JP5388444B2 - Liquid detergent composition - Google Patents

Description

  The present invention relates to a liquid detergent composition that is suitable as a detergent for clothing, and particularly has a high detergency against sock dirt.

  The stains on clothing vary depending on the type, but socks stains are extremely difficult to remove, and are considered to be complex stains such as sebum stains, protein stains, and particle stains. Conventionally, it is known that for socks, a detergent containing an enzyme such as a fatty acid soap excellent in sebum dirt removal and particle dirt dispersion and a protease excellent in protein dirt degradation is effective.

  Patent Document 1 describes a liquid detergent composition for clothing that improves the detergency of mud soil by blending a nonionic surfactant, a chelating agent, monoethanolamine, palmitic acid, and the like. Enzymes and enzyme stabilizers are described as optional components. However, in the examples, since the enzyme is not blended, the sock washing performance is considered insufficient.

  In order to increase the detergency of socks, it is considered effective to add a chelating agent together with a fatty acid and an enzyme. However, since the enzyme is easily changed in structure by the chelating agent, these It was difficult to stably blend these three components simultaneously.

  In order to prevent the inactivation of the enzyme, it may be possible to add an enzyme stabilizer such as calcium chloride. However, in order to obtain sufficient enzyme stability, it is necessary to add a large amount. In this case, there existed the subject with respect to stability that a water-insoluble fatty-acid metal salt was produced | generated in a formulation and a precipitate produced, and the subject that detergency fell.

  Patent Document 2 describes a liquid detergent composition containing a nonionic surfactant, an enzyme, an enzyme stabilizer, and a chelating agent, but there is room for improvement in the detergency of socks.

Patent Document 3 includes a nonionic surfactant having 6 to 18 HLB and an anionic surfactant containing a higher alcohol or acyclic hydrocarbon having 8 to 18 carbon atoms as a micelle growth accelerator. A liquid detergent with excellent and low temperature stability is described. However, Patent Document 3 is a dishwashing detergent, and therefore there is no suggestion regarding the stability of the enzyme, and the composition is also a composition mainly composed of an anionic surfactant. Patent Document 4 discloses a liquid in which foamability is adjusted, which is obtained by ethoxylation of alcohol having 12 to 20 carbon atoms, and contains two types of nonionic surfactants having different ethoxylation numbers, fatty acids, and organic complex builders. Patent Document 5, which describes a detergent, describes a liquid detergent excellent in stability in which two kinds of nonionic surfactants having different specific numbers of added moles of alkylene oxide are blended. Patent Document 6 discloses a liquid detergent that uses a nonionic surfactant having a low ethylene oxide (hereinafter referred to as EO) addition mole number and a high EO addition mole number nonion, and has a distribution range of low EO addition mole number. A liquid cleaning agent having no odor and no odor is described, and an enzyme is disclosed as an optional component. In any case, nothing has been mentioned about the problem of the present invention.
JP 2007-77362 A JP 2002-69488 A JP 2004-91522 A JP 50-22281 A JP-A-53-209 JP 2000-355700 A

  This invention makes it a subject to provide the liquid detergent composition which can mix | blend a fatty acid, an enzyme, a chelating agent, and an enzyme stabilizer simultaneously simultaneously, and can implement | achieve especially high sock washing | cleaning performance.

  The present invention provides (1) a liquid detergent composition containing the following components (a) to (e).

(A) 10 to 50% by mass of a nonionic surfactant containing 6 to 15% by mass of the compound represented by the following general formula (I) in the component (a)
R—O (AO) _n H (I)
[Wherein, R is a hydrocarbon group having 8 to 22 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, and n is a number selected from 0, 1 and 2]
(B) Fatty acid having an average carbon number of 8 to 20 0.5 to 10% by mass
(C) Chelating agent 0.5-5 mass%
(D) Enzyme (e) Enzyme Stabilizer Further, the present invention is obtained by adding (2) the component (a) to the higher alcohol having 8 to 22 carbon atoms with alkylene oxide, preferably ethylene oxide or propylene oxide. A nonionic surfactant comprising a polyoxyalkylene alkyl ether and a compound represented by the general formula (I), wherein the peak value of the addition mole number distribution of alkylene oxide of the nonionic surfactant is between 7 and 20 The liquid detergent composition according to the above (1), which is a nonionic surfactant in the present invention, is also provided.

