JPH10195499A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in detergency and having high stability and fluidity even in highly concentrated system by compounding a liquid detergent with a nonionic surfactant formed by block polymerization between ethylene oxide and propylene oxide in specific ratios. SOLUTION: This composition contains 10-50wt.% of a nonionic surfactant of the formula (R<1> is an 8-18C alkyl or alkenyl; EO is oxyethylene; PO is oxypropylene; (p), (q) and (r) are each average addition number of moles, satisfying the following relationships: (p)>0, (r)>0, (p+q+r)=6-14, (p+r)=5-12, (q) is 1-4), being pref. <=60wt.% in water content. The nonionic surfactant can be easily formed by addition reaction of an alkylene oxide to a higher alcohol. Thus, the respective amounts of any solvent and hydrotropic agent to be added to this composition can be reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid detergent composition excellent in washing performance and stability, such as for clothing and home use.

[0002]

BACKGROUND OF THE INVENTION Surfactants for liquid detergents include one or more of anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc., depending on the purpose. Are mixed and used in various ratios. A major problem with liquid detergents is that, when the proportion of the surfactant in the composition is high, a sharp increase in viscosity is likely to occur, and cloudiness and separation are likely to occur. For this reason, by adding various solvents and hydrotrope agents, the stability is prevented from deteriorating, and the viscosity is adjusted to be easy to use. However,
These solvents and hydrotropes do not directly improve the cleaning performance but increase the cost of the composition.

On the other hand, in recent years, attempts have been made to make liquid detergents more compact by reducing the amount of water used in the compositions by increasing the concentration of surfactants and reducing the amount of water used in the compositions. In particular, alcohol ethoxylate type nonionic surfactant in which ethylene oxide is added to higher alcohol,
In addition to having excellent cleaning performance against oily stains, and having a lower critical micelle concentration than anionic surfactants,
This is advantageous for downsizing. However, when the compounding amount of the nonionic surfactant is increased for the purpose of downsizing, there is a remarkable tendency to generate liquid crystal and the like, to deteriorate the stability of the composition and to lose the fluidity. Various studies have been made to overcome the disadvantages of the ethylene oxide addition type alcohol ethoxylate. JP-A-56-159296, JP-A-54-34306, JP-A-54-157110, JP-A-56-15289
No. 9 discloses a composition containing an alcohol ethoxylate to which ethylene oxide and propylene oxide are added, but the stability in a high-concentration compounding system was not sufficient.

Accordingly, an object of the present invention is to provide a liquid detergent composition which is excellent in stability and fluidity and has a high cleaning effect even when the amount of the alcohol alkoxylate type surfactant is increased. is there.

[0005]

Means for Solving the Problems As a result of various studies, the present inventors have found that a nonionic surfactant obtained by block-polymerizing ethylene oxide and propylene oxide at a specific ratio is blended in a liquid detergent to provide a detergency. It has been found that a liquid detergent composition which is excellent in stability and fluidity even in a high-concentration system, and which can reduce the amount of a solvent or a hydrotrope agent to be obtained, has completed the present invention.

That is, the present invention provides a liquid detergent composition containing 10 to 50% by weight of a nonionic surfactant represented by the following general formula (I). R ¹ -O- (EO) _p- (PO) _q- (EO) _r -H (I) wherein R ¹ represents an alkyl group or an alkenyl group having 8 to 18 carbon atoms, and EO represents an oxyethylene group , PO represents an oxypropylene group, p, q, and r each represent an average number of moles added, and p> 0, r> 0, p + q + r = 6 to 14, and p +
r = 5 to 12, and q = 1 to 4. Hereinafter, the liquid detergent composition of the present invention will be described in detail.

The nonionic surfactant of the present invention has the following general formula:
It is represented by (I). R ¹ -O- (EO) _p- (PO) _q- (EO) _r -H (I) In the general formula (I), R ¹ represents an alkyl group or an alkenyl group having 8 to 18 carbon atoms, And / or an alkyl group derived from a branched primary alcohol and / or a linear secondary alcohol. In the general formula (I), p and r are
Preferably, p ≧ r. If ethylene oxide and propylene oxide are out of the range of the addition order and the addition ratio defined by the above general formula (I), the optimal composition aimed at by the present invention cannot be obtained.

