JP2012188525A - Method for producing liquid bleaching agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid bleaching agent composition which can obtain excellent bleaching effect and cleaning effect even to a plurality of stains such as a hydrophobic stain and a dye stain.SOLUTION: The method for producing a liquid bleaching agent composition includes a process of mixing: (a) hydrogen peroxide or a compound generating hydrogen peroxide in water; (b) specified alkylpolyglycoside; (c1) polyoxyalkylene alkyl ether in which the carbon number of an alkyl group is 8 to 18 and the average addition mole number of an oxyalkylene group is 7 to 12; (c2) polyoxyalkylene alkyl ether in which the carbon number of an alkyl group is 8 to 18 and the average addition mole number of an oxyalkylene group is 2 to 5; and (d) water. Regarding the ratios in all the components to be mixed, the ratio of the (a) is 0.1 to 30 mass% (as hydrogen peroxide), the ratio of the (b) is 0.5 to 10 mass% and the ratio of the total of the (c1) and the (c2) is 1 to 20 mass%, and also, mixing is performed in such a manner that the mass ratio among the (b), the (c1) and the (c2) satisfies (b)/[(c1)+(c2)]=(1/10) to (20/10), and the mass ratio between the (c1) and the (c2) satisfies (c1)/(c2)=(12/1) to (40/1).

Description

  The present invention relates to a method for producing a liquid bleach composition, a liquid bleach composition, and a method for washing clothes.

  Oxygen-based liquid bleaching agents based on hydrogen peroxide are preferred because they can be used for colors and patterns, and can be applied directly to dirt. Oxygen-based liquid bleach is generally used in a washing method with an alkaline detergent in a washing machine, or after being applied directly to a soil and then washed in a washing machine with an alkaline detergent. The effect is not satisfactory.

  For example, Patent Document 1 discloses a foaming composition for bleaching clothing formed from a liquid composition containing hydrogen peroxide, an alkylglycoside surfactant, a polyoxyalkylene alkyl ether, and water. An excellent bleaching effect can be obtained by use, and Patent Document 2 discloses a liquid washing containing an alkyl glycoside surfactant, a water-soluble solvent, a nonionic surfactant having an HLB of 11 to 14 and water. It is disclosed that the agent composition can greatly improve the foamability while maintaining the detergency.

  Furthermore, Patent Document 3 discloses that a liquid bleach composition for clothing containing a plurality of nonionic surfactants having different lengths of hydrogen peroxide and polyoxyethylene groups has a low HLB that exhibits high performance when applied. Patent Document 4 contains a plurality of nonionic surfactants in which hydrogen peroxide and HLB are close to each other, so that high stability, higher bleaching properties and detergency can be expressed in a system containing a nonionic surfactant. The liquid bleach composition has a small change in viscosity with respect to a change in temperature, and there is no decomposition of hydrogen peroxide during storage. Further, Patent Document 5 discloses hydrogen peroxide, a cationic surfactant. And certain surfactant systems, including hydrophilic nonionic surfactants, are disclosed to be superior in bleaching performance at high temperatures.

Japanese Patent Laid-Open No. 2004-76006 JP 2005-325185 A JP 2009-292903 A JP-A-9-188895 Japanese National Patent Publication No. 10-503162

  When the liquid bleach composition described in these patent documents is applied to clothing, there has been a demand for providing a product having a further excellent bleaching and cleaning performance although it has an excellent bleaching effect and a cleaning effect. In particular, there is a need to provide products that can exhibit effective bleaching and cleaning performance even for multiple soils with different properties, such as hydrophobic soils derived from the sebum around the straw and pigment soils derived from plants such as spinach. It was.

  In this regard, although Patent Document 3 or 4 discloses a liquid bleach composition containing a plurality of nonionic surfactants, the bleaching power against a plurality of stains such as hydrophobic stains and pigment stains is There is no description or suggestion about further improving the cleaning power.

  Accordingly, an object of the present invention is to provide a liquid bleaching agent composition that can provide an excellent bleaching effect and cleaning effect against a plurality of stains such as hydrophobic stains and pigment stains.

The present invention includes (a) hydrogen peroxide or a compound that generates hydrogen peroxide in water [hereinafter referred to as component (a)], (b) a compound represented by the following general formula (b1) [hereinafter referred to as (b) (Component)], (c1) polyoxyalkylene alkyl ether having 8 to 18 carbon atoms in the alkyl group and an average addition mole number of oxyalkylene groups of 7 to 12 (hereinafter referred to as (c1) component), (c2) alkyl group A polyoxyalkylene alkyl ether having 8 to 18 carbon atoms and an average addition mole number of oxyalkylene groups of 2 to 5 (hereinafter referred to as component (c2)), and (d) water (hereinafter referred to as component (d)). A process for producing a liquid bleach composition comprising the steps of:
The proportion of all components to be mixed is (a) 0.1 to 30% by mass (as hydrogen peroxide), (b) 0.5 to 10% by mass, and the total of (c1) and (c2) is 1 to 20 And (b), (c1), and (c2) at a mass ratio of (b) / [(c1) + (c2)] = 1/10 to 10/10 (c1) and (c2) c2) and (c1) / (c2) = 12/1 to 40/1 in a mass ratio,
The present invention relates to a method for producing a liquid bleach composition.
R ^1b − (OR ^2b ) _x G _y (b1)
[Wherein R ^1b is a hydrocarbon group having 8 to 16 carbon atoms, R ^2b is an alkylene group having 2 to 4 carbon atoms, G is a residue derived from a reducing sugar, x is a number having an average value of 0 to 6, y Indicates an average value of 1-10. ]

  Moreover, this invention relates to the liquid bleach composition obtained with the manufacturing method of the said invention.

