Deposition substrate

Abstract

The purpose of the present invention is to provide a novel substrate with a film formed thereon, in which a high-density film is formed on at least a part of a metal surface present on a substrate. Provided is a substrate with a film formed thereon, wherein a film which contains a compound having a structural unit derived from a monomer and an adsorption group is formed on at least a part of a metal surface present on a substrate, and the specific gravity of the metal is not more than 19.30 g / cm3.

Description

[Technical Field]

[0001] The present invention relates to a film formation substrate. [Background technology]

[0002] Conventionally, it is known that a substrate on which a film is formed is obtained by applying an initiator to the substrate in advance, polymerizing the monomer by supplying it, and allowing the polymer to be adsorbed on the substrate (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2019 / 131872 Summary of the Invention [Problem to be solved by the invention]

[0004] Conventionally, methods for forming a film on a substrate and modifying the surface have been known, but there has been a demand for a technology for selectively forming a film on the metal portion of a substrate and modifying the surface.

[0005] Therefore, 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 a portion of the metal surface present on the substrate. [Means for solving the problem]

[0006] The present inventors have conducted various studies to achieve the above object and have arrived at the present invention.

[0007] The present disclosure is as follows. [1] A film containing a compound having an adsorption group and a structural unit derived from a monomer is formed on at least a part of a metal surface present on a substrate, The specific gravity of the metal is 19.30 g / cm 3 The following is a deposition substrate.

[0008] [2] The film-formation substrate according to [1], wherein the adsorptive group is at least one type of group selected from the group consisting of an SH group, a phosphate group, a phosphonate group, a carboxylic acid group, an isocyanate group, an unsaturated hydrocarbon group, a halogenated alkyl group, and an amino group.

[0009] [3] The film-formed substrate according to [1] or [2], wherein the structural unit derived from the monomer includes one or more structural units selected from a structural unit derived from a (meth)acrylic acid ester and a structural unit derived from an aromatic group-containing monomer.

[0010] [4] A film containing a compound having an adsorption group and a structural unit derived from a monomer is formed on at least a part of a metal surface present on a substrate; The film-formed substrate according to any one of [1] to [3], having a partitioned portion in which the difference between the carbon element percentage of the film and the carbon element percentage of the substrate, as detected by ESCA, is 5% or more.

[0011] [5] The film-formation substrate according to any one of [1] to [4], wherein the compound has a weight-average molecular weight of 1,000 to 400,000.

[0012] [6] 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 a substrate.

[0013] [7] A method for producing a film-formed substrate, comprising the steps of: (I) supplying a polymerization initiator containing an adsorptive group to at least a portion of a metal surface present on a substrate; (II) supplying a monomer to the metal surface to which the polymerization initiator has been supplied; and (III) polymerizing the monomer. [Effects of the Invention]

[0014] The film-formed substrate of the present disclosure has a high-density film formed on at least a portion of the metal surface present on the substrate, and the formation of such a high-density film can specifically modify the physical properties of the surface, making the film-formed substrate of the present disclosure applicable to various fields such as the construction field, the automotive field, the electrical / electronic field, and the medical field. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present invention will be described in detail below. Note that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

[0016] [Deposition substrate of the present disclosure] <Substrate> The substrate of the present disclosure may contain a metal (hereinafter, sometimes referred to as a metal-containing substrate). Here, the metal-containing substrate includes a substrate formed only from a metal and a substrate formed from a metal and a material other than a metal. The material other than a metal is not particularly limited, but examples thereof include resins. When the substrate contains a metal, it is preferable that the substrate has the metal on at least a portion of its surface.

[0017] Substrates in the present disclosure include, but are not limited to, metal pieces, metallized films, semiconductor wafers, printed circuit boards, metallized films, and the like. As described above, 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-like substrate such as a printed circuit board, and is preferably 10 to 250 μm, more preferably 20 to 200 μm, in the case of a film-like substrate.

[0018] The metal species contained in the substrate of the present disclosure is not particularly limited. Preferably, it is a metal element of Groups 6 to 12, more preferably a metal element of Groups 6, 8 to 11, even more preferably a metal element of Groups 6, 8, 9, and 11, particularly preferably molybdenum, ruthenium, tungsten, cobalt, silver, or copper, and most preferably copper or cobalt. It is sufficient that one metal species is contained, but two or more metal species may also be contained.

[0019] The density of the substrate of the present disclosure is not particularly limited, but is preferably 1 g / cm 3 ~30g / cm3 and more preferably 3 g / cm 3 ~20g / cm 3 and more preferably 10 g / cm 3 ~19.3g / cm 3 is.

[0020] 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, and even more preferably 0.0001 to 95 parts by mass, relative to 100 parts by mass of the metal-containing substrate.

[0021] The specific heat of the substrate containing the metal of the present disclosure is not particularly limited, but is preferably 0.1 KJ·Kg at 25°C. -1 ·K -1 ~1.2KJ·Kg -1 ·K -1 and more preferably 0.12KJ·Kg -1 ·K -1 ~0.8KJ·Kg -1 ·K -1 and more preferably 0.13 KJ·Kg -1 ·K -1 ~0.5KJ·Kg -1 ·K -1 is. The specific heat of the substrate can be measured by a laser flash method, an adiabatic method, a DSC method, or the like.

[0022] The thermal conductivity of the metal-containing substrate of the present disclosure is not particularly limited, but is preferably 10 W m -1 ·K -1 ~500W·m -1 ·K -1 and more preferably 30 W m -1 ·K -1 ~450W·m -1 ·K -1 and more preferably 50 W m -1 ·K -1 ~400W·m -1 ·K -1 is. The thermal conductivity of the substrate can be measured by a temperature gradient method (JIS H7903), a disk heat flow meter method (ASTE E1530), or the like.

[0023] <Membrane> The membrane of the present disclosure contains a compound (hereinafter also referred to as compound A) having an adsorptive group and a structural unit derived from a monomer.

[0024] The adsorptive group is preferably one or more groups selected from a thiol group (SH group), a phosphonic acid group, a phosphoric acid group, a carboxylic acid group, an isocyanate group, an unsaturated hydrocarbon group, a halogenated alkyl group, and an amino group.

