JP4732115B2 - Acid detergent composition for hard surfaces - Google Patents

Description

  The present invention is an acid for hard surfaces that has an appropriate adhesion to vertical surfaces such as toilet toilet bowls and bathroom walls, and is excellent in cleaning and rinsing, and that does not damage tile joints. The present invention relates to a cleaning composition.

  Hard surfaces such as bathrooms and toilets form strong inorganic-organic composite stains that are a mixture of organic and inorganic substances such as calcareous stains, and acidic cleaners that use strong acids such as hydrochloric acid are used to remove this. ing.

  However, since such strong acids have a substrate damage problem such as damage to tile joints, Patent Documents 1 to 5 disclose techniques using organic acids. These publications also describe the use of amine oxide surfactants.

On the other hand, adhering and retaining a cleaning agent on an inclined surface such as a wall is important for cleaning and removing strong composite dirt, and Patent Documents 1, 2, and 5 disclose a technique for imparting viscosity to a composition. ing.
JP 2005-97511 A JP 2003-183697 A JP-T-2001-522397 Japanese National Patent Publication No. 11-514696 Japanese National Patent Publication No. 10-501275

  However, as in Patent Documents 1, 2, and 5, the technique of attaching to the inclined surface by imparting viscosity has the problem that the retention is improved, but there is a problem that the rinsing becomes worse, and both the retention and the rinsing properties are achieved. It is difficult to do. Patent Document 5 attempts to achieve both adhesion retention and rinsing properties by using a surfactant having a branched chain, but has not yet achieved satisfactory rinsing properties.

  Accordingly, an object of the present invention is to provide an acidic detergent composition for hard surfaces that has an appropriate adhesion to an inclined surface of a toilet, a bathroom wall, etc., has excellent cleaning properties and rinsing properties, and does not damage tile joints. The purpose is to provide goods.

  The present invention includes (a) a polyvalent carboxylic acid having a molecular weight of 100 to 500 [hereinafter referred to as component (a)] 2 to 10% by mass, (b) (b1) N-lauryl-N, N-dimethylamine oxide [hereinafter referred to as And (b1) component] and (b2) N-myristyl-N, N-dimethylamine oxide (hereinafter referred to as component (b2)) one or more amine oxides (hereinafter referred to as component (b)) 0 to 10.0% by mass, (c) an alkali metal sulfate or halogenate (hereinafter referred to as component (c)) 2 to 20% by mass, and water, and an acidic detergent composition for hard surfaces .

  According to the present invention, an acidic detergent composition for a hard surface that has an appropriate adhesion to an inclined surface of a toilet or a bathroom wall, is excellent in cleanability and rinsing properties, and does not damage tile joints. Is provided.

  The component (a) used in the present invention is a polycarboxylic acid having a molecular weight of 100 to 500 (polycarboxylic acid) having 2 or more carboxylic acid groups in the molecule, and (i) ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycinediacetic acid. And aminocarboxylic acids selected from alanine diacetic acid, aspartic acid diacetic acid and glutamic acid diacetic acid, and (ii) polyvalent carboxylic acids selected from malic acid, citric acid, tartaric acid, malonic acid, maleic acid and succinic acid. . In the present invention, the polyvalent carboxylic acid selected from (ii) is preferable from the viewpoints of composite soil removal effect, substrate damage properties such as tile joints, adhesion retention, and rinsing properties, and among these, citric acid is most preferable. is there. The composition of this invention contains (a) component 2-10 mass%, Preferably 3-8 mass%. In such a range, satisfactory cleaning performance and low-temperature storage stability can be obtained.

  The composition of the present invention is one or more selected from (b) component N-lauryl-N, N-dimethylamine oxide as component (b1) and N-myristyl-N, N-dimethylamine oxide as component (b2). Of amine oxide. The (b1) component and the (b2) component are preferably used in combination, and the mass ratio between them is (b1) / (b2) = 5/1 to 1/10, more preferably 5/1 to 1/2, especially 4 / 1-1 / 1 is preferred. Within such a range, desirable adhesion and rinsing properties can be obtained.

  Moreover, the composition of this invention contains 1-10 mass% of (b) component. The content is preferably 2 to 7% by mass, particularly preferably 3 to 5% by mass, from the viewpoint of detergency and rinsing properties.

  In the present invention, an alkali metal sulfate or halogenate is contained as the component (c). Sodium and potassium are preferable as the alkali metal. Specific examples of the alkali metal sulfate include sodium sulfate, sodium hydrogen sulfate, potassium sulfate, potassium hydrogen sulfate, and sodium potassium sulfate double salt. Examples of alkali metal halides include sodium chloride and potassium chloride. Of these, sodium sulfate is particularly preferred.

