JP5575466B2 - Cleaning composition for hard surface - Google Patents

Description

  The present invention relates to a hard surface cleaning composition.

  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 becomes easy to get a mark. 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. Patent Documents 1 and 2 disclose a technique of a cleaning agent that imparts quick drying to a hard surface such as tableware containing a cationic polymer compound and a specific amount of a chelating agent.

JP 2006-143843 A JP 2007-308555 A

  However, when a cationic polymer compound and a chelating agent as used in Patent Documents 1 and 2 are used, a precipitate is formed during storage at a low temperature depending on the composition. It has been found that there are problems with stability at low temperatures, such as causing clogging. Patent Document 1 describes that the liquid stability immediately after preparation of the composition is excellent, and Patent Document 2 describes that it is excellent in storage stability at 50 ° C. There is no indication of stability and sprayability using spray containers after storage at low temperatures.

  Therefore, the object of the present invention is to provide a cleaning power that is a basic performance as a cleaning agent and a quick drying effect that allows quick drying without leaving water droplets on the hard surface of water-related equipment such as a bathroom, bathtub, sink, etc. Another object of the present invention is to provide a hard surface cleaning composition that does not have a problem in storage stability at low temperatures, which has not been sufficiently achieved by the prior art.

  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). Polymer compound containing structural unit (a3) [hereinafter referred to as component (a)] 0.001 to 0.3 mass%, (b) chelating agent (hereinafter referred to as component (b)) 0.01 to 2 mass % (However, the mass in the case of salt is hereinafter converted to the mass of the acid form) and (c) water (hereinafter referred to as component (c)), and the mass ratio of (a) and (b) is (A) / (b) = It is related with the cleaning composition for hard surfaces which is 0.1-1.

[Wherein, 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 in the molecule and copolymerizable with a vinyl alcohol lower fatty acid ester. ]

  According to the present invention, it has not been sufficiently achieved with the prior art, which has a detergency and a quick-drying effect that quickly dries without leaving water drops by rinsing after application to a hard surface around water. A hard surface cleaning composition having excellent storage stability at low temperatures can be obtained.

  Partially saponified polyvinyl alcohol that imparts quick-drying properties when adsorbed on a hard surface has low adsorbability on the hard surface and does not exhibit any effect even when applied to a cleaning agent, so it is necessary to impart adsorbability. 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 The structural unit (a1) is included by partially saponifying the structural unit (a2). 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.

Among the constituent units of the component (a), the abundance ratio of the constituent unit (a1), constituent unit (a2) and constituent unit (a3) can be determined from peaks obtained by ¹ H-NMR and ¹³ C-NMR measurements. .

  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, the structural unit (a2), and the structural unit (a3) are factors that affect the adsorption of the component (a) on the hard surface, Furthermore, the structural unit (a3) is considered to be a factor that affects the compatibility and liquid stability of the compounding components. Basically, by containing these components preferably in the above proportions, the effect of imparting quick drying to the hard surface of the present invention can be enjoyed, but copolymerization is possible to the extent that the effects of the present invention are not hindered. Copolymers with other monomers may also 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. The compound, preferably the compound of the general formula (3-1) and / or the compound of the general formula (3-2) and the above-mentioned monomer copolymerizable therewith by a radical polymerization method, preferably in the form of a bulk, solution Or obtained by polymerization in an emulsion 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.

  Content of (a) component in the cleaning composition for hard surfaces of this invention is 0.001-0.3 mass%, Preferably it is 0.05-0.30 mass%, More preferably, it is 0.20-0. .30% by mass. When the content of the component (a) is 0.001% by mass or more, the effect of imparting quick drying to the hard surface is excellent. It is possible to achieve both sprayability using a spray-type container after storage.

  A chelating agent binds to a metal ion by a ligand having a plurality of coordination sites, forms a complex, and has an effect of making the metal ion difficult to interact with other components. Further, in the cleaning scene, it has a role of decomposing dirt by binding with metal ions in the dirt, and the influence on the washing performance is very large.