  Furthermore, the present invention adds (3) (a) component (a-1) an average of 7 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an alcohol having 8 to 22 carbon atoms in the alkyl group. An average of 1 to 4 alkylene oxides having 2 to 4 carbon atoms with respect to the polyoxyethylene alkyl ether type nonionic surfactant and (a-2) an alcohol having 8 to 22 carbon atoms in the alkyl group. A polyoxyalkylene alkyl ether type nonionic surfactant obtained by adding in a mole, and containing 6 to 15% by mass of the compound represented by the general formula (I) in the component (a). The liquid detergent composition according to the above (1), which is a nonionic surfactant having a peak value of at least 7 to 20 in terms of the number of moles added, is also provided.

  In the composition of the present invention, three components of fatty acid, enzyme and chelating agent are blended stably at the same time. For this reason, it has high cleaning performance, and is particularly excellent in cleaning performance against sock dirt.

<(A) component>
As the component (a) of the present invention, a nonionic surfactant that is a main substrate, which is generally known as a washing substrate for clothing, can be used. The compound represented by I) is contained in the component (a) in an amount of 6 to 15% by mass.

R—O (AO) _n H (I)
[Wherein, R is a hydrocarbon group having 8 to 22 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, and n is a number selected from 0, 1 and 2]
The compound of the general formula (I) may be blended as a part of the component (a-1) or the component (a-2) described later, and is separately manufactured and used by adding to a specific nonionic surfactant. May be.

  The present inventors have found that by using a nonionic surfactant containing a compound represented by the general formula (I), an excellent detergency can be exhibited without affecting the stability of the enzyme. It came to complete.

  R of the compound in the general formula (I) is a hydrocarbon group, but in the present invention, R is an alkyl group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms. AO is preferably an oxyethylene group or an oxypropylene group. In the present invention, the number of oxyalkylene groups represented by AO and the concentration thereof are particularly important.

  The content of the compound of the general formula (I) in the component (a) is 6% by mass or more, preferably 7% by mass in the nonionic surfactant from the viewpoint of detergency, and the phase stability of the liquid detergent. Therefore, it is 15 mass% or less, preferably 11 mass% or less.

  In general formula (I), the compound of n = 0 is a higher alcohol, but in the present invention, it may be expressed as “the number of added moles is 0”. This takes into account unreacted alcohol in the reaction step, but may be added separately in the present invention. However, since alcohol affects the odor and stability of the liquid phase, the compound of general formula (I) is preferably combined with a compound of n = 1 and / or 2, more preferably a compound of n = 1 and 2. Combine with it.

  In addition, although the compound of general formula (I) can be manufactured by a well-known manufacturing method, it is preferable to mix | blend as (a-2) component mentioned later. The compound of general formula (I) is analyzed by gas chromatography.

  As the nonionic surfactant other than the general formula (I) contained in the component (a), one kind selected from a hydrophobic group which is an alkyl group having 8 to 22 carbon atoms, a hydroxy group and a polyoxyethylene group A compound having the above hydrophilic group, specifically, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, polyoxyethylene polyoxypropylene Examples include block polymers, fatty acid alkanolamides, alkyl polyglycosides, polyhydroxy fatty acid amides, and polyglycerin monoalkyl ethers. In the present invention, polyoxyalkylene alkyl ether type nonionic surfactants shown below as the component (a-1) are particularly preferable.

  The component (a-1) is an alkylene oxide having 2 to 4 carbon atoms, preferably 7 to 20 moles of ethylene oxide and / or propylene oxide, with respect to 1 mole of alcohol having 8 to 22 carbon atoms in the alkyl group. A polyoxyethylene alkyl ether type nonionic surfactant obtained by adding 7 to 18 mol, most preferably 8 to 15 mol is preferred. However, since butylene oxide and propylene oxide, particularly propylene oxide, imparts hydrophobicity, the average number of added moles of the obtained nonionic surfactant is 3 or less, and the average of ethyne oxides of hydrophilic groups The number is preferably less than the added mole.

