JP2007039598A - Liquid detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition that rapidly disperses/dissolves when diluted, does not damage matter to be deterged and increases its pH when diluted to exhibit enhanced deterging power though it has a high viscosity suitable for use by applying, and a deterging method. <P>SOLUTION: The liquid detergent composition comprises (a) hydrogen peroxide, (b) a nonionic surfactant having an oxyalkylene group, (c) a boron compound, (d) a polyol compound other than the component (e), (e) an alkyl glycoside, and (f) water, wherein the contents of the components (a), (b), (c), (d), (e) and (f) in the composition are 0.1-10 mass%, 3-40 mass%, 0.01-20 mass%, 0.1-30 mass%, 0.1-10 mass% and 30-95 mass%, respectively. The deterging method comprises applying the liquid detergent composition on the matter to be deterged and subsequently diluting the liquid detergent composition with water. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid detergent composition, and more particularly to a liquid detergent composition containing a bleaching agent and having a pH that increases upon dilution. The present invention also relates to a cleaning method in which a liquid cleaning composition is applied to an object to be cleaned. The liquid detergent composition of the present invention is particularly suitable as a detergent for clothing.

  The liquid detergent composition containing hydrogen peroxide is advantageous in that it can be used for colored fabrics of textiles such as clothes, can be directly applied to dirt, and can be washed as it is. However, from the viewpoint of the stability of hydrogen peroxide, it has been common to make the pH of the composition acidic and sacrifice the detergency. In order to improve this, a method is known in which a borate and a polyol are blended and the pH at the time of dilution is increased as compared with that before dilution (see, for example, Patent Documents 1, 2, 3, and 4).

  On the other hand, when the liquid cleaning composition is used on an object to be cleaned such as a textile product, the liquid cleaning composition may remain on the surface and exhibit sufficient cleaning power against dirt. Attempts have been made to increase the viscosity of the liquid detergent composition so that it can be done and from the viewpoint of work. In general, as a method for increasing the viscosity of an aqueous solution, a polymer thickener such as an acrylic acid polymer, xanthan gum or polyvinyl alcohol, or a clay substance such as smectite is included, but it contains hydrogen peroxide. Since the liquid detergent composition is adjusted to be acidic in consideration of stability, the liquid detergent composition is acidic and sufficiently stable, is economically excellent, and does not cause turbidity in appearance. It is difficult to obtain a thickening effect. In order to solve these problems, studies on blending specific nonionic surfactants have been made (see, for example, Patent Documents 5, 6, 7, 8.9, 10, 11).

When such a thickening composition containing a nonionic surfactant is used for an object to be cleaned such as a textile product, once the viscosity of the liquid cleaning composition is increased by dilution, the washing process The liquid detergent composition stays in the object to be cleaned for a while, so that a sufficient cleaning power against dirt can be exhibited. However, in the pH adjustment composition containing the borate and polyol described above, the viscosity increases with dilution and the pH also rises. Therefore, the applied part has a high concentration and high pH locally, and is cleaned with hydrogen peroxide. There is a possibility of damaging things.
Japanese Patent Laid-Open No. 6-100908 JP-A-7-53994 JP-A-7-70593 Japanese Patent Laid-Open No. 10-17895 JP 2005-170995 A JP 2002-80895 A JP-A-10-130893 JP-A-9-188895 JP-A-11-293283 JP 2001-181695 A JP 2001-288497 A

  An object of the present invention is to provide a liquid detergent composition that has a high viscosity suitable for coating use, disperses and dissolves rapidly upon dilution, does not damage the object to be cleaned, and increases the pH when diluted to increase the cleaning power Is to provide. Another object of the present invention is to provide a cleaning method in which a liquid cleaning composition is applied to an object to be cleaned.

