JP2022022564A - Composition for coating formation and method for manufacturing coated body - Google Patents

Abstract

To provide: a composition for coating formation usable for forming a coating excellent in anti-fouling properties and durability; and a method for manufacturing a coated body having a coating excellent in anti-fouling properties and durability.SOLUTION: A composition for coating formation of the invention includes a polymer including a monomer component having a phosphorylcholine group, and a phosphorylcholine group-containing non-polymerized state compound that has a phosphorylcholine group and is a non-polymerized state compound. The composition satisfies a relationship of 1.5≤[X2/(X1+X2)]×100≤30, in which X1 (mass%) is a content rate of the polymer, and X2 (mass%) is a content rate of the phosphorylcholine group-containing non-polymerized state compound.SELECTED DRAWING: None

Description

The present invention relates to a coating composition and a method for producing a coating.

Various techniques for preventing the adhesion of dirt to the surface of the base material have been proposed. For example, as a technique for preventing the adhesion of dirt to the surface of a base material, a method of making the surface of the base material hydrophilic is known.

As a method for hydrophilizing the surface, a technique is known in which the surface of a base material is modified with a photocatalytic material such as titanium oxide to make the surface highly hydrophilic in response to photocatalytic excitation of the photocatalyst (see, for example, Patent Document 1). ).

However, in such surface modification with a photocatalyst, the binder for fixing the photocatalyst to the base material or the base material itself may be decomposed due to the photocatalyst function, and there is a problem in durability.

Further, as a method for hydrophilizing the surface of the base material, for example, there are etching treatment, plasma treatment and the like. Although these methods can make the surface of the substrate highly hydrophilic, the effect is temporary and the hydrophilic state cannot be maintained for a long period of time. Further, since a general hydrophilic material has an ionic group in its structure, it is rather easy to adsorb a component that becomes a stain such as a protein.

Further, although there is a method of coating a base material with a predetermined hydrophilic polymer (see Patent Document 2), it is difficult to sufficiently improve the adhesion between the base material and the hydrophilic polymer, and the base material is used. It has been difficult to make the durability of the coating body coated with the hydrophilic polymer sufficiently excellent. Further, in Patent Document 2, it is also proposed that the base material is subjected to surface treatment such as plasma treatment prior to the application of the hydrophilic polymer, but even when these surface treatments are applied, the base material is hydrophilic. It was difficult to make the adhesion to the polymer sufficiently excellent, and it was difficult to make the durability of the coating body obtained by coating the base material with the hydrophilic polymer sufficiently excellent.
As described above, in the past, it was difficult to achieve both antifouling property and durability at the same time.

International Publication No. 1996/029375 Pamphlet International Publication No. 2018/008663 Pamphlet

An object of the present invention is to provide a film-forming composition that can be used for forming a film having excellent antifouling property and durability, and to provide a coating material having a film having excellent antifouling property and durability. The purpose is to provide a manufacturing method.

Such an object is achieved by the present invention described in the following [1] to [13].
[1] A polymer containing a monomer component having a phosphorylcholine group and
It contains a phosphorylcholine group-containing non-polymerized state compound having a phosphorylcholine group and being a non-polymerized state compound.
When the content of the polymer is X1 [mass%] and the content of the phosphorylcholine group-containing non-polymerized compound is X2 [mass%], 1.5 ≦ [X2 / (X1 + X2)] × 100 ≦ 30. A film-forming composition characterized by satisfying a relationship.

[2] The composition for forming a film according to the above [1], wherein the polymer contains a chemical structure represented by the following formula (1).

（式（１）中、ｌ、ｎは、それぞれ独立に、１以上の整数である。）

(In equation (1), l and n are each independently an integer of 1 or more.)

[3] The film-forming composition according to the above [2], wherein the polymer contains a chemical structure represented by the following formula (2) in addition to the chemical structure represented by the above formula (1).

（式（２）中、ｎは１以上の整数であり、Ｒは、水素、または、置換基を有していてもよい炭化水素基である。）

(In the formula (2), n is an integer of 1 or more, and R is hydrogen or a hydrocarbon group which may have a substituent.)

[4] The content of the monomer corresponding to the chemical structure represented by the above formula (1) in the polymer is X11 [mol], and the monomer corresponding to the chemical structure represented by the above formula (2) in the polymer. The film-forming composition according to the above [3], which satisfies the relationship of 0.5 ≦ X12 / X11 ≦ 2.0 when the content of the above is X12 [mol].

[5] The composition for forming a film according to any one of the above [1] to [4], wherein the polymer has a weight average molecular weight of 8000 or more and 160000 or less.

[6] The film formation according to any one of the above [1] to [5], wherein the monomer component in a non-polymerized state and the phosphorylcholine group-containing non-polymerized state compound have the same chemical structure. Composition for.

[7] The composition for forming a film according to any one of the above [1] to [6], which further contains a polyhydric alcohol in addition to the polymer and the phosphorylcholine group-containing non-polymerized state compound. Composition for film formation.

[8] 0.01 when the content of the polymer in the film-forming composition is XP [mass%] and the content of the polyhydric alcohol in the film-forming composition is XO [mass%]. The film-forming composition according to the above [7], which satisfies the relationship of ≦ XO / XP ≦ 2.0.

[9] The film-forming composition according to the above [7] or [8], wherein the polyhydric alcohol is glycerin.

[10] The composition for forming a film is described in any one of the above [1] to [9], which further contains a volatile solvent in addition to the polymer and the phosphorylcholine group-containing non-polymerized state compound. Composition for forming a film.

[11] The film-forming composition according to the above [10], which contains ethanol as the volatile solvent.

[12] A method for producing a coated body, which comprises a composition applying step of applying the film-forming composition according to any one of the above [1] to [11] to at least a part of the surface of a base material. ..

[13] The method for producing a coating body according to the above [12], wherein the thickness of the coating film is 30 nm or more and 1000 nm or less.