The nonionic surfactant represented by the general formula (I) used in the present invention can be synthesized by a known method, and can be easily obtained by adding an alkylene oxide to a higher alcohol. In the present invention, the method of adding an alkylene oxide is characterized in that, first, ethylene oxide is added, then propylene oxide is block-added, and further ethylene oxide is block-added. The catalyst used in this alkoxylation base catalyst, in addition to the acid catalyst, MgO-ZnO described in JP-A-7-227540, MgO-SnO, MgO- TiO 2 and MgO-SbO and JP-A-1-164437 It can be synthesized using a catalyst that gives a narrow alkylene oxide distribution, such as a similar Mg-based catalyst described in the publication. Among them, it is particularly preferable to use a base catalyst from the viewpoint of cost, and it is most preferable to use potassium hydroxide as a base.

The production conditions when potassium hydroxide is used as a catalyst are shown below. First, the raw material has 8 to 18 carbon atoms.
After charging potassium hydroxide to a saturated or unsaturated higher alcohol, the atmosphere is replaced with nitrogen, and 100 to 110 ° C, 10 to 50 to
Dehydrate at rr for 30 minutes to 1 hour. Then 100-170 ° C, 3
Perform the addition of ethylene oxide with ~6kg / m ^2, then 10
0 to 150 DEG ° C., performs the addition of propylene oxide under the conditions of 3~6kg / m ^2, again 100 to 170 ° C., after adding ethylene oxide under the conditions of 3~6kg / m ^2, the added potassium hydroxide and those It is obtained by neutralization with a molar amount of an acid agent (acetic acid, lactic acid, glycolic acid). The amount of each of ethylene oxide and propylene oxide is added according to the number of moles of the raw material alcohol so as to satisfy the condition of the general formula (I).

Hereinafter, one example of a specific manufacturing method will be described. 500 g of lauryl alcohol (trade name: Calcol 2098, manufactured by Kao Corporation) and potassium hydroxide were placed in a 5-liter rotary stirring autoclave equipped with two measuring tanks for ethylene oxide and propylene oxide.
After charging 3.0 g and purging with nitrogen, the temperature was raised to 110 ° C,
Dehydration was performed for 1 hour at torr. Next, the temperature was raised to 150 ° C., 592 g of ethylene oxide was introduced into the autoclave at a pressure of 3.5 kg / cm ² , and the reaction was continued until the pressure was reduced to a constant level. To 3
12 g was introduced into the autoclave at a pressure of 3.5 kg / cm ² , and the reaction was continued until the pressure decreased and became constant in the same manner as ethylene oxide. Thereafter, the temperature was raised again to 150 ° C., 592 g of ethylene oxide was introduced, and the reaction was continued until the pressure decreased and became constant. After completion of the reaction, the temperature is lowered and neutralized with 3.5 g of acetic acid to obtain the desired polyalkylene glycol lauryl ether of EO-PO-EO addition type.

The nonionic surfactant (I) of the present invention has excellent stability even at a relatively high concentration, and is incorporated in the composition in an amount of 10 to 50% by weight, preferably 20 to 40% by weight. You.

In the present invention, the nonionic surfactant represented by the above general formula (I) can be used in combination with another surfactant, and (A) the nonionic surfactant represented by the above general formula (I) can be used. One or more nonionic surfactants other than the nonionic surfactants, (B) anionic surfactant, (C) cationic surfactant, and (D) amphoteric surfactant are used. be able to. The total amount of surfactant incorporated in the composition is 10
It is preferably from 60 to 60% by weight, more preferably from 20 to 50% by weight.

Hereinafter, surfactants that can be used together will be specifically described. (A) As the nonionic surfactant other than the present invention, the following surfactants (1) to (4) can be used in combination. (1) A polyoxyethylene alkyl ether having an alkyl group derived from a linear primary alcohol or a linear secondary alcohol having 8 to 20 carbon atoms and having an average of 3 to 12 moles of ethylene oxide added thereto. (2) Polyoxyethylene alkyl ethers having an alkyl group derived from a branched alcohol having 8 to 20 carbon atoms and having an average of 3 to 12 moles of ethylene oxide added thereto. (3) An alkyl polysaccharide surfactant represented by the following general formula. R ^2- (OR ³ ) _x G _{y wherein} R ² is a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms, R ³ is an alkylene group having 2 to 4 carbon atoms, and G is The residue derived from the reducing sugar of Formula 5 or 6, x is a number having an average value of 0 to 6, and y is a number having an average value of 1 to 10. (4) Fatty acid alkanolamides and polyhydroxy fatty acid amides.