[0025] The structural unit derived from the monomer refers to a structural unit having the same structure as the structure formed by polymerization of the monomer, and is usually a structure in which at least one of the carbon-carbon unsaturated double bonds contained in the monomer is replaced with a carbon-carbon single bond. Note that the structural unit derived from the monomer does not necessarily have to be a structural unit formed by actual polymerization of the monomer, and even a structural unit formed by a method other than polymerization of the monomer is included in the structural unit derived from the monomer as long as it has the same structure as the structure formed by polymerization of the monomer. For example, in the case of methyl acrylate (CH2=CH(-COOCH3)), the structural unit derived from methyl acrylate can be represented by -CH2-CH(-COOCH3)-.

[0026] The compound A contained in the film of the present disclosure has a structural unit derived from a compound containing an adsorptive group. When the compound containing an adsorptive group is a monomer containing an adsorptive group, the structural unit derived from the compound containing an adsorptive group means a structure in which at least one carbon-carbon unsaturated double bond contained in the monomer containing an adsorptive group is replaced with a carbon-carbon single bond. In the case where the compound containing an adsorptive group is not a monomer, but reacts with a monomer during the production of compound A to form a monomer containing an adsorptive group, this refers to the structural portion derived from the compound containing an adsorptive group in the structure of the monomer containing an adsorptive group.

[0027] The compound containing the adsorbing group may be a compound that has the adsorbing group as it is, or may be a compound that has a structural unit containing the adsorbing group that is formed by the adsorbing group reacting with another functional group. For example, in the case of ethanethiol (CH3-CH2-SH), if the thiol group (-SH) reacts with another functional group to form a structure represented by an -SR group (R represents a structural unit derived from another functional group), the structural unit containing the adsorbing group can be represented by -S-. The compound containing the adsorbing group may have the structure -SH (if it has the adsorbing group as it is).

[0028] The membranes of the present disclosure are capable of binding adsorption groups to metal-containing substrates.

[0029] The bond between the film of the present disclosure and the metal-containing substrate is preferably a bond between the adsorptive group of compound A contained in the film and the metal-containing substrate, but a structural unit derived from a monomer of compound A may also be bonded to the metal-containing substrate. These bonds may be physical bonds or chemical bonds.

[0030] The compound A contained in the film may have one or more adsorption groups, or may have two or more adsorption groups. When compound A has two or more functional groups, the adsorption groups may be the same type of functional group or different types of functional groups. Furthermore, the film may contain only one type of compound corresponding to compound A, or may contain two or more types.

[0031] 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, and most preferably a thiol group. By containing the above adsorptive group, the bonding strength between the film of the present disclosure and the substrate containing a metal tends to be stronger.

[0032] The membrane of the present disclosure contains a compound A having an adsorptive group and a structural moiety derived from a monomer. Compound A may be obtained using a monomer having an adsorptive group as a raw material, or may be obtained by reacting a compound having an adsorptive group with a monomer.

[0033] The monomer is not particularly limited, and examples thereof include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, oleyl (meth)acrylate, palmityl (meth)acrylate, stearyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and benzyl (meth)acrylate. esters; polymerizable unsaturated monomers having a cycloalkyl group such as cyclohexyl (meth)acrylate, 4-methylcyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, and isobornyl (meth)acrylate; 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 (meth)acryloylaziridine and 2-aziridinylethyl (meth)acrylate. unsaturated amides such as (meth)acrylamide, N-methylol (meth)acrylamide, and diacetone acrylamide; basic polymerizable unsaturated monomers such as dimethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, vinylpiperidine, vinylimidazole, vinylpyrrolidone, 4-vinylpyridine, and 2-vinylpyridine; unsaturated aromatic monomers such as styrene, styrene sulfonic acid, vinyltoluene, and α-methylstyrene; unsaturated nitriles having a cyano group such as (meth)acrylonitrile; polyfunctional (meth)acrylic acid esters having two or more polymerizable unsaturated groups in the molecule, such as esters of (meth)acrylic acid with polyhydric alcohols such as ethylene glycol, 1,3-butylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, and trimethylolpropane; and polyfunctional vinyl compounds such as divinylbenzene.More preferred are (meth)acrylic acid esters and aromatic group-containing monomers, and even more preferred are methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, styrene, styrenesulfonic acid, vinyltoluene, 4-vinylpyridine, and 2-vinylpyridine.

[0034] When compound A is obtained by reacting a compound having an adsorptive group with a monomer, examples of the compound having an adsorptive group include 11-mercaptoundecyl 2-bromo-2-methylpropionate, 6-mercaptoundecyl 2-bromo-2-methylpropionate, bis[2-(2'-bromoisobutyryloxy)ethyl]disulfide, and 11-(2-bromoisobutyric acid)-undecyl-1-phosphonic acid. Among these, 11-mercaptoundecyl 2-bromo-2-methylpropionate and 11-(2-bromoisobutyric acid)-undecyl-1-phosphonic acid are preferred. 11-mercaptoundecyl 2-bromo-2-methylpropionate is more preferred.

[0035] The molecular weight of compound A having an adsorptive group and a structural unit derived from a monomer is preferably a weight average molecular weight of 300 to 1,000,000, more preferably 5,000 to 1,000,000, even more preferably 1,000 to 1,000,000, still more preferably 1,000 to 700,000, particularly preferably 1,000 to 500,000, of which particularly preferably 1,000 to 400,000, and most preferably 1,000 to 200,000. The molecular weight of compound A can be measured by the method described in the Examples below.

[0036] The membranes of the present disclosure may be single layer membranes or multilayer membranes.

[0037] The membrane of the present disclosure may contain 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, a polymerization initiator, a catalyst, a co-catalyst, a reducing agent, an antistatic agent, a filler, and a conductive agent.

[0038] The solvent contained in the membrane of the present disclosure is not particularly limited, but examples thereof include ketones such as acetone and 2-butanone; aliphatic hydrocarbons such as pentane, hexane, and heptane; aromatic hydrocarbons such as benzene, toluene, and xylene; acetate esters such as methyl acetate, ethyl acetate, and butyl acetate; ethers such as tetrahydrofuran, diethyl ether, 1,2-dimethylethane, and diethylene glycol dimethyl ether; and alcohols such as methanol, ethanol, isopropyl alcohol, and hexanol.

[0039] The solvent contained in the film of the present disclosure is preferably 0 to 10,000 ppm by mass, more preferably 0 to 5,000 ppm by mass, and even more preferably 0 to 3,000 ppm by mass, relative to the total amount of the film of the present disclosure.

[0040] From the viewpoint of achieving a uniform film surface, the film of the present disclosure is preferably a self-assembled film, which is a film having high molecular orientation due to intermolecular interactions and has high regularity in molecular arrangement due to intermolecular interactions.

