Anti-stain cleaning composition for carpets

Abstract

To provide an anti-fouling detergent composition for a carpet which has detergency capable of sufficiently coping with diversification of dirt and heavy walk, dispenses with large-scale shampoo washing, and can maintain appearance of the carpet in simple daily maintenance.SOLUTION: An anti-fouling detergent composition for a carpet contains the following components (A) to (F), and contains the components (A) to (D) with respect to the whole anti-fouling detergent for the carpet in the following ratios, wherein a pH in "pH measurement method" according to JIS Z-8802:1984 is 6 to 11. (A) Alkali-soluble resin having an average molecular weight (Mw) of 2,000-30,000, and a glass transition point (Tg) of 50-150°C: 0.1-10 mass%. (B) Colloidal silica having an average particle diameter of 3-500 nm: 0.1-5 mass%. (C) Anionic surface active agent: 0.1-5 mass%. (D) Fluorine-based surface active agent: 0.08-2 mass%. (E) Water. (F) Neutralization component.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an antifouling detergent composition for carpets, which is used for cleaning and antifouling carpets installed on floors inside buildings. [Background technology]

[0002] Carpets are superior to other flooring materials in terms of appearance, walking comfort, heat retention, safety, etc., and have traditionally been widely used as a useful flooring material inside buildings such as hotels, office buildings, department stores, halls, airports, retail stores, supermarkets, shopping malls, and entertainment facilities. Maintenance of carpets installed in these buildings is mostly carried out by cleaning the carpets on site, and cleaning is carried out using a combination of carpet detergents, carpet cleaning equipment, tools, etc., after understanding the carpet's material, contamination status, and contamination trends due to foot traffic at the installation site.

[0003] Methods for cleaning such carpets include, for example, shampoo-type cleaning methods, yarn pad (bonnet buffing)-type cleaning methods, extraction-type cleaning methods, and powder-type cleaning methods, but each of these methods has its advantages and disadvantages. Therefore, Patent Document 1 proposes a stain-resistant cleaner for carpets that can utilize the advantages while eliminating the disadvantages. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-101033 Summary of the Invention [Problem to be solved by the invention]

[0005] However, although the product of Patent Document 1 does not require extensive shampooing and can maintain the beauty of the carpet with simple daily maintenance, it may have somewhat insufficient cleaning power when considering the recent diversification of soiling and heavy foot traffic (e.g., in large commercial facilities, etc.). Furthermore, when excess oil adheres to carpets, the surface becomes sticky and there is a risk that the residual cleaning agent cannot be collected using a brush-type vacuum cleaner, so improvements in these areas were desired.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an antifouling detergent composition for carpets which has an excellent detergency capable of sufficiently dealing with a variety of stains and heavy foot traffic, does not require extensive shampooing, and can maintain the beauty of carpets with simple daily maintenance. [Means for solving the problem]

[0007] In order to achieve the above object, the present invention is summarized as follows [1] and [2]. [1] A stain-resistant detergent composition for carpets containing the following components (A) to (F), wherein the components (A) to (D) are contained in the following proportions relative to the total composition of the stain-resistant detergent composition for carpets, and the pH of the stain-resistant detergent composition for carpets is 6 to 11 as measured by JIS Z-8802:1984 "pH measurement method." (A) Alkali-soluble resin having an average molecular weight (Mw) of 2,000 to 30,000 and a glass transition temperature (Tg) of 50 to 150°C: 0.1 to 10% by mass (B) Colloidal silica having an average particle size of 3 to 500 nm: 0.1 to 5% by mass (C) Anionic surfactant: 0.1 to 5% by mass (D) Fluorine-based surfactant: 0.08 to 2% by mass (E)Water (F) Neutralizing component [2] The carpet stain-resistant cleaner composition according to [1], wherein (C) the anionic surfactant is at least one selected from the group consisting of sodium dodecyldiphenyloxide disulfonate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium metaxylene sulfonate, sodium toluenesulfonate, and sodium cumenesulfonate.

[0008] As a result of intensive research into solving the above-mentioned problems, the inventors of the present invention came up with the idea that carpets might be easier to clean and maintain if they focused particularly on water repellency and instead imparted hydrophilicity, the opposite of water repellency, rather than further strengthening the water and oil repellency of conventional stain-resistant cleaners for carpets and water- and oil-repellent finishing agents for textiles.

[0009] That is, conventional stain-repellent agents for carpets and water- and oil-repellent agents for textiles are effective in imparting water- and oil-repellent properties to carpets so that they repel any kind of dirt. Such stain-repellent agents for carpets and water- and oil-repellent agents for textiles are effective in the initial stages of application to carpets and in areas with low foot traffic. However, the water- and oil-repellent properties decrease over time as shown below. First, even carpets that have been given water- and oil-repellent properties gradually wear down due to the introduction and accumulation of soil and sand by foot traffic, heavy foot traffic, etc. At this stage, the water-repellent properties remain to some extent, even if they are not completely removed. Therefore, even if the carpet is washed with a water-based detergent, the water-repellent properties prevent the water-based detergent from penetrating and diffusing into the carpet, preventing sufficient removal of dirt and resulting in "uneven cleaning." As the fibers continue to wear, the water repellency is completely lost, but by that point the oil repellency is gone as well, and the carpet's stain resistance is lost. At this point, the carpet becomes completely soiled, and it becomes difficult to remove the stains using ordinary mild carpet cleaners. The inventors have completed the present invention based on the above findings. [Effects of the Invention]