  The present invention also relates to washing clothes, wherein the foam-like composition formed from the liquid bleach composition obtained by the production method of the present invention is brought into contact with clothes contaminated with a dye having a conjugated double bond. Regarding the method.

  According to the present invention, a production method capable of producing a liquid bleaching composition that provides excellent bleaching effect and cleaning effect, in particular, excellent bleaching effect and cleaning effect for a plurality of stains such as hydrophobic stains and pigment stains. And a method for cleaning clothes.

<Composition ingredients of liquid bleach composition>
[(A) component]
The component (a) is hydrogen peroxide or a compound that generates hydrogen peroxide in water. Examples of the compound that generates hydrogen peroxide in water include percarbonate such as sodium percarbonate, perborate such as sodium perborate, and the like. Hydrogen peroxide can be used as an aqueous solution (hydrogen peroxide solution).

[Component (b)]
In the manufacturing method of the liquid bleach composition of this invention, the compound represented by the following general formula (b1) is mix | blended as (b) component. The component (b) is stable with respect to the component (a), is excellent in that it exhibits sufficient foaming even when other surfactants are present in the composition and provides fine foam. Yes.

R ^1b − (OR ^2b ) _x G _y (b1)
[Wherein R ^1b is a hydrocarbon group having 8 to 16 carbon atoms, preferably 10 to 16 carbon atoms, particularly preferably 10 to 14 carbon atoms, preferably an alkyl group, more preferably a linear alkyl group, and R ^2b is a carbon number. 2 to 4 alkylene groups, preferably ethylene groups or propylene groups, more preferably ethylene groups, G is a residue derived from a reducing sugar, x is an average value of 0-6, preferably 0-3, especially Preferably, it is a number of 0, and y represents an average value of 1 to 10, preferably 1 to 5, particularly preferably 1 to 2. ]

  G is a residue derived from a reducing sugar, and the raw material reducing sugar may be either aldose or ketose, and examples include triose, tetrose, pentose, and hexose having 3 to 6 carbon atoms. Can do. Specific examples of aldose include apiose, arabinose, galactose, glucose, lyxose, mannose, aldose, idose, talose and xylose, and examples of ketose include fructose. In the present invention, among these, aldopentose or aldohexose having 5 or 6 carbon atoms is particularly preferred, and glucose is most preferred.

The method for synthesizing the compound of the general formula (b1) is not particularly limited. For example, the above-described reducing sugar and R ^1b — (OR ^2b ) _x —OH can be acetalized or reacted with an acid catalyst. It can be easily synthesized by a ketalization reaction. In the case of an acetalization reaction, a hemiacetal structure may be used, or a normal acetal structure may be used.

  In the method for producing the liquid bleach composition of the present invention, as the component (c1) and the component (c2), two polyoxyalkylene alkyl ethers having different average addition mole numbers of alkyleneoxy groups are blended in a specific quantitative ratio. There is a feature in the point.

[(C1) component]
In the method for producing the liquid bleach composition of the present invention, the polyoxyalkylene having (c1) component having 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms, and 7 to 12 average added mole number of alkyleneoxy groups as the alkyl group. Add alkyl ether. More specifically, 1 or more types chosen from the compound represented by the following general formula (c1-1) and the compound represented by the following general formula (c1-2) are suitable. The average number of moles of alkyleneoxy group added is 7 or more, preferably 8 or more, from the viewpoint of promoting emulsification of protein soil or sebum soil, and the stability of the foam, that is, the difficulty of foam breaking. From the viewpoint, the number is 12 or less, preferably 10 or less. That is, the number is 7 to 12, and preferably 8 to 10, from the viewpoint that both emulsification of protein stains and sebum stains and foam stability can be achieved.
^{_{R 1c -O- (C 2 H 4}} O) a -H (c1-1)
[Wherein, R ^1c represents a hydrocarbon group having 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms, preferably an alkyl group, more preferably a linear alkyl group. a is a number of 7 to 12, preferably a number of 8 to 10. ]
_{^{R 2c -O - [(C 2}} H 4 O) b / (C 3 H 6 O) c] -H (c1-1)
[Wherein R ^2c represents an alkyl group having 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms. b and c are each independently a number of 2 to 10, and b + c is a number of 7 to 12, preferably 8 to 10. “/” Is a symbol indicating that C ₂ H ₄ O and C ₃ H ₆ O may be random addition or block addition, and R ^2c —O— is replaced with (C ₂ H ₄ O) _b , (C ₃ Those in which blocks are added in the order of H ₆ O) _c are preferred. ]

  Since the component (c1) has low foaming properties, it is generally considered inappropriate to be incorporated into a composition to be applied in the form of foam, but it is advantageous for improving bleaching power and detergency. Is an essential ingredient. In the liquid bleach composition obtained by the production method of the present invention, by using the component (c1) together with the component (c2), and further with the components (a) and (b), excellent bleaching power while maintaining foaming And detergency can be obtained. Furthermore, when the bleaching activator of the component (f) described later is blended, the component (c1) is also an important component for stabilizing the component (f).

