JP2007308555A - Cleanser composition for hard surface - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cleanser composition which can impart good dryness-accelerating effects to the hard surfaces of places equipped with water supplies without deteriorating cleansing power and is excellent in storage stability. <P>SOLUTION: This cleanser composition for hard surfaces comprises (a) a cation group-having polymer containing specific structural units, such as a cation-modified polyvinyl alcohol, (b) an anionic surfactant, (c) a cationic surfactant, and water. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a detergent composition for various hard surfaces such as plastic products (for example, water facilities in the home) and metal products.

  In bathrooms, bathtubs, sinks, etc., which are equipment around water at home, water droplets are likely to adhere to and remain on the surface of equipment after use due to water splashing from a faucet or shower during use. In the case of a bathroom, these water droplets remain damp and tend to cause mold, etc.In the case of a sink, the remaining water droplets are gradually dried while maintaining the shape at the time of attachment, and are in a small ring shape. It will be easier to keep track of. For example, in the case of a sink, the general response of consumers to such an inconvenient state is to wipe the water again with a cloth, etc., and to make efforts to maintain the aesthetics. In the case of, we remove the moisture from the bathroom by opening windows and doors, or by operating a ventilation fan, etc., and we are making efforts to promote drying. However, there are security problems, problems of ingress of pollutants from outside, and energy saving. From the point of view, none of them was a satisfactory coping method.

Under such circumstances, there has been a demand for a treatment method and a treatment agent that allow consumers to quickly dry without leaving water droplets in the water facilities such as bathrooms, bathtubs, and sinks. As a technique that has been disclosed so far for treating hard surfaces, Patent Document 1 discloses a cleaning and antifouling treatment agent for hydrophobic hard surfaces such as painted surfaces of automobiles, which contains a specific surfactant and a soil release polymer. However, Patent Documents 2 and 3 disclose a hard surface cleaning composition containing a surfactant and a specific water-soluble polymer, and Patent Document 4 provides a quick drying property containing a specific cationic copolymer. Agents are disclosed.
JP 2002-265996 A Japanese Patent Application Laid-Open No. 8-25396 Japanese Patent Laid-Open No. 8-253797 JP 2003-183694 A

  However, Patent Documents 1 to 3 do not show the effect of promoting drying on surface materials such as a bathroom, a bathtub, and a sink. Patent Document 4 discloses a technique of a cleaning agent that imparts quick drying to a hard surface such as tableware containing a cationic polymer compound. An anionic surfactant is generally used for the hard surface cleaning agent. However, when an anionic surfactant and a cationic polymer compound are used in combination, they not only cause stability problems such as formation of precipitates during storage, but also cationic polymers. Both the effect of the compound and the cleaning effect (detergency, foaming property) of the anionic surfactant are impaired, resulting in a problem that satisfactory cleaning effect and quick drying cannot be obtained.

  Accordingly, an object of the present invention is to provide quick drying that quickly dries without leaving water droplets on the hard surface of equipment around the water, such as bathrooms, bathtubs, sinks, etc., without impairing the detergency that is the basic performance as a cleaning agent. An object of the present invention is to provide a hard surface cleaning composition that imparts an effect and has no problem in storage stability.

  The present invention is represented by (a) the structural unit (a1) represented by the following general formula (1), the structural unit (a2) represented by the following general formula (2), and the following general formula (3). A polymer compound containing the structural unit (a3) [hereinafter referred to as component (a)] is 0.01 to 5% by mass, (b) an anionic surfactant (hereinafter referred to as component (b)) is 0. The present invention relates to a hard surface cleaning composition containing 0.01 to 10% by mass, 0.01 to 10% by mass of (c) a cationic surfactant (hereinafter referred to as component (c)), and water.

[In the formula, R is an alkyl group having 1 to 3 carbon atoms, and X is a structural unit derived from an unsaturated compound having a cationic group or an amino group in the molecule and copolymerizable with a vinyl alcohol lower fatty acid ester. is there. ]

  According to the present invention, a hard surface that prevents water droplets from remaining, promotes drying, and has excellent storage stability by rinsing after application to a hard surface around water without impairing cleaning power. A cleaning composition is obtained.

