Coatings and articles

Abstract

To provide a coating agent whose durability in an actual use environment is enhanced.SOLUTION: A coating agent includes: quaternary ammonium salt having an alkoxysilyl group; silicate oligomer, and a resin having an alkoxysilyl group.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to coatings and articles. [Background technology]

[0002] The technology of Patent Document 1 ensures antibacterial and antiviral properties by incorporating octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride as an antibacterial and antiviral agent. Patent Document 1 also adds 3-methacryloyloxypropyltrimethoxysilane to eliminate poor adhesion to the target resin surface due to the absence of hydroxyl groups that react with the methoxysilyl groups of octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, ensuring adhesion of the antibacterial and antiviral agent to the target surface. This technology is believed to improve the adhesion of the coating film and enhance abrasion resistance through the interaction between 3-methacryloyloxypropyltrimethoxysilane and the target surface, as well as the interaction between 3-methacryloyloxypropyltrimethoxysilane and the antibacterial and antiviral agent in the coating. Another known technology involves adding trimesic acid (a polycarboxylic acid) to improve water resistance and inhibit leaching of the antibacterial and antiviral agent through ionic bonding between the carboxylic acid of trimesic acid and the antibacterial and antiviral agent in the coating. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-71893 Summary of the Invention [Problem to be solved by the invention]

[0004] These conventional technologies are expected to improve water resistance and abrasion resistance to a certain extent, but because the interactions and ionic bonds are unstable and weak, the active ingredients (antibacterial and antiviral agents) can leach out or become damaged, and durability in actual usage environments is not necessarily sufficient.

[0005] In view of the above circumstances, the present disclosure aims to improve durability in an actual usage environment. [Means for solving the problem]

[0006] a quaternary ammonium salt having an alkoxysilyl group; a silicate oligomer; A coating agent comprising: a resin containing an alkoxysilyl group. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a cross-sectional view of an article having a coating according to one embodiment. [Figure 2] FIG. 2 is a conceptual diagram illustrating an article according to one embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present disclosure will be described in detail below. Note that when a numerical range is described using "to", it includes both the lower limit and the upper limit unless otherwise specified. For example, the description "10 to 20" includes both the lower limit "10" and the upper limit "20". In other words, "10 to 20" has the same meaning as "10 or more and 20 or less".

[0009] 1. Coating agent The coating agent contains a quaternary ammonium salt having an alkoxysilyl group, a silicate oligomer, and a resin containing an alkoxysilyl group.

[0010] (1) Quaternary ammonium salts containing alkoxysilyl groups The quaternary ammonium salt having an alkoxysilyl group is not particularly limited. The quaternary ammonium salt is preferably a compound represented by the following general formula (1). Since the compound represented by general formula (1) has antibacterial and antiviral properties, the coating agent serves as an antibacterial and antiviral coating agent.

[0011] [ka] (In formula (1), n ​​represents an integer of 1 to 4, m represents an integer of 1 to 10, p represents an integer of 10 to 22, and q represents an integer of 1 to 3.)

[0012] In the present disclosure, among the compounds represented by (1) above, the following compound is preferred. Compound (2) is compound (1) in which n=1, m=3, p=18, and q=1, and is dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride. This compound is preferred in terms of its antibacterial and antiviral properties and safety.

[0013] [ka]

[0014] (2) Silicate oligomer The silicate oligomer is not particularly limited. A suitable example of the silicate oligomer is a partially hydrolyzed oligomer of tetraalkoxysilane. Examples of tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropyloxysilane, and tetrabutoxysilane. A suitable example of the silicate oligomer is a partially hydrolyzed oligomer of tetramethoxysilane. The silicate oligomer is represented, for example, by the following general formula (3). Note that m in the following general formula (3) can be adjusted, for example, by controlling the hydrolysis rate.

[0015] [ka] (In formula (3), m represents an integer of 2 to 100.)