[(C2) component]
In the method for producing the liquid bleach composition of the present invention, the polyoxyalkylene having (c2) component having 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms, and an alkyleneoxy group having an average number of added moles of 2 to 5 as an alkyl group. Add alkyl ether. Here, the alkyl group may be a linear alkyl group or an alkyl group having a branched structure, but an alkyl group having a branched structure is preferable from the viewpoint of improving the permeability to dirt. More specifically, 1 or more types chosen from the compound represented by the following general formula (c2-1) and the compound represented by the following general formula (c2-2) are suitable. The average added mole number of the alkyleneoxy group is a number of 2 or more, preferably a number of 2.5 or more, more preferably a number of 3 or more, preferably a number of 5 or less, preferably from the viewpoint of permeability to fat stains. Is a number of 4 or less, more preferably a number of 3.5 or less. That is, the number is 2 to 5, preferably 2.5 to 4, more preferably 3 to 3.5.
R ^3c —O— (C ₂ H ₄ O) _d —H (c2-1)
[Wherein, R ^3c represents an alkyl group having 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms, preferably an alkyl group having a linear or branched structure, more preferably an alkyl group having a branched structure. d is a number of 2 to 5, preferably a number of 2.5 to 4, more preferably a number of 3 to 3.5. ]
_{^{R 4c -O - [(C 2}} H 4 O) e / (C 3 H 6 O) f] -H (c2-2)
[Wherein, R ^4c represents an alkyl group having 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms. e and f are each independently a number of 1 or more, and e + f is a number of 2 to 5, preferably a number of 2.5 to 4, more preferably a number of 3 to 3.5. In addition, “/” indicates that ethylene oxide and propylene oxide may be random addition or block addition, but block addition of ethylene oxide, propylene oxide or ethylene oxide, propylene oxide and ethylene oxide, and further ethylene oxide. , Propylene oxide and ethylene oxide in the order of block addition are preferred. ]

  The component (c2) is an advantageous component because it can improve the permeability of the liquid bleach composition to oil and sebum dirt. In the present invention, by using the component (c1) together with the component (c2) and further the component (b), excellent bleaching power and detergency against a plurality of stains such as hydrophobic stains and pigment stains are obtained.

[Component (d)]
In the manufacturing method of the liquid bleach composition of this invention, water is mix | blended as (d) component. The liquid bleach composition produced according to the present invention is in the form of an aqueous solution (including a dispersed state) in which the above components (a) to (c2) and the components described later are dissolved in water (d). It is what is used. As the water to be used, it is preferable to use ion-exchanged water or distilled water from which a metal dissolved in a trace amount is removed from the viewpoint of storage stability of hydrogen peroxide.

<Method for producing liquid bleach composition>
In the manufacturing method of the liquid bleach composition of this invention, the component containing (a) component, (b) component, (c1) component, (c2) component, and (d) component as a manufacturing raw material of a liquid bleach composition Is used. (C1) component and (c2) component exist separately as a manufacturing raw material, and after determining a compounding quantity, it mixes suitably with another component, and a composition is prepared.

  In the present invention, the ratio of the component (a) in all the components to be mixed (synonymous with all the raw materials for production; hereinafter referred to as blended components) is 0.1 to 30% by mass (as hydrogen peroxide), preferably 0. 0.5 to 10% by mass, more preferably 1 to 5% by mass, and particularly preferably 2 to 4% by mass.

  Moreover, in this invention, the ratio of the (b) component in a compounding component is 0.5-10 mass%, Preferably it is 1-8 mass%, Most preferably, it is 1.5-5 mass%. In such a range, an excellent bleaching effect can be obtained.

  Moreover, in this invention, the ratio of the sum total of (c1) component and (c2) component in a compounding component is 1-20 mass%, Preferably it is 4-15 mass%, More preferably, it is 7-10 mass%.

  Further, in the present invention, the component (b), the component (c1), and the component (c2) are converted to (b) component / [(c1) component + (c2) component] 1/10 to 20/10, preferably 2 / 10-10 / 10, More preferably, it mixes by the mass ratio of 3 / 10-7 / 10. By satisfying this range, the fine foam-like composition formed from the liquid bleach composition can be adhered to and penetrated into clothing, so that the bleaching effect is more remarkably improved.

  In the present invention, the component (c1) and the component (c2) are combined with (c1) / (c2) = 12/1 to 40/1, preferably 14/1 to 30/1, more preferably 15/1. It is mixed at a mass ratio of 25/1, more preferably 16/1 to 20/1.

  The proportion of the component (c1) in the blending component is the sum of the components (c1) and (c2) in the blending component described above, and (b) component / [(c1) component + (c2) component]. It is preferably 1 to 20% by mass, more preferably 2 to 16% by mass, and particularly preferably 4 to 12% by mass after satisfying the mass ratio and the (c1) / (c2) mass ratio.

  Further, the proportion of the component (c2) in the blending component is the sum of the components (c1) and (c2) in the blending component described above, and (b) component / [(c1) component + (c2) component]. After satisfying the mass ratio and (c1) / (c2) mass ratio, it is preferably 0.1 to 2% by mass, more preferably 0.2 to 1.5% by mass, and more preferably 0.3 to 1% by mass. %.

  In the present invention, the proportion of the component (d) in the blending component is preferably 70 to 98% by mass, more preferably 80 to 95% by mass.

In the present invention, the following components can be mixed together with the components (a) to (d).
[(E) component]
The liquid bleach composition produced according to the present invention preferably contains a solvent [hereinafter referred to as component (e)] for the purpose of enhancing the bleaching effect. Therefore, in the manufacturing method of the liquid bleach composition of this invention, it is preferable to use (e) component as a compounding component. As the component (e), (1) a monohydric alcohol having 1 to 5 carbon atoms, (2) a polyhydric alcohol having 2 to 12 carbon atoms, (3) a compound represented by the following general formula (e1), (4) ) 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, (5) a compound represented by the following general formula (e2) is preferred.

