Coating composition and method for producing coated body

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

[Technical Field]

[0001] The present invention relates to a coating composition and a method for producing a coated body. [Background technology]

[0002] Various techniques have been proposed for preventing the adhesion of dirt to the surface of a substrate. For example, a method of making the surface of a substrate hydrophilic is known as a technique for preventing the adhesion of dirt to the surface of a substrate.

[0003] Known methods for making surfaces hydrophilic include modifying the surface of a substrate with a photocatalytic material such as titanium oxide, and making the surface highly hydrophilic in response to photoexcitation of the photocatalyst (see, for example, Patent Document 1).

[0004] However, in such surface modification using a photocatalyst, the photocatalytic function can sometimes cause the binder that fixes the photocatalyst to the substrate or the substrate itself to decompose, resulting in problems with durability.

[0005] In addition, methods for hydrophilizing the surface of a substrate include, for example, etching treatment and plasma treatment. Although these methods can highly hydrophilize the surface of a substrate, the effect is temporary and the hydrophilic state cannot be maintained for a long period of time. Furthermore, since general hydrophilic materials have ionic groups in their structure, they tend to adsorb dirt components such as proteins.

[0006] There is also a method of coating a substrate with a predetermined hydrophilic polymer (see Patent Document 2), but it is difficult to ensure sufficiently good adhesion between the substrate and the hydrophilic polymer, and it is difficult to ensure sufficiently good durability of the coated body obtained by coating the substrate with the hydrophilic polymer. Patent Document 2 also proposes performing a surface treatment such as plasma treatment on the substrate before applying the hydrophilic polymer, but even when such a surface treatment is performed, it is difficult to ensure sufficiently good adhesion between the substrate and the hydrophilic polymer, and it is difficult to ensure sufficiently good durability of the coated body obtained by coating the substrate with the hydrophilic polymer. Thus, it has been difficult to achieve both stain resistance and durability in the past. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 1996 / 029375 Pamphlet [Patent Document 2] International Publication No. 2018 / 008663 Brochure Summary of the Invention [Problem to be solved by the invention]

[0008] An object of the present invention is to provide a film-forming composition that can be used to form a film having excellent antifouling properties and durability, and to provide a method for producing a coated body having a film having excellent antifouling properties and durability. [Means for solving the problem]

[0009] These objectives are as follows:[1]~[ 5 This can be achieved by the present invention described in the above. [1] A polymer containing a monomer component having a phosphorylcholine group; a phosphorylcholine group-containing non-polymerized compound which is a compound having a phosphorylcholine group and being in a non-polymerized state; Glycerin and Ethanol and The polymer is composed of a monomer corresponding to a chemical structure represented by the following formula (1) and a monomer corresponding to a chemical structure represented by the following formula (2), where the content of the monomer corresponding to the chemical structure represented by the formula (1) in the polymer is X11 [mol] and the content of the monomer corresponding to the chemical structure represented by the formula (2) in the polymer is X12 [mol], the relationship of 0.5≦X12 / X11≦2.0 is satisfied; the monomer component in an unpolymerized state and the phosphorylcholine group-containing unpolymerized compound have the same chemical structure, When the content of the polymer is XP [mass%] and the content of the glycerin is XO [mass%], the relationship of 0.01≦XO / XP≦2.0 is satisfied, The ethanol content is 70.0% by mass or more and 99.9% by mass or less, A coating-forming composition characterized by satisfying the relationship 1.5≦[X2 / (X1+X2)]×100≦30, where X1 is the content of the polymer and X2 is the content of the phosphorylcholine group-containing non-polymerized compound. [ka] (In formula (1), l and n each independently represent an integer of 1 or more.) [ka] (In formula (2), n is an integer of 1 or more, and R is hydrogen or a hydrocarbon group which may have a substituent.)

[0015] [ 2 The weight average molecular weight of the polymer is 8,000 or more and 160,000 or less. [1] The film-forming composition according to claim 1.

[0018] [ 3 The above [1], wherein the glycerin content is 0.001% by mass or more and 15.0% by mass or less. or [2] The film-forming composition according to claim 1.

[0022] [ 4 ] Above [1] to [ 3 10. A method for producing a coated body, comprising a composition applying step of applying the coating composition according to any one of claims 1 to 9 to at least a part of the surface of a substrate.

[0023] [ 5 ] The above [ 4 ] A method for producing a coated body according to the present invention. [Effects of the Invention]

[0024] According to the present invention, it is possible to provide a coating composition that can be used to form a coating that has excellent antifouling properties and durability, and to provide a method for producing a coated body having a coating that has excellent antifouling properties and durability. [Brief explanation of the drawings]

[0025] [Figure 1] FIG. 1 is a longitudinal sectional view schematically showing an example of a method for producing a coated body of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0026] Preferred embodiments of the present invention will be described in detail below. <1> Film-forming composition First, the coating composition according to the present invention will be described.

[0027] The coating composition of the present invention contains a polymer containing a monomer component having a phosphorylcholine group and a phosphorylcholine group-containing non-polymerized compound, which is a compound having a phosphorylcholine group and is in a non-polymerized state. When the content of the polymer in the coating composition is X1 [mass %] and the content of the phosphorylcholine group-containing non-polymerized compound in the coating composition is X2 [mass %], the relationship 1.5≦[X2 / (X1+X2)]×100≦30 is satisfied.

