Method for coating an article, use for coating an article, and polymerizable composition

Abstract

To provide a method for coating an article to give long-lasting antibacterial and antiviral effects.SOLUTION: Provided is a method for coating an article, the method comprising: a step for applying, to an article, a polymerizable composition in which a solution having a second polymerizable monomer dissolved in a first solvent is dispersed in a first polymerizable monomer, the first polymerizable monomer being a liquid and the second polymerizable monomer being a solid; and a step for polymerizing the polymerizable composition applied to the article.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for coating an article, to a use for coating an article, and to a polymerizable composition. [Background technology]

[0002] The recent epidemic of new viral infections has led to an increasing demand for sanitary products with antibacterial and antiviral properties. For example, there is a technology in which an antiviral composition containing a specific silicon-containing compound is applied or sprayed onto an article having an oxygen-containing functional group to fix it thereon (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 4830075 Summary of the Invention [Problem to be solved by the invention]

[0004] Conventional techniques for imparting antibacterial, antiviral, or other functions to articles do not provide long-lasting antibacterial or antiviral properties.

[0005] An object of the present invention is to provide a method for coating an article that can provide long-lasting antibacterial and antiviral properties. [Means for solving the problem]

[0006] In one aspect of the present invention, a solution in which a second polymerizable monomer is dissolved in a first solvent is dispersed in a first polymerizable monomer, the first polymerizable monomer being a liquid and being a polyfunctional methacrylate having two or more methacryloyloxy groups, and the second polymerizable monomer being One selected from 2-(methacryloyloxy)ethyltrimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium chloride, (2-(acryloyloxy)ethyl)trimethylammonium chloride, and N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride and polymerizing the polymerizable composition applied to the article. [Effects of the Invention]

[0007] According to one aspect of the present invention, a method for coating an article that can provide long-lasting antibacterial and antiviral properties can be provided. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a schematic diagram illustrating a cross section of a polymerizable composition according to an embodiment. [Figure 2] FIG. 2 is a schematic diagram showing a cross section of a polymerizable composition according to a comparative example. [Figure 3] 1 is an optical microscope photograph of a polymerizable composition according to an embodiment before curing. [Figure 4] 1 is an optical microscope photograph of a polymerizable composition according to a comparative example before curing. [Figure 5] 1 is a photograph showing the appearance of a polymerizable composition according to an embodiment after curing. [Figure 6] 1 is a photograph showing the appearance of a polymerizable composition according to a comparative example after curing. DETAILED DESCRIPTION OF THE INVENTION

[0009] Next, an embodiment of the present invention will be described.

[0010] <Method of covering an article> The method for coating an article according to the present embodiment includes the steps of applying a polymerizable composition to the article and polymerizing the polymerizable composition applied to the article. In this specification, coating refers to covering the surface of the article with the polymerizable composition.

[0011] In this specification, an article is an object to which the polymerizable composition is applied. The material of the article (object) is not particularly limited, and various materials such as metal, ceramic, plastic, wood, and fiber can be used. In addition, coating also includes cases where the surface of the article is not completely covered with the polymerizable composition, but the polymerizable composition is fixed or attached to the surface of the article, leaving an exposed portion.

[0012] In the process of applying the polymerizable composition to an article, the application is preferably any one of spraying, jetting, and coating. Here, spraying refers to emitting a liquid in a mist, jetting refers to emitting a liquid in a linear fashion, and coating refers to spreading a liquid.

[0013] For example, when the application is by spraying or jetting, the polymerizable composition (hereinafter sometimes referred to as a coating liquid or a coating agent) can be filled into a spray can (or a spray container) and sprayed from a nozzle with an adjusted spray angle. When a spray container is used, the spray container may be shaken before use as needed to stir the filled coating liquid before use.

[0014] When the application is by coating, the polymerizable composition can be applied to the surface of the article (target object) using an applicator such as a brush or paintbrush.

[0015] A volatile solvent may be added to the coating liquid to lower its viscosity. However, if the coating agent is cured while the volatile solvent remains, the mechanical strength of the coating agent is reduced. Therefore, when a volatile solvent is added, it is desirable to wait until the volatile solvent has evaporated before curing the coating agent.

[0016] In the method for coating an article of the present embodiment, the polymerizable composition is applied to the article by spraying, jetting, or coating, which makes it easy to fix the polymerizable composition to the surface of the article.

[0017] In the step of polymerizing the polymerizable composition applied to the article, the polymerizable composition is polymerized on the surface of the article to harden, and the hardened polymerizable composition is fixed to the article. The manner in which the polymerizable composition is polymerized is not particularly limited, and for example, step-growth polymerization, chain polymerization, a combination thereof, or the like can be used.

[0018] The step of polymerizing the polymerizable composition applied to the article preferably includes a step of irradiating the article to which the polymerizable composition is applied with light. In the step of irradiating the applied article with light, the polymerizable composition applied to the article is polymerized and cured by the light irradiation to form a cured product (or hardened body), and the cured product of the polymerizable composition is fixed to the article.

[0019] Here, light irradiation refers to irradiation with electromagnetic waves having a wavelength in the range of 350 to 500 nm, for example. Note that, among electromagnetic waves having a wavelength in the range of 350 to 450 nm, the range of 380 nm or less represents ultraviolet light, and the range of more than 380 nm represents visible light.