INDUSTRIAL APPLICABILITY According to the present invention, a film-forming composition that can be used for forming a film having excellent antifouling property and durability is provided, and a coating material having a film having excellent antifouling property and durability is provided. A manufacturing method can be provided.

FIG. 1 is a vertical cross-sectional view schematically showing an example of the method for manufacturing a covering body of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail.
<1> Film-forming composition First, the film-forming composition according to the present invention will be described.

The film-forming composition of the present invention contains a polymer containing a monomer component having a phosphorylcholine group and a phosphorylcholine group-containing non-polymerized state compound having a phosphorylcholine group and being a non-polymerized state compound. When the content of the polymer in the film-forming composition is X1 [mass%] and the content of the phosphorylcholine group-containing non-polymerized compound in the film-forming composition is X2 [mass%]. The relationship of 1.5 ≦ [X2 / (X1 + X2)] × 100 ≦ 30 is satisfied.

By satisfying such conditions, it is possible to provide a film-forming composition that can be used for forming a film having excellent antifouling property and durability. In particular, it is possible to provide a film-forming composition that can be used for forming a film having excellent antifouling properties not only for water-based stains but also for oil-based stains such as oil mist. Further, it is possible to preferably form a film having excellent anti-fog property against water vapor and vaporized oil and capable of maintaining the anti-fog property for a long period of time. Further, even if dirt adheres to the film, it can be easily removed, and the effect of suppressing the adhesion of dirt can be suitably maintained even after that.

The phosphorylcholine group contained in the polymer and the phosphorylcholine group-containing non-polymerized state compound has an amphoteric ionic structure. Therefore, the film formed by using the film-forming composition of the present invention is excellent in hydrophilicity (wetting property) and can effectively suppress non-specific adsorption to various molecules. As a result, antifouling effect, lubrication characteristic effect, friction reduction effect, self-purification (self-cleaning) effect and the like can be exhibited. Further, the phosphorylcholine group is a polar group having the same structure as the polar group of the phospholipid (phosphatidylcholine) which is the main component of the biological membrane. Therefore, the introduction of phosphorylcholine groups can impart very good biocompatibility to the surface of biological membranes, in particular the non-adsorptive and non-activating properties of biomolecules.

The excellent effect as described above is obtained because of the presence of the phosphorylcholine group contained in the polymer and the phosphorylcholine group contained in the phosphorylcholine group-containing non-polymerized state compound, which appropriately contains water and the surface of the coating film. It is considered that this is because a film of water can be suitably formed.

On the other hand, if the above conditions are not satisfied, satisfactory results cannot be obtained.
For example, if a polymer containing a monomer component having a phosphorylcholine group is not contained, a hydrophilic film cannot be formed on the surface of the film, and extremely small water droplets (fog) are likely to occur.

Further, even if a polymer containing a monomer component having a phosphorylcholine group is contained, if the phosphorylcholine group-containing non-polymerized state compound is not contained, the hydrophilicity of the film is lowered, and the surface of the film is made of a hydrophilic film. Cannot be suitably formed, and extremely small water droplets (cloudiness) are likely to occur.

Further, even if a polymer containing a monomer component having a phosphorylcholine group and a non-polymerized state compound containing a phosphorylcholine group are contained, if the value of [X2 / (X1 + X2)] × 100 is less than the lower limit value, the coating film is formed. However, it does not exhibit sufficient hydrophilicity, and extremely small water droplets (cloudiness) are likely to occur.

Further, even if a polymer containing a monomer component having a phosphorylcholine group and a non-polymerized state compound containing a phosphorylcholine group are contained, when the value of [X2 / (X1 + X2)] × 100 exceeds the upper limit value, the polymer The anti-fog effect due to the above cannot be fully exhibited.

As described above, the content of the polymer in the film-forming composition is X1 [mass%], and the content of the phosphorylcholine group-containing non-polymerized compound in the film-forming composition is X2 [mass%]. When this is done, the relationship of 1.5 ≦ [X2 / (X1 + X2)] × 100 ≦ 30 may be satisfied, but it is preferable to satisfy the relationship of 1.6 ≦ [X2 / (X1 + X2)] × 100 ≦ 25. It is more preferable to satisfy the relationship of .7 ≦ [X2 / (X1 + X2)] × 100 ≦ 20, and it is further preferable to satisfy the relationship of 1.8 ≦ [X2 / (X1 + X2)] × 100 ≦ 10.
As a result, the above-mentioned effect is more prominently exhibited.

<1-1> Polymer As described above, the film-forming composition of the present invention contains a polymer containing a monomer component having a phosphorylcholine group.

The polymer may contain a monomer component having a phosphorylcholine group, and the monomer component may have a polymerized structure in any form, but has a chemical structure in which the monomer component having an acrylic skeleton is polymerized. It is preferable to have one.

Examples of the monomer component having an acrylic skeleton and a phosphorylcholine group include 2-methacryloyloxyethylphosphorylcholine, 2-acryloyloxyethylphosphorylcholine, N- (2-methacrylamide) ethylphosphorylcholine, 4-methacryloyloxybutylphosphorylcholine, 6 -Methacryloyloxyhexylphosphorylcholine, 10-methacryloyloxydecylphosphorylcholine, ω-methacryloyldioxyethylenephosphorylcholine, 4-styryloxybutylphosphorylcholine and the like, and the polymer contains one or more selected from these. You may be.

Above all, it is preferable that the polymer contains a chemical structure represented by the following formula (1).

（式（１）中、ｌ、ｎは、それぞれ独立に、１以上の整数である。）

(In equation (1), l and n are each independently an integer of 1 or more.)

Thereby, the solubility in the solvent (polymerization solvent) used for the polymerization reaction to obtain the polymer can be made more suitable.

In the above formula (1), l may be an integer of 1 or more, but is preferably an integer of 1 or more and 10 or less, more preferably an integer of 1 or more and 5 or less, and 1 or more and 3 or less. It is more preferably an integer.

