JP2008056720A - Liquid detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition which, before being diluted with water, lies in a low pH region where the constituent bleach base can be kept stable and which, after being diluted with water, reaches a high pH region where the composition can exhibit bleaching effect and detergency by virtue of the bleach base. <P>SOLUTION: The liquid detergent composition comprises the following components (a) to (c): (a) hydrogen peroxide or a compound which forms hydrogen peroxide in water, (b) germanium or a compound containing germanium, and (c) a compound having at least one site where each of two vicinal carbon atoms has one hydroxy group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a liquid detergent composition.

  In the liquid detergent composition containing a bleaching base such as hydrogen peroxide, the pH during storage of the composition is made acidic (for example, pH 2 to 4) from the viewpoint of achieving both the stability of the composition and the bleaching effect. There is a need.

Patent Document 1 discloses a technique (pH jump technique) for increasing pH by diluting a composition containing a boron compound and a saccharide in water at the time of use in the field of a bleaching composition containing a bleaching base and a cleaning composition. -6. When this technique is used, the pH that rises when diluted with water is around 9 at the maximum. As an achievement means for increasing the pH to 9 or more, the pH of the composition before water dilution (during storage) is adjusted. It is necessary to adjust to 5 or more in advance. However, when the pH during storage is adjusted to 5 or more in this way, there is a problem in the stability of the bleach base in the composition.
Japanese Patent Laid-Open No. 6-100908 JP-A-7-53994 JP-A-7-70593 Japanese Patent Laid-Open No. 10-72595 Japanese Patent Laid-Open No. 10-72596 JP 2000-144187 A

  In a liquid detergent composition containing a bleaching base such as hydrogen peroxide, in order to further improve the bleaching effect of hydrogen peroxide, store it at a lower pH before diluting with water, and at a higher pH when diluting with water There is a need for technology to increase

  An object of the present invention is to provide a liquid detergent composition capable of stably storing a bleaching base in a low pH region before dilution with water, and obtaining a bleaching effect and a cleaning effect by the bleaching base in a high pH region after dilution with water. To provide things.

  As a result of diligent research, the inventors of the present invention express a remarkably high pH jump effect by using germanium or a compound containing germanium and a specific polyhydric alcohol in combination, and use a bleaching base in a low pH range before dilution with water. It has been found that it can be stored stably, and after dilution with water, the bleaching effect and washing effect of the bleaching base can be remarkably improved in a high pH region.

That is, this invention provides the liquid detergent composition containing the following (a) component, (b) component, and (c) component.
(A) Hydrogen peroxide or a compound that generates hydrogen peroxide in water (b) Germanium or a compound containing germanium (c) There are one or more sites each having one hydroxyl group on each of adjacent carbon atoms Compound

  The liquid detergent composition of the present invention can exhibit a remarkably high pH jump effect, can stably store a bleaching base in a low pH region before water dilution, and in a high pH region after water dilution. An excellent bleaching effect and washing effect by the bleaching base can be obtained.

[(A) component]
The liquid detergent 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.

  The content of the component (a) in the liquid detergent composition of the present invention (content as hydrogen peroxide) is preferably 0.1 to 6% by mass, more preferably 0.5 to 5% by mass, and further Preferably it is 1-4.5 mass%, Most preferably, it is 1-3 mass%. In such a range, an excellent bleaching effect can be obtained.

[Component (b) and Component (c)]
The liquid detergent composition of the present invention contains germanium or a compound containing germanium as the component (b). Examples of the compound containing germanium include, but are not limited to, germanium chloride, germanium oxide, germanium bromide, germanium iodide, germanium ethoxide, germanium methoxide, germanium butoxide, germanium isopropoxide, and the like.

  The liquid detergent composition of the present invention contains a compound in which one or more sites each having one hydroxyl group are present on both of the adjacent carbon atoms as component (c).