[0028] By satisfying these conditions, it is possible to provide a film-forming composition that can be used to form a film that has excellent antifouling properties and durability. In particular, it is possible to provide a film-forming composition that can be used to form a film that has excellent antifouling properties not only against aqueous stains but also against oily stains such as oil mist. Furthermore, it is possible to suitably form a film that has excellent antifouling properties against water vapor and evaporated oil and can maintain this antifouling property for a long period of time. Furthermore, even if stains adhere to the film, they can be easily removed, and the effect of inhibiting stain adhesion can be suitably maintained even after that.

[0029] The phosphorylcholine groups contained in the polymer and the phosphorylcholine group-containing non-polymerized compound have a zwitterionic structure. Therefore, the coating formed using the coating composition of the present invention has excellent hydrophilicity (wettability) and can effectively suppress nonspecific adsorption of various molecules. As a result, it can exhibit antifouling effects, lubricating properties, friction-reducing effects, self-cleaning effects, and the like. Furthermore, the phosphorylcholine group is a polar group with a structure similar to that of the polar group of phospholipids (phosphatidylcholine), the main component of biomembranes. Therefore, the introduction of the phosphorylcholine group can impart extremely good biocompatibility to the surface of biomembranes, particularly non-adsorption and non-activation properties of biomolecules.

[0030] The excellent effects described above are believed to be achieved because the presence of phosphorylcholine groups contained in the polymer and the phosphorylcholine groups possessed by the phosphorylcholine group-containing non-polymerized compound allows water to be suitably contained, and a water film to be suitably formed on the surface of the coating.

[0031] On the other hand, if the above conditions are not met, satisfactory results will not be obtained. For example, if the coating does not contain a polymer containing a monomer component having a phosphorylcholine group, a hydrophilic film cannot be formed on the surface of the coating, and minute water droplets (cloudiness) tend to form.

[0032] Furthermore, even if the coating contains a polymer containing a monomer component having a phosphorylcholine group, if it does not contain a phosphorylcholine group-containing non-polymerized compound, the hydrophilicity of the coating will be reduced, a hydrophilic film will not be able to be suitably formed on the surface of the coating, and tiny water droplets (cloudiness) will be more likely to form.

[0033] Furthermore, even if the coating contains a polymer containing a monomer component having a phosphorylcholine group and a non-polymerized compound containing a phosphorylcholine group, if the value of [X2 / (X1+X2)]×100 is less than the lower limit, the coating will not exhibit sufficient hydrophilicity and will be prone to producing tiny water droplets (cloudiness).

[0034] Furthermore, even if the composition contains a polymer containing a monomer component having a phosphorylcholine group and a non-polymerized compound containing a phosphorylcholine group, if the value of [X2 / (X1+X2)]×100 exceeds the upper limit, the anti-fogging effect of the polymer cannot be fully exhibited.

[0035] As described above, when the content of the polymer in the coating composition is X1 [mass %] and the content of the phosphorylcholine group-containing non-polymerized compound in the coating composition is X2 [mass %], it is sufficient to satisfy the relationship of 1.5≦[X2 / (X1+X2)]×100≦30, preferably satisfying the relationship of 1.6≦[X2 / (X1+X2)]×100≦25, more preferably satisfying the relationship of 1.7≦[X2 / (X1+X2)]×100≦20, and even more preferably satisfying the relationship of 1.8≦[X2 / (X1+X2)]×100≦10. This makes the above-mentioned effects more pronounced.

[0036] <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.

[0037] The polymer may contain a monomer component having a phosphorylcholine group, and the monomer component may have a polymerized structure in any form, but it is preferable that the polymer has a chemical structure in which a monomer component having an acrylic skeleton is polymerized.

[0038] Examples of monomer components having an acrylic skeleton and a phosphorylcholine group include 2-methacryloyloxyethyl phosphorylcholine, 2-acryloyloxyethyl phosphorylcholine, N-(2-methacrylamido)ethyl phosphorylcholine, 4-methacryloyloxybutyl phosphorylcholine, 6-methacryloyloxyhexyl phosphorylcholine, 10-methacryloyloxydecylcylphosphorylcholine, ω-methacryloyldioxyethylene phosphorylcholine, and 4-styryloxybutyl phosphorylcholine, and the polymer may contain one or more selected from these.

[0039] Among these, the polymer preferably contains a chemical structure represented by the following formula (1):

[0040] [ka] (In formula (1), l and n each independently represent an integer of 1 or more.)

[0041] This makes it possible to make the solubility in the solvent (polymerization solvent) used in the polymerization reaction to obtain the polymer more suitable.

[0042] In the above formula (1), l may be an integer of 1 or more, preferably an integer of 1 or more and 10 or less, more preferably an integer of 1 or more and 5 or less, and even more preferably an integer of 1 or more and 3 or less.

[0043] The monomer component having a phosphorylcholine group that constitutes the polymer may be a compound other than the compound corresponding to the above formula (1).

[0044] The polymer may contain, in addition to the monomer component having a phosphorylcholine group, a monomer component not having a phosphorylcholine group.

[0045] 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).

[0046] [ka] (In formula (2), n is an integer of 1 or more, and R is hydrogen or a hydrocarbon group which may have a substituent.)

