JP2002069489A - Liquid detergent formation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition which is highly effective in washing against stubborn sebum stain such as stain on collar or cuff, or the like, and excellent in stability of enzyme and solution. SOLUTION: The liquid detergent composition contains (a) a nonionic surfactant represented by the following general formula (I), (b) an enzyme, (c) a stabilizer of the enzyme and (d) an organic polycarboxylic acid and/or its salt. R1O(EO)s/(PO)tH (I) [wherein, R1 is an 8-20C alkyl or an alkenyl group, EO is an ethylene oxy group, PO is a propylene oxy group, s and t are average addition number of moles, s is 4-16, t is 1-5, EO and PO may be added by random addition or block addition, additive order of EO and PO is not in different.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid detergent composition. More specifically, the present invention relates to a liquid detergent composition which has a high cleaning effect on stubborn sebum stains such as collar and cuff stains, and is excellent in enzyme stability and solution stability.

[0002]

2. Prior Art and Problems to be Solved by the Invention
A weak alkaline powder detergent is often used for washing clothes in ordinary households. However, powder detergents inherently have the problem of undissolved residue under adverse conditions (low temperature, low agitation).
On the other hand, liquid detergents are excellent in solubility and can be directly applied to stubborn sebum stains such as collar and cuff stains, but due to restrictions on formulation, sufficient detergent power can be obtained compared to powder detergents. Not not. In order to enhance the detergency of liquid detergents, attempts have been made to incorporate enzymes and the like into liquid detergents. Since enzymes are easily deactivated in an aqueous medium, it is necessary to devise a method for incorporating them into an aqueous liquid detergent. JP-A-52-1890
Japanese Patent Publication No. 4 discloses a liquid detergent composition containing a specific concentration of free calcium ions, which is excellent in enzyme storage stability, and is further effective against stubborn sebum stains such as collar and cuff stains. It is desired to enhance the cleaning effect.

Therefore, an object of the present invention is to provide a liquid detergent composition which has a high cleaning effect on stubborn sebum stains such as collar and cuff stains and is excellent in enzyme stability.

[0004]

[In the formula, R ¹ represents an alkyl group or an alkenyl group having 8 to 20 carbon atoms, EO represents an ethyleneoxy group, and PO represents a propyleneoxy group. s and t are average addition mole numbers, s is 4 to 16 and t is 1 to 5. EO and PO may be either random addition or block addition, and the order of adding EO and PO does not matter. ]

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION <Component (a)> The component (a) of the present invention is represented by the nonionic surfactant represented by the general formula (I), and particularly represented by the following general formula (II). By using a nonionic surfactant, it is possible to obtain high detergency against stains on the collar and cuffs. R ² O(EO) _p (PO) _q (EO) _r H (II) [wherein R ² represents an alkyl group or an alkenyl group having 8 to 20 carbon atoms, preferably 9 to 16 carbon atoms, and EO is an ethyleneoxy group. , PO represents a propyleneoxy group. p, q and r
Represents the average number of moles added, p>0, q=1 to 4, r>
0, p+q+r=6 to 14, and p+r=5 to 12.
Preferably, p+q+r=7-14, p+r=6-12,
q=1 to 2. EO and PO are block additions,
The order of addition is EO, PO, EO. ].

The nonionic surfactant of the general formula (II) is an ethylene oxide (hereinafter referred to as EO) in an alcohol having an alkyl group of R ² which is synthesized by a well-known method or is derived from natural fats and oils. , Propylene oxide (hereinafter referred to as PO) are added in this order, and then EO is added again to synthesize.

The liquid detergent composition of the present invention contains 5 to 50% by weight, more preferably 5 to 40% by weight of the nonionic surfactant as the component (a).
It is preferable that the content thereof be 10% by weight, particularly 10 to 40% by weight.