  The number of carbon atoms of the alkyl group of the higher alcohol is preferably 10 to 18 and more preferably 12 to 16 from the viewpoints of stability and cleaning performance. The higher alcohol may be natural or synthetic, and the alkyl group of the component (a-1) is preferably derived from a primary alcohol. Moreover, there exists average carbon number of an alkyl group, and 10-18 average carbon number is preferable, 10-16 are more preferable, and 12-14 are the most preferable. The average number of added moles of alkylene oxide is preferably 7-18, more preferably 8-15, from the viewpoints of phase solubility with the compound of general formula (I) and detergency.

  The component (a-1) is obtained by adding a specific range of alkylene oxide to 1 mole of the alcohol having the carbon number. Therefore, the component (a-1) is a specific alkylene oxide. Addition mole number (hereinafter sometimes referred to as AO addition mole number), especially in the case of ethylene oxide, AO addition starting from around the number of moles of ethylene oxide added to one mole of alkylene oxide alcohol used in the production process It becomes a mixture having a distribution of the number of moles. That is, in the distribution shown by the graph in which the added mole number of alkylene oxide, preferably ethylene oxide (and propylene oxide) is taken on the horizontal axis, and the mass percentage of the compound by the added mole number in component (a-1) is plotted on the vertical axis. In the present invention, the AO addition mole number of the compound having the highest content (hereinafter sometimes referred to as a peak value) is between 7 and 20, further between 7 and 18, particularly between 8 and 15. Mixtures are preferred.

  The component (a-1) is an alkylene oxide, preferably a compound having an average addition mole number of propylene oxide and ethylene oxide of 7 or more (provided that the average addition mole number of propylene oxide is 3 moles or less). It contains a small amount of compounds with the indicated addition moles of 0, 1 and 2. However, when ethylene oxide is added to an alcohol by a general method, the proportion of the unreacted alcohol or the compound having a low alkylene oxide addition mole number in the component (a-1) is very small. ) It is difficult to satisfy the conditions of the present invention only with the component.

  In addition, as described above, a compound having a low alkylene addition mole number is considered to be an unfavorable substance because it causes odor problems and phase separation, and unreacted alcohol is not included in commercially available nonionic surfactants. A nonionic surfactant with a narrow distribution range of alkylene oxide addition moles has been proposed by using a special catalyst in the production process so as not to be removed by distillation or to contain compounds with low addition moles. There is so much.

  (A) component of this invention mix | blends the compound of general formula (I) with (a-1) component, and does not impair detergency and stability peculiar to a low AO addition nonion. In this case, the component (a) is simply expressed as follows. That is, (a) a polyoxyalkylene alkyl ether obtained by adding an alkylene oxide, preferably ethylene oxide or propylene oxide, to a higher alcohol having 8 to 22 carbon atoms and a compound represented by the general formula (I) An ionic surfactant, wherein the nonionic surfactant has a peak value of the number of added moles of alkylene oxide of 7 to 20, preferably 7 to 18, more preferably 8 to 15; It is. In the present invention, the component (a-1) may be used in combination with a plurality of average added mole numbers. There may be a plurality of peak values in the specific range, or some of them may be outside the range, but the largest peak rises in a part of the range in the distribution of added moles of alkylene oxide. It is preferable.

  As described above, the component (a) is a nonionic surfactant comprising the component (a-1) and the compound of the general formula (I). In the present invention, the compound of the general formula (I) is represented by the following (a-2) It is particularly preferable to blend it as a component from the viewpoints of stability, ease of use and odor.

  That is, the component (a-2) has an average of 1 to 4 moles of alkylene oxide having 2 to 4 carbon atoms, preferably 1 to 1 average of ethylene oxide and / or ethylene oxide, with respect to the alcohol having 8 to 22 carbon atoms in the alkyl group. It is a polyoxyalkylene alkyl ether type nonionic surfactant obtained by adding ~ 4 mol.

  The number of carbon atoms of the alkyl group is preferably 8 to 18 and more preferably 8 to 16 from the viewpoint of stability. When using what mixed the alcohol of different carbon number as raw material alcohol, the average carbon number of the alkyl group of (a-1) component is 8-18, and 8-16 are preferable.

  In the component (a-2), the alkyl group is preferably a linear secondary alkyl group from the viewpoint of stability.

  The average added mole number of alkylene oxide is 1 to 4, preferably 2 to 4. When the average added mole number is within the above range, the enzyme stabilizing effect is high and the detergency is excellent. Further, the alkylene oxide of the component (a-2) is preferably one having only ethylene oxide or both ethylene oxide and propylene oxide. In that case, the average amount of propylene oxide is 2 mol or less, preferably 1 mol or less.