[0047] This can reduce the water solubility of the coating film formed using the coating film-forming composition, and can further improve the adhesion between the substrate and the coating film.

[0048] Examples of the hydrocarbon group include aliphatic hydrocarbon groups such as 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, an t-butyl group, and an n-hexyl group; and aromatic hydrocarbon groups such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, a benzyl group, a naphthyl group, and an anthracenyl group. Of these, a benzyl group is preferred.

[0049] This makes it possible to more suitably reduce the water solubility of the polymer while maintaining the hydrophilicity of the coating.

[0050] Furthermore, when the hydrocarbon group has a substituent, examples of the substituent include a halogeno group such as a fluoro group, a chloro group, a bromo group, or an iodo group, a hydroxyl group, a carboxyl group, an aldehyde group, a ketone group, an ether group, an ester group, a nitro group, an amino group, and a sulfo group.

[0051] The polymer may also contain, for example, compounds represented by the following formula (b1) or (b2) as a monomer component not having a phosphorylcholine group.

[0052] [ka] (In the above formula (b1) and the above formula (b2), n represents an integer of 1 or more.)

[0053] In the above formula (b1) and formula (b2), n may be an integer of 1 or more, preferably an integer of 1 or more and 12 or less, more preferably an integer of 1 or more and 6 or less, and even more preferably 1.

[0054] When the polymer contains a chemical structure represented by the above formula (1) and a chemical structure represented by the above formula (2), when 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 is X12 [mol], it is preferable to satisfy the relationship of 0.5≦X12 / X11≦2.0, more preferably the relationship of 0.7≦X12 / X11≦1.5, and even more preferably the relationship of 0.8≦X12 / X11≦1.2.

[0055] This makes it possible to more suitably reduce the water solubility of the polymer while maintaining the hydrophilicity of the coating.

[0056] When the polymer is a copolymer containing a plurality of types of monomer components, the polymer may be, for example, any of an alternating copolymer, a random copolymer, a block copolymer, and a graft copolymer.

[0057] The content of the monomer component having a phosphorylcholine group relative to the total 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 even more preferably 40 mol% or more and 56 mol% or less.

[0058] This makes it possible to more suitably reduce the water solubility of the polymer while maintaining the hydrophilicity of the coating.

[0059] The polymer may contain a plurality of types of monomer components as the monomer component having a phosphorylcholine group. The polymer may also contain a plurality of types of monomer components as monomer components not having a phosphorylcholine group.

[0060] The polymer may also contain multiple different types of molecules. For example, the polymer may contain molecules having different molecular weights. The polymer may also contain multiple types of molecules having different types of constituent monomers. When the polymer contains molecules formed by polymerization of multiple types of constituent monomers, the polymer may also contain multiple types of molecules having different content ratios of the multiple types of constituent monomers.

[0061] The weight average molecular weight of the polymer is not particularly limited, but is preferably 8,000 or more and 160,000 or less, more preferably 30,000 or more and 150,000 or less, and even more preferably 50,000 or more and 120,000 or less.

[0062] This makes it possible to more effectively prevent the formation of undesired irregularities in a coating formed using the coating composition, thereby making it possible to improve the flatness of the surface of the coating.

[0063] The weight average molecular weight of the polymer can be measured by gel permeation chromatography (GPC).

[0064] The content of the polymer in the coating composition of the present invention is not particularly limited, but is preferably from 0.02% by mass to 10.0% by mass, more preferably from 0.05% by mass to 5.0% by mass, and even more preferably from 0.1% by mass to 2.0% by mass.

[0065] This allows the viscosity of the coating composition to be within a more suitable range, and allows the coating to be formed more efficiently while more effectively preventing undesired variations in thickness and composition from occurring in the coating formed using the coating composition.

[0066] 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.

[0067] The polymer constituting the coating composition may be produced by any method, but can be suitably produced, for example, by a radical polymerization method using a polymerization initiator as described below.

[0068] As a method for radical polymerization, for example, a method using a radical polymerization initiator can be adopted.

[0069] The polymer can be synthesized by radical polymerization using a radical polymerization initiator under specific conditions, specifically, by radical polymerization in an organic solvent.

[0070] The radical polymerization initiator used in the polymerization is not particularly limited, but examples thereof include azo initiators such as 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-amidinopropane) dihydrochloride, 4,4'-azobis(4-cyanopentanoic acid), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide, and potassium persulfate.

[0071] The amount of radical polymerization initiator used can be adjusted depending on the polymerizability of the monomer and the molecular weight of the required polymer, but is preferably 0.001 parts by mass or more and 3 parts by mass or less, and more preferably 0.01 parts by mass or more and 1 part by mass or less, relative to 100 parts by mass of all monomers used in the polymerization.

[0072] Examples of solvents used in 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; ether solvents such as dioxane; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; aromatic solvents such as benzene and toluene; nitrile solvents such as acetonitrile; and halogenated solvents such as methylene chloride, chloroform, and dichloroethane. One or more selected from these can be used in combination. Among these, alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol are preferred.

[0073] The reaction temperature during the polymerization reaction can be appropriately set depending on the molecular weight of the polymer to be synthesized, the type of polymerization initiator, etc., but is preferably 30°C or higher and 100°C or lower.

[0074] After polymerization by the above method or the like, the resulting polymer solution may be purified as needed.