[0020] In the method for coating an article according to the present embodiment, the step of polymerizing the polymerizable composition includes a step of irradiating the applied article with light, which promotes polymerization of the polymerizable composition on the surface of the article and shortens the curing time of the polymerizable composition. Furthermore, the light irradiation efficiently promotes polymerization and curing of the polymerizable composition, thereby increasing the stability of the polymerizable composition fixed to the article.

[0021] In the method for coating an article according to the present embodiment, the polymerizable composition applied to the article comprises a first polymerizable monomer and a first solvent in which the second polymerizable monomer is dispersed. Such a polymerizable composition can be obtained, for example, by performing a step of mixing the first polymerizable monomer, the second polymerizable monomer, and the first solvent (hereinafter referred to as the mixing step).

[0022] In the polymerizable composition used in the method for coating an article of the present embodiment, the first polymerizable monomer is liquid and the second polymerizable monomer is solid. For example, the first polymerizable monomer is liquid at room temperature and normal pressure, and the second polymerizable monomer is solid at room temperature and normal pressure.

[0023] In this case, if the first polymerizable monomer and the second polymerizable monomer are mixed without using the first solvent, it is difficult to control the particle size of the second polymerizable monomer, and therefore the second polymerizable monomer cannot be uniformly localized within the first polymerizable monomer. In this case, the appearance of the polymerizable composition cured on the article is deteriorated, and the function (or performance) derived from the second polymerizable monomer is difficult to impart to the article, or even if the function is imparted, the function does not last for a long time.

[0024] On the other hand, when the first polymerizable monomer, the second polymerizable monomer, and the first solvent are used, the second polymerizable monomer can be uniformly localized in the polymerizable composition. Therefore, in the method for coating an article of this embodiment, the appearance of the cured product of the polymerizable composition cured on the article can be improved, and the article can be endowed with a function (or performance) derived from the second polymerizable monomer, and the function can be maintained for a long period of time.

[0025] For example, when the second polymerizable monomer has a functional group exhibiting antibacterial properties (hereinafter referred to as an antibacterial group), antibacterial properties can be imparted to a cured product of the polymerizable composition.Furthermore, when the second polymerizable monomer has a functional group exhibiting antiviral properties (hereinafter referred to as an antiviral group), antiviral properties can be imparted to a cured product of the polymerizable composition.

[0026] The mass ratio of the first solvent to the second polymerizable monomer is preferably 0.01 to 5, and more preferably 0.1 to 2. When the mass ratio of the first solvent to the second polymerizable monomer is 0.01 or more, the stability of the second polymerizable monomer when dissolved in the first solvent is improved, and when it is 5 or less, the mechanical strength of a cured product of the polymerizable composition is improved.

[0027] The mass ratio of the first polymerizable monomer to the total amount of the second polymerizable monomer and the first solvent is preferably 0.1 to 100, and more preferably 0.5 to 50. When the mass ratio of the first polymerizable monomer to the total amount of the second polymerizable monomer and the first solvent is 0.1 or more, the mechanical strength of the cured product of the polymerizable composition is improved, and when it is 100 or less, the performance derived from the second polymerizable monomer of the cured product of the polymerizable composition is improved.

[0028] In the mixing step of the polymerizable composition used in the method for coating an article of the present embodiment, a surfactant may be added when the first polymerizable monomer, the second polymerizable monomer, and the first solvent are mixed.

[0029] The surfactant is not particularly limited as long as it can improve the dispersibility of the solution, and examples thereof include sodium lauryl sulfate, glycerin fatty acid esters, etc. These surfactants may be used alone or in combination of two or more.

[0030] In the mixing step, when the first polymerizable monomer, the second polymerizable monomer, and the first solvent are mixed, it is preferable to add other components such as a photopolymerization initiator, a tertiary amine, and a polymerization inhibitor and knead them.

[0031] As for other components, it is preferable that the polymerizable composition is substantially free of fillers so as to prevent nozzle clogging when the polymerizable composition is sprayed or sprayed. In this specification, "substantially free" means that components such as fillers are not intentionally blended. Note that components that are substantially free of fillers may be included as unavoidable impurities. Furthermore, the content of components included as unavoidable impurities is preferably less than 1% by mass.

[0032] In the mixing step, when the first polymerizable monomer, the second polymerizable monomer, and the first solvent are mixed, glass and / or a pigment may be added as other components in order to improve the mechanical strength or reduce the transparency of the polymerizable composition after it has been coated on an article.

[0033] In the mixing step of the polymerizable composition used in the method for coating an article of this embodiment, a second solvent may be added to reduce the viscosity of the coating liquid, from the viewpoint of preventing a decrease in the operability of the polymerizable composition that becomes the coating liquid. If the polymerizable composition is cured while the second solvent remains, the mechanical strength decreases, so it is desirable to cure the composition by irradiating it with light after the second solvent has volatilized.

[0034] The other components may be added to the first polymerizable monomer, the second polymerizable monomer, and / or the first solvent before the first polymerizable monomer, the second polymerizable monomer, and the first solvent are mixed in the mixing step, or may be added after the first polymerizable monomer, the second polymerizable monomer, and the first solvent are mixed in the mixing step.

[0035] The mixing step may include a step of dissolving the second polymerizable monomer in the first solvent to obtain a solution, and a step of mixing the solution with the first polymerizable monomer.