  The component (a-2) of the present invention is a compound obtained by adding alkylene oxide, particularly ethylene oxide in a ratio of 1 to 4 mol to 1 mol of alcohol (provided that 2 mol or less of ethylene oxide is converted to propylene oxide. They may be substituted), and they are a mixture of compounds having different numbers of added moles of alkylene oxide, and in particular, a mixture having an alkylene oxide added mole number of 0 to 10 accounts for 80% by mass or more. If the content of unreacted alcohol is high and the odor problem or the liquid phase stability is affected, a product obtained by reducing unreacted alcohol by distillation or the like may be used. In the distribution indicated by the graph in which the component (a-2) has an ethylene oxide (and propylene oxide) addition mole on the horizontal axis and the vertical axis represents the mass% of the compound by the number of added moles in the component (a-2), In the present invention, it is preferable that the most frequently added compound has a number of added moles (sometimes referred to as a peak value as described above) of 0 to 4 mol, particularly 1 to 4 mol. In addition, what added 1 mol of ethylene oxide turns into a compound with most unreacted alcohol in (a-2) component. The component (a-2) may be a mixture of two or more.

  When the component (a-2) is a polyoxyalkylene alkyl ether together with the component (a-1), nonionic surfactants having two different alkylene oxide addition mole number distributions are mixed. Therefore, in the distribution of the number of moles of alkylene oxide added to the individual compounds constituting the component (a), it is broader than that of generally produced compounds. Although the two distributions may overlap, in the graph showing the addition mole number distribution of the alkylene oxide of the mixture, a part of the ridge line near the low AO addition mole number of the component (a-1), specifically ( A distribution having a slight rise or peak in the peak value range of a-2) is preferred, and in particular, a mixture of distributions showing two peaks of component (a-1) and component (a-2). It is preferable.

  Therefore, the preferred component (a) of the present invention can also be expressed as follows. That is, (a) component (a-1) polyoxyethylene obtained by adding an average of 7 to 20 moles of alkylene oxide having 2 to 4 carbon atoms to an alcohol having 8 to 22 carbon atoms in the alkyl group It is obtained by adding an average of 1 to 4 moles of an alkylene group having 2 to 4 carbon atoms to an alkyl ether type nonionic surfactant and (a-2) an alcohol having an alkyl group having 8 to 22 carbon atoms. A polyoxyalkylene alkyl ether type nonionic surfactant, comprising 6 to 15% by mass of the compound represented by the general formula (I) in the component (a), and the peak number of added moles of alkylene oxide Is a nonionic surfactant, at least 7-20. In addition, the other when two peak values are seen is 0-4.

  (A) A component is 10-50 mass% from the point of a detergency, Preferably it is 15-45 mass%, More preferably, it is 20-40 mass%. Moreover, (a-2) / (a-1) which is a compounding ratio (mass ratio) of the component (a-1) and the component (a-2) is preferably 0.05 to 1, more preferably 0. 0.05 to 0.5, most preferably 0.1 to 0.3. When the ratio is within the range, sufficient stability and cleaning effect can be obtained. In particular, from the viewpoint of enzyme stability and low-temperature stability of the liquid, it is most preferable that the component (a-2) is contained in the liquid detergent composition in an amount of 2 to 6% by mass and the balance is the component (a-1). .

<(B) component>
The component (b) is a fatty acid having an average carbon number of 8 to 20, preferably 10 to 18, more preferably 12 to 14, and may be a saturated fatty acid or an unsaturated fatty acid. The component (b) may be a mixed fatty acid or a single fatty acid.

  The blending ratio of the component (b) in the composition is 0.5 to 10% by mass, preferably 0.5 to 5% by mass, and more preferably 0.5 to 3% by mass. If it is 0.5% by mass or more, sock washing performance is good, and if it is 10% by mass or less, stability of the composition is improved.

<(C) component>
As the chelating agent of component (c), known ones used for liquid detergents can be used, and in the present invention, it is preferable to blend a low molecular chelating agent from the viewpoint of liquid stability. A chelating agent of 500 or less is preferred. For example,
Aminopolyacetic acid such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid, diencoric acid (284) or a salt thereof,
Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid and the like, or salts thereof,
Examples thereof include aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), and alkali metal or lower amine salts thereof.

