WO2020166128A1 - 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-treated film, manufacturing method thereof, and article

The present invention relates to a surface-treated film provided on the surface of a base material, a method for producing the same, and an article provided with the surface-treated film.

As a method for modifying a base material, a polymer layer having a group capable of adsorbing or reacting with the base material at its end is applied to the base material to form a polymer layer physically or chemically bonded on the surface of the base material. It has been known. Further, a method is known in which a polymer is grafted from the surface of a base material by polymerizing a monomer starting from a polymerizable group provided on the surface of the base material.

In recent years, so-called "dense polymer brushes" have been studied, which are densely grafted onto a substrate by utilizing the technology of living radical polymerization developed in the 1990s. In this thick polymer brush, polymer chains are grafted onto a substrate at a high density with an interval of 1 to 4 nm. The surface of the base material can be modified with such a thick polymer brush to impart characteristics such as low friction, protein adsorption suppression, size exclusion characteristics, hydrophilicity, and water repellency (for example, Patent Documents 1 and 2). , Non-Patent Documents 1 to 3).

JP, 2008-133434, A JP, 2010-261001, A

Adv. Polym. Sci. , 2006, 197, 1-45 J. Am. Chem. Soc. , 2005, 127, 15843-15847 Polym. Chem. , 2012, 3, 148-153

Rich polymer brushes (hereinafter also simply referred to as "brushes") exhibit low friction in the tribological fields of lubrication, friction, and wear. However, the polymer layer of the brush may be easily detached from the surface of the base material due to the lubricating oil or solvent used during rubbing. The thick polymer brush is formed by forming a polymerization initiation base layer, which is a monomolecular film layer, and then performing polymerization. However, it is considered that the polymer layer is likely to be detached by friction or solvent because the binding force and the adhesiveness of the monolayer are weak.

Also, since the surface of the base material that forms the brush has irregularities, if the polymer layer of the brush cannot cover the irregularities, it may not exhibit low friction properties. In order to cover the roughness of the base material surface, it is possible to form the brush after polishing the base material surface to make it smooth, but this is disadvantageous in terms of cost, etc. because the process of polishing the base material surface increases. It was Note that it is possible to cover the roughness of the surface of the base material by forming a brush having a large film thickness. However, in order to form a brush having a large film thickness, special conditions and equipment are required, such as living radical polymerization under high pressure conditions (for example, 100 to 1,000 MPa) and grafting onto the surface of the substrate. Therefore, it is not always easy to form a brush having a large film thickness, and it is likely to be disadvantageous in terms of cost.

The present invention has been made in view of the problems with such conventional techniques, and the problem is that abrasion resistance, abrasion resistance, chemical resistance, heat resistance, solvent resistance, and the like. An object of the present invention is to provide a surface-treated film capable of imparting durability to the surface of various base materials and having excellent adhesion to the surface of the base material. Another object of the present invention is to provide a method for producing the above surface-treated film and an article provided with the above surface-treated film.

That is, according to the present invention, the following surface treatment film is provided.
[1] A surface-treated film provided on the surface of a base material, the polymer layer (i) being disposed on the surface side of the base material, and a polymer layer (ii) formed on the polymer layer (i). ), and the polymer layer (i) contains a first polymer containing a constitutional unit derived from a monomer represented by the following general formula (1), and the polymer layer (ii) Is represented by the following general formula (1), containing a constitutional unit derived from one or more monomers selected from the group consisting of aromatic vinyl-based monomers, (meth)acrylate-based monomers, and (meth)acrylamide-based monomers. A surface-treated film containing a second polymer elongated from the functional group of the monomer as a polymerization initiation point.

（前記一般式（１）中、Ｒ_１は、水素原子又はメチル基を示し、Ｘは、Ｏ又はＮＨを示し、Ｒ_２は、任意の有機基を示し、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子、アルキル基、アリール基、又はアシル基を示すとともに、Ｒ_３及びＲ_４が結合している炭素原子は第３級炭素原子又は第４級炭素原子であり、Ｙは、塩素原子、臭素原子、又はヨウ素原子を示す）

(In the 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 are each independently. Is 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, and Y is a chlorine atom. , Bromine atom, or iodine atom)

[2] The surface-treated film according to [1], wherein the first polymer contains 30% by mass or more of a structural unit derived from the monomer represented by the general formula (1).
[3] The first polymer is a reactive functional group selected from the group consisting of an alkoxysilyl group, a (meth)acryloyloxy group, an epoxy group, an isocyanate group, a blocked isocyanate group, a hydroxyl group, a carboxy group, and a phosphoric acid group. The surface-treated film as described in [1] or [2] above, further including a structural unit derived from a radically polymerizable monomer having a group.
[4] The surface-treated film as described in [3] above, wherein the first polymer has a crosslinked structure.
[5] The surface-treated film as described in any of [1] to [4] above, wherein the polymer layer (ii) contains a solvent and swells.