_{^{R 1e -O - [(C 2}} H 4 O) p / (C 3 H 6 O) q] -R 2e (e1)
[Wherein, R ^1e and R ^2e each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, except when both R ^1e and R ^2e are hydrogen atoms. p is an average addition mole number of C ₂ H ₄ O and represents a number of 0 to 10, q is an average addition mole number of C ₃ H ₆ O and represents a number of 0 to 10, and both p and q are Except when 0. “/” Is a symbol indicating that C ₂ H ₄ O and C ₃ H ₆ O may be added randomly or in blocks. ]
R ^3e OCH ₂ CH (OH) CH ₂ OH (e2)
[Wherein R ^3e represents an alkyl group having 1 to 8 carbon atoms. ]

  Examples of (1) monohydric alcohol having 1 to 5 carbon atoms generally include ethanol, propyl alcohol, and isopropyl alcohol. By blending these lower alcohols, the stability of the system at low temperatures can be further improved.

  (2) Polyhydric alcohol having 2 to 12 carbon atoms isoprene glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,8-octanediol, 1,9-nonanediol, ethylene glycol , Propylene glycol, diethylene glycol, dipropylene glycol, glycerin and the like.

In the compound of (3), R ^1e and R ^2e in the general formula (e1) are each a hydrocarbon group having 1 to 8, preferably 1 to 6 carbon atoms, such as an alkyl group, an alkenyl group, an aryl group (phenyl group, Benzyl group, etc.). In the general formula (e1), when R ^1e and R ^2e are each a hydrocarbon group, preferably an alkyl group, the number of carbon atoms is preferably 1 to 4 respectively. Further, in the general formula _{(e1), C 2 H 4} O and C ₃ H ₆ average addition number of moles of p and q of O, when both the number of each 0 (p and q are 0 However, the order of addition is not particularly limited, and may be randomly added. Specific examples of the compound (3) include ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, Examples include polyoxyethylene (p = 2 to 3), polyoxypropylene (q = 2 to 3) dimethyl ether, polyoxyethylene (p = 3) phenyl ether, phenyl carbitol, phenyl cellosolve, and benzyl carbitol. Of these, propylene glycol monomethyl ether, diethylene glycol monobutyl ether, and polyoxyethylene (p = 1 to 4) monophenyl ether are preferable from the viewpoint of bleaching / detergency and usability, and diethylene glycol monobutyl ether and polyoxyethylene (p = 1). -4) Monophenyl ether is more preferable, and polyoxyethylene (p = 1 to 4) monophenyl ether is particularly preferable.

In addition, examples of the compound (5) include alkyl glyceryl ether compounds, and R ^3e in the general formula (e2) is preferably a compound having an alkyl group having 3 to 8 carbon atoms.

  Among these, a water-soluble solvent selected from (1), (2), (3) and (5) is preferable from the viewpoint of bleaching power and detergency against a plurality of stains such as hydrophobic stains and pigment stains. Ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, isoprene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, pentyl glyceryl ether, octyl glyceryl ether, polyoxyethylene (p = 1 to 4) A solvent selected from monophenyl ether is preferable.

  Of these, diethylene glycol monobutyl ether and polyoxyethylene (p = 1 to 4) monophenyl ether are preferred from the viewpoint of improving foaming and reducing odor during use, and in particular, polyoxyethylene (p = 1 to 4) monophenyl. Ether is preferred.

  The proportion of the component (e) in the blending component is preferably 0 to 3% by mass, more preferably 0.5 to 2.5% by mass, and particularly preferably 1 to 2.2% by mass.

  The pH at 20 ° C. of the liquid bleach composition produced according to the present invention is preferably 0 to 7, more preferably 1 to 6.5, still more preferably 2 to 5, and particularly preferably 2 to 4. As pH adjusters for adjusting to such pH, 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 and maleic acid, Sodium hydroxide, potassium hydroxide, ammonia and derivatives thereof, amine salts such as monoethanolamine, diethanolamine, triethanolamine, and the like, preferably using an alkali agent such as sodium carbonate or potassium carbonate alone or in combination, In particular, it is preferable to use an acid selected from hydrochloric acid and sulfuric acid and an alkali agent selected from sodium hydroxide and potassium hydroxide.

  Moreover, the liquid bleach composition produced by the present invention has a viscosity at 20 ° C. in the range of 0.5 to 70 mPa · s, preferably in the range of 1 to 30 mPa · s, more preferably in the range of 2 to 15 mPa · s. More preferably, it is in the range of 4 to 12 mPa · s, and more preferably in the range of 6 to 9 mPa · s, from the viewpoint that the fine foamy composition can improve fixing and permeability to clothing. In order to adjust to such a viscosity, a viscosity modifier can be blended in the present invention. As the viscosity modifier, an alkyl group having 1 to 3 carbon atoms, or benzenesulfonic acid which may be substituted with 1 to 3 hydroxy groups, polyethylene glycol or polypropylene glycol having a weight average molecular weight of 3,000 to 100,000, xanthan gum , A sugar polymer compound selected from guar gum and carboxymethyl cellulose, an alkyl group or an alkenyl group having 12 to 20 carbon atoms, preferably 14 to 18 and an average addition mole number of 60 to 200, preferably 100 to 150 polyoxyethylene A nonionic surfactant having a chain and a reaction product of the nonionic surfactant and a diepoxy compound such as vinylcyclohexene diepoxide can be used. The ratio of such a viscosity modifier is preferably 0 to 10% by mass, more preferably 0.01 to 3% by mass in the blending components of the liquid bleach composition.