[0016] The silicate oligomer can be obtained by hydrolyzing a tetraalkoxysilane such as tetramethoxysilane, tetraethoxysilane, tetrapropyloxysilane, or tetrabutoxysilane, or tetraphenoxysilane. m can be adjusted by controlling the hydrolysis rate.

[0017] (3) Resin containing alkoxysilyl groups Examples of resins containing alkoxysilyl groups include alkoxysilyl group-containing acrylic resins, alkoxysilyl group-containing polyesters, alkoxysilyl group-containing epoxy resins, alkoxysilyl group-containing alkyd resins, alkoxysilyl group-containing fluororesins, alkoxysilyl group-containing polyurethanes, alkoxysilyl group-containing phenolic resins, alkoxysilyl group-containing melamine resins, etc. Examples of alkoxysilyl groups include trialkoxysilyl groups, dimethoxysilyl groups, monoalkoxysilyl groups, etc. The resin containing an alkoxysilyl group is preferably an alkoxysilyl group-containing acrylic resin. The alkoxysilyl group-containing acrylic resin has an alkoxysilyl group bonded to an acrylic main chain as a side chain. The alkoxysilyl group-containing acrylic resin is a siloxane-crosslinked silicon-modified acrylic resin (silane-modified acrylic polymer). The weight-average molecular weight of the resin containing an alkoxysilyl group is not particularly limited. From the viewpoint of providing a coating agent with a viscosity suitable for coating, the weight-average molecular weight is, for example, preferably 1,000 or more and 50,000 or less, and more preferably 10,000 or more and 25,000 or less.

[0018] (4) Solvent The coating agent preferably contains a solvent to achieve a viscosity suitable for coating. Suitable examples of the solvent include alcohols such as methanol, ethanol, 1-propanol (n-propyl alcohol), 2-propanol, 1-butanol, 2-butanol, 1-pentanol (pentanol), 2-methyl-2-butanol, cyclohexanol, isopropyl alcohol (IPA), and propylene glycol monomethyl ether, and esters such as propylene glycol monomethyl ether acetate. Other solvents can also be used. Examples of other solvents include water, linear hydrocarbon compounds such as hexane, heptane, octane, decane, and paraffin; aromatic hydrocarbon compounds such as benzene, toluene, xylene, ethylbenzene, cumene, cymene, and styrene; halogenated hydrocarbon compounds such as chloroform, carbon tetrachloride, trichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, dichlorobenzene, trichlorobenzene, ethyl bromide, propyl bromide, bromobenzene, dibromobenzene, and fluorobenzene; phenolic compounds such as phenol, cresol, and xylenol; ether compounds such as diethyl ether, dipropyl ether, dibutyl ether, ethyl vinyl ether, anisole, phenetole, dibenzyl ether, dioxane, trioxane, furan, cineole, diethylene glycol diethyl ether, and acetal; and ketone compounds such as acetone, methyl ethyl ketone, 2-hexanone, and cyclohexanone. The solvent may be used alone or in combination of two or more. The solvent for the coating agent can be, for example, a mixed solvent containing alcohol and water. From the viewpoint of dissolving each component well and achieving a viscosity suitable for coating, the solvent for the coating agent preferably contains 1-pentanol, 1-propanol, propylene glycol monomethyl ether, and water. When 1-pentanol, 1-propanol, and propylene glycol monomethyl ether are used as the solvent, the amount of 1-pentanol is preferably 1 part by mass or more and 10 parts by mass or less, the amount of 1-propanol is preferably 10 parts by mass or more and 30 parts by mass or less, and the amount of propylene glycol monomethyl ether is preferably 40 parts by mass or more and 60 parts by mass or less, based on 100 parts by mass of the entire coating agent.