[0041] The orientation of the self-assembled monolayer can be confirmed by known methods, for example, by analysis using an electron microscope.

[0042] The self-assembled film may be a single molecule or a molecule of two or more molecules as long as the molecules are oriented, but is preferably a single molecule from the viewpoint of being able to make the film thin.

[0043] The film formation substrate of the present disclosure more preferably has a self-assembled film formed from monomolecules (hereinafter, may be referred to as a self-assembled monolayer).

[0044] <Deposition substrate> The film-formation substrate of the present disclosure has a film containing a compound A having an adsorptive group and a structural unit derived from a polymerizable monomer on at least a portion of the metal surface present on the substrate.

[0045] By forming a film containing compound A having an adsorption group and a structural unit derived from a monomer on a substrate such as the film-forming substrate of the present disclosure, it is possible to specifically modify the surface properties of the film-forming portion. The technology of the present disclosure is a technology that makes it possible to impart physical properties to the substrate, such as antifouling properties, friction reduction, water repellency, and hydrophilicity. The film-forming substrate of the present disclosure has a surface-modified function.

[0046] The film-formation substrate of the present disclosure preferably has a film thickness of 1 nm to 1 μm, 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 thickness of the film on the deposition substrate can be measured by cross-sectional SEM (film observation after creating a cross section by FIB-SEM or ion milling), a step gauge, or the like.

[0047] In the film-formed substrate of the present disclosure, the film preferably covers 30% or more of the metal-containing substrate, more preferably 50% or more, even more preferably 60% or more, and most preferably 70% or more.

[0048] In the film-formed substrate of the present disclosure, the degree to which a film is formed on a metal-containing substrate can be calculated by a known method, such as elemental analysis by X-ray photoelectron spectroscopy (also known as ESCA). In the elemental analysis method using ESCA, for example, the amount can be calculated from the difference in the amount of elements measured on the substrate before and after film formation. For example, since the compound has a structural unit derived from an adsorptive group and a monomer, it can be calculated from the difference between the amount of carbon (C) detected on the substrate after film formation and the amount of carbon (C) detected on the substrate before film formation. Alternatively, for example, 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.

[0049] The deposition substrate of the present disclosure preferably has a film having partitioned portions in which the difference between the amount of carbon detected on the substrate after deposition and the amount of carbon (C) detected on the substrate before deposition is 5% or more. More preferably, this difference is 7% or more, even more preferably 10% or more, particularly preferably 12% or more, and most preferably 15% or more. When the deposition substrate of the present disclosure satisfies these ratios, it can be said that a film having a high density of compounds having structural units derived from adsorptive groups and monomers is formed. In the film-formed substrate of the present disclosure, it is sufficient that 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 in at least some of the divided portions of the film formed on the substrate, but it is preferable that the difference in the amount of carbon (C) is 5% or more over 70% or more of the film formed on the substrate, and more preferably that the difference in the amount of carbon (C) is 5% or more over 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 measurement under the conditions described in the Examples.

[0050] The film-formed substrate of the present disclosure preferably has a film in which the ratio of metal elements is 95% or less, when the ratio (%) of metal elements detected on the metal surface of the substrate before film formation is taken as 100. More preferably, it is 60% or less, and even more preferably, it is 50% or less. The ratio of metal elements on the surface of the substrate on which the film is formed can be measured by ESCA under the conditions described in the Examples.

[0051] [Method for manufacturing a film-formed substrate according to the present disclosure] The method for producing a film-formed substrate of the present disclosure is not particularly limited, as long as a film containing a compound having an adsorptive group and a structural unit derived from a monomer is provided on a metal-containing substrate. Examples of the method for producing a film-formed substrate of the present disclosure include a method including a step of forming a film of a composition containing a polymer having adsorptive groups on at least a portion of a metal surface present on a substrate (hereinafter also referred to as production method 1), and a method including a step (I) of supplying a polymerization initiator having adsorptive groups to at least a portion of a metal surface present on a substrate, a step (II) of supplying a monomer to the metal surface to which the polymerization initiator has been supplied, and a step (III) of polymerizing the monomer (hereinafter also referred to as production method 2). The manufacturing methods 1 and 2 will be explained below in order.

[0052] Manufacturing method 1 <Process (I)> 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 may also include a step of producing the polymer used in this step. In the following, 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 a substrate is referred to as step (II), and the step of producing a polymer to be used in step (II) is referred to as step (I). Step (I) will be described first, followed by step (II).

[0053] (Production process (I) of polymer having adsorptive groups) The polymer having adsorptive groups of the present disclosure is formed by polymerizing monomers.

[0054] The adsorptive group is not particularly limited, but is preferably one or more groups selected from an SH group, a phosphate group, a carboxylic acid group, an isocyanate group, an unsaturated hydrocarbon group, a halogenated alkyl group, a phosphonic acid group, and an amino group.

[0055] The method for polymerizing the monomer is not particularly limited, and examples thereof include chain polymerization such as radical polymerization, cationic polymerization, and anionic polymerization, step-growth polymerization, living polymerization, etc. From the viewpoint of selectively protecting the substrate and ease of polymerization operation, radical polymerization, particularly living radical polymerization, is preferred.

[0056] Examples of living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer polymerization (RAFT), nitroxide-mediated radical polymerization (NMP), etc. From the viewpoint of broader monomer selectivity, ATRP polymerization and RAFT polymerization are preferred, and ATRP polymerization is more preferred.

[0057] The initiator for the polymerization reaction of polymerizing the monomer is not particularly limited, but is preferably a compound containing an adsorptive group. By carrying out the polymerization reaction of the monomer using the compound containing an adsorptive group as the initiator, a polymer having the adsorptive group and a structural unit derived from the monomer can be obtained.

[0058] When ATRP polymerization is carried out, it is preferable to use an organic halide or a sulfonyl halide compound as the initiator.

[0059] When the above initiator contains an adsorptive group, examples of the initiator include, but are not limited to, 11-mercaptoundecyl 2-bromo-2-methylpropionate, 6-mercaptoundecyl 2-bromo-2-methylpropionate, bis[2-(2'-bromoisobutyryloxy)ethyl]disulfide, and 11-(2-bromoisobutyric acid)-undecyl-1-phosphonic acid.