[0010] The carpet stain-resistant detergent composition of the present invention (hereinafter sometimes referred to as "detergent composition") has stain-resistant properties that are not water-repellent but are hydrophilic, and therefore has an affinity for aqueous stains, capturing the stains and allowing them to penetrate and diffuse into the carpet fibers, thereby making the stains less noticeable. Moreover, because it has oil-repellent properties, it thoroughly repels stubborn oil stains and soil and sand stains, keeping them away. Furthermore, the detergent composition that has absorbed the dirt from the carpet is dried to form a film integrally with the dirt, and this filmed detergent composition is then removed by scrubbing and sucking with a brush-equipped vacuum cleaner or the like, thereby cleaning even aqueous dirt that has penetrated and diffused into the carpet. Therefore, by performing simple maintenance such as periodic cleaning with the detergent composition, the beautiful appearance of the carpet can be maintained for a long period of time.

[0011] Furthermore, by maintaining the pH of the above-mentioned detergent composition within the neutral to weakly alkaline range of 6 to 11, particularly 6 to 8, the stability of the detergent composition is maintained, safety for the worker and the environment is ensured, and most importantly, deterioration of the carpet is suppressed even when maintenance such as cleaning is performed periodically, making it easier to maintain the quality of the floor covering.

[0012] Furthermore, among the present invention, those that use at least one anionic surfactant selected from the group consisting of sodium dodecyldiphenyloxide disulfonate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium metaxylene sulfonate, sodium toluenesulfonate, and sodium cumenesulfonate tend to dry into a solid or semi-solid state (easily form a film) after being sprayed on a carpet and having the dirt washed away and absorbed, making it easier to suck up with a vacuum cleaner and easier to clean. DETAILED DESCRIPTION OF THE INVENTION

[0013] Next, the embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0014] The detergent composition of the present invention is a stain-resistant detergent composition for carpets containing the following components (A) to (F), wherein the components (A) to (D) are contained in specific set ratios relative to the total amount of the stain-resistant detergent composition for carpets, and the pH of the detergent composition is 6 to 11 as measured by JIS Z-8802:1984 "pH measurement method." (A) Alkali-soluble resin having an average molecular weight (Mw) of 2,000 to 30,000 and a glass transition temperature (Tg) of 50 to 150°C: 0.1 to 10% by mass (B) Colloidal silica having an average particle size of 3 to 500 nm: 0.1 to 5% by mass (C) Anionic surfactant: 0.1 to 5% by mass (D) Fluorine-based surfactant: 0.08 to 2% by mass (E)Water (F) Neutralizing component Each component will be described below.

[0015] <Component (A): Alkali-soluble resin> The alkali-soluble resin of component (A) is blended to support the active ingredients of the detergent composition on the carpet fibers and prolong their effectiveness. It is usually in a solid form at room temperature (23°C) and is neutralized and dissolved according to the liquid properties. The alkali-soluble resin has an average molecular weight (Mw) in the range of 2,000 to 30,000, preferably 3,000 to 25,000, and more preferably 5,000 to 20,000. If the average molecular weight (Mw) of the alkali-soluble resin exceeds 30,000, the resin tends to have poor alkali solubility, and may become significantly more viscous or gel-like, which is undesirable. On the other hand, if the average molecular weight (Mw) of the alkali-soluble resin is less than 2,000, the resin tends to be unable to maintain the hardness required for supporting the active ingredient on the carpet fibers. The average molecular weight (Mw) can be calculated as a weight average molecular weight converted into a standard polystyrene molecular weight. The alkali-soluble resin has a glass transition point (Tg) in the range of 50 to 150°C, preferably 70 to 130°C, and more preferably 90 to 110°C. If the glass transition point of the alkali-soluble resin is less than 50°C, the detergent composition becomes too soft and adheres to the carpet, and the film formed by drying the detergent composition has poor disintegration properties, which is undesirable. On the other hand, if the glass transition point of the alkali-soluble resin exceeds 150°C, polymerization of the alkali-soluble resin tends to become difficult.

[0016] Examples of the alkali-soluble resin include styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-methacrylic acid copolymer, styrene-acrylate-acrylic acid copolymer, styrene-methacrylate-acrylic acid copolymer, styrene-methacrylate-methacrylic acid copolymer, styrene-α-methylstyrene-acrylate-acrylic acid copolymer, styrene-α-methylstyrene-methacrylate-acrylic acid copolymer, styrene-α-methylstyrene-methacrylate-methacrylic acid copolymer, acrylate-acrylic acid copolymer, methacrylate-acrylic acid copolymer, methacrylate-methacrylic acid copolymer, styrene-maleic anhydride copolymer, diisobutylene-maleic anhydride copolymer, rosin-modified maleic acid, shellac, etc. These can be used alone or in combination of two or more.

[0017] Among these, from the viewpoints of ease of combination with other components and ease of industrial availability, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-methacrylic acid copolymer, styrene-acrylic acid ester-acrylic acid copolymer, styrene-methacrylic acid ester-acrylic acid copolymer, styrene-methacrylic acid ester-methacrylic acid copolymer, styrene-α-methylstyrene-acrylic acid ester-acrylic acid copolymer, styrene-α-methylstyrene-methacrylic acid ester-acrylic acid copolymer, and styrene-α-methylstyrene-methacrylic acid ester-methacrylic acid copolymer are preferably used.