Further, according to the present invention, the following method for producing a surface-treated film is provided.
[6] The method for producing a surface-treated film as described in any one of [1] to [5] above, wherein a step of disposing the polymer layer (i) on the surface of the substrate, and an atmospheric pressure to 1 One or more monomers selected from the group consisting of aromatic vinyl-based monomers, (meth)acrylate-based monomers, and (meth)acrylamide-based monomers in the presence of the polymer layer (i) under a pressure condition of 1,000 MPa. Surface-initiated radical polymerization or surface-initiated living radical polymerization to form the polymer layer (ii) on the polymer layer (i).
[7] Further, in the presence of at least one salt selected from the group consisting of a quaternary ammonium halide salt, a quaternary phosphonium halide salt, and an alkali metal halide salt, surface-initiated radical polymerization or surface initiation The method for producing a surface-treated film as described in [6] above, wherein the polymer layer (ii) is formed on the polymer layer (i) by living radical polymerization.

Further, according to the present invention, the following articles are provided.
[8] An article comprising a substrate and the surface-treated film according to any one of [1] to [5] provided on the surface of the substrate.
[9] The article according to the above [8], wherein the film thickness of the polymer layer (i) is thicker than the maximum height Rz of the surface roughness of the surface of the base material.

According to the present invention, it is possible to impart durability such as wear resistance, abrasion resistance, chemical resistance, heat resistance, and solvent resistance to the surface of various base materials, adhesion with the surface of the base material It is possible to provide a surface-treated film having excellent properties. Further, according to the present invention, it is possible to provide a method for producing the above surface-treated film and an article including the above-mentioned surface-treated film.

<Surface treatment film and manufacturing method thereof>
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. The surface-treated film of the present invention is a film provided on the surface of a base material, and comprises a polymer layer (i) arranged on the front surface side of the base material and a polymer layer (i) formed on the polymer layer (i). ii) and having a laminated structure including. The polymer layer (i) contains the 1st polymer containing the structural unit derived from the monomer represented by the following general formula (1). The polymer layer (ii) contains a structural unit derived from at least one monomer selected from the group consisting of aromatic vinyl-based monomers, (meth)acrylate-based monomers, and (meth)acrylamide-based monomers, and the following general It contains a second polymer which is elongated with the functional group of the monomer represented by the formula (1) as a polymerization initiation point. Hereinafter, details of the surface-treated film of the present invention will be described.

(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 arranged on the front surface side of the substrate, and is a layer containing a first polymer containing a constitutional unit derived from a monomer represented by the following general formula (1), and preferably It is a layer substantially formed of the first polymer.

（前記一般式（１）中、Ｒ_１は、水素原子又はメチル基を示し、Ｘは、Ｏ又はＮＨを示し、Ｒ_２は、任意の有機基を示し、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子、アルキル基、アリール基、又はアシル基を示すとともに、Ｒ_３及びＲ_４が結合している炭素原子は第３級炭素原子又は第４級炭素原子であり、Ｙは、塩素原子、臭素原子、又はヨウ素原子を示す）

(In the 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 are each independently. Is 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, and Y is a chlorine atom. , Bromine atom, or iodine atom)

For example, by coating and drying the component (coating liquid) containing the first polymer containing the constitutional unit derived from the monomer represented by the general formula (1) on the surface of the substrate and curing the component, the surface of the substrate The polymer layer (i) can be formed on the substrate. Then, in the presence of the polymer layer (i), one or more monomers selected from the group consisting of aromatic vinyl-based monomers, (meth)acrylate-based monomers, and (meth)acrylamide-based monomers are polymerized by a predetermined method. The second polymer extends with the functional group represented by the following general formula (2) in the first polymer contained in the polymer layer (i) as a polymerization initiation point. 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 the surface-treated film.

（前記一般式（２）中、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子、アルキル基、アリール基、又はアシル基を示すとともに、Ｒ_３及びＲ_４が結合している炭素原子は第３級炭素原子又は第４級炭素原子であり、Ｙは、塩素原子、臭素原子、又はヨウ素原子を示す）

(In the 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 the It is a tertiary carbon atom or a quaternary carbon atom, and Y represents a chlorine atom, a bromine atom, or an iodine atom.)

In the general formula (2), a halogen atom such as a chlorine atom represented by Y is desorbed as a halogen radical by the action of light, heat, and a radical, and a tertiary or quaternary carbon radical is generated. The generated tertiary or quaternary carbon radical attacks and reacts with the above-mentioned monomer having a radical-polymerizable group, 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 (meth)acrylate having an epoxy group such as glycidyl methacrylate. 2-chloropropionic acid, 2-chlorobutyric acid, 2-chloroisobutyric acid, 2-chlorovaleric acid, 2-bromopropionic acid, 2-bromobutyric acid, 2-bromoisobutyric acid, 2-bromovaleric acid, α-bromophenylacetic acid, Examples thereof include halogen-substituted carboxylic acid compounds such as α-bromo-4-chloroacetic acid, and compounds obtained by reacting these acid anhydrides or acid halides. Further, compounds obtained by halogen exchange of chlorine atom or bromine atom in these compounds with iodine atom can be mentioned. Among the compounds represented by the general formula (1), 2-(2-bromoisobutyryloxy)ethyl methacrylate can be mentioned as a relatively easily available commercial product. It is also possible to use 2-(2-iodoisobutyryloxy)ethyl methacrylate in which the bromine atom of this 2-(2-bromoisobutyryloxy)ethyl methacrylate is replaced with an iodine atom.

The first polymer can be obtained by polymerizing the monomer represented by the general formula (1). Further, a polymer obtained by polymerizing the above-mentioned (meth)acrylate having an epoxy group such as (di)hydroxyalkyl(meth)acrylate, N-hydroxyalkyl(meth)acrylamide, and glycidyl methacrylate is added to the above halogen-substituted carboxylic acid. The first polymer can also be obtained by reacting an acid compound or the like.