[0060] In the step (I) of producing the polymer having an adsorptive group, a catalyst may be used. The catalyst of the present disclosure is not particularly limited, but for example, when the polymerization method is ATRP polymerization, preferred catalysts include copper halide catalysts such as copper chloride(I), copper chloride(II), copper bromide(I), and copper bromide(II); titanium halide catalysts such as titanium chloride(II), titanium chloride(III), titanium chloride(IV), and titanium bromide(IV); and the like.

[0061] The halogenation catalyst of the present disclosure may be used in the presence of a ligand as a promoter. Examples of such a promoter include 2,2'-bipyridine, 4,4'-di(5-nonyl)-2,2'-bipyridine, methyl 2-bromopropionate, and ethyl 2-bromoisobutyrate. From the viewpoint of versatility, 2,2'-bipyridine is preferred.

[0062] The halogenated catalyst of the present disclosure may be used in the presence of a reducing agent, which may also function as a co-catalyst. Examples of reducing agents include ascorbic acid, sodium ascorbate, tin(II) 2-ethylhexanoate, cyclodextrin, phenylhydrazine, hydrazine, sodium borohydride, sodium citrate, methylaminoethanol, dimethylaminoethanol, and triethanolamine.

[0063] RAFT polymerization is a method of polymerization in the presence of a RAFT agent. RAFT polymerization uses initiators commonly used in radical polymerization. Examples include peroxides such as hydrogen peroxide, isobutyl peroxide, t-butyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate, and sodium persulfate; azo compounds such as azobisisobutyronitrile (AIBN), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2-methylpropionitrile), and 2,2'-azobis(2-methylbutyronitrile); and redox initiators such as hydrogen peroxide-ascorbic acid, hydrogen peroxide-ferrous chloride, and persulfate-sodium bisulfite. Among these, AIBN is preferred because it allows for smooth operation. RAFT agents used in RAFT polymerization include compounds with a thiocarbonylthio group (-CS-S-) in the molecule. For example, compounds classified by their chemical structure include dithioester compounds, trithiocarbonate compounds, dithiocarbamate compounds, and xanthate compounds.

[0064] The initiator of the present invention is generally 10 -4 mol / L to 3 mol / L, advantageously 10 -3 mol / L to 1 mol / L, particularly preferably 5×10 -2 mol / L ~ 5 x 10 -1 Concentrations in the mole / L range can be used, but should not be considered limiting.

[0065] When a catalyst is used in step (I), the molar ratio of the catalyst of the present disclosure to the initiator is preferably 0.0001:1 to 10:1, more preferably 0.01:1 to 5:1, and even more preferably 0.01:1 to 3:1.

[0066] When a cocatalyst is used in step (I), the molar ratio of the cocatalyst of the present disclosure to the initiator is preferably 0.0001:1 to 10:1, more preferably 0.01:1 to 5:1, and even more preferably 0.01:1 to 3:1.

[0067] The initiator of the present disclosure may contain, 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, a co-catalyst, an antistatic agent, a filler, a conductive agent, or the like.

[0068] Examples of solvents include ketones such as acetone and 2-butanone; aliphatic hydrocarbons such as pentane, hexane, and heptane; aromatic hydrocarbons such as benzene, toluene, and xylene; acetic acid derivatives such as methyl acetate, ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ethers such as tetrahydrofuran, diethyl ether, 1,2-dimethylethane, and diethylene glycol dimethyl ether; and alcohols such as methanol, ethanol, isopropyl alcohol, and hexanol. These solvents may be used alone or in a suitable mixture of two or more. The membrane of the present disclosure has a polymer containing a structural moiety derived from a monomer.

[0069] The weight average molecular weight (Mw) of the polymer is preferably 3 million to 1 million, more preferably 5 million to 1 million, even more preferably 5 million to 700,000, still more preferably 5 million to 500,000, particularly preferably 1,000 to 400,000, and most preferably 1,000 to 200,000. The weight average molecular weight of the polymer can be measured by the method described in the examples below.

[0070] The molecular weight distribution (Mw / Mn) of the polymer is preferably 1.01 to 3.0, more preferably 1.01 to 2, even more preferably 1.01 to 1.7, most preferably 1.01 to 1.5, and most preferably 1.01 to 1.3.

[0071] As the monomer, the same monomers as those explained above as raw materials for compound A can be used, and the same is also preferred.

[0072] The monomer of the present disclosure may contain, 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, a polymerization initiator, a catalyst, a co-catalyst, an antistatic agent, a filler, a conductive agent, or the like.

[0073] For example, the solvent may be the same as the solvent that may be contained in the initiator described above, as well as amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone, and dimethyl sulfoxide. These solvents may be used alone or in a suitable mixture of two or more.

[0074] The above step (I) is preferably carried out at a temperature of from -50 to 250°C, more preferably from 0 to 200°C, and even more preferably from 10 to 150°C.

[0075] The above 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.

[0076] In the above step (I), the origin of the adsorptive group is not particularly limited as long as the resulting polymer has the adsorptive group, and the adsorptive group may be contained in a monomer serving as a raw material for the polymer, or in an initiator. The adsorptive group may also be contained as a component other than the monomer or initiator, or may be generated by decomposing a structure contained in the polymer structure, such as a RAFT agent.

[0077] The adsorptive groups of the polymer obtained in step (I) can be bonded to the substrate to form a film.

[0078] <Process (II)> (Step (II) of applying a composition containing a polymer having an adsorptive group) 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 part of the surface of a metal present on a substrate. The film-formed substrate of the present disclosure can be obtained by forming a film of a polymer-containing composition on a metal-containing substrate. The method for forming a film of a polymer-containing composition on a metal-containing substrate is not particularly limited, and a method of applying a polymer-containing composition to a substrate can be used. Alternatively, the metal-containing substrate may be immersed in the polymer-containing composition.

[0079] Step (II) of production method 1 is preferably carried out at 10 to 300°C, more preferably 10 to 250°C, and even more preferably 15 to 100°C.

[0080] 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.

[0081] The 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).

[0082] The composition used in step (II) of production method 1 preferably contains a polymer having an adsorptive group and a solvent. The proportion of the polymer having an adsorptive group in the composition containing the polymer having an adsorptive group is preferably 0.0001 to 10 mass% relative to 100 mass% of the composition, more preferably 0.0001 to 5 mass%, and even more preferably 0.0001 to 3 mass%.

[0083] The adsorption groups contained in the polymer adsorb to the substrate, thereby forming a film.

[0084] When forming a film of the polymer having an adsorptive group according to the present disclosure, other components may be used. The composition used in step (II) of production method 1 may contain other components such as an antioxidant, a dispersant, a binder, an ultraviolet absorber, an ultraviolet stabilizer, an infrared absorber, an antistatic agent, and a conductive agent.