  The composition of the present invention needs to contain 2 to 20% by mass, preferably 3 to 15% by mass of the component (c), and in such a range, suitable adhesion retention and rinsing properties are realized. It becomes possible.

  In the present invention, as the component (d), the monomer structural unit having a cationic group in the molecule [hereinafter referred to as (d1)] is 10 to 100 mol%, preferably 20 to 80 mol%, based on the total monomer structural unit. In particular, it is preferable to contain a polymer compound having 40 to 70 mol% for the purpose of obtaining a high cleaning effect.

  (D1) is preferably selected from the monomer structural units represented by the following general formula (1) and general formula (2).

[Wherein, R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a hydrogen atom, a methyl group, or a hydroxy group. X is —COOR ¹⁴ —, —CON (R ¹⁵ ) R ¹⁶ —, wherein R ¹⁴ and R ¹⁶ are alkylene groups having 2 to 5 carbon atoms, and R ¹⁵ is a hydrogen atom or a methyl group. Y ^- is an anionic group. R ²¹ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and n is a number of 0 or 1. ]

In the general formula (1), R ¹¹ is preferably a hydrogen atom, and R ¹² is preferably a hydrogen atom or a methyl group. X is preferably —CON (R ¹⁵ ) R ¹⁶ —, and R ¹⁵ is preferably a hydrogen atom. R ¹³ is preferably a methyl group, Y ^- is a halogen ion, sulfate ion, alkyl sulfate ion having 1 to 3 carbon atoms, phosphate ions, fatty acid ion having 1 to 12 carbon atoms, an alkyl group having 1 to 3 carbon atoms 1 A benzenesulfonic acid ion which may be substituted by 3 is preferable, and a chloro ion is particularly preferable.

In general formula (2), R ²¹ is preferably a methyl group, and Y ⁻ is substituted by 1 to 3 halogen ions, sulfate ions, phosphate ions, fatty acid ions having 1 to 12 carbon atoms, and alkyl groups having 1 to 3 carbon atoms. Benzenesulfonic acid ions which may be present are preferred, and chloro ions are particularly preferred. n is preferably 0.

  The component (d) of the present invention can be produced by subjecting a monomer corresponding to the monomer structural unit constituting the component (d) to a normal polymerization reaction. Alternatively, the component (d) may be finally obtained by post-processing the polymer compound. For example, in the case of a polymer compound having a quaternary ammonium group as a cationic group, it has an amino group in addition to a method of obtaining a monomer having a quaternary ammonium group in the initial monomer by a polymerization reaction. The component (d) may be obtained by subjecting a product subjected to a polymerization reaction using a monomer to quaternization treatment. Of course, the same applies to anionic groups. Naturally, the monomer used for obtaining the polymer compound that requires post-treatment is selected to have a structure that takes post-treatment into consideration.

  In the present invention, a monomer constituent unit obtained by polymerizing N, N-diallyl-N, N-dialkyl (C1-3) quaternary ammonium salt as component (d) [this is (d1). Or a quaternizing agent such as methyl chloride, dimethylsulfuric acid, diethylsulfuric acid, ethylene oxide, propylene oxide or the like is used for the monomer structural unit obtained by polymerizing N, N-diallyl-N-alkyl (1 to 3 carbon atoms) amine. And an alkylated monomer structural unit [this is (d1)].

  In addition to (d1), the component (d) of the present invention may contain a monomer structural unit obtained by polymerizing a monomer copolymerizable with the above monomer. In particular, an anionic group-containing monomer selected from acrylic acid or its salt, methacrylic acid or its salt, crotonic acid or its salt, α-hydroxyacrylic acid or its salt, maleic acid or its salt, maleic anhydride, styrene sulfonate And the structural unit derived from sulfur dioxide (hereinafter referred to as (d3)) is preferred, and the moles of (d1) / [(d2) + (d3)] are preferred. A ratio of 5/1 to 1/3, 4/1 to 1/2, and particularly 3/1 to 1/1 are preferable from the viewpoint of cleaning effect. This molar ratio can be calculated as the molar ratio of the monomer derived from (d1), (d2), and (d3).

  The component (d) of the present invention may be obtained by any polymerization method, but a radical polymerization method is particularly preferred, and this can be carried out in a lump, solution or emulsion system.