The present invention contains the following component (a), component (b), component (c), component (d), component (e) and component (f), and the content of component (a) in the composition is 0.1 to 10% by mass, (b) component content is 3 to 40% by mass, (c) component content is 0.01 to 20% by mass, and (d) component content is 0.1 to 10% by mass. 30% by mass, (e) a component containing 0.1 to 10% by mass, a component (f) containing 30 to 95% by mass, and a liquid detergent composition Provided is a cleaning method of diluting the liquid cleaning composition with water after being applied to a cleaning product.
(A) hydrogen peroxide (b) at least one selected from nonionic surfactants having an oxyalkylene group (c) selected from polyol compounds other than at least one (d) (e) component selected from boron compounds At least one (e) alkyl glycoside selected from at least one (e) water (f) Water The present invention further provides the above liquid detergent composition containing a phosphonic acid-based metal scavenger as the component (g).

  The present invention further provides the above liquid cleaning composition containing a phenolic radical trapping agent as component (h).

  The present invention further provides the above liquid detergent composition containing a bleach activator as component (i).

  The liquid detergent composition of the present invention has a high viscosity suitable for application and use, but disperses and dissolves rapidly upon dilution, does not damage the object to be cleaned, and increases the pH by increasing the detergency when diluted. Can do. In addition, by the cleaning method of the present invention, the liquid detergent composition can be applied to the object to be cleaned, and good cleaning power can be obtained without damaging the object to be cleaned.

[(A) component]
The liquid detergent composition of the present invention contains hydrogen peroxide as the component (a).

[Component (b)]
The liquid detergent composition of the present invention contains a nonionic surfactant having an oxyalkylene group as component (b). The oxyalkylene group is preferably an oxyalkylene group having 2 to 3 carbon atoms, and the average added mole number of the oxyalkylene group is preferably 4 to 20, and more preferably 6 to 12.

  Examples of the component (b) include polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, and among these, linear or branched carbon atoms of 8 to 8 carbon atoms. Those having at least one alkyl group or alkenyl group of 24 or those having at least one phenyl group substituted with an alkyl group having 8 to 24 carbon atoms are preferred, from the viewpoint of cleaning performance, stability, and liquid physical properties, Polyoxyalkylene alkyl ether is more preferable, and polyoxyethylene alkyl ether (particularly ethylene oxide average addition mole number of 3 to 15, preferably 4 to 10, carbon number of alkyl group of 10 to 18, preferably 12 to 14) is particularly preferable. .

[Component (c)]
The liquid detergent composition of the present invention contains a boron compound as component (c). Examples of the boron compound include compounds containing boron in the molecule, such as boric acid, sodium borate, potassium borate, ammonium borate, sodium tetraborate, potassium potassium borate, and ammonium ammonium borate. Sodium borate is preferred.

[Component (d)]
The liquid detergent composition of the present invention contains a polyol compound other than the component (e) as the component (d). Examples of polyol compounds include sugars or sugar derivatives such as glucose, mannose, galactose, fructose, ribose, erythrose, xylulose, gluconic acid, galactonic acid, mannonic acid, glucuronic acid, maltose, cellobiose, lactose, sucrose, saccharose, sorbitol, mannitol, etc. Glycerin derivatives such as glycerin and glycerin monoalkyl ether, alkyl diols such as butanediol, hexanediol, octanediol and decanediol, and diol compounds such as ethylene glycol, propylene glycol and hexylene glycol.

  Among these polyol compounds, sugar alcohols are preferable, and sorbitol and / or mannitol are more preferable.

[(E) component]
The liquid detergent composition of the present invention contains an alkyl glycoside as the component (e). As the alkyl glycoside, a compound represented by the following general formula (I) is preferable.

R ¹ − (G) _x (I)
[Wherein, R ¹ represents a linear or branched alkyl group having 10 to 20 carbon atoms, G represents a monosaccharide residue, and x represents an average value of 1 to 10. ]
R ¹ represents an alkyl group having 10 to 20 carbon atoms, preferably an alkyl group having 12 to 18 carbon atoms, particularly 14 to 18 carbon atoms.

