JP4699066B2 - Liquid bleach detergent composition - Google Patents

Description

  The present invention relates to a liquid bleach detergent composition, and more particularly to an alkali metal hypochlorite salt bleach detergent composition.

Conventionally, as a liquid bleach detergent composition for removing mold stains on toilets, bathtubs, etc., (a) a composition containing an alkali metal salt of alkyldiphenyl oxide sulfonate, caustic alkali and sodium hypochlorite (for example, Patent Document- 1), (b) a composition containing an alkali metal salt of alkanesulfonic acid, caustic alkali and alkali hypochlorite (for example, Patent Document 2), (c) an alkylsulfuric acid ester alkali metal salt or polyoxyethylene alkyl ether sulfuric acid A composition containing an ester sodium salt, a caustic alkali and sodium hypochlorite (for example, Patent Document 3), (d) an alkanesulfonic acid alkali metal salt, an alkyldiphenyl oxide sulfonic acid alkali metal salt, an amine oxide, an alkaline substance, and Alkaline gold hypochlorite A composition containing a salt (for example, Patent Document-4), (e) a composition containing an amine oxide, a saturated dibasic acid and an alkali metal hypochlorite (for example, Patent Document-5), (f) an alkanesulfone Compositions containing acid alkali metal salts, alkyl sulfates, amine oxides, caustic alkalis and alkali metal hypochlorites (for example, Patent Document 6) are known.
Japanese Examined Patent Publication No. 38-6268 Japanese Patent Publication No.43-24786 Japanese Patent Publication No.46-13267 JP-A-8-53695 JP 2001-302425 A JP 2000-38596 A

  However, these liquid bleach detergents have insufficient stability of alkali metal hypochlorite, and in particular, the effective chlorine content tends to decrease during storage at a relatively high temperature (eg, 50 ° C.). In addition, there was a problem that the cleaning performance against mold stains containing inorganic substances was insufficient.

  In view of such circumstances, the present inventors have intensively studied to find a liquid bleach detergent that does not impair the stability of alkali metal hypochlorite and that is excellent in cleaning performance against mold stains containing inorganic substances. As a result, the present invention has been reached. That is, the present invention provides at least one anionic surfactant (A) selected from the compound represented by the general formula (1) and the compound represented by the general formula (1 ′), and the alkanesulfone represented by the general formula (2). Acid salt (B), amine oxide (C) represented by general formula (3), alkaline compound (D), alkali metal hypochlorite (E), alkali metal carboxylate (F) and water ( G) an aqueous liquid bleach detergent composition comprising 0.1 to 7% by mass of the total of (A) and (B) based on the mass of the liquid bleach detergent composition, (C) 0.1 to 7 mass%, (D) 0.1 to 10 mass%, (E) 0.5 to 10 mass%, (F) 0.01 to 0.5 mass%, A) / (B) is 1/100 to 1 / 2.5, pH (25 ° C.) is 5 to 13.5, and weak acid value is 0. A liquid bleaching detergent composition which is a 01~0.5mgKOH / g.

In the formula, R ¹ and R ² are alkyl groups having 6 to 16 carbon atoms, M ¹ and M ² are alkali metals, m, n, x and y are each 0 or an integer of 1 to 5, m and n At least one of them is not 0, and at least one of x and y is not 0.

In the formula, R ³ is a branched or straight chain alkyl group having 6 to 20 carbon atoms, M ³ is an alkali metal, and p is 0 or an integer of 1 to 20.

In the formula, R ⁴ and R ⁵ are alkyl groups, the total number of carbon atoms of the two alkyl groups is 8 to 16, and M ⁴ is an alkali metal.

In the formula, R ⁶ is an alkyl group or alkenyl group having 6 to 20 carbon atoms, and R ⁷ and R ⁸ are alkyl groups having 1 to 3 carbon atoms.

  The liquid bleach detergent composition of the present invention is less likely to have an effective chlorine content during storage, particularly at a high temperature of 50 ° C., and has excellent cleaning performance against mold stains containing inorganic substances.

The anionic surfactant (A) in the present invention is at least one selected from the compound represented by the general formula (1) and the compound represented by the general formula (1 ′).
Specific examples of the alkyl group having 6 to 16 carbon atoms of R ¹ and R ² in the general formula (1) include a branched or linear hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, and A hexadecyl group may be mentioned. Of these, preferred are alkyl groups having 8 to 14 carbon atoms, and particularly preferred are branched or straight-chain octyl, nonyl and dodecyl groups. m and n are usually 0 or an integer of 1 to 5, preferably 0 and 1. At least one of m and n is not 0, and preferably the average value of m + n is 0.8 to 1.3. x and y are usually 0 or an integer of 1 to 5, preferably 0 and 1. At least one of x and y is not 0, and preferably the average value of x + y is 1-2.