  The liquid bleach composition produced according to the present invention preferably contains a bleach activator, particularly a hydrophobic bleach activator, as component (f) for the purpose of improving the bleaching effect on sebum soil. Therefore, in the manufacturing method of the liquid bleach composition of this invention, it is preferable to use (f) component as a compounding component. As the component (f), an alkanoyloxybenzene type bleach activator is preferable, and in particular, an alkanoyloxybenzenesulfonic acid having an alkanoyl group having 8 to 14 carbon atoms, preferably 10 to 12 carbon atoms, or preferably 8 to 14 carbon atoms, preferably An alkanoyloxybenzenecarboxylic acid having 10 to 12 alkanoyl groups or a salt thereof is preferred. More specifically, preferred examples include octanoyloxy-p-benzenesulfonic acid, nonanoyloxy-p-benzenesulfonic acid, 3,5,5-trimethylhexanoyloxy-p-benzenesulfonic acid, decanoyloxy-p-benzene. Sulfonic acid, dodecanoyloxy-p-benzenesulfonic acid, octanoyloxy-o- or -p-benzenecarboxylic acid, nonanoyloxy-o- or -p-benzenecarboxylic acid, 3,5,5-trimethylhexanoyloxy- o- or -p-benzenecarboxylic acid, decanoyloxy-o- or -p-benzenecarboxylic acid, dodecanoyloxy-o- or -p-benzenecarboxylic acid, and salts thereof. As these salts, sodium salts, potassium salts, and magnesium salts are preferable, and sodium salts are more preferable from the viewpoint of solubility.

  Among these, nonanoyloxy-p-benzenesulfonic acid, decanoyloxy-p-benzenecarboxylic acid, dodecanoyloxy-p-benzenesulfonic acid and salts thereof are preferable from the viewpoint of bleaching effect, and decanoyloxy-p- Benzenecarboxylic acid, dodecanoyloxy-p-benzenesulfonic acid and salts thereof are more preferable, and dodecanoyloxy-p-benzenesulfonic acid and salts thereof are particularly preferable.

  The proportion of the component (f) in the blending component is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and particularly preferably 0.5 to 1.5% by mass.

  In the present invention, when the component (f) is used as a blending component of the liquid bleach composition, a cationic surfactant other than the component (c1) is used for the purpose of improving the stability of the component (f) in the composition. And / or an amphoteric surfactant [hereinafter referred to as component (g)].

As the cationic surfactant, an ammonium salt type cationic surfactant represented by the following general formula (g1) is suitable.
R ^1g N ⁺ (R ^2g ) (R ^3g ) (R ^4g ) · X ⁻ (g1)

[Wherein R ^1g is an alkyl having 8 to 18 carbon atoms, preferably 10 to 18 carbon atoms, more preferably 12 to 16 carbon atoms, which may have an ester bond or an amide bond (preferably an ester bond) as a linking group. R ^2g , R ^3g and R ^4g are alkyl groups having 1 to 3 carbon atoms which may be the same or different. X < ^- > is an anion, preferably an alkyl sulfate ion having 1 to 3 carbon atoms, a fatty acid ion having 1 to 12 carbon atoms, and an aryl sulfonic acid optionally having 1 to 3 substituents having 1 to 3 carbon atoms An ion, particularly preferably an alkyl sulfate ion having 1 to 3 carbon atoms. ]

  Moreover, as an amphoteric surfactant, the compound represented by the following general formula (g2) is suitable.

^R5g- [ ^AR6g ] _rN ⁺ ( ^R7g ) ( ^R8g ) ( ^R9g- B) (g2)

[Wherein R ^5g 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 ^6g is an alkylene group having 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms. It is a group. A is a group selected from —COO—, —CONH—, —OCO—, —NHCO—, and —O—, and r is a number of 0 or 1. R ^7g and R ^8g are an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ^9g is an alkylene group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms which may be substituted with a hydroxy group. . B is a group selected from —COO ⁻ , —SO ₃ ⁻ , and —OSO ₃ ^— . ]

  The proportion of the component (g) in the blending component is preferably 0 to 2% by mass, more preferably 0.1 to 1% by mass, and particularly preferably 0.2 to 0.6% by mass. The component (f) and the component (g) are preferably (f) / (g) = 1/10 to 5/1, more preferably 1/3 to 3/1, particularly preferably 1/1 to 1. Mixing at a mass ratio of 2/1 is preferable from the viewpoint of the storage stability of the component (f) in the obtained liquid bleach composition.

The liquid bleach composition produced according to the present invention can contain an anionic surfactant as the component (h) for the purpose of improving the cleaning effect. Therefore, in the manufacturing method of the liquid bleach composition of this invention, (h) component can be used as a compounding component. (H) Preferred anionic surfactants for the component are alkyl or alkenyl groups having 10 to 18 carbon atoms, preferably 10 to 16 carbon atoms, more preferably 10 to 15 carbon atoms in the molecule, and —SO ₃ M group and / or or -OSO ₃ M group: anionic surfactants having a [M counterion] is preferred. Specifically, alkylbenzene sulfonic acid having the above carbon number, alkyl (or alkenyl) sulfate, polyoxyalkylene alkyl (or alkenyl) ether sulfate having an average addition mole number of alkylene oxide of 1 to 6, olefin sulfonic acid, alkane sulfonic acid , Α-sulfo fatty acid, α-sulfo fatty acid ester and salts thereof are preferred. Among these, an alkyl (or alkenyl) sulfate ester having an alkyl group or alkenyl group having 10 to 16 carbon atoms, an alkyl group or alkenyl group having 10 to 16 carbon atoms, and ethylene oxide (hereinafter referred to as EO) average From polyoxyethylene alkyl (or alkenyl) ether sulfates having an addition mole number of 1 to 6, preferably 1 to 4, particularly preferably 1 to 3, or alkylbenzene sulfonic acid having 10 to 15 carbon atoms, and salts thereof It is preferable to blend one or more selected. As the salt, sodium salt, potassium salt, ammonium salt and alkanolamine salt are preferable.

  The proportion of the component (h) in the blending component is preferably 0 to 5% by mass, more preferably 0.5 to 4% by mass, and particularly preferably 1 to 3% by mass.