The monomer component having a phosphorylcholine group constituting the polymer may be a compound other than the compound corresponding to the above formula (1).

The polymer may contain a monomer component having no phosphorylcholine group in addition to the monomer component having a phosphorylcholine group.

For example, the polymer may contain a chemical structure represented by the following formula (2) in addition to the chemical structure represented by the above formula (1).

（式（２）中、ｎは１以上の整数であり、Ｒは、水素、または、置換基を有していてもよい炭化水素基である。）

(In the formula (2), n is an integer of 1 or more, and R is hydrogen or a hydrocarbon group which may have a substituent.)

Thereby, the water solubility of the coating film formed by using the coating film forming composition can be lowered, and the adhesion between the base material and the coating film can be further improved.

Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group and the like. Examples thereof include aromatic hydrocarbon groups such as an aliphatic hydrocarbon group, a phenyl group, a trill group, a xylyl group, a mesityl group, a benzyl group, a naphthyl group and an anthrasenyl group, and a benzyl group is preferable.

This makes it possible to more preferably reduce the water solubility of the polymer while maintaining the hydrophilicity of the film.

When the hydrocarbon group has a substituent, the substituent includes, for example, a halogeno group such as a fluoro group, a chloro group, a bromo group and an iodine group, a hydroxyl group, a carboxyl group, an aldehyde group and a ketone group. , Ether group, ester group, nitro group, amino group, sulfo group and the like.

Further, the polymer may contain, for example, a compound represented by the following formula (b1) and the following formula (b2) as a monomer component having no phosphorylcholine group.

（上記式（ｂ１）および上記式（ｂ２）中、ｎは１以上の整数を表す。）

(In the above equation (b1) and the above equation (b2), n represents an integer of 1 or more.)

In the above equation (b1) and the above equation (b2), n may be an integer of 1 or more, but is preferably an integer of 1 or more and 12 or less, and more preferably an integer of 1 or more and 6 or less. It is more preferably 1.

When the polymer contains the chemical structure represented by the above formula (1) and the chemical structure represented by the above formula (2), it corresponds to the chemical structure represented by the above formula (1) in the polymer. When the content of the monomer to be used is X11 [mol] and the content of the monomer corresponding to the chemical structure represented by the above formula (2) in the polymer is X12 [mol], 0.5 ≦ X12 / X11 ≦ It is preferable to satisfy the relationship of 2.0, more preferably satisfy the relationship of 0.7 ≦ X12 / X11 ≦ 1.5, and further preferably satisfy the relationship of 0.8 ≦ X12 / X11 ≦ 1.2. ..

This makes it possible to more preferably reduce the water solubility of the polymer while maintaining the hydrophilicity of the film.

When the polymer is a copolymer containing a plurality of kinds of monomer components, the polymer may be, for example, an alternating copolymer, a random copolymer, a block copolymer, or a graft copolymer. good.

The content of the monomer component having a phosphorylcholine group with respect to all the monomer components constituting the polymer is preferably 30 mol% or more and 67 mol% or less, more preferably 35 mol% or more and 59 mol% or less, and 40 mol% or more and 56 mol. It is more preferably% or less.

This makes it possible to more preferably reduce the water solubility of the polymer while maintaining the hydrophilicity of the film.

The polymer may contain a plurality of types of monomer components as the monomer component having a phosphorylcholine group.
Further, the polymer may contain a plurality of types of monomer components as a monomer component having no phosphorylcholine group.

Further, the polymer may contain a plurality of different types of molecules. For example, the polymer may contain molecules having different molecular weights from each other. Further, the polymer may contain a plurality of types of molecules having different types of constituent monomers. Further, when the polymer contains a molecule formed by polymerizing a plurality of types of constituent monomers, the polymer may contain a plurality of types of molecules having different content ratios of the plurality of types of constituent monomers.

The weight average molecular weight of the polymer is not particularly limited, but is preferably 8,000 or more and 160000 or less, more preferably 30,000 or more and 150,000 or less, and further preferably 50,000 or more and 120,000 or less.

As a result, it is possible to more effectively prevent the formation of undesired irregularities in the coating film formed by using the coating film forming composition, and the flatness of the surface of the coating film is further improved. be able to.

The weight average molecular weight of the polymer can be measured by gel permeation chromatography (GPC) method.

The content of the polymer in the film-forming composition of the present invention is not particularly limited, but is preferably 0.02% by mass or more and 10.0% by mass or less, and 0.05% by mass or more and 5.0. It is more preferably 0.1% by mass or less, and further preferably 0.1% by mass or more and 2.0% by mass or less.

As a result, the viscosity of the film-forming composition can be set in a more suitable range, and it is more effective that the film formed by using the film-forming composition has an undesired thickness variation or composition variation. It is possible to form a film more efficiently while preventing it.

In the film-forming composition of the present invention, the polymer may be contained in a dissolved state, a dispersed state, or a molten state.

The polymer constituting the film-forming composition may be produced by any method, but is suitably produced by, for example, a method of radical polymerization using a polymerization initiator as described below. Can be done.

As a method for radical polymerization, for example, a method using a radical polymerization initiator can be adopted.

The polymer can be synthesized by radical polymerization using a radical polymerization initiator under specific conditions. Specifically, the polymer can be suitably synthesized by radical polymerization in an organic solvent.

The radical polymerization initiator used for the polymerization is not particularly limited, and is, for example, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis (2,4-dimethylvaleronitrile), 2, 2'-azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) Examples thereof include azo-based initiators such as benzoyl peroxide, t-butyl hydroperoxide, and peroxide-based initiators such as potassium persulfate.

The amount of the radical polymerization initiator used can be adjusted according to the polymerizable property of the monomer and the required molecular weight of the polymer, but is 0.001 with respect to 100 parts by mass of all the monomers used for the polymerization. It is preferably 1 part by mass or more and 3 parts by mass or less, and more preferably 0.01 part by mass or more and 1 part by mass or less.