[0019] (5) Mixing ratio The amount of the quaternary ammonium salt having an alkoxysilyl group is not particularly limited. For example, the amount of the quaternary ammonium salt, etc., is preferably 1.0 parts by mass or more and 8.3 parts by mass or less, more preferably 2.7 parts by mass or more and 4.1 parts by mass or less, and particularly preferably 2.9 parts by mass or more and 3.2 parts by mass or less, based on 100 parts by mass of the entire coating agent, from the viewpoint of exhibiting effective antibacterial and antiviral properties and from the viewpoint of safety. The amount of silicate oligomer to be blended is not particularly limited. For example, from the viewpoint of improving durability in an actual use environment, the amount of silicate oligomer to be blended is preferably 1.0 parts by mass or more and 3.0 parts by mass or less, more preferably 1.5 parts by mass or more and 2.5 parts by mass or less, and particularly preferably 1.8 parts by mass or more and 2.2 parts by mass or less, relative to 100 parts by mass of the entire coating agent. The blending amount of the resin containing an alkoxysilyl group is not particularly limited. For example, from the viewpoint of improving durability in an actual use environment, the blending amount of the resin containing an alkoxysilyl group is preferably 3.0 parts by mass or more and 10.0 parts by mass or less, more preferably 3.5 parts by mass or more and 5.5 parts by mass or less, and particularly preferably 4.1 parts by mass or more and 4.5 parts by mass or less, when the total amount of the coating agent is 100 parts by mass.

[0020] (6) Catalyst The coating agent may contain an acid, a non-tin catalyst, or a tin catalyst. When a catalyst is used, the coating agent is preferably composed of a catalyst-free liquid A and a catalyst-containing liquid B. By mixing liquid A and liquid B to form a coating agent during coating, a strong coating film (coating layer) can be rapidly formed while suppressing the curing reaction before use. When liquid A and liquid B are used, liquid A preferably contains a quaternary ammonium salt having an alkoxysilyl group, a silicate oligomer, a resin containing an alkoxysilyl group, and a solvent other than water. Furthermore, liquid B preferably contains a catalyst, water, and a solvent other than water. When liquid A and liquid B are used, liquid A and liquid B are mixed when used on-site, etc. In other words, in this case, the catalyst is added later. In addition, the "100 parts by mass" of the "total coating agent" stated in the above-mentioned "(4) Solvent" and "(5) Blending ratio" columns means that when liquid A and liquid B are used, the total of liquid A and liquid B is 100 parts by mass.

[0021] The acid used as a catalyst is one or more selected from inorganic acids and organic acids. The inorganic acid is not particularly limited. Examples of inorganic acids include divalent acids such as hydrochloric acid, sulfuric acid, nitric acid, chromic acid, carbonic acid, molybdic acid, hydrogen sulfide, sulfurous acid, thiosulfuric acid, selenic acid, telluric acid, tellurous acid, tungstic acid, and phosphonic acid; trivalent acids such as phosphoric acid, phosphomolybdic acid, phosphotungstic acid, and vanadic acid; silicomolybdic acid, silicotungstic acid, pyrophosphoric acid, and tripolyphosphoric acid. When an inorganic acid is used, hydrochloric acid is preferred.

[0022] The organic acid is not particularly limited. Examples of the organic acid include trimesic acid (1,3,5 benzenetricarboxylic acid), citric acid, formic acid, acetic acid, glyoxylic acid, pyruvic acid, lactic acid, mandelic acid, vinylacetic acid, 3-hydroxybutyric acid, oxalic acid, maleic acid, malonic acid, methylmalonic acid, dimethylmalonic acid, phthalic acid, tartaric acid, fumaric acid, malic acid, succinic acid, glutaric acid, oxaloacetic acid, hemimellitic acid, trimellitic acid, mellitic acid, isocitric acid, aconitic acid, oxalosuccinic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, caproic acid, octanoic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, acrylic acid, propiolic acid, methacrylic acid, crotonic acid, isocrotonic acid, and benzoic acid. Examples of organic acids include cinnamic acid, isophthalic acid, terephthalic acid, furancarboxylic acid, thiophenecarboxylic acid, nicotinic acid, isonicotinic acid, glycolic acid, salicylic acid, creosote acid, vanillic acid, syringic acid, pyrocatechuic acid, resorcylic acid, gentisic acid, procatechuic acid, orsellinic acid, gallic acid, tartronic acid, leucinic acid, mevalonic acid, pantoic acid, ricinoleic acid, ricineraidic acid, cerebronic acid, citramalic acid, quinic acid, shikimic acid, mandelic acid, benzilic acid, atrolactic acid, mellotic acid, phloretic acid, coumaric acid, umbellic acid, caffeic acid, ferulic acid, isoferulic acid, and sinapic acid, as well as maleic anhydride, propionic anhydride, succinic anhydride, and phthalic anhydride.