[0036] By mixing the first polymerizable monomer with a solution of the second polymerizable monomer dissolved in the first solvent, the second polymerizable monomer can be more uniformly localized in the polymerizable composition. As a result, the cured product of the polymerizable composition is imparted with the function or performance derived from the second polymerizable monomer, while the appearance of the cured product of the polymerizable composition is improved, and further, the long-term durability of the function (or performance) derived from the second polymerizable monomer can be improved.

[0037] For example, when the second polymerizable monomer has an antibacterial group, it is possible to impart antibacterial properties to a cured product of the polymerizable composition, while further improving the appearance of the cured product of the polymerizable composition and the long-term durability of the function (or performance) derived from the second polymerizable monomer.

[0038] Furthermore, when the second polymerizable monomer has an antiviral group, the appearance of the cured product of the polymerizable composition is further improved while imparting antiviral properties to the cured product of the polymerizable composition, and further improving the long-term durability of the function (or performance) derived from the second polymerizable monomer.

[0039] When the first solvent is water, the second polymerizable monomer may be allowed to absorb moisture from the atmosphere, thereby dissolving the second polymerizable monomer in water.

[0040] Examples of methods for mixing the first polymerizable monomer with a solution in which the second polymerizable monomer is dissolved in the first solvent include a method of kneading the solution with the first polymerizable monomer using a planetary centrifugal mixer, a method of mixing the solution with the first polymerizable monomer using a magnetic stirrer, and a method of mixing the solution with the first polymerizable monomer using a stirrer with stirring blades.

[0041] In the mixing step, when the solution and the first polymerizable monomer are mixed, a surfactant may or may not be added.

[0042] The surfactant is not particularly limited as long as it can improve the dispersibility of the solution, and examples thereof include sodium lauryl sulfate, glycerin fatty acid esters, etc. These surfactants may be used alone or in combination of two or more.

[0043] In the mixing step of the polymerizable composition used in the method for coating an article of the present embodiment, when mixing the solution in which the second polymerizable monomer is dissolved in the first solvent with the first polymerizable monomer, it is preferable to add other components such as a photopolymerization initiator, a tertiary amine, and a polymerization inhibitor and then knead them.

[0044] Other components may be added to the solution and / or the first polymerizable monomer before mixing, or may be added after mixing the solution and the first polymerizable monomer.

[0045] The mixing step may include the steps of: dissolving at least a portion of the first polymerizable monomer and the second polymerizable monomer in a second solvent to obtain a solution; distilling off the second solvent from the solution to obtain a dispersion in which the second polymerizable monomer is dispersed in at least a portion of the first polymerizable monomer; and mixing the dispersion with the first solvent.

[0046] In the mixing step, mixing a dispersion in which the second polymerizable monomer is dispersed in the first polymerizable monomer with the first solvent allows the second polymerizable monomer to be more uniformly localized in the polymerizable composition. As a result, the cured product of the polymerizable composition is imparted with functionality derived from the second polymerizable monomer, and the appearance of the cured product of the polymerizable composition and the long-term durability of the functionality (or performance) derived from the second polymerizable monomer can be further improved.

[0047] For example, when the second polymerizable monomer has an antibacterial group, it is possible to impart antibacterial properties to a cured product of the polymerizable composition, while further improving the appearance of the cured product of the polymerizable composition and the long-term durability of the function (or performance) derived from the second polymerizable monomer.

[0048] Furthermore, when the second polymerizable monomer has an antiviral group, the appearance of the cured product of the polymerizable composition is further improved while imparting antiviral properties to the cured product of the polymerizable composition, and further improving the long-term durability of the function (or performance) derived from the second polymerizable monomer.

[0049] Here, when a part of the first polymerizable monomer is used when obtaining the solution, the dispersion is obtained and then mixed with the remainder of the first polymerizable monomer. At this time, the timing of mixing the dispersion with the remainder of the first polymerizable monomer is not particularly limited, but it is preferable to mix the remainder of the first polymerizable monomer when mixing the dispersion with the first solvent.

[0050] When the solution is obtained, the mass ratio of the second polymerizable monomer to at least a portion of the first polymerizable monomer is preferably 0.01 to 100, more preferably 0.05 to 50. When the mass ratio of the first polymerizable monomer to the second polymerizable monomer is 0.01 to 100, the dispersion state of the dispersion liquid obtained by distilling off the second solvent from the solution becomes good.

[0051] Examples of methods for mixing the dispersion liquid and the first solvent include a method of stirring the dispersion liquid and the first solvent, a method of mixing the dispersion liquid and the first solvent using a magnetic stirrer, and a method of mixing the dispersion liquid and the first solvent using a stirrer with stirring blades.

[0052] In the step of mixing the polymerizable composition used in the method for coating an article of this embodiment, a surfactant may be added when the dispersion and the first solvent are mixed.

[0053] The surfactant is not particularly limited as long as it can improve the dispersibility of the solution, and examples thereof include sodium lauryl sulfate, glycerin fatty acid esters, etc. These surfactants may be used alone or in combination of two or more.

[0054] In the mixing step, it is preferable that after the dispersion liquid and the first solvent are mixed, other components such as a photopolymerization initiator, a tertiary amine, and a polymerization inhibitor are added and kneaded.

[0055] Other components may be added to the dispersion liquid and / or the first solvent before mixing, or may be added when mixing the dispersion liquid and the first solvent.

[0056] <First polymerizable monomer> The first polymerizable monomer is insoluble in the first solvent.

[0057] The first polymerizable monomer is preferably a (meth)acrylate, and more preferably a polyfunctional (meth)acrylate having two or more (meth)acryloyloxy groups.