  The mixing ratio of the component (c) in the composition is 0.5 to 5% by mass, preferably 0.5 to 4% by mass, more preferably 1 to 3% by mass when regarded as the acid type. . If it is 0.5% by mass or more, sock washing performance is good, and if it is 5% by mass or less, enzyme stability is improved.

<(D) component>
Examples of the component (d) enzyme include cellulase, amylase, pectinase, protease, lipase and the like, and protease is preferred.

  A suitable protease is an alkaline protease having an optimum pH of 8 or more, preferably 8-11. Examples of such proteases include Alcalase, Sabinase, Evalase (Novozyme, registered trademark), Perfect (Genenco, registered trademark), KAP4.3G, KAP11.1G (All, Kao, registered trademark). Etc.

  (D) Although the compounding quantity of a component is adjusted suitably, in the case of a protease, the casein decomposition | disassembly activity (henceforth protease activity) of the protease shown below is 1g of cleaning agents from a viewpoint of a mud dirt cleaning property improvement. Preferably, the protease is blended so as to have an activity of 5 to 1000 mPU / g, more preferably 10 to 800 mPU / g, and most preferably 50 to 500 mPU / g. In this case, from the viewpoint of stability, it is desirable to use a protease having an activity per gram of enzyme protein, that is, a specific activity of 5000 mPU / g or more, preferably 20000 mPU / g or more.

<Method for Measuring Casein Degrading Activity of Protease>
After keeping 1.0 mL of 50 mM borate buffer (pH 10) containing 1% (w / v) casein at 30 ° C. for 5 minutes, 0.1 mL of the enzyme solution is added and the reaction is performed for 15 minutes. Add 2.0 mL of the reaction stop solution (0.11 M trichloroacetic acid-0.22 M sodium acetate-0.33 M acetic acid), leave it at room temperature for 30 minutes, filter, and remove the acid-soluble protein in the filtrate from Lowry et al. Quantified by a variation of the method. That is, 2.5 mL of an alkaline copper solution [1% sodium tartrate / potassium: 1% copper sulfate: 1% sodium carbonate = 1: 1: 100] was added to the filtrate and allowed to stand at room temperature for 10 minutes. 0.25 mL of a reagent (Kanto Chemical Co., Ltd. diluted twice with ion-exchanged water) was added, and the mixture was kept at 30 ° C. for 30 minutes, and then the absorbance at 660 nm was measured. One unit of enzyme (PU) was defined as the amount of enzyme required to liberate an acid-soluble proteolysate corresponding to 1 mmol of tyrosine per minute in the above reaction.

<(E) component>
(E) As an enzyme stabilizer of a component, a boron compound, a calcium ion source (calcium ion supply compound), a bihydroxy compound, and formic acid are mentioned. As the boron compound, borax, boric acid, sodium borate, calcium chloride as the calcium ion source, calcium acetate as the bihydroxy compound, glycerin, 1,2-hexanediol, 1,2-dodecanediol, glucose, Preferred examples include sorbitol and maltose. Of these, calcium chloride is particularly preferable.

  The blending ratio of the component (e) in the composition is adjusted by the enzyme used, but it is preferably 0.01 to 5% by mass, more preferably 0.01% to 5% by mass in order to maintain stability and not affect storage stability. It is 0.05-3 mass%, Most preferably, it is 0.05-2 mass%. Enzyme stability is improved above the lower limit, and stability of the composition is good below the upper limit. In the present invention, even when an enzyme stabilizer, particularly a calcium ion source and a fatty acid are used in combination, they can be blended stably without affecting the composition.

<Other ingredients>
<(F) Other surfactant>
Examples of other surfactants other than the component (a) include anionic surfactants, cationic surfactants, and amphoteric surfactants. The anionic surfactant has a branched chain or straight chain alkyl group or alkenyl group having 8 to 20 carbon atoms and an average carbon number of 10 to 18, and a sulfonic acid group as the anionic group Or what has a sulfate group is preferable. As specific surfactants, alkyl benzene sulfonate, alkyl sulfate ester salt, one or two of oxyethylene groups may be oxypropylene groups, polyoxyethylene alkyl ether having an average addition mole number of 1 to 5 Examples thereof include sulfate ester salts (wherein the average added mole number includes alkyl sulfate ester salts) and alkane sulfonates. Preferably, it is an alkyl sulfate ester salt or an alkylbenzene sulfonate. Examples of the salt include alkali metal salts such as sodium and potassium described later, alkanolamine salts described later, or alkaline earth metal salts such as magnesium and calcium. The anionic surfactant may be added in an acid form in the liquid detergent and neutralized with alkali in the system.

