parts by mass.
• the specific heat of the substrate containing the metal of the present disclosure is not particularly limited. It is preferably 0.12 KJ ⁇ Kg ⁇ 1 ⁇ K ⁇ 1 to 0.8 KJ ⁇ Kg ⁇ 1 ⁇ K ⁇ 1 , more preferably 0.13 KJ ⁇ Kg ⁇ 1 ⁇ K ⁇ 1 to 0.5 KJ ⁇ Kg. ⁇ 1 ⁇ K ⁇ 1 .
• the specific heat of the substrate can be measured by a laser flash method, an adiabatic method, a DSC method, or the like.
• the thermal conductivity of the substrate containing the metal of the present disclosure is not particularly limited, but is preferably 10 W ⁇ m ⁇ 1 ⁇ K ⁇ 1 to 500 W ⁇ m ⁇ 1 ⁇ K ⁇ 1 , more preferably 30 W ⁇ m ⁇ 1 ⁇ K ⁇ 1 to 450 W ⁇ m ⁇ 1 ⁇ K ⁇ 1 , more preferably 50 W ⁇ m ⁇ 1 ⁇ K ⁇ 1 to 400 W ⁇ m ⁇ 1 ⁇ K ⁇ 1 .
• the thermal conductivity of the substrate can be measured by a temperature gradient method (JIS H7903), a disc heat flow meter method (ASTE E1530), or the like.
• the membrane of the present disclosure includes a compound (hereinafter also referred to as compound A) having an adsorptive group and a structural unit derived from a monomer.
• the adsorptive group is one or more groups selected from thiol groups (SH groups), phosphonic acid groups, phosphoric acid groups, carboxylic acid groups, isocyanate groups, unsaturated hydrocarbon groups, halogenated alkyl groups, and amino groups. is preferably
• the structural unit derived from the above monomer refers to a structural unit having the same structure as the structure formed by polymerizing the monomer, and usually, the carbon-carbon unsaturated double bond contained in the monomer. At least one is a structure in which a carbon-carbon single bond is replaced.
• the structural unit derived from the monomer does not have to be a structural unit actually formed by polymerization of the monomer, as long as it has the same structure as the structure formed by polymerization of the monomer.
• a structural unit formed by a method other than polymerization of a monomer is also included in the structural unit derived from the monomer.
• the structural unit derived from methyl acrylate can be represented by -CH 2 -CH(-COOCH 3 )-.
• Compound A contained in the membrane of the present disclosure has structural units derived from compounds containing adsorptive groups.
• a structural unit derived from a compound containing an adsorptive group is a carbon-carbon unsaturated double bond contained in a monomer containing an adsorptive group when the compound containing the adsorptive group is a monomer containing the adsorptive group. means a structure in which at least one of is replaced with a carbon-carbon single bond.
• the monomer containing an adsorptive group is used. It means a structural part derived from a compound containing an adsorptive group in the structure of the mer.
• the compound containing the adsorptive group may be a compound having the adsorptive group as it is, or may be a compound having a structural unit containing the adsorptive group formed by reacting the adsorptive group with another functional group.
• a structural unit containing the adsorptive group formed by reacting the adsorptive group with another functional group.
• the structural unit containing an adsorptive group can be represented by -S-.
• a compound containing an adsorptive group may have a structure of —SH (when it has the adsorptive group as it is).
• the membrane of the present disclosure is capable of bonding adsorption groups and substrates containing metals.
• the bond between the film of the present disclosure and the metal-containing substrate is preferably a bond between the adsorption group of the compound A contained in the film and the metal-containing substrate, but is derived from the monomer of the compound A.
• a structural unit and a substrate containing a metal may be combined. These bonds may be physical bonds or chemical bonds.
• Compound A contained in the film may have one or more adsorptive groups, and may have two or more.
• the adsorbing groups may be the same type of functional groups or different functional groups.
• the film may contain only one type of compound corresponding to compound A, or may contain two or more types.
• the adsorptive group is preferably a thiol group, a phosphonic acid group, a phosphoric acid group or an amino group, more preferably a thiol group or a phosphonic acid group, most preferably a thiol group. Containing the adsorptive group tends to increase the bonding strength between the film of the present disclosure and the metal-containing substrate.
• the membrane of the present disclosure contains compound A having structural moieties derived from adsorption groups and monomers.
• the compound A may be obtained by using a monomer having an adsorptive group as a starting material, or may be obtained by reacting a compound having an adsorptive group with a monomer.
• the monomer is not particularly limited, but examples include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, ( meth)lauryl acrylate, isodecyl (meth)acrylate, oleyl (meth)acrylate, palmityl (meth)acrylate, stearyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (Meth)acrylic acid esters such as benzyl (meth)acrylate; cyclohexyl (meth)acrylate, 4-methylcyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, isobornyl (meth)acrylate, etc.