  In the present invention, the component (c) is a compound that can form a mono- or di-form with the component (b) in the liquid detergent composition (see the following general formula), and has 3 or more hydroxyl groups. In addition, a compound having a structure in which one or more sites each having one hydroxyl group are present on both adjacent carbon atoms is preferable.

  Here, an equilibrium reaction such as the following formula exists between the component (b) and the component (c).

  Specific examples of the component (c) include the following compounds (1) to (4), and at least one selected from the group consisting of these compounds can be used.

(1) Glycerin, diglycerin, triglycerin, alkyl (C1-C10) polyglyceryl ether (for example, alkyl (C1-C10) diglyceryl ether, alkyl (C1-C10) triglyceryl ether)
(2) Sugar alcohols selected from sorbitol, mannitol, maltose, inositol, and phytic acid (3) Selected from glucose, apiose, arabinose, galactose, lyxose, mannose, galose, aldose, idose, talose, xylose, and fructose Reducing sugars and their derivatives (alkyl (poly) glycosides, etc.)
(4) A polysaccharide selected from starch, dextran, xanthan gum, guar gum, curdlan, pullulan, amylose, and cellulose.

  In the present invention, the sugar alcohols of (2) above are particularly suitable and can be used alone or in combination. In particular, sorbitol is preferable from the viewpoints of stability and bleaching / washing effect.

  As one embodiment, the liquid detergent composition of the present invention may use a pH jump system composed of the component (b) and the component (c) at a specific composition and ratio. By further having such a specific composition and ratio, the liquid detergent composition of the present invention can exhibit an excellent pH jump effect and excellent hydrogen peroxide stability.

  In the present invention, the pH at 20 ° C. of the diluted solution when diluted with 1000 times volume of water with respect to the liquid cleaning composition may be 8.5 or more and less than 10.5, preferably 9 or more and less than 10.5. It is preferable for the purpose of obtaining a bleaching / washing effect.

  In the present invention, it is preferable that the di-form is a main component of the pH jump system in order to make the pH of the diluted solution 8.5 or more and less than 10.5, and all germanium compounds present in the liquid detergent composition In contrast, the di-isomer content is 70 to 100 mol%, the mono-isomer content is less than 5 mol%, and the germanium and / or germanium compound content present alone is less than 25 mol%. It is preferable that In the present invention, the molar ratio of component (c) / component (b) is preferably 1.0 to 12.0, more preferably 1.5 to 10.0, still more preferably 1.5 to 6.0, By adjusting to 2.0-4.0 especially preferably, the outstanding pH jump effect and the stability of hydrogen peroxide and a bleach activator can be acquired.

  In the present invention, when the component (b) and the component (c) are blended in the liquid detergent composition, the liquid detergent composition is generally converted to the mono- and di-form compounds. . The content of the component (b) in the present invention means the total content of the component (b) existing as a single product and a di product. The content of the component (c) means the total content of the component (c) existing as a single product and a di product. In view of achieving an excellent pH jump effect, the content of the component (b) of the present invention is preferably 0.1 to 3% by mass, more preferably 0.15 to germanium atoms in the liquid detergent composition. It is 3.0 mass%, Most preferably, it is 0.2-3.0 mass%. The content of the component (c) is preferably 0.3 to 35% by mass, more preferably 1 to 30% by mass, and particularly preferably 2 in the liquid detergent composition from the viewpoint of achieving an excellent pH jump effect. ˜20 mass%.

The contents of the converted mono- and di-forms can be calculated by using a combination of germanium ( ³² Ge) NMR spectroscopy and ICP emission spectrometry.

[Liquid detergent composition]
The liquid detergent composition of this invention contains the said (a) component, (b) component, and (c) component as an essential component. Moreover, the liquid detergent composition of this invention can contain a bleaching activator as (d) component.

  In the present specification, the bleach activator means a compound that generates an organic peracid by reacting with an inorganic peroxide. Examples of the bleach activator of the present invention include compounds having an ester bond represented by the following general formula (1).