The first polymer may include a structural unit (other structural unit) other than the structural unit derived from the monomer represented by the general formula (1). By including other structural units, it becomes possible to change the thermal/mechanical properties of the first polymer and to form a three-dimensional network structure, and the adhesion to the substrate, flexibility and resistance It is possible to improve durability such as chemical properties. The first polymer preferably contains 0.1 to 100% by mass of the structural unit derived from the monomer represented by the general formula (1), more preferably 30% by mass or more, and 50% by mass or more. Is particularly preferable. When the amount of the constitutional unit derived from the monomer represented by the general formula (1) in the first polymer is too small, the second polymer is elongated with the functional group of the monomer represented by the general formula (1) as a polymerization initiation point. And the effect of the polymer layer (ii) tends to be insufficient.

The other structural unit can be formed by copolymerizing a monomer (other monomer) other than the monomer represented by the general formula (1) with the monomer represented by the general formula (1). As the other monomer, a conventionally known radically polymerizable monomer can be appropriately selected and used. Above all, by using a radically polymerizable monomer having a reactive functional group, the adhesion of the polymer layer (i) to the substrate is improved or the mechanical strength of the polymer layer (i) is improved. Is preferable because it can Furthermore, by using a compound (crosslinking agent) in which the reactive functional group has self-reactivity or has a group that reacts with the above-mentioned reactive functional group, the polymer layer (i) has a three-dimensional network structure. It is preferable because it can be a cured product having. Examples of the reactive functional group include an alkoxysilyl group, a (meth)acryloyloxy group, an epoxy group, an isocyanate group, a blocked isocyanate group, a hydroxyl group, a carboxy group, and a phosphoric acid group.

When the reactive functional group is an alkoxysilyl group, the alkoxysilyl group undergoes a dehydration condensation reaction with the hydroxyl group on the surface of the base material, or the alkoxysilyl groups self-crosslink 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, it is possible to cure it by irradiating it with ultraviolet rays or electron beams while adding a photoradical generator and the like. In addition, thermal crosslinking can be performed by adding a heat radical generator or the like. Further, a monofunctional monomer such as phenoxyethyl acrylate; an acrylic oligomer such as pentaerythritol tetraacrylate can be used as a crosslinking agent.

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

When the reactive functional group is a carboxy group, a three-dimensional network structure can be formed by using a crosslinking agent such as a melamine crosslinking agent, a carbodiimide crosslinking agent, an oxazoline crosslinking agent, a polyisocyanate crosslinking agent, or a polyepoxy compound. .. Further, when the reactive functional group is a phosphoric acid group and the base material is a metal, a phosphoric acid-metal bond is generated by the reaction with the surface of the metal, so that the base material and the polymer layer (i) are Adhesion can be improved.

The polymer structure of the first polymer may be linear, branched, grafted, block, multiblock, bottlebrush, star, multibranched, dendrimer, particle, crosslinked, etc. Can be mentioned. 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. Of these, radical polymerization and living radical polymerization are preferable because of mild reaction conditions and the like. Further, it can be produced by a conventionally known polymerization method such as bulk polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization and solution polymerization.

The polymer layer (i) is substantially formed of the first polymer, or is formed by curing the first polymer with a crosslinking agent or the like. The polymer layer (i) can be formed by, for example, applying a coating liquid containing the first polymer onto the surface of the base material to form a coat layer, followed by drying and further curing. The coating liquid usually contains, as a component other than the first polymer, a liquid medium such as water or an organic solvent, a crosslinking agent, and other additives. Further, it may further contain a compound having a functional group represented by the general formula (2) as a starting point of polymerization and a group capable of reacting with a reactive functional group in the first polymer. Among such compounds, compounds that react with an alkoxysilyl group include 3-(trimethoxysilyl)propyl 2-bromo-2-methylpropionate and 5-(trimethoxysilyl)pentyl 2-bromo-2- Mention may be made of methyl propionate. Examples of the compound that reacts with the (meth)acryloyloxy group include 2-(2-bromoisobutyryloxy)ethyl (meth)acrylate. Examples of the compound that reacts with the epoxy group include compounds having a functional group represented by the general formula (2) and an amino group or a carboxyl group. Examples of the compound that reacts with an isocyanate group or a blocked isocyanate group include compounds having a functional group represented by the general formula (2) and a hydroxyl group or an amino group. Examples of the compound that reacts with a hydroxyl group include compounds having a functional group represented by the general formula (2) and a carboxy group, and acid anhydrides and acid halides thereof. Examples of the compound that reacts with the carboxy group include compounds having a functional group represented by the general formula (2) and a functional group such as an amino group.

As a method for applying the coating liquid on the surface of the substrate, a screen printing method, a dip coating method, an inkjet method, a spin coating method, a blade coating method, a bar coating method, a slit coating method, an edge casting method, a spray coating method, a roll method. A coating method, a curtain coating method, a gravure printing method, a flexographic printing method, a gravure offset printing method and the like can be mentioned. Among them, the inkjet method is preferable because it can be applied (printed) in an arbitrary shape on demand.