[0023] The amount of catalyst (acid, etc.) is not particularly limited. For example, when the total amount of the coating agent (when a catalyst is used, this means the coating agent after the catalyst is mixed, and when liquid A and liquid B are used, this means the mixture of liquid A and liquid B) is taken as 100 parts by mass, the amount of catalyst is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.1 parts by mass or more and 5 parts by mass or less. The catalyst-containing solution B is an aqueous solution of hydrochloric acid (HCl) with a concentration of 1% by mass to 5% by mass, from the viewpoint of forming a strong coating film with a three-dimensional cross-linked structure by using a resin containing an alkoxysilyl group and a silicate oligomer. aq ) is preferably used.

[0024] 2. Applying and curing the coating agent The method for applying the coating agent to the substrate is not particularly limited and can be selected depending on the properties, viscosity, application amount, etc. of the coating agent. For example, the method can be selected from known methods such as application using a cloth or brush impregnated with the coating agent, spray application, dip application, roller application, and curtain flow coater application. The substrate may be treated with a primer before application of the coating agent.

[0025] The substrate used in the coating agent of the present disclosure is not particularly limited. Examples of the substrate include a resin substrate and a metal substrate. The resin substrate and the metal substrate may have a plating layer. Examples of resins that constitute the resin substrate include olefin-based resins such as polypropylene (PP), low-density polyethylene (LDPE), and high-density polyethylene (HDPE), styrene-based resins such as ABS resin, styrene-acrylonitrile copolymer (SAN resin), and acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS), polyacetal (POM) resins such as polyoxymethylene homopolymer, vinyl chloride-based resins such as polyvinyl chloride and polyvinylidene chloride, vinyl chloride-based copolymer resins such as ethylene-vinyl chloride-vinyl acetate copolymer and ethylene-vinyl chloride copolymer, acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate-based resins such as polycarbonate (PC) and modified polycarbonate, polystyrene, high-impact polystyrene, and medium Examples of suitable resins include rubber-reinforced styrene resins such as impact polystyrene, polyester resins such as polyethylene terephthalate (PETP, PET) and polybutylene terephthalate (PBTP, PBT), polyamide resins such as polyamide 66, polyamide 6, and polyamide 46, polyoxymethylene copolymers, other engineering resins, super engineering resins, thermoplastic polyimide (TPI), polyether ketone (PEK), polyether ether ketone (PEEK), polyphenylene sulfide (PSU), cellulose derivatives such as cellulose acetate (CA), cellulose acetate butyrate (CAB), and ethyl cellulose (EC), and thermosetting resins such as unsaturated polyesters, acrylics, vinyl esters, urethanes, and epoxy resins.

