Sanitary equipment and method for manufacturing sanitary equipment

Abstract

Provided is a means for imparting hydrophilicity to a surface of a sanitary facility by a means that is different from hydrophilic particles. Provided is a sanitary facility having a hydrophilized organic surface, in which the hydrophilized organic surface has at least an organic cationic group and the zeta potential of the hydrophilized organic surface at pH 7 is larger than -40 mV.

Description

[Technical Field]

[0001] The present invention relates to sanitary equipment having a hydrophilically treated organic surface. [Background technology]

[0002] BACKGROUND ART Conventionally, various surface treatments have been carried out on sanitary equipment such as toilets, washbasins, and bathtubs to make the surfaces easier to clean.

[0003] For example, International Publication No. WO 00 / 53689 (Patent Document 1) describes a hydrophilic member comprising at least a substrate and a hydrophilic coating formed on the substrate as an outermost layer. The hydrophilic coating contains at least hydrophilic metal oxide particles and a hydrophilic inorganic amorphous material. The presence of this hydrophilic coating as the outermost layer forms a unique uneven structure on the surface of the hydrophilic member. Patent Document 1 also describes that this configuration provides the technical effect of preventing water droplets and dirt from adhering while maintaining film hardness and durability.

[0004] Japanese Patent Laid-Open Publication No. 2002-80830 (Patent Document 2) also describes a hydrophilic member comprising at least a substrate and a hydrophilic coating formed as an outermost layer on the substrate. The hydrophilic coating contains at least alumina particles and amorphous silica as coating-forming elements. The alumina particles are partially exposed from the surface, and the hydrophilic coating has a surface roughness of 5 to 35 nm in any 5 μm square measured by atomic force microscope. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. WO00 / 53689 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-80830 Summary of the Invention [Problem to be solved by the invention]

[0006] Both Patent Documents 1 and 2 feature a hydrophilic coating of a hydrophilic member that contains hydrophilic metal oxide particles or alumina particles, thereby forming a specific uneven shape on the surface of the hydrophilic coating, thereby exhibiting a high hydrophilic effect. However, when using such particles to achieve a hydrophilic effect, problems can arise, such as the particles not being uniformly dispersed. To uniformly disperse the particles in the composition, it is necessary to control and adjust the viscosity of the composition, for example. If the particles aggregate rather than being uniformly dispersed, the uneven shape on the surface may deviate from the desired range, potentially preventing the desired surface performance. Furthermore, if the uneven shape of the surface is caused by particulate matter, the particulate matter held on the surface may fall off over time or due to external physical forces.

[0007] The present invention is intended to solve the above-mentioned problems of the prior art, and its object is to provide a means for imparting hydrophilicity to a surface by means other than hydrophilic particles. [Means for solving the problem]

[0008] In order to solve the above problems, the present invention provides the following aspects. [1] 1. A sanitary installation having a hydrophilic treated organic surface, The hydrophilically treated organic surface has at least an organic cationic group, The zeta potential of the hydrophilically treated organic surface at pH=7 is greater than −40 mV; Sanitary equipment. [2] The sanitary equipment according to [1], wherein the static contact angle of water on the hydrophilically treated organic surface is 40° or less. [3] The sanitary equipment according to [1] or [2], wherein the hydrophilically treated organic surface has a static contact angle of water of 40° or less after being brought into contact with an aqueous solution containing a cationic surfactant and then rinsed with water. [4] The sanitary equipment according to any one of [1] to [3], wherein the organic cationic group possessed by the hydrophilically treated organic surface is a group bonded to a carbon atom constituting the hydrophilically treated organic surface. [5] the hydrophilically treated organic surface has an organic cationic group and an organic anionic group, Both the organic cationic group and the organic anionic group are groups bonded to carbon atoms constituting the hydrophilically treated organic surface. Sanitary facilities of any of [1] to [4]. [6] The sanitary equipment according to any one of [1] to [5], wherein the organic cationic group is a quaternary ammonium cationic group. [7] the organic cationic group is a quaternary ammonium cationic group, The sanitary equipment according to [5], wherein the organic anionic group is at least one of a sulfonic acid group and an alkali metal salt of a sulfonic acid group. [8] The zeta potential Ei (mV) of the hydrophilically treated organic surface at pH=7, and After contacting the sample with an aqueous solution containing a cationic surfactant and then rinsing with water, the zeta potential Ec (mV) at pH=7 satisfies the relationship shown in the following formula: Sanitary facilities, any of [1] to [7]. |Ec-Ei|<50 [9] [1] to [8] A hydrophilic treatment agent set for manufacturing sanitary equipment, The hydrophilic treatment agent set includes: a first treatment agent containing a silane coupling agent having a radical reactive group; and a second treatment agent containing an anionic compound having a radical reactive group and an organic anionic group, and a cationic compound having a radical reactive group and an organic cationic group; Including, Hydrophilic treatment agent set.

[10] the organic anionic group is at least one of a sulfonic acid group and an alkali metal salt of a sulfonic acid group; The organic cationic group is a quaternary ammonium cationic group. [9] Hydrophilic treatment agent set.