• Polymerizable unsaturated monomers having an alkyl group Polymerizable unsaturated monomers having an epoxy group such as glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and allyl glycidyl ether; ) Polymerizable unsaturated monomers having an aziridinyl group such as acryloylaziridine and 2-aziridinylethyl (meth)acrylate; oxazoline groups such as 2-isopropenyl-2-oxazoline and 2-vinyl-2-oxazoline Polymerizable unsaturated monomers having; unsaturated amides such as (meth)acrylamide, N-methylol (meth)acrylamide, and diacetone acrylamide; dimethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, Basic polymerizable unsaturated monomers such as vinylpiperidine, vinylimidazole, vinylpyrroli
• (meth)acrylic acid esters and aromatic group-containing monomers More preferred are methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylate. 2-ethylhexyl acrylate, styrene, styrenesulfonic acid, vinyltoluene, 4-vinylpyridine, and 2-vinylpyridine.
• examples of the compound having an adsorptive group include 11-mercaptoundecyl 2-bromo-2-methylpropionate, 2 6-mercaptoundecyl-bromo-2-methylpropionate, bis[2-(2'-bromoisobutyryloxy)ethyl]disulfide, 11-(2-bromoisobutyric acid)-undecyl-1-phosphonic acid and the like. .
• 11-mercaptoundecyl 2-bromo-2-methylpropionate and 11-(2-bromoisobutyric acid)-undecyl-1-phosphonic acid are preferred. More preferred is 11-mercaptoundecyl 2-bromo-2-methylpropionate.
• the molecular weight of compound A having a structural unit derived from an adsorptive group and a monomer is preferably a weight-average molecular weight of 300 to 1,000,000, more preferably 5,000,000 to 1,000,000, and still more preferably 1,000 to 1,000,000. 1,000,000, more preferably 1,000,000 to 700,000, particularly preferably 10,000 to 500,000, particularly preferably 10,000 to 400,000, and most preferably 10,000 to 200,000.
• the molecular weight of Compound A can be measured by the method described in Examples below.
• the film of the present disclosure may be a single layer film or a multilayer film.
• the film of the present disclosure may contain other components.
• Such components include anionic polymerization inhibitors, radical polymerization inhibitors, antioxidants, dispersants, solvents, UV absorbers, UV stabilizers, infrared absorbers, polymerization initiators, catalysts, co-catalysts, reducing agents, Examples include antistatic agents, fillers, and conductive agents.
• the solvent contained in the membrane of the present disclosure is not particularly limited, but examples include ketones such as acetone and 2-butanone; aliphatic hydrocarbons such as pentane, hexane, and heptane; aromatic hydrocarbons such as benzene, toluene, and xylene. Hydrocarbons; acetic esters such as methyl acetate, ethyl acetate and butyl acetate; ethers such as tetrahydrofuran, diethyl ether, 1,2-dimethylethane and diethylene glycol dimethyl ether; alcohols such as methanol, ethanol, isopropyl alcohol and hexanol is mentioned.
• ketones such as acetone and 2-butanone
• aliphatic hydrocarbons such as pentane, hexane, and heptane
• aromatic hydrocarbons such as benzene, toluene, and xylene. Hydrocarbons
• the solvent contained in the membrane of the present disclosure is preferably 0 to 10000 ppm by mass, more preferably 0 to 5000 ppm by mass, still more preferably 0 to 3000 mass ppm, relative to the total amount of the membrane of the present disclosure. ppm.
• the film of the present disclosure is preferably a self-assembled film.
• a self-assembled film is a film having high molecular orientation due to intermolecular interactions, and a film having high regularity in molecular arrangement due to intermolecular interactions.
• the orientation of the self-assembled film can be confirmed by a known method. For example, it can be analyzed with an electron microscope.
• the self-assembled film may be a single molecule or two or more molecules as long as the molecules are oriented, but from the viewpoint of thinning the film thickness, it is preferably a single molecule.
• the deposition substrate of the present disclosure more preferably has a self-assembled film formed of monomolecules (hereinafter sometimes referred to as a self-assembled monolayer).
• the film-forming substrate of the present disclosure has a film containing a compound A having structural units derived from an adsorptive group and a polymerizable monomer on at least a portion of a metal surface present on the substrate.
• the surface physical properties of the film-forming portion are specifically modified.
• the technique of the present disclosure is a technique that makes it possible to impart physical properties such as antifouling properties, friction reduction, water repellency, and hydrophilicity to substrates.
• the film formation substrate of the present disclosure has a function of modifying the surface of the substrate.
• the film-forming substrate of the present disclosure preferably has a film thickness of 1 nm to 1 ⁇ m, more preferably 1 nm to 500 nm, and even more preferably 1 nm to 300 nm. Within the above range, it is possible to more sufficiently modify the physical properties of the metal surface.
• the film thickness of the film on the film formation substrate can be measured by a cross-sectional SEM (film observation after cross-section preparation by FIB-SEM or ion milling), step gauge, or the like.
• the film-forming substrate of the present disclosure preferably covers the metal-containing substrate by 30% or more, more preferably 50% or more. More preferably, it is 60% or more, and most preferably 70% or more.
• the degree of film formation on the substrate containing metal can be calculated by a known method.
