TW202104305A - Surface treatment film, method for producing same, and article - Google Patents

Abstract

The present invention provides a surface treatment film which is capable of imparting the surfaces of various base materials with durabilities such as wear resistance, friction resistance, chemical resistance, heat resistance and solvent resistance, and which exhibits excellent adhesion to the surfaces of the base materials. A surface treatment film which is provided on the surface of a base material. This surface treatment film has a multilayer structure that comprises a polymer layer (i) that is arranged on the surface side of the base material and a polymer layer (ii) that is formed on the polymer layer (i); the polymer layer (i) contains a first polymer which contains a constituent unit that is derived from a monomer represented by general formula (1) (wherein R1 represents a hydrogen atom or a methyl group; X represents O or NH; R2 represents an arbitrary organic group; each of R3 and R4 represents a hydrogen atom, an alkyl group, an aryl group or an acyl group; and Y represents a chlorine atom or the like); and the polymer layer (ii) contains a second polymer which contains a constituent unit that is derived from a monomer such as an aromatic vinyl monomer, and which is elongated using a functional group of a monomer represented by general formula (1) as the polymerization starting point.

Description

Surface treatment film, its manufacturing method and article

The present invention relates to a surface treatment film provided on the surface of a substrate, a manufacturing method thereof, and an article provided with the surface treatment film.

As a method for modifying the substrate, it is known that a polymer having a group capable of adsorbing or reacting with the substrate acts on the substrate to form a physical or chemical bond on the surface of the substrate. Polymer layer method. In addition, there is also known a method of forming a polymer layer grafted from the surface of the substrate by polymerizing monomers starting from the polymerizable group provided on the surface of the substrate.

In recent years, research has been conducted on the so-called "dense polymer brush" by using the living radical polymerization technology developed in the 1990s to graft high-density onto the substrate. In the dense polymer brush, polymer chains are grafted onto the substrate at a high density at an interval of 1 to 4 nm. By modifying the surface of the substrate with such a thick polymer brush, it is possible to impart features such as low friction, inhibition of protein adsorption, size exclusion properties, hydrophilicity, and water repellency (for example, Patent Documents 1 and 2, Non-Patent Document 1 ~3).

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2008-133434

[Patent Document 2] Japanese Patent Laid-Open No. 2010-261001

[Non-Patent Literature]

[Non-Patent Document 1] Adv. Polym. Sci., 2006, 197, 1-45

[Non-Patent Document 2] J. Am. Chem. Soc., 2005, 127, 15843-15847

[Non-Patent Document 3] Polym. Chem., 2012, 3, 148-153

The thick polymer brush (hereinafter also referred to as "brush") shows low friction in the field of lubrication, friction, and abrasion. However, there are cases where the polymer layer of the brush is easily detached from the surface of the substrate due to the lubricant or solvent used during friction. The thick polymer brush is formed by polymerization after forming the polymerization starting base layer belonging to the monomolecular film layer. However, it is believed that because the bonding force or adhesion of the monomolecular film layer is weak, the polymer layer is easily detached due to friction or solvents.

In addition, when there are irregularities on the surface of the substrate forming the brush and the polymer layer of the brush cannot completely cover the irregularities, there are cases where low friction properties are not exhibited. In order to cover the roughness of the surface of the substrate, the surface of the substrate can be polished to make it smooth and then a brush is formed. However, since the step of polishing the surface of the substrate is added, it is disadvantageous in terms of cost. Furthermore, a thicker brush can be formed to cover the roughness of the substrate surface. However, to form a brush with a thick film thickness, special conditions or devices such as living radical polymerization under high pressure conditions (for example, 100~1,000MPa) and grafting onto the substrate surface are required. Therefore, it is not necessarily easy to form a brush with a thicker film, and it is also liable to become disadvantageous in terms of cost.

The present invention was made in view of the problems of this conventional technology, and its subject is to provide a method that can impart abrasion resistance, abrasion resistance, chemical resistance, heat resistance, and solvent resistance to the surface of various substrates. Such as durability, and with the surface of the substrate Surface treatment film with excellent adhesion. Furthermore, the subject of the present invention is to provide a method of manufacturing the above-mentioned surface treatment film, and an article provided with the above-mentioned surface treatment film.

That is, according to the present invention, a surface treatment film shown below can be provided.

[1] A surface treatment film, which is provided on the surface of a substrate, and has a polymer layer (i) arranged on the surface side of the substrate, and a polymer layer (i) formed on the polymer layer (i) The laminated structure of the polymer layer (ii); the polymer layer (i) contains a first polymer, and the first polymer contains a constituent unit derived from a monomer represented by the following general formula (1); the polymer layer (ii) Contains a second polymer, which is derived from the group consisting of aromatic vinyl-based monomers, (meth)acrylate-based monomers, and (meth)acrylamide-based monomers The constitutional unit of more than one monomer selected from the group, and the functional group of the monomer represented by the following general formula (1) is used as the polymerization initiation point for extension.

(In the above general formula (1), R ₁ represents a hydrogen atom or a methyl group, X represents O or NH, R ₂ represents an arbitrary organic group, and R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group or The carbon atom to which R ₃ and R ₄ are bonded is a tertiary carbon atom or a quaternary carbon atom, and Y represents a chlorine atom, a bromine atom, or an iodine atom)

[2] The surface treatment film described in the above [1], wherein the first polymer contains 30% by mass or more of the constituent unit derived from the monomer represented by the general formula (1).

[3] The surface treatment film as described in the above [1] or [2], wherein the first polymer further contains a polymer derived from an alkoxysilyl group, a (meth)acryloyloxy group, an epoxy group, Isocyanate group, blocked isocyanate group, hydroxyl group, carboxyl group and phosphoric acid group constituted by the group of reactive functional groups selected as the constituent unit of radical polymerizable monomers.

[4] The surface treatment film described in [3] above, wherein the first polymer has a crosslinked structure.

[5] The surface treatment film described in any one of [1] to [4] above, wherein the polymer layer (ii) contains a solvent and swells.