  The present inventors have found that partially saponified polyvinyl alcohol is effective for imparting quick drying to a hard surface. However, partially saponified polyvinyl alcohol has a low adsorptivity to a hard surface and does not exhibit any effect even when applied to a cleaning agent. The component (a) of the present invention is a component that has improved the adsorptivity to the hard surface of partially saponified polyvinyl alcohol. The structural unit (a1) represented by the general formula (1) and the general formula (2) A high molecular compound containing the structural unit (a2) represented by the formula (3) and the structural unit (a3) represented by the general formula (3).

  The polymer compound (a) is obtained by copolymerizing a monomer compound derived from the structural unit (a2) and a monomer compound derived from the structural unit (a3) to partially saponify. Can be obtained at For example, as a polymer compound in which R in the general formula (2) is a methyl group, a copolymer of a polymerizable cationic monomer (a compound from which the structural unit (a3) is derived) and vinyl acetate is partially saponified. The cationized polyvinyl alcohol obtained by this can be used.

  Here, the monomer compound from which the structural unit (a3) is derived has one or more cationic groups or amino groups in the molecule, and is a vinyl alcohol lower (carbon number 1 to 3) fatty acid ester (structural unit). (A1), a monomer compound derived from (a2)) and a compound copolymerizable with the compound represented by the following general formula (3-1) and the following general formula (3-2). And a compound selected from the following compounds.

[In formula, R < ¹ >, R < ² >, R < ³ >, R < ⁷ >, R <^8> , R <^9> is respectively independently a hydrogen atom or a C1-C3 alkyl group. X ^1, Y are each independently an alkylene group having 1 to 12 carbon ^{atoms, -COOR 12 -, - CONHR 12} -, - OCOR 12 -, - is a group selected - R ¹³ -OCO-R ¹² . Here, R ¹² and R ¹³ are each independently an alkylene group having 1 to 5 carbon atoms. R ⁴ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ¹ R ² C═C (R ³ ) —X ¹ —. R ⁵ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, R ⁶ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and Z ⁻ represents an anion. R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ⁷ R ⁸ C═C (R ⁹ ) —Y—. R ¹¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group. ]

  Specific monomer compounds derived from the structural unit (a3) include diallyldialkyl (the alkyl group has 1 to 3 carbon atoms) ammonium salt, N- (meth) acryloylaminoalkyl (carbon of the alkyl group) The number is 1-5) -N, N-dialkyl (the alkyl group has 1 to 3 carbon atoms) amine, N- (meth) acryloylaminoalkyl (the alkyl group has 1 to 5 carbon atoms) -N, N , N-trialkyl (the alkyl group has 1 to 3 carbon atoms) ammonium salt, N- (meth) acryloyloxyalkyl (the alkyl group has 1 to 5 carbon atoms) -N, N, N-trialkyl ( The alkyl group has 1 to 3 carbon atoms, an ammonium salt, and N- (ω-alkenyl (the alkenyl group has 2 to 10 carbon atoms))-N, N-dialkyl (the alkyl group has 1 to 3 carbon atoms). ) Selected from amine The compounds.

  In the constituent unit of component (a), the sum of the constituent unit (a1), constituent unit (a2) and constituent unit (a3) is 50 to 100 mol%, more preferably 80 to 100 mol%, and particularly substantially 100 mol%. It is preferable from the point of an effect. In the component (a), the molar ratio of the structural unit (a1) to the structural unit (a2) is 100 to 1, preferably 50 to 1.3, and more preferably 20 to (a1) / (a2). 1.5 is preferable from the viewpoint of the compatibility of the blending components and the performance. Furthermore, in the structural unit (a), the structural unit (a3) containing a cationic group is 0.01 to 10 mol%, and more preferably 0.01 to 5 mol%. It is preferable from the point.

  In the present invention, the structural unit having the structural unit (a1) and the structural unit (a2) makes it possible to impart excellent quick drying properties to the object. Among them, the structural unit (a1) imparts hydrophilicity to the hard surface, and the structural unit (a2) and the structural unit (a3) are factors that act on the adsorption to the hard surface, and particularly the structural unit (a3). ) Is considered to be a factor that affects the compatibility and liquid stability of the ingredients. Basically, by containing these components preferably in the above proportions, the excellent effect of the present invention can be enjoyed, but with other monomers copolymerizable to the extent that the effects of the present invention are not hindered. The copolymer may be used.

