WO2008036559A2

WO2008036559A2 - Antifouling detergent composition for hard surface, washing mateiral impregnated with the composition, and washing method using same

Info

Publication number: WO2008036559A2
Application number: PCT/US2007/078472
Authority: WO
Inventors: Shigekazu Ishii
Original assignee: Johnsondiversey, Inc.
Priority date: 2006-09-21
Filing date: 2007-09-14
Publication date: 2008-03-27
Also published as: JP2008074975A; WO2008036559A3; JP5079290B2

Abstract

The present invention provides an antifouling detergent composition for hard surfaces capable of imparting the material surface of bathrooms or bathtubs composed of plastic materials and also articles for bathrooms such as seats, pails, and draining boards with antifouling capability, moderating the adhesion of contamination such as soap residues, sebaceous matter, and inorganic components (scale) such as calcium and magnesium that are hard water components of tap water and well water, and easily washing and removing the adhered contamination thereof, and also provides a washing material impregnated with such a composition and washing methods using the composition and washing material. The antifouling detergent composition for hard surfaces contains: (A) 0.5 to 60 wt.% ethylene oxide - propylene oxide - ethylene oxide copolymer, (B) 0.1 to 15 wt.% surfactant, (C) 0.1 to 15 wt.% chelating agent, (D) 0.1 to 15 wt.% water-soluble solvent, and (E) water as the balance. The washing method using the antifouling detergent composition for hard surfaces or the washing material impregnated with the composition.

Description

ANTIFOULING DETERGENT COMPOSITION FOR HARD SURFACES, WASHING MATERIAL IMPREGNATED WITH THE COMPOSITION, AND WASHING METHOD

USING SAME

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to an antifouling detergent composition for hard surfaces that can be used on bathrooms or bathtubs composed of plastic materials such as polyethylene, polypropylene and FRP and also articles for bathrooms such as seats, pails, and draining boards, thereby causing the adsorption of an ethylene oxide - propylene oxide - ethylene oxide copolymer on the surface of the articles to be washed, forming a hydrophilic monomolecular film, imparting the material surface with antifouling capability, moderating the adhesion of contamination such as soap residues, sebaceous matter, and inorganic components (scale) such as calcium and magnesium that are hard water components of tap water and well water, and enabling to wash and remove easily the adhered contamination.

The FRP is an abbreviation of Fiber Reinforced Plastics and, as a general term, relates to plastics reinforced with glass fibers. Typical examples of such plastics use glass fibers as a reinforcing material and unsaturated polyester resins, epoxy resins, and vinyl ester resins as a matrix (see "FRP Molding", published by Kobunshi Kankokai KK) . 2. Description of the Related Art Most bathrooms, bathtubs, and washstands in business hotels, city hotels, fashion hotels, and tourist hotels are made from plastic materials based on FRP. These items are used by customers on a 24 -hour basis, and the surface of these plastic materials is constantly exposed to hot -water shower, soaps, shampoos, rinses, hand soaps, and cosmetics. As a result, bathroom contamination adhere to the surface of plastic materials. Workers responsible for maintaining the facilities have been using neutral detergents for bathrooms and also acidic to weakly acidic detergents for bathrooms to remove the contamination.

For example, Japanese Patent Application Laid-open Mo. 61-283700 discloses a neutral detergent for bathrooms that contains a cationic surfactant, a nonionic surfactant, and a maleic acid (co) polymer and has excellent washing capacity. Further, Japanese Patent Application Laid-open No. 1-221497 discloses a neutral detergent for bathrooms that contains a cationic surfactant, a nonionic surfactant, and an aminocarboxylic acid and demonstrates excellent washing capacity and ability to prevent the adhesion of silicate scale Further, Japanese Patent Applications Laid-open Nos . 51-71302 and 52-77111 disclose a detergent composition comprising an organic acid, a surfactant, and a water-soluble solvent as an acidic to weakly acidic detergent. Japanese Patent Application Laid-open No. 64-38498 discloses a detergent composition for bathrooms that contains a surfactant, a hydroxy polycarboxylic acid, a polymer (copolymer) of acrylic acid or methacrylic acid, and a water-soluble solvent, where the pH of the composition is 3 to 6.

As a previously filed patent application relating to antifouling performance, Japanese Patent Application Laid-open Mo. 3-197596 discloses a detergent composition containing a silicone such as dimethylsiloxane as the main component and also including a surfactant, a water-soluble solvent, and a sequestering agent. Japanese Patent Application Laid-open No. 2000-198999 discloses an antifouling and bactericidal detergent composition for hard surfaces that contains a cationic surfactant of a quaternary ammonium type and a hydrophilic silicone. Further, Japanese Patent Application Laid-open No. 2004-162041 discloses an antifouling detergent composition containing a polyether amidoamine-modified silicone, a surfactant, and a chelating agent.

However although the above-described neutral and acidic to weakly acidic detergents demonstrate sufficient washing capacity with respect to light bathroom contamination, they cannot sufficiently wash hard bathroom deposits. As a result, cleansers containing abrasives or hard washing pads are used to perform extra scrubbing and the plastic surface of bathtubs is worn, thereby creating poor environment in which contamination such as soap residues and sebaceous matter easily adhere to the surface. Accordingly, there is a demand for simple and easy maintenance and washing of bathroom facilities that cause no damage to bathtubs and bathrooms.

