JP4818657B2 - Liquid bleach composition - Google Patents

Description

  The present invention relates to a liquid bleach composition and a liquid bleach detergent composition.

  Liquid bleaching compositions containing bleaching components such as hydrogen peroxide and bleach activators have acidic pH during storage of the bleaching composition from the viewpoint of achieving both the stability of the bleaching composition and the bleaching effect ( For example, the pH needs to be 2 to 3). On the other hand, in the field of bleaching agents and bleaching detergents, there is known a technology for raising the pH by diluting with water at the time of use (pH jump technology). In order to obtain it, it is necessary to raise the pH of the composition after dilution with water to 9 or more, for example. As an achievement means, it is necessary to adjust the pH of the composition before dilution with water (at the time of storage) to 4 or more in advance. However, when the pH during storage is adjusted to 4 or more in this way, there is a problem in the stability of the bleaching component in the composition. Although the stability of hydrogen peroxide is enhanced by a general radical scavenger, it is difficult to stabilize the bleach activator, and there is a need for an improvement method.

  Patent Document 1 discloses a soil removal composition containing an amide or imide organic peroxyacid / surfactant / pH adjustment system (borate / polyol) having low solubility in water. This Patent Document 1 discloses a stabilization technique in water by a solid dispersion system using a water-insoluble organic peracid, not a system containing hydrogen peroxide, but merely using this technique. The stability of the bleach activator (peracid precursor) is not improved.

  Patent Document 2 discloses a soil removal composition containing a solid, water-insoluble organic peroxyacid / surfactant / pH jump system (borate / polyol) / agar or saccharide. However, the stabilization of the bleach activator in hydrogen peroxide cannot be realized only by using this technique.

  Patent Document 3 discloses a liquid bleach composition in which hydrogen peroxide is stabilized in a high pH range (pH 4 to 7) with a phenol derivative. However, this technique improves the stability of hydrogen peroxide but does not achieve stabilization of the bleach activator.

Patent Document 4 discloses a liquid bleaching agent composition in which a bleaching activator is stabilized in an acidic region (pH 2) with a metal such as Ba, Ti, or Fe. However, even when this technique is used for a liquid bleach composition having a high pH (pH 4 to 7), it is insufficient to obtain the stabilizing effect of the bleach activator.
Japanese Patent Laid-Open No. 6-100908 JP-A-7-70593 Japanese Patent Laid-Open No. 11-181492 Japanese Patent Laid-Open No. 7-305094

  An object of the present invention is to provide a liquid bleaching composition and a liquid bleaching detergent composition in which the stability of the bleaching activator in a weakly acidic region of pH 4 to 7 is dramatically improved.

  As a result of diligent research, the present inventors have dramatically improved the stability of the bleach activator in a weakly acidic region of pH 4 to 7, with a composition containing a salt or oxide of a specific element in a specific ratio. Found to get.

That is, this invention contains the following (a) component, (b) component, and (c) component, The molar ratio of (b) component and (c) component is (b) / (c) = 5-30. And a liquid bleaching composition having a pH of 4 to 7 at 20 ° C., and the following components (a), (b), (c) and (d): c) A liquid bleaching detergent composition in which the molar ratio of the components is (b) / (c) = 5 to 30 and the pH at 20 ° C. is 4 to 7 is provided.
(A) Hydrogen peroxide or a compound that generates hydrogen peroxide in water (b) At least one bleach activator selected from alkanoyloxybenzenesulfonic acid, alkanoyloxybenzenecarboxylic acid and salts thereof (c) Element cycle At least one (d) surfactant selected from the salts and oxides of the elements of Groups 4 to 11 and 5th to 6th periods of the table

  The composition of the present invention can realize stabilization of a bleach activator at pH 4 to 7, has excellent bleach cleaning performance even after storage, and is useful as a liquid bleach and a liquid bleach cleaner.

[(A) component]
The composition of the present invention contains hydrogen peroxide or a compound that generates hydrogen peroxide in water as the component (a). Examples of the compound that generates hydrogen peroxide in water include percarbonate and perborate.