As the (B) anionic surfactant, the following (5) to (8) can be used. (5) An alkylbenzene sulfonate having an alkyl group having an average of 10 to 20 carbon atoms. (6) having an alkyl group derived from a linear primary alcohol or a linear secondary alcohol having an average carbon number of 10 to 20 or an alkyl group derived from a branched alcohol, and adding an average of 0.5 to 5 mol of ethylene oxide in one molecule; Alkyl ether sulfate. (7) An alkyl or alkenyl sulfate having an alkyl or alkenyl group having an average of 10 to 20 carbon atoms. (8) A fatty acid salt comprising a saturated or unsaturated fatty acid salt having an average carbon number of 8 to 20, and a mixture thereof. The counter ion of these anionic surfactants is selected from the group consisting of cations such as sodium, potassium, magnesium, calcium and alkanolamine and mixtures thereof. Particularly, sodium, potassium, monoethanolamine, diethanolamine and monomethyldiethanolamine are preferred. When an anionic surfactant is blended, it may be added to the detergent composition in the form of an acid and neutralized by adding an alkali agent containing these counterions.

As the cationic surfactant (C), amine salts or ammonium salts of mono- or long-chain alkyl having 12 to 20 carbon atoms can be blended.

(D) Examples of the amphoteric surfactant include alkylcarbobetaine, alkylsulfobetaine, alkylamidohydroxysulfobetaine, alkylamidoamine betaine, and alkylimidazoline betaine.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The balance of the composition of the present invention is water, but it is possible to add an optional component which is conventionally known to be added to a detergent. Such components include alcohols such as ethanol, ethylene glycol, polyethylene glycol having a molecular weight of 200 or more,
Glycols such as propylene glycol, and hydrotropes such as paratoluenesulfonic acid and urea can be blended, but it is the gist of the present invention to reduce the blending amounts of these substances other than cleaning components. Therefore, the total amount is preferably 10% by weight or less. In particular, when a lower alcohol such as ethanol is blended in a large amount, alcohol odor increases, which is not only unfavorable, but also lowers a flash point and is dangerous for consumers. Therefore, the amount of the alcohol is preferably 5% by weight or less, particularly preferably 3% by weight or less. Other optional components include polyoxyalkylene benzyl ether and polyoxyalkylene phenyl ether for improving detergency; nitrilotriacetate, ethylenediaminetetraacetate, and hydroxyethyl as polyvalent carboxylic acids having a divalent metal ion scavenging ability. Aminopolyacetates such as iminodiacetic acid and triethylenetetramine hexaacetate; salts such as malonic acid, succinic acid, diglycolic acid, malic acid, tartaric acid, and citric acid; polyacrylic acid having recontamination preventing ability and dispersing ability; Polymaleic acid, carboxymethylcellulose, maleic anhydride-diisobutylene copolymer, maleic anhydride-methylvinyl ether copolymer, maleic anhydride-isobutylene copolymer, maleic anhydride-vinyl acetate copolymer, and naphthalene sulfonate Formalin condensate, etc. Color transfer inhibitors such as polyvinylpyrrolidone; polymer of the polymer, JP-A-59-62614 publication, such as a salt of a polymer compound amylase,
Protease, lipase, cellulase, pectinase,
Enzymes such as glucosidase; enzyme stabilizers such as calcium chloride, calcium sulfate, formic acid, lactic acid, and boron (boron compound); fluorescent dyes such as Tinopearl CBS (manufactured by Ciba Geigy); amino-modified silicone, polyether-modified silicone, and carboxy-modified Fiber-modified silicones such as silicone; silica, silicone oil,
Silicone defoamer consisting of emulsifier; butylhydroxytoluene, distyrenated cresol, sodium sulfite,
Antioxidants such as sodium bisulfite; Proxel B
Antimicrobial preservatives such as DN (manufactured by Zeneca Corporation) and Caisson CG (manufactured by Rohm and Haas Japan KK); and other bluing agents, fragrances and the like.

[0018]

The liquid detergent composition of the present invention has excellent cleaning performance and stability.

[0019]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

<Method of synthesizing nonionic surfactants 1 to 6>
The nonionic surfactants 1 to 6 used in Example 1 were synthesized under the following conditions by changing the amount of ethylene oxide or propylene oxide added according to the number of moles added. The synthesis conditions are shown below. Lauryl alcohol (trade name: Calcol 2098, manufactured by Kao Corporation) was placed in a 5 ml rotary stirring type autoclave equipped with two measuring tanks for ethylene oxide and propylene oxide.
500 g and 3.0 g of potassium hydroxide were charged, and after purging with nitrogen, the temperature was raised to 110 ° C., and dehydration was performed at 40 torr for 1 hour.
Then, the temperature was raised to 150 ° C., and 3.5 kg of ethylene oxide [amount corresponding to p in the general formula (I)] corresponding to the target compound was added.
/ M ^{2 into} the autoclave, react until the pressure decreases and becomes constant, and then cool to 120 ° C. to obtain an amount of propylene oxide [q of the general formula (I) 3.5 kg / in the autoclave.
It was introduced at a pressure of m ² and reacted until the pressure dropped and became constant. Thereafter, the temperature was raised again to 150 ° C., and ethylene oxide (an amount corresponding to r in the general formula (I)) was introduced into the autoclave at a pressure of 3.5 kg / m ² , and the reaction was allowed to proceed until the pressure decreased and became constant. After completion, lower the temperature and add
The desired final product was obtained by adding and neutralizing g.