[0075] The purification method is not particularly limited, but for example, a reprecipitation method can be suitably employed. When a reprecipitation method is employed, 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; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, and isophorone; and halogenated hydrocarbon solvents such as chloromethane, dichloromethane, and chloroform. One or more solvents selected from these may be used in combination.

[0076] The polymer can be purified by, for example, ultrafiltration.

[0077] <1-2> Non-polymerized compound containing a phosphorylcholine group As described above, the coating composition of the present invention contains a phosphorylcholine group-containing non-polymerized compound, which is a compound that has a phosphorylcholine group and is in a non-polymerized state.

[0078] In other words, the film-forming composition of the present invention contains a polymer containing a monomer component having a phosphorylcholine group, as well as a phosphorylcholine group-containing compound (phosphorylcholine group-containing non-polymerized compound) that is not a polymer having a phosphorylcholine group.

[0079] Examples of the phosphorylcholine group-containing non-polymerized compound that can be used include a compound that does not have a functional group that can contribute to a polymerization reaction, and a compound that has a functional group that can contribute to a polymerization reaction but the functional group is not in a polymerized state.

[0080] Examples of phosphorylcholine group-containing non-polymerized compounds that do not have functional groups that can contribute to a polymerization reaction include glycerophosphocholine (α-GPC), lecithin, and polyene phosphatidylcholine represented by the following formula (3):

[0081] [ka] (In formula (3), i, j, k, l, m, and n each independently represent an integer of 1 or more and 10 or less.)

[0082] Examples of compounds that have a functional group that can contribute to a polymerization reaction but in which the functional group is not in a polymerized state include compounds exemplified as monomer components having a phosphorylcholine group that constitute the polymer.

[0083] It is preferable that the monomer component having a phosphorylcholine group in an unpolymerized state (i.e., a compound in which the monomer component having a phosphorylcholine group that constitutes the polymer is in an unpolymerized state) and the phosphorylcholine group-containing non-polymerized compound have the same chemical structure.

[0084] This effectively suppresses undesirable reactions, and also improves the dispersibility of the phosphorylcholine group-containing non-polymerized compound in the coating film, thereby more effectively enhancing the water absorption effect of the coating film.

[0085] The film-forming composition may contain a plurality of different types of molecules as the phosphorylcholine group-containing non-polymerized compound.

[0086] The molecular weight of the phosphorylcholine group-containing non-polymerized compound is not particularly limited, but is preferably 150 to 2,000, more preferably 180 to 1,500, and even more preferably 200 to 800.

[0087] This makes it possible to improve the dispersibility of the phosphorylcholine group-containing non-polymerized compound in the coating film, and more effectively enhance the water absorption effect of the coating film.

[0088] Furthermore, when the coating composition contains a plurality of types of phosphorylcholine group-containing non-polymerized compounds, the average molecular weight can be used as the molecular weight of the phosphorylcholine group-containing non-polymerized compounds.

[0089] The phosphorylcholine group-containing non-polymerized compound may be incorporated into the coating composition by any method, but is usually mixed with the polymer synthesized by the method described above during the production of the coating composition.

[0090] The content of the phosphorylcholine group-containing non-polymerized compound in the coating 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, more preferably 0.001% by mass or more and 1.3% by mass or less, and even more preferably 0.003% by mass or more and 0.4% by mass or less.

[0091] This can further increase the hydrophilicity of the coating.

[0092] <1-3> Polyhydric alcohol The film-forming composition of the present invention may further contain a polyhydric alcohol in addition to the polymer and the phosphorylcholine group-containing non-polymerized compound.

[0093] This makes it possible to more effectively prevent undesired thickness variations in the coating film formed using the coating composition. Furthermore, when used in combination with a monohydric alcohol as a volatile solvent (described later), the dispersibility of the polyhydric alcohol can be improved, and the above-mentioned effects can be more significantly exhibited. These effects are more significantly exhibited when ethanol is used as the volatile liquid.

[0094] The polyhydric alcohol may be one that is liquid at room temperature (23°C) and functions as a solvent that dissolves part of the polymer and the phosphorylcholine group-containing non-polymerized compound in the coating composition.

[0095] Furthermore, in the method for producing a coated body described in detail below, the polyhydric alcohol may be one in which at least a portion is removed after being applied to the substrate, but it is preferable that the majority (e.g., 80% by mass or more) of it remains on the substrate even after being applied to the substrate.

[0096] The polyhydric alcohol may be any compound having a plurality of hydroxyl groups in the molecule, and examples thereof include ethylene glycol, propylene glycol, butylene glycol, glycerin, and polyethylene glycol, with glycerin being preferred. This makes the above-mentioned effects more pronounced.

[0097] The film-forming composition may contain a plurality of different types of molecules as polyhydric alcohols.

[0098] 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 even more preferably 92 or more and 4,000 or less.

[0099] This allows, for example, when used in combination with a monohydric alcohol as a volatile solvent described below, to increase the solubility of the polyhydric alcohol in the volatile solvent and further improve the affinity with the polymer, thereby more significantly exhibiting the effects described above.

[0100] When the composition for forming a coating film contains a plurality of types of polyhydric alcohols, the average molecular weight of the polyhydric alcohols can be used.