Examples of the solvent used for radical polymerization include ester solvents such as ethyl acetate; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol and 1-butanol; ketone solvents such as acetone; and dioxane. Ether solvent; amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide; aromatic solvent such as benzene and toluene; nitrile solvent such as acetonitrile; halogenation of methylene chloride, chloroform, dichloroethane and the like Examples thereof include a solvent, and one or a combination of two or more selected from these can be used. Of these, alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol and 1-butanol are preferable.

The reaction temperature at the time of the polymerization reaction can be appropriately set according to the molecular weight of the polymer to be synthesized, the type of the polymerization initiator, and the like, but is preferably 30 ° C. or higher and 100 ° C. or lower.

After polymerization by the above method or the like, the obtained solution of the polymer may be purified as necessary.

The purification method is not particularly limited, but for example, a reprecipitation method can be preferably adopted.
When the reprecipitation method is adopted, examples of the poor solvent include ether solvents such as diethyl ether, dioxane and tetrahydrofuran; ester solvents such as 3-methoxybutyl acetate, ethyl acetate, isopropyl acetate and butyl acetate; methyl ethyl ketone and acetone. , Methylisobutylketone, cyclohexanone, isophorone and other ketone solvents; halogenated hydrocarbon solvents such as chloromethane, dichloromethane and chloroform, etc., and one or a combination of two or more selected from these can be used. can.

Further, the purification of the polymer can be performed by, for example, ultrafiltration.

<1-2> Phosphorylcholine group-containing non-polymerized state compound As described above, the film-forming composition of the present invention contains a phosphorylcholine group and contains a phosphorylcholine group-containing non-polymerized state compound which is a non-polymerized state compound. is doing.

In other words, the film-forming composition of the present invention contains a phosphorylcholine group-containing compound (phosphorylcholine group-containing non-polymerized state compound) that is not a polymer having a phosphorylcholine group, as well as a polymer containing a monomer component having a phosphorylcholine group. There is.

Examples of the phosphorylcholine group-containing non-polymerized state compound include a compound having no functional group capable of contributing to a polymerization reaction and a compound having a functional group capable of contributing to a polymerization reaction but not in a polymerized state. Can be used.

Examples of the phosphorylcholine group-containing non-polymerized state compound having no functional group capable of contributing to the polymerization reaction include glycerophosphocholine (α-GPC), lecithin, polyenphosphatidylcholine represented by the following formula (3), and the like. ..

（式（３）中、ｉ、ｊ、ｋ、ｌ、ｍ、ｎは、それぞれ独立に、１以上１０以下の整数である。）

(In equation (3), i, j, k, l, m, and n are each independently an integer of 1 or more and 10 or less.)

As the compound having a functional group capable of contributing to the polymerization reaction but not in a polymerized state, for example, a compound exemplified as a monomer component having a phosphorylcholine group constituting the polymer can be used.

The monomer component having a phosphorylcholine group in a non-polymerized state (that is, a compound in which the monomer component having a phosphorylcholine group constituting the polymer is not polymerized) and the phosphorylcholine group-containing non-polymerized state compound are referred to as each other. It is preferably of the same chemical structure.

Thereby, an unfavorable reaction can be effectively suppressed. In addition, the dispersibility of the phosphorylcholine group-containing non-polymerized state compound in the coating film can be made higher, and the water absorption effect of the coating film can be enhanced more effectively.

Further, the composition for forming a film may contain a plurality of different types of molecules as the phosphorylcholine group-containing non-polymerized state compound.

The molecular weight of the phosphorylcholine group-containing non-polymerized state compound is not particularly limited, but is preferably 150 or more and 2000 or less, more preferably 180 or more and 1500 or less, and further preferably 200 or more and 800 or less.

Thereby, the dispersibility in the film of the phosphorylcholine group-containing non-polymerized state compound can be made higher, and the water absorption effect of the film can be more effectively enhanced.

When the film-forming composition contains a plurality of types of phosphorylcholine group-containing non-polymerized state compounds, an average molecular weight can be adopted as the molecular weight of the phosphorylcholine group-containing non-polymerized state compound.

The phosphorylcholine group-containing non-polymerized state compound may be contained in the film-forming composition by any method, but is usually synthesized by the method described above during the production of the film-forming composition. It is to be mixed with the above-mentioned polymer.

The content of the phosphorylcholine group-containing non-polymerized state compound in the film-forming composition of the present invention is not particularly limited, but is preferably 0.0003% by mass or more and 3.3% by mass or less, preferably 0.001% by mass. It is more preferably 1.3% by mass or less, and further preferably 0.003% by mass or more and 0.4% by mass or less.

This makes it possible to further increase the hydrophilicity of the coating film.

<1-3> Polyhydric Alcohol The composition for forming a film of the present invention may further contain a polyhydric alcohol in addition to the polymer and the phosphorylcholine group-containing non-polymerized state compound.

As a result, it is possible to more effectively prevent an undesired variation in thickness from occurring in the coating film formed by using the coating film forming composition. Further, when used in combination with monohydric alcohols as a volatile solvent described later, the dispersibility of the polyhydric alcohol can be enhanced, and the above-mentioned effects can be more remarkably exhibited. Such an effect is more remarkable when ethanol is used as the volatile liquid.

The polyhydric alcohol is liquid at room temperature (23 ° C.) and functions as a solvent for dissolving a part of the polymer and the phosphorylcholine group-containing non-polymerized state compound in the film-forming composition. You may.

Further, the polyhydric alcohol may be one in which at least a part of the polyhydric alcohol is removed after being applied to the base material in the method for producing a covering body described in detail later, but most of the polyhydric alcohol is also applied after being applied to the base material. It is preferable that (for example, 80% by mass or more) remains on the substrate.

The polyhydric alcohol may be a compound having a plurality of hydroxyl groups in the molecule, and examples thereof include ethylene glycol, propylene glycol, butylene glycol, glycerin, and polyethylene glycol, but glycerin is preferable.
As a result, the above-mentioned effect is more prominently exhibited.