[0018] The alkali-soluble resin (component (A)) is blended in an amount ranging from 0.1 to 10% by mass, more preferably from 0.5 to 3.0% by mass, based on the total detergent composition. In other words, if the blending amount is less than 0.1% by mass, the detergent composition will not form a film, failing to achieve the desired effect, and the stickiness of the surfactant will tend to be insufficient. In contrast, if the blending amount is more than 10% by mass, the film strength will be too high, causing adhesion to carpet fibers, resulting in problems such as loss of fiber texture, a noticeable white film that mars the appearance, and difficulty in removal with a vacuum cleaner. Furthermore, the stability of colloidal silica (component (B)) in the detergent composition will tend to decrease, leading to separation and sedimentation of silica (silicon dioxide).

[0019] There are no particular limitations on the method for producing the alkali-soluble resin of component (A), but it is preferable to employ emulsion polymerization, solution polymerization, or bulk polymerization.

[0020] To produce the alkali-soluble resin (A) by the emulsion polymerization method, for example, the emulsifiers, polymerization initiators, etc. described below can be used.

[0021] Examples of the emulsifier include anionic surfactants such as sodium dialkylsuccinate, sodium alkylbenzenesulfonate, sodium alkyl sulfate, polyoxyethylene alkylphenyl ether sodium sulfate, sodium alkyldiphenylethersulfonate, polyoxyethylene alkylsodium sulfate, sodium dialkylsulfosuccinate, and formalin condensates of naphthalenesulfonic acid; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol fatty acid esters, and sorbitan fatty acid esters; reactive emulsifiers such as sodium styrenesulfonate, sodium alkylallyl sulfonate, sodium alkylallyl sulfosuccinate, polyoxyethylene alkylallylglycerin ether sulfate, and polyoxyethylene alkylphenol alkylglycerin ether sulfate; and polymeric surfactants such as polyvinyl alcohol, polyacrylic acid, water-soluble acrylic acid ester copolymers, water-soluble methacrylic acid ester copolymers, styrene-maleic acid copolymers and salts thereof, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, and salts thereof, polyacrylamide copolymers, and polymethacrylamide copolymers. These may be used alone or in combination of two or more.

[0022] The preferred amount of the emulsifier used is usually 0.05 to 5% by mass of the monomer mass. If the amount of emulsifier used is less than 0.05% by mass, emulsifying properties will be poor, while if it exceeds 5% by mass, water resistance may be poor.

[0023] Examples of the polymerization initiator that can be used include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, and peroxides such as hydrogen peroxide, benzoyl peroxide, and t-butylhydroxyperoxide. These may be used as a redox system in combination with a reducing agent such as sodium hydrogen sulfite, sodium pyrobisulfite, ascorbic acid, and sodium formaldehyde sulfoxylate.

[0024] More specifically, the alkali-soluble resin of component (A) can be obtained by adding the above-mentioned monomer, emulsifier, polymerization initiator, reducing agent, chain transfer agent, chelating agent, pH adjuster, etc. to an aqueous medium and carrying out a polymerization reaction at a temperature of 30 to 100° C. for about 1 to 30 hours. Commercially available alkali-soluble resins may be used as the alkali-soluble resin of component (A). The alkali-soluble resin of component (A) has a transparent appearance in the solution after being neutralized with a neutralizing component (F) described below.

[0025] <Component (B): Colloidal silica> The colloidal silica (component (B)) acts as a film strength adjuster to brittle and powder the coating of the alkali-soluble resin in the detergent composition, improving the recoverability of the dried residue of the composition after washing and drying by vacuuming with a brush-type vacuum cleaner, and is also incorporated to impart hydrophilicity to carpets. A dispersion of finely divided silica (silicon dioxide) in water is preferably used. The average particle size of the silica is 3 to 500 nm, and the colloidal silica (component (B)) is incorporated in an amount of 0.1 to 5 mass %, more preferably 0.2 to 3 mass %, and even more preferably 0.3 to 1 mass %, in terms of solid content, based on the total detergent composition. The average particle size is measured by laser diffraction. If the content of component (B) colloidal silica is too high, it will have a negative effect on storage stability and a large amount of dried residue will adhere to the carpet fibers, making the white color of the film more noticeable and tending to mar the appearance of the carpet.On the other hand, if the content is too low, it will tend to decrease hydrophilicity and not be able to fully fulfill its role as the film strength adjuster mentioned above.

[0026] <Component (C): Anionic surfactant> The anionic surfactant (C) is used to enhance cleaning properties. Examples of such anionic surfactant (C) include alkyl sulfates, alkyl sulfate ester salts, alkylbenzene sulfates, α-olefin sulfonates, toluene sulfonates, meta-xylene sulfonates, para-xylene sulfonates, cumene sulfonates, and dodecyldiphenyloxide disulfonates. The counter ions of these anionic surfactants are sodium, magnesium, ammonium, ethanolamine, and the like. Among these, sodium lauryl sulfate, ammonium lauryl sulfate, magnesium lauryl sulfate, sodium dodecyldiphenyloxide disulfonate, sodium toluenesulfonate, and sodium cumenesulfonate, which do not contain ethylene oxide, are preferred because they tend to dry easily when sprayed onto a carpet, making it easier to form the cleaning composition into a solid or semi-solid film and reducing stickiness on the carpet after cleaning. These can be used alone or in combination of two or more.

