JP2010013623A - Scale deposition preventing agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a scale deposition preventing agent, which is applied to facilities in a wet-area or the like, for forming a slowly-soluble coating film provided with water-resistance to a water flow. <P>SOLUTION: The scale deposition preventing agent contains a salt of zinc (II) ion, polyacrylamide and water as a solvent, and 0.01-100 mM of the salt and 0.001-10 mass% of polyacrylamide relative to the liquid agent are contained. A ratio of an amount (mol) of the salt relative to an amount (mol) of a unit structure of polyacrylamide is 1/100-10. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a scale adhesion preventing agent capable of washing away dirt adhering to the surface by gradually dissolving the surface of the coating in contact with water and maintaining the hydrophilicity of the coating surface continuously.

  In general, in an environment where water flows temporarily, such as the inside of a toilet in a flush toilet, the inside of a wash basin, the floor / wall in a bathroom washing place, and the inside of a kitchen sink, microbial stains and scale stains are generated. Featuring stool on the toilet, darkening / yellowing, sebum stains / soap residue stains / scale stains in the bathroom, microbial stains such as black mold and pink slime, etc. Stains occur. Examples of methods for preventing the adhesion of these unpleasant stains and washing are as follows.

  Patent Document 1 discloses the first and second inventions. As a first invention, a water-soluble polymer and an active ingredient are applied to a toilet bowl to form a film, and the active ingredient held inside the film is eluted by dissolution of the polymer, and a liquid composition and cleaning that exhibits detergency A method is disclosed. Surfactants are disclosed as active ingredients that exhibit detergency.

  In addition, as a second invention, the liquid agent containing the liquid agent of the first invention and the liquid agent containing borax are respectively applied to a toilet and reacted to form a film, and the active ingredient held inside is dissolved while the film dissolves. Thus, a liquid composition and a cleaning method that exhibit cleaning properties are disclosed.

  Patent Document 2 proposes a polymer that makes the surface hydrophilic by forming it on the surface of floors, tiles, walls, sinks, and the like. Specifically, N-vinylimidazole N-vinylpyrrolidone (PVPVI) polymer is proposed. Polyvinylpyrrolidone copolymer such as, and the like, and by adding polyvalent metal ions to this, the polymer and polyvalent metal ions interact to form a crosslink of the polymer to form a uniform polymer matrix And reducing the viscosity of the composition.

  Patent Document 3 proposes an antibacterial liquid composition that hardly causes coloring or precipitation by using a cationic polymer and / or a basic polymer in combination with an antibacterial inorganic metal-containing component. It has been disclosed that when a metal oxide supporting an anionic silver nanocolloid is coated with a cationic polylysine, it is less susceptible to direct light, so that coloring and precipitation are less likely to occur.

However, in the techniques such as the first invention of Patent Document 1 and Patent Documents 2 and 3, the water resistance of the polymer component is small and a continuous effect cannot be obtained.
In addition, the water resistance of the coating is improved by crosslinking the polymer and borax as in the second invention of Patent Document 1, but since the mechanical strength is low, water with a high flow rate flows at a high frequency as in the toilet. In the part or the part where the hot water heated to 40 ° C. or more is touched like the part or the bathroom, the coating dissolves and disappears quickly and it is difficult to exert the cleaning effect continuously.

  Patent Document 4 discloses that a slow-dissolving film is formed on a surface that comes into temporary contact with water, such as a toilet toilet or a washbasin, a floor / wall in a bathroom washroom, or a kitchen sink. Specific examples include hydrophilic polymers such as polyvinyl alcohol, polyacrylamide, and hydroxycellulose, and metal salts of Al, Fe, Cu, and Cr as metal salts that form hydroxides thereon. It is described that the polymer and metal ions interact with each other to form a slow-dissolving film with durability against water flow, thereby producing a continuous antifouling effect and antibacterial effect. ing.

JP 2005-187511 A Special table 2003-524681 gazette JP 2006-151907 A Japanese Patent No. 3826954

  An object of the present invention is to provide a scale adhesion preventing agent for forming a slow-dissolving film having durability against water flow without coloring an applied portion.

  The scale adhesion preventing agent according to the present invention comprises a salt of zinc (II) ions, polyacrylamide, and water as a solvent, wherein the salt is 0.01 mM or more and 100 mM or less, and the polyacrylamide is used with respect to the liquid agent. 0.001% by mass or more and 10% by mass or less, and the ratio of the substance amount (mol) of the salt to the substance amount (mol) of the unit structure of polyacrylamide is 1/100 or more and 10 or less. And

  According to the present invention, since a colorless and transparent, slowly soluble coating can be formed at room temperature, the adhesion of scale on the surface of the coating is continuously performed without coloring the portion to be applied to the portion temporarily contacting water on the hard surface. Can be prevented.

  In order to facilitate understanding of the present invention, terms used in the present invention are defined and explained below.

(Applicable part)
The scale adhesion preventing agent of the present invention can be applied to a portion of a substrate having a hard surface that is temporarily in contact with water. Substrates with a hard surface include painted surfaces of automobiles, bicycles and motorcycles, metal surfaces such as tile wheels, window glass surfaces, outdoor tile building material surfaces and painted surfaces, indoor water-related article surfaces, etc. Point to. Preferably, it is a part that is temporarily in contact with water, such as an indoor water-related article, a painted surface of an automobile body, or a window glass.
The parts of water-related items that come into temporary contact with water are the items that make up the space of toilets, bathrooms, kitchens, washrooms, etc., which are dry when not in use, but water flows when used. Or it refers to the part where water can flow. Specifically, the surface of the toilet bowl or hand-washing bowl where water flows, the wall, floor, door or mirror of the bathroom where hot water in the bathroom flows, the surface of the kitchen sink where water flows when cooking or washing dishes, the area around the drain, the face wash and toothpaste It refers to the surface of a bowl in a bathroom where water sometimes flows.
The part of the car body that comes in contact with water temporarily refers to the part of the car body that is usually dry but comes into contact with moisture when it rains or snows.
The part of the window glass that comes into contact with water is specifically the indoor side of the window glass surface where condensation occurs due to the temperature difference between indoor and outdoor in the winter, and the outdoor side is usually dry. It refers to the surface of a window glass that comes into contact with moisture when it rains or snows.