[0101] The content of the polyhydric alcohol in the coating composition of the present invention is not particularly limited, but is preferably from 0.001% by mass to 15.0% by mass, more preferably from 0.010% by mass to 6.0% by mass, and even more preferably from 0.10% by mass to 2.2% by mass.

[0102] This makes it possible to improve the uniformity of the coating without impairing the properties of the coating composition and the coating formed from the coating composition.

[0103] When the content of the polymer in the coating composition is XP [mass %] and the content of the polyhydric alcohol in the coating composition is XO [mass %], it is preferable that the relationship of 0.01≦XO / XP≦2.0 is satisfied, it is more preferable that the relationship of 0.10≦XO / XP≦1.5 is satisfied, and it is even more preferable that the relationship of 0.80≦XO / XP≦1.2 is satisfied.

[0104] This makes it possible to improve the uniformity of the coating without impairing the properties of the coating composition and the coating formed from the coating composition.

[0105] <1-4> Volatile solvents The film-forming composition of the present invention may contain a volatile solvent. This makes it easier to handle the film-forming composition, and also makes it possible to improve the flatness of the film formed using the film-forming composition, thereby more effectively preventing undesired variations in the thickness of the film.

[0106] In the method for producing a coated body described in detail below, most of the volatile solvent is usually removed after application to a substrate. Specifically, the volatile solvent contained in the coating composition is preferably removed from the substrate in an amount of 80 mass % or more, more preferably 90 mass % or more, and even more preferably 98 mass % or more, after application to the substrate.

[0107] The boiling point of the volatile solvent at 1 atmosphere is preferably 50°C or higher and 160°C or lower, more preferably 55°C or higher and 120°C or lower, and even more preferably 60°C or higher and 100°C or lower.

[0108] Examples of volatile solvents include water, monohydric alcohols such as methanol, ethanol, and isopropyl alcohol, and ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, and isophorone, and one or more selected from these can be used in combination. However, the volatile solvent does not include the aforementioned polyhydric alcohols.

[0109] In particular, the film-forming composition of the present invention preferably contains ethanol as the volatile solvent.

[0110] This makes it possible to improve the solubility of the polymer and the phosphorylcholine group-containing non-polymerized compound in volatile solvents (particularly the solubility of the polymer and the phosphorylcholine group-containing non-polymerized compound having the preferred composition as described above), and to more effectively prevent undesired variations in thickness and composition from occurring in the coating formed using the coating composition, while enabling the coating to be formed more efficiently.

[0111] When the coating composition of the present invention contains ethanol as a volatile solvent, the proportion of ethanol in the total volatile solvents is preferably 50% by mass or more, more preferably 60% by mass or more and 99.8% by mass or less, and even more preferably 65% ​​by mass or more and 99% by mass or less. This makes the above-mentioned effects more pronounced.

[0112] The content of the volatile solvent in the coating 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, more preferably 90.0% by mass or more and 99.8% by mass or less, and even more preferably 95.0% by mass or more and 99.6% by mass or less.

[0113] This allows the viscosity of the coating composition to be within a more suitable range, and allows for more efficient coating formation while more effectively preventing undesired variations in thickness and composition in the coating formed using the coating composition. Furthermore, this allows for efficient removal of the volatile solvent from the coating composition applied to the substrate (workpiece), improving the productivity of the coated body having the substrate and the coating.

[0114] <1-6> Other ingredients The film-forming composition of the present invention may contain components other than the components described above (hereinafter also referred to as "other components").

[0115] Examples of other components include colorants such as pigments and dyes, various fillers, dispersants, ultraviolet absorbers, antioxidants, pH adjusters, preservatives, mildew inhibitors, rust inhibitors, polymers other than the above-mentioned polymers, and the like, and one or more selected from these may be used in combination.

[0116] The pH adjuster is not particularly limited, but inorganic salts are preferred. Examples of the inorganic salt include phosphates such as disodium hydrogen phosphate and sodium dihydrogen phosphate; carbonates such as sodium hydrogen carbonate and sodium carbonate; and one or more selected from these may be used in combination. Among these, phosphates are preferred, and disodium hydrogen phosphate dihydrate or disodium hydrogen phosphate dodecahydrate is more preferred.

[0117] In addition, in order to adjust the pH to a desired level, for example, bases such as sodium hydroxide and potassium hydroxide; acids such as sulfuric acid, hydrochloric acid and nitric acid, and the like may be used.

[0118] However, the content of other components in the coating composition of the present invention (when multiple types of other components are contained, the sum of their contents) is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0119] The pH (pH at 23° C.) of the coating forming composition of the present invention is not particularly limited, but is preferably 3 or more and 11 or less, and more preferably 3 or more and 7 or less.

[0120] The coating composition of the present invention may be applied to a substrate (workpiece) on which a coating is to be formed, or may be diluted and used, or may be mixed with other components. Furthermore, multiple types of coating compositions of the present invention having different conditions may be mixed and used.

[0121] <2> Manufacturing method of the coated body Next, a method for producing the coated body of the present invention will be described. FIG. 1 is a longitudinal sectional view schematically showing an example of a method for producing a coated body of the present invention.

[0122] As shown in FIG. 1, the method for producing the coated body 100 of this embodiment includes a substrate preparation step (1a) of preparing a substrate 1, a composition application step (1b) of applying a coating composition 2′ of the present invention to at least a portion of the surface of the substrate 1, and a solvent removal step (1c) of removing the volatile solvent from the coating composition 2′ applied to the substrate 1.