[0085] <Other processes> In addition to the above-described steps (I) and (II), the manufacturing method 1 of the present disclosure may include a step of cleaning and drying the metal-containing substrate (cleaning and drying step-1). Furthermore, the manufacturing method 1 of the present disclosure may include a step of cleaning and drying the film formation substrate (cleaning and drying step-2).

[0086] The solvent used for washing in washing / drying step-1 and washing / drying step-2 of manufacturing method 1 of the present disclosure is not particularly limited, and examples thereof include ketones such as acetone and 2-butanone; aliphatic hydrocarbons such as pentane, hexane, and heptane; aromatic hydrocarbons such as benzene, toluene, and xylene; acetate esters such as methyl acetate, ethyl acetate, and butyl acetate; ethers such as tetrahydrofuran, diethyl ether, 1,2-dimethylethane, and diethylene glycol dimethyl ether; and alcohols such as methanol, ethanol, isopropyl alcohol, and hexanol.

[0087] In the washing and drying step-1 and washing and drying step-2, the drying time is preferably 0.05 to 24 hours, more preferably 0.05 to 12 hours, and even more preferably 0.05 to 5 hours. The drying temperature is preferably 5 to 300°C, more preferably 10 to 250°C, and even more preferably 20 to 150°C.

[0088] Manufacturing method 2 <Process (I)> 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.

[0089] (initiator) The initiator containing an adsorptive group is not particularly limited, but examples of the adsorptive group include a thiol group, a phosphoric acid group, a carboxylic acid group, an amino group, an isocyanate group, an alkyl halide, and a phosphonic acid group.

[0090] 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, and 11-(2-bromoisobutyric acid)-undecyl-1-phosphonic acid.

[0091] (Other ingredients) The initiator used in Production Method 2 of the present disclosure may contain, 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, a polymerization initiator, a catalyst, a co-catalyst, an antistatic agent, a filler, a conductive agent, and the like.

[0092] Other components contained in the initiator used in Production Method 2 of the present disclosure include, for example, a solvent. The solvent is not particularly limited, but examples include the same solvents as those that may be contained in the initiator in Step (I) of Production Method 1 described above. These solvents may be used alone or in a suitable mixture of two or more.

[0093] Step (I) of manufacturing method 2 of the present disclosure is a step of supplying an initiator containing an adsorptive group to a metal-containing substrate, but the method of supplying the initiator to the metal-containing substrate is not particularly limited, and the initiator may be applied to the metal-containing substrate, or the metal-containing substrate may be immersed in an initiator solution.

[0094] Step (I) in Production Method 2 of the present disclosure may be carried out once, or may be carried out two or more times.

[0095] Step (I) of Production Method 2 of the present disclosure is carried out at a temperature of preferably 10 to 300°C, more preferably 10 to 250°C, and even more preferably 15 to 100°C.

[0096] 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.

[0097] <Process (II)> Step (II) of Production Method 2 of the present disclosure is a step of supplying a monomer to the metal surface to which a polymerization initiator has been attached. (monomer) The monomer used in Production Method 2 of the present disclosure is not particularly limited, but the same monomers as those described above as raw materials for Compound A can be used, and the same is also preferred.

[0098] (Other ingredients) The monomer used in Production Method 2 of the present disclosure may contain, 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, a polymerization initiator, a catalyst, a co-catalyst, an antistatic agent, a filler, a conductive agent, and the like.

[0099] The solvent contained as another component in the monomer used in Production Method 2 of the present disclosure is not particularly limited, but may be, for example, the same solvent as the solvent that may be contained in the initiator in Step (I) of Production Method 1 described above. These solvents may be used alone or in a suitable mixture of two or more.

[0100] In step (II) of manufacturing 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 has been supplied. The method may involve applying a monomer solution to the metal surface of the substrate, or immersing a metal-containing substrate in the monomer solution.

[0101] Step (II) in Production Method 2 of the present disclosure may be carried out once or twice or more times.

[0102] Step (II) of Production Method 2 of the present disclosure is carried out at a temperature of preferably 0 to 300°C, more preferably 10 to 250°C, and even more preferably 20 to 150°C.

[0103] 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.

[0104] Step (II) and step (III) in production method 2 of the present disclosure may be started simultaneously.

[0105] <Process (III)> 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 to which a polymerization initiator has been supplied. The method for polymerizing the monomer in step (III) of production method 2 of the present disclosure is not particularly limited, and examples thereof include chain polymerization such as radical polymerization, cationic polymerization, and anionic polymerization, and step-growth polymerization. From the viewpoint of selectively protecting the substrate and ease of polymerization operation, radical polymerization, particularly living radical polymerization, is preferred. Examples of living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer polymerization (RAFT), NMP polymerization, etc. ATRP polymerization is more preferred.

[0106] Step (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.

[0107] 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, and most preferably 1 to 500 minutes.

[0108] Step (II) and step (III) in production method 2 of the present disclosure may be started simultaneously.

[0109] (Catalyst addition process) In step (III) of production method 2 of the present disclosure, a catalyst or the like may be used as appropriate depending on the polymerization initiator and polymerization method. For example, a step of adding a catalyst or a co-catalyst (catalyst addition step) may be included to increase the initiation or rate of polymerization.

[0110] The catalyst used in Production Method 2 of the present disclosure is not particularly limited, but for example, when the polymerization method is ATRP polymerization, a halogenated catalyst is preferred. Examples of the halogenated catalyst include copper halide catalysts such as copper chloride(I), copper chloride(II), copper bromide(I), and copper bromide(II); titanium halide catalysts such as titanium chloride(II), titanium chloride(III), titanium chloride(IV), and titanium bromide(IV).

[0111] The halogenation catalyst used in Production Method 2 of the present disclosure may contain a ligand as a co-catalyst, such as bipyridine, 4,4'-di(5-nonyl)-2,2'-bipyridine, methyl 2-bromopropionate, or ethyl 2-bromoisobutyrate.

[0112] The halogenated catalyst used in Production Method 2 of the present disclosure may be coexistent with a reducing agent. This may also function as a co-catalyst. Examples of reducing agents include ascorbic acid, sodium ascorbate, tin(II) 2-ethylhexanoate, cyclodextrin, phenylhydrazine, hydrazine, sodium borohydride, sodium citrate, methylaminoethanol, dimethylaminoethanol, and triethanolamine.