Specific examples of the branched or straight chain alkyl group having 6 to 20 carbon atoms of R ³ in the general formula (1 ′) include hexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, Examples include a tetradecyl group, a hexadecyl group, an octadecyl group, and an eicosyl group. Among these, a branched or straight chain alkyl group having 10 to 16 carbon atoms is preferable. p is preferably 0 or 1 to 3, more preferably 0 from the viewpoint of detergency against inorganic-containing mold stains.

The alkanesulfonic acid (B) in the present invention is represented by the general formula (2). In the general formula (2), the average value of the total number of carbon atoms of the alkyl groups R ⁴ and R ⁵ is usually 8 to 16, and contains an inorganic substance. From the viewpoint of detergency against mold stains, it is preferably 12-14.

M ^{1 to} M ⁴ in the general formulas (1), (1 ′), and (2) are alkali metals, and examples of the alkali metal include Na, K, and Li. Of the alkali metals, Na is preferred from the viewpoint of detergency against inorganic-containing mold stains.

In the general formula (3) representing amine oxide (C), the alkyl group or alkenyl group having 6 to 20 carbon atoms of R ⁶ may be a branched or straight chain hexyl group, octyl group, decyl group, dodecyl group, dodecenyl group. Group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group and the like. Among these, a branched or straight chain alkyl group having 8 to 16 carbon atoms is preferable, but a mixture of alkyl groups having different carbon numbers derived from natural products (such as coconut oil) may be used. Examples of the alkyl group having 1 to 3 carbon atoms of R ⁷ and R ⁸ include a methyl group, an ethyl group, and a propyl group, and a methyl group is preferable. Specific examples of the compound represented by the general formula (3) include lauryl dimethylamine oxide, myristyl dimethylamine oxide and coconut dimethylamine oxide.

Examples of the alkaline substance (D) include alkali metals (Na, K, Li, etc.), hydroxides (NaOH, KOH, LiOH, etc.), carbonates (Na ₂ CO ₃ , K ₂ CO ₃ , KHCO ₃ , LiCO ₃ etc.), phosphates (Na ₂ HPO ₄ , K ₂ HPO ₄ , sodium tripolyphosphate, sodium hexametaphosphate etc.), silicates (Na ₂ SiO ₃ etc.) and mixtures of two or more of these. . Among these, preferred are alkali metal hydroxides, and particularly preferred are sodium hydroxide and potassium hydroxide from the viewpoint of detergency against inorganic-containing mold stains.

  Examples of the alkali metal hypochlorite (E) include sodium hypochlorite and potassium hypochlorite, and sodium hypochlorite is usually used.

Examples of the alkali metal carboxylate (F) include the following (F1) to (F3). (F1) Alkali metal salt of monocarboxylic acid having 1 to 18 carbon atoms (including carbon of carbonyl group, the same shall apply hereinafter); for example, sodium acetate, sodium propionate, sodium octoate, sodium laurate and sodium oleate Can be mentioned.
(F2) Mono-trialkali metal salts of di- or tricarboxylic acids having 2 to 18 carbon atoms; for example, mono-trisodium salts such as malonic acid, succinic acid, glutaric acid, fumaric acid, maleic acid, adipic acid and sebacic acid Etc.
(F3) Alkali metal salt of hydroxycarboxylic acid having 2 to 18 carbon atoms;
(F31) Alkali metal salt of monohydroxymonocarboxylic acid having 2 to 18 carbon atoms: for example, sodium hydroxyacetate, sodium β-hydroxypropionate, sodium hydroacrylate, sodium salicylate, sodium benzoate and the like.
(F32) C1-C18 monohydroxydi or mono-trialkali metal salt of tricarboxylic acid: for example, sodium citrate, sodium malate, sodium tartronate and the like.
(F33) Alkali metal salt of dihydroxymonocarboxylic acid having 3 to 18 carbon atoms: for example, sodium glycerate, sodium dihydroxymethylpropionate, sodium 2,2 bis (hydroxymethyl) butyrate and the like.
(F34) Monohydroxy-trialkali metal salt of dihydroxydi or tricarboxylic acid having 4 to 18 carbon atoms: for example, sodium tartrate, sodium dihydroxysuccinate, sodium dihydroxyfumarate, sodium dihydroxymaleate and the like.
(F35) Mono-polyalkali metal salt of mono-polycarboxylic acid having 3 to 6 or more hydroxyl groups having 6 to 18 carbon atoms: for example, sodium gluconate, sodium glucarate, sodium galactate, etc. It is done.
Of these, (F3) is preferred from the viewpoint of the stability of the effective chlorine content at 50 ° C. and the cleaning performance against mold stains containing inorganic substances, (F32) is more preferred, and particularly preferred is (F32). Sodium malate and sodium citrate. A carboxylic acid alkali metal salt having a hydroxyl group and a carboxyl group in one molecule, particularly a carboxylic acid alkali metal salt having one hydroxyl group and two or three carboxyl groups is a compound (D) exhibiting alkalinity. Even if a relatively large amount is contained, the effect of improving the stability of the effective chlorine content at 50 ° C. is particularly excellent.

