JP4509746B2 - Liquid bleach composition - Google Patents

Description

  The present invention relates to compositions useful as liquid bleaches and liquid bleach detergents.

  In a liquid bleaching composition containing a bleaching agent useful in terms of bleaching effects on stains and the like, the pH during storage of the composition is made weakly acidic from the viewpoint of achieving both bleaching stability and bleaching effect. A technique (pH jump technique) for increasing pH by diluting in water at the time of use is known. In order to obtain a satisfactory bleaching effect and washing effect when diluted in water, for example, it is necessary to raise the pH to 9 or higher, and as a means for achieving this, it is necessary to adjust the pH of the composition to 5 or higher in advance. is there. In this case, however, there is a problem with the stability of the bleach. 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.
Japanese Patent Laid-Open No. 6-100908 JP-A-7-70593 Japanese Patent Laid-Open No. 11-181492

  The problem of the present invention is that it is useful as a liquid bleaching agent and a liquid bleaching detergent that dramatically improves the stability of the bleach activator in a weakly acidic region of pH 4-7 and exhibits excellent bleaching performance even after storage. It is to provide a composition.

  The present invention provides (a) hydrogen peroxide, (b) a bleach activator, and (c) a liquid bleach composition containing catechins, and (d) a liquid bleach composition containing a surfactant. provide.

  The present invention also provides a liquid bleaching agent comprising (a) hydrogen peroxide, (b) a bleach activator, and (c) a catechin-containing composition, and (a) hydrogen peroxide, (b) bleaching. Provided is a liquid bleach cleaner comprising a composition comprising an activator, (c) catechins, and (d) a surfactant.

  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, Useful as a liquid bleach and liquid bleach cleaner.

[Component (b)]
Examples of the bleach activator of the component (b) of the present invention include at least one selected from alkanoyloxybenzenesulfonic acid having 8 to 14 carbon atoms in the alkanoyl group, carboxylic acid or a salt thereof, and good storage From the viewpoint of obtaining stability, an alkanoyloxybenzenesulfonic acid or carboxylic acid having a branched alkanoyloxy group having 8 to 14 carbon atoms, or a salt thereof is preferred, and the α-position or β-position of the carbon atom forming the ester bond of the alkanoyloxy group More preferred is an alkanoyloxybenzenesulfonic acid or carboxylic acid having a side chain at the position or a salt thereof.

  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 (2-1) to (2-4), and compounds represented by the formulas (2-1) to (2-2) preferable.

[Component (c)]
The catechins as the component (c) of the present invention are generic names of polyoxy derivatives of 3-oxyflavan, and since the asymmetric carbon atoms are in the 2nd and 3rd positions, the four isomers d-, l-, There are d-epi-, l-epi- and their racemates. Catechins isolated from nature include catechin (3,5,7,3 ′, 4′-pentaoxyflavan) in the narrow sense, gallocatechin and their 3-galloyl derivatives and afzelechin.

  The catechins used in the present invention are preferably at least one selected from the compounds represented by the general formula (1).

[In formula, R < ¹ > -R < ⁴ > shows a hydrogen atom or a C1-C5 alkyl group each independently, and at least 1 is a hydrogen atom. R ⁵ represents a residue obtained by removing OH from a hydrogen atom or a carboxyl group of gallic acid, and R ⁶ represents a hydrogen atom or a hydroxyl group. ]
Among the compounds represented by the general formula (1), a compound represented by the formula (1-1) in which all of R ^{1 to} R ⁶ are hydrogen atoms, R ^{1 to} R ⁴ are hydrogen atoms, and R ⁵ is A compound represented by the formula (1-2) in which R ⁶ is a residue obtained by removing OH from the carboxyl group of gallic acid is preferred.

[Liquid bleach composition]
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. . The content of the component (c) is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, from the viewpoint of improving the stability of the component (b). More preferred is mass%.

  When used as a liquid bleaching detergent, the composition of the present invention preferably contains a surfactant [hereinafter referred to as component (d)] 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 (3) is preferable.

R ^3a -O (EO) _p (PO) _q -H (3)
[Wherein, R ^3a represents an alkyl or alkenyl group having 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms. EO is an oxyethylene group, PO is an oxypropylene group, p is a number from 0 to 20 indicating the average number of added moles of EO, q is a number from 0 to 20 indicating the average number of added moles of PO, Except when both are zero. Preferably, p is a number of 6 to 15, more preferably 7 to 12, and q is a number of 0 to 10, more preferably 1 to 5, particularly preferably 1 to 3. ]
In the general formula (3), EO and PO may be arranged in either a random addition form or a block addition form.