[11] the radical reactive group of the silane coupling agent, the radical reactive group of the anionic compound, and the radical reactive group of the cationic compound are each independently at least one selected from an acrylamide group, an acryloyl group, a methacryloyl group, an allyl group, a vinyl group, a styryl group, and a mercapto group; [9] or

[10] Hydrophilic treatment set.

[12] A method for producing a sanitary equipment according to any one of [1] to [8], comprising the following steps: a first treatment agent coating step of coating a surface of the object to be coated with a first treatment agent containing a silane coupling agent having a radical reactive group; and a second treatment agent application step of applying a second treatment agent containing an anionic compound having a radical reactive group and an organic anionic group, and a cationic compound having a radical reactive group and an organic cationic group, to the surface applied with the first treatment agent; encompasses, Manufacturing method.

[13] the organic anionic group is at least one of a sulfonic acid group and an alkali metal salt of a sulfonic acid group; The organic cationic group is a quaternary ammonium cationic group.

[12] Manufacturing method.

[14] The manufacturing method according to

[12] or

[13] , further comprising a radical reaction promoting step of applying heat or active energy rays after the second treatment agent coating step. [Effects of the Invention]

[0009] The hydrophilic treated organic surface of the sanitary equipment of the present invention is rendered hydrophilic by means other than the presence of hydrophilic particles on the surface. The hydrophilic treated organic surface has good hydrophilicity and therefore good stain-resistant properties. The hydrophilic treated organic surface also has the advantage of excellent durability of the stain-resistant properties. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hydrophilic organic surface Hereinafter, a sanitary equipment having a hydrophilic treated organic surface will be described. The hydrophilic treated organic surface is characterized by having at least an organic cationic group and having a zeta potential of greater than -40 mV at pH=7.

[0011] The hydrophilically treated organic surface exhibits good hydrophilicity continuously by having a zeta potential of greater than -40 mV at pH 7. Commonly used cleaning agents contain cationic surfactants. If the initial zeta potential of the hydrophilically treated organic surface is greater than -40 mV, the cationic surfactant is less likely to adsorb. Therefore, an increase in the contact angle is suppressed over a long period of time. Another feature of the hydrophilically treated organic surface is that the surface having the zeta potential contains organic cationic groups. The zeta potential of the hydrophilically treated organic surface at pH 7 is preferably greater than -40 mV and less than 40 mV, more preferably greater than -40 mV and less than 20 mV, even more preferably greater than -40 mV and less than 0 mV, and particularly preferably greater than -35 mV and less than 0 mV. Within this range, mineral components (limescale) that may be contained in tap water, such as calcium, are easily removed.

[0012] In this specification, the zeta potential of the hydrophilically treated organic surface can be measured using a commercially available zeta potential meter (for example, a laser zeta potential meter).

[0013] When the zeta potential of the hydrophilically treated organic surface at pH=7 satisfies the above condition, it is advantageous in that good hydrophilicity is exhibited. In particular, when the zeta potential of the hydrophilically treated organic surface at pH=7 satisfies the above condition, it is possible to suppress a significant increase in the zeta potential of the surface after the hydrophilically treated organic surface is brought into contact with an aqueous solution containing a cationic surfactant. Furthermore, it is possible to suppress a significant increase in the zeta potential after the hydrophilically treated organic surface is brought into contact with an aqueous solution containing a cationic surfactant and then washed with water. This has the advantage that good hydrophilicity is maintained for a long period of time, for example, even when the hydrophilically treated organic surface comes into contact with an aqueous solution containing a cationic surfactant.

[0014] For example, it is preferable that the zeta potential Ei (mV) of the hydrophilically treated organic surface at pH=7 and the zeta potential Ec (mV) at pH=7 after contact with an aqueous solution containing a cationic surfactant and subsequent rinsing with water satisfy the relationship |Ec-Ei|<50. In all of the above cases, the zeta potential Ei of the hydrophilically treated organic surface at pH=7 (i.e., the zeta potential before contacting the hydrophilically treated organic surface with an aqueous solution containing a cationic surfactant) is small relative to the zeta potential Ec at pH=7 after contact with an aqueous solution containing a cationic surfactant and subsequent rinsing with water (i.e., the zeta potential after contacting the hydrophilically treated organic surface with an aqueous solution containing a cationic surfactant and subsequent rinsing with water), and the difference in potential values ​​between Ec and Ei is small. A small increase in potential makes it easier to maintain good hydrophilicity over a long period of time, even when, for example, an aqueous solution containing a cationic surfactant is contacted with the hydrophilically treated organic surface.

[0015] In the aqueous solution containing the cationic surfactant, the concentration of the cationic surfactant is 0.0001% by mass or more and 70% by mass or less. This aqueous solution is applied to a 1 cm2 area of ​​the hydrophilic treated organic surface at room temperature (20°C or more and 25°C or less). 2The contact time is 5 to 20 seconds. If further washing with water is required, the hydrophilic treated organic surface is exposed to a water flow of 3 to 7 liters (L) / minute for 15 to 60 seconds.