  G represents a monosaccharide residue, and examples of the monosaccharide include triose, tetrose, pentose, and hexose having 3 to 6 carbon atoms. Specific examples include apiose, arabinose, galactose, glucose, lyxose, mannose, gulose, aldose, idose, talose, and xylose. Of these, pentose or hexose having 5 or 6 carbon atoms is particularly preferred in the present invention, and glucose is most preferred.

  x represents an average value of 1 to 10, preferably 1 to 5, particularly preferably 1 to 2.

The compound represented by the general formula (I) is a reducing end of the monosaccharide or an oligosaccharide obtained by condensing a plurality of these monosaccharides, preferably 2 to 5 condensed oligosaccharides, more preferably 2 to 3 condensed oligosaccharides. And an alcohol represented by R ¹ —OH (R ¹ has the above meaning) can be easily synthesized by acetalization reaction or ketalization reaction using an acid catalyst. In the case of an acetalization reaction, a hemiacetal structure or a normal acetal structure may be used.

[Liquid detergent composition]
The liquid detergent composition of the present invention contains the above component (a), component (b), component (c), component (d), component (e), and component (f).

  The content of the component (a) in the composition of the present invention is 0.1 to 10% by mass from the viewpoint of cleaning performance and stability, preferably 0.5 to 6% by mass, and 1 to 4% by mass. More preferred. (B) Content of a component is 3-40 mass% from a viewpoint of washing | cleaning performance and a viscosity physical property, 5-36 mass% is preferable, and 8-32 mass% is more preferable. (C) Content of component is 0.01-20 mass% from a viewpoint of washing | cleaning performance, stability, and pH adjustment, 0.05-15 mass% is preferable, and 0.1-10 mass% is more preferable. 0.5-5 mass% is still more preferable. (D) Content of a component is 0.1-30 mass% from a viewpoint of washing | cleaning performance, stability, and pH adjustment, 0.5-25 mass% is preferable, 1-20 mass% is more preferable, 5 More preferred is ˜15% by mass. (E) Content of a component is 0.1-10 mass% from a cleaning performance, a viscosity physical property, and a soluble viewpoint, 0.5-8 mass% is preferable and 1-6 mass% is more preferable. (F) Content of a component is 30-95 mass% from a viewpoint of a viscosity physical property and stability, 35-90 mass% is preferable, and 40-80 mass% is more preferable.

  The liquid detergent composition of the present invention preferably further contains a phosphonic acid-based metal scavenger as the component (g) from the viewpoint of stability and liquid physical properties. 0.01-2 mass% is preferable, as for content of the (g) component in the composition of this invention, 0.05-1.5 mass% is more preferable, and 0.1-1 mass% is still more preferable.

  Examples of the phosphonic acid-based metal scavenger include 1-hydroxyethane-1,1-diphosphonic acid, ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, hydroxyethane-1,1,2- Triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, hydroxymethanephosphonic acid, ethylenediaminetetra (methylenephosphonic acid), nitrilotri (methylenephosphonic acid), 2-hydroxyethyliminodi (methylenephosphonic acid) And organic phosphonic acid derivatives such as hexamethylenediaminetetra (methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic acid) and salts thereof. Among these, 1-hydroxyethane-1,1-diphosphonic acid and its salt are preferable.

  The liquid detergent composition of the present invention preferably contains a phenolic radical trapping agent as the component (h) from the viewpoints of stability and liquid physical properties. 0.05-5 mass% is preferable, as for content of (h) component in the composition of this invention, 0.1-3 mass% is more preferable, and 0.5-2 mass% is still more preferable.