• an elemental analysis method using X-ray photoelectron spectroscopy also called ESCA
• it can be calculated from the difference in the amount of elements measured on the substrate before and after film formation.
• the amount of carbon (C) detected on the substrate after film formation and the amount detected on the substrate before film formation It can be calculated from the difference from the amount of carbon (C).
• it may be calculated from the difference between the amount of metal detected on the metal surface of the substrate before film formation and the amount of metal detected on the metal surface of the substrate after film formation.
• the difference between the amount of carbon detected on the substrate after film formation and the amount of carbon (C) detected on the substrate before film formation is 5% or more. It is preferable to have a membrane having It is more preferably 7% or more, still more preferably 10% or more, particularly preferably 12% or more, and most preferably 15% or more. If the deposition substrate of the present disclosure satisfies such a ratio, it can be said that a film is formed in which the compound having structural units derived from the adsorption group and the monomer has a high density.
• the amount of carbon detected on the substrate after deposition and the amount of carbon detected on the substrate before deposition should be 5% or more, but in the range of 70% or more of the film formed on the substrate, the difference in the amount of carbon (C) is 5% or more. preferably. More preferably, the difference in the amount of carbon (C) is 5% or more in the entire film formed on the substrate.
• the difference between the amount of carbon detected on the substrate after film formation and the amount of carbon (C) detected on the substrate before film formation can be measured by ESCA under the conditions described in Examples. can.
• the deposition substrate of the present disclosure may have a film with a metal element ratio (%) of 95% or less when the metal element ratio (%) detected on the metal surface of the substrate before film formation is 100.
• a metal element ratio (%) of 95% or less when the metal element ratio (%) detected on the metal surface of the substrate before film formation is 100.
• it is 60% or less, and still more preferably 50% or less.
• the ratio of metal elements on the film formation substrate surface can be measured by ESCA measurement under the conditions described in Examples.
• the method for producing the film-formed substrate of the present disclosure is not particularly limited as long as a film containing a compound having a structural unit derived from an adsorptive group and a monomer can be provided on a metal-containing substrate.
• a method for producing a film-formed substrate of the present disclosure includes a step of forming a film of a composition containing a polymer having an adsorptive group on at least a portion of a metal surface present on the substrate (hereinafter, production method 1 the step (I) of supplying a polymerization initiator containing an adsorptive group to at least a portion of the metal surface present on the substrate, and supplying a monomer to the metal surface to which the polymerization initiator has been supplied
• a method including step (II) and step (III) of polymerizing the monomer (hereinafter also referred to as production method 2) can be mentioned. Manufacturing methods 1 and 2 will be described in order below.
• Production method 1 includes a step of forming a film of a composition containing a polymer having an adsorptive group on at least a portion of a metal surface present on a substrate, and a step of producing the polymer used in this step. may contain.
• step (II) is a step of forming a film of a composition containing a polymer having an adsorptive group on at least a portion of a metal surface present on a substrate, and a polymer used in step (II) is produced.
• the step (I) is defined as the step (I), and the step (I) will be described first, and then the step (II) will be described.
• Polymers with adsorptive groups of the present disclosure are formed by polymerizing monomers.
• the adsorptive group is not particularly limited, at least one group selected from an SH group, a phosphoric acid group, a carboxylic acid group, an isocyanate group, an unsaturated hydrocarbon group, a halogenated alkyl group, a phosphonic acid group, and an amino group.
• an SH group a phosphoric acid group
• carboxylic acid group an isocyanate group
• an unsaturated hydrocarbon group a halogenated alkyl group
• a phosphonic acid group a phosphonic acid group
• amino group is not particularly limited, at least one group selected from an SH group, a phosphoric acid group, a carboxylic acid group, an isocyanate group, an unsaturated hydrocarbon group, a halogenated alkyl group, a phosphonic acid group, and an amino group.
• the method of polymerizing the monomers is not particularly limited, but may include chain polymerization such as radical polymerization, cationic polymerization, anionic polymerization, sequential polymerization, and living polymerization. Radical polymerization, particularly living radical polymerization, is preferred from the viewpoint of selectively protecting the substrate and ease of polymerization operation.
• Living radical polymerization includes atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer polymerization (RAFT), and nitroxide-mediated radical polymerization (NMP). ATRP polymerization and RAFT polymerization are preferred, and ATRP polymerization is more preferred, from the viewpoint of wide selectivity of monomers.
• ATRP atom transfer radical polymerization
• RAFT reversible addition-fragmentation chain transfer polymerization
• NMP nitroxide-mediated radical polymerization
• the polymerization initiator for polymerizing the monomer is not particularly limited, it is preferably a compound containing an adsorptive group.
• a polymer having an adsorptive group and a structural unit derived from the monomer is obtained by performing a polymerization reaction of the monomer using a compound containing an adsorptive group as an initiator.
• the initiator may be, but not limited to, 11-mercaptoundecyl 2-bromo-2-methylpropionate, 6-mercaptoundecyl 2-bromo-2-methylpropionate, bis[2 -(2'-bromoisobutyryloxy)ethyl]disulfide, 11-(2-bromoisobutyric acid)-undecyl-1-phosphonic acid and the like.