Moreover, the composition for forming a film may contain a plurality of different types of molecules as a polyhydric alcohol.

The molecular weight of the polyhydric alcohol is not particularly limited, but is preferably 62 or more and 30,000 or less, more preferably 76 or more and 20,000 or less, and further preferably 92 or more and 4000 or less.

Thereby, for example, when used in combination with monohydric alcohols as a volatile solvent described later, the solubility of the polyhydric alcohol in the volatile solvent can be enhanced, and the affinity with the polymer can be further improved. It is possible, and the above-mentioned effect is more prominently exhibited.

When the film-forming composition contains a plurality of types of polyhydric alcohols, an average molecular weight can be adopted as the molecular weight of the polyhydric alcohols.

The content of the polyhydric alcohol in the film-forming composition of the present invention is not particularly limited, but is preferably 0.001% by mass or more and 15.0% by mass or less, and 0.010% by mass or more and 6.0. It is more preferably 0% by mass or less, and further preferably 0.10% by mass or more and 2.2% by mass or less.

Thereby, the uniformity of the film can be further improved without impairing the characteristics of the film-forming composition and the film formed by the film-forming composition.

When the content of the polymer in the film-forming composition is XP [mass%] and the content of the polyhydric alcohol in the film-forming composition is XO [mass%], 0.01 ≦ XO / XP. It is preferable to satisfy the relationship of ≤2.0, more preferably the relationship of 0.10≤XO / XP≤1.5, and further satisfy the relationship of 0.80≤XO / XP≤1.2. preferable.

Thereby, the uniformity of the film can be further improved without impairing the characteristics of the film-forming composition and the film formed by the film-forming composition.

<1-4> Volatile solvent The film-forming composition of the present invention may contain a volatile solvent.
As a result, the handling of the film-forming composition becomes easier, and the flatness of the film formed by using the film-forming composition can be made higher, and the thickness of the film is unwilling. Variation can be prevented more effectively.

Most of the volatile solvent is usually removed after being applied to the substrate in the method for producing a coating body described in detail later. Specifically, it is preferable that 80% by mass or more of the volatile solvent contained in the film-forming composition is removed from the substrate after being applied to the substrate. It is more preferable that the mass% or more is removed from the substrate, and it is further preferable that 98% by mass or more is removed from the substrate.

The boiling point of the volatile solvent under 1 atm is preferably 50 ° C. or higher and 160 ° C. or lower, more preferably 55 ° C. or higher and 120 ° C. or lower, and further preferably 60 ° C. or higher and 100 ° C. or lower.

Examples of the volatile solvent include monohydric alcohols such as water, methanol, ethanol and isopropyl alcohol, and ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone and isophorone, which are selected from these. One type or a combination of two or more types can be used. However, the volatile solvent does not include the above-mentioned polyhydric alcohol.

Above all, the film-forming composition of the present invention preferably contains ethanol as a volatile solvent.

Thereby, the solubility of the polymer and the phosphorylcholine group-containing non-polymerized state compound in a volatile solvent (particularly, the solubility of the polymer having a preferable composition as described above and the phosphorylcholine group-containing non-polymerized state compound) is further increased. It can be made excellent, and a film can be formed more efficiently while more effectively preventing unintentional thickness variation and composition variation in the film formed by using the film forming composition. can do.

When the film-forming composition of the present invention contains ethanol as a volatile solvent, the proportion of ethanol in the entire volatile solvent is preferably 50% by mass or more, and 60% by mass or more 99. It is more preferably 8.8% by mass or less, and further preferably 65% by mass or more and 99% by mass or less.
As a result, the above-mentioned effect is more prominently exhibited.

The content of the volatile solvent in the film-forming composition of the present invention is not particularly limited, but is preferably 70.0% by mass or more and 99.9% by mass or less, and 90.0% by mass or more and 99. It is more preferably 8% by mass or less, and further preferably 95.0% by mass or more and 99.6% by mass or less.

As a result, the viscosity of the film-forming composition can be set in a more suitable range, and it is more effective that the film formed by using the film-forming composition has an undesired thickness variation or composition variation. It is possible to form a film more efficiently while preventing it. In addition, the volatile solvent can be efficiently removed from the film-forming composition applied to the substrate (work), and the productivity of the coating body having the substrate and the coating can be further improved. be able to.

<1-6> Other components The film-forming composition of the present invention may contain components other than the above-mentioned components (hereinafter, also referred to as “other components”).

Other components include, for example, colorants such as pigments and dyes, various fillers, dispersants, ultraviolet absorbers, antioxidants, pH adjusters, preservatives / fungicides, rust inhibitors, and polymers other than the above-mentioned polymers. Examples thereof include polymers, and one or a combination of two or more selected from these can be used.

The pH adjuster is not particularly limited, but an inorganic salt is preferable. Examples of the inorganic salt include phosphates such as disodium hydrogen phosphate and sodium dihydrogen phosphate; and carbonates such as sodium hydrogen carbonate and sodium carbonate, and one or two selected from these. The above may be used in combination. Of these, phosphate is preferable, and disodium hydrogen phosphate dihydrate or disodium hydrogen phosphate dodecahydrate is more preferable.

Further, in order to adjust the pH to a desired value, for example, bases such as sodium hydroxide and potassium hydroxide; acids such as sulfuric acid, hydrochloric acid and nitric acid may be used.

However, the content of other components in the film-forming composition of the present invention (when a plurality of other components are contained, the sum of these contents) is preferably 10% by mass or less. It is more preferably 5% by mass or less, and further preferably 3% by mass or less.

The pH of the film-forming composition of the present invention (pH at 23 ° C.) is not particularly limited, but is preferably 3 or more and 11 or less, and more preferably 3 or more and 7 or less.