(Polymer layer (ii))
A specific monomer is subjected to surface-initiated radical polymerization or surface-initiated living radical polymerization in the presence of the polymer layer (i) arranged on the surface of the substrate. This makes it possible to extend the second polymer using the functional group of the monomer represented by the general formula (1) as a polymerization initiation point to form the polymer layer (ii) on the polymer layer (i).

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

Examples of aromatic vinyl-based monomers include styrene, vinyltoluene, vinylhydroxybenzene, chloromethylstyrene, vinylnaphthalene, vinylbiphenyl, vinylethylbenzene, vinyldimethylbenzene, α-methylstyrene and the like.

Examples of the (meth)acrylate-based monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-methylpropane (meth)acrylate, t- 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, tetradecyl (meth)acrylate, octadecyl (meth)acrylate, behenyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexylmethyl (meth)acrylate, isobornyl (Meth)acrylate, trimethylcyclohexyl (meth)acrylate, cyclodecyl (meth)acrylate, cyclodecylmethyl (meth)acrylate, benzyl (meth)acrylate, t-butylbenzotriazole phenylethyl (meth)acrylate, phenyl (meth)acrylate, Examples thereof include aliphatic, alicyclic and aromatic alkyl (meth)acrylates such as naphthyl (meth)acrylate and allyl (meth)acrylate.

As the (meth)acrylate-based monomer, a (meth)acrylate-based compound containing a hydroxyl group, glycol group, acid group (carboxy group, sulfonic acid group, phosphoric acid group, etc.), oxygen atom, amino group, nitrogen atom, etc. It can also be used.

Examples of the (meth)acrylamide-based monomer include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, and (meth)acryloylmorpholine. And so on.

The second polymer is obtained by surface-initiating radical polymerization or surface-initiating living radical polymerization under a pressure condition of atmospheric pressure to 1,000 MPa, preferably 100 MPa or more, using an organic solvent, an additive, a catalyst and the like. Can be formed. Since the polymerization is initiated from the polymerization initiation group having a halogen atom, it is preferable to polymerize the monomer by atom transfer radical polymerization using a conventionally known metal complex. Examples of the metal complex include complexes of copper chloride and copper bromide with polyamines such as dinonylbipyridine, tridimethylaminoethylamine and pentamethyldiethylenetriamine; and dichlorotris(triphenylphosphine)ruthenium. The atom transfer radical polymerization may be bulk polymerization or solution polymerization using an organic solvent or the like. As the organic solvent, a hydrocarbon solvent, an ester solvent, a glycol solvent, an ether solvent, an amide solvent, an alcohol solvent, a sulfoxide solvent, a urea solvent, an ionic liquid, or the like can be used.

ㆍSince heavy metals are used in atom transfer radical polymerization, it is necessary to consider coloring and environmental load and also to remove them from the reaction system. Therefore, the polymerization is preferably performed in the presence of a general-purpose organic compound that does not use heavy metals. Specifically, in the presence of at least one salt selected from the group consisting of a quaternary ammonium halide salt, a quaternary phosphonium halide salt, and an alkali metal halide salt, surface-initiated radical polymerization or surface initiation Living radical polymerization is preferred. Thereby, it is possible to polymerize with a commercially available inexpensive organic material or inorganic salt. Further, since it is not necessary to remove the metal, the load on the environment can be reduced and the process can be simplified.

▽Y (halogen) in the general formula (1) is desorbed as a radical, and a monomer is inserted into the carbon radical generated along with the desorption of Y, and the polymerization proceeds. At that time, by coexisting with the above-mentioned specific salt, abstraction or halogen exchange of the halogen radical occurs, and the polymerization of the monomer proceeds from the generated carbon radical to form the second polymer.

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

It is preferable to use an iodide salt as the salt. By using an iodide salt, living radical polymerization proceeds and a second polymer having a narrower molecular weight distribution can be obtained. Further, it is preferable to use a salt that can be dissolved in a polymerization solution such as a quaternary ammonium iodide salt, a quaternary phosphonium iodide salt, and an alkali metal iodide salt, and a quaternary ammonium iodide salt is used. More preferable. Examples of the quaternary ammonium iodide salt include benzyltetrabutylammonium iodide, tetrabutylammonium iodide, tetraoctylammonium iodide, dodecyltrimethylammonium iodide, octadecyltrimethylammonium iodide, and trioctadecylmethylammonium iodide. Can be mentioned.

From the viewpoint of increasing the activity and obtaining a more concentrated and high molecular weight second polymer, the amount of the salt with respect to the polymerization initiation group is preferably equimolar or more, more preferably 10 times or more, and 100 times or more. It may be molar or more.

In the method using the quaternary salt or halide salt, the polymerization conditions are not particularly limited. It is performed under conventionally known conditions. Preferably, the temperature is 60° C. or higher, and it is preferable to use an organic solvent as the solvent. A conventionally known solvent can be used as the solvent and is not particularly limited. As the solvent, the conventionally known organic solvent described above can be used, but it is preferable to use a solvent capable of dissolving a salt, such as alcohol-based, glycol-based, amide-based, urea-based, sulfoxide-based, and ionic liquid polar solvents. Higher organic solvents are preferred.

Polymerization is carried out under a pressure condition 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 entire polymerization vessel containing the monomer and the base material is polymerized while uniformly applying pressure through a medium such as water. By radical polymerization under pressure, the termination reaction can be suppressed and a second polymer having a higher molecular weight can be formed.