(Slow dissolution film)
Slow solubility refers to the property that when water is applied or when water flows, the entire coating does not dissolve at once, but a portion near the surface dissolves. Since the film has a slow solubility, the surface of the film dissolves every time it comes into contact with water and flows away along with the attached dirt, so that a continuous antifouling property can be exhibited.
Further, the slow-dissolving film is a film showing the above-mentioned slow-dissolving property. In the present invention, a slowly soluble coating can be obtained by containing polyacrylamide and a salt of zinc (II) ions. On the other hand, for example, it is possible to form a film having water resistance even if only polyvinyl alcohol having a high saponification degree is used, but since the entire film swells and softens in an environment where water flows, it adheres closely to the substrate. The film is peeled off from the interface and is washed away.

(Anti-scale agent)
The scale adhesion preventing agent of the present invention comprises a salt of zinc (II) ions, polyacrylamide, and water as a solvent. The slow-dissolving film formed by the scale adhesion preventive agent of the present invention contains zinc (II) ions, and has an excellent antimicrobial effect against microbial stains such as black mold and pink slime that are generated around water. Is expressed.
The microorganism mentioned here refers to bacteria, yeast, mold and the like. The antimicrobial effect described herein refers to suppressing the activity, metabolism, or stopping the activity, reducing the number of individuals, or eliminating the living individuals with respect to the microorganisms described above.
Furthermore, the slow-dissolving film formed by the scale adhesion preventive agent of the present invention contains a zinc (II) ion salt and polyacrylamide, so that it exhibits durability against water flow and is sustained at the site around the water. An antimicrobial effect is obtained. This is presumed that the zinc (II) ion salt and polyacrylamide exhibit some durability against water flow due to some interaction.

(Polyacrylamide)
The polyacrylamide used for the scale adhesion preventing agent of the present invention is water-soluble N such as acrylamide, methacrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, diacetone acrylamide and the like. It comprises a constitutional unit derived from at least one acrylamide monomer selected from substituted alkylacrylamides. As polyacrylamide, either unmodified polyacrylamide or modified polyacrylamide can be used. Examples of the modified polyacrylamide include amphoteric, anionic, cationic, and nonionic polyacrylamide, and at least one functional group selected from the group of nonionic group, cationic group, and anionic group is a polyacrylamide molecule. Contains in. Such a modified polyacrylamide is, for example, a copolymer of the monomer or the macromer composed of the monomer and a monomer or macromer having at least one functional group of an anionic group, a cationic group, and a nonionic group. Is mentioned. The polyacrylamide that can be used in the present invention preferably contains 10 mol% or more and 100 mol% or less of a structural unit derived from an acrylamide-based monomer having polyacrylamide as a structural unit, and the preferred lower limit is 20 mol% or more, more Preferably it is 30 mol% or more.

  Examples of monomers or macromers having an anionic group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, dicarboxylic acids such as maleic acid, phthalic acid, itaconic acid, and citraconic acid, vinyl sulfonic acid, and styrene. Examples thereof include sulfonic acids such as sulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid, or sodium salts and potassium salts of these various organic acids, and macromers containing at least one of these. These may be used singly or in combination of two or more.

Examples of monomers or macromers having a cationic group include (meth) acrylic acid ester derivatives such as dialkylaminoethyl (meth) acrylate and dialkylaminopropyl (meth) acrylate which are monomers having a tertiary amino group, dialkylamino Tertiary amino groups such as (meth) acrylamide derivatives such as propyl (meth) acrylamide, dialkylaminopropyl (meth) acrylamide, (meth) acrylamide-3-methylbutyldimethylamine, dimethyldiallylammonium chloride and dimethyldiallylammonium chloride And a monomer having at least one of them and a macromer containing at least one of them.
The salt of a monomer having a tertiary amino group such as dimethyldiallylammonium chloride or dimethyldiallylammonium chloride may be a salt with an inorganic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as formic acid or acetic acid. It may be a salt with. Further, alkyl halides such as methyl chloride and methyl bromide, alkyl halides such as benzyl chloride and benzyl bromide, quaternary salts in which tertiary amino groups are quaternized with dimethyl sulfate, epicudolhydrin, etc. may be used. . Moreover, these may be used independently and may be used in mixture of 2 or more types.
Copolymers of acrylamide, acrylic acid, 2- (acryloyloxy) ethyltrimethylammonium chloride, 2- (methacryloyloxy) ethyltrimethylammonium chloride copolymer, acrylamide / 2- (acryloyloxy) ethyltrimethylammonium chloride copolymer, etc. A polymer may be used.

  Examples of the monomer or macromer having a nonionic group include methacrylonitrile, acrylonitrile, alkyl acrylate, hydroxy acrylate, vinyl acetate, styrene, α-methyl styrene, and a macromer containing at least one of these, and these Can be used as long as the water solubility of polyacrylamide is not impaired.

  As the polyacrylamide used for the scale adhesion preventing agent of the present invention, one having a mass average molecular weight of 10,000 to 20,000,000 is selected. However, the mass average molecular weight here refers to a value measured by gel permeation chromatography using polystyrene as a standard sample. If it is in such a range, it is easy to obtain a desired film thickness, and the operability at the time of liquid preparation is good, which is preferable. When the molecular weight exceeds 20000000, problems such as the liquid agent being likely to pull the yarn occur, which is not preferable.

