JP2001200300A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition excellent in detergency against clothes having extraordinary stains such as sebum stains or the like stuck thereto, exhibiting high antifungal effects and improved in liquid stability. SOLUTION: The liquid detergent composition comprises (a) a nonionic surfactant represented by general formula (I): R-O-(R1O)n-H and (b) an antifungal agent each in a specific ratio. In the formula, R is an 8-18C hydrocarbyl group; R1 is a 2-4C alkylene group; the average (nAV) of n is 5-15. The total weight of components having a number of moles added of at least (nMAX+3) is not more than 20 wt.%, where nMAX is a number of moles added of components comprising the largest weight percentage.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid detergent composition.

[0002]

2. Description of the Related Art In recent years, awareness of hygiene has increased, and even in the field of laundry detergents, it is possible to suppress the generation of raw dry odor of clothes after washing and offensive odor due to long-term storage after washing.
Products with antibacterial effects are on the market. Also,
Since many bleaching agents have antibacterial effects, attempts have been made to add chlorine-based or oxygen-based bleaching agents to laundry detergents. However, the chlorine-based bleaching agent, which is known to have a high antibacterial effect, is widely known as a problem of discoloration of colored patterns. Oxygen-based bleach also has a problem of discoloration,
It is clear in the art that decolorization in the presence of metals and the like is known, and that it is difficult to stably compound it in a heavy liquid detergent for clothes, which is generally weakly alkaline.

On the other hand, cationic antibacterial agents, which are widely used as detergents in the hygiene field, have a wide antibacterial spectrum band and are characterized by their fast-acting properties, so that attempts have been made to incorporate them into laundry detergents. However, when an anionic surfactant is used as a surfactant or in the presence of a substance having an anionic charge such as a protein, the problem that the activity of the cationic antibacterial agent is significantly reduced and the stability of the solution are stable. There was a problem of poor sex. Japanese Unexamined Patent Publication No. Hei 1-197598 discloses a stable antibacterial effect obtained by blending a specific anionic surfactant, a cationic surfactant type antibacterial agent, and a benzoate with a nonionic surfactant as a main component. Liquid laundry detergents are disclosed. However, the composition disclosed in the above-mentioned patent publication is not sufficient in antibacterial effect although it is excellent in storage stability, and in particular, the antibacterial effect is remarkably reduced for clothing to which stubborn dirt such as sebum dirt is attached. there were.

[0004]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a liquid detergent having an excellent antibacterial effect and a high liquid stability, which is excellent in detergency even for clothes having severe dirt such as sebum dirt. To provide a composition.

[0005]

[In the formula, R is a hydrocarbon group having 8 to 18 carbon atoms, R ¹ is an alkylene group having 2 to 4 carbon atoms, and the average value (n _AV ) of n is 5 to 15. Further, when the addition mole number having the highest weight% is n _MAX , the total weight of the components having the addition mole number of (n _MAX +3) or more is 20 weight% or less. ]

[0006]

[In the formula, R is a hydrocarbon group having 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms, preferably an alkyl group or an alkenyl group, and R ¹ is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or propylene. Group, more preferably an ethylene group, and the average value of n (n _AV ) is 5 to 15, preferably 5 to 10. When the addition mole number having the largest weight% is n _MAX , the total weight of the components having the addition mole number of (n _MAX +3) or more is 20% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight. % Or less. ]

The total weight of the components of n=0 and n=1 is 10% by weight.
It is preferably 5% by weight or less, more preferably 3% by weight or less.

Such a nonionic surfactant is NaO.
It is also possible to produce by removing the unreacted alcohol and a large amount of adduct by carrying out an addition reaction of ethylene oxide and an alcohol, for example, using H or KOH as a catalyst, and distillative purification. JP-A-7-227540 It is economically preferable to carry out the addition reaction by the method described in the publication.

In the present invention, such a nonionic surfactant is contained in the composition in an amount of 10 to 60% by weight, preferably 20 to 50% by weight, more preferably 30 from the viewpoints of cleaning performance and antibacterial performance of the antibacterial agent. ˜50% by weight.