Furthermore, according to the present invention, it is possible to provide a method for manufacturing the surface treatment film shown below.

[6] A method for manufacturing a surface treatment film, which is the method for manufacturing a surface treatment film as described in any one of [1] to [5] above, which has the following steps: disposing the above-mentioned substrate on the surface of the above-mentioned substrate Polymer layer (i); and under normal pressure to 1,000 MPa, in the presence of the above polymer layer (i), from aromatic vinyl monomers, (meth)acrylate monomers One or more monomers selected from the group consisting of a monomer and a (meth)acrylamide-based monomer undergo surface-initiated radical polymerization or surface-initiated living radical polymerization to form on the above-mentioned polymer layer (i) The above-mentioned polymer layer (ii).

[7] The method for producing a surface treatment film as described in [6] above, which is further based on at least one salt selected from the group consisting of halogenated quaternary ammonium salts, halogenated quaternary phosphonium salts, and halogenated alkali metal salts Under the coexistence of the above, surface-initiated radical polymerization or surface-initiated living radical polymerization is performed, and the above-mentioned polymer layer (ii) is formed on the above-mentioned polymer layer (i).

Furthermore, according to the present invention, there is provided an article shown below.

[8] An article comprising a substrate and the surface treatment film described in any one of [1] to [5] above provided on the surface of the substrate.

[9] The article according to [8] above, wherein the film thickness of the polymer layer (i) is thicker than the maximum height Rz of the surface roughness of the substrate.

According to the present invention, it is possible to provide a surface treatment that can impart durability such as abrasion resistance, abrasion resistance, chemical resistance, heat resistance, and solvent resistance to the surface of various substrates, and has excellent adhesion to the surface of the substrate. membrane. Furthermore, according to the present invention, it is possible to provide a method of manufacturing the above-mentioned surface treatment film, and an article provided with the above-mentioned surface treatment film.

<Surface treatment film and its manufacturing method>

Hereinafter, the embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. The surface treatment film of the present invention is a film disposed on the surface of a substrate, and has a polymer layer (i) disposed on the surface side of the substrate, and a polymer layer (i) formed on the polymer layer (i). ii) The multi-layer structure. The polymer layer (i) contains a first polymer, and the first polymer contains a structural unit derived from a monomer represented by the following general formula (1). In addition, the polymer layer (ii) contains a second polymer that is derived from aromatic vinyl monomers, (meth)acrylate monomers, and (meth)acrylamide monomers. The constitutional unit of more than one monomer selected by the group constituted by the body, and the functional group of the monomer represented by the following general formula (1) is used as the polymerization initiation point for extension. The details of the surface treatment film of the present invention will be described below.

(Polymer layer (i))

The surface treatment film has a laminated structure including a polymer layer (i) and a polymer layer (ii). The polymer layer (i) is a layer disposed on the surface side of the substrate, and it is a layer containing a first polymer, preferably a layer substantially formed of a first polymer, and the first polymer includes The constituent unit of the monomer represented by the general formula (1).

(In the above general formula (1), R ₁ represents a hydrogen atom or a methyl group, X represents O or NH, R ₂ represents an arbitrary organic group, and R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group or The carbon atom to which R ₃ and R ₄ are bonded is a tertiary carbon atom or a quaternary carbon atom, and Y represents a chlorine atom, a bromine atom, or an iodine atom)

For example, a component (coating liquid) containing a first polymer containing a structural unit derived from the monomer represented by the general formula (1) can be coated on the surface of the substrate and dried to harden it, thereby coating the substrate The polymer layer (i) is formed on the surface. In addition, in the presence of the polymer layer (i), it is made from aromatic vinyl monomers, (meth)acrylate monomers, and (meth)acrylamide monomers by a predetermined method. Polymerization of one or more monomers selected by the constituent group, the second polymer uses the functional group represented by the following general formula (2) in the first polymer contained in the polymer layer (i) as the polymerization starting point Make an extension. Thereby, the polymer layer (ii) containing the second polymer, preferably substantially formed of the second polymer, can be formed on the polymer layer (i) to obtain a surface treatment film.

(In the above general formula (2), R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group or an acyl group, and _{the carbon atom to which R 3} and R ₄ are bonded is a tertiary carbon atom or a quaternary carbon atom Carbon atom, Y represents chlorine atom, bromine atom or iodine atom)

In the general formula (2), halogen atoms such as chlorine atoms represented by Y are separated into halogen radicals by the action of light, heat, free radicals, etc., and tertiary or quaternary carbon radicals are generated. The generated tertiary or quaternary carbon radicals attack the above-mentioned monomers having groups capable of radical polymerization to react, and the second polymer is elongated.

Specific examples of the monomer represented by the general formula (1) include (di)hydroxyalkyl (meth)acrylate, N-hydroxyalkyl (meth)acrylamide, and glycidyl methacrylate Etc. (meth)acrylates with epoxy groups, etc. and 2-chloropropionic acid, 2-chlorobutyric acid, 2-chloroisobutyric acid, 2-chloropentanoic acid, 2-bromopropionic acid, 2-bromobutyric acid , 2-bromoisobutyric acid, 2-bromopentanoic acid, α-bromophenylacetic acid, α-bromo-4-chloroacetic acid and other halogen-substituted carboxylic acid compounds, and compounds obtained by reacting such anhydrides or halides . Furthermore, compounds obtained by halogen-exchanging chlorine atoms or bromine atoms and iodine atoms in these compounds can be cited. Among the compounds represented by the general formula (1), commercially available products that are relatively easily available include 2-(2-bromoisobutyroxy)ethyl methacrylate. In addition, 2-(2-iodoisobutanoyloxy)ethyl methacrylate obtained by substituting bromine atoms of 2-(2-bromoisobutyroxy)ethyl methacrylate with iodine atoms can also be used. ester.