The film-forming composition of the present invention may be, for example, directly applied to a substrate (work) on which a film is to be formed, diluted and used, or other components. It may be used in combination with. Further, a plurality of kinds of coating composition for forming a film of the present invention having different conditions may be mixed and used.

<2> Method for manufacturing a covering body Next, a method for manufacturing a covering body of the present invention will be described.
FIG. 1 is a vertical cross-sectional view schematically showing an example of the method for manufacturing a covering body of the present invention.

As shown in FIG. 1, in the method for producing the covering body 100 of the present embodiment, the base material preparing step (1a) for preparing the base material 1 and the film forming composition 2'of the present invention are applied to the surface of the base material 1. It has a composition applying step (1b) to be applied to at least a part of the above, and a solvent removing step (1c) to remove a volatile solvent from the film-forming composition 2'applied to the base material 1.

By satisfying such conditions, it is possible to provide a method for producing a coated body having a coating film having excellent antifouling property and durability. In particular, it is possible to provide a method for producing a coated body having a coating film having excellent antifouling properties not only for water-based stains but also for oil-based stains such as oil mist. Further, it is possible to suitably produce a coating body having a coating film which is excellent in anti-fog property against water vapor and vaporized oil and can maintain the anti-fog property for a long period of time. Further, it is possible to provide a method for producing a coating body, which can easily remove dirt even if it adheres to the coating film, and can suitably maintain the effect of suppressing the adhesion of dirt even after that.

<2-1> Base material preparation step In the base material preparation step, a base material 1 as an object to be treated, which will be subjected to the treatment described in detail later, is prepared (see FIG. 1 (1a)).
The base material 1 usually constitutes a main portion of the covering body 100.

The base material 1 may be made of any material, and the constituent material of the base material 1 includes, for example, various single metals such as Ti, Au, Cu, and Fe, and at least one of them. Metallic materials such as alloys (various stainless steels, duralumin, etc.), carbon materials such as silicon, diamond, graphite, diamond-like carbon, Al ₂ O ₃ , TiO ₂ , ZrO ₂ , silicon oxide (SiO ₂ ), Ta ₂ O _5. Metal compound materials such as mica, hydroxyapatite, ZnO, ITO, IGZO, various glass materials, acrylic resins such as poly (meth) methyl acrylate, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polystyrene, Various thermoplastic elastomers such as polycarbonate polyvinylpyrrolidone and polyvinyl chloride-based thermoplastic elastomers, various plastic materials such as copolymers thereof and polymer blends, various rubber materials such as various silicone rubbers such as polydimethylsiloxane (PDMS), etc. , And one or a combination of two or more selected from these can be used. Further, the base material 1 may be one in which the constituent materials have different portions, for example, a laminated body having layers composed of different materials. Further, the base material 1 may have a portion made of a functionally graded material whose composition changes in an inclined manner.

In particular, when at least the portion of the base material 1 on which the coating film 2 should be formed is formed of a glass material, a plastic material, or a metal material, the adhesion between the base material 1 and the coating film 2 is further improved. It is possible to make the durability of the covering body 100 more excellent.

Usually, the shape of the base material 1 is determined by the covering body 100 to be manufactured, and is usually substantially the same shape as the covering body 100 to be manufactured. Examples thereof include plate-like, tubular, porous, granular, fibrous and the like. Further, the base material 1 may be provided with, for example, a hole, a groove, a protrusion, or the like.

The formation of the coating film 2 described in detail later is performed on at least a part of the surface of the base material 1.

For example, when the base material 1 has a hollow portion, the formation of the coating film 2 described in detail later may be performed on at least the inner wall surface of the hollow portion of the base material 1.

The base material 1 may be subjected to a pretreatment such as a cleaning treatment before being subjected to, for example, a step described later. More specifically, for example, washing with water, pickling, alkaline washing, washing with a detergent such as a neutral detergent, washing with an organic solvent, or the like may be performed.

<2-2> Composition-imparting step In the composition-imparting step, the film-forming composition 2'of the present invention is applied to at least a part of the surface of the base material 1 (see FIG. 1 (1b)).

The coating composition 2'is applied to the substrate 1 by, for example, various coating methods such as a roll coating method, a bar coating method, a spray method, various printing methods such as a screen printing method and an inkjet method, and a dipping method. It can be done by various methods of.

A part of the base material 1 may be masked for the purpose of selectively applying the film-forming composition 2'to a predetermined portion of the base material 1.

When the film-forming composition 2'is applied to the substrate 1 by an immersion method, the immersion time of the substrate 1 in the film-forming composition 2'is not particularly limited, but is 1 second or more and 60 minutes or less. It is preferably 10 seconds or more and 30 minutes or less, and more preferably 30 seconds or more and 15 minutes or less.

<2-3> Solvent removal step In the solvent removal step, the volatile solvent is removed from the film-forming composition 2'applied to the substrate 1 to form the film 2 (see FIG. 1 (1c)).

By performing the solvent removing step, the film 2 in a flattened state can be suitably formed, and it is preferable that the volatile solvent unwillingly remains in the finally obtained coating body 100. Can be prevented.

The solvent removing step can be performed, for example, by natural drying.
As a result, it is possible to effectively prevent unintentional modification of the constituent components of the film-forming composition and unintentional roughening of the surface of the film, and the base material 1 of the film 2 to be formed can be effectively prevented. It is possible to improve the adhesion to the coating material and the reliability of the covering body 100.

When the solvent removing step is carried out by natural drying, the time is preferably 0.5 minutes or more and 120 minutes or less, more preferably 1 minute or more and 60 minutes or less, and 2 minutes or more and 10 minutes or less. Is even more preferable.

As a result, the productivity of the covering body 100 can be made more excellent, and the reliability of the covering body 100 can be made more excellent.

Further, the solvent removing step can be performed by heating.
When the solvent removing step is performed by heating, the treatment temperature (heating temperature) in the solvent removing step is preferably 60 ° C. or higher and 150 ° C. or lower, more preferably 70 ° C. or higher and 140 ° C. or lower, and more preferably 80 ° C. or higher. It is more preferably 130 ° C. or lower.