  Examples of the copolymerizable monomer include (meth) acrylic acid (salt), maleic acid (salt), maleic anhydride, styrene, styrene sulfonic acid (salt), acrylamide, ethylene, propylene, N-butylene, isobutylene, N-pentene, isoprene, 2-methyl-1-butene, N-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, Examples thereof include styrene and vinyl toluene.

The component (a) of the present invention may be obtained by any polymerization method, but is unsaturated vinyl alcohol lower (1 to 3 carbon atoms) fatty acid ester and a cationic group and copolymerizable with vinyl alcohol lower fatty acid ester. A compound, preferably a compound of general formula (3-1) and / or a compound of general formula (3-2), and optionally the above-mentioned monomer copolymerizable therewith, a radical polymerization method, particularly preferably a bulk, solution Alternatively, this can be done in an emulsifying system. Radical polymerization may be initiated by heating, but as an initiator, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (N, N-dimethyleneisobutylamidine) Azo initiators such as dihydrochloride, hydrogen peroxide and organic peroxides such as benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide, perbenzoic acid, sodium persulfate, Existing radical initiators such as persulfates such as potassium persulfate and ammonium persulfate, redox initiators such as hydrogen peroxide-Fe ³⁺ may be used, and in the presence or absence of a photosensitizer. The polymerization may be initiated by light irradiation or radiation irradiation.

  In the present invention, a part of the structural unit derived from the vinyl alcohol lower (carbon number 1 to 3) fatty acid ester of the polymer obtained by the polymerization thus obtained is saponified. The method for saponification is not particularly limited, and a general method can be adopted.

  For example, the copolymer is dissolved in an alcohol or a hydrous alcohol and, if necessary, saponification is carried out with an acid catalyst or an alkali catalyst after neutralization of the acid component in the polymer or simultaneously with the neutralization. Examples of the alcohol include methanol, ethanol, propanol, tert-butanol and the like, and methanol is particularly preferably used. The concentration of the copolymer in the alcohol is appropriately selected depending on the viscosity of the system, but is usually selected from the range of 10 to 60% by mass. Catalysts used for the saponification include alkali catalysts such as alkali metal hydroxides and alcoholates such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate and potassium methylate, or sulfuric acid and hydrochloric acid. An acid catalyst is used. The amount of the catalyst used is appropriately selected depending on the saponification method, the target saponification degree, etc., but usually 0.1 to 10 mol% is appropriate for the lower vinyl alcohol (1 to 3 carbon atoms) fatty acid ester. is there. The saponification reaction temperature is not particularly limited and is appropriately selected according to the target saponification degree, and is usually selected from the range of 10 to 60 ° C., preferably 20 to 50 ° C. The saponification reaction is performed for 5 to 240 minutes. .

  The weight average molecular weight of the component (a) is preferably 10,000 to 1,000,000, more preferably 10,000 to 500,000, and particularly preferably 10,000 to 200,000. The weight average molecular weight here can be determined using a mixed solvent of acetonitrile and water (phosphate buffer solution) as a developing solvent and using polyethylene glycol as a standard by gel permeation chromatography.