[0027] The content of the anionic surfactant of component (C) is in the range of 0.1 to 5 mass % of the total detergent composition, and more preferably in the range of 0.5 to 1.5 mass %. When the content of the anionic surfactant of component (C) is within the above range, not only can sufficient cleaning performance be exhibited, but excess foaming during cleaning can also be suppressed, preventing stickiness due to residue of the detergent composition on the carpet.

[0028] <Component (D): Fluorine-based surfactant> The fluorine-based surfactant of component (D) is blended to improve the wetting (leveling) of the carpet, as well as to impart hydrophilicity and oil repellency, which are key features of the present invention. Examples of such fluorosurfactants for component (D) include perfluorosulfonic acid (PFOS) surfactants synthesized by electrolytic fluorination, perfluorocarboxylic acid (PFOA) surfactants synthesized by telomerization, and fluorinated ethylene polymer surfactants synthesized by oligomerization. Among these, perfluorocarboxylic acid surfactants and fluorinated ethylene polymer surfactants are preferably used, and these can be used alone or in combination of two or more kinds. In the present invention, it is also effective to incorporate a fluorine-containing surfactant as component (D) so that the surface tension of the detergent composition is 30 dyn / cm or less.

[0029] The content of the fluorosurfactant (component (D)) is in the range of 0.08 to 2 mass% of the total detergent composition, and more preferably in the range of 0.1 to 1 mass%. The content of the fluorosurfactant (D) is higher than that of conventional detergent compositions, which is one of the features of the present invention. That is, the detergent composition contains a higher amount of fluorosurfactant than conventional detergent compositions, and the balance of the components (A) to (E) as well as the synergistic effect of the colloidal silica (component (B)) and the fluorosurfactant (component (D)) contained in the respective predetermined proportions give the detergent composition of the present invention excellent hydrophilicity and oil repellency, enabling easy cleaning and long-lasting aesthetics. Furthermore, when the content of the fluorosurfactant of component (D) is within the above range, excellent hydrophilicity and oil repellency are obtained, and excess foaming that impairs cleaning workability can be suppressed, resulting in excellent ease of cleaning.

[0030] Therefore, the balance between the content of the fluorosurfactant of component (D) and the content of the colloidal silica of component (B) is also important, and the ratio of the fluorosurfactant of component (D) to the colloidal silica of component (B) (D / B) is preferably in the range of 0.016 to 20, more preferably 0.2 to 10. A detergent composition in which the ratio of the fluorosurfactant of component (D) to the colloidal silica of component (B) (D / B) falls within the above range can exhibit superior hydrophilicity, oil repellency, and stain resistance, the durability of which is enhanced, and ease of cleaning.

[0031] <Component (E): Water> Examples of the water (E) include pure water, ion-exchanged water, soft water, distilled water, and tap water. These can be used alone or in combination of two or more. The "water" mentioned above refers to the sum of water contained in the form of water of crystallization or an aqueous solution derived from each component constituting the detergent composition, and water added from outside, and is blended in such a way that the total amount of the detergent composition is 100% by mass.

[0032] <(F) Neutralizing component> The neutralizing component (F) can be used as a neutralizing solubilizer for the alkali-soluble resin (A) of the detergent composition, and examples thereof include alkali 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. Among these, sodium hydroxide is preferred because of its ease of handling. These can be used alone or in combination of two or more. The detergent composition of the present invention can maintain its stability, ensure operational and environmental safety, and prevent adverse effects on carpet materials by adjusting the pH to the range of 6 to 11. If the pH is acidic, i.e., less than 6, the alkali-soluble resin precipitates and becomes a solid, impairing the stability of the detergent composition system. On the other hand, if the pH is alkaline and exceeds 11, the fine colloidal silica particles of component (B) will aggregate, precipitate, and settle, resulting in a loss of stability of the detergent composition. In the detergent composition of the present invention, it is particularly preferred to set the pH to 6 to 8, as this provides an excellent balance between the stability of the detergent composition system and its detergency. The pH value is measured at 25°C according to JIS Z-8802:1984 "pH measurement method."

[0033] The detergent composition of the present invention is prepared using the above components (A) to (F) as essential components, but various optional components can also be appropriately blended. Such optional components include, for example, preservatives, water-soluble solvents, fragrances, dyes, thickeners, disinfectants, etc. These can be used alone or in combination of two or more.

[0034] <Optional ingredient: preservatives> Examples of the preservative include isothiazolinone-based, triazine-based, and bronopol-based preservatives. These can be used alone or in combination of two or more. When the preservative is used, its content is preferably set within the range of 0.1 to 0.8% by mass, more preferably 0.2 to 0.6% by mass, based on the total mass of the detergent composition. In other words, if the amount of preservative is too large, no additional effect can be expected and the preservative will simply become an excess component, while if the amount is too small, the preservative effect tends to be inferior.