[0016] The static contact angle of water on the hydrophilically treated organic surface is preferably 40° or less. The contact angle of water on the hydrophilically treated organic surface can be measured using a commercially available contact angle meter in accordance with JIS R 3257 "Test method for wettability of substrate glass surfaces" (using the sessile drop method as the type of test method). When the static contact angle of water is 40° or less, it can be said that the hydrophilically treated organic surface has hydrophilicity. The static contact angle of water on the hydrophilically treated organic surface is more preferably 30° or less, and particularly preferably 25° or less.

[0017] The static contact angle of water on the hydrophilically treated organic surface after contact with an aqueous solution containing a cationic surfactant and subsequent rinsing with water is also preferably 40° or less. The static contact angle here refers to the static contact angle of water under the conditions in which the zeta potential Ec is measured. A water contact angle of 40° or less under these conditions means that the hydrophilicity of the surface is well maintained even after contact with an aqueous solution containing a cationic surfactant and subsequent rinsing with water.

[0018] Hydrophilic treatment agent set The hydrophilic treated organic surface can be formed, for example, by using a hydrophilic treatment agent set including a first treatment agent containing a silane coupling agent having a radical reactive group, and a second treatment agent containing a cationic compound having a radical reactive group and an organic cationic group, and an anionic compound having a radical reactive group and an organic anionic group. For example, using the hydrophilic treatment agent set, the first treatment agent is applied to the surface of a substrate (first treatment agent application step), and then the second treatment agent is applied to the surface coated with the first treatment agent (second treatment agent application step), thereby obtaining a hydrophilic-treated organic surface. The hydrophilic treatment agent set will be described in detail below.

[0019] First treatment agent The first treatment agent constituting the hydrophilic treatment agent set includes a silane coupling agent having a radical reactive group. The silane coupling agent having a radical reactive group is a compound having both a reactive silyl group and a radical reactive group in the molecule. Examples of the reactive silyl group include groups that generate silanol groups upon hydrolysis. Specific examples of the reactive silyl group include trialkoxysilyl groups (the alkoxy group preferably contains 1 to 7 carbon atoms) and dialkoxyalkyl groups (the alkoxy group preferably contains 1 to 7 carbon atoms, and the alkyl group preferably contains 1 to 7 carbon atoms). More specific examples include trimethoxysilyl groups, triethoxysilyl groups, tripropoxysilyl groups, tris(2-methoxyethoxy)silyl groups, dimethoxyalkylsilyl groups, diethoxyalkylsilyl groups, dipropoxyalkylsilyl groups, and bis(2-methoxyethoxy)alkylsilyl groups (the alkyl group may be a linear or branched alkyl group having 1 to 7 carbon atoms).

[0020] Examples of the radical reactive group include an acrylamide group, an acryloyl group, a methacryloyl group, an allyl group, a vinyl group, a styryl group, a mercapto group, etc. These radical reactive groups may be contained in one kind only, or in two or more kinds.

[0021] Specific examples of the silane coupling agent include: vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, vinylmethyldimethoxysilane, p-styryltrimethoxysilane, p-steel R methyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-octanoylthio-1-propyltriethoxysilane, Examples include:

[0022] The above silane coupling agents having a radical reactive group may be used alone or in combination of two or more kinds.

[0023] The silane coupling agent having the radical reactive group may be a silane coupling agent having two or more radical reactive groups, which has the advantage of further improving the durability of the dirt-repellent performance.

[0024] Commercially available silane coupling agents can also be used, including various silane coupling agents available from Shin-Etsu Chemical Co., Ltd., Momentive Corporation, Toagosei Co., Ltd., Asahi Kasei Corporation, and the like.

[0025] When a silane coupling agent having the above-mentioned radical reactive group is used, it is believed that a silanol group generated by hydrolysis of the reactive silyl group undergoes a bonding reaction on the surface of the substrate.

[0026] The amount of silane coupling agent contained in the first treatment agent is preferably in the range of 0.1 parts by mass or more and 10 parts by mass or less, and more preferably in the range of 1 part by mass or more and 5 parts by mass or less, per 100 parts by mass of the first treatment agent.

[0027] The first treatment agent may contain a catalyst in addition to the silane coupling agent. Examples of the catalyst include acidic catalysts (e.g., aqueous hydrochloric acid solutions, aqueous sulfuric acid solutions, aqueous nitric acid solutions, aqueous phosphoric acid solutions, and aqueous solutions of compounds having a carboxylic acid such as formic acid, acetic acid, and propionic acid), and basic catalysts (e.g., aqueous ammonia solutions, morpholine, N-methylmorpholine, N-ethylmorpholine, piperazine, hydroxyethylpiperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, cis-2,6-dimethylpiperazine, triethylamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N-(β-aminoethyl)ethanolamine, N-methyldiethanolamine, Nn-butylethanolamine, Nn-butyldiethanolamine, Nt-butylethanolamine, Nt-butyldiethanolamine, N-(β-aminoethyl)isopropanolamine, N,N-diethylisopropanolamine, 2-amino-2-methyl-1-propanol, aqueous sodium hydroxide solutions, and aqueous potassium hydroxide solutions).