Component (b) As the antibacterial agent of component (b), a cloth in which 1% by weight of the compound is uniformly adhered to a cotton rag #2003 is used.
Compounds which show an inhibition zone when subjected to an antibacterial test by a method according to 1902 “Test method for antibacterial properties of textile products” are preferable.

The liquid detergent composition of the present invention contains the antibacterial agent (b) in an amount of 0.1 to 10 in terms of cleaning performance and antibacterial performance.
20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight.

The antibacterial agent (b) includes the following (b-1) to (b-
One or more selected from the antibacterial compounds of 3) are preferable,
1 selected from the antibacterial compounds of (b-1) to (b-2)
One or more kinds are more preferable, and one or more kinds selected from the antibacterial compound (b-2) are particularly preferable.

(B-1) has a molecular weight of 100 to 4
20, preferably 150 to 410, a water-insoluble antibacterial compound containing no quaternary ammonium group, and
Examples thereof include those having a melting point of 40° C. or higher (excluding organic peracid or organic peroxide). Here, the water-insoluble compound is a compound satisfying the property that the solubility in 100 g of water at 20° C. is preferably less than 1 g, more preferably 0.5 g or less.

Preferred compounds satisfying the property (b-1) are triclosan, bis-(2-pyridylthio-1-oxide) zinc, 2,4,5,6-tetrachloroisophthalonitrile, trichlorocarbanilide, One or more selected from 8-oxyquinoline, dehydroacetic acid, benzoic acid esters, chlorocresols, chlorothymol, chlorophen, dichlorophen, bromochlorophen, and hexachlorophen. Especially, triclosan is preferable from the viewpoint of odor suppressing effect. In addition, JP-A-11-18
The triclosans described in 9975 are also good, and specifically dichlorohydroxydiphenyl ether and monochlorohydroxydiphenyl ether are preferable.

Examples of (b-2) include water-soluble quaternary ammonium type antibacterial compounds having at least one alkyl group having 8 to 16 carbon atoms. Here, the water-soluble compound means a compound which has a solubility in 100 g of water at 20° C. of 1 g/100 g or more.

The compound (b-2) is preferably one or more selected from the compounds represented by the following general formulas (II) to (IV).

[0016]

[Chemical 4]

[Wherein R²And R⁷Is a carbon number of 5 to 19
An alkyl group or an alkenyl group, R ³, R^FourHas 1 carbon
~3 alkyl groups or hydroxyalkyl groups. X
Is -COO-, -OCO-, -CONH-, -NHCO
-Or

[0018]

[Chemical 5]

[0019] R ⁵ is an alkylene group having 1 to 3 carbon atoms, and R ⁶ is an alkylene group having 1 to ⁶ carbon atoms or —(O
-R ⁸⁾ _n - is. Here, R ⁸ is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group, and n is a number of 1 to 10. m is 0 or 1.
Y ⁻ is an anion group, preferably a halogen ion, an alkylsulfate ion having 1 to 3 carbon atoms or a fatty acid ion. ]

[0020]

[Chemical 6]

[In the formula, two or more, preferably two of R ^{9 to} R ¹² are alkyl groups having 8 to 10 carbon atoms, and other than that are alkyl groups or hydroxyalkyl groups having 1 to 3 carbon atoms. Of these, a methyl group, an ethyl group and a hydroxyethyl group are preferable. Y ⁻ is an anion group, preferably a halogen ion, an alkylsulfate ion having 1 to 3 carbon atoms or a fatty acid ion. ].

In the general formula (II), when X is a paraphenylene group (--C ₆ H ₄ --) and m=1, R ² preferably has 5 to 16 carbon atoms, more preferably 6 to 13 carbon atoms, Most preferably, it is an alkyl group having 7 to 10 carbon atoms, and R ⁶
Preferably _{^{- (O-R 8) n}} - is a group, R ⁸ is preferably an ethylene group, n is preferably a number of 1 to 5, R ³ and R ⁴ are preferably methyl or hydroxy It is an ethyl group and R ⁵ is preferably a methylene group. In the general formula (II), when m=0 (1-2
a) or X is -COO-, -OCO-, -CON
In the case of H-, -NHCO- and m=1 (1-2-b), R
² is preferably an alkyl group having 7 to 18 carbon atoms, more preferably 9 to 17 carbon atoms, and most preferably 11 to 16 carbon atoms, R ⁶ is preferably a methylene group, and R ³ and R ⁴ are preferably Is a methyl group or a hydroxyethyl group, and R ⁵ is preferably a methylene group.