(Amount of polyacrylamide)
The amount of polyacrylamide used in the scale adhesion preventing agent of the present invention is 0.001% by mass or more and 10% by mass or less, preferably 0.001% by mass or more and 8.0% by mass with respect to the liquid adhesion preventing agent. It is 0.001 mass% or less, More preferably, it is 0.001 mass% or less. Within such a range, it is possible not only to obtain a film thickness for sufficiently exhibiting the slow solubility, but also to facilitate spraying and spreading during film formation, and handling is good. In particular, when spraying, the content is preferably 0.001% by mass or more and 2.0% by mass or less, more preferably 0.001% by mass or more and 1.0% by mass or less. Within such a range, the liquid agent is discharged in the form of a mist, and the construction efficiency is good.
The spray described here refers to applying pressure to a liquid to eject droplets. Moreover, when spreading a scale adhesion preventing agent on a base material, 0.005 mass% or more and 10% or less are preferable, More preferably, it is 0.005 mass% or more and 8.0 mass% or less, More preferably, it is 0. It is 1 mass% or more and 8.0 mass% or less. Within such a range, a thick film can be formed at one time and the workability is good.

(Zinc (II) ion salt)
The zinc (II) ion salt used in the scale adhesion preventing agent of the present invention is preferably a zinc (II) ion salt having a solubility in water at 20 ° C. of at least 0.01% by mass. A preferable salt of zinc (II) ion is at least one of an organic acid salt and an inorganic acid salt. Examples of the organic acid salt include zinc acetate, zinc citrate, zinc gluconate, and zinc lactate. Examples of inorganic acid salts include hydrochlorides, sulfates, nitrates, and phosphates.
Further, from the viewpoint of ensuring safety to the human body, it is preferable that the LD ₅₀ value for oral administration of salt to rats is 300 mg / kg or more. The LD ₅₀ value for oral administration indicates a half-lethal dose after oral intake, and generally indicates a value measured by animal experiments in accordance with OECD guidelines: OECD 420 (effective in 2001). The organic acid salt satisfies this preferable range and is particularly preferable.

(Amount of zinc (II) ion salt)
The concentration of the zinc (II) ion salt (hereinafter referred to as “zinc salt”) in the scale adhesion preventing agent of the present invention is 0.01 mM or more and 100 mM or less, preferably 0.1 mM or more and 30 mM or less, more preferably. Is 0.2 mM to 30 mM, more preferably 0.5 mM to 20 mM.
The ratio of the substance amount (mol) of the zinc salt to the substance amount (mol) of the unit structure of polyacrylamide is preferably 1/100 or more and 10 or less. In particular, when spraying in the form of a mist, the ratio of the substance amount (mol) of the zinc salt to the substance amount (mol) of the unit structure of polyacrylamide is preferably 1/50 or more and 10 or less. When it is in such a range, the film thickness retention rate becomes high and it is convenient when spraying. Furthermore, when it is desired to obtain a higher antimicrobial effect by spraying, the ratio of the substance amount (mol) of the zinc salt to the substance amount (mol) of the unit structure of polyacrylamide is preferably 1/30 or more and 10 or less, More preferably, it is 1/15 or more and 10 or less. Within such a range, even when the concentration of the scale adhesion preventing agent is low, a sufficient antibacterial effect and a high film thickness retention rate can be obtained because sufficient zinc salt is contained. In addition, when this ratio exceeds 10, the stability of a liquid agent falls or a coating film becomes easy to become cloudy. A preferable upper limit of the ratio is 3 or less.
In addition, when spreading an anti-scale adhesion agent on a base material, the ratio of the amount (mol) of zinc salt to the amount (mol) of polyacrylamide unit structure is 1/100 or more and 1 / 2.5 or less. Preferably, it is 1/50 or more and 1/10 or less. Within such a range, even when a slow solubility is developed and the concentration of the scale adhesion inhibitor is high, an antimicrobial effect can be obtained while maintaining a transparent appearance.
The unit structure of polyacrylamide refers to a structure derived from the acrylamide monomer that constitutes polyacrylamide. Within such a range, the liquid agent stability is excellent and a transparent film can be obtained. Further, the slow dissolution can be controlled, and a more continuous antifouling effect can be obtained. That is, it becomes possible to design coatings having different film thickness retention rates after contact with a water flow for a certain time, and a continuous antifouling effect can be obtained.

Here, the substance amount (mol) of the unit structure of polyacrylamide is the mass of polyacrylamide contained in the scale adhesion preventive agent is “MPAA”, the chemical formula amount of the average constituent unit of polyacrylamide is “CMAA”, When the molar fraction of the structural unit derived from the acrylamide monomer is “RAA”, the amount of the polyacrylamide unit structure (mol) = MPAA / CMAA × RAA
Can be obtained. When there are a plurality of structural units derived from acrylamide monomers, the amount of the substance is calculated from the sum of the individual mole fractions.
In addition, in said formula, the chemical formula amount (CMAA) of the average structural unit of polyacrylamide points out the average chemical formula amount of the structural unit derived from the monomer which comprises polyacrylamide. Therefore, when polyacrylamide is a copolymer containing structural units A, B, and C having the chemical formula amounts a, b, and c in the ratio of x, y, and z, the chemical formula amount of the average structural unit of polyacrylamide ( (CMAA) is obtained by a × x + b × y + c × z. Here, x + y + z = 1, and A, B, and C represent structural units derived from an acrylamide monomer, an anionic monomer, a cationic monomer, a nonionic monomer, and the like.

(liquid)
When actually used, in consideration of safety with respect to the human body and peripheral members, it is preferable that the pH of the scale adhesion preventing agent measured at a liquid temperature of 20 ° C. is 3 or more and 10 or less. More preferably, it is 4 or more and 8 or less.