The cationic surfactant is a primary to tertiary amine having a long-chain alkyl group (excluding alkanolamine described later), preferably having an ether bond, an ester bond or an amide bond in the middle. Mention may be made of cationic surfactants having one or two alkyl groups having 8 to 22 carbon atoms, the remainder being a hydrogen atom or an alkyl group optionally having a hydroxy group having 4 or less carbon atoms. it can. As the liquid detergent, the long chain alkyl group is preferably one quaternary ammonium type surfactant or a tertiary amine.
Examples of the amphoteric surfactant include sulfobetaine or carbobetaine whose alkyl group has 10 to 18 carbon atoms.

  In the case of an anionic surfactant, the surfactant is in the acid form. In the case of a cationic surfactant, the counter anion is not counted in the case of a quaternary salt. When converted as a hydrogen atom, it is preferably 1 to 20% by mass, more preferably 5 to 15% by mass in the present composition.

<Other ingredients>
<(G) Alkaline agent>
The liquid detergent composition of the present invention preferably contains an alkaline agent. Examples of the alkali agent include alkanolamines having 1 to 3 alkanol groups having 2 to 4 carbon atoms in general alkanols in liquid detergents, in addition to alkali metal hydroxides, alkali metal carbonates, and the like. Of these, the alkanol is preferably a hydroxyethyl group. Except for the alkanol group, they are a hydrogen atom, a methyl group or an ethyl group. In the present invention, monoethanolamine and triethanolamine are preferable, and monoethanolamine is particularly preferable.

  The alkaline agent can be used as a pH adjuster described later. Moreover, although it may mix | blend as a counter salt of above-mentioned (b) component, (c) component, and (g) component, the presence of an alkaline agent is judged by the pH in a composition being alkaline at 25 degreeC. be able to.

  In this invention, Preferably alkanolamine is contained 0.5-8 mass%, More preferably, 1-5 mass% is contained.

  In the composition of the present invention, components that are conventionally known to be blended in liquid detergents can be blended. For example, alcohols such as ethanol and propanol, glycols such as ethylene glycol, diethylene glycol, propylene glycol, diethylene glycol monobutyl ether, etc., which are classified as so-called solvents, as viscosity reducers and solubilizers, have a molecular weight of 200 or more and several thousand low Polyalkylene glycols such as polyethylene glycol and polypropylene glycol with molecular weight, polyoxyalkylene benzyl ether, polyoxyalkylene phenyl ether (phenoxyethanol, polyoxyethylene alkylphenyl ether [EO average addition mole number 0 to 5]), etc .; other than solvent As phase adjusters, so-called hydrotropes, para-toluenesulfonic acid, benzoates (also effective as preservatives), urea, etc .; recontamination inhibitors and dispersions Polyacrylic acid, acrylic acid-maleic acid copolymer, and polymers described in claims 1 to 21 (page 1, column 3, line 5 to page 3, column 4, line 14) of JP-A-59-62614 Polymers having a carboxylic acid group, etc .: Polyvinyl pyrrolidone, etc. as a color transfer inhibitor; Tinopearl CBS (made by Ciba Specialty Chemicals), Whitetex SA (made by Sumitomo Chemical), etc. as fluorescent dyes; Silica, silicone as an antifoaming agent, butylhydroxytoluene, distyrenated cresol, sodium sulfite, sodium hydrogensulfite and the like as an antioxidant; coloring agents; fragrances; antibacterial preservatives and the like.

  The composition of this invention mix | blends water with said each component. Water is the adjustment amount which makes the whole 100 mass%.

  The pH of the composition of the present invention (7.2 of JIS Z 8802) is preferably 8 to 11 (25 ° C.) from the viewpoint of detergency. The pH is adjusted with a known alkali or acid.