  The anionic surfactant which is the component (b) of the present invention includes one hydrocarbon group having 8 to 18 carbon atoms, a carboxylic acid (salt) group, a sulfonic acid (salt) group, or a sulfate ester (salt). An anionic surfactant having one group is preferred. Specifically, a saturated or unsaturated fatty acid (salt) having 10 to 16 carbon atoms, preferably 10 to 14 carbon atoms, an alkyl group having 8 to 16 carbon atoms, preferably 8 to 14 carbon atoms, and a polyoxy having an average addition mole number of 1 to 10 Polyoxyalkylene alkyl ether carboxylic acid (salt) having an alkylene (2 or 3 carbons) group, an alkyl group having 8 to 16, preferably 8 to 14 carbon atoms, and a polyoxyalkylene having 1 to 6 average added moles (carbon) 2 or 3) polyoxyalkylene alkyl ether sulfate having a group, alkyl sulfate having 8 to 16 carbon atoms, preferably 8 to 14 alkyl, alkyl having 10 to 18 carbon atoms (or alkenyl group) (Or alkenyl) benzene sulfonate, α-olefin sulfonate having 10 to 18 carbon atoms, secondary alkane having 13 to 18 carbon atoms Sulfonates, sulfonates of fatty acid lower alcohol (C1-3) esters having 8-18 carbon atoms, preferably 14-18 carbon atoms, fatty alcohols having 8-18 carbon atoms, preferably 10-16 carbon atoms, and sulfosuccinic acid Examples include esters (salts). Sodium salts, potassium salts, and alkanolamine salts are preferred as the salt. In addition, (salt) means each salt.

  The above-mentioned anionic surfactant is used for the purpose of imparting foaming properties and detergency, but when used in combination with the component (a), both the effects of the component (a) and the effect of the component (b) are reduced. Or the storage stability such as formation of a precipitate during storage is impaired. This is considered to be because the anionic surfactant acts on the structural unit (a3) of the component (a). In the present invention, it has been found that this problem can be solved by using a cationic surfactant as component (c) together.

From the viewpoint of storage stability, the cationic surfactant as component (c) is preferably one having the longest hydrocarbon group not exceeding 10 carbon atoms, particularly those having 6 to 10 carbon atoms. A quaternary comprising a hydrocarbon group having 6 to 10 carbon atoms, further 6 to 8 carbon atoms, particularly one or two alkyl groups, and the remaining group is an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms. An ammonium compound, and (ii) a hydrocarbon group other than a benzyl group having 6 to 10 carbon atoms, and further 6 to 8 carbon atoms, particularly one alkyl group, one benzyl group, and the remaining group having 1 carbon atom Cationic surfactants selected from quaternary ammonium compounds consisting of ˜3 alkyl groups or hydroxyalkyl groups are preferred. More specifically, it is a compound represented by the general formula (4).

[Wherein, R ¹⁴ is an alkyl group having 6 to 10 carbon atoms, particularly 6 to 8 carbon atoms, and R ¹⁵ is an alkyl group having 6 to 10 carbon atoms, particularly 6 to 8 carbon atoms, having 1 to 3 carbon atoms. An alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms. R ¹⁶ is an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ¹⁷ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a benzyl group. When R ¹⁷ is a benzyl group, R ¹⁵ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. W ^- is an anion, preferably a chloro ion. ]

  Specifically, hexyltrimethylammonium chloride, octyltrimethylammonium chloride, decyltrimethylammonium chloride, dihexyldimethylammonium chloride, dioctyldimethylammonium chloride, didecyldimethylammonium chloride, hexyldimethylbenzylammonium chloride, octyldimethylbenzylammonium chloride, decyldimethylbenzyl Ammonium chloride can be mentioned, and a monoalkyl quaternary ammonium salt having a benzyl group is particularly preferable.

  In the present invention, a surfactant other than the above-mentioned component (b) and component (c) [hereinafter referred to as component (d)] can be contained. Specifically, as the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkylene ether, polyoxyethylene sorbitan fatty acid ester, alkyl polyglycoside, sucrose fatty acid ester, alkyl polyglycerin ether, amphoteric surfactant Examples thereof include amine oxides such as alkyldimethylamine oxide, betaines such as alkyl-N, N-dimethylacetic acid betaine, fatty acid amidopropyl-N, N-dimethylacetic acid betaine, and alkylcarboxymethylhydroxyethylimidazolium betaine.

  These surfactants are preferably used in combination.

  In the present invention, a solvent [hereinafter referred to as component (e)] can be contained from the viewpoint of improving storage stability and from the viewpoint of detergency. Specifically, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, isoprene glycol, diethylene glycol monoalkyl (carbon number 4 to 8) ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Water solubility selected from glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, polyoxyethylene (ethylene oxide average addition mole number 3) phenyl ether and monoalkyl glyceryl ether having 3 to 8 carbon atoms in the alkyl group A solvent is mentioned. Among these, glycol ether solvents are preferable from the viewpoint of storage stability and detergency, and diethylene glycol monoalkyl (carbon number 4 to 8) ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol. Monobutyl ether and dipropylene glycol monobutyl ether are preferred.