In particular, with the acidic to weakly acidic detergents, there is a risk of being poisoned by chlorine gas generated due to combined use of a chlorine-containing detergent and a bleaching agent, the articles to be washed such as metals and plastics are easily damaged, and there is a risk that the detergent that accidentally adhered to skin will cause inflammation.

On the other hand, compositions containing dimethylpolysiloxane or a silicone modified with hydrophilic functional groups as the main component have been suggested as detergent compositions demonstrating antifouling performance, but none of them produced a satisfactory antifouling effect.

SUMMARY OF THE INVENTION

With the foregoing in view, it is an object of the present invention to provide an antifouling detergent composition for hard surfaces that can be used on bathrooms or bathtubs composed of plastic materials such as polyethylene, polypropylene and FRP and also articles for bathrooms such as seats, pails, and draining boards, thereby causing the adsorption of an ethylene oxide - propylene oxide - ethylene oxide copolymer on the surface of the articles to be washed, forming a hydrophilic monomolecular film, imparting the material surface with antifouling capability, moderating the adhesion of contamination such as soap residues, sebaceous matter, and inorganic components (scale) such as calcium and magnesium that are hard water components of tap water and well water, and making it possible to wash and remove easily the adhered contamination, and also to provide a washing material impregnated with the composition and a washing method using them.

In order to attain this object, the first gist of the present invention resides in an antifouling detergent composition for hard surfaces, comprising: (A) 0.5 to 60 wt . % ethylene oxide - propylene oxide - ethylene oxide copolymer represented by the formula below; (B) 0.1 to 15 wt . % surfactant; (C) 0.1 to 15 wt . % chelating agent; (D) 0.1 to 15 wt . % water-soluble solvent; and (E) water as the balance: HO- (C₂H₄O)_n- (C₃H₆) _m- (C₂H₄O)_n-H (where n is integer other than 0).

The second gist of the present invention resides in the antifouling detergent composition for hard surfaces in which an average molecular weight of the ethylene oxide - propylene oxide - ethylene oxide copolymer of the component (A) is 4,000 or more and 25,000 or less.

The third gist of the present invention resides in the antifouling detergent composition for hard surfaces in which the ratio of ethylene oxide in the average molecular weight of the ethylene oxide - propylene oxide - ethylene oxide copolymer of the component (A) is 50 to 85 wt . % .

The fourth gist of the present invention resides in the antifouling detergent composition for hard surfaces that is used for bathrooms and bathtubs . The fifth gist of the present invention resides in the antifouling detergent composition for hard surfaces in which a pH (determined by "pH Measurement Methods" of JIS Z-8802:1984) of a stock solution of the antifouling detergent composition for hard surfaces is set to 6 to 8 at 25°C.

The sixth gist of the present invention resides in a washing material impregnated with the antifouling detergent composition.

The seventh gist of the present invention resides in a washing method comprising the steps of: wiping contamination of a hard surface by using the washing material; and wiping the detergent composition remaining on the hard surface with a towel or duster containing water.

The eighth gist of the present invention resides in a washing method comprising the steps of: spraying or coating, on a hard surface, a washing solution prepared by diluting with water the antifouling detergent composition for hard surfaces at a ratio of 2 to 10; and rinsing with water.

The results of a comprehensive research of materials that can demonstrated an antifouling washing effect with respect to bathroom contamination that adhered to bathrooms or bathtubs composed of plastic materials such as polyethylene, polypropylene and FRP and also articles for bathrooms such as seats, pails, and draining boards show that none of a variety of fluorine compounds, modified silicone compounds, and acrylic polymer compounds produces the desired effect, whereas the satisfactory effect is produced by an ethylene oxide - propylene oxide - ethylene oxide copolymer. This finding led to the creation of the present invention.

Thus, the antifouling detergent composition for hard surfaces in accordance with the present invention is used on bathrooms or bathtubs composed of plastic materials such as polyethylene, polypropylene and FRP and also articles for bathrooms such as seats, pails, and draining boards (these articles will be together referred to hereinbelow as "bathroom articles"), thereby causing the adsorption of an ethylene oxide - propylene oxide - ethylene oxide copolymer on the surface of the articles to be washed, forming a hydrophilic monomolecular film, imparting the material surface with antifouling capability, moderating the adhesion of contamination such as soap residues, sebaceous matter, and inorganic components (scale) such as calcium and magnesium that are hard water components of tap water and well water, and making it possible to wash and remove easily the adhered contamination. Therefore, the amount of labor and daily washing load on workers can be greatly reduced, operation efficiency can be increased, appearance of bathrooms can be improved, and sanitary level can be maintained.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The preferred embodiments of the present invention will be described below in greater detail .

The antifouling detergent composition for hard surfaces in accordance with the present invention (also referred to hereinbelow as "the present composition") comprises the following essential components : (A) an ethylene oxide - propylene oxide - ethylene oxide copolymer, (B) surfactant, (C) a chelating agent, (D) a water-soluble solvent, and (E) water as the balance.