[0026] The article having a coating film formed using the coating agent of the present disclosure is not particularly limited. A cross-sectional view of an article having a coating film is shown in Figure 1. Reference numeral 1 indicates the article, reference numeral 3 indicates the substrate, and reference numeral 5 indicates the coating film. Note that another layer (such as a primer layer) may be present between the substrate and the coating film. The coating film formed using the coating agent of the present disclosure is an antibacterial and antiviral coating with high water resistance and abrasion resistance, and is therefore suitable for use on items that are frequently touched by hands in restrooms or kitchen sinks. From this perspective, suitable examples of such items include toilet seats, toilet lids, flush levers, toilet paper dispensers, remote controls, faucet handles, and door handles. The coating film formed using the coating agent of the present disclosure has a high designability and is therefore suitable for use on household appliances that are frequently touched, such as light switches, entrance door handles, kitchen countertops, cabinet handles, and window sashes. Furthermore, the coating agent of the present disclosure can also be applied to entrance steps, flooring, entrance tiles, floor tiles, etc. Fig. 2 shows a toilet seat 7 as an example of an article.

[0027] 3. Mechanism of action and effects of coating agents The coating agent disclosed herein contains silicate oligomer. Therefore, as shown in the estimated diagram below, it is possible to covalently immobilize silane-modified quaternary ammonium (quaternary ammonium salt with alkoxysilyl groups), an antibacterial and antiviral agent. Furthermore, the alkoxysilyl-containing resin and silicate oligomer are thought to create a strong coating film with a three-dimensional crosslinked structure, increase the bond between the coating film and the substrate, and strengthen adhesion. It is presumed that in the coating, the quaternary ammonium salt and the silicate oligomer are bonded by a siloxane bond (-Si-O-Si-), and that in the coating, the silicate oligomer and the resin containing an alkoxysilyl group are bonded by a siloxane bond (-Si-O-Si-). It should be noted that the above-mentioned mechanism of action is merely a presumed mechanism of action, and even if the effect of the present disclosure is achieved by another mechanism other than this mechanism of action, the scope of the rights of the present disclosure will not be interpreted in a limited manner based on the above-mentioned mechanism of action.

[0028] The coating agent disclosed herein can realize an antibacterial and antiviral coating with high water resistance and abrasion resistance. Because of its high durability, it is also alcohol-resistant, making it suitable for use with alcohol wipes, which are commonly used as a COVID-19 countermeasure. The coating film formed by the coating agent of the present disclosure is less likely to become matte (less likely to become matte) and has high designability. In addition, the coating film formed by the coating agent of the present disclosure has high transparency and high designability.

[0029] [ka] [Example]

[0030] The present invention will be described in detail below with reference to examples.

[0031] <<Experiment A>> The following experiments were carried out. Experimental Examples 1, 2, 3, and 4 all correspond to examples of the present application. 1. Preparation of evaluation samples for experimental examples (1) Preparation of coating agent (1.1) Preparation of Solutions A and B To prepare the coating agent, liquids A and B with the compositions shown below were prepared. The chemicals other than the solvent in Table 1 are as follows. Liquid A functions to impart antibacterial and antiviral properties to the coating film, and liquid B functions as a curing accelerator. AEM5700 (antiviral agent, active ingredient 45% by mass): silane-modified quaternary ammonium salt (dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride solution) 8SQ-1175 (silicone-modified acrylic resin, active ingredient 50% by weight): 8SQ-1175 silicone-modified acrylic resin manufactured by Taisei Fine Chemical Co., Ltd. MS56 (silicate oligomer, active ingredient 100% by mass): "MKC Silicate MS56" manufactured by Mitsubishi Chemical Corporation

[0032] [Table 1]

[0033] [Table 2]

[0034] (1.2) Preparation of coating agent (mixing of liquid A and liquid B) Liquid A and liquid B were mixed so that the active ingredient of the antiviral agent, the active ingredient (solid content) of the silicon-modified acrylic resin, the active ingredient (solid content) of the silicate oligomer, the solvent, and the hydrochloric acid were in the following blending ratio (by mass):

[0035] [Table 3]

[0036] (2) Preparation of evaluation samples Various evaluation samples (hereinafter also referred to as coated products) were prepared for each experimental example shown in Table 4. Details of the substrates are as follows. ABS: ABS resin base material SUS430: SUS430 base material Cr plating: A base material in which the surface of a brass base is plated with Ni and then plated with Cr. Acrylic urethane: A base material made of PP (polypropylene) coated with acrylic urethane paint.