  As the chelating agent for component (b), tripolyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, hexametaphosphoric acid and alkali metal salts thereof; ethylenediaminetetraacetic acid, hydroxyiminodiacetic acid, dihydroxyethylglycine, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, Diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid and alkali metal salts or alkaline earth metal salts thereof; aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphone Acid, aminotrimethylenephosphonic acid, and alkali metal salts or alkaline earth metal salts thereof; a single polymer of monomers selected from acrylic acid and methacrylic acid, or Polymer, acrylic acid-maleic acid copolymer, poly α-hydroxyacrylic acid and alkali metal salts thereof; polyvalent carboxylic acid selected from citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid One or more selected from acids and alkali metal salts thereof; alkylglycine-N, N-diacetic acid, aspartic acid-N, N-diacetic acid, serine-N, N-diacetic acid, glutamic acid diacetic acid, ethylenediamine disuccinic acid Examples thereof include acids or salts thereof. Of these, ethylenediaminetetraacetic acid and citric acid or their salts are particularly preferred in the present invention.

  In addition, when a chelating agent is a salt, what was converted into the mass of an acid form below is made into the mass of a chelating agent.

  Content of (b) component in the cleaning composition for hard surfaces of this invention is 0.01-2 mass%, Preferably it is 0.2-2.00 mass%, More preferably, it is 0.50-2.00. % By mass. (B) When the content of the component is 0.01% by mass or more, the detergency is improved. When the content is 2% by mass or less, the storage stability at low temperature is excellent, and the spray type container after storage at low temperature is provided. The sprayability used can be compatible.

  Moreover, mass ratio of (a) component content and (b) component content in the cleaning composition for hard surfaces of this invention is (a) / (b) = 0.1-1, Preferably it is 0.00. 11 to 0.50, more preferably 0.15 to 0.33. When (a) / (b) is 0.1 or more, the storage stability at low temperature is excellent, and when it is 1 or less, the hard surface is excellent in quick drying, and the spray-type container after being stored at fast drying and low temperature is used. The sprayability used can be compatible.

  In the present invention, for the purpose of further improving the detergency, glycol ether and / or alcohol [hereinafter referred to as component (d)] can be contained. 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, from the viewpoint of detergency, ethanol, isopropyl alcohol, diethylene glycol monoalkyl (4 to 8 carbon atoms) ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene Glycol monobutyl ether is preferable, and ethanol and butyl carbitol are more preferable.

  The detergent composition for hard surfaces of the present invention preferably contains a surfactant from the viewpoint of detergency. Examples of the surfactant include one or more surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. One or more surfactants selected from anionic surfactants, nonionic surfactants and amphoteric surfactants (hereinafter referred to as “component (e)”) are difficult to prevent the effect of imparting quick-drying properties to hard surfaces. preferable.

  Anionic surfactants include higher fatty acid salts, higher alcohol sulfates, phosphate esters, fatty acid ester sulfates, fatty acid ester sulfonates, higher alcohol ether sulfates, and higher alcohol ether-substituted acetates. , Fatty acid and amino acid condensates, fatty acid amide alkylol sulfate ester, fatty acid amide alkylated sulfonate, sulfosuccinate ester salt, alkylbenzene sulfonate, alkylphenol sulfonate, alkylnaphthalene sulfonate, alkylbenzo Imidazole sulfonate, amide ether carboxylic acid or its salt, ether carboxylic acid or its salt, N-acyl-N-methyltaurine or its salt, amide ether sulfuric acid or its salt, N-acyl glutamic acid or its salt, -Amidoethyl-N-hydroxyethylacetic acid or a salt thereof, acyloxyethanesulfonic acid or a salt thereof, N-acyl-β-alanine or a salt thereof, N-acyl-N-carboxyethyltaurine or a salt thereof, N-acyl-N- Examples thereof include carboxyethyl glycine or a salt thereof, and alkyl or alkenylaminocarbonylmethyl sulfate or a salt thereof. Of these, sulfates of higher alcohol ethers and alkylbenzene sulfonates are preferable.

  Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylene ethers, polyoxyethylene sorbitan fatty acid esters, alkyl polyglycosides, sucrose fatty acid esters, alkyl polyglycerin ethers, and amine oxides such as alkyl dimethylamine oxide. Can be mentioned. Among these, alkyl polyglycosides, alkyl benzene sulfonates, and amine oxides are preferable.

  Examples of amphoteric surfactants include alkyl-N, N-dimethylacetic acid betaine, fatty acid amidopropyl-N, N-dimethylacetic acid betaine, alkyl-N, N-dimethylethanesulfobetaine, fatty acid amidopropyl-N, N-dimethyl- Examples thereof include betaines such as 2-hydroxypropylsulfobetaine and alkylcarboxymethylhydroxyethylimidazolium betaine. Of these, fatty acid amidopropyl-N, N-dimethylacetic acid betaine and fatty acid amidopropyl-N, N-dimethyl-2-hydroxypropylsulfobetaine are preferable.

  These surfactants are preferably used in combination.

  The hard surface cleaning composition of the present invention comprises a hydrotrope such as p-toluenesulfonic acid, m-xylenesulfonic acid, p-cumenesulfonic acid, and ethylbenzenesulfonic acid, a fragrance, an antibacterial agent, a viscosity modifier, a pigment, Optional components such as dyes and suspending agents can be contained.

<Cleaning composition for hard surface>
The hard surface cleaning composition of the present invention is a liquid composition, and the component (a) is 0.001 to 0.3% by mass, preferably 0.05 to 0.30% by mass, more preferably 0.00. It contains 20 to 0.30% by mass. When the content of the component (a) is 0.001% by mass or more, the effect of imparting quick drying to the hard surface is excellent. When the content is 0.3% by mass or less, the storage stability at low temperature is excellent. It is possible to achieve both sprayability using a spray-type container after storage. Moreover, (b) component is 0.01-2 mass%, Preferably it is 0.20-2.00 mass%, More preferably, 0.50-2.00 mass% is contained. (B) When the content of the component is 0.01% by mass or more, the detergency is improved. When the content is 2% by mass or less, the storage stability at low temperature is excellent, and the spray type container after storage at low temperature is provided. The sprayability used can be compatible. The mass ratio of the component (a) to the component (b) is (a) / (b) = 0.1-1, preferably 0.11-1 from the viewpoint of storage stability at low temperature and imparting detergency. It is 1.00, More preferably, it is 0.15-1.00. When (a) / (b) is 0.1 or more, the storage stability at low temperature is excellent, and when it is 1 or less, the effect of imparting quick drying to a hard surface is excellent. It is possible to achieve both sprayability using a spray container.

  Although component (d) is optional, it is preferably contained in order to enhance the detergency, and is contained in the composition in an amount of 0.1 to 20% by mass, further 1 to 15% by mass, particularly 5 to 15% by mass. Is preferred.

  Further, the surfactant and further the component (e) can be used for the purpose of improving the detergency and foaming property, but it is also possible to add a large amount of the surfactant and further the component (e). In the present invention, it is preferably 0.1 to 10% by mass, more preferably 0.1 to 8% by mass, and particularly preferably 0.1 to 3.5% by mass.

  In the present invention, it is preferably in the form of an aqueous solution in which (a) component to (b) component and optionally (d) component to (e) component are dissolved in water as component (c), and the pH at 20 ° C. Is preferably from 13 to 13, more preferably from 7 to 12, especially from 7.5 to 11 in terms of safety during work and damage to the substrate. As pH adjusters, 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. In addition, the compound which has chelate ability among these pH adjusters is handled as (b) component.