  In the present invention, it is preferable to contain a chelating agent (hereinafter referred to as component (f)) from the viewpoint of enhancing the cleaning effect. Examples of the chelating agent include tripolyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, hexametaphosphoric acid and alkali metal salts thereof; ethylenediamine Tetraacetic acid, hydroxyiminodiacetic acid, dihydroxyethylglycine, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid and their alkali metal or alkaline earth metal salts; aminotrimethylenephosphonic acid, 1 -Hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, aminotrimethylenephosphonic acid, and alkali metal salts or amines thereof Potassium earth metal salts; homopolymers or copolymers of monomers selected from acrylic acid and methacrylic acid, acrylic acid-maleic acid copolymers, poly-α-hydroxyacrylic acid and alkali metal salts thereof; citric acid, succinic acid One or more polycarboxylic acids selected from acids, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid and alkali metal salts thereof; alkylglycine-N, N-diacetic acid, aspartic acid-N, Examples thereof include N-diacetic acid, serine-N, N-diacetic acid, glutamic acid diacetic acid, ethylenediamine disuccinic acid, and salts thereof. Of these, ethylenediaminetetraacetic acid and citric acid are particularly preferred in the present invention.

  In the present invention, optional components such as hydrotropes such as p-toluenesulfonic acid, m-xylenesulfonic acid, p-cumenesulfonic acid and ethylbenzenesulfonic acid, fragrances, antibacterial agents, viscosity modifiers, pigments, dyes and suspending agents [Hereinafter referred to as component (g)] can be added.

<Cleaning composition for hard surface>
The hard surface cleaning composition of the present invention is a liquid composition and contains 0.01 to 5% by mass, preferably 0.03 to 3% by mass of component (a). Moreover, (b) component is 0.01-10 mass%, Preferably it is 0.01-8 mass%, More preferably, 0.1-5 mass% is contained. Moreover, (c) component is 0.01-10 mass%, Preferably it is 0.01-8 mass%, More preferably, 0.1-5 mass% is contained. The mass ratio of component (b) / component (c) is preferably 1/9 to 14/1, more preferably 1/8 to 10/1, and particularly preferably 1/5 to 5/1. Furthermore, the mass ratio of (a) component / [(b) component + (c) component] is 1/500 to 2/1, more preferably 1/100 to 1/1, and particularly 1/50 to 1/2. preferable.

  Although component (d) can be used for the purpose of improving detergency and foaming properties, blending a large amount of component (d) may reduce the effect of component (a). % Or less, further 0.1 to 8% by mass, particularly 0.1 to 6% by mass is preferable. Although the component (e) is optional, it is preferable to contain it because it can enhance detergency and improve storage stability, and is preferably contained in the composition in an amount of 0.1 to 20% by mass, more preferably 1 to 15% by mass, especially 5 It is preferable to contain -15 mass%. Furthermore, component (f) is also preferably contained since a detergency enhancing effect is obtained, and is preferably contained in the composition in an amount of 0.1 to 15% by mass, and more preferably 0.1 to 10% by mass.

  In this invention, it is preferable that it is a form of the aqueous solution which dissolved (a) component-(c) component and (d) component-(g) component in water depending on necessity, and the pH in 20 degreeC is 2-11, Further, 3 to 10, particularly 4 to 8, are preferable from the viewpoint of safety during work and damage to the substrate. As pH regulators, acid agents such as inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid, sodium hydroxide and potassium hydroxide, Alkaline agents such as sodium carbonate and potassium carbonate such as ammonia and derivatives thereof, amine salts such as monoethanolamine, diethanolamine, and triethanolamine may be used alone or in combination. In addition, these acid agents and alkali agents may be used in combination as a buffer system.

  The hard surface cleaning composition of the present invention adjusts the composition according to the treatment of the hard surface. Moreover, each concentrated solution can be prepared and can be diluted and used at the time of use.

