JP3013758B2 - Liquid detergent composition - Google Patents

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, and more particularly, to a low-foaming liquid detergent composition capable of maintaining enzyme activity for a long period of time.

[0002]

2. Description of the Related Art In general, as a cleaning agent used at home, a compound having an excellent foaming property is used. This is due to the fact that many consumers evaluate the performance of cleaning agents by their foaming properties.

However, detergents for automatic dishwashers, household detergents for gas stoves and furniture, detergents for washing dishes in cafeterias, etc., detergents for dry cleaning, industrial machine detergents, automobiles and railways In the case of cleaning agents for vehicles, cleaning agents for metal parts, etc., foaming properties are not necessarily required, and conversely, low-foaming cleaning agents are often used.

[0004] In the above-mentioned field, the use of a foaming detergent causes poor cleaning, foaming of drainage due to foaming at the time of rinsing or after rinsing, and bubbles forming on the surface of the article to be cleaned. Drying while remaining causes adverse effects such as uneven color and burning.

[0005] On the other hand, liquid detergents containing enzymes have been known so far, but generally lack enzyme stability as compared with powdered detergents. This is thought to be due to the presence of water in the formulation and other formulations such as surfactants and alkaline agents reducing enzyme activity.

As a method for maintaining the activity of the enzyme in the liquid detergent, the amount of the enzyme is increased in advance, or a polyhydric alcohol such as butanediol, propylene glycol or glycerin, calcium chloride or the like is used as a stabilizer. It is known to mix an inorganic salt of alkanolamine such as triethanolamine (Novo Nordisk Bioindustry technical data, etc.). However, increasing the amount of enzyme is not economical, and various stabilizers of the related art do not have sufficient enzyme stabilizing action and do not have surface activity, so that they do not contribute much to detergency.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a low-foaming liquid detergent composition which is excellent in detergency and hardly loses its activity even when stored for a long period of time.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, a cleaning agent containing a specific polyhydric alcohol ethylene oxide adduct and a specific nonionic surfactant as essential cleaning agents. As a component, a liquid detergent composition having a specific composition has been found to exhibit a predetermined effect, and the present invention has been completed based on such knowledge.

That is, the cleaning composition according to the present invention is a liquid cleaning composition containing an enzyme, characterized by containing the following components (A) and (B).

(A) An average of 0.3 to 3 equivalents of a hydroxyl group of a tri- to hexa-valent aliphatic polyhydric alcohol having 3 to 6 carbon atoms.
Aliphatic polyhydric alcohol ethylene oxide adduct to which 2 to 2 mol of ethylene oxide is added: 10 to 90% by weight

(B) a polyoxyalkylene alkyl (or alkenyl) ether (B-
1); a polyoxyalkylene alkyl (or alkenyl) ester represented by the general formula (2) (B-2); an alkylene oxide 10 to 60 mol adduct of an alcohol selected from lanolin alcohol, reduced lanolin alcohol and abiethyl alcohol One or more nonionic surfactants selected from (B-3): 0.1 to 20% by weight

R ¹ —O— (AO) aH (1) wherein R ¹ is an alkyl group having 6 to 36 carbon atoms and 6 carbon atoms
Represents an alkenyl group having 6 to 36 carbon atoms, an alkylphenyl group having an alkyl group having 6 to 36 carbon atoms, or an alkenylphenyl group having an alkenyl group having 6 to 36 carbon atoms. AO represents alkylene oxide. a represents a positive number of 5 to 60. ]

R ² —CO—O— (AO) b —H (2) wherein R ² is an alkyl group having 5 to 35 carbon atoms, and 5 carbon atoms.
~ 35 alkenyl groups. AO represents alkylene oxide. b represents a positive number of 10 to 100. ]

The component (A) according to the present invention has 3 to 6 carbon atoms.
Is a compound prepared by adding a predetermined amount of ethylene oxide to a tri- to hexa-valent aliphatic polyhydric alcohol having the following general formula:

The compound is excellent in enzyme stabilizing action and also has surface activity, so that it exhibits an excellent action on detergency and stability of appearance of the composition, and is economically and economically efficient. Also excellent.

Examples of the aliphatic polyhydric alcohol include glycerin, mesoerythritol, pentaerythritol, sorbitol and the like, and glycerin and sorbitol are particularly recommended.