[0058] Examples of the first polymerizable monomer include ethoxylated bisphenol A dimethacrylate, neopentyl glycol dimethacrylate, urethane dimethacrylate, glycerin dimethacrylate, triethylene glycol dimethacrylate, tricyclodecane dimethanol dimethacrylate, etc. These first polymerizable monomers may be used alone or in combination of two or more.

[0059] The content of the first polymerizable monomer used in the method for coating an article of the present embodiment is not particularly limited, but is preferably, for example, 1% by mass or more and 99.9% by mass or less, more preferably 1.5% by mass or more and 79% by mass or less, and even more preferably 2% by mass or more and 49% by mass or less.

[0060] When the content of the first polymerizable monomer in the polymerizable composition is 1% by mass or more, the mechanical strength of the cured product of the polymerizable composition is improved, and when the content is 99.9% by mass or less, the function or performance derived from the second polymerizable monomer of the cured product of the polymerizable composition is improved.

[0061] <Second polymerizable monomer> The second polymerizable monomer is soluble in the first solvent and insoluble in the first polymerizable monomer.

[0062] The second polymerizable monomer is preferably a (meth)acrylate, and more preferably a monofunctional (meth)acrylate having one (meth)acryloyloxy group.

[0063] The second polymerizable monomer preferably has a functional group exhibiting at least one of antibacterial and antiviral properties. Note that a functional group exhibiting at least one of antibacterial and antiviral properties refers to a case where one functional group exhibits both antibacterial and antiviral properties, or a case where one functional group exhibits either an antibacterial group or an antiviral group. Furthermore, a functional group exhibiting antibacterial and antiviral properties also includes a case where the functional group has both an antibacterial functional group and an antiviral functional group.

[0064] The functional group exhibiting at least one of antibacterial and antiviral properties is not particularly limited, but examples thereof include quaternary ammonium bases, etc. The quaternary ammonium bases can function as both antibacterial and antiviral groups.

[0065] Examples of the second polymerizable monomer having a functional group exhibiting at least one of antibacterial and antiviral properties include monofunctional polymerizable monomers such as 2-(methacryloyloxy)ethyltrimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium chloride, (2-(acryloyloxy)ethyl)trimethylammonium chloride, N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride, dimethylaminopropylacrylamide methyl chloride quaternary salt, dimethylaminoethyl acrylate methyl chloride quaternary salt, and dimethylaminoethyl acrylate benzyl chloride quaternary salt; diallyl type quaternary ammonium salts such as diallyldimethylammonium chloride and diallyldiethylammonium chloride; and compounds represented by the following chemical formula:

[0066] [ka] These second polymerizable monomers having a functional group exhibiting at least one of antibacterial and antiviral properties may be used alone or in combination of two or more.

[0067] Examples of the second polymerizable monomer having neither an antibacterial group nor an antiviral group include phenoxyethylene glycol methacrylate and dimethylaminoethyl methacrylate.

[0068] The second polymerizable monomers having neither an antibacterial group nor an antiviral group may be used singly or in combination of two or more kinds.

[0069] The content of the second polymerizable monomer in the polymerizable composition is not particularly limited, but is preferably, for example, 0.01% by mass or more and 99% by mass or less, more preferably 0.02% by mass or more and 79% by mass or less, and even more preferably 0.03% by mass or more and 49% by mass or less.

[0070] When the content of the second polymerizable monomer in the polymerizable composition is 0.01% by mass or more, the function or performance derived from the second polymerizable monomer of the cured product of the polymerizable composition is improved, and when the content is 99% by mass or less, the mechanical strength of the cured product of the polymerizable composition is improved.

[0071] <First Solvent> Examples of the first solvent include water, glycerin, propylene glycol, ethylene glycol, polyethylene glycol having an average molecular weight of 1200 or less, butylene glycol, etc. These first solvents may be used alone or in combination of two or more.

[0072] The content of the first solvent in the polymerizable composition is not particularly limited, but is preferably, for example, 0.01% by mass or more and 40% by mass or less, more preferably 0.02% by mass or more and 35% by mass or less, and even more preferably 0.03% by mass or more and 30% by mass or less.

[0073] When the content of the first solvent in the polymerizable composition of the present embodiment is 0.01% by mass or more, the function or performance derived from the second polymerizable monomer of the cured product of the polymerizable composition is improved, and when the content is 40% by mass or less, the mechanical strength of the cured product of the polymerizable composition is improved.

[0074] <Second Solvent> Examples of the second solvent include organic solvents such as ethanol, acetone, hexane, etc. These second solvents may be used alone or in combination of two or more.

[0075] The content of the second solvent in the solution is not particularly limited, but is preferably, for example, 10% by mass or more and 99% by mass or less. When the content of the second solvent in the solution is 10% by mass or more, the dissolution stability of the polymerizable monomer is improved, and when it is 99% by mass or less, the second solvent can be easily removed by distillation from the solution.

[0076] <Photopolymerization initiator> Examples of the photopolymerization initiator include camphorquinone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzil ketal, diacetyl ketal, benzil dimethyl ketal, benzil diethyl ketal, benzil bis(2-methoxyethyl) ketal, 4,4'-dimethyl(benzyl dimethyl ketal), anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1,2-benzanthraquinone, 1-hydroxyanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, and 1-bromoanthraquinone. Examples of photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, bis(4-dimethylaminophenyl)ketone, and 4,4'-bis(diethylamino)benzophenone. These photopolymerization initiators may be used alone or in combination of two or more.