It is difficult and not practical to prepare a container or device that can withstand a pressure of over 1,000 MPa. As the molecular weight of the second polymer formed increases, the film thickness of the polymer layer (ii) increases. By increasing the thickness of the polymer layer (ii), the surface of the base material can be modified so as to exhibit unprecedented characteristics. The thickness of the polymer layer (ii) can be, for example, several nm to several μm, preferably 10 nm or more, more preferably 100 nm or more.

As the polymerization vessel, it is preferable to use a vessel that can be sealed and can withstand high pressure. Further, since pressure needs to be transmitted to the inside of the container, it is preferable to use a container having a portion that is deformed by pressure, such as a plastic soft portion or a stretchable portion. Specifically, various containers such as polyethylene bottles, PET bottles, retort pouches, and blister containers can be used. Further, a container made of a material having heat resistance, which does not easily deform at the temperature during polymerization, is preferable. Furthermore, a container made of a material having characteristics such as chemical resistance and solvent resistance, which is hard to be attacked by a polymerization solvent or the like, is preferable. Examples of materials forming the polymerization container include polyolefin-based resins, fluorine-based resins, polyester-based resins, polyamide-based resins, engineered plastics, and the like. In addition, during polymerization, it is preferable to prevent gas from entering the polymerization container as much as possible. For example, it is preferable to charge the polymerization solution to 90% or more of the capacity of the polymerization container.

As described above, the polymer layer of the base material is prepared by charging the polymerization solution of the base material, the monomer, the catalyst and the like into a polymerization vessel and applying the atmospheric pressure or the external pressure of the atmospheric pressure or more and 1000 MPa or less, preferably by heating to perform the polymerization. A polymer is generated from (i), and the surface of the base material can be modified. The surface of the base material can be modified to have arbitrary properties depending on the type of monomer used and the like. For example, by using a fluorine-based monomer, it is possible to form a polymer layer (ii) having a low surface tension that easily repels water and oil. By using a monomer having a polyethylene glycol group, a carboxy group, or the like, it is possible to form a hydrophilic polymer layer (ii) in which the hit steam immediately becomes a water drop and is hard to be clouded. Furthermore, it is also possible to manufacture a biocompatible substrate to which proteins and the like are less likely to adhere. Further, the formed polymer layer (ii) may be swollen with a lubricating oil or the like to form a lubricating film, which may be an extremely low friction polymer layer.

It cannot be said that it is easy to verify the molecular weight of the second polymer forming 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 initiating group monomer having the same initiating group as the initiating group. This forms free polymer that is not included in polymer layer (ii). Then, the molecular weight of the second polymer constituting the polymer layer (ii) can be estimated by measuring the molecular weight of the formed free polymer according to a standard method. The polystyrene-equivalent number average molecular weight (Mn) of the formed free polymer measured by gel permeation chromatography (GPC) is usually 1,000 to 10,000,000, and preferably 100,000 or more. Is.

ㆍA compound having the same group as the polymerization initiation group is used as the initiation group monomer. Specifically, 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 thereof. By swelling with a solvent, the film thickness of the polymer layer (ii) can be increased. Furthermore, the swollen polymer layer (ii) is preferable because it exhibits unique properties such as strong resistance to compression and low friction. The polymer layer (ii) can be swollen by, for example, immersing the substrate having the surface-treated film formed on its surface in a solvent.

<Article>
The article of the present invention comprises a base material and the above-mentioned surface-treated film provided on the surface of the base material. The type of base material is not particularly limited, and any of natural materials, artificial materials, inorganic members, and organic members can be used. Above all, it is preferable to use a substrate that can withstand the polymerization solution. Specific examples of the base material include metal, metal oxides, metal nitrides, metal carbides, ceramics, wood, silicon compounds, thermoplastic resins, thermosetting resins, cellulose, mechanical parts such as glass, films, fibers, sheets. And so on.

　Substrate may be surface treated. The surface treatment includes inorganic treatment such as silane coupling treatment, silica coating treatment, and silica alumina treatment; cleaning such as plasma treatment, ultraviolet irradiation treatment, ozone oxidation treatment, radiation treatment, X-ray treatment, electron beam treatment, and laser treatment. Examples include activation and surface treatment functional group imparting treatment.

The film thickness of the polymer layer (i) is preferably thicker than the maximum height Rz of the surface roughness of the surface of the base material. The surface of a general substrate usually has irregularities ranging from nano units to micron units. If the polymer layer (i) is too thin, the projections may be exposed without being able to completely cover the projections and depressions. Even if the protrusions are barely covered, the surface shape of the polymer layer (i) reflects the irregularities of the substrate, and the surface of the polymer layer (ii) formed thereon is likely to be irregular. Therefore, by making the film thickness of the polymer layer (i) thicker than the maximum height Rz of the surface roughness of the surface of the base material, the entire surface of the base material can be uniformly coated and smoothed. .. Further, a smooth polymer layer (ii) can be formed on the entire surface of the polymer layer (i). The film thickness of the polymer layer (i) is, for example, a measuring method using a precision instrument such as an atomic force microscope or an ellipsometer, a measuring method by observation using an electron microscope, a measuring method using a film thickness measuring instrument, etc. Can be measured by

By providing a surface-treated film having a laminated structure including a polymer layer (i) that adheres to the base material and imparts mechanical strength, and a polymer layer (ii) that exhibits unique properties on the surface of the base material, It can be an article of the present invention to which performance as a part is imparted or performance is improved. The article of the present invention is suitable as an article used in various fields such as medical members, electronic materials, display materials, semiconductor materials, mechanical parts, sliding members, and battery materials.

Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples. In addition, "part" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.

<Synthesis of Initiating Group Polymer (First Polymer)>
(Synthesis Example 1: Initiating group polymer 1)
150 parts of propylene glycol monomethyl ether acetate (PGMAc) was put into a reaction vessel equipped with a stirring device, a stirring blade, a thermometer, a cooling tube, a nitrogen introducing device, and a dropping device. The mixture was stirred while blowing nitrogen and heated to 80° C. over 30 minutes. In a separate container, 75 parts of 2-(2-bromoisobutyryloxy)ethyl methacrylate (BBEM), 25 parts of 3-methacryloxypropylmethyldiethoxysilane (MPES), and 2,2'-azobis(2,4- 1.5 parts of dimethylvaleronitrile (V-65) was added and stirred to prepare a uniform monomer mixture solution. After adding 1/3 of the prepared monomer mixed solution into the reaction vessel, the remaining monomer mixed solution was added dropwise over 1 hour. Immediately after dropping, 0.5 part of V-65 was added. After 1 hour, 0.5 part of V-65 was further added and the mixture was polymerized at 80° C. for 7 hours to obtain a slightly yellowish low viscosity liquid containing the initiator group polymer 1. The solid content of the obtained liquid was 40.1%, and the polymerization rate was about 100%. The polystyrene equivalent number average molecular weight (Mn) of the starting group polymer 1 measured using a GPC apparatus (developing solvent: tetrahydrofuran (THF)) was 12,000, and the molecular weight distribution (Mw/Mn, dispersity PDI) was It was 3.56.

(Synthesis example 2: Initiating group polymer 2)
100 parts of PGMAc was put into a reaction container similar to the reaction container used in Synthesis Example 1, stirred while blowing nitrogen, and heated to 65° C. over 30 minutes. In a separate container, BBEM 50 parts, methyl methacrylate (MMA) 15 parts, butyl methacrylate (BMA) 15 parts, 2-ethylhexyl methacrylate (2EHMA) 10 parts, 2-[O-(1'-methylpropylideneamino)carboxyamino] 10 parts of ethyl methacrylate (blocked isocyanate monomer, trade name "Karenzu MOI-BM", manufactured by Showa Denko KK) and 1 part of V-65 were added and stirred to prepare a uniform monomer mixture. After adding 1/2 of the prepared monomer mixture solution to the reaction vessel, the remaining monomer mixture solution was added dropwise over 2 hours. After polymerization for 3 hours, 0.5 part of V-65 was further added and polymerization was carried out for 5 hours to obtain a slightly yellowish viscous solution containing the initiator group polymer 2. The solid content of the obtained liquid was 50.3%, and the polymerization rate was about 100%. The Mn of Initiating Group Polymer 2 was 18,600 and the PDI was 2.06.

(Synthesis Examples 3-5: Initiating Group Polymers 3-5)
A solution containing each of the starting group polymers 3 to 5 was obtained in the same manner as in Synthesis Example 1 except that the types and amounts (unit: parts) of monomers shown in the middle row of Table 1 were used. Physical properties and the like of the obtained starting group polymer are shown in the lower part of Table 1.

<Production of coating liquid for forming polymer layer (i)>
(Production Example 1: COT-1)
A coating liquid (COT-1) was obtained by mixing 100 parts of the liquid containing the starting group polymer 1 and 60.4 parts of PGMAc.

(Production Example 2: COT-2)
A coating liquid (COT-2) was obtained by mixing 100 parts of a liquid containing the starting group polymer 2, 2 parts of polyethyleneimine (trade name "Epomin SP-003", manufactured by Nippon Shokubai Co., Ltd.), and 107.2 parts of PGMAc. ..

(Production Examples 3-5: COT-3-5)
Coating liquids (COT-3 to 5) were obtained in the same manner as in Production Example 1 except that the components shown in the middle row of Table 2 were used. The appearance and solid content (%) of each of the obtained coating solutions are shown in the lower part of Table 2.

<Production of polymer layer (i)-applied substrate>
(Production Example 6: SUB-1)
A silicon wafer that had been cleaned and surface-activated by UV ozone was prepared as a base material. COT-1 was applied to the surface of the prepared base material, and was coated under the conditions of 2,000 rpm and 30 seconds using a spin coater. After being placed in an oven at 80° C. and dried for 5 minutes, placed in an oven at 120° C. and heated for 12 hours to be cured to form a polymer layer (i), and the polymer layer (i)-imparting substrate SUB- Got 1. The film thickness of the polymer layer (i) measured by spectroscopic ellipsometry was 1,286 nm. The obtained SUB-1 was immersed in THF and ultrasonically cleaned for 5 minutes, and then 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) was scarcely changed before the cleaning, and that the sufficiently cured polymer layer (i) was formed.