<Component (b)> Examples of the component (b) of the present invention include cellulases, amylases, pectinases, proteases, lipases and the like. Among them, one or more selected from cellulases and proteases are preferable. Suitable cellulases include bacterial cellulase and fungal cellulase, and those having an optimum pH of 5 to 9.5 are particularly preferable. As the cellulase, Japanese Patent Laid-Open No.
Those described in JP-A-3-264699, page 4, upper right column, line 13 to page 5, lower right column, line 12 can be used, and particularly, the alkaliphilic microorganism Bacillus sp. KSM-635.
It is preferable to use an alkaline cellulase produced from (FERM BP-1485) or a mutant strain thereof.
Also, JP-A-8-53699, column 5, line 3 to 21.
It is also possible to use the cellulase in the row. More specifically, KAC500 (manufactured by Kao Corporation), cellzyme, carezyme (all manufactured by Novo Nordisk) and the like can be mentioned. Further, a suitable protease is an alkaline protease having an optimum pH of 8 or more, preferably 8 to 11. Examples of such proteases include alcalase, savinase, evalase (all are registered trademarks of Novo Nordisk, Inc.), Plafect (registered trademark of Genenco, Inc.), KAP4.3G, KAP11.1G.
(These are all registered trademarks of Kao Co., Ltd.), but KAP4.3G and KAP11.1G are particularly excellent.

The liquid detergent composition of the present invention contains the component (b) in an amount of 0.005 to 3% by weight, particularly 0.0
It is preferable to contain 1 to 2% by weight.

<Component (c)> Examples of the enzyme stabilizer which is the component (c) of the present invention include a boron compound, a calcium ion source (calcium ion supplying compound) and a bihydroxy compound. Boron, boric acid and sodium borate as the boron compound, calcium chloride and calcium acetate as the calcium ion source, glycerin, 1,2-hexanediol as the bihydroxy compound,
Preferred examples include 1,2-dodecanediol, glucose, sorbitol and maltose. Among them, calcium chloride is particularly excellent in economic efficiency. The liquid detergent composition of the present invention contains (C) component which is an enzyme stabilizer in an amount of 0.01 to 3% by weight, preferably 0.01 to 2% by weight, and 0.01 to 0.5% by weight. Is more preferable.

<Component (d)> The component (d) of the present invention includes (d1) nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, Aminopolyacetic acid such as triethylenetetraaminehexaacetic acid and dienecoric acid or salts thereof, (d2) diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, Organic acids such as gluconic acid, carboxymethyl succinic acid, and carboxymethyl tartaric acid, or salts thereof, and (d3) polyacrylic acid or salts thereof, polymaleic acid or salts thereof, carboxymethyl cellulose or salts thereof, acrylic acid-maleic acid copolymer Compound or salt thereof, maleic anhydride-diisobutylene copolymer or salt thereof, maleic anhydride-methyl vinyl ether copolymer or salt thereof, maleic anhydride-isobutylene copolymer or salt thereof, maleic anhydride-vinyl acetate copolymer Carboxylic acid-based polymers such as polymers or salts thereof, and JP-A-59-626.
The polymers and the like described in claims 1 to 21 (page 1, column 3, line 5 to page 3, column 4, line 14) of JP-A-14 are mentioned. Among them, citric acid or a salt thereof from the viewpoint of solution low temperature stability. And carboxylic acid type polymers are preferable, and carboxylic acid type polymers are particularly preferable.

The liquid detergent composition of the present invention preferably contains the component (d) in an amount of 0.01 to 10% by weight, further 0.01 to 5% by weight, and particularly 0.01 to 3% by weight.

<Other Components> The liquid detergent composition of the present invention has (e) 8 to 14 carbon atoms in view of foaming and rinsing properties.
The saturated fatty acid and/or salt thereof (hereinafter referred to as component (e)) can be contained. Examples of the component (e) include caprylic acid, capric acid, lauric acid and myristic acid. As the salt, alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium,
Examples include mono-, di-, alkanolamine salts such as triethanolamine salt, etc., but especially in terms of improving liquid stability,
Alkanolamine salts are preferred. In addition, (e) component as a main component manufactured by Kao Lunack L-50, and (e)
Lunack L-70 and Lunack L- made by Kao
Commercially available products such as 98 can be used as a feedstock for the component (e). Although fatty acids other than the component (e) may be contained in the final composition, they are preferably 0 to 5% by weight, more preferably 0 to 3% by weight in the composition, from the viewpoint of detergency and liquid stability. %. The liquid detergent composition of the present invention contains the component (e) in an amount of 1 to 10% by weight, further 1 to 5% by weight, and particularly 1 to 3% by weight.
It is preferable to contain.