The average number of moles of ethylene oxide added per equivalent of hydroxyl group of the aliphatic polyhydric alcohol is 0.3 to 0.3.
It is 2 moles, especially 0.5 to 1.5 moles is recommended.
If the amount is out of the range of 0.3 to 2 mol, the desired effect cannot be sufficiently obtained.

Specific compounds that are recommended include 1.5 to 4.5 moles of ethylene oxide adduct of glycerin,
Sorbitol ethylene oxide 3 to 6 mole adducts.

The content of the component (A) in the detergent composition according to the present invention is from 10 to 90% by weight, and particularly preferably from 30 to 90% by weight.
~ 50% by weight is recommended. If the amount is less than 10% by weight, good detergency and enzyme stability cannot be obtained. If the amount exceeds 90% by weight, enzymes and other components are precipitated, and unrecoverable sedimentation and separation during coagulation occur. .

The nonionic surfactant of the component (B) is roughly classified into the following (B-1), (B-2) and (B-3).
Particularly, a compound having a cloud point of 70 ° C. or more in the 1% by weight aqueous solution is recommended.

The nonionic surfactant (B-1) is represented by the general formula (1) and adds a predetermined amount of alkylene oxide to a predetermined aliphatic alcohol or aromatic alcohol according to a conventional method. The compound is prepared by

As the aliphatic alcohol, either a natural alcohol or a synthetic alcohol can be used, and the carbon chain may be saturated or unsaturated. Specifically, octanol, decanol, dodecanol, tetradecanol, hexadecanol, hexadecanol, oleyl alcohol, behenyl alcohol, sophthanol (manufactured by Nippon Shokubai Co., Ltd.), 2-octyldodecanol, 2-decyltetradecanol, Garbet alcohols such as 2-hexyldecanol are exemplified.

Examples of the aromatic alcohol include octylphenol, nonylphenol, dodecylphenol and the like.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, 1,2-epoxyoctane, 1,2-epoxydodecane, and 1,2-epoxytetradecane. These alkylene oxides are used alone or by appropriately selecting two or more kinds. When two or more types are selected and polymerized, the order does not matter.

The number of moles of the alkylene oxide added to each of the above alcohols is 5 to 60 moles, preferably 10 to 10 moles.
４０40 mol.

Recommended Nonionic Surfactant (B-1)
Examples thereof include poly (degree of polymerization 25) oxyethylene octyl dodecyl ether, poly (degree of polymerization 35) oxyethylene tallow alcohol ether, and poly (degree of polymerization 12) oxyethylene oleyl ether. In addition, polyoxyethylene polyoxypropylene alkyl ether (for example, trade name “Rikanon EP-100”, manufactured by Shin Nippon Rika Co., Ltd.) is also recommended.

The nonionic surfactant (B-2) is represented by the general formula (2), and a predetermined amount of alkylene oxide (specifically, as described above) for a predetermined fatty acid based on a conventional method. Is a compound prepared by adding

The fatty acid may be a natural carboxylic acid or a synthetic carboxylic acid, or a saturated carboxylic acid or an unsaturated carboxylic acid. Specifically, caproic acid, caprylic acid, capric acid, undecanoic acid, lauric acid, tridecane Examples include acid, myristic acid, palmitic acid, stearic acid, isostearic acid, dimer acid, oleic acid, behenic acid, 2-octyldodecanoic acid, linoleic acid, linolenic acid, and the like.

The number of moles of the alkylene oxide added to each of the alcohols is 10 to 100 moles.

The recommended nonionic activator (B-2) includes an alkyl group (or alkenyl group) having 16 carbon atoms.
-18, wherein the ratio of the molecular weight of the alkylene oxide moiety to the molecular weight of the whole molecule is 60 to 95%, and examples thereof include polyoxyalkylene alkyl (alkenyl) esters,
Specific examples include poly (degree of polymerization 30) oxyethylene stearyl ester and poly (degree of polymerization 10) oxyethylene oleyl ester.

The nonionic surfactant (B-3) is obtained by adding a predetermined amount of alkylene oxide (specifically as described above) to an alcohol selected from lanolin alcohol, reduced lanolin alcohol and abiethyl alcohol. It is a compound consisting of

The number of moles to be added is 10 to 60 moles,
Among them, 15 to 40 mol is preferable.

Recommended Nonionic Surfactant (B-3)
Examples thereof include poly (degree of polymerization 20) oxyethylene reduced lanolin alcohol ether.