• a catalyst may be used in the production step (I) of the polymer having an adsorptive group.
• the catalyst of the present disclosure is not particularly limited. ); and titanium halide catalysts such as titanium (II) chloride, titanium (III) chloride, titanium (IV) chloride, and titanium (IV) bromide.
• the halogenated catalyst of the present disclosure may coexist with a ligand as a co-catalyst.
• a ligand for example, 2,2'-bipyridine, 4,4'-di(5-nonyl)-2,2'-bipyridine, methyl 2-bromopropionate, ethyl 2-bromoisobutyrate and the like are included. From this point of view, 2,2'-bipyridine is preferred.
• a reducing agent may coexist in the halogenated catalyst of the present disclosure. In some cases, it functions as a co-catalyst.
• reducing agents include ascorbic acid, sodium ascorbate, tin (II) 2-ethylhexanoate, cyclodextrin, phenylhydrazine, hydrazine, sodium borohydride, sodium citrate, methylaminoethanol, dimethylaminoethanol, triethanolamine and the like.
• RAFT polymerization is a method of polymerizing in the presence of a RAFT agent.
• initiators commonly used in radical polymerization are used.
• Peroxides such as, for example, hydrogen peroxide, isobutyl peroxide, t-butyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate, sodium persulfate; Azobisisobutyronitrile (AIBN), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2-cyclopropylpropionitrile), 2,2′ - azo compounds such as azobis (2-methylpropionitrile) and 2,2'-azobis (2-methylbutyronitrile); hydrogen peroxide - ascorbic acid, hydrogen peroxide -
• RAFT agents used in RAFT polymerization include compounds having a thiocarbonylthio group (--CS--S--) in the molecule.
• RAFT agents when classified according to the characteristics of their chemical structures, they include dithioester compounds, trithiocarbonate compounds, dithiocarbamate compounds, xanthate compounds, and the like.
• the initiators according to the invention are generally from 10 ⁇ 4 mol/L to 3 mol/L, preferably from 10 ⁇ 3 mol/L to 1 mol/L, particularly preferably from 5 ⁇ 10 ⁇ 2 mol/L to 5 ⁇ 10 ⁇ 2 mol/L. Concentrations in the range 10 ⁇ 1 mol/L can be used, but should not be limited thereby.
• the molar ratio of catalyst to initiator of the present disclosure is preferably from 0.0001:1 to 10:1, more preferably from 0.01:1 to 5:1. Yes, more preferably 0.01:1 to 3:1.
• the molar ratio of cocatalyst to initiator of the present disclosure is preferably from 0.0001:1 to 10:1, more preferably from 0.01:1 to 5:1 and more preferably 0.01:1 to 3:1.
• the initiator of the present disclosure includes, as other components, an anionic polymerization inhibitor, a radical polymerization inhibitor, an antioxidant, a dispersant, a solvent, an ultraviolet absorber, an ultraviolet stabilizer, an infrared absorber, other polymerization initiators, and co-catalysts. , an antistatic agent, a filler, a conductive agent, and the like.
• solvents examples include ketones such as acetone and 2-butanone; aliphatic hydrocarbons such as pentane, hexane and heptane; aromatic hydrocarbons such as benzene, toluene and xylene; methyl acetate, ethyl acetate and butyl acetate. , acetic acid derivatives such as propylene glycol monomethyl ether acetate; ethers such as tetrahydrofuran, diethyl ether, 1,2-dimethylethane and diethylene glycol dimethyl ether; alcohols such as methanol, ethanol, isopropyl alcohol and hexanol. These solvents may be used alone, or two or more of them may be appropriately mixed and used.
• the membranes of the present disclosure have polymers containing structural moieties derived from monomers.
• the weight-average molecular weight (Mw) of the polymer is preferably 3,000,000 to 1,000,000, more preferably 5,000,000 to 1,000,000. More preferably 5-700,000, still more preferably 5-500,000, particularly preferably 10-400,000, most preferably 1000-200,000.
• the weight average molecular weight of the polymer can be measured by the method described in Examples below.
• the molecular weight distribution (Mw/Mn) of the polymer is preferably 1.01 to 3.0, more preferably 1.01 to 2, still more preferably 1.01 to 1.7, and most It is preferably between 1.01 and 1.5, and most preferably between 1.01 and 1.3.
• the monomer the same as the monomer explained as the raw material of compound A can be used, and the preferred ones are also the same.
• the monomers of the present disclosure include, as other components, anionic polymerization inhibitors, radical polymerization inhibitors, antioxidants, dispersants, solvents, UV absorbers, UV stabilizers, infrared absorbers, polymerization initiators, catalysts, A co-catalyst, an antistatic agent, a filler, a conductive agent, etc. may be included.
• amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, etc., Dimethyl sulfoxide can be mentioned. These solvents may be used alone, or two or more of them may be appropriately mixed and used.