  The liquid bleach composition produced according to the present invention can contain a compound having dispersibility [hereinafter referred to as component (i)] for the purpose of enhancing the bleaching effect. In particular, polyacrylic acid or a salt thereof or polymethacrylic acid or a salt thereof having a weight average molecular weight of 5,000 to 40,000, preferably 5,000 to 10,000, a weight average molecular weight of 10,000 to 100,000, preferably 30,000 to 70,000. A nonionic polymer selected from a carboxylic acid-based polymer selected from a copolymer of acrylic acid and maleic acid or a salt thereof, and polyethylene glycol having a weight average molecular weight of 4,000 to 20,000, preferably 5,000 to 10,000 is preferable.

  The proportion of the component (i) in the blending component is preferably 0.05 to 14% by mass, and more preferably 0.1 to 8% by mass.

  Furthermore, the liquid bleach composition produced according to the present invention preferably contains a sequestering agent [hereinafter referred to as component (j)] for the purpose of improving the bleaching effect. Therefore, in the manufacturing method of the liquid bleach composition of this invention, it is preferable to use (j) component as a compounding component. (J) As the component, (1) a phosphoric acid compound such as phytic acid, or an alkali metal salt or alkanolamine salt thereof, (2) ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphone Acid, ethane-1-hydroxy-1,1-diphosphonic acid (1-hydroxyethylidene-1,1-diphosphonic acid) and derivatives thereof, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-di Phosphonic acids such as carboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid or alkali metal salts or alkanolamine salts thereof, (3) 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3 4-tricarboxylic acid, phosphonocarboxylic acid such as α-methylphosphonosuccinic acid, or alkali metal salts thereof Lucanolamine salts, (4) amino acids such as aspartic acid, glutamic acid, glycine, or alkali metal salts or alkanolamine salts thereof, (5) nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol ether diamine tetra Aminopolyacetic acid such as acetic acid, hydroxyethyliminodiacetic acid, triethylenetetramine hexaacetic acid, diencoric acid or alkali metal salt or alkanolamine salt thereof, (6) diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, Organic acids such as lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid, or alkali metal salts or alkanolamine salts thereof (7 ) Alkali metal salt or alkanolamine salt of aluminosilicate represented by zeolite A, (8) Aminopoly (methylenephosphonic acid) or its alkali metal salt or alkanolamine salt, or Polyethylenepolyamine poly (methylenephosphonic acid) or its alkali metal Mention may be made of salts or alkanolamine salts.

  Among these, at least one selected from the group consisting of the above (2), (5), (6) and (7) is preferable, and at least one selected from the group (2) is more preferable. Particularly preferred are -1,1-diphosphonic acid and ethane-1-hydroxy-1,1-diphosphonic acid (1-hydroxyethylidene-1,1-diphosphonic acid).

  The proportion of the component (j) in the blending component is preferably 0.005 to 5 mass%, more preferably 0.01 to 2 mass%.

  In addition, in the present invention, Tinopearl CBS (manufactured by Ciba-Geigy), Tinopearl SWN (manufactured by Ciba-Geigy), Color Index fluorescent whitening agent 28, and the like are used as fluorescent whitening agents in order to increase the bleaching effect on bleached fibers. , 40, 61, 71, etc., and enzymes (cellulase, amylase, protease, lipase) can be used as blending components to improve bleaching performance. Moreover, you may mix | blend appropriate amounts of various trace additives, such as coloring agents, such as dye and a pigment, a fragrance | flavor, silicones, a disinfectant, and an ultraviolet absorber.

  In the present invention, the components (a) to (d) and other components are mixed, but the mixing method and the mixing order are not particularly limited. In the production of the liquid bleach composition, the raw materials at the time of blending and the blending amount thereof are determined based on the final composition. In the present invention, a component containing at least the components (a) to (d) is used as a raw material, and the total of the components (c1) and (c2), the mass ratio of (b) / [(c1) + (c2)] And the mass ratio of (c1) / (c2) is set to a specific range at the time of blending.

<Liquid bleach composition>
According to the present invention, (a) hydrogen peroxide or a compound that generates hydrogen peroxide in water, (b) a compound represented by the following general formula (b1), (c1) an alkyl group having 8 to 18 carbon atoms, oxy Polyoxyalkylene alkyl ether having an average addition mole number of alkylene group of 7 to 12, (c2) polyoxyalkylene alkyl ether having an alkyl group of 8 to 18 carbon atoms and an average addition mole number of oxyalkylene group of 2 to 5, And (d) a liquid bleach composition comprising a component containing water,
The proportion of all the ingredients is (a) 0.1 to 30% by mass (as hydrogen peroxide), (b) 0.5 to 10% by mass, and the total of (c1) and (c2) is 1 to 20% by mass. And the mass ratio of (b), (c1), and (c2) is (b) / [(c1) + (c2)] = 1/10 to 10/10, and (c1) and (c A liquid bleaching composition is provided in which the mass ratio to c2) is (c1) / (c2) = 12/1 to 40/1.
R ^1b − (OR ^2b ) _x G _y (b1)
[Wherein R ^1b is a hydrocarbon group having 8 to 16 carbon atoms, R ^2b is an alkylene group having 2 to 4 carbon atoms, G is a residue derived from a reducing sugar, x is a number having an average value of 0 to 6, y Indicates an average value of 1-10. ]

  This liquid bleaching composition is preferably produced by the production method of the present invention, and the description of the production method of the present invention can be applied to preferred embodiments of each component, preferred blending ratio, optional components that can be blended, and the like.

  Moreover, this invention relates to the liquid bleach composition obtained with the manufacturing method of the said invention.