[0113] 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 %, and even more preferably 0.005 to 4 mol %, relative to the total amount of monomers.

[0114] When a ligand is used in Production Method 2 of the present disclosure, the amount of the ligand used is preferably 0.0001 to 10 mol %, more preferably 0.0001 to 8 mol %, and even more preferably 0.0001 to 5 mol %, relative to the total amount of monomers.

[0115] When a catalyst addition step is performed in Production Method 2 of the present disclosure, the catalyst addition step may be performed before or after step (I), before or after step (II), before or after step (III), or during the performance of steps (I), (II), and (III).

[0116] In the catalyst addition step of Production Method 2 of the present disclosure, other components may be included, for example, a solvent. The solvent is not particularly limited, and examples thereof include the same solvents as those that may be contained in the initiator in step (I) of the above-mentioned production method 1.

[0117] (Washing and drying process) In addition to the steps described above, manufacturing method 2 of the present disclosure may also include a step of cleaning and drying the metal-containing substrate (cleaning and drying step-1). Furthermore, the manufacturing method 2 of the present disclosure may include a step of cleaning and drying the film formation substrate (cleaning and drying step-2).

[0118] The solvent used for washing in the washing and drying step-1 and the washing and drying step-2 in the manufacturing method 2 of the present disclosure is not particularly limited, but examples thereof include the same solvents as those used for washing in the washing and drying step-1 and the washing and drying step-2 in the manufacturing method 1 of the present disclosure.

[0119] In the cleaning and drying step-1 and the cleaning and drying step-2 of the manufacturing method 2 of the present disclosure, the drying time and the drying temperature are the same as those in the cleaning and drying step-1 and the cleaning and drying step-2 of the manufacturing method 1 of the present disclosure.

[0120] (Mixing process) In the manufacturing method 2 of the present disclosure, instead of step (I) of supplying a polymerization initiator containing an adsorption group to at least a portion of a metal surface present on a substrate and step (II) of supplying a monomer to the metal surface to which the polymerization initiator has been supplied, a step (mixing step) of mixing the initiator and monomer used in the manufacturing method 2 of the present disclosure and a step (mixture supplying step) of supplying the composition obtained in the mixing step to at least a portion of the metal surface present on a substrate may be performed. Such a production method in which the mixing step and mixture supplying step are carried out instead of steps (I) and (II) of production method 2 of the present disclosure can also be called production method 3 of the present disclosure.

[0121] The initiator and monomer used in the mixing step of Production Method 3 of the present disclosure may contain other components that may be contained in the initiator and monomer used in Production Method 2, as described above. In the mixture supplying step, the method is not particularly limited as long as the composition obtained in the mixing step is supplied to the metal-containing substrate, and the composition obtained in the mixing step may be applied to the metal-containing substrate, or the substrate may be immersed in the composition obtained in the mixing step. Also, the monomer may be polymerized in the mixing step.

[0122] [Uses of the film-formed substrate of the present disclosure] The film-formed substrate of the present disclosure can be applied to various fields such as architecture, automobiles, electrical and electronics, and medical fields. For example, in the electrical and electronics field, the substrate can be mounted in notebook personal computers, tablet terminals, mobile phones, smartphones, digital video cameras, digital cameras, digital clock supercomputers, etc. [Example]

[0123] [Molecular weight] The molecular weight of the synthesized polymer was measured by dissolving and diluting it in THF, filtering it, and then measuring it with the following equipment. Apparatus: Tosoh Corporation: HLC-8420GPC Standard material: Standard polystyrene Eluent:THF Separation column: 2 TSKgel Superrmultipore HZ-M (manufactured by Tosoh Corporation)

[0124] [Film evaluation] <IR measurement> Equipment: NEXUS 670 (manufactured by Thermo Nicolet), Ge-ATR method Analysis method: For the film-forming substrate, peaks derived from the polymer were confirmed by the above IR measurement. The film-forming state was judged by the presence or absence of the following peaks. Polymethyl methacrylate (PMMA): 1730 cm -1 Polystyrene (PSt): 1450 and / or 1490 cm -1 Judgment criteria: ○: The above peak is present (film formed) ×: The above peak is absent (film not formed) <ESCA measurement> The surface analysis of the film-formed substrate was measured with an X-ray photoelectron spectrometer under the following conditions. Equipment: AXIS-NOVA manufactured by SHIMADZU Corporation Measurement conditions / Excitation source: Al Kα 10 mA 10 kV, Pass Energy: 40 eV For each substrate, the number of measurement points was set to 2, and the average surface element ratio was adopted as the value. <Contact angle>[[ID=三十五]] Equipment: Product number: DM-501Hi manufactured by Kyowa Interface Science Co., Ltd. Measurement method: To evaluate the water repellency of the film-formed substrate, water was dropped onto the substrate, and the contact angle after 0.5 seconds was measured. Judgment criteria: ◎: Contact angle of film-formed substrate - Contact angle of non-film-formed substrate is 20° or more ○: Contact angle of film-formed substrate - Contact angle of non-film-formed reference substrate is 4° or more and less than 20° ×: Contact angle of film-formed substrate - Contact angle of non-film-formed reference substrate is less than 4° When forming a film on Cu, it is calculated based on Cu, and when forming a film on SiO2, it is calculated based on the SiO2 substrate.

[0125] [Synthesis of initiator 1] <Synthesis example 1> Synthesis of 11-mercaptoundecyl 2-bromo-2-methylpropionate (MUB) A dried 1 L three-neck flask was equipped with a thermometer, condenser, dropping funnel, and magnetic stirrer, and the atmosphere was replaced with N2. N2 was circulated through the top of the condenser, and the exhaust side was connected to an alkali trap (10% KOH aq.: 500 g). 300 mL of methylene chloride was placed in the three-neck flask. 9 g of 11-mercaptoundecanol (11-MU) (44 mmol), 3.2 g of pyridine (40 mmol), and 0.1 g of N,N-dimethylaminopyridine (DMAP) (1.0 mmol) were added. Subsequently, 60 mL of methylene chloride and 9.2 g of 2-bromoisobutyryl bromide (BiBB) (40 mmol) were placed in the dropping funnel. The flask was placed in an ice bath, and the solution was added dropwise over 30 minutes. After the addition was complete, the flask was stirred in the ice bath for 1 hour. The ice bath was removed, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 16 hours. The reaction was stopped by adding 220 ml of ion-exchanged water. After separation, the aqueous layer was extracted with methylene chloride (150 ml x 2), and the organic layer was concentrated. The concentrate was dissolved in 100 ml of diethyl ether and washed with saturated aqueous NH4Cl (100 ml x 3). Magnesium sulfate was added to the organic layer and dried. Filtration was performed, and the filtrate was concentrated to obtain 16.9 g of oily Crede. The crude was purified using a neutral silica gel column (developing solvent: hexane:ethyl acetate / 6:1) to obtain 11.1 g of the target product (oily liquid).