• step (I) is preferably carried out at -50 to 250°C, more preferably 0 to 200°C, still more preferably 10 to 150°C.
• step (I) is preferably carried out for 1 to 2000 minutes, more preferably 1 to 1000 minutes, even more preferably 1 to 800 minutes, and most preferably 1 to 500 minutes.
• the origin of the adsorptive group is not particularly limited as long as the resulting polymer has an adsorptive group, and the adsorptive group may be contained in the monomer that is the raw material of the polymer. well, it may be included in the initiator. Further, it may be contained as a component other than the monomer and the initiator, and may be generated by decomposing a structure contained in the polymer structure such as a RAFT agent.
• a film can be formed by binding the adsorption groups of the polymer obtained in step (I) to the substrate.
• Step (II) of production method 1 is a step of forming a film of a composition containing a polymer having an adsorptive group on at least a portion of the metal surface present on the substrate.
• the film-forming substrate of the present disclosure is obtained by forming a film of a composition containing a polymer on a substrate containing metal.
• a method for forming a film of a composition containing a polymer on a substrate containing a metal is not particularly limited, and a method of coating a composition containing a polymer on a substrate can be used. Alternatively, a substrate containing metal may be immersed in a composition containing a polymer.
• the step (II) of production method 1 is preferably carried out at 10 to 300°C, more preferably 10 to 250°C, even more preferably 15 to 100°C.
• the step (II) of production method 1 is preferably carried out for 0.1 to 2000 minutes, more preferably 0.3 to 1800 minutes, and even more preferably 1 to 1500 minutes.
• composition used in step (II) of production method 1 may contain a polymer having an adsorptive group, but is preferably the composition obtained in step (I).
• the composition used in step (II) of production method 1 preferably contains a polymer having an adsorptive group and a solvent.
• the ratio of the polymer having an adsorptive group in the composition containing the polymer having an adsorptive group is preferably 0.0001 to 10% by mass with respect to 100% by mass of the composition. More preferably 0.0001 to 5% by mass, still more preferably 0.0001 to 3% by mass.
• a film can be formed by adsorbing the adsorption groups contained in the polymer to the substrate.
• composition used in step (II) of production method 1 contains, as other components, an antioxidant, a dispersant, a binder, an ultraviolet absorber, an ultraviolet stabilizer, an infrared absorber, an antistatic agent, a conductive agent, and the like. You can
• the manufacturing method 1 of the present disclosure may have a step of cleaning and drying the metal-containing substrate (cleaning/drying step-1) in addition to the steps (I) and (II) described above. Further, the manufacturing method 1 of the present disclosure may have a step of cleaning and drying the film formation substrate (cleaning/drying step-2).
• the solvent used for washing is not particularly limited, but examples include ketones such as acetone and 2-butanone; pentane and hexane. , heptane and other aliphatic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; methyl acetate, ethyl acetate, butyl acetate and other acetic esters; tetrahydrofuran, diethyl ether, 1,2-dimethylethane, diethylene glycol ethers such as dimethyl ether; alcohols such as methanol, ethanol, isopropyl alcohol and hexanol;
• the drying time is preferably 0.05 to 24 hours, more preferably 0.05 to 12 hours, and still more preferably. is between 0.05 and 5 hours.
• the drying temperature is preferably 5 to 300°C, more preferably 10 to 250°C, still more preferably 20 to 150°C.
• Step (I) of production method 2 of the present disclosure is a step of supplying an initiator containing an adsorptive group to a metal-containing substrate.
• Initiator Initiator containing adsorbing groups are not particularly limited, but adsorbing groups include thiol groups, phosphoric acid groups, carboxylic acid groups, amino groups, isocyanate groups, alkyl halides and phosphonic acid groups.
• the initiator is more preferably an organic halide or a sulfonyl halide compound. Specifically, 11-mercaptoundecyl 2-bromo-2-methylpropionate, 6-mercaptoundecyl 2-bromo-2-methylpropionate, bis[2-(2′-bromoisobutyryloxy)ethyl]disulfide, 11 -(2-bromoisobutyric acid)-undecyl-1-phosphonic acid.
• the initiator used in the production method 2 of the present disclosure includes other components such as an anionic polymerization inhibitor, a radical polymerization inhibitor, an antioxidant, a dispersant, a solvent, an ultraviolet absorber, an ultraviolet stabilizer, an infrared absorber, and polymerization. It may contain initiators, catalysts, co-catalysts, antistatic agents, fillers, conductive agents, and the like.
• solvents are not particularly limited, but includes the same solvent as the solvent that the initiator may contain in step (I) of production method 1 described above. These solvents may be used alone, or two or more of them may be appropriately mixed and used.
• Step (I) of production method 2 of the present disclosure is a step of supplying an initiator containing an adsorptive group to a substrate containing a metal, but the method of supplying the initiator to a substrate containing a metal is not particularly limited. Alternatively, the initiator may be applied to the metal-containing substrate, or the metal-containing substrate may be immersed in the initiator solution.
• the step (I) of the production method 2 of the present disclosure may be performed once or twice or more.