  The components shown in Tables 1 and 2 were mixed to obtain compositions of Examples and Comparative Examples. The following evaluations were performed using the obtained compositions. The results are shown in Tables 1 and 2. Comparative Example 7 could not be evaluated because the composition was separated. The pH was adjusted with an aqueous sodium hydroxide solution and an aqueous hydrochloric acid solution.

[Enzyme stability evaluation]
After holding 1 mL of 50 mM borate buffer (pH 10.5) containing 1% (w / v) casein (Hammerstein; manufactured by Merck) for 5 minutes at 30 ° C., add 0.1 mL of enzyme solution. And reacted at 30 ° C. for 15 minutes.

  Next, 2 mL of TCA solution (0.11 M trichloroacetic acid, 0.22 M sodium acetate, 0.33 M acetic acid) was added and allowed to stand at room temperature for 10 minutes, and then the acid-denatured protein was removed by filtration and contained in the filtrate. The acid-soluble protein degradation product was quantified by the Raleigh method. That is, 2.5 mL alkaline copper solution [1% (w / v) potassium sodium tartrate aqueous solution, 1% (w / v) copper sulfate aqueous solution, sodium carbonate 0.1 M sodium hydroxide aqueous solution dissolved in 0.5 mL of filtrate (A mixture of sodium carbonate concentration 2% (w / v) at 1: 1: 100 (v / v)), and kept at 30 ° C. for 10 minutes, then 0.25 mL of diluted phenol reagent (phenol Further, a reagent diluted twice with ion-exchanged water) was added and kept at 30 ° C. for 30 minutes, and then the absorbance at 660 nm was measured.

The result of adding the enzyme solution after adding the TCA solution and allowing to stand at room temperature for 10 minutes was used as a blank. The enzyme activity stability was determined by the following formula from the enzyme activity before storage of the liquid detergent composition shown in Table 1 and the enzyme activity after storage at 40 ° C. for 14 days.
Enzyme activity stability (%) = ([Enzyme activity after storage at 40 ° C./14 days] / [Enzyme activity before storage]) × 100
It can be judged that the enzyme stability is excellent at 80% or more.

[Sock cleaning performance]
10 pairs of socks worn by adult boys (Gunze Co., Ltd., material: cotton, nylon, polyurethane, color: white) were divided into two pairs on the left and right, and each was washed in a washing machine with a standard detergent and an evaluation detergent. (Detergent usage 37.5g / 45L, 20 ℃ tap water). Ten professional panelists compared socks after washing with a pair of white lights, and judged according to the following criteria.

1 point: Good stain removal compared to the standard detergent 0 point: Equivalent to the standard detergent -1 point: Bad stain removal compared to the standard detergent 10 panel judgment results were summed up for each paneler. The average value of the names was obtained, and the decimal point was rounded off to be used as a score for removing dirt. It can be judged that dirt removal is excellent with an evaluation score of 4 or more. Detergents used for cleaning evaluation are shown below.

Socks cleaning performance (1); reference detergent is Comparative Example 2 (immediately after compounding), evaluation detergents are Examples 1 to 5 and Comparative Examples 1 to 8 (immediately after compounding; except for Comparative Example 2)
Socks cleaning performance (2); reference detergent is Comparative Example 2 (immediately after preparation), evaluation detergents are Examples 1 to 5 and Comparative Examples 1 to 8 (after storage at 40 ° C. for 2 weeks; except for Comparative Example 2)