[Component (b)]
The composition of the present invention contains at least one bleach activator selected from alkanoyloxybenzenesulfonic acid, alkanoyloxybenzenecarboxylic acid and salts thereof as component (b). In the component (b) of the present invention, from the viewpoint of obtaining good storage stability, the alkanoyloxy group is preferably a linear or branched alkanoyloxy group having 8 to 14 carbon atoms, and further the alkanoyloxy group is More preferably, it is a branched alkanoyloxy group having 8 to 14 carbon atoms and has a side chain at the α-position or β-position of the carbon atom forming the ester bond of the alkanoyloxy group.

  Examples of the alkanoyloxy group having a side chain at the α-position or β-position of the carbon atom forming the ester bond include 2-ethylhexanoyl group, 2-propylheptanoyl group, 3,5,5-trimethylhexanoyl group, and the like. Benzenesulfonic acid or carboxylic acid having a branched alkanoyloxy group or a salt thereof is particularly preferable. As the salt, sodium salt, potassium salt, and magnesium salt are preferable, and sodium salt is particularly preferable from the viewpoint of solubility.

  Specific examples of the component (b) include compounds represented by the following formulas (1-1) to (1-4), and compounds represented by the formulas (1-1) to (1-2) preferable.

[Component (c)]
The composition of the present invention contains, as component (c), at least one selected from salts and oxides of elements in Groups 4 to 11 of the Periodic Table of Elements and Periods 5 to 6.

  Among the elements of Groups 4 to 11 and 5 to 6 of the periodic table, elements of Groups 5 to 11 and 5 to 6 of the Periodic Table are preferable. Further, elements of Groups 6 to 11 and 5th to 6th periods of the periodic table are more preferable. Specific examples of these elements include Mo, Nb, Ta, Zr, Rh, Ir, Ag, Au, Pd, Pt, Ru, Re, W, and the like. Mo, Nb, Ta, Zr, Rh, Ir, Ag, Au, Pd, and Pt are preferable.

  Specific examples of the component (c) include gold chloride, platinum chloride, palladium chloride, iridium chloride, molybdenum bromide, tantalum chloride, ruthenium chloride, silver chloride and other halide salts, rhenium sulfate, zirconium sulfate, niobium sulfate and the like. Examples include nitrates such as sulfates and silver nitrates, sodium salts such as sodium molybdate and sodium tungstate, and oxides such as palladium oxide, rhodium oxide, rhenium oxide, molybdenum oxide, ruthenium oxide, niobium oxide, tantalum oxide, and silver oxide. It is done. Among these, iridium chloride, silver nitrate, and molybdenum oxide are preferable from the viewpoint of stabilization of the bleach activator.

[Component (d)]
When used as a liquid bleaching detergent, the composition of the present invention preferably contains a surfactant from the viewpoint of obtaining excellent detergency. As the surfactant, at least one selected from an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant can be used.

  Examples of the anionic surfactant (hereinafter referred to as (d1) component) include alkylbenzene sulfonates having 10 to 18 carbon atoms or alkenyl groups, polyoxyalkylene alkyl ether sulfates, alkyl sulfates, α- Examples thereof include olefin sulfonates, α-sulfo fatty acid salts, and α-sulfo fatty acid lower alkyl ester salts.

Any alkylbenzene sulfonate can be used as long as it has an alkyl group having an average carbon number of 8 to 16 among those commonly distributed in the detergent surfactant market. For example, Kao Corporation Neoperex F25 made by Shell, Dobs102 made by Shell, etc. can be used. Industrially, alkylbenzene widely distributed as a detergent raw material can be obtained by sulfonation using an oxidizing agent such as chlorosulfonic acid or sulfurous acid gas. As for the average carbon number of an alkyl group, 10-14 are preferable. In addition, as polyoxyalkylene alkyl ether sulfate, an average of 0.5 to 5 moles of ethylene oxide per molecule is added to a linear or branched primary alcohol or linear secondary alcohol having an average carbon number of 10 to 18, This can be obtained by sulfation using, for example, the method described in JP-A-9-137188. The average carbon number of the alkyl group is preferably 10-16. The alkyl sulfate salt is obtained by sulfonating a linear or branched primary alcohol or linear secondary alcohol having 10 to 16 carbon atoms, preferably 10 to 14 with SO ₃ or chlorosulfonic acid, and neutralizing. it can. As the α-olefin sulfonate, a 1-alkene having 8 to 18 carbon atoms can be sulfonated with SO ₃ , and can be formed through hydration and neutralization. A mixture of compounds in which an unsaturated bond is present. In addition, as the α-sulfo fatty acid lower alkyl ester salt, the fatty acid residue preferably has 10 to 16 carbon atoms, and methyl ester or ethyl ester is preferable from the viewpoint of cleaning effect. As the salt, sodium salt, potassium salt, magnesium salt, calcium salt, alkanolamine salt, and ammonium salt are preferable, and sodium salt, potassium salt, and magnesium salt are preferable from the viewpoint of cleaning effect.