  Examples of the phenol radical trapping agent include a compound having a phenolic hydroxyl group, an ester derivative of a phenolic hydroxyl group, an ether derivative, and the like. More specifically, as such a compound, cresol, thymol, chlorophenol, bromophenol, methoxyphenol, nitrophenol, hydroxybenzoic acid, salicylic acid, hydroxybenzenesulfonic acid, di-t-butyl-hydroxytoluene, naphthol, Examples include hydroquinone, catechol, pyrogallol, phenoxyethanol, and phenol. Among these, 4-methoxyphenol, 4-hydroxybenzoic acid, hydroquinone, and catechol are more preferable, and considering the stability of the radical trapping agent, 4-methoxyphenol and 4-hydroxybenzoic acid are more preferable among these. 4-methoxyphenol is particularly preferred.

  The liquid detergent composition of the present invention preferably contains a bleach activator as the component (i) from the viewpoint of washing performance and stability. The content of the component (i) in the composition of the present invention is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, still more preferably 0.2 to 3% by mass, and 4 to 1% by mass is particularly preferable.

  As the bleach activator, an alkanoyloxybenzene type bleach activator is preferable, and in particular, an alkanoyloxybenzenesulfonic acid having an alkanoyl group having 8 to 14 carbon atoms, preferably 8 to 13 carbon atoms, or preferably 8 to 14 carbon atoms, preferably Alkanoyloxybenzenecarboxylic acids having 8 to 13 alkanoyl groups or salts thereof are preferred. More specifically, preferred examples include octanoyloxy-p-benzenesulfonic acid, nonanoyloxy-p-benzenesulfonic acid, 3,5,5-trimethylhexanoyloxy-p-benzenesulfonic acid, decanoyloxy-p- Benzenesulfonic 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 the salt, sodium salt, potassium salt, and magnesium salt are preferable, and sodium salt is particularly preferable from the viewpoint of solubility. Among these, nonanoyloxy-p-benzenesulfonic acid, decanoyloxy-p-benzenecarboxylic acid, dodecanoyloxy-p-benzenesulfonic acid and salts thereof are particularly preferable from the viewpoint of bleaching effect.

  In the liquid detergent composition of the present invention, the pH at 20 ° C. measured by the method described in JIS K3362: 1998 is preferably 3 to 7, more preferably 3.5, from the viewpoints of stability, washing performance, and liquid physical properties. It is -6.8, More preferably, it is 4-6.5. Further, from the viewpoint of cleaning performance, the pH is preferably increased by 0.5 or more by dilution, more preferably 1 or more, still more preferably 1.5 or more, and particularly preferably 2 or more.

  Further, the liquid detergent composition of the present invention preferably has a pH at 20 ° C. of a 0.1% by mass aqueous solution measured by the method described in JIS K3362: 1998, preferably from 7 to 10, from the viewpoint of cleaning performance and liquid physical properties. More preferably, it is 7.2-9.5, More preferably, it is 7.5-9.

  PH adjusting agents for adjusting to such pH include inorganic acids such as hydrochloric acid and sulfuric acid, or acids such as organic acids such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid and maleic acid. Or alkali agents such as sodium hydroxide, potassium hydroxide, ammonia and derivatives thereof, amine salts (monoethanolamine, diethanolamine, triethanolamine, etc.), sodium carbonate, potassium carbonate, etc. may be used alone or in combination. It is particularly preferable to use an acid agent selected from hydrochloric acid and sulfuric acid, or an alkali agent selected from sodium hydroxide and potassium hydroxide.

Moreover, the viscosity at 20 ° C. of the liquid detergent composition of the present invention is preferably 50 to 200 mPa · s, more preferably 60 to 150 mPa · s, and still more preferably 70 to 100 mPa · s, from the viewpoint of cleaning performance and liquid physical properties. s.
The viscosity of the liquid detergent composition of the present invention was measured using a B-type viscometer [manufactured by Tokyo Keiki Co., Ltd., VISCOMETER MODEL DVM-B]. Measured under conditions.