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 an aqueous solution the content of the component (a) is in the above range, can be carried out by sprayed about per 10cm ² 0.1~10mL treating stretched coated thin with a sponge or the like. The cleaning composition of the present invention is excellent in storage stability at a low temperature, does not produce a precipitate upon storage at a low temperature, and is excellent in sprayability. Therefore, the spray-type hard surface cleaner article obtained by filling the spray-type container with the hard-surface cleaner composition of the present invention is a good sprayable article even after storage at a low temperature. Examples of the spray container include a spray container equipped with a trigger sprayer (referred to as a trigger spray container). Examples of the trigger type spray container include a container body containing a liquid detergent composition, and a trigger type liquid ejector attached to the mouth part of the container body, and further, the mouth part of the container body. Is mounted with a trigger sprayer for ejecting a liquid detergent composition, a vertical pipe and a horizontal pipe are formed in the trigger sprayer, and the vertical pipe and the horizontal pipe are formed in the vertical pipe. A spray container (referred to as spray container (I)) in which a valve for blocking communication with the road is provided. The volume of the horizontal line in the spray container (I) is preferably 0.1~0.28cm ^3, volume under the valve of the vertical pipe is preferably 0.06~0.19cm ^3. The spray container (I) is provided with a cylinder at a lower position of the horizontal pipe, and a spin element is mounted at the tip of the horizontal pipe, and a nozzle having a nozzle hole is fitted at the tip of the spin element. It is fixed. The spray container (I) pulls the trigger, discharges the air in the cylinder to the outside, and when the trigger is returned, the liquid detergent composition is sucked up through a vertical pipe immersed in the liquid detergent composition of the container body. By filling the cylinder with liquid and pulling the trigger again, the liquid in the cylinder is pushed out and led to the vertical pipe, and the liquid flow is spun through the horizontal pipe and the spin element, and finally from the nozzle. It is of the type that erupts. As the trigger type spray container, for example, a trigger spray container of “Bath Magiclin Foaming Spray” (Kao Co., Ltd.) washed and dried can be used.

  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. 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 water outage phenomenon (for example, the surface is once covered with a water film and then slowly drained from the upper end, 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 cleaning composition for hard surfaces shown in Tables 1 and 2 was prepared, and the cleaning power, storage stability, running out of water, and sprayability after storage were evaluated. The results are shown in Tables 1 and 2. In addition, the mass% of (b) component was based on the quantity converted into the acid form, and pH of the composition was adjusted with sodium hydroxide and hydrochloric acid.

<Detergency evaluation>
Soak 5 ml of hard surface cleaning composition into a urethane sponge cut into a cubic shape with a side of 3 cm, and rub the bath chair used for 3 months 10 times without washing in the actual bathroom. The rinse rate was visually evaluated after rinsing with water. Specifically, about 30 vertical lines (width 5 mm) are made with vinyl tape on the outer side surface of a circular polypropylene bath chair (the spacing between the lines is 3 cm at regular intervals), and one sponge is soaked with cleaning liquid. The portion between the lines was rubbed 10 times in the vertical direction (in the direction parallel to the lines), and the degree of soiling of the rubbed portion was evaluated. This operation was performed 10 times for the part between different lines of the same bath chair, and the average value was taken as the cleaning rate. The bath chairs used for the evaluation of each composition had almost the same degree of dirt adhesion.
100%: The rubbed part was completely cleaned.
50%: Half of the dirt was removed from the rubbed area.
0%: Dirt on the rubbed part was not removed at all.