R ^1a -C (= O) -LG (1)
[In formula, R ^<1a> is a C5-C20 linear or branched alkyl group or alkenyl group, an aryl group, or an alkyl group (C1-C3) substituted aryl group. LG is a leaving group. ]
In the general formula (1), R ^1a is preferably a branched alkyl group having 5 to 13 carbon atoms, and a branched chain having 5 to 13 carbon atoms having a side chain at the α-position or β-position with respect to the carbonyl carbon. An alkyl group is more preferred. Such a bleaching activator having a branched alkyl group can ensure improved storage stability in a weakly acidic region as compared with a bleaching activator having a straight chain alkyl group. A cleaning effect can be imparted to the liquid detergent composition.

  Further, in the general formula (1), examples of the leaving group represented by LG include groups selected from the following groups.

(Where R ^1b is an alkylene group, preferably an alkylene group having 1 to 5 carbon atoms, p is 0 or 1, and M is a hydrogen atom, an alkali metal or an alkaline earth metal.)
Specific preferred compounds of component (d) include compounds represented by the following general formula (2).

[In the formula, R ^2a —CO— represents an alkanoyl having a total carbon number of 6 to 21, preferably 6 to 13, and more preferably 7 to 13 having a side chain at least one of the α-position and the β-position with respect to the carbonyl carbon. R ^2a -is preferably the following α-position branched type or β-position branched type.

Here, R ^2b is an alkyl group having 4 to 10 carbon atoms, and R ^2c is a group selected from a methyl group, an ethyl group, a propyl group, and a butyl group. X is a group selected from —COOM and —SO ₃ M, and M is a hydrogen atom, an alkali metal, or an alkaline earth metal. ]
As the component (d) of the present invention, R ^2a —CO— in the general formula (2) is a 2-ethylhexanoyl group, 3,5,5-trimethylhexanoyl group, 2-ethylpentanoyl group, or 3, A 6,8,8-tetramethylnonanoyl group is preferred, and a 3,5,5-trimethylhexanoyl group is particularly preferred. A compound in which X is —COOH or —SO ₃ M is suitable, and a compound having —SO ₃ M in the p-position is most preferred.

  The content of the component (d) in the liquid detergent composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and particularly preferably 0.2 to 2% by mass. It is.

  The liquid detergent composition of the present invention can contain a surfactant as the component (e). The surfactant is at least one selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. The powder detergent for clothing) "The surfactant described in Japan Patent Office, March 26, 1998, P4-22 can be used.

  The surfactant used in the present invention preferably contains a nonionic surfactant. As a nonionic surfactant, the compound represented by following General formula (3) is preferable, and the nonionic surfactant whose HLB calculated | required by the Griffin method is 13-17 is still more preferable.

^R3a- O [(EO) _m / (PO) _n ] -H (3)
[Wherein, R ^3a represents an alkyl or alkenyl group having 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms. m represents the number of the number average added moles of 0 to 20, n represents the number of the number average added moles of 0 to 20, and the case where both m and n are 0 is excluded. Preferably, the number average addition mole number of m is 6 to 15, more preferably 7 to 12, and the number average addition mole number of n is 0 to 10, more preferably 0 to 5, particularly preferably 0 to 3. . Moreover, EO and PO may be arranged in any form of a random copolymer or a block copolymer. ]
Here, HLB calculated | required with the Griffin method is HLB calculated | required with the following formula | equation.

HLB value = 20 × total formula weight of hydrophilic part / molecular weight Among these nonionic surfactants, polyoxyethylene alkyl ether type nonionic surfactants having an HLB of 13 to 17 determined by the Griffin method, In addition, at least one selected from polyoxyalkylene alkyl ether type nonionic surfactants having an oxyethylene group and an oxypropylene group is preferable, and specific examples include compounds represented by the following general formula. It is not limited.