The ethylene oxide - propylene oxide - ethylene oxide copolymer that is the component (A) used in accordance with the present invention is compounded with the object of causing the adsorption of the ethylene oxide - propylene oxide - ethylene oxide copolymer on the surface of the articles to be washed, forming a hydrophilic monomolecular film, imparting the material surface with antifouling capability, moderating the adhesion of contamination such as soap residues, sebaceous matter, and inorganic components (scale) such as calcium and magnesium that are hard water components of tap water and well water, and making it possible to wash and remove easily the adhered contamination when the antifouling detergent composition is used on bathrooms or bathtubs composed of plastic materials such as polyethylene, polypropylene and FRP and also articles for bathrooms such as seats, pails, and draining boards. One or a combination of two or more such copolymers may be used.

Ethylene oxide - propylene oxide - ethylene oxide copolymers can be manufactured by block polymerization or random polymerization, but the ethylene oxide - propylene oxide - ethylene oxide copolymer that is the component (A) used in accordance with the present invention is synthesized by block polymerization, more specifically by using propylene glycol as a stating source material, initially blowing propylene oxide gas thereinto in a reaction polymerization tank under a high temperature and a high pressure, conducting a reaction to form polypropylene glycol, and then blowing ethylene oxide gas and conducting a reaction. In the component (A) thus produced, ethylene oxide is added to propylene oxide serving as a center on both sides thereof.

The ethylene oxide - propylene oxide - ethylene oxide copolymer that is the component (A) preferably has an average molecular weight of 4,000 or more to less than 25,000 and a ratio of ethylene oxide in the average molecular weight of 50 to 85 wt . % . A copolymer with an average molecular weight of 8,000 to 23,000 and an addition ratio of ethylene oxide of 60 to 85% is more preferred, and a copolymer with an average molecular weight of 20,000 and an addition ratio of ethylene oxide of 80% is even more preferred.

Where the average molecular weight of the ethylene oxide - propylene oxide - ethylene oxide copolymer is less than 4,000, the capacity of the copolymer to be adsorbed by plastic materials is weak and the formation of hydrophilic monomolecular film is insufficient. As a result, antifouling performance is insufficient. On the other hand, the upper limit of the average molecular weight is set to less than 25,000 because the copolymers with an average molecular weight of 25,000 or more are not available on the market, but if the copolymers with an average molecular weight of 25,000 or more were available, the use thereof would not be prohibited by the essence of the present invention.

Further, where the addition ratio of ethylene oxide is less than 50 wt.%, the addition ratio of ethylene oxide is low and the addition ratio of propylene oxide increases. As a result, the capacity to be adsorbed by plastic materials is weak, a hydrophilic monomolecular film cannot be formed, and no antifouling property is demonstrated. Further, the present detergent composition cannot be foamed and solubilization capacity thereof decreases. As a result, the desired stability of the present detergent composition in storage cannot be attained.

Further, where the addition ratio of ethylene oxide exceeds 85 wt.%, hydrophility becomes too high. As a result, the undesirable tendency to foaming becomes stronger.

Further, the ethylene oxide - propylene oxide - ethylene oxide copolymer specified as described hereinabove is compounded at a ratio within a range of 0.5 to 60 wt.% based on the entire present composition in accordance with the present invention.

Thus, where the compounding ratio is less than 0.5 wt.%, the amount adhered to the surface of bathrooms or bathtubs composed of plastic materials such as polyethylene, polypropylene and FRP and also articles for bathrooms Is insufficient and a monomolecular film is not formed. As a result, the material surface does not demonstrate the antifouling property and the adhesion of bathroom contamination cannot be moderated. On other hand, when the ratio exceeds 60 wt.%, the effect of alleviating the adhesion of contamination reaches saturation, the surface becomes sticky and uneven, and rinsing ability is degraded. Therefore, it is preferred that within the above-described range, the ethylene oxide - propylene oxide - ethylene oxide copolymer be compounded at a ratio within a range of 1 to 40 wt.%, even more preferably within a range of 2 to 20 wt.% based on the entire present composition in accordance with the present invention.

Examples of surfactants (component B) for use in accordance with the present invention include nonionic surfactants, amphoteric surfactants, anionic surfactants, and cationic surfactants. Examples of nonionic surfactants suitable as the component (B) include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyalkylene alkylphenyl ethers , alkyl polyglucosides, fatty acid polyglycerin esters, fatty acid cane sugar esters, and fatty acid alkanolamides .

In accordance with the present invention, from among these nonionic surfactants, polyoxyalkylene alkyl ethers, alkyl polyglucosides, and fatty acid alkanolamides are preferred .

Examples of amphoteric surfactants include alkylcarboxybetaines, alkylsulfobetaines , alkylhydroxysulfobetaines , alkylamidobetaines , imidazoliniumbetaines , alkyldiaminoethylglycines, dialkyldiaminoethylglycines, alkyl amine oxides, alkyl etheramine oxides, and amidoamine oxides.

In accordance with the present invention, from among these amphoteric surfactants, alkylamidobetaines and alkyl amine oxides are preferred.

Examples of anionic surfactants include alkylsulfuric acid salts, alkylsulfuric acid ester salts, alkylbenzenesulfuric acid salts, alpha-olefinsulfonic acid salts, metaxylenesulfonic acid salts, paraxylenesulfonic acid salts, and cumenesulfonic acid salts.