The content of each component (A) to (F) in the composition of the present invention is as follows based on the mass of the composition.
The total of (A) and (B) is usually 0.1 to 7%, preferably 0.3 to 5%, more preferably 1 to 4%, particularly preferably from the viewpoint of detergency against inorganic-containing mold stains. 2 to 3.5% (Unless otherwise limited,% represents mass%). If it is less than 0.1%, the foaming power is insufficient, and addition exceeding 7% is not actually required. Further, (A) / (B) is 1/100 to 1 / 2.5, preferably from 1/20 to 1 / 2.5, more preferably from 1/10 to 1 / 2.5, from the viewpoint of detergency against inorganic-containing mold stains. 1/3, particularly preferably 1/6 to 1/3.
The amine oxide (C) is usually 0.1 to 7%, preferably from 0.1 to 5%, more preferably from 1 to 4%, particularly preferably from 1.5 to 3 from the viewpoint of detergency against inorganic-containing mold stains. %.
The substance (D) exhibiting alkalinity is usually 0.1 to 10%, preferably 0.5 to 5%, more preferably 1 to 4%, particularly preferably 1.5 from the viewpoint of detergency against inorganic-containing mold stains. ~ 3%.
The alkali metal hypochlorite (E) is usually 0.5 to 10%, preferably 2 to 7%, more preferably 3 to 6%, and particularly preferably 3.5 to 5%. If (E) is less than 0.5%, the bleaching power is insufficient, and addition exceeding 10% is not actually required.
Carboxylic acid alkali metal salt (F) is usually 0.01 to 0.5%, preferably 0.03 to 0.4%, more preferably 0.05 to 0.1%. If (F) is less than 0.01%, the cleaning performance against mold stains containing inorganic substances is insufficient, and addition exceeding 0.5% is not actually required.

  In addition to the above components, the composition of the present invention may contain other surfactants, chelating agents, fragrances, coloring agents, solubilizing agents and the like in amounts that do not interfere with the effects of the present invention.

Other surfactants include the following.
(1) Nonionic surfactants, for example, polyethylene glycol type nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene ether, and polyoxyethylene alkyl ester, Polyhydric alcohol type nonionic surfactants such as glycerol fatty acid ester, pentaerythritol fatty acid ester, and sorbitan fatty acid ester, fatty acid alkanolamide type nonionic surfactant, etc .;
(2) Anionic surfactants such as dialkyl sulfosuccinates, sulfonic acid type anionic surfactants such as polyoxyethylene alkylphenyl ether sulfonates, higher alcohol phosphate salts, polyoxyethylene higher alcohol phosphate salts, etc. Phosphate ester type anionic surfactants of
(3) amphoteric surfactants such as amino acid type amphoteric surfactants, betaine type amphoteric surfactants;
(4) Cationic surfactants such as quaternary ammonium salt type surfactants, amine salt type surfactants; and combinations thereof.

  Examples of chelating agents include aminocarboxylic acids having 6 to 12 carbon atoms (ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, triethylenetetraminehexaacetic acid, etc .; natural flavors (rose oil, Jasmine oil, lavender oil, lemon oil, musk oil, etc.), synthetic fragrances (limonene, farnesol, citral, rose oxide, etc.), etc .;

  The amount of the above-mentioned other surfactants used is usually 10% or less, preferably 1 to 3%, based on the total weight of (A) to (F) in the present invention. Each of the agent and the solubilizer is usually 5% or less, preferably 3% or less, and each of the fragrance and the colorant is usually 1% or less, preferably 0.5% or less.