_{C 12 H 25 -O (C 2} H 4 O) m1 -H (m1 = 7~20, HLB = 13.1~16.9)
_{C 14 H 29 -O (C 2} H 4 O) m2 -H (m2 = 7~24, HLB = 13.1~17.0)
_{C 12 H 25 -O (C 2} H 4 O) p1 (C 3 H 6 O) 2 (C 2 H 4 O) r1 -H (p1 + r1 = 5~18, HLB = 13.4~17.0)
As an example of the compound represented by these general formulas, polyoxyethylene lauryl ether (oxyethylene average addition mole number 8, HLB13.1), C ₁₂ H ₂₅ —O (C ₂ H ₄ O) ₇ — (C ₃ H ₆ O) _2- (C ₂ H ₄ O) ₄ -H (HLB15.8).

  Among these nonionic surfactants, polyoxyalkylene alkyl ether type nonionic surfactants having an oxyethylene group and an oxypropylene group are particularly preferable. The polyoxyalkylene alkyl ether type nonionic surfactant may be arranged in any form of a random copolymer or a block copolymer, and among them, a block copolymer is preferable. As the form of the block copolymer, a compound represented by the following general formula (4) and having an HLB of 13 to 17 determined by the Griffin method is particularly preferable.

R ^4a -O (EO) _a (PO) _b (EO) _c -H (4)
[Wherein, R ^4a represents an alkyl or alkenyl group having 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms. a is the number of the number average addition mole number 1-20, b is the number of the number average addition mole number 1-20, c shows the number of the number average addition mole number 1-20. Preferably, the number average addition mole number of a is 6 to 15, more preferably 7 to 12, and the number average addition mole number of b is 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3. And the number average added mole number of c is 6 to 15, more preferably 7 to 12. ]
Nonionic surfactants can be formulated as a mixture of two or more.

  The content of the component (e) in the liquid detergent composition of the present invention is preferably 1.0 to 70% by mass, more preferably 10 to 70% by mass, and further preferably 15 to 15% from the viewpoint of improving the cleaning performance. It is 70 mass%, Most preferably, it is 20-65 mass%.

  The liquid detergent composition of the present invention may contain a sequestering agent as the component (f) from the viewpoint of improving the stability of hydrogen peroxide and a bleach activator. As the sequestering agent, phosphonic acid compounds are preferably used. Specific examples thereof include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonate, ethane-1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1, Examples thereof include organic phosphonic acid derivatives such as 2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, nitrilotrimethylenephosphonic acid, and ethylenediaminetetrakismethylenephosphonic acid. These can be used alone or in combination. Of these, ethane-1-hydroxy-1,1-diphosphonic acid, ethylenediaminetetrakismethylenephosphonic acid and the like are preferable.

  The content of the component (f) in the liquid detergent composition of the present invention is preferably 0.05 to 1.0% by mass, more preferably from the viewpoint of improving the stability of hydrogen peroxide and the bleach activator. 0.1 to 0.5% by mass.

  The liquid detergent composition of the present invention may contain a radical trapping agent from the viewpoint of improving the stability of hydrogen peroxide and the bleach activator. As the radical trapping agent, phenol-based compounds, that is, derivatives having phenolic OH groups, derivatives thereof such as ester derivatives and ether derivatives thereof are preferable. Preferable examples include dimethoxyphenol, catechol, hydroquinone, methoxyphenol, dibutylhydroxytoluene (BHT) and the like.

  The liquid detergent composition of the present invention may contain a hydrotrope from the viewpoint of stabilizing various components such as fragrances. Examples of the hydrotrope include monohydric alcohols such as ethanol, isopropanol, and phenyl polyoxyethylene alcohol, and polyhydric alcohols such as ethylene glycol, propylene glycol, polyethylene glycol, and glycerin.

  In addition, the liquid detergent composition of the present invention may contain optional components such as silicones, bactericides, fluorescent dyes, enzymes, and fragrances. The liquid detergent composition of the present invention contains water, and usually the balance of the composition is water. As a fragrance | flavor, the fragrance | flavor as described in patent publication 2003-213295 paragraphs [0007]-[0022] can be used, for example.