[0028] The first treatment agent may contain various solvents, various additives, etc., as needed. Examples of preferred solvents include water, methanol, ethanol, isopropyl alcohol, and n-propyl alcohol. Examples of additives include surface conditioners, compatibilizers, leveling agents, plasticizers, antifoaming agents, UV absorbers, antioxidants, and viscosity control agents. Only one of these additives may be contained, or two or more may be contained.

[0029] The first treatment agent can be prepared by mixing the silane coupling agent having the radical reactive group and other components as required by a method commonly used by those skilled in the art.

[0030] Second treatment agent The second treatment agent constituting the hydrophilic treatment agent set preferably contains an anionic compound having a radical reactive group and an organic anionic group, and a cationic compound having a radical reactive group and an organic cationic group, which allows the organic anionic group and the organic cationic group to be introduced into the substrate, thereby forming a surface that exhibits hydrophilicity.

[0031] The radical reactive group of the anionic compound may be at least one selected from the group consisting of an acrylamide group, an acryloyl group, a methacryloyl group, an allyl group, a vinyl group, a styryl group, and a mercapto group. The radical reactive group of the cationic compound may be at least one selected from the group consisting of an acrylamide group, an acryloyl group, a methacryloyl group, an allyl group, a vinyl group, a styryl group, and a mercapto group.

[0032] The anionic and cationic compounds may have a condensation-type reactive group instead of a radical-reactive group. Examples of the condensation-type reactive group include at least one selected from the group consisting of a carboxy group, a hydroxy group, an amino group, an epoxy group, a ureido group, an isocyanate group, and an isocyanurate group.

[0033] Examples of the organic anionic group possessed by the anionic compound include sulfonic acid groups and alkali metal salts of sulfonic acid groups. These may be contained alone or in combination with two or more types. In this specification, the term "organic anionic group" refers to an anionic group possessed by an organic compound. The term "organic anionic group" is used herein to distinguish it from an anionic group contained in an inorganic compound. When the second treatment agent contains the anionic compound, the resulting hydrophilically treated organic surface possesses organic anionic groups. The organic anionic groups are bonded to carbon atoms (specifically, carbon atoms contained in the anionic compound) that constitute the hydrophilically treated organic surface. Because the anionic compound is bonded to the substrate via a silane coupling agent, it is difficult to detach even with frequent washing with water, etc. This facilitates long-term hydrophilicity.

[0034] The anionic compound preferably has no hydrophilic moieties other than those at the ends of the molecular chain. The "hydrophilic moiety" in the anionic compound refers to sulfonic acid groups and other hydrophilic groups possessed by the anionic compound. When the anionic compound has such a structure, the hydrophilic groups of the anionic compound can be concentrated on the coating surface, not on the substrate side, which has the advantage of imparting sufficient cleanability and cleaning durability even when used in components that are frequently washed with water, such as sanitary equipment.

[0035] Specific examples of the anionic compound include: sodium vinyl sulfonate, vinyl sulfonic acid, Nt-butylacrylamidosulfonic acid lithium, Sodium Nt-butylacrylamidosulfonate, Potassium Nt-butylacrylamidosulfonate, 2-sodium sulfoethyl methacrylate, Sodium allyl sulfonate, Sodium p-styrenesulfonate, sodium sulfonate-containing urethane acrylate, Nt-butylacrylamidosulfonic acid, The anionic compounds may be used singly or in combination of two or more. The anionic compounds may be neutralized by adding an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to form a sulfonate.

[0036] Commercially available products may be used as the anionic compound. Examples of commercially available products include ATBS (registered trademark)-Na from Toagosei Co., Ltd., N-SVS-25 from Asahi Kasei Finechem Corporation, Antox MS-2N from Nippon Nyukazai Co., Ltd., and Spinomer (registered trademark) NaSS from Tosoh Organic Chemical Co., Ltd. The anionic compound may also be prepared by commonly used techniques. For example, sodium sulfonate-containing urethane acrylates can be prepared by commonly used techniques by those skilled in the art.

[0037] The anionic compound preferably has a number average molecular weight of 70 or more and 500 or less. When the number average molecular weight is within the above range, there is an advantage in that hydrophilicity can be imparted more satisfactorily.

[0038] cationic compounds Examples of organic cationic groups possessed by the cationic compound include quaternary ammonium cationic groups. In this specification, the term "organic cationic group" refers to a cationic group possessed by an organic compound. The term "organic cationic group" is used herein to distinguish it from cationic groups contained in inorganic compounds. When the second treatment agent contains the cationic compound, the resulting hydrophilically treated organic surface contains organic cationic groups. The organic cationic groups are bonded to carbon atoms (specifically, carbon atoms contained in the cationic compound) that constitute the hydrophilically treated organic surface. Because the cationic compound is bonded to the substrate via a silane coupling agent, it is difficult for the cationic compound to be detached even by frequent washing with water or the like. This facilitates long-term hydrophilicity.