(solvent)
The solvent is mainly composed of water. As an optional component, an organic solvent can be appropriately blended for the purpose of dissolving the component, drying property, storage stability, and the like.
Specific examples of the organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, s-butanol, t-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, Diethylene glycol monoethylene ether, diethylene glycol monopropyl ether, diethylene glycol also includes nobutyl ether, glycerin, alkyl glyceryl ether, phenoxyethanol, etc.
Of these, alcohols such as ethanol and propanol are preferable in order to obtain stability of the liquid, workability, and drying properties. These organic solvents may be used alone or in combination of two or more.
The blending amount of the organic solvent is preferably 0% by mass or more and 20% by mass or less, more preferably 0% by mass or more and 10% by mass or less. When the content exceeds 20% by mass, the quality of the liquid agent is deteriorated, such as a decrease in stability, influence on members, and generation of a remarkable solvent odor.

(viscosity)
The scale adhesion preventing agent of the present invention is measured using a B-type viscometer (for example, “TV-10 viscometer” manufactured by Toki Sangyo Co., Ltd.) under the conditions of a liquid temperature of 20 ° C., a rotation speed of 60 rpm, and a rotation time of 30 sec. The measured viscosity is preferably 1 mPa · s or more and 2000 mPa · s or less. In addition, it measures by changing the kind of rotor with the viscosity to measure. When the viscosity is less than 10 mPa · s, an L adapter is used. When the viscosity is 10 mPa · s or more, an optimum rotor is appropriately selected and used according to the measurement range of the rotor. Moreover, in the case of 10 mPa * s or more, it measures by putting a scale adhesion prevention agent in a glass container of 110 mL capacity | capacitance of 40 mm x 120 mm (body diameter x full length). When the viscosity is 1 mPa · s or more, the liquid agent adheres and remains on various non-horizontal members and a desired film thickness can be obtained.
In particular, when spraying, 1 mPa · s or more and 1000 mPa · s or less is preferable, more preferably 1 mPa · s or more and 100 mPa · s or less, and further preferably 1 mPa · s or more and 50 mPa · s or less. With a viscosity of 50 mPa · s or less, a spray pattern can be formed and the construction efficiency is good.

(Other optional ingredients)
In addition to the water-soluble zinc salt and polyacrylamide, the scale adhesion preventing agent of the present invention includes the following surfactants, fragrances, water-soluble polymers other than polyacrylamide, and salts of zinc (II) ions. Antimicrobial agents, stabilizers, natural extracts, antistatic agents, fillers, antifoaming agents, deodorizing agents and the like can be optionally blended.

(Surfactant)
A surfactant can be appropriately blended for the purpose of imparting wettability to each substrate by reducing the adsorptivity to the substrate and the surface tension, or for the purpose of detergency and foaming. As the surfactant, commonly used ones such as an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, and a cationic surfactant can be used.
Specific examples of anionic surfactants include alkyl sulfates, alkyl ether sulfates, polyoxyethylene alkyl sulfates, alkylbenzene sulfonates, α-olefin sulfonates, fatty acid salts, ether carboxylates, alkyls. Examples of the counter ion (cation) include alkali metal ions, alkaline earth metal ions, alkanolamine ions, and ammonium ions.
Examples of amphoteric surfactants include alkyl diaminoethyl glycine chloride, alkyl carboxy betaine, alkyl sulfo betaine and the like.
Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, fatty acid polyglycerin ester, fatty acid sucrose ester, fatty acid alkanolamide, alkylamine oxide, alkylamidoamine. Examples include oxides.
Examples of the cationic surfactant include alkyltrimethylammonium salt type cationic surfactants and dialkyldimethylammonium salt type cationic surfactants. More specifically, trimethylpalmitylammonium chloride, dimethylammonium distearyl chloride, lauryldimethylbenzylammonium chloride, didecyldimethylammonium adipate, 1,4-bis (3,3 ′-(1-decylpyridinium) methyloxy) Examples include butane dibromide.
Surfactants may be used alone or in combination of two or more.

(Fragrance)
In the scale adhesion preventing agent of the present invention, a fragrance can be appropriately blended as an optional component for the purpose of flavoring or the like.
Although it does not specifically limit to a fragrance | flavor component, As specific examples, it is alcohol, such as aliphatic hydrocarbons, terpene hydrocarbon, aromatic hydrocarbons, aliphatic alcohol, terpene alcohol, aromatic alcohol, etc. , Ethers such as aliphatic ethers and aromatic ethers, oxides such as aliphatic oxides and terpene oxides, aliphatic aldehydes, terpene aldehydes, hydrogenated aromatic aldehydes, aldehydes such as thioaldehydes and aromatic aldehydes , Ketones such as aliphatic ketones and aromatic ketones, acetals, ketals, phenols, phenol ethers, aliphatic, terpene carboxylic acids, hydrogenated aromatic carboxylic acids, acids such as aromatic carboxylic acids, Acid amides, aliphatic lactones, macrocyclic lactones, terpene lactones, hydrogenation Lactones such as aromatic lactones and aromatic lactones, aliphatic esters, furan carboxylic acid esters, aliphatic cyclic carboxylic acid esters, cyclohexyl carboxylic acid esters, terpene carboxylic acid esters, aromatic carboxylic acid esters and the like And synthetic fragrances such as nitrogen-containing compounds such as nitromusks, nitriles, amines, pyridines, quinolines, pyrrole and indole, and natural fragrances from plants. A fragrance | flavor component may use individually or 2 types or more, and multiple are normally used.