[0037] [Table 4]

[0038] (2.1) Degreasing of the substrate The surface of each substrate (surface to be coated) was degreased. Alcohol (IPA (isopropyl alcohol)) was used for degreasing. Specifically, the surface of the substrate was wiped with a cloth soaked in alcohol.

[0039] (2.2) Primer application In Experimental Examples 1 and 4, a primer was applied to the surface of the substrate and dried. The primer used was Auroren AE301 (special modified polyolefin resin) manufactured by Nippon Paper Industries Co., Ltd. In Experimental Examples 2 and 3, no primer was applied.

[0040] (2.3) Coating agent application (top coat application) In Experimental Examples 1 and 4, the coating agent prepared in section (1.2) was applied to the surface of the substrate coated with primer, and then the substrate was dried to prepare an evaluation sample. In Experimental Examples 2 and 3, the coating agent prepared in section (1.2) was applied to the surface of the substrate, and then the substrate was dried to prepare an evaluation sample.

[0041] 2. Evaluation Method The evaluation samples were subjected to the various evaluations listed in Table 4. (1) Appearance evaluation The surface of the coating film was visually inspected and the appearance was evaluated according to the following criteria. A: The coating film is colorless and transparent with no repellency, whitening or cracking, and has a good appearance. The coating film has a glossy finish. A': The coating film is colorless and transparent with no repellency, whitening or cracking, and has a good appearance. The coating film is matte. B: The coating film has either peeling, whitening, or cracking, and the appearance is poor.

[0042] (2) Adhesion of the coating to the substrate (cross-cut test) According to JIS K 5600-5-6, the coating film was cross-cut into 2 mm x 2 mm grids (10 x 10 = 100 squares), adhesive tape was applied to the grids, and the grids that remained unpeeled were counted visually and evaluated according to the following criteria: 100 / 100 indicates that 0% of the coating film had peeled off; for example, 90 / 100 indicates that 10% of the coating film had peeled off; and 50 / 100 indicates that 50% of the coating film had peeled off.

[0043] (3) Evaluation of antiviral activity The antiviral activity value was measured using the plaque assay method of ISO 21702:2019. The test virus used was influenza A virus (H3N2) (A / Hong Kong / 8 / 68; TC adapted ATCCVR-1679), and the virus infectivity value was measured after 24 hours. The difference in virus infectivity value with the blank film was taken as the antiviral activity value. An antiviral activity value of 2.0 or higher indicates good antiviral properties. The test outline is shown below. <Test Overview> Test virus: Influenza A virus (H3N2) (A / Hong Kong / 8 / 68; TC adapted ATCCVR-1679) Host cells: MDCK cells (canine kidney-derived cells) Washout solution: SCDLP medium ·Leaving conditions: Leaving temperature 25℃ Leave on for 24 hours Sample size: 5cm x 5cm Adhesive film: PET film (4cm x 4cm) Test virus suspension inoculation volume: 0.4 mL Cleaning of test specimen: The entire surface of the test specimen was lightly wiped with local gauze absorbed with ethanol of 99% or higher purity, and then thoroughly dried.

[0044] The antiviral properties were evaluated by measuring the antiviral activity value after carrying out the durability test described in Table 4 on the evaluation sample. The antiviral activity value before the durability test (initial period) was also measured. The "initial" in Table 4 refers to the evaluation of the painted product in its initial state. In other words, the painted product was evaluated as it was after painting. The "after water resistance test" in Table 4 was evaluated for the coated product after it had been immersed in water at room temperature (22°C) for 16 hours. The "After alcohol resistance test" in Table 4 was evaluated for the coated product after it was immersed in isopropyl alcohol for 10 minutes. For the "after abrasion resistance test" shown in Table 4, a cloth was used as the contactor to apply a pressure of 245 Pa (1 kgf load per 5 cm x 5 cm area) to the surface of the coating film of the coated product, and the test piece was rubbed 1,500 times with a sliding abrasion tester. After this, the above-mentioned antiviral test was conducted and the coated product after abrasion was evaluated.