[0077] <Tertiary amine> The tertiary amine may be either a tertiary aliphatic amine or a tertiary aromatic amine, but is preferably a tertiary aromatic amine, and more preferably an alkyl p-dialkylaminobenzoate.

[0078] Examples of tertiary aliphatic amines include N,N-dimethylaminoethyl methacrylate and triethanolamine.

[0079] Examples of alkyl p-dialkylaminobenzoates include methyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, propyl p-dimethylaminobenzoate, amyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, and propyl p-diethylaminobenzoate.

[0080] Examples of tertiary aromatic amines other than alkyl p-dialkylaminobenzoates include 7-dimethylamino-4-methylcoumarin, N,N-dimethylaniline, N,N-dibenzylaniline, N,N-dimethyl-p-toluidine, N,N-diethyl-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N,2,4,6-pentamethylaniline, N,N,2,4-tetramethylaniline, and N,N-diethyl-2,4,6-trimethylaniline.

[0081] These tertiary amines may be used alone or in combination of two or more.

[0082] <Polymerization inhibitor> Examples of the polymerization inhibitor include dibutylhydroxytoluene (2,6-di-tert-butyl-p-cresol), 6-tert-butyl-2,4-xylenol, etc. These polymerization inhibitors may be used alone or in combination of two or more.

[0083] <Use of polymerizable composition for coating an article> The use of the polymerizable composition according to this embodiment for coating an article is a use of the polymerizable composition for coating an article, in which a solution of a second polymerizable monomer dissolved in a first solvent is dispersed in a first polymerizable monomer, the first polymerizable monomer being a liquid, and the second polymerizable monomer being a solid.

[0084] The mode of use of the polymerizable composition according to this embodiment is not particularly limited, and is, for example, the above-mentioned method for coating an article. Specifically, a method for coating an article including a step of applying a polymerizable composition to an article and a step of polymerizing the polymerizable composition applied to the article is one mode of use of the polymerizable composition according to this embodiment for coating an article.

[0085] The first polymerizable monomer used in the above-described method for coating an article can be used as the first polymerizable monomer when using the polymerizable composition of this embodiment. The second polymerizable monomer used in the above-described method for coating an article can be used as the second polymerizable monomer when using the polymerizable composition of this embodiment. Furthermore, the first solvent used in the above-described method for coating an article can be used as the first solvent when using the polymerizable composition of this embodiment.

[0086] When the polymerizable composition according to this embodiment is used to coat an article, the same effects as those obtained by the above-described method for coating an article can be obtained by using the first polymerizable monomer, the second polymerizable monomer, and the first solvent used in the above-described method for coating an article.

[0087] Specifically, by using a first polymerizable monomer, a second polymerizable monomer, and a first solvent, the second polymerizable monomer can be uniformly localized in the polymerizable composition. Therefore, by using the polymerizable composition of this embodiment, the appearance of the cured product of the polymerizable composition cured on an article can be improved, and the article can be endowed with a function (or performance) derived from the second polymerizable monomer, and the function can be maintained for a long period of time.

[0088] In using the polymerizable composition of this embodiment, the second polymerizable monomer preferably has a functional group exhibiting at least one of antibacterial and antiviral properties. Here, the second polymerizable monomer having a functional group exhibiting at least one of antibacterial and antiviral properties can be a second polymerizable monomer having an antibacterial group and / or an antiviral group used in the above-mentioned method for coating an article.

[0089] Specifically, the antibacterial group and / or antiviral group used in the second polymerizable monomer may be a quaternary ammonium base or the like used in the above-mentioned method for coating an article.

[0090] In the use of the polymerizable composition according to this embodiment, the second polymerizable monomer has an antibacterial group and / or an antiviral group, and when the second polymerizable monomer has an antibacterial group, antibacterial properties can be imparted to a cured product of the polymerizable composition as a function derived from the second polymerizable monomer.Furthermore, when the second polymerizable monomer has an antiviral group, antiviral properties can be imparted to a cured product of the polymerizable composition as a function derived from the second polymerizable monomer.

[0091] <Polymerizable composition> The polymerizable composition of this embodiment is a polymerizable composition used for coating an article. This polymerizable composition comprises a first polymerizable monomer and a solution of a second polymerizable monomer dissolved in a first solvent dispersed therein. Here, the first polymerizable monomer is a liquid, and the second polymerizable monomer is a solid.

[0092] The polymerizable composition according to this embodiment is not particularly limited, but for example, the polymerizable composition used in the above-described method for coating an article can be used as is.

[0093] The first polymerizable monomer used in the polymerizable composition of this embodiment can be the same as the first polymerizable monomer used in the above-mentioned method for coating an article. The content of the first polymerizable monomer in the polymerizable composition can be the same as the content of the first polymerizable monomer used in the above-mentioned method for coating an article.

[0094] The second polymerizable monomer used in the polymerizable composition of this embodiment may be the same as the second polymerizable monomer used in the above-described method for coating an article. The content of the second polymerizable monomer in the polymerizable composition may be the same as the content of the second polymerizable monomer used in the above-described method for coating an article.

[0095] Furthermore, the first solvent used in the polymerizable composition of this embodiment can be the same as the first solvent used in the above-mentioned method for coating an article. The content of the first solvent in the polymerizable composition can be the same as the content of the first solvent used in the above-mentioned method for coating an article.