(Water-soluble polymers other than polyacrylamide)
The water scale adhesion preventive agent of the present invention can be appropriately mixed with a water-soluble polymer other than polyacrylamide as an optional component for the purpose of film formation assistance, physical improvement, thickening and the like.
Specific examples of the water-soluble polymer include polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), polyethylene glycol (PEG), hydroxyethyl cellulose (HEC), polyvinyl pyrrolidone (PVP), xanthan gum and the like. The water-soluble polymer may be used alone or in combination of two or more.

(PH adjuster)
The scale adhesion preventive agent of the present invention may be appropriately mixed with a pH adjusting agent as an optional component for the purpose of eliminating irritation to the human body and contamination of the applied member and storage stability. it can.
Specific examples of the pH adjuster include acid agents such as inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid, and sodium hydroxide. And alkaline agents such as sodium carbonate and potassium carbonate, and amine salts such as monoethanolamine, diethanolamine and triethanolamine. The pH adjuster may be used alone or in combination of two or more.

(Antimicrobial agent)
An antimicrobial agent, that is, an antibacterial agent, an antifungal agent, or an antiseptic agent can be appropriately added as an optional component to the scale adhesion preventing agent of the present invention, depending on the purpose such as storage stability.
The microorganism mentioned here refers to bacteria, yeast, mold and the like. The antimicrobial effect described herein refers to suppressing the activity, metabolism, or stopping the activity, reducing the number of individuals, or eliminating the living individuals with respect to the microorganisms described above.
Specific examples of the antimicrobial agent include the above-mentioned cationic surfactants, methyl paraben, ethyl paraben, propyl paraben, butyl paraben, sorbic acid, potassium sorbate, dehydroacetic acid, sodium dehydroacetate, sodium acetate, benzoic acid, Examples thereof include sodium benzoate, paraoxybenzoate, benzalkonium chloride, phenoxyethanol, isopropylmethylphenol, EDTA, capric acid monoglyceride, and thiabendazole. These antimicrobial agents may be used alone or in combination of two or more.

(Preparation of scale adhesion preventive agent)
The scale adhesion preventing agent of the present invention is prepared by mixing water as a solvent, zinc salt, polyacrylamide, and optional components.

(Formation of film at room temperature)
In order to apply an anti-scaling agent for film formation, the target surface of a water-filled article may be applied by flow coating, spray coating as shown in FIG. 3, or by using an auxiliary tool such as a wool roller or sponge. Any method such as a method of spreading or rubbing the part with a nonwoven fabric impregnated with a liquid agent can be used. Even if the target surface is dry or wet with water, it can be constructed without problems. In addition, you may wash | clean the surface of an application site | part before application. Moreover, a heating process is not particularly required for forming a film, and a film exhibiting slow solubility can be formed under the curing conditions of drying at room temperature for about 30 minutes.

(Film thickness)
The scale adhesion preventive agent of the present invention can be applied repeatedly, and the formed film is gradually dissolved from the surface in contact with the water flow, so that the film thickness can be appropriately set according to the desired effect duration. For example, when applied to the application site by spraying, a film thickness of 1 nm or more and 10 μm or less is preferable, and when long-term sustainability is required, a film thickness of 10 nm or more and 10 μm or less is preferable. More preferably, it is 20 nm or more and 1.0 μm or less. The film thickness is a film thickness measured by a stylus type surface roughness meter. For example, it is measured in a cross-section observation mode using “SURFCOM 1500DX-12” manufactured by Tokyo Seimitsu Co., Ltd.

(Subsidiary properties of slow dissolution)
The slow solubility expresses the film thickness retention rate of the coating as a substitute characteristic. A liquid sample is flow-coated on an upright slide glass and dried at 25 ° C. for 12 hours to obtain a test piece. In addition, when a sufficient film thickness for measuring the film thickness cannot be obtained by one flow coating, overcoating is performed several times. As shown in FIG. 1, a part of the formed film is peeled off, and the film surface A and the surface of the slide glass substrate are continuously scanned with a probe to calculate the film thickness A obtained by measuring the cross-sectional shape. In addition, the film thickness of the film actually measured is in the range of about 0.01 μm to 10 μm. Next, the film thickness B is measured after the test piece is immersed in ion-exchanged water at 20 ° C. for 10 minutes under the conditions shown in FIG. The film thickness retention rate (%) is calculated by the following equation as a ratio of the film thickness B to the film thickness A.
Film thickness retention (%) = [film thickness B / film thickness A] × 100
The film thickness retention rate (%) is preferably 10% or more and 85% or less. In the case of 10% or more, the coating component necessary for developing the antimicrobial effect remains on the surface of the substrate, so that the antimicrobial property and antifouling property are maintained. Dirt can be washed away by dissolving the membrane surface. The film thickness retention rate is designed in the above range, so that it is possible to exert a continuous antimicrobial effect and a continuous antifouling effect due to the slow dissolution even at sites where water flows temporarily. It becomes.

(Available functions and applications)
By using the scale adhesion preventing agent of the present invention, functionalities such as aromaticity, antibacterial property, antifungal property, deodorant property, deodorant property, antifouling property and hydrophilicity can be expressed.
Possible uses are as follows.

(Anti-fouling property)
For example, since the surface of the coating is dissolved and the surface is renewed when the toilet cleaning water flows, the surface is renewed, so that a clean surface is obtained each time the toilet is cleaned. By utilizing the same action, it can be applied to indoor urinal articles such as a urinal, a bowl surface of a urinal, a bowl surface of a basin of a vanity, a sink in a kitchen, and each part in a bathroom. It can also be used on painted surfaces of automobile bodies and window glass surfaces facing indoors and outdoors. Effective for preventing stool, water stains, watermarks, sebum stains, soap scum and oil stains.