  The liquid detergent composition of the present invention can contain at least one selected from an anionic surfactant, a cationic surfactant and an amphoteric surfactant from the viewpoint of obtaining excellent cleaning performance. A surfactant is preferred. The content of these surfactants in the composition is preferably 0.01 to 20% by mass, and more preferably 0.5 to 10% by mass.

  Examples of the anionic surfactant include a linear or branched anionic surfactant having at least one alkyl group or alkenyl group having 8 to 24 carbon atoms, or aryl substituted with an alkyl group having 8 to 24 carbon atoms. Anionic surfactants having at least one group, such as alkylbenzene sulfonate, soap, alkyl sulfate, polyoxyethylene alkyl sulfate, aliphatic α-sulfomethyl ester, α-olefin sulfonic acid A salt etc. can be mentioned. Among these, alkylbenzene sulfonate, α-olefin sulfonate, and alkyl sulfate are preferable.

  Examples of the cationic surfactant include mono- or dialkylamines and their polyoxyethylene adducts, mono- or di-long alkyl quaternary ammonium salts, and the like. Examples of amphoteric surfactants include carbobetaine-based, sulfobetaine-based, and hydroxysulfobetaine-based amphoteric surfactants.

  Furthermore, the liquid detergent composition of the present invention preferably contains a dispersant for the purpose of enhancing the bleaching effect, and the content of the dispersant in the composition is preferably 0.05 to 14% by mass, 8 mass% is more preferable. As the dispersant, polyacrylic acid or a salt thereof or a 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 3 A carboxylic acid polymer selected from 10,000 to 70,000 copolymers of acrylic acid and maleic acid or a salt thereof, and / or a non-polymer selected from polyethylene glycol having a weight average molecular weight of 4,000 to 20,000, preferably 5,000 to 10,000. Ionic polymers are preferred.

  Further, the liquid detergent composition according to the present invention is used as a fluorescent brightening agent to increase the bleaching effect on bleached fibers, such as Tinopearl CBS (manufactured by Ciba-Geigy), Tinopearl SWN (manufactured by Ciba-Geigy), An optical brightener such as the index fluorescent brightener 28, 40, 61, 71 or the like, or an enzyme (cellulase, amylase, protease, lipase) can be added to improve the 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.

[Cleaning method]
The cleaning method of the present invention is a method of diluting the liquid cleaning composition with water after applying the liquid cleaning composition of the present invention to an object to be cleaned.

Examples 1-7 and Comparative Examples 1-6
A liquid cleaning composition having the composition shown in Table 1 was prepared using the following components. About the obtained liquid detergent composition, evaluation of decoloring property and application cleaning power were performed by the method shown below. The results are shown in Table 1.

<Compounding ingredients>
(A) Component a-1; Hydrogen peroxide (b) Component b-1; CH ₃ (CH ₂ ) ₁₁ —O— (C ₂ H ₄ O) ₆ —H
b-2; CH ₃ (CH ₂ ) ₁₁ —O— (C ₂ H ₄ O) ₁₀ —H
(C) component c-1; orthoboric acid c-2; metaboric acid (d) component d-1; sorbitol d-2; mannitol (e) component e-1; lauryl glucoside (in formula (I), R ¹ is An alkyl group having 12 carbon atoms, G is a glucose residue, and x is 1.3)
e-2: Myristyl glucoside (in the formula (I), R ¹ is an alkyl group having 14 carbon atoms, G is a glucose residue, and x is 1.8)
(G) Component g-1; 1-hydroxyethane-1,1-diphosphonic acid (Diquest 2010, manufactured by Solusia)
(H) Component h-1; 4-methoxyphenol h-2; Phenolsulfonic acid (i) Component i-1; Dodecanoyloxy-p-benzenesulfonic acid i-2; Nonanoyloxy-p-benzenesulfonic acid i-3 ; 3,5,5-trimethyl hexanoyl oxy -p- benzenesulfonic acid other ingredients LAS-Na: sodium ES linear alkyl benzene sulfonic acid 10 to 14 carbon _{atoms; C 12 H 25 -O (CH} 2 CH 2 O) _n SO ₃ Na (ethylene oxide average added mole number n = 3)
PEG; polyethylene glycol (average molecular weight: 8000)
<Evaluation method for decolorization>
(1) Preparation of decoloring test cloth 100% cotton knit smooth, mercerized processed dye (CI Reactive Red 41) after exhaust dyeing to a concentration of 4% with respect to the cloth, water washing, soaping The test cloth was 10 × 10 cm.