  In the present invention, a polyoxyethylene alkylsulfuric acid ester salt having 10 to 14 carbon atoms, an ethylene oxide average addition mole number of 1 to 3 and an alkylbenzene sulfonic acid salt having 11 to 15 carbon atoms are particularly preferable from the viewpoint of cleaning effect.

  As the nonionic surfactant (hereinafter referred to as component (d2)), a compound represented by the following general formula (2) is preferable.

R ^2a —O (EO) _m (PO) _n —H (2)
[Wherein R ^2a represents a hydrocarbon group having 8 to 18 carbon atoms, preferably 10 to 18 carbon atoms, more preferably 12 to 14 carbon atoms, preferably an alkyl group or an alkenyl group. EO is an oxyethylene group, PO is an oxypropylene group, m is a number from 0 to 20 indicating the average number of added moles of EO, n is a number from 0 to 20 indicating the average number of added moles of PO, Except when both are zero. Preferably, m is a number of 6 to 15, more preferably 7 to 12, and n is a number of 0 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. ]
In the general formula (2), EO and PO may be arranged in either a random addition form or a block addition form, but from the viewpoint of storage stability of the bleach activator, the following general formula The compound represented by (3) is particularly preferred.

^{_{R 3a -O- (C 2 H 4}} O) p - (C 3 H 6 O) q - (C 2 H 4 O) r H (3)
[In formula, R < ^3a > is a C8-C18 hydrocarbon group, p, q, and r are the numbers of 1-10 each independently. ]
In the general formula (3), R ^3a is a hydrocarbon group having 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms, more preferably an alkyl group or an alkenyl group, and still more preferably an alkyl group. p, q, and r are each independently a number of 1 to 10, and a number of 2 to 8 is preferable.

  As a cationic surfactant (hereinafter referred to as component (d3)), one or two hydrocarbon groups having 10 to 18 carbon atoms which may be separated by an ester group or an amide group, and the remainder are 1 to 3 carbon atoms. A quaternary ammonium salt which is an alkyl group or a hydroxyalkyl group, preferably an alkyl sulfate salt having 1 to 3 carbon atoms, is suitable.

  As the amphoteric surfactant (hereinafter referred to as component (d4)), at least one selected from the compounds represented by the following general formula (4) or general formula (5) is preferable from the viewpoint of cleaning effect.

[Wherein, R ^4a is a linear alkyl group or alkenyl group having 8 to 16, preferably 10 to 16, particularly preferably 10 to 14 carbon atoms, and R ^4c and R ^4d each independently represents 1 to 1 carbon atoms. 3 is an alkyl group or a hydroxyalkyl group, preferably a methyl group, an ethyl group or a hydroxyethyl group. R ^4b is an alkylene group having 1 to 5 carbon atoms, preferably 2 or 3 carbon atoms. A is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and s is a number of 0 or 1. ]

[Wherein R ^5a is an alkyl group or alkenyl group having 9 to 23 carbon atoms, preferably 9 to 17 carbon atoms, particularly preferably 9 to 15 carbon atoms, and R ^5b is an alkylene group having 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms. It is a group. B is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and t is a number of 0 or 1. R ^5c and R ^5d are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ^5e is an alkylene having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms optionally substituted with a hydroxy group. It is a group. D is a group selected from —COO ⁻ , —SO ₃ ⁻ , and —OSO ₃ ^— . ]
In the present invention, as the component (d), a surfactant selected from (d1) and (d2) is preferable, and the component (d2) is most preferable from the viewpoint of cleaning effect, and particularly oxyethylene. A polyoxyalkylene alkyl ether type nonionic surfactant having a group and / or an oxypropylene group is suitable, and in the general formula (2), m is 8 to 12, and n is 0 to 3. Nonionic surfactants are most preferred.