[0039] The second treatment agent constituting the hydrophilic treatment agent set contains a cationic compound in addition to the anionic compound, which has the advantage of providing good stain-preventing properties and good durability of stain-preventing performance. Without being bound by any particular theory, it is believed that the inclusion of a cationic compound in addition to the anionic compound effectively prevents basic cleaning ingredients such as quaternary ammonium salts, which may be contained in commercially available detergents, from forming ionic bonds with sulfonic acids derived from the anionic compound, thereby providing good durability of stain-preventing performance.

[0040] The cationic compound preferably has no hydrophilic moieties other than those at the ends of the molecular chain. The "hydrophilic moiety" in the cationic compound refers to the quaternary ammonium cationic group and other hydrophilic groups contained in the cationic compound. When the cationic compound has such a structure, the hydrophilic groups of the cationic compound can be concentrated on the coating film surface, not on the inorganic substrate side, which has the advantage of imparting sufficient cleanability and cleaning durability even when used on components that are frequently washed with water, such as sanitary ware.

[0041] Specific examples of the cationic compound include: (3-acrylamidopropyl)trimethylammonium chloride, (3-Acrylamidepropyl)trimethylammonium bromide [3-(Methacryloylamino)propyl]trimethylammonium chloride 2-(Acryloyloxy)-N,N,N-trimethylethanaminium chloride 2-(Methacryloyloxy)ethyltrimethylammonium chloride The above cationic compounds may be used alone or in combination of two or more.

[0042] The cationic compound may be a commercially available product or may be prepared by a commonly used method.

[0043] The cationic compound preferably has a number average molecular weight of 70 or more and 500 or less. When the number average molecular weight is within the above range, there is an advantage in that hydrophilicity can be imparted more satisfactorily.

[0044] The mass ratio of the anionic compound to the cationic compound contained in the second treatment agent is preferably anionic compound:cationic compound = 15:85 to 85:15, and more preferably 20:80 to 80:20. Having this ratio within this range has the advantage of providing good durability of the stain adhesion prevention performance.

[0045] When the anionic compound and the cationic compound each have a radical-reactive functional group, the average number of carbon atoms present between the radical-reactive functional group of the anionic compound and the anionic group (typically, a sulfonic acid group) is defined as (n1), and the average number of carbon atoms present between the radical-reactive functional group of the cationic compound and the organic cationic group (typically, a quaternary ammonium cationic group) is defined as (n2), The above (n1) and the above (n2) (n2)>(n1) It is preferable that the relationship be: When the average number of carbon atoms (n1) and the average number of carbon atoms (n2) satisfy the relationship (n2) > (n1), after the second treatment agent is applied to a substrate and reacted, it is believed that the cationic groups of the cationic compound will be present at a higher proportion on the surface side than the anionic groups of the anionic compound. This is believed to enable the achievement of better durability of the stain adhesion prevention performance. The difference between the average number of carbon atoms (n1) and the average number of carbon atoms (n2) is more preferably 1 or more, and even more preferably 2 or more.

[0046] Other ingredients When the components contained in the first treatment agent and the second treatment agent have radical reactive functional groups, they preferably further contain a radical polymerization initiator. The radical polymerization initiator is a compound that decomposes when exposed to light or heat to generate radicals. Radical polymerization initiators are classified into photoradical polymerization initiators that decompose when exposed to light and thermal radical polymerization initiators that decompose when exposed to heat. The radical polymerization initiator is preferably water-soluble.

[0047] Preferred examples of the photoradical polymerization initiator include benzophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, a mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propionyl)-benzyl}phenyl]-2-methyl-1-propan-1-one, oxyphenylacetic acid, a mixture of 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester and oxyphenylacetic acid and / or 2-(2-hydroxyethoxy)ethyl ester, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. If necessary, a sensitizer such as ethyl p-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.) can also be added to the photoradical polymerization initiator. Commercially available products of these include Omnirad (registered trademark) 184, Omnirad (registered trademark) 500, Omnirad (registered trademark) 2959, DAROCURE (registered trademark) 1173, Omnirad (registered trademark) 127, Omnirad (registered trademark) 754, and Omnirad (registered trademark) 819DW manufactured by IGM Resins.

[0048] The thermal radical polymerization initiator is 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride. Bazo compounds such as 2,2'-azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis(propane-2-carboxamidine) dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]n-hydrate, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 4,4'-azobis(4-cyanopentanoic acid), persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, hydrogen peroxide, cumylperneodecanoate, and 1,1,3,3-tetramethylbutylperoxyneodecaine. mosquito Neoate, t-Hexylperoxyneode mosquito Noate, t-butylperoxyneode mosquito Preferred are peroxides such as tert-butyl peroxypivalate, tert-hexyl peroxypivalate, and tert-butyl peroxypivalate. Furthermore, water or the like can be added to the thermal radical polymerization initiator as needed. Commercially available products include VA-044, VA-046B, VA-061, V-50, VA-057, VA-086, and V-501 from Wako Pure Chemical Industries, Ltd., Percumyl ND-50E, Perocta ND-50E, Perhexyl ND-50E, Perbutyl ND-50E, Perhexyl PV-50E, and Perbutyl PV-40E from NOF Corporation, and reagents from various companies can be used.