If the monomer represented by the general formula (1) is polymerized, the first polymer can be obtained. In addition, the above-mentioned (di)hydroxyalkyl (meth)acrylate, N-hydroxyalkyl (meth)acrylamide, glycidyl methacrylate, and other epoxy-containing (meth)acrylates are polymerized To obtain a polymer, the polymer is reacted with the above halogen-substituted carboxylic acid compound, etc. Should, the first polymer can also be obtained.

The first polymer may include structural units (other structural units) other than the structural unit derived from the monomer represented by the general formula (1). By including other constituent units, the thermal properties and mechanical properties of the first polymer can be changed, or a three-dimensional network structure can be formed, which can improve durability such as adhesion to the substrate, flexibility, and chemical resistance. The first polymer preferably contains 0.1 to 100% by mass of structural units derived from the monomer represented by the general formula (1), more preferably 30% by mass or more, and particularly preferably 50% by mass or more. If the amount of the constituent unit derived from the monomer represented by the general formula (1) in the first polymer is too small, the functional group of the monomer represented by the general formula (1) is used as the polymerization initiation point for the second extension When the amount of polymer decreases, the effect of the polymer layer (ii) tends to become insufficient.

Other structural units can be formed by copolymerizing a monomer (other monomer) other than the monomer represented by the general formula (1) and the monomer represented by the general formula (1). As other monomers, conventionally known radical polymerizable monomers can be appropriately selected and used. Among them, by using a radically polymerizable monomer having a reactive functional group, the adhesion of the polymer layer (i) to the substrate can be improved, or the mechanical strength of the polymer layer (i) can be improved, which is preferred. Furthermore, the polymer layer (i) can be made into a hardened body having a three-dimensional network structure by using the reactive functional group having self-reactivity or using a compound (crosslinking agent) having a group reactive with the above-mentioned reactive functional group , So better. Examples of reactive functional groups include alkoxysilyl groups, (meth)acryloxy groups, epoxy groups, isocyanate groups, blocked isocyanate groups, hydroxyl groups, carboxyl groups, and phosphoric acid groups.

When the reactive functional group is an alkoxysilyl group, the alkoxysilyl group and the hydroxyl group on the surface of the substrate undergo a dehydration condensation reaction, or the alkoxysilyl group undergoes a self-crosslinking reaction with each other to form a three-dimensional network structure. Examples of the crosslinking agent that reacts with the alkoxysilyl group include silane coupling agents such as tetraethoxysilane.

When the reactive functional group is a (meth)acryloyloxy group, a photo-radical generator or the like can be added, and it can be cured by irradiating it with ultraviolet rays or electron beams. In addition, if a thermal radical generator or the like is added, thermal crosslinking can be performed. Furthermore, monofunctional monomers, such as phenoxyethyl acrylate, and acrylic oligomers, such as pentaerythritol tetraacrylate, can be used as a crosslinking agent.

When the reactive functional group is an epoxy group, an epoxy cured body can be formed by adding a photocation generator, or a curing agent such as a polyamine compound or an acid anhydride. When the reactive functional group is an isocyanate group or a blocked isocyanate group, if a compound with more than two hydroxyl groups or amino groups is added to form a urethane bond, a polymer with strong toughness can be formed Layer (i). When the reactive functional group is a hydroxyl group, a polycarboxylic acid compound or a polyisocyanate compound can be used as a crosslinking agent.

唑啉交聯劑、聚異氰酸酯交聯劑、聚環氧化合物等交聯劑，則可形成立體網狀構造。又，於反應性官能基為磷酸基之情形時，若基材為金屬，則藉由與金屬之表面之反應而生成磷酸-金屬鍵，故可提昇基材與聚合物層(i)之密接性。 When the reactive functional group is a carboxyl group, if a melamine crosslinking agent, carbodiimide crosslinking agent,

Crosslinking agents such as oxazoline crosslinking agents, polyisocyanate crosslinking agents, and polyepoxy compounds can form a three-dimensional network structure. In addition, when the reactive functional group is a phosphoric acid group, if the substrate is a metal, a phosphoric acid-metal bond is formed by the reaction with the surface of the metal, so the adhesion between the substrate and the polymer layer (i) can be improved Sex.

Examples of the polymer structure of the first polymer include: linear, branched, grafted, block, multi-block, bottle brush structure, star structure, multi-branched structure, dendritic polymer Type, particle type, cross-linked structure type, etc. The number average molecular weight of the first polymer is preferably 1,000 or more. The first polymer can be formed by various polymerization methods such as radical polymerization, living radical polymerization, anionic polymerization, living anionic polymerization, cationic polymerization, and living cationic polymerization. Among them, in terms of mild reaction conditions, etc., radical polymerization or living radical polymerization is preferred. Furthermore, bulk polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization, solution polymerization, etc. can be used It is manufactured by the well-known polymerization method.

The polymer layer (i) is substantially formed of the first polymer, or formed by curing the first polymer with a crosslinking agent or the like. The polymer layer (i) can be formed, for example, by applying a coating liquid containing the first polymer on the surface of the substrate to form a coating layer, followed by drying, and then curing it. The coating liquid usually contains a liquid medium such as water or an organic solvent, a crosslinking agent, other additives, and the like as components other than the first polymer. In addition, it may further contain a compound having a functional group that becomes a polymerization starting point represented by the general formula (2) and a group capable of reacting with the reactive functional group in the first polymer. Among such compounds, as compounds that react with alkoxysilyl groups, 3-(trimethoxysilyl)propyl 2-bromo-2-methylpropionate, 2-bromo-2-methyl 5-(Trimethoxysilyl)pentyl propionate. As a compound which reacts with a (meth)acryloxy group, 2-(2-bromoisobutoxy)ethyl (meth)acrylate etc. are mentioned. As a compound which reacts with an epoxy group, the compound which has a functional group represented by general formula (2) and an amino group or a carboxyl group is mentioned. Examples of the compound that reacts with an isocyanate group or a blocked isocyanate group include a compound having a functional group represented by the general formula (2) and a hydroxyl group or an amino group. As a compound which reacts with a hydroxyl group, the compound which has a functional group and a carboxyl group represented by general formula (2), or its acid anhydride and halides, etc. are mentioned. As a compound which reacts with a carboxyl group, the compound which has functional groups, such as a functional group represented by General formula (2), and an amino group, is mentioned.