  The liquid bleach composition according to the present invention is preferably applied to a textile product (processing object) such as clothing in the form of foam. Specifically, the liquid bleach composition is formed from the liquid bleach composition according to the present invention. It is preferably used in a method for bleaching clothing in which a foam-like composition is brought into contact with a textile product such as clothing. Furthermore, the washing | cleaning method of the clothing which makes the foam-like composition formed from the liquid bleach composition which concerns on this invention contact the clothing contaminated with the pigment | dye which has a conjugated double bond is preferable. In this case, the foam-like composition is brought into contact with a site contaminated with a pigment having a conjugated double bond in clothing. A chlorophyll is mentioned as a pigment | dye which has a conjugated double bond. Chlorophyll is a hard-to-drop pigment contained in plants such as spinach, and the liquid bleach composition according to the present invention exhibits excellent bleaching and cleaning effects against such pigment stains.

  The foam-like composition used in the present invention is a foam composed of the liquid bleach composition described above and a gas (typically air). In particular, in the present invention, “foam” means that the apparent volume per unit mass of the composition when adhered to the target surface is twice or more due to the inclusion of bubbles, and is twice or more even after 1 minute has passed. This means that the apparent volume is maintained.

  The bubbles constituting the foam composition preferably have an average particle size of 1 to 10,000 μm, more preferably 10 to 5,000 μm, and particularly preferably 100 to 3,000 μm.

  As a method of forming such a foam-like composition and bringing it into contact with clothing, the liquid bleach composition is impregnated into a soft and breathable flexible material that can hold a solution such as sponge, fabric, and nonwoven fabric. In addition to the method of rubbing with foam by hand and rubbing this foam against clothes, a mechanism that forms bubbles by taking in air at the time of discharge by pump or squeeze operation (hereinafter referred to as foam formation mechanism) ). In the present invention, from the viewpoint of simplicity and ease of use, it is preferable to use a container having a discharge means having a foam formation mechanism. Such a container is not particularly limited, but for example, a container having a foam forming function described in paragraphs 0056 to 0078 of JP-A-2004-76006 can be used.

  In addition, as an example of a trigger type sprayer having a foam formation mechanism, in addition to a trigger having a discharge device described in Japanese Patent Application Laid-Open No. 11-100594 and registered utility model No. 3044068, Japanese Patent Application Laid-Open No. 2000-185247, JP 2001-334178 A, JP 2002-20266 A, JP 7-256162 A, JP 8-71463 A, JP 9-285746 A, JP 10-85637 A, Japanese Utility Model 7-9451 gazette, Japanese Utility Model Laid-Open No. 7-9492 gazette and the like.

  Examples of squeeze foamers include the Japanese Utility Model Publication No. 58-174272, Japanese Utility Model Publication No. 62-42787, Japanese Patent Publication No. 52-16567, and the like, and the head of a cap equipped with a pump mechanism is pressed with fingers. Examples of the pump former that discharges bubbles by doing so include Japanese Utility Model Publication No. 3-7963 and Japanese Utility Model Application Publication No. 62-103458.

It is preferable from the viewpoint of obtaining a high bleaching effect that the amount of the foam-like composition attached to clothing is 0.1 to 1 g / cm ² , and more preferably 0.1 to 0.5 g / cm ² . The contact time between the foam-like composition and the garment is preferably 1 to 600 minutes, more preferably 3 to 300 minutes, and particularly preferably 5 to 60 minutes. After such treatment, it is preferably washed with a common alkaline detergent.

  The foam-like composition formed from the liquid bleach composition according to the present invention is used for a plurality of soils composed of hydrophobic soil derived from the sebum around the cocoon and herbaceous soil derived from plants such as spinach. It is valid. That is, although the washing mechanism is not necessarily clear, when washing clothes by bringing the foam-like composition into contact with clothes contaminated with a dye having a conjugated double bond, for example, chlorophyll, which is a green dye component. Is considered particularly effective. In the present invention, component (c1) and (c2) are mixed under specific conditions to produce a liquid bleach composition. As a result, in the obtained composition, when a single polyoxyalkylene alkyl ether is blended, the alkylene oxide addition mole number distribution (preferably ethylene oxide addition mole number distribution) and the structure of the alkyl group (straight chain and The distribution of the branched chain) is different, and by mixing the component (a) and the component (f) if necessary, it is further used as a foam-like composition, so that hydrophobic stains and grass juice stains can be obtained. It is inferred that it exhibits excellent bleaching and cleaning effects against such multiple stains.

<Blending ingredients>
The components used in the following examples are shown.
B-1: R ^1b in the general formula (b1) is an alkyl group having 12 carbon atoms, G is a residue derived from glucose, x is 0, and y is an alkyl polyglucoside with 1.3. C1-1; alkyl A polyoxyethylene lauryl ether having 12 carbon atoms, a linear primary alkyl group having an alkyl group and an average addition mole number of oxyethylene group of 8 [HLB (Griffin method, the same shall apply hereinafter) 13.1]
C2-1: polyoxyethylene alkyl ether having 12 carbon atoms in the alkyl group, secondary alkyl group in the alkyl group, and an average addition mole number of oxyethylene group of 3 (HLB 7.9)
C2-2: a polyoxyethylene lauryl ether having 12 carbon atoms in the alkyl group, a linear primary alkyl group in the alkyl group, and an average oxyethylene group addition mole number of 2 (HLB 6.4)
D-1: ion-exchanged water e-1: polyoxyethylene monophenyl ether [a compound in which R ^1e in the general formula (e1) is a phenyl group, R ^2e is a hydrogen atom, p is 3, and q is 0]
E-2: diethylene glycol monobutyl ether [a compound in which R ^1e in the general formula (e1) is a butyl group, R ^2e is a hydrogen atom, p is 2, and q is 0]
・ F-1: Sodium dodecanoyloxy-p-benzenesulfonate ・ g-1; Lauroyloxy-N, N-dimethyl-N-ethylammonium ethyl sulfate ・ j-1; Dequest 2010 (trade name, Thermophos 1-hydroxyethylidene-1,1-diphosphonic acid manufactured by Japan Co., Ltd.)