Examples of counter-ions of these anionic surfactants include sodium, magnesium, ammonium, and ethanolamine . In accordance with the present invention, from among these anionic surfactants, sodium lauryl sulfate, ammonium lauryl sulfate, sodium salts of laurylsulfuric acid esters, and ammonium salts of laurylsulfuric acid esters are preferred.

Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylammonium adipates, benzalkonium salts, benzenethonium salts, pyridinium salts, imidazolinium salts, and biguanido compounds. Halogens are examples of counter-ions of these cationic surfactants.

In accordance with the present invention, from among these cationic surfactants, benzalkonium chloride and dialkyldimethylammonium chlorides are preferred.

By compounding the surfactant that is the component (B) , washing capacity, leveling ability on the surface to be washed, ability to impart suitable foaming, good rinsing ability, and bactericidal ability can be attained, and the appropriate surfactant can be selected for use according to the requirements placed on the aforementioned properties. These surfactants may be used individually or in combination of two or more thereof. The "leveling ability" is "wetting ability" and means the ability of the composition to wet and spread uniformly, without separation from the surface, when the composition is coated or sprayed on the surface to be washed.

The surfactant that is the component (B) is compounded within a range of 0.1 to 15 wt . % based on the entire composition of the present invention. Where the compounding ratio of the surfactant is less than 0.1 wt.%, washing capacity, leveling ability on the surface to be washed, foaming ability and bactericidal ability are poor, and when the compounding ratio is more than 15 wt.%, the above- mentioned performance such as washing capacity is at a saturation state and the addition is cost inefficient .

From the standpoint of performance, the compounding ratio of the surfactant is preferably within a range of 1 to 15 wt.%, and from the standpoint of cost efficiency, the compounding ratio is preferably within a range of 1 to 10 wt . % .

Examples of suitable chelating compounds suitable as the component (C) used in accordance with the present invention include polymers and copolymers of carboxyl group-containing monomers of at least one kind selected from acrylic acid, maleic acid, methacrylic acid, and aconitic acid, and water- soluble metal salts thereof, or organic acids such as citric acid, malic acid, tartaric acid, succinic acid, gluconic acid, and phthalic acid, and alkali metal salts thereof. Examples of suitable water-soluble alkali metal salts include sodium salts, potassium salts, ammonium salts and ethanolamine salts. Among them, sodium salts and ammonium salts are preferred.

More specifically, examples of polymers and copolymers of carboxyl group-containing monomers of at least one kind selected from acrylic acid, maleic acid, methacrylic acid, and aconitic acid, and water-soluble alkali metal salts thereof include sodium polyacrylate, sodium polymaleate, sodium polymethacrylate, sodium polyaconitate, acrylic acid - vinyl compound copolymer, styrene - maleic acid copolymer, isoamylene - maleic anhydride copolymer, methylvinyl ether - maleic acid copolymer, acrylic acid - maleic acid copolymer, sodium salt of acrylic acid - vinyl compound copolymer, sodium salt of styrene - maleic acid copolymer, sodium salt of isoamylene - maleic anhydride copolymer, sodium salt of methylvinylether - maleic acid copolymer, and sodium salt of acrylic acid - maleic acid copolymer.

Examples of organic acids such as citric acid, malic acid, tartaric acid, succinic acid, gluconic acid, and phthalic acid, and alkali metal salts thereof include sodium citrate, sodium maleate, sodium tartrate, sodium succinate, sodium gluconate, sodium phthalate, potassium citrate, potassium gluconate, and ammonium citrate.

These chelating agents may be used individually or in combination of two or more thereof.

Among these chelating agents that are suitable as the component (C) , a polymer or a copolymer having at least one acid from among maleic acid and acrylic acid as a monomer, and water-soluble alkali salts thereof are preferred, specific examples including maleic acid polymer, acrylic acid polymer, polymer of maleic acid and acrylic acid, and water-soluble alkali metal salts thereof. The especially preferred among them are sodium polymaleate, sodium polyacrylate, and sodium salt of acrylic acid and maleic acid copolymer. Citric acid, malic acid, and water-soluble alkali salts thereof are especially preferred.

It is preferred that maleic acid polymer, acrylic acid polymer, and water-soluble alkali metal salts thereof be used that have an average molecular weight of 600 to 15,000, more preferably 1,000 to 15,000. It is preferred that maleic acid - acrylic acid copolymer and water-soluble alkali metal salts thereof be used that have an average molecular weight of 1,000 to 100,000, more preferably 50,000 to 80,000. The chelating agents can be used upon pH adjustment and neutralization, but because they are themselves acidic, they sometimes demonstrate a pH adjusting function for neutralizing other components.

By compounding the above-descried chelating agent that is the component (C) , it is possible to soften hard water (also described hereinbelow as "hard water softening ability") and improve washing ability with respect to soap residues that adhered to baths and bathtubs .

The chelating agent that is the component (C) is compounded within a range of 0.1 to 15 wt . % based on the entire present composition in accordance with the present invention. Where the quantity thereof is less than 0.1 wt.%, hard water softening ability and washing ability are poor, and when the chelating agent is compounded at more than 15 wt.%, the improvement of hard water softening ability and the like reaches saturation and the addition is cost inefficient . From the standpoint of performance, the compounding ratio of the chelating agent is preferably within a range of 0.5 to 15 wt.%, and from the standpoint of cost efficiency, it is more preferred to be within a range of 0.5 to 10 wt.%.