[0045] 3.Results (1) Appearance The evaluation results are also shown in Table 4. The appearance was good in all of Experimental Examples 1, 2, 3, and 4. Experimental Examples 1, 2, 3, and 4 were not yellowish and had a glossy appearance.

[0046] (2) Adhesion of the coating to the substrate In Experimental Examples 1, 2, 3, and 4, the results of the cross-cut test were 100 / 100, and the adhesion of the coating film to the substrate was very good.

[0047] (3) Antiviral In Experimental Examples 1, 2, 3, and 4, the initial antiviral activity value was greater than 3.5, and the antiviral activity was good. In Experimental Examples 1, 2, 3, and 4, the antiviral activity value was 2.0 or higher even after various durability tests (after water resistance test, after alcohol resistance test, after abrasion resistance test), and the antiviral properties were maintained satisfactorily. This is presumably because the antibacterial and antiviral agent (quaternary ammonium salt) was firmly fixed by a covalent bond.

[0048] <<Experiment B>> The following experiments were carried out. Experimental Example 5 corresponds to an example of the present application, and Experimental Example 6 corresponds to a comparative example of the present application. 1. Preparation of evaluation samples for experimental examples The evaluation sample of Experimental Example 5 was prepared in the same manner as Experimental Example 1 of Experiment A, except that a base material of PP (polypropylene) was used. The evaluation sample of Experimental Example 6 was prepared using a PP (polypropylene) substrate in the same manner as in Example 1 of JP 2015-067657 A (Patent No. 6141162). In the evaluation sample of Experimental Example 6, a coating film was formed in which a polycarboxylic acid and a quaternary ammonium salt were ionic bonded.

[0049] [Table 5]

[0050] 2. Evaluation Method The evaluation samples were subjected to the various evaluations listed in Table 5. (1) Appearance evaluation Evaluation was carried out in the same manner as in Experiment A.

[0051] (2) Evaluation of antiviral activity Evaluation was carried out in the same manner as in Experiment A.

[0052] (3) Antibacterial evaluation Antibacterial properties were evaluated in accordance with the evaluation method described in JIS Z 2801:2012, using Escherichia coli and changing the contact time with the bacterial solution to 4 hours. The antibacterial activity value was measured after the test. If the antibacterial activity value was 2.0 or higher, the antibacterial properties were good. The "initial" in Table 5 refers to the evaluation of the painted product in its initial state. In other words, the painted product was evaluated as it was after painting. The "after water resistance test" in Table 5 was evaluated for the coated product after it had been immersed in water at room temperature (22°C) for 16 hours. The "After alcohol resistance test" in Table 5 was evaluated for the coated product after it had been immersed in ethanol for 10 minutes. For the "after abrasion resistance test" shown in Table 5, a cloth was used as the contactor to apply a pressure of 245 Pa (1 kgf load per 5 cm x 5 cm area) to the surface of the coating film of the coated product, and the test piece was rubbed 15,000 times using a sliding abrasion tester. After this, the above-mentioned antibacterial test was conducted, and the coated product after abrasion was evaluated.

[0053] 3.Results (1) Appearance The evaluation results are also shown in Table 5. In Experimental Example 5, the coating film had a glossy appearance and was good in appearance, while in Experimental Example 6, the coating film had a matte finish.

[0054] (2) Antiviral In Experimental Examples 5 and 6, the initial antiviral activity value was 3.5 or more, and the antiviral activity was good.