The content of the component (B) is 0.1 to 20% by weight, preferably 1 to 10% by weight. If the amount is less than 0.1% by weight, a sufficient cleaning effect cannot be obtained, and even if the amount exceeds 20% by weight, no improvement in the detergency due to an increase in the amount of the component (B) is observed. Absent.

The type of the enzyme is appropriately selected depending on the use of the detergent composition. For example, protease, amylase, lipase and the like can be selected for dishwashing detergent, and cellulase, protease, lipase and the like can be selected for clothing detergent including dry cleaning. Also, in the case of cleaning agents for metals and the like, the same enzymes as those for clothing can be selected. These enzymes may be used alone, or two or more enzymes may be used at the same time as long as the enzymes do not mutually reduce the activity in the detergent.

[0036] The amount of the enzyme to be applied is appropriately selected depending on the application. Specifically, for example, in the case of a detergent having a high dilution ratio at the time of use, such as a metal detergent, 2 to 10% by weight is preferable,
For clothing, automatic dishwashers, etc., 0.01 to 5
% By weight is preferred. If the amount used is less than this, the effect cannot be said to be sufficient, and the washability and the finish after washing become insufficient. On the other hand, if it exceeds, it is not preferable because it causes economic disadvantage.

The water content in the detergent is preferably not more than 70% by weight, particularly preferably not more than 50% by weight, in consideration of the stability of the enzyme. Water is basically a factor that lowers the activity of the enzyme, but if it exceeds 70%, the surfactant in the enzyme is significantly reduced, and sufficient enzyme stability is obtained even when other conditions are satisfied. Is difficult.

The pH of the detergent composition according to the present invention is preferably in a range that does not inhibit the activity of the enzyme. Concrete p
H varies depending on the type and characteristics of the enzyme and cannot be specified, but is generally in a neutral region, that is, pH 6-8.
Is preferred. Further, within this range, no damage to glass and metal is observed. Further, if the pH is made neutral, the safety is relatively high as compared with an acidic or alkaline cleaning agent even in the case of accidental ingestion or misuse, and it is advantageous in terms of skin irritation. In addition, even in a situation where a large amount is used, the pH in the environmental water is rarely increased or decreased as in the case of an acidic or alkaline cleaning agent.

The pH may be adjusted using an appropriate acid or alkali.

Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid and boric acid, and organic acids such as acetic acid, oxalic acid, formic acid and citric acid. When a strong acid such as hydrochloric acid, sulfuric acid or formic acid is used, it is desirable to adjust the pH before adding the enzyme.

When the pH is adjusted with an alkali, organic alkalis such as monoethanolamine, diethanolamine and triethanolamine, and inorganic alkalis such as sodium carbonate, potassium carbonate, sodium metasilicate and sodium orthophosphate can be used.

In the cleaning composition according to the present invention, other anionic surfactants, nonionic surfactants, amphoteric surfactants or cationic surfactants can be used in combination.
These are added for the purpose of improving the washing property, alleviating the irritation, and the like, and can be added as needed as long as the low foam property according to the use is not impaired.

Examples of the anionic surfactant include an alkyl (alkenyl) sulfate, a polyoxyethylene alkyl (alkenyl) sulfate, an alkylbenzene sulfonate, a secondary alcohol sulfate, and a sulfosuccinic acid mono (di) salt.
Examples thereof include alkyl (alkenyl) ester salts.

Examples of the nonionic surfactant include polyoxypropylene-polyoxyethylene polymer, alkyl glucoside, sucrose fatty acid ester, sorbitan ester, polyglycerin ester, polyoxyethylene higher fatty acid alkanolamide, higher fatty acid alkanolamide,
Mono (di) alkyldi (mono) methylamine oxide,
Examples thereof include polyoxyethylene mono (di) alkyldi (mono) methylamine oxide.

Examples of the amphoteric surfactant include betaine type (carboxybetaine and sulfobetaine), aminocarboxylate type, imidazoline derivative type, and derivatives of these polyoxyethyleneamines.

Examples of the cationic surfactant include an alkyldimethylammonium salt, a dialkyldimethylammonium salt, an alkylpyridinium salt and an alkylamidoalkylammonium salt.

Further, the detergent composition according to the present invention does not refuse to blend other optional components, for example, a low-temperature stabilizer, a builder, an enzyme stabilizer, and other additives. The following components can also be used.