As a result, the productivity of the covering body 100 can be made more excellent, and the reliability and productivity of the covering body 100 can be made more excellent.

When the solvent removing step is performed by heating, the treatment time (heating time) in the solvent removing step is preferably 30 minutes or more and 600 minutes or less, more preferably 45 minutes or more and 480 minutes or less, and 60 minutes or more and 300 minutes or more. It is more preferably less than a minute.

As a result, the productivity of the covering body 100 can be made more excellent, and the reliability and productivity of the covering body 100 can be made more excellent.

The thickness of the film 2 is not particularly limited, but is preferably 30 nm or more and 1000 nm or less, more preferably 40 nm or more and 700 nm or less, and further preferably 50 nm or more and 500 nm or less.

As a result, the coating film 2 can be formed more precisely on the surface of the base material 1 in a shorter time and more efficiently while suppressing unevenness more efficiently. As a result, the antifouling property, antifog property, and durability of the coating film 2 can be made more excellent.

The solvent removing step may be performed simultaneously with the composition applying step. Further, when the film-forming composition does not contain a volatile solvent, the solvent removing step can be omitted.

<3> Covering body The covering body 100 according to the present invention obtained as described above includes a base material 1 and a coating film 2. The coating film 2 is excellent in antifouling property and durability. In particular, it has excellent antifouling properties not only for water-based stains but also for oil-based stains such as oil mist. Further, the coating film 2 is excellent in anti-fog property against water vapor and vaporized oil, and the anti-fog property can be maintained for a long period of time. Further, even if dirt adheres to the film 2, it can be easily removed, and the effect of suppressing the adhesion of dirt can be suitably maintained even after that.

The use of the covering 100 is not particularly limited, but for example, various medical devices such as dental materials, dental instruments, and endoscopes, contact lenses, artificial organs, biochips, biosensors, oxygen-rich membranes, and cell preservation instruments. Medical equipment such as automobile front glass, ship bottom paint and the like. Examples of the dental material include a denture with a floor, a denture, an implant denture, a dental prosthesis such as a crown, an orthodontic material, and a denture lining material.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto.

For example, the method for producing a covering may have steps other than those described above.
More specifically, for example, prior to the composition applying step, the substrate is subjected to ultraviolet irradiation treatment, ozone treatment, plasma treatment, corona discharge treatment, frame treatment, hydrogen peroxide solution / Fenton reaction solution treatment, cup. It may have a step of performing various treatments such as treatments using a ring agent.

Further, when the composition applying step is performed with the mask arranged on the substrate, the mask removing step may be provided to remove the mask.
Further, a cleaning step may be provided after the composition applying step and the solvent removing step.

Hereinafter, the present invention will be described in detail based on Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the treatment and the measurement which did not show the temperature condition were performed at 23 degreeC.

<4> Polymer synthesis (Synthesis Example 1)
2-methacryloyloxyethyl phosphorylcholine (MPC) as a monomer (C ₁₁ H ₂₂ NO ₆ P Mw = 295.27 CAS 67881-98-5) and benzyl methacrylate (BzMA), azo as a random polymerization initiator (oxidizer) Azobisisobutyronitrile (AIBN) is blended in a predetermined ratio, dissolved in 360 mL of ethanol as a reaction solvent so that the monomer concentration becomes 0.5 mol / L, and then the solution is transferred to a eggplant flask and subjected to argon bubbling. The oxygen in the system was degassed (20 minutes).

Next, the eggplant flask was plugged and heated (60 ° C.) in an oil bath to carry out a polymerization reaction (24 hours).

Then, the reaction vessel was opened, reprecipitation was carried out with THF, unreacted substances were removed, recovered and dried under reduced pressure to obtain a purified polymer.

The weight average molecular weight (Mw) of the obtained polymer was 90000. The weight average molecular weight (Mw) of the polymer was determined by gel permeation chromatography (GPC) method.

(Synthesis Examples 2 to 5)
A polymer was obtained in the same manner as in Synthesis Example 1 except that the types and amounts of raw materials used in the synthesis reaction were adjusted so that the conditions of the polymer to be synthesized were as shown in Table 1.

Table 1 summarizes the conditions of the polymers obtained in each of the synthetic examples. In Table 1, 2-methacryloyloxyethyl phosphorylcholine is "MPC", benzylmethacrylate is "BzMA", n-butylmethacrylate is "BMA", and Phosmer M (acid phoxyethyl _methyllate ) (C 6H ₁₁ O ₆ P Mw). = 210.12 CAS 24599-21-1) is shown as "PhosmerM".

<5> Production of film-forming composition (Example 1)
The polymer obtained in Synthesis Example 1, 2-methacryloyloxyethyl phosphorylcholine as a phosphorylcholine group-containing non-polymerized state compound, and a 99.5% by mass ethanol aqueous solution as a volatile solvent are mixed at a predetermined ratio. As a result, a film-forming composition was obtained.

(Examples 2 to 10)
A film-forming composition was produced in the same manner as in Example 1 except that the types and amounts of each component used as raw materials were shown in Table 2.

(Comparative Examples 1 to 3)
A film-forming composition was produced in the same manner as in Example 1 except that the types and amounts of each component used as raw materials were shown in Table 2.

The compositions of the film-forming compositions of each of the Examples and Comparative Examples are summarized in Table 2. In Table 2, 2-methacryloyloxyethyl phosphorylcholine is shown as "MPC".

<6> Production of Cover A cover was produced as follows using the film-forming compositions of the above-mentioned Examples and Comparative Examples.

First, a glass plate-shaped base material (diameter 25 mm) was prepared.
Next, this base material was washed with ethanol, and a predetermined amount of the film-forming composition was applied to one surface of the base material by a flow-coating method.

Then, the volatile solvent was removed by natural drying to obtain a coating body having a coating film on one surface of the substrate.