(Antimicrobial / deodorant)
The film formed by the scale adhesion preventing agent of the present invention contains a zinc salt. Therefore, the applied portion is not colored, and an excellent antimicrobial effect is exhibited against microbial stains such as black mold and pink slime that are generated around the water. Furthermore, due to the above-mentioned slow dissolution effect, the zinc (II) ion salt and the antimicrobial agent contained as an optional component are gradually released every time the surface of the coating dissolves, so that it is likely to occur at sites that come into contact with water. Proliferation of fungi and mold microorganisms can be suppressed. Furthermore, since a clean surface is formed each time water is applied, adhesion of sebum stains and soap residue stains that are nutrients for microorganisms can be suppressed, and an antimicrobial effect can be more effectively exhibited. Further, it is possible to prevent odor caused by microbial propagation. Such applications can be applied to urinals, urinal bowl surfaces, basin bowl surfaces of bathroom vanities, kitchen sinks and drain outlets, bathroom parts, and the like.

(Hydrophilic / Water film forming property)
Since the coating film formed by the scale adhesion preventing agent of the present invention has a hydrophilic surface, it exhibits a continuous antifogging effect when used on a mirror in a washstand, a mirror in a bathroom, or the like. Furthermore, since a clean surface is formed each time water is applied, adhesion of sebum stains and soap residue stains, which are nutrients for microorganisms, can be suppressed, and propagation of microorganisms such as black mold and pink slime can be suppressed. Therefore, it is possible to provide an antifogging agent that can suppress dirt (sebum dirt, soap residue dirt, scale dirt, microbial dirt, etc.) generated in the area around the water. In addition, since the film formed by applying the scale adhesion preventing agent of the present invention has a hydrophilic surface or forms a water film, the washing water easily spreads on the surface at the time of washing with water, and the contaminants attached with a smaller amount of water are washed away. It becomes possible. Furthermore, since it has slow solubility, hydrophilicity lasts for a long time.

(Aromatic)
When a fragrance is added as an optional component, the fragrance is gradually released by the above-described slow dissolution effect, so that a fragrance can be imparted to the space. Applications that can be applied include toilets and urinals where bad odors are a concern, and peripheral areas of drains in bathrooms and kitchens.

(Deodorant)
When a deodorant is added as an optional component, the deodorant is gradually released each time water is applied due to the above-mentioned slow dissolution effect, so that it is possible to deodorize malodors every time water is applied. Applications that can be applied include toilets and urinals where bad odors are a concern, and peripheral areas of drains in bathrooms and kitchens.

(Spraying device)
The scale adhesion preventing agent of the present invention can be filled in a container equipped with a spraying device. Sprayers can be sprayers such as aerosol, trigger, and manual pumps. Among them, sprayers such as trigger or manual pumps, which are manual spray devices, are preferred. preferable. The manual spray device has a liquid temperature of 20 ° C. and a spray of 0.1 g to 2.0 g, preferably 0.2 g to 1.5 g, particularly preferably 0.3 g to 1.3 g. What the composition squirts is good. Furthermore, when the composition having a liquid temperature of 20 ° C. is sprayed from a location 20 cm away from the substrate, the area where the composition adheres to the substrate by one spray is 2.5 cm ² or more and 200 cm ² or less, preferably 10 cm ^2. The spraying device is preferably 200 cm ² or less, more preferably 20 cm ² or more and 120 cm ² or less, and still more preferably 30 cm ² or more and 100 cm ² or less. Moreover, it is preferable that the spray apparatus applicable to this invention is provided with the member which seals the discharge outlet from which a liquid agent is discharged. A preferred embodiment of the sealing member is a lid for preventing the liquid agent inside the discharge port from being dried during storage, and the lid is preferably removable or openable.

The following were prepared as raw materials for scale adhesion inhibitors.
Zinc salt component, zinc acetate (II) dihydrate, zinc gluconate (II) trihydrate, zinc citrate dihydrate, zinc lactate trihydrate All of these zinc salts are reagent special grade or equivalent Grade ones were used.
Water-soluble polymer component, polyacrylamide (mass average molecular weight 16 million, unmodified)
・ Polyacrylamide (mass average molecular weight 8 million, no denaturation)
・ Polyacrylamide (mass average molecular weight 500,000, no denaturation)
Cationic polyacrylamide (mass average molecular weight 4 million, acrylamide 2- (acryloyloxy) ethyltrimethylammonium chloride copolymer, acrylamide 60 mol%)
Cationic polyacrylamide (mass average molecular weight 400,000, Hoffman degradation product (acrylamide-vinylamine copolymer), acrylamide 90 mol%)

Anionic polyacrylamide (mass average molecular weight 2.9 million, acrylamide 90 mol%, chemical formula weight of polyacrylamide average structural unit: 70.8)
Polyvinyl alcohol (saponification degree 95%, polymerization degree 1700, no modification)
-Cationic polyacrylamide (mass average molecular weight 5 million, acrylamide, acrylic acid, 2- (acryloyloxy) ethyltrimethylammonium chloride, 2- (methacryloyloxy) ethyltrimethylammonium chloride copolymer, acrylamide 40 mol%, average of polyacrylamide Chemical amount of structural unit: 148.7)
Solvent / water (distilled water)
・ Ethanol (special grade reagent)
Surfactant / amphoteric surfactant (main component: alkyldiaminoethylglycine chloride)
・ Nonionic surfactant (main component: polyoxyethylene lauryl ether)
・ Anionic surfactant (main component: sodium polyoxyethylene alkyl ether sulfate)
・ Cationic surfactant (main component: didecyldimethylammonium adipate)
Fragrance / Natural essential oil PEPPERMINT OIL (manufactured by Toyoda Fragrance Co., Ltd.)

Various zinc components dissolved in advance, various water-soluble polymer components, and other components described above were added to water as a solvent so as to have the concentrations shown in Table 1 and mixed.
Table 1 summarizes the liquid composition of Examples and Comparative Examples of the present invention. The following evaluation tests were performed on the various liquids obtained.