The method of applying the cleaning composition of the present invention to the hard surface can be selected according to the width (area) of the hard surface. For example, it can be performed by spraying about 0.1 to 10 mL of an aqueous solution having a component (a) content of 0.5% by mass per 10 cm ^{2 and} spreading it thinly using a sponge or the like.

  The cleaning composition of the present invention has a cleaning effect on oil stains, protein stains, sebum stains, etc., and can impart good hydrophilicity to a hydrophobic hard surface, and its sustained effect Also excellent. Therefore, according to the present invention, there is provided a method for treating a hard surface in which the hard surface cleaning composition of the present invention is applied to a hydrophobic surface to impart persistent hydrophilicity. Moreover, the cleaning composition of the present invention not only simply hydrophilizes the hard surface but also promotes drying. This is because the hard surface is hydrophilized, causing a water drop phenomenon (for example, a phenomenon in which water is slowly drained from the upper end after the surface is covered with a water film, etc.) As a result, it is considered that drying of the hard surface is promoted. Moreover, the above-mentioned water drainage phenomenon also occurs on hydrophilic surfaces such as glass and tiles, and drying is promoted. Since the hard surface to which these effects are imparted is less prone to mold, the cleaning composition of the present invention is also suitable for mold prevention treatment. Further, since the hydrophilic property is good, dirt adhering to the hard surface, particularly hydrophobic dirt, can be easily washed away with water, so that the cleaning composition of the present invention is also suitable for antifouling treatment.

  The cleaning composition of the present invention is preferably applied to a hard surface constituting equipment around water, for example, a hydrophobic hard surface made of a material selected from plastic, ceramics and metal. Is preferably applied to reinforced plastic (FRP), polyvinyl chloride, polypropylene, polyethylene, ABS, nylon, stainless steel, tile, and the like.

  The hard surface cleaning composition shown in Table 1 was prepared and evaluated as follows. The results are shown in Table 1. The pH of the composition was adjusted with sodium hydroxide and hydrochloric acid.

(1) Compatibility The state of the composition immediately after preparation was visually observed, and the compatibility was evaluated according to the following criteria.
○: A precipitate was not generated, and it was dissolved transparently.
X: Precipitation or turbidity occurred.

(2) Water drainage Using an FRP bathtub (60 cm × 100 cm × 55 cm), 5 adults took a bath, left standing overnight (9 hours), then drained, and a naturally dried bathtub was used for evaluation. A commercial sprayer was filled with the cleaning composition shown in Table 1, sprayed with 10 mL of the bath, lightly rubbed with a sponge, rinsed with water, and visually judged whether or not a water drainage phenomenon occurred. In addition, 2 mL was sprayed onto a PVC plate (30 cm × 30 cm), lightly rubbed with a sponge, rinsed with water, and visually judged whether or not a water drainage phenomenon occurred. At that time, drainage was evaluated according to the following criteria.
○: Water drainage phenomenon occurs.
X: Water drainage phenomenon does not occur.

(3) Foaming Commercially available sprayers were filled with the detergent composition shown in Table 1, sprayed with 10 mL of the FRP bath, and foaming when lightly rubbed with a sponge was visually determined. At that time, foaming was evaluated according to the following criteria.
○: Foaming is sufficient.
Δ: Not very foamy.

(4) Detergency 0.05 g of the detergent composition shown in Table 1 was applied to a bathroom chair used for one month in a general household and allowed to stand at room temperature for a certain time (5 minutes or 10 minutes). Thereafter, it was washed away with water, and stain removal was visually judged according to the following criteria.
A: Dirt is removed cleanly after standing for 5 minutes.
○: The stains are cleanly removed after standing for 10 minutes.

(5) Storage stability After storing the cleaning composition of Table 1 at 50 ° C. for one month, the state of the composition was visually determined. At that time, the storage stability was evaluated according to the following criteria.
○: Insoluble matter does not occur.
X: Insoluble matter is generated.