As a method of applying the coating liquid on the surface of the substrate, there can be mentioned: screen printing method, dip coating method, inkjet method, spin coating method, knife coating method, bar coating method, slit Type coating method, edge casting method, spraying method, roller coating method, curtain coating method, gravure printing method, flexographic printing method, gravure offset printing method, etc. Among them, an inkjet method capable of coating (imprinting) into any shape as required is preferred.

(Polymer layer (ii))

In the presence of the polymer layer (i) disposed on the surface of the substrate, a specific monomer is subjected to surface-initiated radical polymerization or surface-initiated living radical polymerization. Thereby, the second polymer can be extended with the functional group of the monomer represented by the general formula (1) as the polymerization starting point, and the polymer layer (ii) can be formed on the polymer layer (i).

As the specific monomer, one or more monomers selected from the group consisting of aromatic vinyl monomers, (meth)acrylate monomers, and (meth)acrylamide monomers are used. Among them, (meth)acrylate-based monomers are preferred in terms of high polymerization rate and mild polymerization conditions.

Examples of aromatic vinyl monomers include styrene, vinyl toluene, vinyl hydroxybenzene, chloromethyl styrene, vinyl naphthalene, vinyl biphenyl, vinyl ethyl benzene, vinyl dimethyl Benzene, α-methylstyrene, etc.

酯、(甲基)丙烯酸三甲基環己酯、(甲基)丙烯酸環癸酯、(甲基)丙烯酸環癸基甲酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸第三丁基苯并三唑苯基乙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸烯丙酯等脂肪族、脂環族、芳香族(甲基) 丙烯酸烷基酯等。 Examples of (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, (meth) )Butyl acrylate, 2-methylpropane (meth)acrylate, tertiary butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, (meth) Myristyl acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth) Tertiary butyl cyclohexyl methyl acrylate, (meth) acrylate iso

Ester, trimethylcyclohexyl (meth)acrylate, cyclodecyl (meth)acrylate, cyclodecylmethyl (meth)acrylate, benzyl (meth)acrylate, tertiary butyl (meth)acrylate Aliphatic, cycloaliphatic, aromatic (meth)acrylic acid such as phenyl ethyl benzotriazole, phenyl (meth)acrylate, naphthyl (meth)acrylate, allyl (meth)acrylate, etc. Base ester and so on.

Furthermore, as (meth)acrylate monomers, (meth)acrylic acid ester-based monomers containing hydroxyl groups, glycol groups, acid groups (carboxyl groups, sulfonic acid groups, phosphoric acid groups, etc.), oxygen atoms, amine groups, nitrogen atoms, etc. may also be used. Base) Acrylate-based compounds.

啉等。 In addition, examples of (meth)acrylamide-based monomers include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(methyl) ) Acrylamide, N-hydroxyethyl (meth) acrylamide, (meth) acrylamide

Morpho etc.

By using organic solvents, additives and catalysts, surface-initiated radical polymerization or surface-initiated living radical polymerization can be carried out under pressure conditions of normal pressure to 1,000 MPa, preferably above 100 MPa, Thus, the second polymer is formed. As far as polymerization is initiated by a polymerization initiation group having a halogen atom, it is preferable to perform monomer polymerization by conventionally known atom transfer radical polymerization using metal complexes. Examples of metal complexes include: copper chloride, copper bromide and polyamine complexes such as dinonylbipyridine, tris-dimethylaminoethylamine, and pentamethyldiethylenetriamine, Or dichloro ginseng (triphenylphosphine) ruthenium and so on. Atom transfer radical polymerization may be bulk polymerization or solution polymerization using organic solvents or the like. As the organic solvent, hydrocarbon-based solvents, ester-based solvents, glycol-based solvents, ether-based solvents, amide-based solvents, alcohol-based solvents, sulfite-based solvents, urea-based solvents, ionic liquids, and the like can be used.

Due to the use of heavy metals in atom transfer radical polymerization, coloring or environmental load needs to be considered, and it also needs to be removed from the reaction system. Therefore, it is preferable to polymerize in the presence of general-purpose organic compounds that do not use heavy metals. Specifically, it is preferable to perform surface initiation radical polymerization or surface initiation in the coexistence of at least one salt selected from the group consisting of halogenated quaternary ammonium salt, halogenated quaternary phosphonium salt, and halogenated alkali metal salt. Living free radical polymerization. In this way, commercially available cheap organic materials or inorganic salts can be used Perform polymerization. In addition, since it is not necessary to remove the metal, the environmental load can be reduced and the steps can also be simplified.

Y (halogen) in the general formula (1) is detached into a radical, and a carbon radical is generated at the same time as Y is detached, and the monomer is inserted into the carbon radical to be polymerized. At this time, by allowing the above-mentioned specific salt to coexist, extraction of halogen radicals or halogen exchange occurs, and the generated carbon radicals undergo monomer polymerization to form a second polymer.

Examples of quaternary ammonium halide salts include benzyltrimethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetraoctylammonium iodide, nonylpyridinium chloride, and choline chloride Alkali etc. Examples of halogenated quaternary phosphonium salts include tetraphenylphosphonium chloride, methyltributylphosphonium bromide, and tetrabutylphosphonium iodide. Examples of halogenated alkali metal salts include lithium bromide, potassium iodide, and the like.

As the salt, an iodide salt is preferably used. By using an iodide salt to perform living radical polymerization, a second polymer with a narrower molecular weight distribution can be obtained. In addition, it is preferable to use a salt that is soluble in the polymerization solution, such as a quaternary ammonium iodide salt, a quaternary phosphonium iodide salt, and an alkali metal iodide salt, and it is more preferable to use a quaternary ammonium iodide salt. Examples of the quaternary ammonium iodide salt include: benzyltetrabutylammonium iodide, tetrabutylammonium iodide, tetraoctylammonium iodide, dodecyltrimethylammonium iodide, and octadecane iodide. Trimethylammonium, trioctadecylmethylammonium iodide, etc.