[Liquid bleach composition and liquid bleach detergent composition]
The liquid bleach composition of this invention contains (a) component, (b) component, and (c) component as an essential component. From the viewpoint of obtaining a bleaching effect, the content of the component (a) in the composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.5 to 10% by mass, and 1 to 6% by mass. Further preferred. The content of the component (b) is preferably 0.1 to 10% by mass, more preferably 0.1 to 6% by mass, and still more preferably 0.1 to 3% by mass, from the viewpoint of developing an excellent bleaching effect. . From the viewpoint of improving the stability of the component (b), the component (c) has a molar ratio of the component (b) to the component (c) of (b) / (c) = 5 to 30, Is preferable, and 15 to 30 is more preferable.

  In the present invention, by controlling the ratio of the component (b) and the component (c), the component (b) and the component (c) form a complex in the surfactant micelle to suppress the reaction with hydrogen peroxide. In addition, the stability of the component (b) can be remarkably improved.

  The composition of the present invention preferably contains the component (d) from the viewpoint of imparting excellent detergency, and the content of the component (d) in the composition is preferably 10 to 40% by mass, and 15 to 15%. 40 mass% is more preferable, and 20-35 mass% is still more preferable.

  The composition of the present invention can achieve stabilization of the bleach activator at pH 4-7, preferably 4.6-7, more preferably 5-7, and has excellent bleach washing performance even after storage, It is useful as a liquid bleach composition and a liquid bleach detergent composition. The pH is measured after cooling (20 ° C.) using a pH meter F52 manufactured by Horiba, Ltd. and a pH electrode 6367-S004.

  As the pH adjuster, inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid can be used as acid agents, and sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like can be used as alkaline agents.

  The composition of the present invention preferably contains a sequestering agent as the component (e) from the viewpoint of further improving the bleaching effect. The sequestering agent used in the present invention is preferably a compound having a phosphonic acid group or a phosphonic acid group. Specific compounds having a phosphonic acid group or phosphonic acid group include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, and ethane. Phosphonic acid selected from hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, or an alkali metal salt or alkanolamine salt thereof, 2-phosphonobutane And phosphonocarboxylic acids selected from -1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid, and alkali metal salts or alkanolamine salts thereof. Phosphonic acid or an alkali metal salt thereof, preferably ethane-1-hydride Carboxy-1,1-diphosphonic acid or alkali metal salts thereof are most preferred.

  The content of the component (e) in the composition is preferably 0.05% by mass or more and less than 0.3% by mass, more preferably 0.1 to 0.25% by mass, and 0.15 to 0.2% by mass. Particularly preferred.

  In order to impart a pH jump effect to the composition of the present invention, that is, to maintain the pH of the composition at the time of storage low and to increase the pH value when diluted at the scene of use, a boron compound is used as component (f). It is preferable to contain. Examples of the boron compound include boric acid, sodium borate, potassium borate, ammonium borate, sodium tetraborate, potassium potassium borate, and ammonium ammonium borate. Among the boron compounds, it is preferable that the di-form is a main component in order to make the pH of the diluted solution 9 or more and less than 10.5, and 70 to 100 mol% of the boron compound is contained in the composition of the present invention. The di-form is preferable. The content of the mono form is preferably less than 5 mol% of the boron compound, and it is preferable that the contents of boric acid, borax and borate present alone are less than 25 mol% of the boron compound. .

  The content of the component (f) in the composition is preferably 0.05 to 1% by mass, more preferably 0.15 to 0.5% by mass, and 0.2 to 0.4% by mass as a boron atom. Particularly preferred.

  In order to maintain the pH control effect under high dilution conditions, the composition of the present invention preferably contains a polyol compound such as a saccharide as the component (g). As the polyol compound, the following compounds (1) to (4) are suitable.

(1) Glycerin, diglycerin, triglycerin, alkyl glyceryl ether having 1 to 10 carbon atoms of alkyl group, alkyl diglyceryl ether, alkyl triglyceryl ether; glycerol or glycol selected from ethylene glycol and 1,2-propylene glycol (2) Sugar alcohols selected from sorbitol, mannitol, maltose, inositol, phytic acid (3) Reduction selected from glucose, apiose, arabinose, galactose, lyxose, mannose, galose, aldose, idose, talose, xylose, fructose Sugars (4) A polysaccharide selected from starch, dextran, xanthan gum, guar gum, curdlan, pullulan, amylose and cellulose.