[0035] <Optional ingredient: Water-soluble solvent> The water-soluble solvent is used as a solubilizer for the fluorosurfactant (D), and examples thereof include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, and diethylene glycol monomethyl ether. These may be used alone or in combination of two or more. When the water-soluble solvent is used, it is preferable to dissolve, for example, Neos Corporation's sodium perfluoroalkenyloxybenzenesulfonate, "FT-100" (hereinafter sometimes referred to as "FT-100"), in the water so that the solvent contains 30 to 60% by mass, and more preferably 40 to 50% by mass. When the blending ratio of the fluorosurfactant (D) to the water-soluble solvent is within the above range, the fluorosurfactant (D) can be efficiently solubilized in water.

[0036] The cleaning composition of the present invention can be prepared using the essential components (A) to (F) and other components blended as needed, according to a method for preparing a conventional cleaning composition.

[0037] The detergent composition thus obtained can be used as a cleaning and antifouling agent, for example, as follows.

[0038] That is, the detergent composition of the present invention can be used as is or diluted about 2 to 10 times with water or lukewarm water depending on the degree of soiling of the carpet surface. The above-mentioned detergent composition is usually sprayed in an amount of 20 to 60 g / m 2 However, when using a large self-propelled carpet cleaning machine, the spray amount should be approximately 20 to 40 g / m. 2 In a normal atmosphere (temperature 23°C, humidity around 40%), the water in the cleaning composition evaporates in 20 to 30 minutes, forming a film that can be vacuumed. This significantly improves work efficiency and provides a simple cleaning method for workers, reducing the labor required.

[0039] To clean a carpet using the detergent composition of the present invention, the detergent composition or a diluted cleaning solution thereof (hereinafter sometimes referred to as "detergent composition, etc.") is usually sprayed onto the carpet surface as described above, followed by brushing, and then the carpet surface onto which the detergent composition, etc. has been sprayed is dried, and the detergent composition, etc. that has encapsulated the dirt and formed a film thereon is sucked and removed with a vacuum cleaner with a brush. Specifically, for example, the following methods (1) to (3) can be mentioned. (1) When cleaning a carpet laid over a large section (a large working area), a cleaning method comprising the steps of: using a self-propelled carpet cleaning machine equipped with a spraying mechanism for spraying a detergent composition or the like and a brushing mechanism, spraying and brushing the detergent composition or the like simultaneously to encapsulate the stains on the carpet in the detergent composition or the like; and, after drying the carpet, using a self-propelled vacuum cleaner or the like equipped with a brushing mechanism and a suction mechanism to suck and remove the stains together with the detergent composition or the like. (2) When cleaning a carpet installed in a middle section, a cleaning method comprising the steps of spraying a detergent composition or the like onto the carpet using an electric sprayer or the like, and using a microfiber pad attached to a polisher to encapsulate the dirt on the carpet in the detergent composition or the like, and then drying the carpet and sucking and removing the dirt together with the detergent composition or the like using a vacuum cleaner equipped with a brushing mechanism and a suction mechanism. (3) When cleaning a carpet installed in a small area, a cleaning method comprising the steps of spraying a detergent composition or the like onto the carpet using an electric sprayer or the like, brushing the carpet using a brush with a handle, etc., so that the detergent composition or the like is absorbed into the carpet fibers, thereby encapsulating the dirt on the carpet in the detergent composition or the like, and then drying the carpet, and sucking and removing the dirt together with the detergent composition or the like using a vacuum cleaner equipped with a brushing mechanism and a suction mechanism.

[0040] As described above, the detergent composition of the present invention, which is hydrophilic rather than water-repellent, exhibits affinity for aqueous stains, capturing the stains and allowing them to penetrate and diffuse into carpet fibers, thereby making the stains less noticeable. On the other hand, due to its oil-repellent properties, it completely repels stubborn oil stains and sandy soils, making them less noticeable. Therefore, the detergent composition of the present invention has sufficient cleaning power for adhering stains, and regular maintenance, such as spraying the composition on a carpet and vacuuming it up with a vacuum cleaner, can maintain the carpet's beautiful appearance for a long period of time. Furthermore, since the pH is set to a predetermined value, it does not damage the carpet material. The detergent composition can be sprayed on stains adhering to and accumulating on carpet fibers, followed by brushing or other procedures to encapsulate the stains in the detergent composition. After drying the carpet surface, the detergent composition, which has formed a film integral with the stains, can be removed by vacuuming or removing it with a brush-equipped vacuum cleaner or the like. This eliminates the need for extensive procedures, such as removing the carpet and transporting it to a cleaning plant, and allows for easy stain removal. [Example]

[0041] Next, examples will be described together with comparative examples, but the present invention is not limited to the following examples. Prior to the Examples and Comparative Examples, the following components were prepared. Details of each component and its effective concentration (%) are as follows, and the values ​​in Tables 1 to 3 indicate the pure content of each component.

[0042] <(A) Alkali-soluble resin> a-1: Alkali-soluble resin (glass transition temperature 50°C, average molecular weight (Mw) 8100, acid value 53) Product name: Joncryl 611, manufactured by BASF a-2: Alkali-soluble resin (glass transition temperature 102°C, average molecular weight (Mw) 16500, acid value 240) Product name: Joncryl 690, manufactured by BASF a-3: Alkali-soluble resin (glass transition temperature 128°C, average molecular weight (Mw) 17250, acid value 214) Product name: HDP-671, manufactured by BASF

[0043] <(B) Colloidal Silica> b-1: Colloidal silica (average particle size 10-20 nm, non-volatile content 20%) Product name: Snowtex C, manufactured by Nissan Chemical Industries, Ltd. b-2: Colloidal silica (average particle size 450 nm, non-volatile content 40%) Product name: Snowtex MP-4540M, manufactured by Nissan Chemical Industries, Ltd.