From the viewpoint of improving the activity and obtaining a denser and higher molecular weight second polymer, the amount of the salt relative to the polymerization starting group is preferably equal to or greater than equal mol, more preferably 10 times mol The above can also be set to 100 times or more moles.

In the method of using the quaternary salt or halide salt, the polymerization conditions are not particularly limited. Under the conditions of familiarity and public knowledge. Preferably, the temperature is 60°C or higher, and it is preferable to use an organic solvent as the solvent. As the solvent, conventionally known solvents can be used The agent is not particularly limited. The solvent can use the above-mentioned conventional and well-known organic solvents, but it is preferable to use a solvent that dissolves the salt, preferably an alcohol-based, glycol-based, amide-based, urea-based, sulfite-based, ionic liquid, and other high-polarity solvents. Organic solvents.

The polymerization is carried out under pressure conditions of normal pressure to 1,000 MPa, preferably 100 to 1,000 MPa, more preferably 200 to 800 MPa, and particularly preferably 300 to 600 MPa. Specifically, the polymerization is carried out while uniformly applying pressure to the entire polymerization vessel containing the monomer and the substrate via a medium such as water. By performing radical polymerization under pressure, the stop reaction can be suppressed, and a second polymer with a higher molecular weight can be formed.

Containers or devices that can withstand pressures exceeding 1,000 MPa are difficult to prepare and impractical. As the molecular weight of the second polymer formed becomes larger, the film thickness of the polymer layer (ii) also becomes thicker. By increasing the film thickness of the polymer layer (ii), the surface of the substrate can be modified to exhibit unprecedented characteristics. The film thickness of the polymer layer (ii) can be, for example, several nm to several μm, preferably 10 nm or more, and more preferably 100 nm or more.

As the polymerization container, it is preferable to use a container that can be sealed and can withstand high pressure. In addition, since it is necessary to transmit pressure to the inside of the container, it is better to use a container with a plastic soft part or a flexible part equal to the part that deforms under pressure. Specifically, various containers such as polyethylene bottles, PET bottles, high-temperature sterilization bags, and foaming containers can be used. In addition, it is preferably a container containing a heat-resistant material that is not easily deformed at the temperature during polymerization. Furthermore, it is preferable that it is a container containing the material which has characteristics, such as chemical resistance and solvent resistance, which is not easily corroded by a polymerization solvent etc.. Examples of materials constituting the polymerization container include polyolefin resins, fluorine resins, polyester resins, polyamide resins, and engineering plastics. In addition, it is preferable to prevent gas from entering the polymerization vessel as much as possible during polymerization. For example, it is preferable to fill a polymerization solution that occupies more than 90% of the capacity of the polymerization vessel.

In the above, the polymerization solution such as the substrate, monomer, catalyst, etc. is charged into the polymerization vessel, and the normal pressure is applied, or an external pressure above the normal pressure and below 1000 MPa. It is preferably heated and polymerized, whereby the substrate can be polymerized. The polymer layer (i) generates polymer to modify the surface of the substrate. The surface of the substrate can be modified to any properties according to the types of monomers used. For example, by using a fluorine-based monomer, it is possible to form a polymer layer (ii) with a low surface tension that is easy to repel water or oil. By using monomers with polyethylene glycol groups or carboxyl groups, it is possible to form a hydrophilic polymer layer (ii) that makes the water vapor in contact immediately turn into water droplets and is not prone to fogging. Furthermore, it is also possible to manufacture a biocompatible substrate to which proteins and the like are not easily adhered. In addition, the formed polymer layer (ii) can be swelled with lubricating oil or the like to form a lubricating film to form a polymer layer with extremely low friction.

It is not easy to verify the molecular weight of the second polymer constituting the formed polymer layer (ii). Therefore, it is preferable to perform surface-initiated radical polymerization or surface-initiated living radical polymerization in the coexistence of an initiator monomer having the same initiator as the polymerization initiator. Thereby, a free polymer not contained in the polymer layer (ii) is formed. Furthermore, the molecular weight of the free polymer formed is measured in accordance with the conventional practice, whereby the molecular weight of the second polymer constituting the polymer layer (ii) can be estimated. The number average molecular weight (Mn) of the formed free polymer measured by gel permeation chromatography (GPC) in terms of polystyrene is usually 1,000-10,000,000, preferably 100,000 or more.

As the starting group monomer, a compound having the same group as the polymerization starting group is used. Specifically, the compounds represented by the following formulas (3) to (5) can be used as the starting group monomer.

The polymer layer (ii) is preferably swollen by containing a solvent such as water, an organic solvent, or a mixed solvent of these. By swelling with a solvent, the film thickness of the polymer layer (ii) can be increased. Furthermore, the swollen polymer layer (ii) exhibits specific properties such as strong resistance to compression or low friction, so it is preferred. For example, the polymer layer (ii) can be swelled by immersing the substrate on which the surface treatment film is formed in the solvent.

<Item>

The article of the present invention includes a substrate and the above-mentioned surface treatment film provided on the surface of the substrate. The type of the substrate is not particularly limited, and any of natural materials, artificial materials, inorganic components, and organic components can be used. Among them, it is preferable to use a substrate that can withstand polymerization solutions. Specific examples of substrates include: metal, metal oxide, metal nitride, metal carbide, ceramics, wood, silicon compounds, thermoplastic resins, thermosetting resins, cellulose, glass and other mechanical parts, films, Fiber, sheet, etc.

Surface treatment can also be applied to the substrate. Surface treatments include inorganic treatments such as silane coupling treatment, silicon coating treatment, silicon aluminum treatment, plasma treatment, ultraviolet irradiation treatment, ozone oxidation treatment, radiation treatment, X-ray treatment, electron beam treatment, laser treatment, etc. Net, activation, and surface treatment, functional group imparting treatment, etc.