[0123] By satisfying these conditions, it is possible to provide a method for producing a coated body having a coating that has excellent antifouling properties and durability. In particular, it is possible to provide a method for producing a coated body having a coating that has excellent antifouling properties not only against aqueous stains but also against oily stains such as oil mist. It is also possible to suitably produce a coated body having a coating that has excellent antifouling properties against water vapor and evaporated oil and that can maintain this antifogging property for a long period of time. It is also possible to provide a method for producing a coated body that can easily remove stains even if they adhere to the coating and that can suitably maintain the stain adhesion suppression effect even after that.

[0124] <2-1> Substrate preparation process In the substrate preparation step, a substrate 1 is prepared as an object to be treated, which will be treated in detail later (see FIG. 1(1a)). The substrate 1 usually constitutes the main part of the coating 100 .

[0125] Substrate 1 may be made of any material, including, for example, metals such as Ti, Au, Cu, and Fe, and alloys containing at least one of these metals (such as various stainless steels and duralumin); carbons such as silicon, diamond, graphite, and diamond-like carbon; metal compound materials such as Al2O3, TiO2, ZrO2, silicon oxide (SiO2), Ta2O5, mica, hydroxyapatite, ZnO, ITO, and IGZO; various glass materials; acrylic resins such as polymethyl(meth)acrylate; polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate; thermoplastic elastomers such as polystyrene, polycarbonate polyvinylpyrrolidone, and polyvinyl chloride thermoplastic elastomers; various plastic materials such as copolymers and polymer blends of these; and various rubber materials such as various silicone rubbers such as polydimethylsiloxane (PDMS). Substrate 1 may also be made of one or more materials selected from these materials, such as a laminate having layers composed of different materials. Furthermore, the substrate 1 may have a portion made of a gradient material whose composition changes in a gradient manner.

[0126] In particular, if at least the portion of the substrate 1 where the coating 2 is to be formed is made of a glass material, a plastic material, or a metal material, the adhesion between the substrate 1 and the coating 2 can be improved, and the durability of the coating 100 can be improved.

[0127] The shape of the substrate 1 is usually determined by the coated body 100 to be produced, and is usually approximately the same shape as the coated body 100 to be produced, but examples include plate shapes such as flat, curved, and bent plates, as well as cylindrical, porous, granular, and fibrous shapes. The substrate 1 may also be provided with, for example, holes, grooves, protrusions, and the like.

[0128] The coating 2, which will be described in detail later, is formed on at least a part of the surface of the substrate 1.

[0129] For example, when the substrate 1 has a hollow portion, the coating 2, which will be described in detail later, may be formed at least on the inner wall surface of the hollow portion of the substrate 1.

[0130] The substrate 1 may be subjected to pretreatment such as washing before being subjected to the steps described below. More specifically, for example, washing with water, acid washing, alkali washing, washing with a detergent such as a neutral detergent, washing with an organic solvent, etc. may be performed.

[0131] <2-2> Composition application step In the composition application step, the coating composition 2' of the present invention is applied to at least a part of the surface of the substrate 1 (see FIG. 1(1b)).

[0132] The coating composition 2' can be applied to the substrate 1 by various methods, such as various coating methods such as roll coating, bar coating, and spraying, various printing methods such as screen printing and inkjet printing, and dipping.

[0133] For the purpose of selectively applying the film-forming composition 2' to a predetermined portion of the substrate 1, a part of the substrate 1 may be masked.

[0134] When the coating composition 2' is applied to the substrate 1 by an immersion method, the immersion time of the substrate 1 in the coating composition 2' is not particularly limited, but is preferably from 1 second to 60 minutes, more preferably from 10 seconds to 30 minutes, and even more preferably from 30 seconds to 15 minutes.

[0135] <2-3> Solvent removal process In the solvent removal step, the volatile solvent is removed from the composition for forming a coating 2' applied to the substrate 1 to form a coating 2 (see FIG. 1(1c)).

[0136] By performing the solvent removal process, it is possible to preferably form a flattened coating 2, and it is also possible to preferably prevent volatile solvents from unintentionally remaining in the finally obtained coating body 100.

[0137] The solvent removal step can be carried out, for example, by natural drying. This effectively prevents undesired denaturation of the components of the coating composition and undesired roughening of the surface of the coating, thereby improving the adhesion of the coating 2 to the substrate 1 and the reliability of the coated body 100.

[0138] When the solvent removal step is carried out by natural drying, the time is preferably from 0.5 to 120 minutes, more preferably from 1 to 60 minutes, and even more preferably from 2 to 10 minutes.

[0139] This makes it possible to improve the productivity of the coated body 100 and also improve the reliability of the coated body 100.

[0140] The solvent removal step can also be carried out by heating. When the solvent removal step is carried out by heating, the treatment temperature (heating temperature) in the solvent removal step is preferably 60°C or higher and 150°C or lower, more preferably 70°C or higher and 140°C or lower, and even more preferably 80°C or higher and 130°C or lower.

[0141] This makes it possible to improve the productivity of the coated body 100, and also improve the reliability and productivity of the coated body 100.