[0126] [Polymer synthesis 1] <Synthesis Example 2> The column was packed with alumina and methyl methacrylate was passed through to remove the inhibitor. 10 g of column-treated MMA, 8 g of methanol, and 2 g of ion-exchanged water were weighed into a two-neck flask (a) and sealed with a three-way cock. After repeated vacuum and N2 degassing three times, N2 was bubbled through for 30 min. Into another two-neck flask (b), 0.002 g of copper(II) bromide, 0.006 g of 2,2'-bipyridine, and 0.315 g of ascorbic acid were weighed and sealed with a three-way stopcock. The pressure was reduced and the contents of the flask (a) were replaced with N2 by degassing three times. The contents of flask (a) were added to (b), and 0.106 g of the initiator synthesized in Synthesis Example 1 was added to initiate the reaction at room temperature. The reaction solution was stirred with a stirrer during polymerization. After 3 hours, the polymerization was terminated. The resulting gel was dissolved in toluene and reprecipitated in hexane. The precipitate was filtered and the resulting solid was dried in a vacuum dryer to obtain a dry solid. The resulting polymer with adsorption groups had an Mn of 9200 and a molecular weight distribution of 1.44.

[0127] [Production of film-formed substrate 1] Example 1 (Substrate pre-treatment) A wafer with Cu (thickness 725 μm) provided by Philtech was prepared. The substrate was immersed in toluene for 10 minutes, then immersed in 10 mL of isopropyl alcohol (IPA) for 1 minute, then immersed in a 1% aqueous citric acid solution, then immersed in ultrapure water, rinsed with water, and dried under a stream of N2 gas. (Application of a composition containing a polymer) 0.056 g of the polymer solid obtained in Synthesis Example 2 was dissolved in 12.24 g of N,N-dimethylformamide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereafter referred to as DMF), and a cleaned substrate was immersed in the polymer solution for 19 hours. After 19 hours, the substrate was removed, immersion-washed with toluene, and then rinsed with IPA. The substrate was then rinsed with ultrapure water and dried with N2. After drying for 1 hour in a vacuum dryer, a substrate with a film formed on its entire surface was obtained. The results of IR, ECSA, and contact angle measurements of the obtained substrate with a film are shown in Table 1.

[0128] <Example 2> A substrate with a film formed thereon 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 11,000, Mw / Mn <1.1) purchased from Adrich. The results of IR measurement, ECSA measurement, and contact angle measurement of the obtained substrate with a film formed thereon are shown in Table 1.

[0129] <Comparative Example 1> A substrate was obtained in the same manner as in Example 1, except that the substrate was changed to an SiO2 substrate manufactured by Philtech Co., Ltd. The results of IR measurement, ECSA measurement, and contact angle measurement of the obtained substrate are shown in Table 1.

[0130] <Comparative Example 2> A substrate was obtained in the same manner as in Example 2, except that the substrate was changed to an SiO2 substrate manufactured by Philtech Co., Ltd. The results of IR measurement, ECSA measurement, and contact angle measurement of the obtained substrate are shown in Table 1.

[0131] [Table 1]

[0132] The results in Table 1 reveal that the film-formed substrate produced by production method 1 of the present disclosure is water-repellent, and is therefore a novel film-formed substrate having a high-density film with a modified metal surface.

[0133] [Polymer synthesis 2] <Synthesis Example 3> The column was packed with alumina and styrene was passed through to remove the inhibitor. A glass test tube containing a stirrer was charged with 8.5 g of the above styrene, 8.5 g of anisole, 0.034 g of AIBN, and 0.205 g of 2-cyanoprop-2-yl dithiobenzoate, and placed in a ChemStation (Tokyo Rikakikai Co., Ltd.). Degassing and N2 replacement were repeated five times, and the reactor was heated with stirring until the internal temperature reached 60°C. After heating for 30 hours, the reaction was terminated by cooling. The product was reprecipitated in methanol, filtered under reduced pressure, and dried. As a result, 2.1 g of polymer powder 1 was obtained. A glass test tube containing a stirrer was charged with 1.6 g of polymer powder 1 and 21.5 g of THF. After replacing the atmosphere with N2, butylamine was added dropwise using a syringe and the mixture was stirred at room temperature overnight. The mixture was reprecipitated in MeOH, filtered under reduced pressure, and dried to obtain polymer powder 2. 1.3 g of polymer powder 2, dithiothreitol, and DMF were placed in a glass test tube containing a stirrer. After degassing with N2, the mixture was heated at 60°C for 20 hours to terminate the reaction. The reaction solution was reprecipitated in MeOH, filtered under reduced pressure, and vacuum dried to obtain a polymer powder having SH groups at the terminus. The number-average molecular weight Mn of the resulting polymer was 2400, and the molecular weight distribution was 1.1.

[0134] [Production of deposition substrate 2] 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 to be formed into a film was changed to the polymer obtained in Synthesis Example 3.

[0135] 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 (Mn 11000).

[0136] <Example 5> A patterned substrate supplied by GBN was immersed in toluene for 10 minutes, then immersed in 10 mL of isopropyl alcohol (IPA) for 1 minute, then immersed in a 1% citric acid solution, then immersed in ultrapure water, rinsed with water, and dried under a stream of N2 gas. The polymer obtained in Synthesis Example 3 was dissolved in DMF to a solid content of 0.1%, and 0.1 g of the polymer solution was applied by spin coating using a MIKASA spin coater MS-A100 at 3200 rpm for 15 seconds to form a spin coating film.

[0137] Example 6 Film formation was carried out in the same manner as in Example 5, except that the polymer was changed to PSt-SH (Mn 11000) obtained from Aldrich.