Example 1 Liquid detergent compositions shown in Table 1 were prepared, and the cleaning performance, stability (appearance of the composition) and viscosity were measured by the following methods. Table 1 shows the results.

(1) 90 ml of the liquid detergent composition is placed in a 100 ml colorless and transparent glass bottle, sealed and left for 24 hours.
The appearance was observed and the viscosity was measured. The viscosity was measured at a composition temperature of 20 ° C. using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). The evaluation criteria for the appearance of the composition are as follows. Judgment of appearance: ○ Uniform and transparent. × Cloudy or separated.

(2) Detergency test method The used sebum stained cloth (artificially stained cloth) is obtained by uniformly applying 2 g of a model sebum stain having the following composition to a 10 × 10 cm cotton cloth. [Model sebum dirt composition] Cottonseed oil 60% Oleic acid 10% Palmitic acid 10% Solid paraffin 10% Liquid paraffin 10% [Cleaning conditions and evaluation method] The above-mentioned artificially stained cloth was placed in 1 liter of a diluted aqueous solution of the detergent composition for evaluation. It was then washed with a tergotometer at 100 rpm under the following conditions. <Washing conditions> Washing time 10 minutes Washing agent concentration 0.07% Water hardness 4 ° DH water temperature 20 ° C Rinse for 5 minutes with tap water Washing power is the original cloth before contamination and the reflectance at 550 nm before and after washing by self-recording color. Total (Z-300A, manufactured by Nippon Denshoku Co., Ltd.)
The cleaning rate (%) was determined by the following formula (the average value of the cleaning rates of five sheets is shown in the table).

[0024]

(Equation 1)

[0025]

[Table 1]

(Note) ・ Nonionic surfactant 1; straight-chain primary alcohol ethoxylate having 12 carbon atoms ・ Nonionic surfactant 2; straight-chain primary alcohol ethoxylate having 12 carbon atoms ・ Nonionic surfactant 3: straight-chain primary alcohol ethoxylate having 12 carbon atoms-nonionic surfactant 4: straight-chain primary alcohol ethoxylate having 12 carbon atoms-nonionic surfactant 5: straight-chain primary alcohol ethoxylate having 12 carbon atoms Rate Non-ionic surfactant 6; straight-chain primary alcohol ethoxylate having 12 carbon atoms Non-ionic surfactant 7; straight-chain secondary alcohol ethoxylate having 12 to 14 carbon atoms, trade name "Softanol 70" (stock) Example 2 Liquid detergent compositions shown in Table 2 were prepared, and the stability and cleaning performance were measured in the same manner as in Example 1. Table 2 shows the results.

[0027]

[Table 2]

(Note) ・ Alkyl glucoside; dodecyl glucoside (average degree of sugar condensation = 1.5) ・ LAS-Na; sodium alkylbenzene sulfonate ・ AES-Na; polyoxyethylene (average number of moles of ethylene oxide added: 4) alkyl (C ₁₂ ) ) Ether sulfonate ・ Fatty acid; Lunac L-55 (Kao Corporation) ・ Cationic surfactant; Cotamine 86W (Kao Corporation) ・ Savinase 16.OL; Novo Nordisk Industries ・ B; Amount to do

Claims (4)

[Claims] 1. A liquid detergent composition containing 10 to 50% by weight of a nonionic surfactant represented by the following general formula (I). R ¹ -O- (EO) _p- (PO) _q- (EO) _r -H (I) wherein R ¹ represents an alkyl group or an alkenyl group having 8 to 18 carbon atoms, and EO represents an oxyethylene group , PO represents an oxypropylene group, p, q, and r each represent an average number of moles added, and p> 0, r> 0, p + q + r = 6 to 14, and p +
r = 5 to 12, and q = 1 to 4. ] 2. The liquid detergent composition according to claim 1, wherein the water content is 60% by weight or less. 3. The liquid detergent composition according to claim 1, wherein the total amount of the surfactant containing the nonionic surfactant represented by the general formula (I) is 10 to 60% by weight. 4. The liquid cleaning composition according to claim 1, wherein p ≧ r in the general formula (I).