[0049] The amount of the radical polymerization initiator to be blended is preferably 1 part by mass or more and 75 parts by mass or less, and more preferably 5 parts by mass or more and 60 parts by mass or less, per 100 parts by mass of the total amount (solid content mass) of the anionic compound and the cationic compound contained in the second treatment agent.

[0050] The first and second treatment agents may contain a solvent, if necessary. The inclusion of a solvent has the advantage of being able to effectively dissolve or disperse, for example, anionic compounds and cationic compounds. Examples of preferred solvents include water, methanol, ethanol, isopropyl alcohol, and n-propyl alcohol. These solvents can be appropriately selected depending on the type and content of each compound.

[0051] In addition to the above components, the first and second treatment agents may contain additives as needed. Examples of additives include surface conditioners, compatibilizers, leveling agents, plasticizers, antifoaming agents, UV absorbers, antioxidants, and viscosity control agents. These additives may be contained alone or in combination with one or more of them.

[0052] Examples of compatibilizers that can be used as additives include amide compounds such as urea, melamine, acryloylmorpholine, dimethylacrylamide, dimethylaminopropylacrylamide, isopropylacrylamide, diethylacrylamide, and hydroxyethylacrylamide; aprotic polar solvents such as dimethyl sulfoxide, acetonitrile, and N,N-dimethylformamide; polyhydric alcohols such as ethylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, erythritol, erythritol, and dipentaerythritol; trioses, tetroses, pentoses, hexoses; Sedoheptulose Examples of suitable compatibilizers include sugars such as glucose, maltose, sucrose (cane sugar), lactose, cellobiose, raffinose, acarbose, oligosaccharides, cyclodextrin, dextrin, and starch; polar resins such as sodium carboxymethylcellulose, polyvinylpyrrolidone, sodium polyacrylate, and modified urea; and inorganic salts such as sodium bicarbonate, sodium carbonate, sodium hydrogen sulfate, and sodium sulfate. When a compatibilizer is included, the content is preferably 10 parts by mass or more and 100 parts by mass or less relative to 100 parts by mass of the total amount (solid content mass) of the anionic compound and cationic compound contained in the second treatment agent.

[0053] The solid content concentration of the first treatment agent is preferably 0.1% by mass or more and 60% by mass or less. The solid content concentration of the second treatment agent is preferably 0.1% by mass or more and 60% by mass or less. Having the solid content concentration within the above ranges has the advantage of being able to obtain good stain adhesion prevention properties, etc.

[0054] Furthermore, the second treatment agent may contain a nonionic compound having a nonionic group, such as a hydroxyl group, an ethoxy group, or an ester group, if necessary.

[0055] The nonionic compound preferably has a radical reactive group in addition to the nonionic group, such as at least one selected from the group consisting of an acrylamide group, an acryloyl group, a methacryloyl group, an allyl group, a vinyl group, a styryl group, and a mercapto group.

[0056] Specific examples of the nonionic compound include polyethylene glycol mono(meth)acrylate. Commercially available products may also be used as the nonionic compound. Specific examples of commercially available products include photocurable monomers having a nonionic group, such as those sold by Shin-Nakamura Chemical Co., Ltd., Dai-ichi Kogyo Seiyaku Co., Ltd., and Kyoeisha Chemical Co., Ltd.

[0057] The second treatment agent may contain various solvents, various additives, etc., as needed. Examples of preferred solvents include water, methanol, ethanol, isopropyl alcohol, and n-propyl alcohol. Examples of additives include surface conditioners, compatibilizers, leveling agents, plasticizers, antifoaming agents, UV absorbers, antioxidants, and viscosity control agents. Only one of these additives may be contained, or two or more may be contained.

[0058] The second treatment agent can be prepared by mixing the above components and other components as required by a method commonly used by those skilled in the art.

[0059] Hydrophilic treatment agent set The present disclosure also provides a hydrophilic treatment set comprising the first treatment agent and the second treatment agent. This hydrophilic treatment set is a set for forming a hydrophilic treated organic surface on the surface of sanitary equipment. Preferred aspects of the first treatment agent and the second treatment agent are the same as those described above.

[0060] Other embodiments of the hydrophilic treatment agent set include, for example, an embodiment in which the anionic compound and the cationic compound are stored separately. These embodiments can be selected appropriately depending on the storage stability and reactivity of each component.

[0061] The mass ratio of the first treatment agent and the second treatment agent in the hydrophilic treatment agent set can be selected as desired depending on the intended use of the target equipment, etc.