  The weight average molecular weight of the component (d) of the present invention is 1,000 to 100,000, preferably 2,000 to 80,000, particularly preferably 5,000 to 60,000, and this weight average molecular weight is developed using a mixed solvent (phosphate buffer) of acetonitrile and water. This was obtained by using polyethylene glycol as a standard substance by gel permeation chromatography as a solvent.

  The composition of the present invention preferably contains 0.01 to 5 mass%, more preferably 0.02 to 3 mass%, particularly 0.05 to 1 mass% of the component (d).

  In the present invention, a surfactant other than the component (b) [hereinafter referred to as the component (e)] can be contained, but the effect of the present invention may be hindered. The proportion of the component (b) in all the surfactants is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and particularly preferably 70 to 100% by mass for the purpose of obtaining the effects of the present invention.

  Examples of component (e) include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

  Examples of the anionic surfactant include alkylbenzene sulfonate having an alkyl group having 10 to 15 carbon atoms, an alkyl sulfate ester salt having 10 to 16 carbon atoms, an alkyl group having 10 to 16 carbon atoms and an oxyalkylene group (preferably oxy Ethylene group) having an average addition mole number of 1 to 6, more preferably 1 to 5, especially 1 to 4, polyoxyalkylene alkyl ether sulfate, C10 to C16 alkyl group and oxyalkylene group (preferably oxyethylene group) ) Polyoxyalkylene alkyl ether methyl carboxylate having an average addition mole number of 1 to 12, a fatty acid salt having 8 to 18 carbon atoms, an alkane sulfonate salt having 8 to 16 carbon atoms, and an olefin sulfonic acid having 8 to 16 carbon atoms. A salt can be mentioned as a specific example. In addition, since the alkyl sulfate ester salt and the polyoxyalkylene alkyl ether sulfate ester salt are easily decomposed when the acidity of the composition is strong, the blending thereof is limited. In particular, when pH is 4.0 or less, it is desirable not to mix substantially.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ethers having an average addition mole number of 1 to 12 carbon atoms of an alkyl group having 10 to 16 carbon atoms and an oxyethylene group.

  As the cationic surfactant, one or two of the groups substituted on the nitrogen atom is an alkyl group having 8 to 16 carbon atoms, and the remaining is an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl having 1 to 3 carbon atoms. And quaternary ammonium which is a benzyl group.

  As the amphoteric surfactant, N, N, N-trialkyl-N-sulfopropyl ammonium betaine having one alkyl group having 8 to 16 carbon atoms and two alkyl groups having 1 to 3 carbon atoms, carbon number 8 to N, N, N-trialkyl-N- (2-hydroxysulfopropyl) ammonium betaine having one alkyl group having 16 and two alkyl groups having 1 to 3 carbon atoms, 1 alkyl group having 8 to 16 carbon atoms And N, N, N-trialkyl-N-carboxymethyl ammonium betaine having two alkyl groups having 1 to 3 carbon atoms.

  In the acidic detergent composition for hard surfaces of the present invention, in addition to the above components, additives blended in ordinary detergents within the range not impairing the effects of the present invention, such as perfumes, antibacterial agents, and pigments , Dyes and the like can be added.

  The acidic detergent composition of the present invention is in the form of a liquid composition in which the above components (a) to (c) and optional components are dissolved or dispersed in water, and the water content in the composition is preferably It is 50-95 mass%, Most preferably, it is 70-90 mass%.

  The composition of the present invention is acidic, and the pH at 25 ° C. is preferably 1-4, more preferably 1.5-3.5, and particularly preferably 2-3, and an excellent detergency can be obtained in such a range. And there is no problem of substrate damage. Adjustment to such a pH can be achieved by adjusting the content of the component (a), but it is possible to use inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, etc. It is also possible to finely adjust the pH.

  The following tests were conducted on the liquid detergent composition containing the components shown in Table 1. The results are shown in Table 1.