Example 1
b-1 is 3.0% by mass (ratio in the blending components, the same applies hereinafter), c1-1 is 8% by mass, d-1 is 70% by mass, e-1 is 2% by mass, and g-1 is 0.00%. After 5% by mass and j-1 of 0.2% by mass were uniformly mixed, 0.5% by mass of c2-1 and 1% by mass of f-1 were added and mixed uniformly. Then, d-1 was added in such an amount that 2.5% by mass of a-1 and 100% by mass of the total amount of the blending components were added and mixed uniformly. The liquid bleach composition was prepared by adjusting the pH at 20 ° C. to 2.5.

  The obtained liquid bleach composition is extracted from a commercially available cleaning agent in a trigger container (Family Sink Cleaner manufactured by Kao Corporation, 0.8 g sprayed with one stroke, forming bubbles in the present invention). Washed several times with water and filled into the dried product. Using this, the bleaching effect was evaluated by the method described below. The results are shown in Table 1.

<Permeability to hydrophobic soil>
To the center of the glass petri dish, 0.3 g of model sebum is dropped, and then 5 ml of the liquid bleach composition is added. The time until the liquid bleach composition penetrates the entire model sebum is measured. Here, the model sebum is composed of 30% by mass of oleic acid, 30% by mass of triolein and 40% by mass of cholesterol oleate, and is used as a model of hydrophobic soil.

<Bleaching property against pigment stain>
(Preparation of cloth contaminated with grass juice)
First, the stem portion of spinach is removed and only the leaves are collected, and then rinsed with running water. Next, after sufficiently pulverizing with a juicer mixer (MX-X108 manufactured by Panasonic, mode: strong stirring, pulverization time: 10 minutes), it is strained with a cotton cloth (# 2023) to collect only the grass juice. Then, it applied to cotton cloth (# 2023) by the gravure method. Then, it was pressed and subjected to an experiment as a 10 cm × 10 cm test cloth.

(Evaluation method)
The liquid bleach composition is sprayed from the container as a foamy composition, applied to 4 sheets of the grass-stained cloth prepared as described above, 0.8 g, left at 20 ° C. for 5 minutes, and then has a concentration of 0.0667% by mass. After washing with a targotometer using a commercially available detergent (manufactured by Kao Corporation, Attack) solution (80 rpm × 10 minutes), it was rinsed with tap water and dried, and the washing rate was determined by the following formula. Table 1 shows the average value of the cleaning rates of the four sheets.

  The reflectance was measured using NDR-10DP manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter.

Examples 2-5, Comparative Examples 1-5
The ratio of the blending components in the liquid bleach composition was changed as shown in Table 1, a liquid bleach composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Claims (7)

(A) Hydrogen peroxide or a compound that generates hydrogen peroxide in water, (b) a compound represented by the following general formula (b1), (c1) an alkyl group having 8 to 18 carbon atoms and an average of oxyalkylene groups A polyoxyalkylene alkyl ether having 7 to 12 addition moles, (c2) a polyoxyalkylene alkyl ether having 8 to 18 carbon atoms in the alkyl group and an average addition mole number of oxyalkylene groups of 2 to 5, and (d) A method for producing a liquid bleach composition comprising a step of mixing water,
The proportion of all components to be mixed is (a) 0.1 to 30% by mass (as hydrogen peroxide), (b) 0.5 to 10% by mass, and the total of (c1) and (c2) is 1 to 20 And (b), (c1), and (c2) at a mass ratio of (b) / [(c1) + (c2)] = 1/10 to 10/10 (c1) and (c2) c2) and (c1) / (c2) = 12/1 to 40/1 in a mass ratio,
A method for producing a liquid bleach composition.
R ^1b − (OR ^2b ) _x G _y (b1)
[Wherein R ^1b is a hydrocarbon group having 8 to 16 carbon atoms, R ^2b is an alkylene group having 2 to 4 carbon atoms, G is a residue derived from a reducing sugar, x is a number having an average value of 0 to 6, y Indicates an average value of 1-10. ]   Furthermore, (e) The manufacturing method of the liquid bleach composition of Claim 1 which mixes 0.1-10 mass% (ratio in all the components mixed) of the water-soluble solvent. The manufacturing method of the liquid bleach composition of Claim 2 whose (e) is a compound represented by the following general formula (e1).
_{^{R 1e -O - [(C 2}} H 4 O) p / (C 3 H 6 O) q] -R 2e (e1)
[Wherein, R ^1e and R ^2e represent a hydrogen atom and a hydrocarbon group having 1 to 8 carbon atoms, respectively, except when both R ^1e and R ^2e are hydrogen atoms. p is an average addition mole number of C ₂ H ₄ O and represents a number of 0 to 10, q is an average addition mole number of C ₃ H ₆ O and represents a number of 0 to 10, and both p and q are Except when 0. “/” Is a symbol indicating that C ₂ H ₄ O and C ₃ H ₆ O may be added randomly or in blocks. ]   The manufacturing method of the liquid bleach composition of any one of Claims 1-3 whose alkyl group of (c2) is an alkyl group which has a branched structure.   The liquid bleach composition obtained by the manufacturing method of any one of Claims 1-4.   A foam-like composition formed from the liquid bleach composition obtained by the production method according to any one of claims 1 to 4 is brought into contact with clothing contaminated with a dye having a conjugated double bond. How to wash clothes.   The method for washing clothes according to claim 6, wherein the pigment having a conjugated double bond is chlorophyll.