[0096] The polymerizable composition of this embodiment may contain a second solvent and a surfactant, similar to the polymerizable composition used in the above-mentioned method for coating an article. The content of the second solvent in the polymerizable composition may be the same as the content of the second solvent used in the above-mentioned method for coating an article. Furthermore, the content of the surfactant in the polymerizable composition may be the same as the content of the surfactant used in the above-mentioned method for coating an article.

[0097] The polymerizable composition of this embodiment may contain, as other components, a photopolymerization initiator, a tertiary amine, a polymerization inhibitor, and the like, similar to the polymerizable composition used in the above-described method for coating an article.

[0098] In the polymerizable composition according to this embodiment, the first polymerizable monomer, the second polymerizable monomer, and the first solvent used in the above-described method for coating an article are used, and thereby the same effects as those obtained in the above-described method for coating an article can be obtained.

[0099] Specifically, by using a first polymerizable monomer, a second polymerizable monomer, and a first solvent, the second polymerizable monomer can be uniformly localized in the polymerizable composition. Therefore, the polymerizable composition of this embodiment can improve the appearance of a cured product of the polymerizable composition cured on an article, and can impart a function (or performance) derived from the second polymerizable monomer to the article, while maintaining the function for a long period of time.

[0100] In the polymerizable composition of this embodiment, the second polymerizable monomer preferably has a functional group exhibiting at least one of antibacterial and antiviral properties. Here, the second polymerizable monomer having a functional group exhibiting at least one of antibacterial and antiviral properties may be a second polymerizable monomer having an antibacterial group and / or an antiviral group used in the above-mentioned method for coating an article.

[0101] Specifically, the antibacterial group and / or antiviral group used in the second polymerizable monomer may be a quaternary ammonium base or the like used in the above-mentioned method for coating an article.

[0102] In the polymerizable composition according to this embodiment, the second polymerizable monomer has an antibacterial group and / or an antiviral group, and when the second polymerizable monomer has an antibacterial group, antibacterial properties can be imparted to a cured product of the polymerizable composition as a function derived from the second polymerizable monomer.Furthermore, when the second polymerizable monomer has an antiviral group, antiviral properties can be imparted to a cured product of the polymerizable composition as a function derived from the second polymerizable monomer.

[0103] The use of the polymerizable composition of the present embodiment is not particularly limited as long as it is used to coat an article. For example, the polymerizable composition of the present embodiment is used to impart antibacterial, antiviral, or other properties to an article. Furthermore, the material of the article to which the polymerizable composition of the present embodiment is applied is not particularly limited, and the composition can be applied to any material, such as metal, ceramic, plastic, wood, or fiber. [Example]

[0104] The present embodiment will be described below using examples. In the following, numerical values ​​without units or "%" are based on mass (% by mass) unless otherwise specified.

[0105] Example 1 4 g of 2-(methacryloyloxy)ethyltrimethylammonium chloride (hereinafter referred to as MTMAC) as a second polymerizable monomer and 1 g of distilled water as a first solvent were added to a lidded bottle, and then the mixture was stirred with a stirrer to obtain an aqueous solution of MTMAC.

[0106] 14 g of ethoxylated bisphenol A dimethacrylate (hereinafter referred to as BisMEPP) and 12 g of neopentyl glycol dimethacrylate (hereinafter referred to as NPG) as the first polymerizable monomer were mixed, and then 0.04 g of (±)-camphorquinone, 0.1 g of ethyl p-dimethylaminobenzoate, and 4 g of an aqueous solution of MTMAC were added, and the mixture was stirred at 1000 rpm for 10 minutes using a planetary centrifugal mixer to obtain a coating solution.

[0107] The coating liquid was placed in a spray container and sprayed evenly onto a 5cm x 5cm, 5mm thick acrylic plate, with a wavelength of 365-465nm and an irradiation intensity of 1200mW / cm. 2 The coated test piece was obtained by irradiating the test piece with light from an LED of 1000 kJ / s for 5 minutes to polymerize it.

[0108] FIG. 1 shows the state of Example 1 after the coating liquid is evenly sprayed onto the acrylic plate and before the LED is irradiated.

[0109] <Example 2> 16 g of MTMAC and 4 g of distilled water were added to a bottle with a lid, and then stirred with a stirrer to obtain an aqueous solution of MTMAC.

[0110] After mixing 18 g of BisMEPP and 14 g of NPG, 0.04 g of (±)-camphorquinone, 0.1 g of ethyl p-dimethylaminobenzoate, and 14 g of an aqueous solution of MTMAC were added, and the mixture was stirred at 1000 rpm for 10 minutes using a planetary centrifugal mixer to obtain a coating solution.

[0111] A coated test piece was obtained in the same manner as in Example 1, except that the obtained coating liquid was used.

[0112] Example 3 4 g of MTMAC and 1 g of distilled water were added to a bottle with a lid, and then stirred with a stirrer to obtain an aqueous solution of MTMAC.

[0113] After mixing 15 g of BisMEPP and 14 g of NPG, 0.04 g of (±)-camphorquinone, 0.1 g of ethyl p-dimethylaminobenzoate, and 1 g of an aqueous solution of MTMAC were added, and the mixture was stirred at 1000 rpm for 10 minutes using a planetary centrifugal mixer to obtain a coating solution.

[0114] A coated test piece was obtained in the same manner as in Example 1, except that the obtained coating liquid was used.