<Adhesion evaluation>
As shown in FIG. 1 (a), a square earthenware panel 1 (10 cm × 10 cm) with strings 3, 3 ′ attached to one side is held in a horizontal state, and is kept constant at 25 ° C. at a position 3 cm from one side. About 1 g of the cleaning composition 2 is applied in parallel with one side of the panel 1 so as to draw a straight line so as to have a uniform amount. Next, as shown in FIG. 1B, the panel 1 is installed so as to be perpendicular to the ground. At this time, the panel 1 is installed so that a sufficient distance is produced for the composition 2 to drip from its lower end. After standing for 30 seconds in a vertical state, the weight of the cleaning composition remaining on the panel was measured, and the adhesion rate was calculated by the following formula. The test was performed three times for each sample, and evaluation was performed according to the following evaluation criteria based on the average adhesion rate.
Adhesion rate (%) = {residual weight (g) / coating composition weight (g)} × 100
* Adhesion evaluation criteria ○: Average adhesion rate is 30% or more Δ: Average adhesion rate is 15% or more to less than 30% ×: Average adhesion rate is less than 15%

<Rinseability evaluation>
Similar to the above-described adhesion evaluation, except that the panel 1 coated with the liquid cleaning composition 2 with the standing time in the state of FIG. 1B being 25 seconds is inclined by 45 ° as shown in FIG. Then, running water is applied for 5 seconds at a rate of 4 L / min at 25 ° C. between the portion where the composition 2 is applied and the upper side. At this time, the panel is moved in the direction of the left and right arrows in FIG. 2 at a speed of about 10 cm / second (side). The removal state of the surface composition was visually observed. The test was performed three times for each sample, and the evaluation was performed according to the following criteria based on the evaluation.
* Rinse evaluation criteria ○: No detergent remaining △: There is a little detergent remaining ×: There is detergent remaining

<Composite dirt cleaning test>
Detergency against inorganic / organic composite dirt in flush toilets that could not be removed by rubbing with a brush was evaluated as follows. In particular, stubborn inorganic dirt and organic compound dirt are attached to the inside of the toilet rim. Therefore, in this evaluation method, about 6-7 g of the dirt on the front edge of the urinal toward the toilet of a Western-style toilet is washed over about 30 cm. The agent composition was applied evenly, and after 3 minutes, the state of removal of the soil when lightly rubbed with a brush was visually observed and evaluated according to the following evaluation criteria.
* Composite dirt cleaning power evaluation criteria
○: Good △: Slightly good ×: Bad

<Soap residue cleaning test>
The detergency was evaluated as follows for a bath bath made of polypropylene that was used under the same conditions for six months and was not washed. After the cloth containing the cleaning composition was adhered to the soil for 1 minute, the state of removal of the soil after rubbing with a sponge was visually observed and evaluated according to the following evaluation criteria.
* Soap residue cleaning power evaluation criteria ○: Good △: Slightly good ×: Bad

<Joint damage test>
Each cleaning composition was sprinkled on the tile joint, and the tile joint after 5 minutes was visually observed and evaluated according to the following evaluation criteria.
* Evaluation criteria for joint damage test ○: No damage ×: Damaged

(Note) The components in the table are as follows.
(B1): N-lauryl-N, N-dimethylamine oxide (b2): N-myristyl-N, N-dimethylamine oxide (d-1): diallyldimethylammonium chloride, maleic acid and sulfur dioxide ( (Molar ratio 2/1/1) copolymer, weight average molecular weight 30,000 · (d-2): copolymer of diallyldimethylammonium chloride and maleic acid (molar ratio 2/1), weight average molecular weight 60,000 · (E-1): linear alkyl (carbon number 12) benzenesulfonic acid sodium salt (e-2): polyoxyethylene (average number of moles of ethylene oxide added 10) lauryl ether (e-3): cocoalkyltrimethyl Ammonium chloride

Schematic which shows the evaluation method of the adhesiveness in an Example

Schematic which shows the evaluation method of the rinse property in an Example

Explanation of symbols

1: Ceramic panel 2: Liquid detergent composition 3, 3 ': String

Claims (5)

(A) 2 to 10% by mass of a polycarboxylic acid having a molecular weight of 100 to 500, (b) (b1) N-lauryl-N, N-dimethylamine oxide and (b2) N-myristyl-N, N-dimethylamine oxide one or more amine oxide 1.0 to 10.0 wt% selected from, (c) 2 to 20 wt% sulfuric acid salt or halide salt of an alkali metal, and contains water, 1 a pH at 25 ° C. 4, an acidic detergent composition for hard surfaces. The acidic detergent composition for hard surfaces according to claim 1, wherein (a) is citric acid. The acidic detergent composition for hard surfaces according to claim 1 or 2, wherein the ratio of (b1) and (b2) in the total surfactant is 30 to 100% by mass. The acidic cleaner composition for hard surfaces according to any one of claims 1 to 3, wherein (c) is sodium sulfate. (D) The hard surface according to any one of claims 1 to 4, comprising a polymer compound having 10 to 100 mol% of a monomer constituent unit having a cationic group in the molecule based on all monomer constituent units. Acid detergent composition for use.

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