[0142] When the solvent removal step is carried out by heating, the treatment time (heating time) in the solvent removal step is preferably 30 minutes or more and 600 minutes or less, more preferably 45 minutes or more and 480 minutes or less, and even more preferably 60 minutes or more and 300 minutes or less.

[0143] This makes it possible to improve the productivity of the coated body 100, and also improve the reliability and productivity of the coated body 100.

[0144] The thickness of the coating 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 even more preferably 50 nm or more and 500 nm or less.

[0145] This allows the coating 2 to be formed more efficiently in a shorter time, while more efficiently suppressing unevenness, and more densely on the surface of the substrate 1. As a result, the coating 2 can be made to have more excellent antifouling properties, antifogging properties, and durability.

[0146] The solvent removal step may be carried out simultaneously with the composition application step. If the coating composition does not contain a volatile solvent, the solvent removal step can be omitted.

[0147] <3> covering body The coated body 100 according to the present invention obtained as described above comprises a substrate 1 and a coating 2. The coating 2 has excellent antifouling properties and durability. In particular, it has excellent antifouling properties not only against aqueous stains but also against oily stains such as oil mist. The coating 2 also has excellent antifouling properties against water vapor and evaporated oil, and can maintain this antifouling property for a long period of time. Even if stains adhere to the coating 2, they can be easily removed, and the effect of inhibiting stain adhesion can be favorably maintained even after the stains adhere.

[0148] The uses of the coating 100 are not particularly limited, and examples thereof include dental materials, dental instruments, various medical devices such as endoscopes, contact lenses, artificial organs, biochips, biosensors, oxygen-enriched membranes, medical instruments such as cell preservation instruments, automobile windshields, ship bottom paints, etc. Examples of dental materials include dental prostheses such as removable dentures, bridge dentures, implant dentures, and crowns, orthodontic materials, denture lining materials, etc.

[0149] Although the preferred embodiments of the present invention have been described above, the present invention is not limited to these.

[0150] For example, the method for producing the coated body may include steps other than those described above. More specifically, for example, prior to the composition application step, the method may include a step of subjecting the substrate to various treatments such as ultraviolet irradiation treatment, ozone treatment, plasma treatment, corona discharge treatment, flame treatment, hydrogen peroxide water / Fenton reaction solution treatment, and treatment using a coupling agent.

[0151] Furthermore, when the composition applying step is carried out in a state where a mask is placed on the substrate, a mask removing step of removing the mask may be included. Furthermore, a washing step may be carried out after the composition application step and the solvent removal step. [Example]

[0152] The present invention will be described in detail below based on examples and comparative examples, but the present invention is not limited to these. Treatments and measurements for which no temperature conditions are specified were carried out at 23°C.

[0153] <4> Polymer synthesis (Synthesis Example 1) 2-Methacryloyloxyethyl phosphorylcholine (MPC) (C 11 H 22 NO6P (Mw=295.27 CAS 67881-98-5), benzyl methacrylate (BzMA), and azobisisobutyronitrile (AIBN) as a random polymerization initiator (oxidizing agent) were mixed in a predetermined ratio and dissolved in 360 mL of ethanol as a reaction solvent to a monomer concentration of 0.5 mol / L. The solution was then transferred to a recovery flask and argon was bubbled through to remove oxygen from the system (20 minutes).

[0154] Next, the recovery flask was stoppered and heated in an oil bath (60°C) to carry out a polymerization reaction (24 hours).

[0155] Thereafter, the reaction vessel was opened, and reprecipitation was carried out with THF, and unreacted materials were removed. The polymer was recovered and dried under reduced pressure to obtain a purified polymer.

[0156] 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).

[0157] (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 for the polymer synthesis were as shown in Table 1.

[0158] The conditions for the polymers obtained in each of the synthesis examples are summarized in Table 1. In Table 1, 2-methacryloyloxyethyl phosphorylcholine is abbreviated as "MPC," benzyl methacrylate as "BzMA," n-butyl methacrylate as "BMA," Phosmer M (acid phosphoethyl methacrylate) (CH 11 O6P Mw=210.12 CAS 24599-21-1) was designated as "Phosmer M".

[0159] [Table 1]

[0160] <5> Production of film-forming composition Example 1 A composition for forming a coating was obtained by mixing the polymer obtained in Synthesis Example 1, 2-methacryloyloxyethyl phosphorylcholine as a phosphorylcholine group-containing non-polymerized compound, and 99.5% by mass ethanol aqueous solution as a volatile solvent in a predetermined ratio.

[0161] Examples 2 to 10 A coating composition was produced in the same manner as in Example 1, except that the types and amounts of the components used as raw materials were as shown in Table 2.

[0162] (Comparative Examples 1 to 3) A coating composition was produced in the same manner as in Example 1, except that the types and amounts of the components used as raw materials were as shown in Table 2.

[0163] The compositions of the coating-forming compositions of the examples and comparative examples are shown in Table 2. In Table 2, 2-methacryloyloxyethyl phosphorylcholine is abbreviated as "MPC."

[0164] [Table 2]

[0165] <6> Manufacturing of the coating Using the coating compositions of the above examples and comparative examples, coated bodies were produced as follows.

[0166] First, a glass plate-shaped substrate (diameter 25 mm) was prepared. Next, the substrate was washed with ethanol, and a predetermined amount of a coating composition was applied to one surface of the substrate by flow coating.