[0138] For the film-forming substrates of Examples 5 and 6, the film-forming property was evaluated by ESCA measurement. The results are shown in Table 2. <ESCA Measurement> Measurement conditions / Excitation source: Al Kα 15 mA 15 kV Pass Energy: 160 eV The measurement was performed on the Cu and SiO2 portions of the Cu / SiO2 = 100 / 100 (μm / μm) portion on a patterned substrate (a substrate having metal and non-metal portions on one substrate). As a result of the analysis, the film-forming property was judged by the difference (%) of the C element present on the substrate surface after film formation compared to the substrate before film formation of the polymer. Film-forming property judgment criteria: C ratio of the substrate after film formation - C ratio of the substrate before film formation (%) is 15% or more: ◎ C ratio of the substrate after film formation - C ratio of the 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 the substrate after film formation - C ratio of the substrate before film formation (%) is less than 5%: ×

[0139]

Table 2

[0140] From the results in Table 2 (Examples 5 and 6), it was confirmed that among the patterned substrates, the polymer was selectively formed only on the metal portion.

[0141] [Manufacture of Film-Forming Substrate 3] <Example 7> (Washing Treatment of Substrate) A wafer with Cu provided by Filtec was prepared. [[ID=4T]] The substrate was immersed in toluene for 10 minutes, then immersed in 10 mL of isopropyl alcohol (IPA) for 1 minute. Then, the substrate was immersed in a 1% aqueous citric acid solution, then immersed in ultrapure water, rinsed, and dried by flowing N2.

[0142] (Process (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 removed and immersion-washed in IPA and ultrapure water for 1 minute each, then rinsed with ultrapure water, dried under N2 flow, and vacuum-dried for 30 minutes.

[0143] (Step (II)) The column was packed with alumina and methyl methacrylate was passed through 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 the atmosphere was purged with N2 for 30 minutes. 10 g of column-treated MMA, 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 initiator-coated substrate, the glass container containing the catalyst, and the two-neck flask were placed in a glove box (GB) filled with N2 and with an oxygen concentration of 0.1% or less. The monomer solution was added to the glass container containing the catalyst, the lid was put on, and the mixture was stirred thoroughly. Then, the substrate was added and the mixture was polymerized for 3 hours. After 3 hours, the substrate was removed and immersed in toluene under air. After several toluene rinses, the substrate was immersed in IPA. The substrate was then rinsed with ultrapure water, dried under N2 flow, and dried in a vacuum oven for 1 hour to obtain the coated substrate. The results of IR, ECSA, and contact angle measurements of the resulting coated substrate are shown in Table 3.

[0144] Example 8 A substrate with a film formed thereon was obtained by the same procedure as in Example 3, except that 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 ion-exchanged water to 0 g, and the polymerization time from adding the substrate was changed from 3 hours to 24 hours. The results of IR measurement, ECSA measurement, and contact angle measurement of the obtained substrate with a film formed thereon are shown in Table 3.

[0145] <Comparative Example 3> A substrate was obtained in the same manner as in Example 7, except that the substrate was changed to an SiO2 substrate manufactured by Philtech Co., Ltd. The results of IR measurement, ECSA measurement, and contact angle measurement of the obtained substrate are shown in Table 3.

[0146] <Comparative Example 4> A substrate was obtained in the same manner as in Example 8, except that the substrate was changed to an SiO2 substrate manufactured by Philtech Co., Ltd. The results of IR measurement, ECSA measurement, and contact angle measurement of the obtained substrate are shown in Table 3.

[0147] [Table 3]

[0148] The results in Table 3 reveal that the film-formed substrate produced by production method 2 of the present disclosure is water-repellent, and is therefore a novel film-formed substrate having a high-density film with a modified metal surface.

[0149] Example 9 The same procedure as in Example 8 was carried out, except that the substrate was changed to a patterned substrate supplied by Global Net, to obtain a substrate on which a film was formed. For the Cu / SiO2 = 100 / 100 (μm) portion of the obtained substrate on which a film was formed, ESCA measurements were carried out on the Cu and SiO2 portions to determine film formability. The results are shown in Table 4.

[0150] [Table 4]

[0151] The results in Table 4 confirmed that the patterned substrate had a polymer film formed on the metal surface.

Claims

1. a film containing a compound having an adsorptive group and a structural unit derived from a monomer is formed on at least a portion of a metal surface present on a substrate; the adsorptive group is at least one group selected from the group consisting of an SH group, a phosphate group, a phosphonate group, a carboxylic acid group, an isocyanate group, an unsaturated hydrocarbon group, a halogenated alkyl group, and an amino group; the structural units derived from the monomer include one or more structural units selected from the group consisting of structural units derived from a (meth)acrylic acid ester and structural units derived from an aromatic group-containing monomer; The adsorption group is contained as a structure derived from an initiator, The substrate is a patterned substrate formed of a metal and a material other than a metal, The specific gravity of the metal is 19.30 g / cm ３ The following is a deposition substrate.

2. a film containing a compound having an adsorptive group and a structural unit derived from a monomer is formed on at least a portion of a metal surface present on a substrate; 2. The film-formed substrate according to claim 1, having a partitioned portion in which the difference between the carbon element percentage of the film and the carbon element percentage of the substrate, as detected by ESCA, is 5% or more.

3. 3. The film-formation substrate according to claim 1, wherein the compound has a weight-average molecular weight of 1,000 to 400,000.

4. The method includes forming a film of a composition containing an adsorbing group and a polymer having structural units derived from a monomer on at least a portion of a metal surface present on a substrate, the adsorptive group is at least one group selected from the group consisting of an SH group, a phosphate group, a phosphonate group, a carboxylic acid group, an isocyanate group, an unsaturated hydrocarbon group, a halogenated alkyl group, and an amino group; the structural units derived from the monomer include one or more structural units selected from the group consisting of structural units derived from a (meth)acrylic acid ester and structural units derived from an aromatic group-containing monomer; The adsorption group is contained as a structure derived from an initiator, The substrate is a patterned substrate formed of a metal and a material other than a metal. A method for manufacturing a film-formed substrate.

5. The method includes: a step (I) of supplying a polymerization initiator containing an adsorptive group to at least a part of a metal surface present on a substrate; a step (II) of supplying a monomer to the metal surface to which the polymerization initiator has been supplied; and a step (III) of polymerizing the monomer; the adsorptive group is at least one group selected from the group consisting of an SH group, a phosphate group, a phosphonate group, a carboxylic acid group, an isocyanate group, an unsaturated hydrocarbon group, a halogenated alkyl group, and an amino group; the monomer includes at least one selected from a (meth)acrylic acid ester and an aromatic group-containing monomer, The substrate is a patterned substrate formed of a metal and a material other than a metal. A method for manufacturing a film-formed substrate.

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