[0062] Hydrophilically treated organic surfaces, sanitary equipment and method for producing sanitary equipment By using the first treatment agent and the second treatment agent, or a hydrophilic treatment agent set including the first treatment agent and the second treatment agent, a hydrophilic treated organic surface having at least an organic cationic group can be obtained, and the zeta potential of the hydrophilic treated organic surface at pH=7 can be reduced to -40m V Larger hydrophilic treated organic surfaces can be formed on the surfaces of the sanitary equipment, and the hydrophilic treated organic surfaces preferably have a zeta potential that satisfies the above-mentioned conditions.

[0063] The present disclosure also provides sanitary equipment having the above-described hydrophilic treated organic surface. Sanitary equipment in this specification refers to, for example, the equipment itself and components of the equipment that constitute plumbing facilities in homes, such as toilet bowls, urinals, washbasins, bathtubs, tiles, mirrors, glass, enamel, siding materials, sashes, walls, ceiling surfaces, floor surfaces, protective panels, and ceramics. The hydrophilic organic surface can also be provided on glass surfaces that constitute windows in homes, etc.

[0064] The hydrophilic treated organic surface can be prepared, for example, by the following steps: a first treatment agent coating step of coating a surface of the object to be coated with a first treatment agent containing a silane coupling agent having a radical reactive group; and a second treatment agent application step of applying a second treatment agent containing a cationic compound having a radical reactive group and an organic cationic group, and an anionic compound having a radical reactive group and an organic anionic group, to the surface applied with the first treatment agent; The "substrate" referred to here corresponds to sanitary equipment. By the above method, a hydrophilic treated organic surface can be formed on the sanitary equipment.

[0065] In the above method, it is preferable to apply heat or active energy rays after the second treatment agent coating step to promote the radical reaction. By carrying out these treatments, the durability of the hydrophilic treated organic surface can be further improved.

[0066] The light irradiation may be performed using active energy rays. More specifically, active energy rays, more preferably ultraviolet rays having a wavelength of 220 to 450 nm, may be irradiated using, for example, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, or an ultraviolet LED lamp. Examples of the heating conditions include heating using a commonly used heating furnace, a hot air dryer, or an IR heater, and thermal irradiation using an infrared heat irradiation device. Regarding the heating conditions, the heating temperature may be, for example, 80°C or higher and 150°C or lower. [Example]

[0067] The present invention will be described in more detail with reference to the following examples, but is not limited thereto. In the examples, "parts" and "%" are by weight unless otherwise specified.

[0068] Example 1 Preparation of first treatment agent After 1 part of 3-methacryloxypropyltrimethoxysilane (silane coupling agent) and 98 parts by mass of 1-methoxy-2-propanol were mixed by stirring at room temperature, 1 part by mass of a 3% aqueous hydrochloric acid solution was added, and the mixture was further stirred for 30 minutes to carry out hydrolysis, and the first treatment agent was obtained. preparation did. Preparation of second treatment agent 27.5 parts by weight of ion-exchanged water and 10 parts by weight of urea were mixed and stirred until the urea was dissolved, and then 5 parts by weight of sodium vinyl sulfonate (anionic compound), 45 parts by weight of sodium Nt-butylacrylamidosulfonate (anionic compound), 50 parts by weight of (3-acrylamidopropyl)trimethylammonium chloride (cationic compound), 50 parts by weight of 2-hydroxy-2-methyl-1-phenylpropan-1-one (polymerization initiator), and 100 parts by weight of isopropyl alcohol were added and stirred until a transparent, homogeneous solution was obtained, thereby preparing a second treatment agent.

[0069] Preparation of hydrophilic organic surfaces The first treatment agent obtained above was applied to the surface of ceramic sanitary equipment having silicon oxide on the surface, and the surface was dried at 60°C for 30 minutes in an electric oven, and then left to stand at room temperature for 30 minutes. Next, the second treatment agent prepared above was applied, and then a high-pressure mercury lamp was used to irradiate the surface with an integrated light dose of 1000 mJ / cm 2 . 2 By irradiating the ceramic with ultraviolet light, which provides the energy required for the formation of a hydrophilic organic surface,

[0070] Examples 2 to 12 and Comparative Examples 1 to 3 In Examples 2 to 12 and Comparative Examples 1 to 3, a hydrophilic treated organic surface was formed in the same manner as in Example 1, except that the type of silane coupling agent, and the types and amounts of anionic compounds, cationic compounds, polymerization initiators, etc. were changed according to the table below.

[0071] The hydrophilic treated organic surfaces formed in the above Examples and Comparative Examples were evaluated as follows, and the evaluation results are shown in the table below.

[0072] Zeta potential measurement The zeta potential of the hydrophilically treated organic surface at around pH 7 was measured using a commercially available zeta potential meter, ELSZ-2000ZS (manufactured by Otsuka Electronics Co., Ltd.), and the zeta potential (mV) at pH = 7 was calculated by calculating the value at pH = 7 from the approximation curve of the measurement results. As the zeta potential, (1) Zeta potential (Ei) after the hydrophilic treated organic surface formed in the above Examples and Comparative Examples was washed with distilled water and dried (2) The zeta potential (Ec) after applying 1 ml of a cationic surfactant, Sanpol (trade name), to the hydrophilic treated organic surface, leaving it for 10 seconds, washing with a water flow of 5 L / min for 30 seconds, and drying. Both were measured.