Evaluation 1: Evaluation of slow solubility For the various scale adhesion preventive agents of Examples 1 to 29, a slow solubility evaluation test was evaluated according to the procedure described in paragraph (0038). The determination was made based on the film thickness retention rate, and the retention rates of 10% or more and 85% or less were “OK”, and the retention rates of less than 10% and over 85% were “NG”.

Evaluation 2: Appearance evaluation of the coating The appearance evaluation of the coating was performed as follows for various scale adhesion preventive agents. Various scale adhesion inhibitors of Examples 1 to 21 and Examples 23 to 29 were flow coated on a glass plate and dried at 25 ° C. for 12 hours to prepare test pieces. When the appearance of the prepared test piece was visually transparent, “OK” was designated, and when the coating was visually colored or clouded, “NG” was designated.

The evaluation results of Evaluation 1 and Evaluation 2 are summarized in Table 4.

As shown in Table 4, the film thickness retentions of the films prepared using the liquid agents of Examples 1 to 19 and Examples 24 to 29 were all 10% to 85%, and the solubility was appropriately controlled. Demonstrates slow solubility.
On the other hand, the film formed with the liquid agent of Examples 20 to 23 (comparative) could not be detected after the solubility test.

Evaluation 3: Antifungal evaluation The antifungal evaluation test was conducted as follows for various scale adhesion inhibitors. Various scale adhesion inhibitors were spread on a glass plate and dried at 25 ° C. for 12 hours to prepare test pieces. Next, antifungal properties before and after the hot water resistance test were evaluated. The hot water resistance test was performed by immersing the test piece in ion exchange water at 50 ° C. for 10 minutes. In the test, Cladosporium sp. I tried. On the test piece, 500 μl of a nutrient solution obtained by diluting a nutrient solution containing 0.8% by mass of glucose and 0.2% by mass of peptone to 1/50 and Cladosporium sp. 5 × 10 ³ spores / ml were inoculated and cultured at a temperature of 27 ° C. and a humidity of 90% or more for 1 week. In the judgment, the test result before the dissolution test is evaluated as “OK” (good) when the antifungal level is 1 and “NG” (not good) when the antifungal level is 2 or more, and the test result after the dissolution test is The antifungal level 2 or lower was evaluated as “OK” (good), and the antifungal level 3 or higher was evaluated as “NG” (not good).
“Anti-mold level 1”: Mold growth cannot be confirmed with the naked eye at the inoculation site of the test piece.
“Anti-mold level 2”: Slight mold growth is observed at the inoculation site of the specimen with the naked eye.
“Anti-mold level 3”: Mold growth almost equal to that of the blank piece is observed.
“Anti-fungal level 4”: Growth of mold more than blank piece is observed.

  The evaluation results of Evaluation 3 are summarized in Table 5.

  As shown in Table 5, in the test pieces coated with the liquids of Examples 5, 7 to 15, 17, 18 and 27, the antifungal level on the coating surface was “OK” before and after the dissolution test was performed. It was. The test pieces coated with the solutions of Example 20 (Comparative), Example 21 (Comparative) and Example 23 (Comparative) were “NG” at the initial antifungal level.

Evaluation 4: Antibacterial Evaluation limescale preventive agent was conducted evaluation tests of the antimicrobial in the following manner. Various scale adhesion inhibitors were spread on a glass plate and dried at 25 ° C. for 12 hours to prepare test pieces. Antibacterial performance before and after performing the dissolution test described in paragraph (0038) was evaluated using E. coli (IFO 3972) with reference to JIS Z 2801. The antibacterial activity value R of the test piece coating surface after the dissolution test calculated by the following formula was “OK” when the antibacterial activity value R was 2 or more, and “NG” when it was less than 2.

Antibacterial activity value R = Log ₁₀ (Cs / Cb)
Cs: number of E. coli on the liquid-coated surface after 24 hours of culture Cb: number of E. coli on the uncoated glass surface after 24 hours of culture

The evaluation results of Evaluation 4 are summarized in Table 6.

  As shown in Table 6, in the test piece coated with the liquid of Example 1, Example 2, Example 5, Example 7 to Example 9, Example 11, Example 12, Example 14, Example 17, Example 18, Example 25 to Example 27 Before and after the dissolution test, the antibacterial property of the coating surface was “OK”.

Evaluation 5: Antibacterial evaluation in bathroom The antibacterial adhesion evaluation agents of Examples 11 and 27 were evaluated for antibacterial activity against a bathroom part using a monitor that answered that microbial dirt was generated in the bathroom space. First, the scale type spray pump (Z-305 series, manufactured by Mitani Valve Co., Ltd.) was filled with the scale adhesion preventing agent of Examples 11 and 27. Next, the scale adhesion preventive agent was sprayed evenly once a day to areas where microbial stains were likely to occur, such as bathroom floors, walls, drain openings, bath lids, and bath chairs (FIG. 3). The target site after 2 weeks is “OK” when the microbial stain is not visually recognized with respect to the site that has not been sprayed. What was recognized was designated as “NG”.

  From the result of evaluation 5, in the target site sprayed with the scale adhesion preventing agent of Examples 11 and 27, no microbial stain was observed after 2 weeks. On the other hand, microbial stains such as black mold and pink slime were observed in the areas not sprayed.

Evaluation 6: Scale adhesion suppression effect Evaluation of the liquid agent of Example 1 on a 10 cm square nickel chrome plated plate and dried at 25 ° C. for 12 hours in order to promote scale adhesion on the surface of the coating obtained by 297. 5 “Evian” ® was sprayed 5 times. Then, “OK” was defined as “OK” when no dirt adhesion was visually observed after 12 hours at 25 ° C.