[0167] Thereafter, the volatile solvent was removed by natural drying, and a coated body having a coating film on one surface of the substrate was obtained.

[0168] The coated bodies manufactured for each of the examples and comparative examples had coating thicknesses of 51 nm, 76 nm, 102 nm, 509 nm, 1000 nm, and 1360 nm, respectively. The coating thicknesses were measured using an OPTM-A1 manufactured by Otsuka Electronics Co., Ltd.

[0169] <7> evaluation The coated bodies according to the examples and comparative examples prepared as described above were evaluated as follows. As a control (reference example), a glass substrate without a coating was also evaluated.

[0170] <7-1> Antifouling properties (resistance to oil mist adhesion) First, pork and the coating were placed in a closed space. In this closed space, the pork was heated to about 600°C using a nichrome wire to generate oil mist, and the coated surface of the coating was exposed to the oil mist and evaluated according to the following criteria. A reference example without a coating was also evaluated in the same manner as above.

[0171] A: No stains are observed. B: Dirt is observed on less than 10% of the surface. C: Dirt is observed on less than 30% of the surface. D: Dirt is observed on less than 50% of the surface. E: Overall staining is observed.

[0172] <7-2> Anti-fogging properties The surfaces of the coatings of the coatings according to the examples and comparative examples were left for 30 minutes in an environment of 37°C temperature and 90% RH, and the state of cloudiness was visually observed and evaluated according to the following criteria: Reference examples not provided with a coating were also evaluated in the same manner as above.

[0173] A: No cloudiness is observed. B: Clouding is observed on less than 10% of the surface. C: Clouding is observed on less than 30% of the surface. D: Clouding is observed on less than 50% of the surface. E: Overall cloudiness is observed.

[0174] <7-3> Duration of anti-fogging properties The surfaces of the coatings of the coatings according to the examples and comparative examples were left for a certain period of time in an environment of 37°C temperature and 90% RH, and the state of cloudiness was visually observed and evaluated according to the following criteria. The reference examples, which had no coating, were also evaluated in the same manner as above.

[0175] A: No fogging is observed for more than 2 hours. B: No fogging observed for 1.5 hours or more but less than 2 hours. C: No fogging observed for 1 hour or more but less than 1.5 hours. D: No fogging observed for 30 minutes or more but less than 1 hour. E: Clouding observed in less than 30 minutes.

[0176] <7-4>Durability The coated bodies according to the examples and comparative examples were immersed in pure water at room temperature for 1 hour and evaluated according to the following criteria. The reference examples without a coating were also evaluated in the same manner as above.

[0177] A: The surface wettability is maintained. B: The surface wettability is slightly reduced. C: The wettability of the surface is partially reduced. D: Almost no wettability of the surface is observed. E: No wettability of the surface is observed.

[0178] These results are summarized in Table 3.

[0179] [Table 3]

[0180] As is clear from Table 3, excellent results were obtained in each of the above Examples, whereas satisfactory results were not obtained in each of the Comparative Examples and Reference Examples.

[0181] In addition, coated bodies were produced in the same manner as in the above-mentioned Examples and Comparative Examples, except that the substrate was changed from glass to cycloolefin polymer (COP) or SUS304, and the same evaluations were carried out as above, and the same trends as above were confirmed. [Explanation of symbols]

[0182] 100…covering body 1...Base material 2...Coating 2'...Film forming composition

Claims

1. a polymer containing a monomer component having a phosphorylcholine group; a phosphorylcholine group-containing non-polymerized compound which is a compound having a phosphorylcholine group and being in a non-polymerized state; Glycerin and Ethanol and The polymer is composed of a monomer corresponding to a chemical structure represented by the following formula (1) and a monomer corresponding to a chemical structure represented by the following formula (2), where the content of the monomer corresponding to the chemical structure represented by the formula (1) in the polymer is X11 [mol] and the content of the monomer corresponding to the chemical structure represented by the formula (2) in the polymer is X12 [mol], the relationship of 0.5≦X12 / X11≦2.0 is satisfied, the monomer component in an unpolymerized state and the phosphorylcholine group-containing unpolymerized compound have the same chemical structure, When the content of the polymer is XP [mass%] and the content of the glycerin is XO [mass%], the relationship of 0.01≦XO / XP≦2.0 is satisfied, The ethanol content is 70.0% by mass or more and 99.9% by mass or less, A coating-forming composition characterized by satisfying the relationship 1.5≦[X2 / (X1+X2)]×100≦30, where X1 is the content of the polymer and X2 is the content of the phosphorylcholine group-containing non-polymerized compound. 【Chemistry 1】 (In formula (1), l and n each independently represent an integer of 1 or more.) 【Chemistry 2】 (In formula (2), n is an integer of 1 or more, and R is hydrogen or a hydrocarbon group which may have a substituent.)

2. 2. The film-forming composition according to claim 1, wherein the weight-average molecular weight of the polymer is 8,000 or more and 160,000 or less.

3. 3. The composition for forming a coating film according to claim 1, wherein the glycerin content is 0.001% by mass or more and 15.0% by mass or less.

4. A method for producing a coated body, comprising a composition applying step of applying the coating composition according to any one of claims 1 to 3 to at least a part of the surface of a substrate.

5. The method for producing a coated body according to claim 4, wherein the thickness of the coating is 30 nm or more and 1000 nm or less.

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