  The liquid detergent composition of the present invention has an improved stability, particularly bleaching activity, when the pH at 20 ° C. is preferably 3 to 7, more preferably 3.5 to 6, and still more preferably 3.7 to 5.5. Further stabilization in the case of blending an agent can be realized, and excellent bleaching washing performance is exhibited even after storage.

Examples 1-13, Comparative Examples 1-6
A liquid detergent composition having the composition shown in Table 1 was prepared using the following ingredients. About the obtained liquid detergent composition, pH jump performance and bleaching performance were evaluated by the following methods. The results are shown in Table 1.

<Composition ingredients>
(A) Component / a-1; Hydrogen peroxide (b) Component / b-1; Germanium oxide / b-2; Germanium chloride (b ′) component (Comparative product of component (b))
B'-1; boric acid b'-2; sodium tetraborate pentahydrate (c) component c-1 sorbitol c-2 mannitol (d) component d-1 decanoyloxy sodium benzenesulfonate _{(n-C 9 H 19 COOC} 6 H 4 SO 3 Na)
D-2; sodium iso-nonanoyloxybenzenesulfonate represented by the following formula

(E) Component e-1; Polyoxyethylene lauryl ether (oxyethylene average addition mole number 8, HLB13.1)
_{· E-2; C 12 H} 25 O- (C 2 H 4 O) 7 - (C 3 H 6 O) 2 - (C 2 H 4 O) 4 -H (HLB15.8)
(F) Component f-1; ethane-1-hydroxy-1,1-diphosphonic acid (Daiquest 2010, manufactured by Solusia)
<Evaluation method of pH jump performance>
1 mL of the liquid detergent composition and 1000 mL of 4 ° DH were mixed, and the pH at 20 ° C. was measured. The pH is measured using a pH meter F52 manufactured by HORIBA, Ltd. and a pH electrode 6367-S004.

<Evaluation method of bleaching performance>
After mixing 1 mL of the liquid detergent composition and 1000 mL of 4 ° DH, meat sauce-contaminated cloth (4 sheets) prepared by the following method was added thereto, and bleaching was performed for 10 minutes at 20 ° C. and 80 rpm using a tartometer. The reflectance of the cloth surface before and after the treatment was measured, and the bleaching rate was determined by the following formula.

・ Preparation of Meat Sauce Contaminated Cloth Solid content of Meat Sauce (Ripe Tomato Meat Sauce (May 27, 2007 Expiration Date, Lot Number: D5527JF) / Canned 259 g in Can)) Mesh (open eye; 500 μm) ), And the resulting liquid was heated until boiling. Cotton gold cloth # 2003 was immersed in this solution and boiled for 15 minutes. After removing from the fire as it was for about 2 hours and leaving it to 30 ° C., the cloth was taken out and the excess liquid was removed with a spatula and allowed to dry naturally. Thereafter, it was pressed and subjected to an experiment as a 10 × 10 cm test cloth.

Claims (5)

The liquid detergent composition containing the following (a) component, (b) component, and (c) component.
(A) Hydrogen peroxide or a compound that generates hydrogen peroxide in water (b) Germanium or a compound containing germanium (c) There are one or more sites each having one hydroxyl group on each of adjacent carbon atoms Compound   The liquid detergent composition according to claim 1, wherein the molar ratio of component (c) / component (b) is 1.0 to 12.0.   The liquid detergent composition according to claim 1 or 2, further comprising a bleach activator as component (d).   Furthermore, the liquid detergent composition in any one of Claims 1-3 which contains surfactant as (e) component.   (E) The polyoxyethylene alkyl ether type nonionic surfactant whose component is HLB calculated | required by the Griffin method is 13-17, and the polyoxyalkylene alkyl ether type nonionic interface which has an oxyethylene group and an oxypropylene group The liquid detergent composition according to claim 4, comprising at least one selected from activators.