(note)
The components in the table are as follows.
Cation-modified PVA (a): Partial saponification product of a copolymer of vinyl acetate and N-methacryloylaminopropyl-N, N, N-trimethylammonium chloride (the structural unit (a1), structural unit ( The total of a2) and the structural unit (a3) is 100 mol%, the structural unit (a3) is 1.7 mol%, and the molar ratio of the structural unit (a1) and the structural unit (a2) is (a1) / (A2) = 7.3, the molecular weight is about 90,000.)
Cation-modified PVA (I): Partial saponification product of a copolymer of vinyl acetate and diallyldimethylammonium chloride (the total of the structural unit (a1), the structural unit (a2) and the structural unit (a3) in all the structural units is 100 mol%, the structural unit (a3) is 0.9 mol%, and the molar ratio of the structural unit (a1) to the structural unit (a2) is (a1) / (a2) = 6.7. Is about 90,000.)
Anion-modified PVA: partially saponified product of a copolymer of vinyl acetate and maleic acid (saponification degree 96 mol%, anion modification degree 2 mol%, molecular weight is about 80,000)
Unmodified PVA: polyvinyl alcohol (saponification degree 88 mol%, molecular weight is about 80,000)
-Sodium alkylbenzene sulfonate: alkyl group having 10 to 16 carbon atoms
・ Sodium α-olefin sulfonate: C10-18
・ Sodium alkyl ether sulfate: polyoxyethylene (ethylene oxide average addition mole number 2.0) alkyl (carbon number 12 to 16) ether sulfate sodium ・ Higher fatty acid sodium: sodium myristate ・ Alkylaminopropionate sodium: alkyl group Of carbon number 10-14
・ Alkyldimethylbenzylammonium chloride: C8 of alkyl group
Polyoxyethylene alkyl ether: ethylene oxide average addition mole number 10, carbon number 12-16 of alkyl group
-Alkyl glycoside: alkyl (C10-16) polyglucose (average sugar condensation degree 1-2)
-Fatty acid amidopropyl betaine: Amidopropyl laurate-N, N-dimethyl-acetic acid betaine-Amine oxide: C10-14 of an alkyl group
Chelating agent: EDTA-4Na / citric acid = 4 (mass ratio) mixture

Claims (5)

(A) The structural unit (a1) represented by the following general formula (1), the structural unit (a2) represented by the following general formula (2), and the structural unit (a3 represented by the following general formula (3) ) Containing 0.01 to 5% by mass of the polymer compound, (b) 0.01 to 10% by mass of the anionic surfactant, and (c) 0.01 to 10% of the cationic surfactant. %, And a hard surface cleaning composition containing water.

[In the formula, R is an alkyl group having 1 to 3 carbon atoms, and X is a structural unit derived from an unsaturated compound having a cationic group or an amino group in the molecule and copolymerizable with a vinyl alcohol lower fatty acid ester. is there. ] The hard surface cleaning composition according to claim 1, wherein the total of the structural unit (a1), the structural unit (a2), and the structural unit (a3) is 50 to 100 mol% in the structural unit (a). The cleaning composition for hard surfaces according to claim 1 or 2, wherein in the structural unit (a), the total of the structural units (a3) is 0.01 to 10 mol%. The molar ratio of the structural unit (a1) and the structural unit (a2) in (a) is 100-1 in (a1) / (a2), The hard surface cleaning agent in any one of Claims 1-3 Composition. In the structural unit (a), the structural unit (a3) is derived from a compound selected from a compound represented by the following general formula (3-1) and a compound represented by the following general formula (3-2). The cleaning composition for hard surfaces according to any one of claims 1 to 4.

[In formula, R < ¹ >, R < ² >, R < ³ >, R < ⁷ >, R <^8> , R <^9> is respectively independently a hydrogen atom or a C1-C3 alkyl group. X ^1, Y are each independently an alkylene group having 1 to 12 carbon ^{atoms, -COOR 12 -, - CONHR 12} -, - OCOR 12 -, - is a group selected - R ¹³ -OCO-R ¹² . Here, R ¹² and R ¹³ are each independently an alkylene group having 1 to 5 carbon atoms. R ⁴ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ¹ R ² C═C (R ³ ) —X ¹ —. R ⁵ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, R ⁶ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and Z ⁻ represents an anion. R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ⁷ R ⁸ C═C (R ⁹ ) —Y—. R ¹¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group. ]