The film thickness of the polymer layer (i) is preferably thicker than the maximum height Rz of the surface roughness of the substrate surface. Generally, the surface of the substrate usually has irregularities ranging from nanometers to micrometers. If the polymer layer (i) is too thin, the unevenness may not be completely covered and the protrusions may be exposed. Moreover, even if the convex portions are barely covered, the surface shape of the polymer layer (i) reflects the base material The surface of the polymer layer (ii) formed thereon is also easy to become uneven. Therefore, by making the film thickness of the polymer layer (i) thicker than the maximum height Rz of the surface roughness of the substrate surface, the entire surface of the substrate can be uniformly covered and made smooth. In addition, a smoother polymer layer (ii) can be formed on the entire surface of the polymer layer (i). The film thickness of the polymer layer (i) can be measured by, for example, a measurement method using precision equipment such as an atomic force microscope or an ellipsometer, a measurement method using an electron microscope observation, a measurement method using a film thickness measuring machine, or the like.

By providing a surface treatment film with a laminated structure including a polymer layer (i) that is in close contact with the substrate and imparts mechanical strength and a polymer layer (ii) that exhibits specific properties on the surface of the substrate, it can be made The article of the present invention that is given the performance of the part or the performance improvement. The article of the present invention is suitably used as articles used in various fields such as medical components, electronic materials, display materials, semiconductor materials, mechanical parts, sliding members, and battery materials.

[Example]

Hereinafter, the present invention will be specifically explained based on examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, the "parts" and "%" in the examples and comparative examples are quality standards.

<Synthesis of starting base polymer (first polymer)>

(Synthesis Example 1: Starting Base Polymer 1)

Put 150 parts of propylene glycol monomethyl ether acetate (PGMAc) into a reaction vessel equipped with a stirring device, a stirring blade, a thermometer, a cooling tube, a nitrogen introduction device, and a dripping device. While blowing in nitrogen while stirring, it took 30 minutes to heat up to 80°C. Put 75 parts of 2-(2-bromoisobutoxy)ethyl methacrylate in another container (BBEM), 25 parts of 3-methacryloxypropylmethyl diethoxysilane (MPES), and 1.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) ( V-65) and stir to prepare a uniform monomer mixture. After adding 1/3 of the prepared monomer mixture into the reaction vessel, add the remaining monomer mixture dropwise over 1 hour. After dropping, add 0.5 part of V-65 immediately. After 1 hour, further add 0.5 part of V-65, and polymerize at 80°C for 7 hours to obtain a slightly yellowish low-viscosity liquid containing the starting base polymer 1. The solid content of the obtained liquid was 40.1%, and the polymerization rate was about 100%. The polystyrene conversion number average molecular weight (Mn) of the starting base polymer 1 measured with a GPC device (developing solvent: tetrahydrofuran (THF)) was 12,000, and the molecular weight distribution (Mw/Mn, PDI) was 3.56.

(Synthesis Example 2: Starting Base Polymer 2)

Put 100 parts of PGMAc into the same reaction vessel as the reaction vessel used in Synthesis Example 1, and stir while blowing in nitrogen gas, and heat to 65°C over 30 minutes. Put 50 parts of BBEM, 15 parts of methyl methacrylate (MMA), 15 parts of butyl methacrylate (BMA), 10 parts of 2-ethylhexyl methacrylate (2EHMA), and 10 parts in another container 2-[O-(1'-Methylpropyleneamino)carboxyamino]ethyl methacrylate (blocked isocyanate monomer, trade name "Karenz MOI-BM", manufactured by Showa Denko), and 1 Part V-65 and stir to prepare a uniform monomer mixture. After adding 1/2 of the prepared monomer mixture to the reaction vessel, drop the remaining monomer mixture over 2 hours. After 3 hours of polymerization, 0.5 part of V-65 was added and polymerization was performed for 5 hours to obtain a slightly yellow viscous solution containing the starting base polymer 2. The solid content of the obtained liquid was 50.3%, and the polymerization rate was about 100%. The Mn of the starting base polymer 2 is 18,600, and the PDI is 2.06.

(Synthesis examples 3~5: starting base polymer 3~5)

Using the monomers of the type and amount (unit: parts) shown in the middle section of Table 1, except for this, in the same manner as in Synthesis Example 1 above, solutions containing 3 to 5 starting base polymers were obtained. The physical properties of the obtained starting base polymers are shown in the lower section of Table 1.

[Table 1]

<Manufacturing of coating liquid for forming polymer layer (i)>

(Manufacturing Example 1: COT-1)

100 parts of the liquid containing the starting base polymer 1 and 60.4 parts of PGMAc were mixed to obtain a coating liquid (COT-1).

(Manufacturing Example 2: COT-2)

100 parts of the liquid containing the starting base polymer 2, 2 parts of polyethyleneimine (trade name "Epomin SP-003", manufactured by Nippon Shokubai Co., Ltd.), and 107.2 parts of PGMAc were mixed to obtain a coating liquid (COT-2 ).

(Manufacturing example 3~5: COT-3~5)

Except for using the components of the type and amount (unit: parts) shown in the middle section of Table 2, the coating liquid (COT-3 to 5) was obtained in the same manner as in the above-mentioned Production Example 1. The appearance and solid content (%) of the obtained coating liquids are shown in the lower part of Table 2.

[Table 2]

<Manufacturing of polymer layer (i) imparting base material>

(Manufacturing Example 6: SUB-1)

Prepare a silicon wafer that has been cleaned and surface-activated by UV ozone as the substrate. Coat COT-1 on the surface of the prepared substrate, and use a spin coater to coat at 2,000 rpm for 30 seconds. Put it in an oven at 80℃ and dry for 5 minutes Afterwards, it is placed in an oven at 120° C. and heated for 12 hours for curing to form the polymer layer (i), and obtain the SUB-1 that belongs to the polymer layer (i) and gives the substrate. The thickness of the polymer layer (i) measured by spectroscopic ellipsometry was 1,286 nm. After immersing the obtained SUB-1 in THF for 5 minutes to perform ultrasonic cleaning, the film thickness of the polymer layer (i) was measured again. As a result, it was confirmed that the film thickness of the polymer layer (i) hardly changed from before washing, and a sufficiently hardened polymer layer (i) was formed.