Examples of the water-soluble solvent that is the component (D) used in accordance with the present invention, include (1) alcohols such as monohydric alcohols, e.g. ethanol , propanol , isopropanol, and butanol, alkylene glycols, e.g., ethylene glycol, diethylene glycol, isoprene glycol, and propylene glycol, and polyhydric alcohols such as glycerin, polyglycerin, and 1 , 3-butanediol , (2) glycol ethers including alkylene glycol (mono, di) alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, triethylene glycol monobutyl ether, and tripropylene glycol dimethyl ether, and (3) pyrrolidone compounds such as 2- pyrrolidone, 3 -pyrrolidone, N-alkyl -2 -pyrrolidones such as N- methyl -2 -pyrrolidone, N-ethyl -2 -pyrrolidone, and N-propyl-2- pyrrolidone, 5-alkyl-2 -pyrrolidones such as 5-methyl-2- pyrrolidone, 5-ethyl -2 -pyrrolidone, and 5-propyl -2 -pyrrolidone, and N-alkyl-3-pyrrolidones such as N-vinyl-2 -pyrrolidone, N- methyl-3 -pyrrolidone, N-ethyl -3 -pyrrolidone, and N-propyl-3- pyrrolidone .

In accordance with the present invention, among these water-soluble solvents that are suitable as the component (D) , ethanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and N-methyl-2 -pyrrolidone are preferred.

By compounding the water-soluble solvent that is the component (D) , it is possible to maintain washing ability in particular with respect to sebaceous matter, and this component can be appropriately selected and used as necessary. The aforementioned water-soluble solvents may be used individually or in combinations of two or more thereof.

The compounding ratio of the water-soluble solvent that is the component (D) is within a range of 0.1 to 15 wt . % based on the entire composition in accordance with the present invention. Where this ratio is less than 0.1 wt.%, washing ability with respect to sebaceous matter and stability of the present composition in storage are poor, and when the water- soluble solvent is compounded at more than 15 wt.%, the effect reaches saturation and the addition thereof is cost inefficient. From the standpoint of performance, it is preferred that the compounding ratio of the water-soluble solvent be within a range of 1 to 15 wt.%, and from the standpoint of cost efficiency, a range of 1 to 10 wt.% is more preferred.

Examples of water, which is the (E) component used in accordance with the present invention, include pure water, ion-exchange water, soft water, distilled water, and tap water, These kinds of water may be used individually or in combinations of two or more thereof. From the standpoint of stability of the present composition in storage, ion-exchange water is preferred. The "water" as referred to hereinabove is a sum total of water contained in the form of water of crystallization of water solution originating from the components constituting the present composition of the present invention and water added from the outside, and the water is compounded to obtain a balance of 100% for the entire present composition.

A pH of the stock solution for the present composition in accordance with the present invention is adjusted to a neutral range to ensure operational and environmental safety and avoid any adverse effect on the material of the article to be washed, Examples of substances that demonstrate alkalinity and can be used for pH adjustment include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, silicates such as sodium silicate and potassium silicate, amines such as monoethanolamine and diethanolamine, and ammonia. Further, examples of substances that demonstrate acidity and can be used for pH adjustment include inorganic acids such as hydrochloric acid and sulfuric acid and organic acids such as citric acid and acetic acid. Among them, ammonia is especially preferred and can be appropriately added to obtain the aforementioned pH range.

The pH (determined by "pH Measurement Methods" of JIS Z- 8802:1984) of a stock solution of the present composition is set to 6 to 8 at 25°C.

When pH adjustment is performed using the aforementioned pH adjusting agents, the compounding ratio of the chelating agent that is the components (C) has to be prevented from being outside a range of 0.1 to 15 wt . % .

Further, a fragrant material, a thickening agent, a bactericidal agent, and a preservative can be compounded at random with the present composition within ranges in which the object of the present invention is not affected.

Examples of washing materials include woven fabrics, nonwoven fabrics, sandwiched and laminated sheets thereof, and mats from natural animal and vegetable fibers such as hemp, cotton, cellulose, wool, and silk, and synthetic fibers or foamed materials comprising rayon, polyolefins, polyesters, acryl, Nylon, and polyurethanes, pulp paper, synthetic paper, paper laminates thereof, or sponges.

By using the antifouling detergent composition for hard surfaces in accordance with the present invention that is obtained by using the above-described essential components and optional components especially with respect to bathrooms or bathtubs composed of plastic materials such as polyethylene, polypropylene and FRP and also articles for bathrooms such as seats, pails, and draining boards, it is possible to cause the adsorption of the ethylene oxide - propylene oxide - ethylene oxide copolymer by the surface of these articles to be washed, form a hydrophilic monomolecular coating film, impart antifouling ability to the surface, moderate the adhesion of contamination such as soap residues, sebaceous matter, and inorganic components (scale) such as calcium and magnesium that are hard water components of tap water and well water, and easily wash and remove the adhered contamination. Further, this antifouling detergent composition has appropriate washing capacity and excels in stability in storage.

Another merit of the antifouling detergent composition is that even when it adheres to skin, because the irritation ability of the composition is lower that that of the conventional acidic detergents and alkaline detergents, washing of bathtubs can be performed with improved safety. In addition, because the pH of the discarded wastewater containing the washing liquid is neutral, the environmental load is lowered.