The composition of the present invention can be obtained by mixing each component of (A) to (F) and, if necessary, other components with water (G) in a predetermined amount.
The concentration of components other than water in the composition of the present invention is usually 5 to 25%, preferably 10 to 20%. The composition of the present invention is usually an aqueous liquid.

The composition of the present invention has a pH (25 ° C.) of 5 to 13.5, preferably 8 to 13.4, more preferably 10 to 13.3, and particularly preferably 12.5 to 13.3. The pH of the composition of the present invention can be measured with a pH meter (for example, “pH-METER M-12” manufactured by Horiba, Ltd.) at the same concentration at 25 ° C.
Particularly, it is preferable that the pH is 10 to 13.5, especially 12.5 to 13.3 because the effect of stabilizing the effective chlorine content by the addition of the above-mentioned (F) is easily exhibited.
On the other hand, if it exceeds 13.5, the detergency against mold stains containing inorganic substances is poor.

The composition of the present invention has a weak acid value of 0.03 to 0.5 mg KOH / g, preferably 0.03 to 0.3, and more preferably 0.03 to 0.1.
If the weak acid value is less than 0.03, the detergency against mold stains containing inorganic substances is poor, and if it exceeds 0.5, the effective chlorine content tends to decrease during storage, especially at high temperatures. Is inferior.
The weak acid value can be measured by the following measuring method.
(1) About 20 g of liquid bleach detergent composition is sampled and weighed accurately, and dissolved in 100 ml of methanol / acetone = 1/1 solution.
(2) Adjust the pH to 3 or less with dilute hydrochloric acid, measure with a 0.1 mol / L potassium hydroxide methyl alcohol standard solution with a potentiometric automatic titrator, and calculate the weak acid value by the following formula.
Weak acid value = (A−B) × f × 5.661 / S
Here, A: ml number of 0.1 mol / L potassium hydroxide standard solution required for this test B: ml number of 0.1 mol / L potassium hydroxide standard solution required for blank test f: 0.1 Potency of mol / L potassium hydroxide standard solution S: Sampling amount (g)

The effective chlorine content of the composition of the present invention is usually 1 to 4%, preferably 1.5 to 3.5%, more preferably 2 to 3%.
The effective chlorine content can be measured by a method in which potassium iodine and acetic acid are reacted with a sample and titrated with sodium thiosulfate (JIS L0844-1986 effective chlorine measurement method).

The change rate of the effective chlorine content in the composition of the present invention at 50 ° C. for 1 week is preferably 30% or less, more preferably 28% or less, and particularly preferably 25% or less.
Here, one week may be one week immediately after producing the composition or one week after several months have passed at room temperature (for example, 15 to 25 ° C.).
Liquid bleach detergent compositions may be stored in direct sunlight, such as bathrooms, kitchens, and toilets, especially in the summer, and may be around 50 ° C, and the rate of change in effective chlorine content If it is 30% or less, the bleach detergency after storage is further improved.
The rate of change in effective chlorine content can be determined by measuring the effective chlorine content before and after the composition is stored at 50 ° C. for one week, and calculating the rate of change (%) of the effective chlorine content at 50 ° C. using the following formula. it can.
Effective chlorine content change rate (%) = [(C ₀ −C ₁ ) / C ₀ ] × 100
Here, C ₀ : Effective chlorine content (%) at the start of stationary storage
C ₁ : Effective chlorine content (%) after standing at -50 ° C. for 1 week

The composition of the present invention is applied directly to dirt adhered to floors, walls, drain pipes, etc. in bathrooms, kitchens, toilets and toilets, or is used by a method such as spraying in the form of foam by spraying. be able to.
The composition of the present invention has an excellent detergency against mold stains containing inorganic substances.
Examples of inorganic substances include carbonates such as sodium carbonate, silicates such as potassium silicate, and oxides such as calcium oxide. Such mold stains containing inorganic substances are likely to occur on floors, walls, drain pipes and the like of bathrooms, kitchens, toilets and toilets, for example.
Furthermore, the composition of this invention is excellent also in foamability.

[Example]
Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited thereto.

Examples 1-4, Comparative Examples 1-3
The raw materials listed in Table 1 were blended in the number of parts listed in Table 1 to prepare liquid bleach detergent compositions of the present invention and comparative examples.
The abbreviations in Table 1 are as follows.
DDPS: sodium dodecyl diphenyl oxide sulfonate
[The average of m + n in the general formula (1) is 1.08, and the average of x + y is 1.8]
AES: Polyoxyethylene alkyl (carbon number 12, 13) ether (EO = 2 mol) Sulfate ester Na salt AS: Alkanesulfonic acid Na salt [average carbon number of two alkyl groups in the general formula (2) is 12]
AMOX: Palm dimethylamine oxide hypochlorite: Sodium hypochlorite

  The results of measuring each pH and weak acid value are shown in Table 1.