(Manufacturing Example 7: SUB-2)

Prepare a cleaned and surface activated glass plate (Rz=15nm) with UV ozone as the substrate. Coat COT-2 on the surface of the prepared substrate, and use a spin coater to coat at 2,000 rpm for 30 seconds. After drying for 5 minutes in an oven at 80°C, it is placed in an oven at 140°C and heated for 1 hour to harden to form the polymer layer (i), and obtain the SUB- which belongs to the polymer layer (i) to give the substrate. 2. The thickness of the polymer layer (i) measured by spectroscopic ellipsometry was 1,331 nm. After immersing the obtained SUB-2 in THF for 5 minutes and ultrasonic cleaning, the film thickness of the polymer layer (i) was measured again. As a result, it was confirmed that the film thickness of the polymer layer (i) hardly changed from before washing, and a sufficiently hardened polymer layer (i) was formed.

(Manufacturing example 8~10: SUB-3~5)

Except for the conditions shown in the lower stage of Table 3, in the same manner as in the above-mentioned Production Examples 6 and 7, SUB-3 to 5 belonging to the polymer layer (i) providing the base material were obtained.

[table 3]

(Comparative Manufacturing Example 1: SUB-C-1)

Put a mixture of 0.2 parts of 2-bromo-2-methylpropionic acid 3-(trimethoxysilylpropyl) ester (BPM), 2 parts of concentrated ammonia, and 45 parts of ethanol into the polystyrene culture Dish. Prepare a sufficiently cleaned glass plate (Rz=15nm) as the substrate. Put the prepared substrate in a petri dish, immerse it in the solution, and let it stand at room temperature for 12 hours, and then wash it thoroughly with ethanol. Thereby, SUB-C-1 with a monomolecular film with a polymerization starting point formed on the surface of the glass plate is obtained.

(Comparative Manufacturing Example 2: SUB-C-2)

A SUS plate (Rz=0.8μm) was used instead of the glass plate as the base material. Except for this, in the same manner as in Comparative Production Example 1 above, a monomolecular film with a polymerization initiation point formed on the surface of the SUS plate was obtained. SUB-C-2.

<Manufacturing of Surface Treatment Film for Substrate>

(Example 1: SUB-6)

In an argon atmosphere, 0.00054 parts of ethyl 2-bromoisobutyrate (EBiB) and 55.5 parts of 3-methoxy-N,N-dimethylpropanamide (trade name "KJCMPA-100", KJ Chemical (KJCMPA), 55.1 parts of MMA, and 0.41 part of tetrabutylammonium iodide (TBAI) were put into the flask and stirred to prepare a polymerization solution. Put the SUB-1 that belongs to the polymer layer (i) as the base material in a screw-top container made of PTFE, fill the container with the prepared polymer solution, then add a stopper, and wrap a paraffin film on the lid. The container was put into an aluminum laminate bag, and heat-sealed while evacuating the gas. Put the container together with the aluminum laminate bag into a high-pressure device (trade name "PV-400", manufactured by Sincorporation) containing water as a pressurizing medium, and heat to 75°C and pressurize to 400MPa for 4 Hour polymerization. A high-viscosity solution containing polymer is generated in the high-pressure device, and a part of the polymer is taken as a sample for measurement. The Mn of the polymer is 2,378,000 and the PDI is 1.42. Use THF to thoroughly clean the substrate taken out of the container. The film thickness of the film formed on the surface of the silicon wafer was measured by spectroscopic ellipsometry, and the result was 1,962nm. It was confirmed that it became thicker than the film thickness of the polymer layer (i), and it was confirmed that the surface treatment film which laminated|stacked the polymer layer (ii) on the polymer layer (i) was formed. The obtained substrate (surface-treated film-imparting substrate) was set to SUB-6.

(Example 2: SUB-7)

In an argon atmosphere, 0.00098 parts of EBiB, 0.080 parts of copper(II) bromide (CuBr ₂ ), 0.46 parts of copper(I)(CuBr), 3.2 parts of 4,4'-dinonyl-2,2 '-Bipyridine (dNbpy), 100.1 parts of MMA, and 103.9 parts of anisole were put into a flask and stirred to prepare a polymerization solution. Put the SUB-2 which belongs to the polymer layer (i) as the base material into the screw-top container made of PTFE, fill the container with the prepared polymer solution, then add a stopper, and wrap a paraffin film on the lid. The container was put into an aluminum laminate bag, and heat-sealed while evacuating the gas. Put the container together with the aluminum laminate bag into a high-pressure device (PV-400) containing water as a pressurizing medium, heat it to 60°C, and pressurize it to 400MPa for 4 hours of polymerization. A high-viscosity solution containing polymer is generated in a high-pressure device, and a part of the polymer is taken as a sample for measurement. The Mn of the polymer is 2,463,000 and the PDI is 1.09. Use THF to thoroughly clean the substrate taken out of the container. The film thickness of the film formed on the surface of the glass plate was measured by spectroscopic ellipsometry, and the result was 2,028 nm. It was confirmed that it became thicker than the film thickness of the polymer layer (i), and it was confirmed that the surface treatment film which laminated|stacked the polymer layer (ii) on the polymer layer (i) was formed. The obtained substrate (surface-treated film-imparting substrate) was set to SUB-7.

(Examples 3~5, Comparative Examples 1, 2: SUB-8~10, SUB-C-3, 4)

The polymer layer (i) of the type shown in Table 4 was used to impart the substrate and the monomer, except for this, in the same manner as in Example 1 or 2 above, SUB-8 to 10 belonging to the surface treatment film imparted substrate were obtained. , SUB-C-3, 4. Table 4 shows the details of applying the obtained surface treatment film to the substrate.