As the surfactant, a conventionally known surfactant can be used. In order to improve the detergency, it is preferable to use an anionic surfactant or a nonionic surfactant as the main surfactant as the surfactant.
From the viewpoint of enzyme stability, it is preferable to use a nonionic surfactant as the main surfactant.

The anionic surfactant has 10 carbon atoms.
Alkali metal salts such as linear alkylbenzene sulfonates having an alkyl chain of -18, alkyl sulfate ester salts, polyoxyalkylene alkyl ether sulfate salts, alpha sulfo fatty acid alkyl salts, and preferably methyl ester salts are preferred. As the counterion of the anionic surfactant, in addition to alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and/or alkanolamines such as mono-, di-, triethanolamine and the like are used, but especially alkanolamines. The use of is preferable because the liquid stability is improved.

As the nonionic surfactant, the following (1) to (3) can be used in addition to the component (a) of the present invention. (1) Having an alkyl group derived from a linear primary alcohol or a linear secondary alcohol having an average carbon number of 8 to 20 or an alkyl group or an alkenyl group derived from a branched alcohol, and adding 1 to 20 mol of EO on average. Polyoxyethylene alkyl or alkenyl ether. (2) A polysaccharide surfactant represented by the following general formula (III). R ³ —(OR ⁴ ) _x G _y (III) [wherein R ³ is a linear or branched alkyl group having 8 to 18 carbon atoms, an alkenyl group, or an alkylphenyl group, R ⁴
Represents an alkylene group having 2 to 4 carbon atoms, G represents a residue derived from a reducing sugar having 5 or 6 carbon atoms, x represents a number having an average value of 0 to 6, and y represents a number having an average value of 1 to 10. (3) Fatty acid alkanolamide and polyhydroxy fatty acid amide.

In order to impart flexibility to clothes and the like,
It is preferable to add a cationic surfactant such as a mono-long-chain alkyl or alkenyl quaternary ammonium salt, but in the present invention, it is preferable that the cationic surfactant is not substantially contained from the viewpoint of enzyme stability. ..

Further, in the detergent composition of the present invention, alkali metal hydroxides, silicates, carbonates such as sodium carbonate, and alkali agents such as alkanolamines of 0.01 to
10% by weight; alcohols such as ethanol, glycols such as ethylene glycol and propylene glycol,
Paratoluenesulfonic acid, benzoate (also effective as a preservative), and a thinning agent or solubilizing agent such as urea 0.0
1 to 30% by weight; 0.01 to 10% by weight of phase modifier or detergency improver such as polyoxyalkylene benzyl ether, polyoxyalkylene phenyl ether; polyethylene glycol having an average molecular weight of 5000 or more, naphthalene sulfonate formalin condensate 0.01 to 10% by weight of anti-staining agent or dispersant such as polyvinylpyrrolidone 0.01 to 10% by weight of bleaching agent such as sodium percarbonate or sodium perborate %;
Tetraacetylethylenediamine, JP-A-6-3167
0.01 to 10% by weight of a bleaching activator such as a bleaching activator represented by the general formula (I-2) to (I-7) of No. 00; Chinopearl CBS (manufactured by Ciba Specialty Chemicals) or Whitex SA (Sumitomo Chemical Co., Ltd.) fluorescent dye
001 to 1% by weight; 0.1 to 2% by weight of the soft base such as silicone according to claim 1 of JP-A-10-60480; 0.01 to 2% by weight of antifoaming agent such as silica; butylhydroxy Antioxidants such as toluene, distyrenated cresol, sodium sulfite and sodium bisulfite 0.0
1 to 2% by weight; a bluing agent, a fragrance, an antibacterial preservative and the like can be added. The composition of the present invention has the above (a),
It consists of components (b), (c), (d), and (e), optional components, and the balance water.