• the step (I) of production method 2 of the present disclosure is preferably carried out at 10 to 300°C, more preferably 10 to 250°C, even more preferably 15 to 100°C.
• Step (I) of production method 2 of the present disclosure is preferably carried out for 0.1 to 2000 minutes, more preferably 0.3 to 1800 minutes, and even more preferably 1 to 1500 minutes.
• Step (II) of production method 2 of the present disclosure is a step of supplying a monomer to the metal surface to which the polymerization initiator is adhered.
• the monomer used in the production method 2 of the present disclosure is not particularly limited, but the same monomers as those described above as the raw material of compound A can be used, and the preferred ones are also the same.
• the monomer used in the production method 2 of the present disclosure includes, as other components, an anionic polymerization inhibitor, a radical polymerization inhibitor, an antioxidant, a dispersant, a solvent, an ultraviolet absorber, an ultraviolet stabilizer, an infrared absorber, Polymerization initiators, catalysts, co-catalysts, antistatic agents, fillers, conductive agents and the like may also be included.
• the solvent contained as another component in the monomer used in the production method 2 of the present disclosure is not particularly limited, but for example, in the step (I) of the production method 1 described above, the solvent that the initiator may contain and similar solvents. These solvents may be used alone, or two or more of them may be appropriately mixed and used.
• step (II) of production method 2 of the present disclosure the method is not limited as long as the monomer is supplied to the metal surface of the substrate to which the polymerization initiator is supplied.
• the monomer solution may be applied, or the metal-containing substrate may be dipped into the monomer solution.
• the step (II) of production method 2 of the present disclosure may be performed once, or may be performed twice or more.
• the step (II) of production method 2 of the present disclosure is preferably carried out at 0 to 300°C, more preferably 10 to 250°C, and even more preferably 20 to 150°C.
• Step (II) of production method 2 of the present disclosure is preferably carried out for 0 to 300 minutes, more preferably 0 to 250 minutes, and even more preferably 0 to 200 minutes.
• Step (II) and step (III) of production method 2 of the present disclosure may be started at the same time.
• Step (III) of production method 2 of the present disclosure is a step of polymerizing the monomer supplied to the metal surface of the substrate supplied with the polymerization initiator.
• the method of polymerizing the monomers in step (III) of production method 2 of the present disclosure is not particularly limited, but chain polymerization such as radical polymerization, cationic polymerization, and anionic polymerization, sequential polymerization, and the like can be mentioned.
• Radical polymerization, particularly living radical polymerization is preferred from the viewpoint of selectively protecting the substrate and ease of polymerization operation.
• Living radical polymerization includes atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer polymerization (RAFT), NMP polymerization, and the like. More preferred is ATRP polymerization.
• Process (III) of production method 2 of the present disclosure is not particularly limited, but is preferably carried out at -50 to 250°C, more preferably 0 to 200°C, and even more preferably 10 to 150°C.
• Step (III) of production method 2 of the present disclosure is preferably carried out for 1 to 4000 minutes, more preferably 1 to 2000 minutes, even more preferably 1 to 1000 minutes, most preferably 1 to 500 minutes. be.
• Step (II) and step (III) of production method 2 of the present disclosure may be started at the same time.
• a catalyst or the like may be used as appropriate depending on the polymerization initiator and polymerization method.
• a step of adding a catalyst or co-catalyst may be included in order to initiate polymerization or speed up the polymerization rate.
• Halogenated catalysts include, for example, copper halide catalysts such as copper (I) chloride, copper (II) chloride, copper (I) bromide, copper (II) bromide; titanium (II) chloride, titanium (III) chloride ), titanium halide catalysts such as titanium (IV) chloride and titanium (IV) bromide.
• the halogenated catalyst used in production method 2 of the present disclosure may coexist with a ligand as a co-catalyst.
• a ligand examples include bipyridine, 4,4'-di(5-nonyl)-2,2'-bipyridine, methyl 2-bromopropionate, ethyl 2-bromoisobutyrate and the like.
• a reducing agent may coexist in the halogenated catalyst used in production method 2 of the present disclosure. In some cases, it functions as a co-catalyst.
• reducing agents include ascorbic acid, sodium ascorbate, tin (II) 2-ethylhexanoate, cyclodextrin, phenylhydrazine, hydrazine, sodium borohydride, sodium citrate, methylaminoethanol, dimethylaminoethanol, triethanolamine and the like.
• the catalyst used in production method 2 of the present disclosure is preferably 0.0001 to 10 mol%, more preferably 0.001 to 5 mol%, still more preferably 0.001 to 10 mol%, relative to the total amount of monomers. 005 to 4 mol %.
• the amount of ligand used is preferably 0.0001 to 10 mol%, more preferably 0.0001 to 8, relative to the total amount of monomers. mol %, more preferably 0.0001 to 5 mol %.
• the catalyst addition step may be performed before or after step (I), and may be performed before or after step (II). , may be performed before or after step (III). It may also be carried out during the steps (I), (II) and (III).
• the solvent is not particularly limited, but includes, for example, the same solvent as the solvent that the initiator may contain in step (I) of production method 1 described above.