(A) Component (Note)
(A-1) Component (a-1-1): A secondary alcohol having 12 to 14 carbon atoms added with an average of 7 moles of EO, containing no unreacted alcohol and having a peak value of 7 Activator (Softanol 70; manufactured by Nippon Shokubai Co., Ltd.)
(A-1-2): Nonionic surfactant having an average of 10 moles of EO added to a primary alcohol having 10 to 14 carbon atoms and having a peak value of 11 (a-1-3): A primary alcohol having 10 to 14 carbon atoms in which EO is averaged to 7 moles, PO is averaged to 2 moles, and EO is averagely 3 moles in order, and the peak value of the total moles of EO and PO Is a nonionic surfactant having 12 (a-1-4): a primary alcohol having 10 to 14 carbon atoms in which EO is added in an average of 10 moles and PO is added in an order of 1 mole in the order of EO and Nonionic surfactant component (a-2) having a peak value of 12 among the total number of moles of PO added (a-2): 3 moles of EO is added on average to secondary alcohols having 12 to 14 carbon atoms. A non-ionic field that contains no unreacted alcohol and has a peak value of 3 Active agent (SOFTANOL 33; Co. Nippon Shokubai)
(A-2-2): A nonionic surfactant having an average of 1 mol of EO added to a primary alcohol having 10 to 14 carbon atoms and having a peak value of 0.
(A-2-3): A nonionic surfactant having an average of 4 moles of EO added to a primary alcohol having 10 to 14 carbon atoms and having a peak value of 3.
(A-2-4) A nonionic surfactant obtained by adding an average of 1 mol of PO to lauryl alcohol and having a peak value of 1.
(A-2-5) Non-ion having a peak value of the total number of added moles of EO and PO, which is obtained by adding an average of 1 mole of EO and 1 mole of PO to secondary alcohol having 12 carbon atoms Surfactant.
Note: The numerical values represented by the general formula (I) are shown in Tables 1 and 2. In the compositions of Tables 1 and 2, the peak value of the AO addition mole number distribution in the nonionic surfactant of the component (a) was the same as the peak value of the component with the largest amount.
(B) Component (b-1): LUNAC L-55 (coconut oil fatty acid; manufactured by Kao Corporation)
(B-2): LUNAC SO-90L (oleic acid; manufactured by Kao Corporation)
(C) Component (c-1): Citric acid (c-2): Dequest 2010 (manufactured by Solusia Japan)
(C-3): EDTA
(D) Component (d-1): Everase 16.0L-EX (protease, Novozyme)
A protease with a casein degradation activity of 8400 PU / L was used. The substrate used for the measurement of protease activity was derived from milk (Hammersten formulation) and purchased from Wako Pure Chemical Industries. Incidentally, the protease activity when the protease product is mixed in the detergent at a concentration of 1% by mass is 84 mPU / g per gram of the detergent.

(E) component (e-1): calcium chloride (e-2): borax (e-3): formic acid (others)
Anionic surfactant (1): Polyoxyethylene alkyl ether sulfate (linear alkyl having 10 to 14 carbon atoms, EO average addition mole number 3, sodium salt)
Anionic surfactant (2): Linear alkylbenzene sulfonic acid having 10 to 14 carbon atoms Polymer (1): Polymer compound synthesized by the method of Synthesis Example 1 on page 4, paragraph 0020 of JP-A-10-60476 (2): Polyethylene glycol (weight average molecular weight 2000)
Fluorescent dye: Chino Pearl CBS-X (manufactured by Ciba Specialty Chemicals)
Dye (1): Kayashi Ontakis ENA
Dye (1): Green No. 202 pH adjuster; hydrochloric acid or sodium hydroxide (mixed to adjust stock solution pH)

Claims (3)

A liquid detergent composition containing the following components (a) to (e):
(A) (a-1) Polyoxyalkylene alkyl ether type obtained by adding an average of 7 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an alcohol having 8 to 22 carbon atoms in the alkyl group A polyoxy compound obtained by adding an average of 1 to 4 moles of an alkylene oxide having 2 to 4 carbon atoms to a nonionic surfactant and (a-2) an alcohol having 8 to 22 carbon atoms in the alkyl group. It consists of an alkylene alkyl ether type nonionic surfactant, contains 6 to 15% by mass of the compound represented by the following general formula (I) in the component (a), and has a peak value of the added mole number of alkylene oxide at least. Nonionic surfactant in 7-20 10-50% by weight
R—O (AO) _n H (I)
[Wherein, R is a hydrocarbon group having 8 to 22 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, and n is a number selected from 0, 1 and 2]
(B) Fatty acid having an average carbon number of 8 to 20 0.5 to 10% by mass
(C) Chelating agent 0.5-5 mass%
(D) Enzyme (e) Enzyme stabilizer The liquid according to claim 1, wherein (a-2) / (a-1), which is a blending ratio (mass ratio) of the component (a-1) and the component (a-2), is 0.05 to 1. Detergent composition. The liquid detergent composition according to claim 1 or 2, wherein the component (e) is an enzyme stabilizer selected from a boron compound, a calcium ion source (calcium ion supply compound), and formic acid.