[0044] <(C) Anionic surfactants> c-1: Sodium dodecyldiphenyloxide disulfonate (effective concentration 46%) Product name: Dowfax 2A-1, manufactured by The Dow Chemical Company c-2: Sodium lauryl sulfate with carbon number C12 (effective concentration 92%) Product name: Emar 10N-HD, manufactured by Kao Corporation c-3: Sodium meta-xylene sulfonate (effective concentration 40%) Product name: Teikatox N1140, manufactured by Teika Co., Ltd. c-4: Sodium lauryl sulfate with carbon number C12 (effective concentration 30%) Product name: Teika Light N2030, manufactured by Teika C-5: Sodium cumene sulfonate (effective concentration 40%) Product name: Teikatox N5040, manufactured by Teika Co., Ltd.

[0045] <(D) Fluorine-based surfactant> d-1: PFOA, perfluorocarboxylic acid surfactants Product name: Zonyl FSJ (effective concentration 40%), manufactured by SIGMA-RBI d-2: FTOHs, fluorinated ethylene polymer surfactants Product name: Futergent 100 (effective concentration 100%), manufactured by Neos d-3: PFOA, perfluorocarboxylic acid surfactant, C6-based environmentally friendly product Product name: Surflon S-231 (effective concentration 30%), manufactured by AGC Seimi Chemical Co., Ltd. d-4: PFOA, perfluorocarboxylic acid surfactants, C6-based environmentally friendly products Product name: Surflon S-232 (effective concentration 30%), manufactured by AGC Seimi Chemical Co., Ltd. d-5: PFOA, perfluorocarboxylic acid surfactants Product name: Capstone FS-60 (effective concentration 40%), manufactured by Chemours

[0046] <(E)Water> Ion-exchanged water <(F) Neutralizing component> Sodium hydroxide Product name: 25% liquid caustic soda (effective concentration 25%), manufactured by Toagosei

[0047] <Other ingredients> Water and oil repellent finishing agent for textiles (fluorine-based material, perfluoroacrylate and polyoxyethylene group-containing copolymer) Product name: Asahi Guard E Series AG-E081 (effective concentration 20%), manufactured by AGC Seimi Chemical Co., Ltd. Modified silicone (amide polyether modified silicone oil) Product name: Dowsil BY16-906 (effective concentration 100%), manufactured by Dow Corning Toray Co., Ltd. Block polymer (polyoxyethylene polyoxypropylene glycol) Product name: Newpol PE-128 (effective concentration 100%), manufactured by Sanyo Chemical Industries, Ltd. PVA (fully saponified polyvinyl alcohol, saponification rate 98%) Product name: J-Poval JC-40 (effective concentration 100%), manufactured by Nippon Vaccination & Poval Co., Ltd. Preservative: Isothiazolinone preservative Product name: Acticide MV-4 (effective concentration 4%), manufactured by So Japan Water-soluble solvent: Ethylene glycol monobutyl ether Product name: Butycenol 20, manufactured by Kyowa Hakko Kogyo Co., Ltd.

[0048] a'-1: Alkali-soluble resin (glass transition temperature 19°C, molecular weight 60,000, acid value 65) Product name: PDX-6102B, manufactured by BASF b'-1: Fine powder fumed silica (surface area 200 m 3 / g, average particle size 0.014μm) Product name: CAB-O-SIL M-5, manufactured by Cabot Corporation in the United States c'-1: Nonionic surfactant [C12 polyoxyethylene polyoxypropylene lauryl ether (effective concentration 99% or more)] Product name: Adeka Toll LB-83, manufactured by Adeka Corporation

[0049] [Examples 1 to 7, Comparative Examples 1 to 14] Carpet stain-resistant cleaners were prepared with the compositions shown in Tables 1 to 3 below (the units of values ​​in each table are mass %), and were evaluated for stain resistance and its persistence, hydrophilicity, oil repellency, ease of cleaning, and storage stability. Their pH was also measured. Among the above carpet stain-resistant cleaners, those containing a neutralizing component (F) neutralize the dissolved alkali-soluble resin (A) to adjust the pH of the entire carpet stain-resistant cleaner. The pH of all carpet stain-resistant cleaners containing a neutralizing component (F) was adjusted to fall within the range of 6 to 11. These results are shown in Tables 1 to 3 below. The test methods and evaluation criteria for each item are as follows:

[0050] [Stain resistance and its durability] (Introduction) To more accurately evaluate subtle differences in the stain-resistant properties and their durability between compositions, it is more convenient to use plain-woven cotton fabric rather than carpet. This is because carpets do not have a white hue suitable for evaluation, and even if they are stained black with artificial soil, a large difference in brightness is not obtained. In contrast, with off-white plain-woven cotton fabric, the difference in brightness between different levels of soiling is large and easy to distinguish visually. Carpets are usually made primarily of nylon, polyester, etc., and although they are made of different fibers than cotton cloth, there is no difference in stain resistance or durability between the different fibers, and it has been confirmed that they can be treated equally.