• the production method 2 of the present disclosure may have a step of cleaning and drying the metal-containing substrate (cleaning/drying step-1) in addition to the steps described above. Further, the manufacturing method 2 of the present disclosure may have a step of cleaning and drying the film formation substrate (cleaning/drying step-2).
• the solvent used for washing is not particularly limited, but washing/drying step-1 and washing of production method 1 of the present disclosure ⁇
• the same solvent as the solvent used for washing can be used.
• the drying time and drying temperature are the same as the cleaning/drying step-1 and cleaning/drying step- of production method 1 of the present disclosure.
• the drying time and drying temperature in 2 are the same.
• the step (I) of supplying a polymerization initiator containing an adsorptive group to at least a part of the metal surface present on the substrate instead of the supplying step (II), the initiator used in the production method 2 of the present disclosure and the step of mixing the monomer (mixing step), and the composition obtained in the mixing step are placed on the substrate You may perform the process (mixture supply process) of supplying to at least one part of a metal surface.
• Such a production method in which the mixing step and the mixture supply step are performed instead of the steps (I) and (II) of the production method 2 of the present disclosure can also be referred to as the production method 3 of the present disclosure.
• the initiators and monomers used in the mixing step of production method 3 of the present disclosure may contain other components that the initiators and monomers used in production method 2 may contain, respectively.
• the method is not particularly limited as long as the composition obtained in the mixing step is supplied to the metal-containing substrate.
• the substrate may be immersed in the composition obtained in the mixing step.
• the monomers may be polymerized in the mixing step.
• the film-forming substrate of the present disclosure can be applied to various fields such as the construction field, the automobile field, the electrical/electronic field, and the medical field.
• the electric/electronic field it can be installed in notebook personal computers, tablet terminals, mobile phones, smart phones, digital video cameras, digital cameras, digital clock supercomputers, and the like.
• the molecular weight of the synthesized polymer was determined by dissolving and diluting with THF, filtering through a filter, and measuring with the following equipment.
• Apparatus manufactured by Tosoh Corporation: HLC-8420GPC Standard material: standard polystyrene Eluent: THF Separation column: TSKgel SupermultiporeHZ-M x 2 (manufactured by Tosoh Corporation)
• ⁇ contact angle of the film-formed substrate - contact angle of the non-film-formed substrate is 20 ° or more
• ⁇ contact angle of the film-formed substrate - contact angle of the non-film-formed reference substrate is 4 ° or more and less than 20 °
• ⁇ contact angle of the film-formed substrate - Non-film-formed reference substrate Contact angle less than 4° Calculated based on Cu when film is formed on Cu, and on SiO2 substrate when film is formed on SiO2 .
• Example 1 (Pretreatment of substrate) A wafer with Cu (thickness 725 ⁇ m) provided by Filtec was prepared. After immersing the substrate in toluene for 10 minutes, it was immersed in 10 mL isopropyl alcohol (IPA) for 1 minute. Thereafter, the substrate was immersed in a 1% aqueous citric acid solution, immersed in ultrapure water, spray-washed, and dried by flowing N 2 gas.
• IPA isopropyl alcohol
• Example 2 A substrate on which a film was formed was obtained in the same manner as in Example 1 except that the polymer was changed to 0.056 g of Polystyrene thiol terminated (average Mn 11000, Mw/Mn ⁇ 1.1) purchased from Adrich. Table 1 shows the results of IR measurement, ECSA measurement, and contact angle measurement of the obtained film-formed substrate.
• Example 1 A substrate was obtained in the same manner as in Example 1, except that the substrate was changed to a SiO 2 substrate manufactured by Filtec. Table 1 shows the results of IR measurement, ECSA measurement, and contact angle measurement of the obtained substrate.
• Example 2 A substrate was obtained in the same manner as in Example 2, except that the substrate was changed to a SiO 2 substrate manufactured by Filtec. Table 1 shows the results of IR measurement, ECSA measurement, and contact angle measurement of the obtained substrate.
• the film-forming substrate produced by the production method 1 of the present disclosure has water repellency. rice field.
• polymer powder 1 was obtained.
• polymer powder 1 and 21.5 g of THF were placed in a glass test tube container containing a stirrer. After N2 substitution, butylamine was added dropwise via syringe and stirred overnight at room temperature. After reprecipitation in MeOH, filtration under reduced pressure and drying, polymer powder 2 was obtained.
• polymer powder 2, dithiotreol, and DMF were put into a glass test tube container containing a stirrer. After N2 degassing, the reaction was terminated by heating at 60° C. for 20 hours.
• the reaction solution was reprecipitated in MeOH, filtered under reduced pressure, and dried in vacuum to obtain a polymer powder having SH at the terminal.
• the obtained polymer had a number average molecular weight Mn of 2400 and a molecular weight distribution of 1.1.
• Example 3 A film-formed substrate was obtained in the same manner as in Example 2, except that the substrate was a patterned substrate provided by GBN, and the polymer for film formation was changed to the polymer obtained in Synthesis Example 3.