The composition of the present invention is used as a stock solution or a washing liquid obtained by diluting with water or tepid water at a ratio of 2 to 10.

Examples of washing methods for hard surfaces using the stock solution or diluted solution of the present composition in accordance with the present invention include the following methods .

(1) A method by which a hard surface is wiped and washed with, e.g., a sponge impregnated with the stock solution or diluted solution of the present composition in accordance with the present invention and then rinsed with water.

(2) A method by which the stock solution or diluted solution of the composition in accordance with the present invention is sprayed or coated on the surface to be washed, and then rinsed with water. (3) A method by which a nonwoven fabric or the like is impregnated with the stock solution or diluted solution of the present composition in accordance with the present invention, applied to an elevated hard surface, allowed to stay thereon for a certain time, and then rinsed with water.

(4) A method by which contamination on a hard surface is wiped with a washing material impregnated with the stock solution or diluted solution of the present composition in accordance with the present invention, and then wiping is performed with a towel containing water.

In the method (2), the stock solution or diluted solution of the present composition in accordance with the present invention may be rinsed immediately after spraying or coating, but in order to improve the washing performance, rinsing may be performed after allowing the stock solution or diluted solution of the present composition to stay for 30 sec to several minutes according to the type and amount of contamination, preferably for about 1 min, As a result, a high antifouling effect can be obtained, fEmbodiments]

The present invention will be described below in greater detail based on embodiments of the antifouling detergent composition for a hard surface in accordance with the present invention and comparative examples. The present invention is not limited to the embodiments.

The antifouling detergent compositions for a hard surface of Embodiments 1 to 18 and Comparative Examples 1 to 20 that are shown in Tables 1 to 8 below were evaluated with respect to three items: stability in storage, antifouling ability, and washing ability. The results are shown in Tables 1 to 8 below, the components of the chelating agents were neutralized and the pH adjustment function of the entire composition was realized with ammonia water, and the pH value was set to 6 to 8.

The sum total of components (A) to (E) was 100 wt . % as a whole .

Test methods relating to each item are described below. (1) Stability in storage [Test Method]

A sample of the present composition, 200 mL, was introduced into a transparent polyethylene bottle with a capacity of 250 mL and the bottle was placed into a thermostat (model KAX- 734, manufactured by Kobayashi Rika Kikai Kogyo KK) at 5O⁰C and a refrigerator freezer (model HRF-90P, manufactured by Hoshizaki co . , Ltd) at 5°C and allowed to stay therein for 1 month after the preparation of the composition. The appearance of the composition was visually observed periodically, and stability in storage was evaluated according to the following evaluation criteria. [Evaluation criteria]

Θ: absolutely no changes in appearance such as separation or precipitation and turbidity are observed after 1 month. O: slight changes in appearance such as separation or precipitation and turbidity are observed after 2 weeks.

Δ: slight changes in appearance such as separation or precipitation and turbidity are observed after 1 week. x: changes in appearance such as separation or precipitation and turbidity are observed within 1 day.

(2) Antifouling ability

[Test Method]

A test piece of a plastic material that is widely used in bath units (FRP piece, 15 x 7 cm) was washed thoroughly with a sponge containing a stripping detergent for floors

(Get-Off 5 times-diluted liquid, Johnson Professional Co., Ltd.), rinsed, and dried. Then, 1 mL of the sample of the present composition was dropped on the test piece, spread uniformly with a paper cloth, and allowed to stay for 1 min at room temperature. The test piece was then rinsed with hot water (40⁰C) for 2-3 sec and wiped thoroughly with a paper cloth.

The test pieces was then set almost vertically, artificial contaminants of the following two types were blown on the test piece at a ratio of 0.5 to 1.0 mL, and the test piece was allowed to stay overnight at room temperature. (1) Artificial soap residue contaminant A mixture of a solid soap (0.4%), Sebamu (0.04%, a mixture of stearic acid with oils and fats) , water with a hardness of 150 ppra (33.55%}, and ion exchange water (66.01%). (2) Artificial hard water contaminant (150 mg/L As CaCO₃) Obtained by dissolving calcium chloride dehydrate {163.5 mg) , magnesium sulfate heptahydrate (95.1 mg} , and sodium hydrogen carbonate (183.0 mg) in distilled water to obtain 1 L.

The amount of the artificial contaminants that adhered to the test piece was then visually checked and the antifouling ability was evaluated according to the following evaluation criteria .

[Evaluation criteria]

®: the artificial contaminants practically did not adhere to the test piece (adhesion ratio was less than 25%) . O: a certain amount of artificial contaminants adhered to the test piece (adhesion ratio 25% or more to less than 50%) . Δ: a large amount of artificial contaminants adhered to the test piece (adhesion ratio 50% or more to less than 75%) . x: a very large amount of artificial contaminants adhered to the test piece (adhesion ratio 75% or more to 100%) .