[0073] Measurement of static contact angle of water The contact angle of a water droplet on the surface, obtained in accordance with JIS R 3257 "Test method for wettability of substrate glass surfaces" (the sessile drop method was used as the type of test method), was used as a criterion for evaluating the durability of hydrophilic-treated organic surfaces (hydrophilic treatment). Specifically, 4 μL of distilled water was dropped onto the coating film using DSA20E manufactured by KRUSS, and the contact angle (static contact angle of water) was measured 60 seconds later. The static contact angle of water is (1) The static contact angle of water after the hydrophilic treated organic surfaces formed in the above Examples and Comparative Examples were washed with distilled water and dried. (2) The static contact angle of water after applying 1 ml of an undiluted solution of Sanpol (trade name), a cationic surfactant, to the hydrophilic treated organic surface and leaving it for 10 seconds, then washing with a water flow of 5 L / min for 30 seconds and drying (the static contact angle of water under the condition for measuring the above-mentioned zeta potential Ec), Both were measured.

[0074] [Table 1]

[0075] In all of the Examples, the zeta potential of the hydrophilically treated organic surfaces at pH 7 was greater than -40 mV. It was also confirmed that in these Examples, the static contact angle of water was 40° or less, and furthermore, the static contact angle of water after contact with an aqueous solution containing a cationic surfactant and subsequent rinsing with water was also 40° or less. This confirmed that the hydrophilically treated organic surfaces of the Examples were highly hydrophilic and maintained their hydrophilicity even after contact with an aqueous solution containing a cationic surfactant. In all of the comparative examples, the hydrophilically treated organic surfaces had a zeta potential of −40 mV or less at pH 7. The hydrophilically treated organic surfaces in these examples showed a large static contact angle with water, particularly after being brought into contact with an aqueous solution containing a cationic surfactant and then rinsed with water, confirming a decrease in hydrophilicity. [Industrial Applicability]

[0076] The above disclosure provides a means for imparting hydrophilicity to the surface of sanitary equipment by means other than hydrophilic particles. The hydrophilic organic surface is formed on the surface of sanitary equipment, and has the advantage that the hydrophilic organic surface has at least organic cationic groups and the zeta potential of the hydrophilically treated organic surface at pH=7 is greater than -40 mV, thereby achieving good hydrophilicity and hydrophilic durability.

[0077] This application claims priority based on Japanese Patent Application No. 2020-044438, filed on March 13, 2020, the entire contents of which are incorporated herein by reference.

Claims

1. A substrate having a hydrophilically treated organic surface (excluding the case where hydrophilic particles are present), the hydrophilically treated organic surface has at least an organic cationic group; the zeta potential of the hydrophilically treated organic surface at pH 7 before contact with an aqueous solution containing an acidic cationic surfactant is greater than −40 mV; The hydrophilically treated organic surface has a static contact angle of water of 40° or less after being brought into contact with an aqueous solution containing an acidic cationic surfactant and then rinsed with water, the method comprising the steps of: a first treatment agent coating step of coating a surface of the object to be coated with a first treatment agent containing a silane coupling agent having a radical reactive group; and a second treatment agent application step of applying a second treatment agent containing an anionic compound having a radical reactive group and an organic anionic group, and a cationic compound having a radical reactive group and an organic cationic group, to the surface applied with the first treatment agent; encompasses, Manufacturing method.

2. The manufacturing method described in claim 1, wherein the static contact angle of water on the hydrophilically treated organic surface is 40° or less.

3. A manufacturing method described in claim 1 or 2, wherein the organic cationic group possessed by the hydrophilically treated organic surface is a group bonded to a carbon atom constituting the hydrophilically treated organic surface.

4. The hydrophilic treated organic surface has an organic cationic group and an organic anionic group, Both the organic cationic group and the organic anionic group are groups bonded to carbon atoms constituting the hydrophilically treated organic surface. The manufacturing method according to any one of claims 1 to 3.

5. A manufacturing method described in any one of claims 1 to 4, wherein the organic cationic group is a quaternary ammonium cationic group.

6. The zeta potential Ei (mV) of the hydrophilically treated organic surface at pH=7 before contact with an aqueous solution containing an acidic cationic surfactant, and After contacting the surface of the polymer with an aqueous solution containing an acidic cationic surfactant and then washing with water, the zeta potential Ec (mV) at pH 7 satisfies the relationship shown in the following formula: The manufacturing method according to any one of claims 1 to 5. |Ec-Ei|<50

7. the organic anionic group is at least one of a sulfonic acid group and an alkali metal salt of a sulfonic acid group, The organic cationic group is a quaternary ammonium cationic group. The manufacturing method according to any one of claims 1 to 6.

8. The method according to any one of claims 1 to 7, further comprising a radical reaction promoting step of applying heat or active energy rays after the second treatment agent coating step.

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