(2) Evaluation of decolorization performance 2 g of the liquid detergent composition was uniformly applied to one test cloth prepared as described above. A set of 5 sheets per sample.
Five test cloths, each having a liquid detergent composition uniformly applied to 2 L of tap water, were immersed for 30 minutes, washed with water, dehydrated and dried. Such treatment was repeated 20 times, and the ΔE ^* value of the washed fabric was examined by the following method.

(3) Color measurement method Using a color difference meter (Nippon Denshoku Industries Co., Ltd .: ND (F) -300A type), the L ^* value, a ^* value, and b ^* value before and after the test are measured, and the following equation is obtained. The ΔE ^* value was determined by A smaller ΔE ^* value means less discoloration due to cumulative cleaning.

<Coating cleaning power>
A No. 111 contaminated cloth purchased from EMPA was used as an 8 cm × 8 cm test piece (blood-contaminated cloth).
The liquid detergent composition was adjusted to 20 ° C., and 1 g of the liquid detergent composition was uniformly applied to one blood-contaminated cloth. A set of 5 sheets per sample.
After leaving for 5 minutes after application, using an indicator detergent solution (determination without fluorescent brightener) described in JIS K 3362: 1998, washed with a tartometer at 20 ° C. for 10 minutes, then washed with water and dried The bleaching rate was determined by the following formula.
The reflectometer was measured using NDR-101DP manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter.

Claims (9)

The following (a) component, (b) component, (c) component, (d) component, (e) component, and (f) component are contained, and content of (a) component in a composition is 0.1- 10 mass%, the content of component (b) is 3-40 mass%, the content of component (c) is 0.01-20 mass%, the content of component (d) is 0.1-30 mass%, (E) The liquid detergent composition whose content of a component is 0.1-10 mass% and whose content of (f) component is 30-95 mass%.
(A) hydrogen peroxide (b) at least one selected from nonionic surfactants having an oxyalkylene group (c) at least one selected from boron compounds (d) selected from polyol compounds other than component (e) At least one (f) water selected from at least one (e) alkyl glycoside   The liquid detergent composition according to claim 1, wherein the component (b) is at least one selected from polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl ether and polyoxyalkylene alkyl phenyl ether. The liquid detergent composition according to claim 1 or 2, wherein the component (e) is a compound represented by the following general formula (I).
R ¹ − (G) _x (I)
[Wherein, R ¹ represents a linear or branched alkyl group having 10 to 20 carbon atoms, G represents a monosaccharide residue, and x represents an average value of 1 to 10. ]   Furthermore, the liquid detergent composition in any one of Claims 1-3 which contains a phosphonic acid type metal scavenger as (g) component.   Furthermore, the liquid cleaning composition in any one of Claims 1-4 which contains a phenol-type radical trap agent as (h) component.   Furthermore, the liquid cleaning composition in any one of Claims 1-5 containing a bleaching activator as (i) component.   The liquid detergent composition according to any one of claims 1 to 6, which has a pH of 3 to 7 measured at 20 ° C according to JIS K3362: 1998.   The liquid detergent composition according to any one of claims 1 to 7, wherein the pH of a 0.1 mass% aqueous solution measured at 20 ° C described in JIS K3362: 1998 is 7 to 10. A cleaning method of diluting the liquid cleaning composition with water after applying the liquid cleaning composition according to claim 1 to an object to be cleaned.