[Table 4]

<evaluation>

(Evaluation (1): SUB-7)

The SUB-7 obtained in Example 2 was immersed in toluene overnight to swell the surface treatment film. Using a friction tester (trade name "Heidon Friction Tester Model 14", manufactured by Shinto Scientific Co., Ltd.), 1,000 reciprocating ball indenter reciprocating sliding under the conditions of a load of 1,000g, an amplitude of 30mm, and a sliding speed of 200mm/min test. As a result of data analysis, the friction coefficient is 0.0020, and there is no change in the friction coefficient after 1,000 round trips. The surface after the sliding test was observed with a laser microscope, and no wear was found. In summary, it is confirmed that SUB-7 has low friction and high durability.

(Evaluation (2): SUB-10)

Except that it was immersed in diisotridecyl adipate instead of toluene, a sliding test was performed on the SUB-10 obtained in Example 5 in the same manner as in the above-mentioned evaluation (1). As a result, the coefficient of friction was 0.0018, and there was no change in the coefficient of friction even after 1,000 round trips. The surface after the sliding test was observed with a laser microscope, and no wear was found. In summary, it is confirmed that SUB-10 has low friction and high durability.

(Evaluation (3): SUB-C-3)

In the same manner as in the above evaluation (1), a sliding test was performed on the SUB-C-3 obtained in Comparative Example 1. As a result, the initial friction coefficient was 0.002, but the friction coefficient gradually increased after about 500 reciprocations, and the friction coefficient after 1,000 reciprocations became 0.05. The surface after the sliding test was observed with a laser microscope, and as a result, abrasion marks were observed. SUB-C-3 is directly formed on the glass plate (Rz=15nm) without forming the polymer layer (i) (ii) Person. It is considered that since the polymer layer (i) is not present, the abrasion progresses due to the surface roughness of the glass plate, and the friction coefficient increases.

(Evaluation (4): SUB-C-4)

In the same manner as in the above evaluation (1), the SUB-C-4 obtained in Comparative Example 2 was subjected to a sliding test. As a result, the initial friction coefficient was 0.09, the friction coefficient gradually increased, and the friction coefficient became 0.2 after about 100 round trips. The surface after the sliding test was observed with a laser microscope, and as a result, clear abrasion marks were observed. SUB-C-4 is directly formed on the SUS board (Rz=0.8μm) without forming the polymer layer (i) but directly forming the polymer layer (ii). It is believed that due to the rough surface of the SUS board, the lubricity generated by the polymer layer (ii) is lacking, and the durability is significantly reduced.

(Industrial availability)

The surface treatment film of the present invention can impart properties such as low friction, anti-adhesion, hydrophilicity, hydrophobicity or water repellency to the surface of the substrate. Furthermore, the adhesion to the substrate is high, and the durability of the substrate can be improved. Therefore, if the surface treatment film of the present invention is used, various articles such as parts used in various fields such as medical parts, electronic materials, display materials, semiconductor materials, mechanical parts, sliding parts, and battery materials can be provided.

Claims (9)

A surface treatment film, which is arranged on the surface of the substrate, It has a laminated structure including a polymer layer (i) arranged on the surface side of the above-mentioned substrate, and a polymer layer (ii) formed on the above-mentioned polymer layer (i), The polymer layer (i) contains a first polymer, and the first polymer contains a structural unit derived from a monomer represented by the following general formula (1), The polymer layer (ii) contains a second polymer, and the second polymer contains a monomer derived from an aromatic vinyl monomer, a (meth)acrylate monomer, and a (meth)acrylamide monomer The constituent unit of one or more monomers selected by the constituted group, and the functional group of the monomer represented by the following general formula (1) is used as the polymerization starting point for extension;

(In the above general formula (1), R ₁ represents a hydrogen atom or a methyl group, X represents O or NH, R ₂ represents an arbitrary organic group, and R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group or The carbon atom to which R ₃ and R ₄ are bonded is a tertiary carbon atom or a quaternary carbon atom, and Y represents a chlorine atom, a bromine atom, or an iodine atom). The surface treatment film of claim 1, wherein the first polymer contains 30% by mass or more of the constituent unit derived from the monomer represented by the general formula (1). The surface treatment film of claim 1, wherein the above-mentioned first polymer system further comprises a polymer having a alkoxysilyl group, a (meth)acryloyloxy group, an epoxy group, an isocyanate group, and a blocked isocyanate group. The group consisting of cyanate, hydroxyl, carboxyl and phosphoric acid groups The constituent unit of the radical polymerizable monomer of the selected reactive functional group. The surface treatment film of claim 3, wherein the first polymer has a cross-linked structure. The surface treatment film according to any one of claims 1 to 4, wherein the polymer layer (ii) contains a solvent and swells. A method for manufacturing a surface treatment film, which is the method for manufacturing a surface treatment film according to any one of claims 1 to 5, and has the following steps: Disposing the aforementioned polymer layer (i) on the surface of the aforementioned substrate; and Under normal pressure~1,000MPa pressure conditions, in the presence of the above polymer layer (i), from aromatic vinyl monomers, (meth)acrylate monomers and (meth)acrylic acid monomers One or more monomers selected from the group consisting of amine-based monomers undergo surface-initiated radical polymerization or surface-initiated living radical polymerization to form the above-mentioned polymer layer (ii) on the above-mentioned polymer layer (i). Such as the method of manufacturing a surface treatment film of claim 6, which further performs surface treatment under the coexistence of at least one salt selected from the group consisting of halogenated quaternary ammonium salt, halogenated quaternary phosphonium salt, and halogenated alkali metal salt. Initiation of radical polymerization or surface initiation of living radical polymerization, and the above-mentioned polymer layer (ii) is formed on the above-mentioned polymer layer (i). An item that has: Substrate, and The surface treatment film of any one of claims 1 to 5 provided on the surface of the above-mentioned substrate. The article according to claim 8, wherein the film thickness of the polymer layer (i) is thicker than the maximum height Rz of the surface roughness of the substrate.