As the covering body, those having a coating thickness of 51 nm, 76 nm, 102 nm, 509 nm, 1000 nm, and 1360 nm were manufactured for each of the Examples and Comparative Examples, respectively. The thickness of the coating film was measured using OPTM-A1 manufactured by Otsuka Electronics Co., Ltd.

<7> Evaluation The following evaluations were performed on the coverings according to the above-mentioned Examples and Comparative Examples manufactured as described above. In addition, as a control (reference example), the above-mentioned base material made of glass on which a film was not formed was also evaluated.

<7-1> Antifouling property (difficulty of oil mist adhesion)
First, the pork and the covering were placed in a closed space. By heating the pork to about 600 ° C. using a nichrome wire in this closed space, oil mist is generated, and the surface on which the coating film of the coating is provided is exposed to this oil mist, and the following criteria are used. Evaluated according to. Reference examples without a coating were also evaluated in the same manner as described above.

A: No dirt is found.
B: Dirt is found on less than 10% of the surface.
C: Dirt is found on less than 30% of the surface.
D: Dirt is found on less than 50% of the surface.
E: Dirt is found on the whole.

<7-2> Anti-fog property The surface on which the coating film of each of the above-mentioned Examples and Comparative Examples is provided is left in an environment of temperature: 37 ° C. and humidity: 90% RH for 30 minutes to be in a cloudy state. Was visually observed and evaluated according to the following criteria. Reference examples without a coating were also evaluated in the same manner as described above.

A: No cloudiness is observed.
B: Cloudiness is observed on less than 10% of the surface.
C: Cloudiness is observed on less than 30% of the surface.
D: Cloudiness is observed on less than 50% of the surface.
E: Cloudy is observed overall.

<7-3> Duration of anti-fog property The surface of the coating material according to each of the Examples and Comparative Examples was left to stand for a certain period of time in an environment of temperature: 37 ° C. and humidity: 90% RH. , The cloudy state was visually observed and evaluated according to the following criteria. Reference examples without a coating were also evaluated in the same manner as described above.

A: No cloudiness is observed for 2 hours or more.
B: No cloudiness is observed for 1.5 hours or more and less than 2 hours.
C: No cloudiness is observed for 1 hour or more and less than 1.5 hours.
D: No cloudiness is observed for 30 minutes or more and less than 1 hour.
E: Cloudy is observed in less than 30 minutes.

<7-4> Durability The coverings according to each of the Examples and Comparative Examples were immersed in pure water for 1 hour at room temperature and evaluated according to the following criteria. Reference examples without a coating were also evaluated in the same manner as described above.

A: The wettability of the surface is maintained.
B: The wettability of the surface is slightly reduced.
C: The wettability of the surface is partially reduced.
D: Almost no surface wettability is observed.
E: No surface wettability is observed.

These results are summarized in Table 3.

As is clear from Table 3, excellent results were obtained in each of the above-mentioned examples. On the other hand, satisfactory results were not obtained in each of the comparative examples and the reference examples.

Further, a covering body was produced in the same manner as in each of the above Examples and Comparative Examples except that the base material was changed from the one made of glass to the one made of cycloolefin polymer (COP) and SUS304. When the same evaluation as above was performed, the same tendency as described above was confirmed.

100 ... Cover 1 ... Base material 2 ... Film 2'... Composition for film formation

Claims (13)

A polymer containing a monomer component having a phosphorylcholine group and
It contains a phosphorylcholine group-containing non-polymerized state compound having a phosphorylcholine group and being a non-polymerized state compound.
When the content of the polymer is X1 [mass%] and the content of the phosphorylcholine group-containing non-polymerized compound is X2 [mass%], 1.5 ≦ [X2 / (X1 + X2)] × 100 ≦ 30. A film-forming composition characterized by satisfying a relationship. The film-forming composition according to claim 1, wherein the polymer contains a chemical structure represented by the following formula (1).

(In equation (1), l and n are each independently an integer of 1 or more.) The film-forming composition according to claim 2, wherein the polymer contains a chemical structure represented by the following formula (2) in addition to the chemical structure represented by the above formula (1).

(In the formula (2), n is an integer of 1 or more, and R is hydrogen or a hydrocarbon group which may have a substituent.) The content of the monomer corresponding to the chemical structure represented by the above formula (1) in the polymer is X11 [mol], and the content of the monomer corresponding to the chemical structure represented by the above formula (2) in the polymer. The film-forming composition according to claim 3, wherein when is X12 [mol], the relationship of 0.5 ≦ X12 / X11 ≦ 2.0 is satisfied. The film-forming composition according to any one of claims 1 to 4, wherein the polymer has a weight average molecular weight of 8,000 or more and 160000 or less. The film-forming composition according to any one of claims 1 to 5, wherein the monomer component in a non-polymerized state and the phosphorylcholine group-containing non-polymerized state compound have the same chemical structure. The film-forming composition according to any one of claims 1 to 6, further comprising a polyhydric alcohol in addition to the polymer and the phosphorylcholine group-containing non-polymerized state compound. thing. When the content of the polymer in the film-forming composition is XP [mass%] and the content of the polyhydric alcohol in the film-forming composition is XO [mass%], 0.01 ≦ XO /. The film-forming composition according to claim 7, which satisfies the relationship of XP ≦ 2.0. The film-forming composition according to claim 7 or 8, wherein the polyhydric alcohol is glycerin. The film-forming composition according to any one of claims 1 to 9, further comprising a volatile solvent in addition to the polymer and the phosphorylcholine group-containing non-polymerized state compound. Composition. The film-forming composition according to claim 10, which contains ethanol as the volatile solvent. A method for producing a coated body, which comprises a composition applying step of applying the film-forming composition according to any one of claims 1 to 11 to at least a part of the surface of a base material. The method for producing a coating body according to claim 12, wherein the thickness of the coating film is 30 nm or more and 1000 nm or less.

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