  In the present invention, the sugar alcohols of the above (2) are particularly preferable, and sorbitol is particularly preferable from the viewpoint of stability and bleaching / washing effect.

  Moreover, since there is a risk of impairing the stability of hydrogen peroxide when the polyol compound is present in excess, from the viewpoint of satisfying both the excellent pH jump effect and the stability of hydrogen peroxide, the ratio of the polyol compound and the boron compound is , Polyol compound / boron compound molar ratio (however, in the case of borax and sodium tetraborate, since it contains 4 boron atoms, it is considered to be 4 equivalents), preferably 1.5 to 2.7, more preferably It is 2.0 to 2.7, particularly preferably 2.2 to 2.7.

  The content of the component (g) in the composition is preferably 3 to 35% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 20% by mass.

Examples 1-7 and Comparative Examples 1-6
A liquid bleach composition having the composition shown in Table 1 was prepared using the following components. About this liquid bleach composition, the storage stability of the bleach activator was evaluated by the following method. The results are shown in Table 1.

<Blending ingredients>
a-1; hydrogen peroxide b-1; bleach activator b-2 represented by the above formula (1-1); bleach activator c-1 represented by the above formula (1-3); AgNO _Three
c-2; IrCl ₃
c-3; MoO ₂
c′-1; FeSO ₄
c′-2; magnesium sulfate d-1; sodium laurylbenzenesulfonate d-2; polyoxyethylene lauryl ether (oxyethylene average addition mole number 8, HLB13.1)
_{d-3; C 12 H 25} O- (C 2 H 4 O) 7 - (C 3 H 6 O) 2 - (C 2 H 4 O) 4 -H
e-1; sequestering agent; ethane-1-hydroxy-1,1-diphosphonic acid (Daiquest 2010 (Daiquest manufactured by Solusia))
<Method for evaluating storage stability of bleach activator>
80 g of the liquid bleach composition was placed in a 100 mL glass sample bottle and stored at 20 ° C. for 2 months. The content of the bleach activator in the liquid bleach composition before and after storage was measured by high performance liquid chromatography, and the residual ratio of the bleach activator was determined by the following formula.

Claims (6)

The following (a) component, (b) component, and (c) component are contained, The molar ratio of (b) component and (c) component is (b) / (c) = 5-30, and 20 degreeC The liquid bleach composition whose pH in is 4-7.
(A) Hydrogen peroxide or a compound that generates hydrogen peroxide in water (b) at least one bleach activator selected from alkanoyloxybenzenesulfonic acid, alkanoyloxybenzenecarboxylic acid and salts thereof (c) Mo, At least one selected from halogenated salts, nitrates and oxides of elements selected from Ir and Ag   The content of the component (a) in the composition is 0.1 to 30% by mass, the content of the component (b) is 0.1 to 10% by mass, and the content of the component (c) is 0.01 to 1%. The liquid bleach composition of Claim 1 which is 0 mass%. (B) The liquid bleach composition of Claim 1 or 2 whose alkanoyloxy group which a component has is a C8-C14 linear or branched alkanoyloxy group. (B) The alkanoyloxy group of the component is a branched alkanoyloxy group having 8 to 14 carbon atoms and has a side chain at the α-position or β-position of the carbon atom forming the ester bond of the alkanoyloxy group The liquid bleach composition according to any one of claims 1 to 3 . Furthermore, the liquid bleach composition in any one of Claims 1-4 containing (d) surfactant. The following (a) component, (b) component, (c) component, and (d) component are contained, and the molar ratio of (b) component and (c) component is (b) / (c) = 5-30. A liquid bleach detergent composition having a pH of 4 to 7 at 20 ° C.
(A) Hydrogen peroxide or a compound that generates hydrogen peroxide in water (b) at least one bleach activator selected from alkanoyloxybenzenesulfonic acid, alkanoyloxybenzenecarboxylic acid and salts thereof (c) Mo, At least one (d) surfactant selected from halides and nitrates of elements selected from Ir and Ag, and oxides