• Example 4 A film-formed substrate was obtained in the same manner as in Example 3, except that the polymer was changed to Pst-SH (Mn11000).
• Example 5 A patterned substrate supplied from GBN was immersed in toluene for 10 minutes and then immersed in 10 mL isopropyl alcohol (IPA) for 1 minute. Thereafter, the substrate was immersed in a 1% aqueous citric acid solution, immersed in ultrapure water, spray-washed, and dried by flowing N 2 gas.
• the polymer obtained in Synthesis Example 3 was dissolved in DMF to a solid content of 0.1%, spun at 3200 rpm for 15 s using a MIKASA spin coater MS-A100, and 0.1 g of the polymer solution was applied. Then, spin coating film formation was performed.
• Example 6 Film formation was carried out in the same manner as in Example 5 except that the polymer was changed to PSt-SH (Mn11000) obtained from Aldrich.
• the film formation substrates of Examples 5 and 6 were evaluated for film formability by ESCA measurement. Table 2 shows the results.
• ESCA measurement> Measurement conditions/excitation source: Al K ⁇ 15mA 15kV Pass Energy: 160eV
• the film formability was judged by the difference (%) in the C element present on the substrate surface after film formation compared to the substrate before film formation.
• C ratio of the substrate after film formation - C ratio (%) of the substrate before film formation is 15% or more: ⁇ C ratio of substrate after film formation - C ratio (%) of substrate before film formation is 10% or more and less than 15%: ⁇ C ratio of the substrate after film formation - C ratio (%) of the substrate before film formation is 5% or more and less than 10%: ⁇ C ratio of substrate after film formation - C ratio (%) of substrate before film formation is less than 5%: ⁇
• the patterned substrate was a substrate in which the polymer was selectively deposited only on the metal portion.
• Example 7 (Substrate cleaning treatment) A wafer with Cu provided by Filtec was prepared. After immersing the substrate in toluene for 10 minutes, it was immersed in 10 mL isopropyl alcohol (IPA) for 1 minute. After that, the substrate was immersed in a 1% citric acid aqueous solution, then immersed in ultrapure water, spray-washed, and N 2 was flowed to dry the substrate.
• IPA isopropyl alcohol
• Step (I) 0.056 g of the initiator synthesized in Synthesis Example 1 was dissolved in 12.24 g of isopropyl alcohol (hereinafter referred to as IPA), and the wafer was immersed in the initiator solution for 19 hours. After 19 hours, the wafer was taken out, washed by immersion in IPA and ultrapure water for 1 minute each, spray-washed with ultrapure water, dried by N 2 flow, and dried by vacuum drying for 30 minutes.
• IPA isopropyl alcohol
• Step (II) A column was packed with alumina and passed through with methyl methacrylate to remove the inhibitor. 0.002 g of copper (II) bromide, 0.006 g of 2,2′-bipyridine, and 0.315 g of ascorbic acid were weighed into a glass container and purged with N 2 for 30 minutes. 10 g of MMA after column treatment, 8 g of methanol, and 2 g of ion-exchanged water were weighed into a two-necked flask, degassed, and then bubbled with N2 for 30 min.
• the substrate coated with the initiator, the glass vessel containing the catalyst and the two-necked flask were placed in a N2 - filled glove box (GB) with an oxygen concentration of ⁇ 0.1%.
• the monomer solution was placed in a glass container containing a catalyst, covered with a lid, and thoroughly stirred. After 3 hours, the substrate was taken out, washed by immersion in toluene under air, spray-washed with toluene several times, and then immersed and washed in IPA. Thereafter, the substrate was spray-washed with ultrapure water, dried with N 2 flow, and dried in a vacuum dryer for 1 hour to obtain a substrate with a film formed thereon.
• Table 3 shows the results of IR measurement, ECSA measurement, and contact angle measurement of the obtained film-formed substrate.
• Example 8> In step (II) of Example 7, the monomer was changed from 10 g of MMA to 10 g of styrene, the polymerization solvent was changed from 8 g of methanol to 10 g, and from 2 g of deionized water to 0 g, and the polymerization time after the substrate was placed was changed from 3 hours to 24 hours. Except for this, the same operation as in Example 3 was performed to obtain a substrate on which a film was formed. Table 3 shows the results of IR measurement, ECSA measurement, and contact angle measurement of the obtained film-formed substrate.
• Example 3 A substrate was obtained in the same manner as in Example 7, except that the substrate was changed to a SiO 2 substrate manufactured by Filtec. Table 3 shows the results of IR measurement, ECSA measurement, and contact angle measurement of the obtained substrate.
• Example 4 A substrate was obtained in the same manner as in Example 8, except that the substrate was changed to a SiO 2 substrate manufactured by Filtec. Table 3 shows the results of IR measurement, ECSA measurement, and contact angle measurement of the obtained substrate.
• the film-forming substrate produced by production method 2 of the present disclosure has water repellency. rice field.
• the substrate was a film-formed substrate in which a polymer film was formed on the metal surface of the patterned substrate.

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