[0051] (Test Method) First, brand new cotton cloth that had been treated with starch was washed in a washing machine to remove the starch, dried, ironed, and then cut into small pieces (5 cm x 10 cm). Furthermore, a chemical floor piece of the same size (white homogeneous style, Toli MS Plane 5626) was used as a base, and these were stacked and stapled at the four corners to prepare a cloth piece. The prepared carpet stain-resistant cleaner was sprayed onto the surface (cotton side) of the above cloth pieces using a hand sprayer (spray amount: 50 to 100 g / m 2 After that, the mixture was left to dry at room temperature to prepare test specimens. (1) The test piece was evenly sprinkled with the following artificial soil and sand grime (hereinafter referred to as "grime") (amount of grime applied: 0.7 g), and then the grime was rubbed with a clothes brush (lint brush) in a circular motion about 20 times to distribute it evenly. The grime adhering to the test piece was then cleaned with a vacuum cleaner equipped with a crevice nozzle, rubbing the tip of the nozzle thoroughly and sucking up as much of it as possible. The artificial soil and dirt used is a mixture of 96.6 parts by mass of the following artificial dirt specified in JIS L 1023, 8.1, and 3.4 parts by mass of canola oil. JIS-specified artificial dirt: Peat moss 20g, Portland cement 8.50g, silicic acid soil 8.50g, carbon black 0.05g, iron (III) oxide for ferrite 0.07g, Nujol 4.38g. (2) After cleaning, the test piece was visually inspected for cleanliness. This inspection was designated the "initial inspection." (3) The above procedure (1) was repeated three times, and the test piece after the third procedure was visually inspected for cleanliness in the same manner as in (2) above. This observation was designated as the "observation after three times." (4) Based on the results of the initial observation and the observation after three times, the stain resistance and its durability of each test piece were evaluated based on the following evaluation criteria.

[0052] (Evaluation criteria) ◎: There was no difference in the cleanliness of the test piece between the first observation and the third observation, and neither was stainable and was very clean. ○: The cleanliness of the test piece observed after three times was slightly dirty compared to the test piece observed for the first time, but was generally clean. △: The cleanliness of the test piece observed after three times was such that some parts appeared black and dirty compared to the test piece observed for the first time. ×: The cleanliness of the test piece observed three times was generally black and dirty compared to the test piece observed initially.

[0053] [Hydrophilicity] (Test Method) First, a nylon tile carpet (Toli GA-1033, stain-resistant, light gray, pre-cut to a 25cm square) was prepared. To remove the stain-resistant agent from the surface, the carpet was thoroughly wetted with a neutral carpet detergent (carpet shampoo, C.B.S., diluted 10 times). The carpet was then thoroughly scrubbed with a stiff hand brush (scrubbing time: 3 minutes). The neutral detergent was then thoroughly rinsed with tap water, the carpet was left to dry at room temperature, and the resulting pieces were cut into 12.5cm square pieces. Spray the prepared carpet stain-resistant cleaner onto the small pieces using a hand sprayer (spray amount: 50-100g / m 2After that, the mixture was left to dry at room temperature to prepare test specimens. Next, a trace amount of blue dye was added to ion-exchanged water to prepare colored water (0.0005% Sumilite turquoise blue dye diluted water). 0.4 g of this colored water was sucked up with a dropper and dripped onto the surface of the above-mentioned test piece, which was placed horizontally, from a height of 10 cm from the surface of the test piece, and left to stand for 1 hour. The degree of coloration on the surface of the test piece was then visually confirmed and evaluated based on the following evaluation criteria. It has been confirmed that water-based stains and dirt that diffuse and soak into the test piece fade in color and become less noticeable as stains. Furthermore, because they can be removed by cleaning with the carpet stain-resistant cleaner of the present invention, the following evaluation criteria were adopted.

[0054] (Evaluation criteria) ○: After being dropped, the colored water immediately diffused and soaked into the test piece, and the blue color of the stain was not noticeable and appeared pale. △: After being dropped, the colored water remained on the surface of the test piece for several minutes, but then soaked in spots without diffusing, leaving noticeable blue stains. ×: After the colored water was dropped, it remained on the surface of the test piece and dried as it was, and the blue color of the stain remained strong (concentrated) and was noticeable.

[0055] [Oil repellency] (Test Method) First, a test piece was prepared in the same manner as in the evaluation of hydrophilicity. Next, a small amount of red pigment was added to the canola oil to produce a colored oil (0.02% of Sudan's pigment). A solution of colored oil (dissolved oil) was prepared, and 0.3 g of this colored oil was drawn up with a dropper and dropped onto the surface of the above-mentioned test piece, which had been placed horizontally, from a height of 10 cm from the surface of the test piece. After leaving it for one hour, the colored oil was wiped off with a paper cloth. The degree of removal (coloration) of the colored oil from the surface of the test piece was then visually confirmed and evaluated based on the following evaluation criteria. Note that once viscous edible oils such as canola oil soak into the carpet, they are difficult to wipe off with a paper cloth or the like, so a complicated cleaning process using a professional carpet detergent is required for cleaning. Therefore, from the standpoint of stain prevention, it is preferable to thoroughly repel oil stains and dirt without allowing them to penetrate the carpet, and therefore the following evaluation criteria were adopted.