[0055] (3) Antibacterial properties In Experimental Example 5, the antibacterial activity value was 2.0 or higher even after various durability tests (after water resistance test, after alcohol resistance test, after abrasion resistance test), and the antibacterial properties were well maintained. This is presumably because the antibacterial and antiviral agent (quaternary ammonium salt) was fixed by a covalent bond. In Experimental Example 6, the antibacterial performance significantly decreased after the alcohol resistance test and the abrasion resistance test compared to the initial performance. This is thought to be because the antibacterial and antiviral agent (quaternary ammonium salt) was weakly fixed by ionic bonds in Experimental Example 6. The decrease in antibacterial performance after the durability test is presumed to be due to the elution or loss of the antibacterial and antiviral agent. Therefore, it is presumed that the antiviral performance of Experimental Example 6 also decreased after the alcohol resistance test and the abrasion resistance test. [Explanation of symbols]

[0056] 1...article, 3...substrate, 5...coating film, 7...toilet seat

Claims

1. a quaternary ammonium salt having an alkoxysilyl group; a silicate oligomer; A coating agent comprising: a resin containing an alkoxysilyl group.

2. The coating agent according to claim 1 , wherein the quaternary ammonium salt is represented by the following formula (1): 【Chemical 1】 (In formula (1), n ​​represents an integer of 1 to 4, m represents an integer of 1 to 10, p represents an integer of 10 to 22, and q represents an integer of 1 to 3.)

3. 2. The coating agent according to claim 1, wherein the quaternary ammonium salt is present in an amount of 1.0 part by mass or more and 8.3 parts by mass or less, based on 100 parts by mass of the entire coating agent.

4. 2. The coating agent according to claim 1, wherein the quaternary ammonium salt is present in an amount of 1.0 part by mass or more and 8.3 parts by mass or less, and the silicate oligomer is present in an amount of 1.0 part by mass or more and 3.0 parts by mass or less, when the entire coating agent is taken as 100 parts by mass.

5. 2. The coating agent according to claim 1, wherein the quaternary ammonium salt is present in an amount of 1.0 part by mass or more and 8.3 parts by mass or less, the silicate oligomer is present in an amount of 1.0 part by mass or more and 3.0 parts by mass or less, and the resin containing an alkoxysilyl group is present in an amount of 3.0 parts by mass or more and 10.0 parts by mass or less, when the entire coating agent is taken as 100 parts by mass.

6. The coating agent according to claim 1 , further comprising a catalyst.

7. 2. The coating agent according to claim 1, further comprising a catalyst, wherein the quaternary ammonium salt is present in an amount of 1.0 part by mass or more and 8.3 parts by mass or less, and the catalyst is present in an amount of 0.01 part by mass or more and 10 parts by mass or less, when the entire coating agent is taken as 100 parts by mass.

8. 2. The coating agent according to claim 1, further comprising a catalyst, wherein, when the entire coating agent is taken as 100 parts by mass, the quaternary ammonium salt is present in an amount of 1.0 part by mass or more and 8.3 parts by mass or less, the silicate oligomer is present in an amount of 1.0 part by mass or more and 3.0 parts by mass or less, and the catalyst is present in an amount of 0.01 part by mass or more and 10 parts by mass or less.

9. 2. The coating agent according to claim 1, further comprising a catalyst, wherein, when the entire coating agent is taken as 100 parts by mass, the quaternary ammonium salt is present in an amount of 1.0 part by mass to 8.3 parts by mass, the silicate oligomer is present in an amount of 1.0 part by mass to 3.0 parts by mass, the resin containing an alkoxysilyl group is present in an amount of 3.0 parts by mass to 10.0 parts by mass, and the catalyst is present in an amount of 0.01 parts by mass to 10 parts by mass.

10. An article having a coating film formed using the coating agent according to any one of claims 1 to 9.

11. The article according to claim 10, which is selected from the group consisting of a toilet seat, a toilet lid, a flush lever, a toilet paper dispenser, a remote control, a faucet handle, a door handle, a light switch, a front door handle, a kitchen countertop, a cabinet handle, a window sash, a front door sill, flooring, a front door tile, and a floor tile.

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