The nickel chrome plated plate coated with the liquid of Example 1 was “OK” because no dirt adhered to the scale was observed. On the other hand, the untreated nickel chrome plating plate was found to be “NG” due to water stain adhesion.

Evaluation 7: Hydrophilic and water film forming property The liquid preparation of Evaluation Example 1 is spread on a φ140 mm end plate, ion-exchanged water is sprayed five times with a trigger spray, and the entire mirror becomes hydrophilic visually, or a water film “OK” was defined as “OK”, and “NG” was defined as water repellent visually and a water film not formed.

In the end plate coated with the scale adhesion preventive agent of Example 1, a water film was formed on the entire mirror and was “OK”. On the other hand, the untreated end plate was “NG” without forming a water film.

Evaluation 8: The antifogging evaluation example 1 was spread on a φ140 mm end plate, water vapor generated from a steam generator was applied for 1 minute, and then the entire mirror was not fogged visually as “OK”. “NG” was defined as the entire mirror being clouded visually.

  In the end plate to which the liquid preparation of Example 1 was applied, the entire mirror was not cloudy and was “OK”. On the other hand, in the untreated end plate, the entire mirror was cloudy and was “NG”.

Evaluation 9: Evaluation of anti-stool adhesion prevention The solution of Evaluation Example 1 was applied evenly to the half of the surface of the pottery in the toilet bowl, which had been brush-washed in advance, with a brush and dried for 60 minutes. After that, the use of the toilet is started. Compared with the untreated surface, those with no or less stool adherence are designated as “OK”, and those with stool adherence as with the untreated surface are designated as “NG”. did.

  As a result of evaluation, stool adhesion was observed on the untreated surface, but stool adhesion was not observed on the surface coated with the liquid preparation of Example 1, and the result was “OK”. By coating the liquid preparation of Example 1, a continuous antifouling property was developed.

Evaluation 10: Evaluation of liquid agent stability of Example 1, Example 2, Example 4, Example 5, Example 6, Example 8, Example 9, Example 10, Example 12, Example 13, Example 16, Example 17, Example 18, Example 22 The liquid was allowed to stand in a room temperature room for 3 months, and visual appearance and state change were evaluated. “OK” indicates that there is no precipitation, gelation, or coloring appearance change, and “NG” indicates that precipitation, gelation, or coloring appearance change occurs.

The evaluation results of Evaluation 10 are shown in Table 7.

  Example 1, Example 2, Example 4, Example 5, Example 6, Example 8, Example 9, Example 10, Example 12, Example 13, Example 16, Example 17, Example 18 showed no change in appearance or condition. It had excellent storage stability and was “OK”. On the other hand, the liquid preparation of Example 22 (comparative) had a white precipitate and was “NG”.

Evaluation 11: Spray pattern evaluation example 9, Example 13, Example 16, Example 23, Example 27 solution at 20 ° C. and ion-exchanged water were applied to trigger type spray (TS01-MC190P, manufactured by Kono Resin Co., Ltd.). Filled, water-absorbing paper was placed perpendicular to the spray port at a location 20 cm away from the trigger spray port, and the composition was sprayed once. Water "○" those areas to which the composition is adhered is in the range of 10 cm ² or more 200 cm ² or less in absorption paper, less than ² adhered area is 10 cm, or in excess of 200 cm ² from the "△", a trigger spray nozzle A paper that did not reach the paper and did not adhere to the water-absorbing paper was marked “x”.

  The liquid agent was used for various evaluations after the constituent raw materials were formulated with the composition described in the table and allowed to stand for 1 day. Here, the viscosity was evaluated according to the conditions described in paragraph (0028).

  The evaluation results of Evaluation 11 are summarized in Table 8.

As shown in Table 8, when the liquid agents of Example 9, Example 13, Example 16, Example 23, and Example 27 were sprayed, the liquid agent adhered to the water absorbent paper. Furthermore, for the liquid agents of Example 9, Example 13, Example 16, and Example 27, the area adhered to the water-absorbent paper was in the range of 10 cm ² or more and 200 cm ² or less. The viscosity is about 100 mPa · s or more Example 23, the area attached to the absorption paper, was less than 2.5 cm ² or more 10 cm ^2.

The figure which showed the film thickness evaluation method of the formed film typically The figure which showed typically the dissolution processing method of the test piece which formed the film on the surface The figure which showed the application method to the member of the bathroom

Claims (7)

A salt of zinc (II) ions, polyacrylamide, and water as a solvent,
A substance having a unit structure of polyacrylamide, wherein the salt is contained in an amount of 0.01 mM to 100 mM and the polyacrylamide is contained in an amount of 0.001% by mass to 10% by mass with respect to the liquid agent. A scale adhesion preventive agent having a ratio to the amount (mol) of 1/100 or more and 10 or less.   The scale adhesion preventing agent according to claim 1, wherein the salt has a solubility in water at 20 ° C of at least 0.01% by mass.   The scale adhesion preventing agent according to claim 1 or 2, wherein the salt is selected from the group consisting of zinc acetate, zinc gluconate, zinc lactate, and zinc citrate.   The scale adhesion according to any one of claims 1 to 3, wherein the polyacrylamide contains at least one functional group selected from the group of a nonionic group, a cationic group, and an anionic group. Inhibitor.   The scale adhesion preventing agent according to any one of claims 1 to 4, wherein the polyacrylamide has a mass average molecular weight (measured by gel permeation chromatography using polystyrene as a standard sample) of 10,000 or more and 20000000 or less.   The scale adhesion preventing agent according to any one of claims 1 to 5, which has a pH of 3 to 10.   The scale adhesion preventing agent according to any one of claims 1 to 6, further comprising an alcohol having 2 or 3 carbon atoms as a solvent.

Images