  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.

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

[Wherein, R ^4a is a linear alkyl group or alkenyl group having 8 to 16 carbon atoms, preferably 10 to 16 carbon atoms, 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 r 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 s 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 an oxypropylene group is suitable, and in general formula (3), p is 8 to 12, and q is 0 to 3 polyoxyalkylene alkyl ether type nonionic Surfactants are most preferred.

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

  The composition of the present invention preferably contains a sequestering agent [hereinafter referred to as component (e)] from the viewpoint of further improving the bleaching effect. As the component (e) used in the present invention, a compound having a phosphonic acid group or a phosphonic acid group is preferable. Specific compounds having a phosphonic acid group or a 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-hydroxy-1,1-diphosphonic acid or an alkali thereof. Most preferred are metal salts.

  The content of the component (e) in the composition of the present invention is preferably 0.05% by mass or more and less than 0.3% by mass from the viewpoint of obtaining a more preferable pH jump effect and the stability of hydrogen peroxide. 0.1 to 0.25% by mass is more preferable, and 0.15 to 0.2% by mass is particularly preferable.

  The composition of the present invention preferably contains a boron compound in order to impart a pH jump effect, that is, to keep the pH of the composition low during storage and to increase the pH value when diluted in use. . 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 boron compound content in the composition of the present invention 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. Is 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 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 alcohol selected from sorbitol, mannitol, maltose, inositol, phytic acid (3) Selected from glucose, apiose, arabinose, galactose, lyxose, mannose, galose, aldose, idose, talose, xylose, fructose Reducing sugars (4) Polysaccharides selected from starch, dextran, xanthan gum, guar gum, curdlan, pullulan, amylose, cellulose In the present invention, the above-mentioned (2) Sugar alcohols are preferred, and sorbit is particularly preferred from the standpoints of stability and bleach / washing effect.

  The content of the polyol compound in the composition of the present invention is preferably 3 to 35% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 20% by mass.

  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 Is 2.0 to 2.7, particularly preferably 2.2 to 2.7.

Examples 1-5 and Comparative Examples 1-4
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 (2-1); bleach activator c-1 represented by the above formula (2-3); Compound c-2 represented by formula (1-1); Compound c′-1 represented by formula (1-2); 4-methoxyphenol d-1; Sodium laurylbenzenesulfonate d-2; Poly Oxyethylene 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; 1-hydroxyethylidene-1,1-diphosphonic acid <Method for evaluating the storage stability of a bleach activator>
80 g of the liquid bleach composition was placed in a 100 mL glass sample bottle and stored at 20 ° C. for 1 month. 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 (7)

A liquid bleach composition containing (a) hydrogen peroxide, (b) a bleach activator, and (c) catechins and having a pH of 4 to 7 at 20 ° C. The liquid bleach composition according to claim 1, wherein the catechin as component (c) is at least one selected from the compounds represented by formula (1).

[In formula, R < ¹ > -R < ⁴ > shows a hydrogen atom or a C1-C5 alkyl group each independently, and at least 1 is a hydrogen atom. R ⁵ represents a residue obtained by removing OH from a hydrogen atom or a carboxyl group of gallic acid, and R ⁶ represents a hydrogen atom or a hydroxyl group. ]   The bleach activator of component (b) is at least one selected from alkanoyloxybenzenesulfonic acid having a branched alkanoyloxy group having 8 to 14 carbon atoms, carboxylic acid or a salt thereof. Liquid bleach composition.   The bleach activator of component (b) is an alkanoyloxybenzenesulfonic acid or carboxylic acid having a side chain at the α-position or β-position of the carbon atom forming the ester bond of the alkanoyloxy group, or a salt thereof. The liquid bleach composition in any one of -3. Furthermore, the liquid bleach composition in any one of Claims 1-4 containing (d) surfactant. (A) hydrogen peroxide, (b) bleach activators, and (c) Ri Do from compositions containing catechins, liquid bleach has a pH of 4-7 at 20 ° C.. (A) hydrogen peroxide, (b) bleach activator, (c) catechin, and (d) Ri Do from a composition containing a surfactant, a liquid bleach wash pH at 20 ° C. is 4-7 Agent.