[0115] Example 4 After weighing 4 g of MTMAC onto a weighing dish, the dish was left to stand for 3.5 hours at a temperature of 23°C and a relative humidity of 50% to allow the MTMAC to absorb the moisture in the environment, obtaining an aqueous solution of MTMAC. At this time, the mass of the weighing dish had increased by 1 g.

[0116] A coated test piece was obtained in the same manner as in Example 1, except that the obtained aqueous solution of MTMAC was used.

[0117] <Example 5> 5 g of MTMAC and 5 g of glycerin were added to a lidded bottle and stirred with a stirrer to obtain a solution of MTMAC in glycerin.

[0118] A coated test piece was obtained in the same manner as in Example 1, except that a glycerin solution of MTMAC was used instead of the aqueous solution of MTMAC.

[0119] Example 6 5 g of MTMAC and 5 g of propylene glycol were added to a bottle with a lid, and then stirred with a stirrer to obtain a propylene glycol solution of MTMAC.

[0120] After mixing 14 g of BisMEPP and 12 g of NPG, 0.04 g of (±)-camphorquinone, 0.1 g of ethyl p-dimethylaminobenzoate, 0.02 g of sodium dodecyl sulfate (hereinafter referred to as SDS) as a surfactant, and 4 g of a propylene glycol solution of MTMAC were added, and the mixture was stirred at 1000 rpm for 10 minutes using a planetary centrifugal mixer to obtain a coating solution.

[0121] A coated test piece was obtained in the same manner as in Example 1, except that the obtained coating liquid was used.

[0122] Example 7 4 g of (3-acrylamidopropyl)trimethylammonium chloride (hereinafter referred to as AATMAC) as a second polymerizable monomer and 1 g of distilled water were added to a bottle with a lid, and the mixture was stirred with a stirrer to obtain an aqueous solution of AATMAC.

[0123] A coated test piece was obtained in the same manner as in Example 1, except that an aqueous solution of AATMAC was used instead of the aqueous solution of MTMAC.

[0124] Example 8 4 g of (2-(acryloyloxy)ethyl)trimethylammonium chloride (hereinafter referred to as ATMAC) as a second polymerizable monomer and 1 g of distilled water were added to a bottle with a lid, and the mixture was stirred with a stirrer to obtain an aqueous solution of ATMAC.

[0125] A coated test piece was obtained in the same manner as in Example 1, except that an aqueous solution of ATMAC was used instead of the aqueous solution of MTMAC.

[0126] Example 9 4 g of N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride (hereinafter referred to as ABDMAC) as a second polymerizable monomer and 1 g of distilled water were added to a lidded bottle, and the mixture was stirred with a stirrer to obtain an aqueous solution of ABDMAC.

[0127] A coated test piece was obtained in the same manner as in Example 1, except that an aqueous solution of ABDMAC was used instead of the aqueous solution of MTMAC.

[0128] <Comparative Example 1> An acrylic plate measuring 5 cm x 5 cm and 5 mm thick was used for the test without any coating.

[0129] <Comparative Example 2> After mixing 14 g of BisMEPP and 6 g of NPG as the first polymerizable monomer, 0.04 g of (±)-camphorquinone, 0.1 g of ethyl p-dimethylaminobenzoate, 4 g of MTMAC as the second polymerizable monomer, and 6 g of NPG as the first polymerizable monomer were added, and the mixture was kneaded in an agate mortar until it became a uniform paste, and then stirred at 1000 rpm for 10 minutes using a planetary centrifugal mixer to obtain a coating liquid.

[0130] The coating liquid was poured into a spray container and spraying was attempted, but the solid matter clogged the container. Therefore, the coating was evenly applied with a brush to a 5cm x 5cm, 5mm thick acrylic plate, with a wavelength of 365-465nm and an irradiation intensity of 1200mW / cm. 2 The coated test piece was obtained by irradiating the test piece with light from an LED of 1000 kJ / s for 5 minutes to polymerize it.

[0131] FIG. 2 shows the state of Comparative Example 2 after the coating liquid was evenly sprayed onto the acrylic plate and before the LED was irradiated onto it.

[0132] <Comparative Example 3> A 35% ethanol solution of the compound represented by the following chemical formula was placed in a spray container and sprayed evenly onto a 5 cm x 5 cm, 10 mm thick glass plate. The plate was left at room temperature for 30 minutes to evaporate the ethanol, yielding a test piece coated with the compound below.

[0133] [ka]

[0134] Next, the test specimens were evaluated for appearance, antibacterial activity, durability of antibacterial activity, antiviral activity, and durability of antiviral activity.

[0135] <Appearance of test piece> The surface of the photopolymerized test piece, 15 mm in diameter and 1 mm in thickness, was visually inspected for irregularities and evaluated for appearance.

[0136] Fig. 3 shows an optical microscope photograph at 100x magnification of the state of the acrylic plate after the coating liquid was evenly sprayed onto the plate and before the LED irradiation in Example 1. Fig. 4 shows an optical microscope photograph at 100x magnification of the state of the acrylic plate after the coating liquid was evenly sprayed onto the plate and before the LED irradiation in Comparative Example 2. Fig. 5 shows the appearance of the test piece of Example 1 (after curing), and Fig. 6 shows the appearance of the test piece of Comparative Example 2 (after curing).