[0019]

The liquid detergent composition of the present invention has a high cleaning effect on stubborn sebum stains such as collar and cuff stains.
Excellent enzyme stability and solution stability.

[0020]

EXAMPLES The liquid detergent compositions shown in Table 1 were prepared, and the obtained compositions were used for the following evaluation of detergency, low temperature stability and enzyme activity stability. The results are shown in Table 1.

[Evaluation of Detergency] Collar Stain Test Piece The neck portion of a cotton/polyester blended shirt that had been worn for 3 days was cut and collected, and the collar pieces were divided into five groups according to the degree of dirt, and the second piece from the one with the most dirt. Using the collar pieces of the above group, they were subjected to cleaning evaluation. Washing conditions A two-tub type washing machine (Toshiba Galaxy 3.6 VH-360S1) was prepared, and 40 liters of tap water was put into the washing tub, and 1.4 kg of cotton underwear and 0.6 kg of cotton / I put on an underwear shirt that was not worn with polyester blend. Thirty
One piece was prepared by sewing 5 pieces of a collar piece for cleaning evaluation to a cotton cloth of 30 cm ² and placed in a washing tub, and 26.67 mL of the liquid detergent composition shown in Table 1 was placed therein and washed for 10 minutes. Then, it was dehydrated for 1 minute and rinsed under running water for 15 minutes at a flow rate of 15 l/min. Then, it was dehydrated for 5 minutes and naturally dried in a room. Detergency Criteria A collar stain detergency was judged by one skilled panelist (hereinafter referred to as one experienced panelist) according to the following criteria. ◎: Stain is removed and satisfactory level ○: Stain is slightly left but satisfactory level △: Slight stain is left and unsatisfactory level ×: Stain is not removed much and unsatisfactory level The reliability of the judgment results of the panelists was confirmed by the Scheffe's one-pair comparison method by ten other panelists. That is, ◎ and ○ among the collar stain test pieces judged by one skilled panelist,
When the other 10 panelists tested by the Scheffe's one-pair comparison method using test pieces with adjacent results such as ○ and △, △ and × as samples, the judgment result of one skilled panelist was 95% confidence limit. It was judged that there was a significant difference.

[Evaluation of enzyme activity stability] 1% (w/v)
50 including casein (Hamastein; manufactured by Merck)
After holding 1 mL of mM borate buffer (pH 10.5) at 30° C. for 5 minutes, 0.1 mL of enzyme solution was added, and 3
The reaction was carried out at 0°C for 15 minutes. Next, TCA solution (0.11
M trichloroacetic acid, 0.22M sodium acetate, 0.3
3M acetic acid) (2 mL) was added, the mixture was allowed to stand at room temperature for 10 minutes, the acid-denatured protein was removed by filtration, and the acid-soluble protein hydrolyzate contained in the filtrate was quantified by the Lowry method. That is, 2.5 mL of an alkaline copper solution [1% (w/v) potassium sodium tartrate aqueous solution, 1% (w/v) copper sulfate aqueous solution, 0.1 M sodium hydroxide aqueous solution of sodium carbonate was dissolved in 0.5 mL of the filtrate. Substance (sodium carbonate concentration 2% (w/v) 1:1:100 (v/v)
Mixture) was added, and the mixture was kept at 30°C for 10 minutes, and then 0.25 mL of diluted phenol reagent (phenol reagent double diluted with ion-exchanged water) was added and kept at 30°C for 30 minutes. After that, the absorbance at 660 nm was measured. The TCA solution was added, the mixture was allowed to stand at room temperature for 10 minutes, and then the enzyme solution was added. The enzyme activity stability was determined by the following formula from the enzyme activity of the liquid detergent composition in Table 1 before storage 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.

The stability of the obtained enzyme activity was evaluated according to the following criteria. A: Enzyme activity stability of 80% or more B: Enzyme activity stability of 50% or more and less than 80% B: Enzyme activity stability of 30% or more and less than 50% X: Enzyme activity stability of less than 30%.