(Production Example 7: SUB-2)
A glass plate (Rz=15 nm) that had been cleaned and surface-activated by UV ozone was prepared as a substrate. COT-2 was applied to the surface of the prepared base material, and was coated under the conditions of 2,000 rpm and 30 seconds using a spin coater. After being placed in an oven at 80° C. and dried for 5 minutes, placed in an oven at 140° C. and heated for 1 hour to be cured to form a polymer layer (i), and the polymer layer (i)-imparting substrate SUB- Got 2. The film thickness of the polymer layer (i) measured by spectroscopic ellipsometry was 1,331 nm. The obtained SUB-2 was immersed in THF and ultrasonically cleaned for 5 minutes, and then 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) was scarcely changed before the cleaning, and that the sufficiently cured polymer layer (i) was formed.

(Production Examples 8 to 10: SUB-3 to 5)
Substrates SUB-3 to 5 as polymer layer (i)-applied base materials were obtained in the same manner as in Production Examples 6 and 7 except that the conditions shown in the lower part of Table 3 were used.

(Comparative Production Example 1: SUB-C-1)
A solution obtained by mixing 0.2 part of 3-(trimethoxysilylpropyl)-2-bromo-2-methylpropionate (BPM), 2 parts of concentrated aqueous ammonia, and 45 parts of ethanol was put in a petri dish made of polystyrene. As a base material, a sufficiently washed glass plate (Rz=15 nm) was prepared. The prepared substrate was placed in a petri dish, immersed in the solution, allowed to stand at room temperature for 12 hours, and then thoroughly washed with ethanol. As a result, SUB-C-1 in which a monomolecular film having a polymerization initiation point was formed on the surface of the glass plate was obtained.

(Comparative Production Example 2: SUB-C-2)
A monomolecular film having a polymerization initiation point was formed on the surface of the SUS plate in the same manner as in Comparative Production Example 1 described above, except that a SUS plate (Rz=0.8 μm) was used as the substrate instead of the glass plate. The obtained SUB-C-2 was obtained.

<Manufacture of substrate for surface treatment film>
(Example 1: SUB-6)
In an argon atmosphere, ethyl 2-bromoisobutyrate (EBiB) 0.00054 parts, 3-methoxy-N,N-dimethylpropanamide (trade name "KJCMPA-100", manufactured by KJ Chemicals) (KJCMPA) 55.5 parts, 55.1 parts of MMA and 0.41 part of tetrabutylammonium iodide (TBAI) were put into a flask and stirred to prepare a polymerization solution. The polymer layer (i)-applied substrate SUB-1 was placed in a PTFE screw cap container, the prepared polymerization solution was poured into the container and the container was capped, and the lid was wrapped with a paraffin film. This container was placed in an aluminum laminate bag and heat-sealed while removing gas. Put the container together with the aluminum laminate bag in a high-pressure device (trade name “PV-400”, manufactured by Shin Corporation) containing water as a pressurizing medium, heat to 75° C., pressurize to 400 MPa and polymerize for 4 hours did. A high-viscosity solution containing a polymer was formed in the high-pressure apparatus, and the Mn of the polymer measured by sampling a part was 2,378,000 and the PDI was 1.42. The base material taken out from the container was thoroughly washed with THF. The film thickness of the film formed on the surface of the silicon wafer was measured by spectroscopic ellipsometry and found to be 1,962 nm. Since it was thicker than the polymer layer (i), it was confirmed that the surface-treated film in which the polymer layer (ii) was laminated on the polymer layer (i) was formed. The obtained base material (surface-treated film-added base material) is referred to as SUB-6.

(Example 2: SUB-7)
EBiB 0.00098 parts, copper (II) bromide (CuBr ₂ ) 0.080 parts, copper (I) bromide (CuBr) 0.46 parts, 4,4′-dinonyl-2,2′-under an argon atmosphere. 3.2 parts of bipyridyl (dNbpy), 100.1 parts of MMA, and 103.9 parts of anisole were put into a flask and stirred to prepare a polymerization solution. SUB-2, which is the base material to which the polymer layer (i) was applied, was placed in a PTFE screw cap container, the prepared polymerization solution was poured into the container and the container was plugged, and the lid portion was wrapped with a paraffin film. This container was placed in an aluminum laminate bag and heat-sealed while removing gas. The container was placed together with the aluminum laminate bag in a high-pressure device (PV-400) containing water as a pressurizing medium, heated to 60° C. and pressurized to 400 MPa to polymerize for 4 hours. A high-viscosity solution containing a polymer was formed in the high-pressure device, and Mn of the polymer measured by sampling a part was 2,463,000 and PDI was 1.09. The base material taken out from the container was thoroughly washed with THF. When the film thickness of the film formed on the surface of the glass plate was measured by spectroscopic ellipsometry, it was 2,028 nm. Since it was thicker than the polymer layer (i), it was confirmed that the surface-treated film in which the polymer layer (ii) was laminated on the polymer layer (i) was formed. The obtained base material (surface-treated film-attached base material) is referred to as SUB-7.

(Examples 3 to 5, Comparative Examples 1 and 2, SUB-8 to 10, SUB-C-3, 4)
Substrates SUB-8 to 10 and SUB, which are surface-treated film-added substrates, were prepared in the same manner as in Example 1 or 2 above, except that the polymer layer (i)-provided substrates and monomers of the types shown in Table 4 were used. -C-3, 4 were obtained. Table 4 shows the details of the obtained surface-treated film-coated substrate.