In the general formula (III), R ⁷ is preferably an alkyl group having 8 to 18 carbon atoms, more preferably 11 to 17 carbon atoms.

In the general formula (IV), preferably two of R ^{9 to} R ¹² are alkyl groups having 8 to 10 carbon atoms, and the remaining two are methyl groups or hydroxyethyl groups.

In the present invention, the compound of the general formula (IV) can be used alone, but it is preferable to use it in combination with at least one of the compounds of the general formula (II) and the general formula (III), from the viewpoint of the effect, and the weight ratio. Is [compound of general formula (IV)]/[compound of general formula (II)+compound of general formula (III)]=1/10
-10/1, especially 1/5-5/1 is preferred.

Examples of (b-3) include one or more compounds selected from 2-(4-thiocyanomethylthio)benzimidazole, polylysine, polyhexamethylene biguanide and chlorhexidine glucuronic acid.

The liquid detergent composition of the present invention contains 0.5 to 0.5 of polyethylene glycol having an average molecular weight of 200 to 5,000, more preferably 500 to 2,000, particularly from the viewpoint of cleaning performance.
It is preferably contained in an amount of up to 20% by weight, more preferably 1 to 15% by weight.

The liquid detergent composition of the present invention may contain an anionic surfactant, a cationic surfactant or an amphoteric surfactant as a surfactant.

As the anionic surfactant, alkylbenzene sulfonate, fatty acid salt, alkyl or alkenyl sulfate, alkyl or alkenyl ether carboxylate, alkyl sulfate ester salt, alkenyl sulfate ester salt, alpha sulfo fatty acid methyl ester salt, You may mix|blend an olefin sulfonate, an alkane sulfonate, etc. At that time, when the component (b-2) is used as an antibacterial agent component, from the viewpoint of antibacterial property, [(b-2) component]>[anionic surfactant×1], especially [(b-2) Ingredients>>
It is preferably blended in the composition in a molar ratio of [anionic surfactant×1.1].

Examples of the counterion of the anionic surfactant include alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and/or alkanolamines such as mono-, di- and triethanolamine, and the like.
In particular, the use of alkanolamine improves the liquid stability. Further, an anionic surfactant may be added to the composition in an acid form, or may be neutralized with a separately added alkali agent (alkanolamine or the like).

In order to improve the texture, it is preferable to use a cationic surfactant such as a mono long-chain alkyl quaternary ammonium salt in combination.

As the amphoteric surfactant, amine oxide, alkylcarbobetaine, alkylsulfobetaine, alkylamidohydroxysulfobetaine, alkylamidoamine type betaine, alkylimidazoline type betaine and the like can be blended.

The liquid detergent composition of the present invention may contain, as an optional component, components conventionally known to be contained in detergents. As such optional components, alcohols such as ethanol, glycols such as ethylene glycol and propylene glycol, paratoluenesulfonic acid, benzoate (also effective as a preservative), and viscosity reducing agents such as urea and solubilizing agents. Agent; phase modifier and polyoxyalkylene benzyl ether for improving detergency, polyoxyalkylene phenyl ether; nitrilotriacetate, ethylenediaminetetraacetate, imino as polyvalent carboxylic acid salt having divalent metal ion capturing ability Diacetic acid salts, diethylenetriamine pentaacetic acid salts, glycol ether diamine tetraacetic acid salts, hydroxyethyliminodiacetic acid salts and aminopolyacetic acid salts such as triethylenetetramine hexaacetic acid salts, malonic acid, succinic acid, diglycolic acid, malic acid, tartaric acid, Salts such as citric acid; color transfer inhibitors such as polyvinylpyrrolidone; enzymes such as amylase, protease, lipase, cellulase; enzyme stabilizers such as calcium chloride, calcium sulfate, formic acid, boric acid (boron compound); Tinopearl CBS ( Ciba Specialty Chemicals Co., Ltd.), Whitetex SA (Sumitomo Chemical Co., Ltd.) and other fluorescent dyes; silicone for the purpose of imparting flexibility; silica as a defoaming agent, silicone; butylhydroxytoluene, distyrenated cresol, sodium sulfite, Antioxidants such as sodium bisulfite; bluing agents; fragrances and the like.