[0056] (Evaluation criteria) ○: The colored oil did not soak in, remained on the surface of the test piece, and could be wiped off almost entirely with a paper cloth. △: After being dropped, the colored oil remained on the surface of the test piece for several minutes, but then it did not diffuse but soaked into spots, could not be wiped off sufficiently with a paper cloth, and a red stain was noticeable. ×: After being dropped, the colored oil did not immediately spread over the test piece but soaked into spots, and could hardly be wiped off with a paper cloth, leaving a strong, noticeable red stain.

[0057] [Easy to clean] (Test Method) First, test pieces were prepared in the same manner as in the evaluation of antifouling properties and their durability. Next, the test specimen was evenly sprayed with the following artificial soil and sand grime (hereinafter sometimes referred to as "grime") (spray amount: 0.7 g), and then the grime was rubbed with a clothes brush (lint brush) in a circular motion about 20 times to distribute it evenly. The grime adhering to the test specimen was then cleaned using a vacuum cleaner equipped with a crevice nozzle, rubbing the tip of the nozzle thoroughly and sucking up as much of it as possible. After this cleaning, the test specimen was washed using a washability tester (manufactured by Tester Sangyo Co., Ltd.) under the following cleaning conditions, rinsed, and then dried. The artificial soil and dirt used is a mixture of 96.6 parts by mass of the following artificial dirt specified in JIS L 1023, 8.1, and 3.4 parts by mass of canola oil. JIS-specified artificial dirt: Peat moss 20g, Portland cement 8.50g, silicic acid soil 8.50g, carbon black 0.05g, iron (III) oxide for ferrite 0.07g, Nujol 4.38g. The dirt remaining on the surface of the test piece after cleaning was visually inspected, and the ease with which the dirt could be removed (cleanability) was evaluated based on the following evaluation criteria. The washability tester is a testing machine for evaluating wash resistance and wet abrasion resistance, and has a reciprocating washing part that can automatically perform scrubbing and cleaning. The cleaning conditions for the washability tester were as follows: 1 g of carpet stain-resistant cleaner was dripped onto the test piece, and after leaving it to stand for 5 seconds, a cleaning pad (white pad, manufactured by 3M) attached to the operating part of the washability tester was used to run the tester back and forth 5 times, and the test piece was rinsed after cleaning by dipping it in and out of pooled water several times.

[0058] (Evaluation criteria) ◎: Dirt has been removed very well, and the condition is almost the same as that of new cotton cloth. ○: A small amount of dirt remains as black stains, but the overall condition is clean. △: Dirt remains in some places as uneven cleaning, and the overall state is not clean. ×: A lot of dirt remains as uneven cleaning, and dirt remains all over.

[0059] [Storage stability] (Test Method) 200 mL of the carpet stain-resistant cleaner was placed in a 250 mL sample bottle (a transparent polyethylene plastic bottle) and stored for one month in a thermostatic chamber (KAX-734, manufactured by Kobayashi Rika Kikai Kogyo Co., Ltd.) maintained at 50°C and in a refrigerator-freezer (HRF-90P, manufactured by Hoshizaki Corporation) maintained at 5°C. During the storage period, the carpet stain-resistant cleaner in the sample bottle was visually observed every day and its storage stability was evaluated based on the following evaluation criteria.

[0060] (Evaluation criteria) ○: No changes such as cloudiness, sedimentation, or separation were observed even after 30 days. △: After 14 days, slight changes such as cloudiness, sedimentation, or separation were observed. ×: After several days, any of the following changes was clearly observed: cloudiness, sedimentation, or separation.

[0061] [Table 1]

[0062] [Table 2]

[0063] [Table 3]

[0064] The above results show that Examples 1 to 7 received generally excellent ratings in all evaluation items. On the other hand, Comparative Examples 1 to 14, which did not contain any of the components (A) to (E) or whose contents were outside the ranges specified in the present invention, received either an "X" rating in any evaluation item or two or more "△" ratings, indicating that they had problems with either stain resistance and its persistence, hydrophilicity, oil repellency, ease of cleaning, or storage stability, or were inferior in overall performance. [Industrial Applicability]

[0065] The present invention can be used as an antifouling detergent composition for carpets that can clean carpets installed on floors inside buildings and the like without removing them from the installation site and impart antifouling properties to the carpets.

Claims

1. A stain-resistant detergent composition for carpets containing the following components (A) to (F), wherein the components (A) to (D) are contained in the following proportions relative to the total amount of the stain-resistant detergent composition for carpets, the mass ratio of component (D) to component (B) (D / B) is in the range of 0.2 to 0.45, and the pH, as measured by JIS Z-8802:1984 "pH measurement method," is 6 to 11. (A) Alkali-soluble resin having an average molecular weight (Mw) of 2,000 to 30,000 and a glass transition temperature (Tg) of 50 to 150°C: 0.5 to 10% by mass (B) Colloidal silica having an average particle size of 3 to 500 nm: 0.3 to 5 mass% (C) Anionic surfactant: 0.5 to 5% by mass (D) Fluorine-based surfactant: 0.1 to 2% by mass (E) Water (F) Neutralizing component

2. 2. The carpet stain-resistant cleaner composition according to claim 1, wherein (C) the anionic surfactant is at least one selected from the group consisting of sodium dodecyldiphenyloxide disulfonate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium metaxylene sulfonate, sodium toluenesulfonate, and sodium cumenesulfonate.

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