As the low-temperature stabilizer, ethylene glycol, polyethylene glycol, propylene glycol,
Glycerin, trimethylolpropane, ethanol, methanol and the like are exemplified.

Examples of the builder for improving the detergency include citric acid, malic acid, gluconic acid, zeolite and salts thereof.

As the enzyme stabilizer, generally, boric acid,
Examples thereof include lower organic acids and inorganic acids such as formic acid and oxalic acid, and alkaline earth metal salts such as calcium chloride and magnesium chloride.

Examples of the other additives include fragrances, pigments, bleaching agents, bactericides, hydrotropes, chelating agents, hand roughness inhibitors and the like.

The method for preparing the liquid detergent composition of the present invention is the same as the method for producing an ordinary liquid detergent, and is not particularly limited. Specifically, it is preferable that a predetermined surfactant is first mixed and homogenized, and that an enzyme and a fragrance are added in the final stage.

The liquid detergent composition according to the present invention can be used as a detergent for automatic dishwashers, a liquid detergent for kitchens, a detergent for household use such as a gas stove and furniture, a detergent for clothing including dry cleaning, and an industrial machine wash. The present invention can be used for cleaning agents, cleaning agents for vehicles such as automobiles and railways, cleaning agents for metal parts, hard surface cleaning agents, and the like, but is not limited thereto.

[0054]

The present invention will be specifically described below with reference to examples and comparative examples. In addition, the test method and evaluation method in an Example are as follows.

(A) Washing test (1) Dishwashing test As a “composite stain”, 10 g of commercially available curry rice was applied to a dish and left for 24 hours at a temperature of 25 ° C. and a humidity of 60%. As a "fat stain", lard was applied to a stainless steel fork and allowed to stand at a temperature of 25 ° C. and a humidity of 60% for 24 hours. As “starch stain”, 5 g of cooked cooked rice was spread on a plate and left for 20 minutes. These test dishes were stored in a home automatic dishwasher / dryer, and 3.5 g of the liquid detergent composition was charged, followed by washing in a standard course of the washer. The cleaning properties at that time were evaluated by the following several methods.

[0056] Based on the cleaning of cleaning rate, it was carried out by the following criteria. ：: Almost washed (washing rate 90% or more) Δ: Partially left (washing rate 50 to 89%) ×: Hardly washed (washing rate less than 50%)

Ten minutes after the start of the defoaming cleaning, the number of revolutions of the nozzle of the washer was visually observed to evaluate a decrease in the number of revolutions of the nozzle of the washer due to foaming. The criteria are as follows. ：: good (40 rpm or more) △: rotation speed slightly decreases (30 to 39 rpm) ×: rotation speed greatly decreases (less than 30 rpm)

The odor in the refrigerator 10 minutes after the start of the odor cleaning was evaluated in the following two stages. ○: no odor, ×: odor

Water Spots The following three grades were evaluated based on the number of traces of water droplets (water spots) remaining on the dishes after drying. ：: less than 10 △: 10 to 29, ×: 30 or more

Gloss of Tableware The glass tableware after drying was visually evaluated as ○ when it was transparent and glossy, and x when white and less glossy.

(2) Glass washing test A commercially available window glass sheet of 60 cm square was left outdoors for one month or more, and the stained one was used as a sample, which was cut into four pieces each of 15 cm using a sponge tape. Separated. Each compartment was washed using a commercially available dishwashing sponge, then rinsed with water and air-dried. The detergent used in the test was prepared by diluting the detergent composition 100 times. The evaluation items were washability, odor, rinseability, and the finished state of the glass surface after air drying. These evaluation results were evaluated for the finish of the glass surface based on the presence or absence of oil droplets and fogging, and the other items were evaluated on a three-point scale of △, Δ, and ×.

(3) Clothes washing test A wet-stained cloth manufactured by The Laundry Association was used as a test cloth, and a 25% aqueous solution containing 0.1% of the active ingredient of the sample was measured using a tergotometer.
Washed at ° C. The evaluation was performed in the following three stages from the cleaning rate calculated from the surface reflectance of the test cloth before and after cleaning. ：: Washing rate is 40% or more △: Washing rate is 30 to 39% ×: Washing rate is less than 30%

(B) Stability of enzyme The sample to which the enzyme was added was allowed to stand at 37 ° C. for 100 days, and the stability was evaluated based on the residual ratio of the enzyme titer at this time. The criteria are as follows. ：: good (residual rate 70% or more) △: normal (residual rate 40 to 69%) ×: bad (residual rate less than 40%)

(C) Appearance From the appearance of the sample, the sample was evaluated as ○ when the sample was transparent and uniform, and × when the sample was clouded or precipitated.