The adhesion ratio of artificial contaminants on the test piece that was not treated with the sample present composition was taken as 100%) . (3) Washing ability [Test method]

The test piece obtained according to the method for testing the antifouling ability of section (2) above was set horizontally, a weight (300 g) having a paper cloth attached thereto was placed on the test piece, and the test piece was scrubbed by moving the weight reciprocatingly till the artificial contaminants were completely removed ("washed" in the evaluation criteria is taken to indicate a state in which the artificial contaminants were completely removed) . The number of reciprocating movements of the weight was measured (number of scrubbing cycles) and the washing ability was evaluated according to the following criteria) . [Evaluation criteria]

®: the artificial contaminants on the test piece could be washed with 5 or less cycles of reciprocating movement. 0: the artificial contaminants on the test piece could be washed with 6 to 10 cycles of reciprocating movement. Δ: 11 to 20 cycles of reciprocating movement were necessary to wash the artificial contaminants on the test piece. x: the artificial contaminants on the test piece were not washed even after 21 or more cycles of reciprocating movement. (The artificial contaminants on the test piece that was not treated with the sample present composition could not be washed even after 25 or more cycles of reciprocating movement)

Components employed in the embodiments and comparative examples shown in Tables 1 to 8 below and effective components thereof {wt . % is represented below as "%") are described in greater detail below. Numerical values in the tables represent actual numbers. [Component A] Ethylene oxide - propylene oxide - ethylene oxide copolymer

- Polyoxyethylene polyoxypropylene glycol 1:

(Molecular weight about 4,100, weight ratio of added ethylene oxide 50%)

Trade name: Newpol PE-75, manufactured by Sanyo Chemical Industries, Ltd.

- Polyoxyethylene polyoxypropylene glycol 2 :

(Molecular weight about 8,750, weight ratio of added ethylene oxide 80%)

Trade name: Newpol PE- 68, manufactured by Sanyo Chemical Industries, Ltd.

- Polyoxyethylene polyoxypropylene glycol 3 :

(Molecular weight about 10,250, weight ratio of added ethylene oxide 80%)

Trade name: Newpol PE-78, manufactured by Sanyo Chemical Industries, Ltd.

- Polyoxyethylene polyoxypropylene glycol 4 :

(Molecular weight about 16,250, weight ratio of added ethylene oxide 80%)

Trade name: Newpol PE-108, manufactured by Sanyo Chemical Industries, Ltd.

- Polyoxyethylene polyoxypropylene glycol 5 :

(Molecular weight about 20,000, weight ratio of added ethylene oxide 80%) Trade name: Newpol PE-128, manufactured by Sanyo Chemical Industries, Ltd. [Component B] Surfactants

- Surfactant 1 :

(Alkyldimethylamine oxide having 10 to 24 carbon atoms) Trade name: Genaminox 1014, effective component 32%, manufactured by Clariant Japan Co., Ltd.

- Surfactant 2 :

(Guerbet alcohol having 10 carbon atoms, ethylene oxide - propylene oxide adduct)

Trade name: Noigen XL- 80, effective component 99% or more, manufactured by Daiichi Kogyo Seiyaku Co., Ltd) .

- Surfactant 3 :

(Isodecyl alcohol having 10 carbon atoms, ethylene oxide

7 mol adduct)

Trade name: Naroacty ID-70, effective component 99% or more, manufactured by Sanyo Chemical Industries, Ltd.

- Surfactant 4 :

(Alkyl ether having 9 to 11 carbon atoms, ethylene oxide

8 mol adduct)

Trade name: Neodol 91-8T, effective component 99% or more, manufactured by Shell Chemicals Co., Ltd.

- Surfactant 5 :

(Alkyl dimethylbenzyl ammonium chloride) Trade name: Cation G-50, effective component 51%, manufactured by Sanyo Chemical Industries, Ltd. [Component C] Chelating agent

- Chelating agent 1:

Sodium polyacrylate (average molecular weight 4,000} . Trade name: Sokalan PA-25CL, effective component 45% manufactured by BASF Corp.

- Chelating agent 2 :

Ammonium citrate.

Trade name: Diamonium Citrate, content 98% or more, manufactured by Iwata Chemical Co., ltd. [Component D] Water-soluble solvent

- Water-soluble solvent 1:

Propylene glycol monomethyl ether.

Trade name: MFG, manufactured by Nippon Yukazai Co., Ltd.

- Water-soluble solvent 2 :

Dipropylene glycol monomethyl ether. Trade name: MFDG, manufactured by Nippon Yukazai Co., Ltd.

- Water-soluble solvent 3 :

N-methyl -2 -pyrrolidone (NMP).

Trade name: M-Pyrrole, manufactured by ISP Co., Ltd. [Optional Components] Neutralizing agent for pH adjustment

- Neutralizing agent:

Ammonia. Trade name: Ammonia Water, effective component 25%, manufactured by Takasugi Pharmaceutical Co., Ltd. [Components for comparative examples]

- Reverse-type, polyoxypropylene polyoxyethylene glycol 1:

Molecular weight about 2,500, weight ratio of added ethylene oxide 10%)

Trade name: Pluronics 25R- 1, ADEKA Co., Ltd.

- Reverse-type, polyoxypropylene polyoxyethylene glycol 2:

Molecular weight about 2,500, weight ratio of added ethylene oxide 20%)

Trade name: Pluronics 25R-2, ADEKA Co., Ltd.

- Polyethylene oxide adduct polymer

(Average molecular weight 600 to 8,000,000) Trade name: PΞO-18Z, manufactured by Sumitomo Seika KK)

- Polyethylene glycol adduct polymer

(Average molecular weight 20,000)

Trade name: PEG 20000, manufactured by Nippon Oils and Fats Co. , Ltd. )

- Modified silicone

Polyether aminoamide-modified organopolysiloxane Trade name: BYl6- 906, manufactured by Toray - Dow Corning Silicone Co., Ltd.)