[0137] The criteria for judging the appearance of the test piece are as follows:

[0138] Excellent: There are no irregularities on the surface of the test piece and the appearance of the test piece is good. Unacceptable: The surface of the test piece is uneven and the appearance of the test piece is poor.

[0139] <Antibacterial> The antibacterial properties of the test specimens were evaluated in accordance with JIS Z 2801:2012 Antibacterial processed products - Antibacterial test methods and antibacterial effects.

[0140] The test bacteria used was S. mutans.

[0141] In addition, as the medium for inoculating the test bacteria onto the test specimens, 1 / 10 BHI medium was used instead of 1 / 500 bouillon medium, in order to ensure that the antibacterial properties would be exerted even under more severe conditions.

[0142] The criteria for judging the antibacterial properties of the test specimens are as follows:

[0143] Excellent: When the antibacterial activity value of the test specimen is 2 or more Not acceptable: If the antibacterial activity value of the test specimen is less than 2

[0144] <Sustained antibacterial properties> The test specimens were immersed in a neutral phosphate buffer solution for one month, and then the antibacterial properties of the test specimens were evaluated in the same manner as above.

[0145] <Antiviral> In accordance with ISO 21702 Antiviral Properties (Non-Textile Products), the antiviral properties of the test specimens were evaluated using the enveloped virus porcine epidemic diarrhea virus as the test virus.

[0146] The criteria for judging the antiviral properties of the test strips are as follows:

[0147] Excellent: When the antiviral activity value of the test specimen is 2 or more Not acceptable: If the antiviral activity value of the test strip is less than 2

[0148] <Sustained antiviral effect> The test specimens were immersed in a neutral phosphate buffer solution for one month, and then the antiviral properties of the test specimens were evaluated in the same manner as above.

[0149] Table 1 shows the evaluation results of the test specimen's appearance, antibacterial activity, antibacterial activity persistence, antiviral activity, and antiviral activity persistence.

[0150] [Table 1]

[0151] Table 1 shows that the coated test pieces of Examples 1 to 9 have high appearance, antibacterial properties, antibacterial property durability, antiviral properties, and antiviral property durability. For example, in Example 1, as shown in Figure 1, in the uncured polymerizable composition 20 fixed to the surface of the acrylic plate (article) 10, it is considered that the solution 40 in which the second polymerizable monomer is dissolved in the first solvent is uniformly dispersed in the first polymerizable monomer 30 (the droplets of the solution 40 in which the second polymerizable monomer is dissolved in the first solvent have small diameters).

[0152] The test piece of Comparative Example 1 was not coated and therefore did not have antibacterial or antiviral properties.

[0153] The test piece of Comparative Example 2 was produced without using the first solvent, and therefore had poor appearance and poor durability of antibacterial and antiviral properties. For example, in Comparative Example 2, as shown in Figure 2, it is thought that the second polymerizable monomer 50 is not uniformly dispersed in the first polymerizable monomer 30 (the particle size of the second polymerizable monomer 50 is coarse) in the uncured polymerizable composition 20 fixed to the acrylic plate (article) 10 (Figure 2).

[0154] It is thought that the test piece of Comparative Example 3 temporarily bonded to the glass surface due to the silane treatment and exhibited temporary antibacterial and antiviral properties, but because the silane treatment is reversible due to hydrolysis, the antibacterial and antiviral properties did not last.

[0155] Although the embodiments of the present invention have been described above, the present invention is not limited to the specific embodiments, and various modifications and changes are possible within the scope of the invention described in the claims. [Explanation of symbols]

[0156] 10 Acrylic board (item) 20 Polymerizable composition 30 First polymerizable monomer 40 Solution in which the second polymerizable monomer is dissolved in the first solvent 50 Second polymerizable monomer

Claims

1. a solution of a second polymerizable monomer dissolved in a first solvent is dispersed in the first polymerizable monomer; the first polymerizable monomer is a liquid polyfunctional methacrylate having two or more methacryloyloxy groups, the second polymerizable monomer is one selected from 2-(methacryloyloxy)ethyltrimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium chloride, (2-(acryloyloxy)ethyl)trimethylammonium chloride, and N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride, applying it to an article; and polymerizing the polymerizable composition applied to the article; Methods for coating articles.

2. The polymerizing step includes a step of irradiating the article to which the polymerizable composition is applied with light.

10. The method of claim 1.

3. The application is by spraying, spraying, or painting.

3. A method for coating an article according to claim 1 or 2.

4. a solution of a second polymerizable monomer dissolved in a first solvent is dispersed in the first polymerizable monomer; the first polymerizable monomer is a liquid polyfunctional methacrylate having two or more methacryloyloxy groups, the second polymerizable monomer is one selected from 2-(methacryloyloxy)ethyltrimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium chloride, (2-(acryloyloxy)ethyl)trimethylammonium chloride, and N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride; Use for coating articles.

5. 1. A polymerizable composition for use in coating an article, comprising: a solution of a second polymerizable monomer dissolved in a first solvent is dispersed in the first polymerizable monomer; the first polymerizable monomer is a liquid polyfunctional methacrylate having two or more methacryloyloxy groups, the second polymerizable monomer is one selected from 2-(methacryloyloxy)ethyltrimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium chloride, (2-(acryloyloxy)ethyl)trimethylammonium chloride, and N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride; Polymerizable composition.

6. the second polymerizable monomer has a functional group that exhibits at least one of antibacterial and antiviral properties; The polymerizable composition according to claim 5 .

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