Examples 1 to 3 and Comparative Examples 1 to 7 A dishwashing test was carried out using a detergent composition comprising a predetermined amount of a component and water (remainder) as shown in Table 1, and the washing property, the defoaming property, The odor, tableware gloss, appearance and enzyme stability were evaluated. Table 1 shows the obtained results.

[0066]

[Table 1]

Examples 4 to 8 and Comparative Examples 8 to 10 A dishwashing test was carried out using a detergent composition comprising a predetermined amount of a component and water (remainder) as shown in Table 2, and the washing property, the defoaming property, Tableware was evaluated for gloss, water spot, appearance and enzyme stability. Table 2 shows the obtained results.

[0068]

[Table 2]

Examples 9 to 11 and Comparative Examples 11 to 16 Glass cleaning tests were carried out using a cleaning composition comprising a predetermined amount of the components and water (remainder) described in Table 3, and the cleaning properties, rinsing properties, and finish were determined. The condition and odor were evaluated. Table 3 shows the obtained results.

[0070]

[Table 3]

Examples 12 to 13 and Comparative Examples 17 to 22 Clothes washing tests were carried out using a detergent composition comprising a predetermined amount of components and water (remainder) as shown in Table 4 to evaluate the detergency, odor and enzyme. The stability was evaluated. Table 4 shows the obtained results.

[0072]

[Table 4]

[0073]

The liquid detergent composition according to the present invention has a low foaming property and maintains the activity of the enzyme for a long period of time. Therefore, even when the pH is neutral, the cleaning composition is not inferior to an alkaline powder detergent. It shows stability and stability under long-term storage. Further, in the case of washing with a machine, since it is a liquid, it is easy to measure, and it is possible to put it into a washing machine by automatic weighing.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-132699 (JP, A) JP-A-57-209999 (JP, A) JP-A-59-15495 (JP, A) JP-A-6-159 17095 (JP, A) JP-A-6-302942 (JP, A) JP-A-8-20795 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 1/68 CA ( STN) CAOLD (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A liquid detergent composition containing an enzyme, comprising the following components (A) and (B). (A) An aliphatic polyhydric alcohol ethylene oxide adduct obtained by adding 0.3 to 2 mol of ethylene oxide on average per equivalent of hydroxyl group of a tri- to hexa-valent aliphatic polyhydric alcohol having 3 to 6 carbon atoms: 10 (B) polyoxyalkylene alkyl (or alkenyl) ether (B-1) represented by the general formula (1); polyoxyalkylene alkyl (or alkenyl) ester represented by the general formula (2) ( B-2); alkylene oxides of alcohols selected from lanolin alcohol, reduced lanolin alcohol and abiethyl alcohol
One or more nonionic surfactants selected from 0 mol adduct (B-3): 0.1 to 20% by weight R ¹ -O- (AO) a-H (1) R ¹ is an alkyl group having 6 to 36 carbon atoms,
Represents an alkenyl group having 6 to 36 carbon atoms, an alkylphenyl group having an alkyl group having 6 to 36 carbon atoms, or an alkenylphenyl group having an alkenyl group having 6 to 36 carbon atoms. AO represents alkylene oxide. a represents a positive number of 5 to 60. R ² —CO—O— (AO) b —H (2) wherein R ² is an alkyl group having 5 to 35 carbon atoms, and 5 carbon atoms.
~ 35 alkenyl groups. AO represents alkylene oxide. b represents a positive number of 10 to 100. ] 2. The liquid detergent composition according to claim 1, wherein the aliphatic polyhydric alcohol according to the component (A) has 3 or 6 carbon atoms. 3. The nonionic surfactant as the component (B) has a cloud point of 70 ° C. or more in the 1% by weight aqueous solution, and the content ratio is 1 to 10% by weight. Item 3. A liquid detergent composition according to Item 2. 4. The method according to claim 1, wherein the water content is 50% or less.
The liquid detergent composition according to claim 3. 5. The liquid detergent composition according to claim 1, wherein the pH of the detergent composition is from 6 to 8.