- Fluorine emulsion:

Emulsion based on fluorine-containing urethane resin. Trade name: AG-3001, amount of nonvolatiles : 20%, manufactured by Meisei Chemical Works, Ltd) - Acryl polymer

Acrylic resin-based polymer.

Trade name: SURF SlOO, concentration of effective component: 20%, manufactured by Rhodia Co., Ltd.

Table 1

Table 2

Embodiments

6 7 8 9 10

A Polyoxyethylene polyoxypropylene glycol 1 60.0

Polyoxyethylene polyoxypropylene glycol 2 25.0 15.0

Polyoxyethylene polyoxypropylene glycol 3

Table 4

Table 5

Table 6

Comparative Examples

6 7 E 1 9 10

A Polyoxyethylene polyoxypropylene glycol 1 60. 0 57.0

Polyoxyethylene polyoxypropylene glycol 2

Table 7

Comparative Examples

11 12 13 14 15

A Polyoxyethylene polyoxypropylene glycol 1

Polyoxyethylene polyoxypropylene glycol 2 20.0

Polyoxyethylene polyoxypropylene glycol 3 10.0

Polyoxyethylene polyoxypropylene glycol 4

Polyoxyethylene polyoxypropylene glycol 5 5.0

Reverse-type polyoxypropylene 10.0 polyoxyethylene glycol 1

Reverse-type polyoxypropylene 10.0 polyoxyethylene glycol 2

Polyethylene oxide addition polymer

Polyethylene glycol addition polymer

Modified silicone

Fluorine-containing emulsion

Acrylic polymer

B Surfactant 1 5.0 5.0 5.0 5.0 5.0

Table 8

Comparative Examples

16 17 18 19 20

Polyoxyethylene polyoxypropylene glycol 1

Polyoxyethylene polyoxypropylene glycol 2

Polyoxyethylene polyoxypropylene glycol 3

Polyoxyethylene polyoxypropylene glycol 4

Polyoxyethylene polyoxypropylene glycol 5

Reverse-type polyoxypropylene polyoxyethylene glycol 1

Reverse-type polyoxypropylene polyoxyethylene glycol 2

Polyethylene oxide addition polymer 0.5

Polyethylene glycol addition polymer 30.0

Modified silicone 10.0

The results present above show that the products of Embodiments 1 to 18 demonstrate good performance with respect to all test items, that is, stability in storage, antifouling ability, and washing ability.

As described hereinabove, the antifouling detergent composition for hard surfaces in accordance with the present invention demonstrates excellent antifouling effect and excellent washing effect with respect to surfaces to be washed by using a combination of specific ethylene oxide - propylene oxide - ethylene oxide copolymer (component A) , surfactant (component B) , chelating agent (component C) , water-soluble solvent (component D) , and water (component E) in predetermined amounts.

Therefore, the antifouling detergent composition for hard surfaces in accordance with the present invention can be advantageously used as an antifouling detergent especially with respect to bathrooms or bathtubs composed of plastic materials such as polyethylene, polypropylene and FRP and also articles for bathrooms such as seats, pails, and draining boards .

Claims

What Is Claimed Is:

1. An antifouling detergent composition for hard surfaces, comprising: {A) 0.5 to 60 wt . % ethylene oxide - propylene oxide - ethylene oxide copolymer represented by the formula below; (B) 0.1 to 15 wt . % surfactant; (C) 0.1 to 15 wt .% chelating agent; (D) 0.1 to 15 wt . % water-soluble solvent; and (E) water as the balance:

HO-(C₂H₄O)_n-(C₃Hg)₁₁₁-(C₂H₄O)_n-H (where n and m are integers other than 0) .

2. The antifouling detergent composition for hard surfaces according to claim 1, wherein an average molecular weight of the ethylene oxide - propylene oxide - ethylene oxide copolymer of said component (A) is 4,000 or more and 25, 000 or less.

3. The antifouling detergent composition for hard surfaces according to claim 1 or 2 , wherein the ratio of ethylene oxide in the average molecular weight of the ethylene oxide - propylene oxide - ethylene oxide copolymer of said component (A) is 50 to 85 wt . % .

4. The antifouling detergent composition for hard surfaces according to any one of claims 1 to 3 , that is used for bathrooms and bathtubs .

5. An antifcoiling detergent composition for hard surfaces, wherein a pH (determined by "pH Measurement Methods" of JIS Z-8802:1984) of a stock solution of the antifouling detergent composition for hard surfaces according to any one of claims 1 to 4 is set to 6 to 8 at 25°C.

6. A washing material that is impregnated with the antifouling detergent composition for hard surfaces according to any one of claims 1 to 5.

7. A washing method comprising the steps of: wiping contamination of a hard surface by using the washing material according to claim 6; and wiping the detergent composition remaining on said hard surface with a towel or duster containing water.

8. A washing method comprising the steps of: spraying or coating, on a hard surface, a washing solution prepared by diluting with water the antifouling detergent composition for hard surfaces according to any one of claims 1 to 5 at a ratio of 2 to 10; and rinsing with water.