<Evaluation>
(Evaluation (1): SUB-7)
The SUB-7 obtained in Example 2 was immersed in toluene overnight to swell the surface-treated film. Using a friction tester (trade name "Heidon friction tester type 14", manufactured by Shinto Kagaku Co., Ltd.), 1,000 reciprocating balls under the conditions of a load of 1,000 g, an amplitude width of 30 mm, and a sliding speed of 200 mm/min. An indenter reciprocating sliding test was conducted. As a result of data analysis, the friction coefficient was 0.0020, and the friction coefficient did not change even after 1,000 reciprocations. When the surface after the sliding test was observed with a laser microscope, no abrasion was observed. From the above, it was confirmed that SUB-7 has low friction and high durability.

(Evaluation (2): SUB-10)
A sliding test was conducted on the SUB-10 obtained in Example 5 in the same manner as in the above-mentioned evaluation (1) except that it was immersed in diisotridecyl adipate instead of toluene. As a result, the friction coefficient was 0.0018, and there was no change in the friction coefficient even after 1,000 reciprocations. When the surface after the sliding test was observed with a laser microscope, no abrasion was observed. From the above, it was confirmed that SUB-10 has low friction and high durability.

(Evaluation (3): SUB-C-3)
A sliding test was conducted on the SUB-C-3 obtained in Comparative Example 1 in the same manner as in the evaluation (1). As a result, the initial friction coefficient was 0.002, but after about 500 reciprocations, the friction coefficient gradually increased, and after 1,000 reciprocations, the friction coefficient was 0.05. When the surface after the sliding test was observed with a laser microscope, wear marks were observed. SUB-C-3 is one in which the polymer layer (ii) is directly formed without forming the polymer layer (i) on the glass plate (Rz=15 nm). It is considered that the polymer layer (i) was not present and the abrasion progressed due to the surface roughness of the glass plate, and the friction coefficient increased.

(Evaluation (4): SUB-C-4)
A sliding test was conducted on the SUB-C-4 obtained in Comparative Example 2 in the same manner as in the evaluation (1). As a result, the initial coefficient of friction was 0.09, the coefficient of friction gradually increased, and the coefficient of friction after about 100 reciprocations was 0.2. When the surface after the sliding test was observed with a laser microscope, clear wear marks were observed. SUB-C-4 is one in which the polymer layer (i) is directly formed without forming the polymer layer (i) on the SUS plate (Rz=0.8 μm). It is considered that since the surface of the SUS plate was rough, the lubricity due to the polymer layer (ii) was poor and the durability was significantly reduced.

The surface-treated film of the present invention can impart properties such as low friction property, anti-adhesion property, hydrophilic property, hydrophobic property, or water repellency to the surface of the base material. Further, the adhesion to the base material is high, and the durability of the base material can be enhanced. Therefore, by using the surface-treated film of the present invention, various articles such as parts used in various fields such as medical materials, electronic materials, display materials, semiconductor materials, mechanical parts, sliding members, and battery materials can be provided. can do.

Claims (9)

A surface treatment film provided on the surface of a base material,
A laminated structure including a polymer layer (i) arranged on the front surface side of the substrate and a polymer layer (ii) formed on the polymer layer (i),
The polymer layer (i) contains a first polymer containing a constitutional unit derived from a monomer represented by the following general formula (1),
The following general formula, in which the polymer layer (ii) contains structural units derived from one or more monomers selected from the group consisting of aromatic vinyl-based monomers, (meth)acrylate-based monomers, and (meth)acrylamide-based monomers. A surface-treated film containing a second polymer extended from the functional group of the monomer represented by (1) as a polymerization initiation point.

(In the 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 are each independently. Is 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, and Y is a chlorine atom. , Bromine atom, or iodine atom) The surface-treated film according to claim 1, wherein the first polymer contains 30% by mass or more of constituent units derived from the monomer represented by the general formula (1). The first polymer has a reactive functional group selected from the group consisting of an alkoxysilyl group, a (meth)acryloyloxy group, an epoxy group, an isocyanate group, a blocked isocyanate group, a hydroxyl group, a carboxy group, and a phosphoric acid group. The surface-treated film according to claim 1, further comprising a constituent unit derived from a radically polymerizable monomer. The surface-treated film according to claim 3, wherein the first polymer has a crosslinked structure. The surface-treated film according to any one of claims 1 to 4, wherein the polymer layer (ii) contains a solvent and is swollen. The method for producing a surface-treated film according to any one of claims 1 to 5,
Disposing the polymer layer (i) on the surface of the substrate,
One selected from the group consisting of an aromatic vinyl-based monomer, a (meth)acrylate-based monomer, and a (meth)acrylamide-based monomer in the presence of the polymer layer (i) under a pressure condition of normal pressure to 1,000 MPa. A method for producing a surface-treated film, comprising the step of forming the polymer layer (ii) on the polymer layer (i) by surface-initiating radical polymerization or surface-initiating living radical polymerization of the above monomers. Furthermore, in the presence of at least one salt selected from the group consisting of a quaternary ammonium halide salt, a quaternary phosphonium halide salt, and an alkali metal halide salt, surface-initiated radical polymerization or surface-initiated living radical polymerization is performed. The method for producing a surface-treated film according to claim 6, wherein the polymer layer (ii) is formed on the polymer layer (i). Base material,
An article comprising the surface-treated film according to any one of claims 1 to 5, which is provided on the surface of the base material. 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 surface of the base material.