<Evaluation results>
Immediately after preparing the composition, it is left to stand at 50 ° C. for 1 week, and the effective chlorine content (%) is measured according to JIS L0844-1986. The change rate (%) of the effective chlorine content at 50 ° C. is expressed by the following formula. Calculated.

Effective chlorine content change rate (%) = [(C ₀ −C ₁ ) / C ₀ ] × 100
Here, C ₀ : Effective chlorine content (%) at the start of stationary storage
C ₁ : Effective chlorine content (%) after standing at -50 ° C. for 1 week

Furthermore, the cleaning property of mold stains containing inorganic substances was evaluated by the following method.
A previously prepared inorganic aqueous solution (20 parts of sodium carbonate, 20 parts of potassium silicate and 70 parts of water) and black mold were mixed at a mass ratio of 1/1 to prepare a black mold test solution. 0.5 ml of this was applied to a silicone resin plate 40 mm long × 40 mm wide × 2 mm thick. Thereafter, the cells were cultured in a constant temperature and humidity chamber at 80% relative humidity and 30 ° C. for 2 weeks, then removed and air-dried at 25 ° C. for 24 hours. This test plate was immersed in a liquid bleach detergent composition for 5 minutes, washed with 200 ml of water at 25 ° C., air-dried, and visually judged.
Judgment criteria: ○: Mold stains are completely removed.
Δ: Slight mold stain remains.
X: About half of mold stains remain.

The evaluation results are shown in Table 1.

  The liquid bleach detergent composition of the present invention has excellent stability of alkali metal hypochlorite and excellent cleaning performance against mold stains containing inorganic substances, so that it can be used in bathrooms, kitchens, toilets, toilets, etc. It can be used as a liquid bleach detergent composition for mold stains adhering to floors, walls, drain pipes, etc.

Claims (5)

One or more anionic surfactants (A) selected from a compound represented by the general formula (1) and a compound represented by the general formula (1 ′), an alkane sulfonate (B) represented by the general formula (2) ), Amine oxide (C) represented by general formula (3), alkaline compound (D), alkali metal hypochlorite (E), alkali metal carboxylate (F) and water (G). An aqueous liquid bleach detergent composition based on the mass of the liquid bleach detergent composition, the total of (A) and (B) is 0.1 to 7% by mass, and (C) is 0.1 -7 mass%, (D) 0.1-10 mass%, (E) 0.5-10 mass%, (F) 0.01-0.5 mass%, (A) / ( B) is 1/100 to 1 / 2.5, pH (25 ° C.) is 5 to 13.5, and weak acid value is 0.03 to 0.5 mg. A liquid bleaching detergent composition characterized by being KOH / g.

Wherein R ¹ and R ² are alkyl groups having 6 to 16 carbon atoms, M ¹ and M ² are alkali metals, m, n
, X and y are each 0 or an integer of 1 to 5, and at least one of m and n is not 0, and at least one of x and y is not 0. )

(Wherein R ³ is a branched or straight chain alkyl group having 6 to 20 carbon atoms, M ³ is an alkali metal, and p is 0.
Or it is an integer of 1-20. )

(In the formula, R ⁴ and R ⁵ are alkyl groups, the total number of carbon atoms of the two alkyl groups is 8 to 16, and M4 is an alkali metal.)

(In the formula, R ⁶ is an alkyl group or alkenyl group having 6 to 20 carbon atoms, and R ⁷ and R ⁸ are alkyl groups having 1 to 3 carbon atoms.)

The liquid bleach detergent composition according to claim 1, wherein in the compound represented by the general formula (1 '), R ³ is an alkyl group having 10 to 16 carbon atoms, and p is 0.   The liquid bleach cleaning composition according to claim 1 or 2, wherein the carboxylic acid alkali metal salt (F) is a C2-C18 hydroxycarboxylic acid alkali metal salt.   The liquid bleach cleaning composition according to any one of claims 1 to 3, which has a pH of 10 to 13.5.   The liquid bleach cleaning composition according to any one of claims 1 to 4, wherein the change rate of the effective chlorine content at 50 ° C for one week is 30% by mass or less.