[Evaluation of low temperature stability] 50 mL sample bottle (No. 6 wide-mouth standard bottle, glass, diameter 40 m
m, the height of 80 mm) was filled with 40 mL of the liquid detergent composition shown in Table 1, covered with a lid, and then stored in a thermostatic chamber at -5°C for 3 hours.
Let stand for 0 days. Regarding the stability of the liquid, the appearance was visually evaluated according to the following criteria. ◯: A homogeneous liquid phase with excellent fluidity ×: Separation or precipitation is observed

[0025]

[Table 1]

(Note) A-1: Nonionic surfactant, average of 7 mol of EO and average of 2 of PO in a linear primary alcohol having 12 to 14 carbon atoms.
Molar, EO in an average of 3 moles in block order. A-2: Nonionic surfactant, average of 5 moles of EO and average of 2 moles of PO in a linear primary alcohol having 12 to 14 carbon atoms.
Molar and EO block-added in the order of 3 mols on average. A-3: E to a linear primary alcohol having an average carbon number of 12
An average of 12 moles of O and an average of 2 moles of PO were randomly added. A-4: E to a linear primary alcohol having an average carbon number of 12
Randomly added O of 8 mol on average and PO of 1 mol on average. Protease: Evalase 16.0 L-EX, manufactured by Novo Nordisk Bioindustry Co., Ltd. Carboxylic acid polymer: 1 of JP-A-10-60476.
Phenoxypolyethylene glycol, acrylic acid, maleic acid copolymer synthesized by the method described on page 1, lines 6 to 13 (weight average molecular weight 10000, solid content 51.2%)-nonionic surfactant 1: softanol 70H, carbon An average of 7 mol of EO added to a secondary alcohol having a number of 12 to 14, manufactured by Nippon Shokubai Co., Ltd. Anionic surfactant 1: The number of carbon atoms in the alkyl group is 10
14 linear alkylbenzene sulfonic acids (average molecular weight 3
23) ・Anionic surfactant 2: sodium salt of alkyl ether sulfate obtained by adding 3 mol of EO to an average linear chain primary alcohol having 12 carbon atoms ・anionic surfactant 3: linear chain having an average carbon number of 14 Primary alkylsulfate sodium salt-Chinopearl CBS: fluorescent dye, manufactured by Ciba Specialty Chemicals

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshihiro Oki 1334 Minato Minato, Wakayama, Wakayama Prefecture Kao Co., Ltd. (72) Inventor Toshio Miyake 1334 Minato Minato, Wakayama, Wakayama F Term, Kao Co., Ltd. (reference) 4H003 AB03 AB27 AB31 AC08 AC09 AC23 BA12 DA01 EA12 EA18 EA19 EB04 EB05 EB14 EB22 EB32 EB34 EC02 ED02 ED29 FA16 FA47

Claims (3)

[Claims] 1. A nonionic surfactant represented by the following general formula (I), (b) an enzyme, (c) an enzyme stabilizer and (d) an organic polyvalent carboxylic acid and/or a salt thereof. A liquid detergent composition containing. R ¹ O(EO) _s /(PO) _t H (I) [In the formula, R ¹ represents an alkyl group or an alkenyl group having 8 to 20 carbon atoms, EO represents an ethyleneoxy group, and PO represents a propyleneoxy group. s and t are average addition mole numbers,
s is 4 to 16 and t is 1 to 5. EO and PO may be either random addition or block addition. EO and PO
The addition order of is not limited. ] 2. The liquid detergent composition according to claim 1, further comprising (e) a saturated fatty acid having 8 to 14 carbon atoms and/or a salt thereof. 3. The liquid detergent composition according to claim 1, wherein the nonionic surfactant (a) is a compound represented by the following general formula (II). R ² O(EO) _p (PO) _q (EO) _r H (II) [In the formula, R ² represents an alkyl group or an alkenyl group having 8 to 20 carbon atoms, EO is an ethyleneoxy group, and PO is a propyleneoxy group. Represents. p, q and r represent the average number of moles added, p>0, q=1 to 4, r>0, p+q+r=6-1
4, p+r=5-12. EO and PO are block additions, and the order of addition is EO, PO, EO. ]