<Low temperature storage stability evaluation>
The hard surface cleaning composition is placed in a polypropylene container and stored in a sealed state for 11.5 hours at 20 ° C., then cooled to −20 ° C. in the next 0.5 hour, and remains at −20 ° C. 11 Store for 5 hours and raise to 20 ° C in the next 0.5 hour. This operation was performed once, and the state after being repeated a plurality of times was visually observed and evaluated according to the following criteria. The visual observation was performed at the completion of one cycle operation (every 24 hours).
3: Precipitation was not observed for 15 cycles or more, and the state before storage was maintained without liquid separation.
2: Precipitation occurred within 10 to 14 cycles.
Precipitation occurred within 1: 9 cycle.

<Evaluation of running out of water>
A vinyl chloride plate (80 mm × 150 mm × 2 mm) is dipped in the hard surface cleaning composition for 10 seconds and washed with running water (tap water). Immediately after washing with water, the plate was placed in a vertical state, and the number of water droplets on the plate surface after 10 seconds was counted. This operation was performed 10 times, and the average score was shown in the table.
5: No water droplets remained.
4: One water droplet remained.
3: Two water droplets remained.
2: Three water droplets remained.
1: 4 or more water droplets remained.

<Evaluation of sprayability after storage>
One cycle of the hard surface cleaning composition is stored at 20 ° C. for 11 hours, cooled to −20 ° C. over 1 hour, stored at −20 ° C. for 11 hours, and heated to 20 ° C. over 1 hour. 10 cycles are performed. After cleaning the hard surface cleaning composition after the end of 10 cycles at room temperature (around 20 ° C.), a pre-washed sprayer (commercial bath magic phosphorus foaming spray (Kao Co., Ltd.)) produced in FY2009 was washed. It was used after being dried.) And sprayed 30 times to evaluate the spread of the liquid during spraying.
3: The liquid spread sufficiently and normal spraying was possible.
2: Although spraying was possible, the spread of the liquid at the time of spraying became a little narrow.
1: The liquid did not spread and the liquid did not come out normally from the sprayer nozzle.

(Note) The components in the table are as follows.
Cation-modified PVA (1): partially saponified 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 (2): partially saponified product of a copolymer of vinyl acetate and diallyldimethylammonium chloride (the total of structural unit (a1), structural unit (a2) and structural unit (a3) in all 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.)
Unmodified PVA: Polyvinyl alcohol (degree of saponification 88 mol%, molecular weight is about 80,000)
-Sodium alkylbenzene sulfonate: alkyl group having 10 to 16 carbon atoms
・ Alkylamine oxide: Alkyl (carbon number 12) dimethylamine oxide ・ Alkyl ether sulfate sodium salt :: Polyoxyethylene (ethylene oxide average addition mole number 2.0) Alkyl (carbon number 12 to 16) ether sulfate sodium salt ・ Fatty acid Amidopropyl betaine: Amidopropyl laurate-N, N-dimethyl-betaine acetate / alkylglycoside: alkyl (carbon number 12) polyglucose (average degree of sugar condensation 1-2)

Claims (4)

(A) a structural unit (a1) represented by the following general formula (1), a structural unit (a2) represented by the following general formula (2), a compound represented by the following general formula (3-1), and 0.001 to 0.3% by mass of a polymer compound containing a structural unit (a3) derived from a compound selected from compounds represented by the following general formula (3-2) , (b) a chelating agent 0.01 to 2% by mass (however, the mass in the case of salt is converted to the mass of the acid form), and (c) contains water, and the mass ratio of (a) and (b) is (a) / (b) = 0 .1 to 1 hard surface cleaning composition.

[Wherein, R Ru der alkyl group having 1 to 3 carbon atoms. ]

[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. ] Furthermore the component (d) as a glycol ether and / or alcohol containing 0.1 to 50 wt% claim 1 hard surface detergent composition. Furthermore, the detergent composition for hard surfaces of Claim 1 or 2 which contains 0.01-20 mass% of anionic surfactant, nonionic surfactant, and / or amphoteric surfactant as (e) component. A spray-type hard surface cleaning article, comprising a spray-type container filled with the hard-surface cleaning composition according to any one of claims 1 to 3 .