The liquid detergent composition of the present invention has the above (a)
To (b) component and optional component and water, pH is 7.5
-11 (25 degreeC) is preferable. It is preferable to add an alkaline agent in an amount necessary for the pH. Examples of the alkaline agent include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, methylmonoethanolamine, dimethylethanolamine and 3-aminopropanol, sodium hydroxide, potassium hydroxide, sodium silicate, sodium carbonate and the like. Inorganic salts can be used, and one or more selected from monoethanolamine, sodium hydroxide and potassium hydroxide are particularly preferable.

The liquid detergent composition according to the present invention uses a cloth in which 1% by weight of the liquid detergent composition is evenly adhered to a cotton rag #2003 and conforms to JIS L 1902 “Test method for antibacterial properties of textile products”. It is preferable that the inhibition zone is observed by conducting an antibacterial test by the above method.

[0036]

EXAMPLES Examples 1 to 4 and Comparative Examples 1 to 3 Liquid detergent compositions shown in Table 1 were prepared, and antibacterial properties and liquid stability were evaluated by the following methods. The results are shown in Table 1.

[Evaluation of Antibacterial Property] Cotton Gold Width #2003 (2
cm x 2 cm) 10 wt% triolei for each 2
0.2 ml of ethanol solution was applied to the centrifuge tube (M.
Put it in SEIDO Co., Ltd., capacity 50ml, sterilized) and dry,
A model soiled cloth with lipophilic stains was used. Then the above dirt
Bacterial fluid [Staphylococcus aureus IF
O 12732 (Staphylococcus aureus) 1 x 10⁹cells/ml]
0.1 ml was added, and the liquid detergent composition was further washed with sterile water.
Add 10 ml of diluted 5% by weight solution (20° C.),
Stir for minutes. Then remove the cloth and sterilize the saline.
Extract the liquid part soaked in the cloth with 20 ml of water (20℃)
did. Apply 0.1 ml of this extract to SCDLP agar medium.
Colonies of the obtained fungus by squirting and culturing at 37℃ for 24 hours
Counted the number. Cloth 1 cm²1 colony per hit
×10³If less than cells: 1 x 10³cells or more, 1
×10^FiveLess than cells is △, 1×10^Fivex above cells
evaluated. 1 x 10 ³Pass if less than cells.

[Evaluation of liquid stability] 50 mL sample bottle (No. 6 wide-mouth standard bottle, glass, diameter 40 mm,
80m high cylinder), 40m liquid detergent composition
After being filled with L and covered with a lid, it was allowed to stand in a constant temperature room at 25° C. for 30 days. Regarding the stability of the liquid, the appearance was visually evaluated according to the following criteria. ◯: It is a uniform liquid phase and has excellent liquid stability. Δ: Appearing to be slightly separated or precipitated, but not noticeable. X: Separation or precipitation is observed.

[0039]

[Table 1]

A-1: an average of 8 moles of EO added to a linear primary alcohol having 12 to 14 carbon atoms, n _MAX is 7, and a mole number of EO addition of 10 or more is 4.
3% by weight-A-2: a linear secondary alcohol having 10 to 14 carbon atoms with an average of 7 moles of EO added, and n _MAX of 6
And 4.5% by weight of 9 or more moles of EO added. A-3: A linear primary alcohol having 12 to 14 carbon atoms with 8 moles of EO added on average, and n _MAX Is 7
And an EO-added mole number of 10 or more is 28% by weight. A-4: An average of 20 moles of EO added to a linear secondary alcohol having 10 to 14 carbon atoms, and n _MAX is 1
8 and having an EO addition mole number of 21 or more of 3.6% by weight

[0041]

[Chemical 7]

LAS: linear alkylbenzene sulfonic acid having 10 to 14 carbon atoms-fatty acid: coconut fatty acid-PEG 1000: polyethylene glycol (average molecular weight 1000)-sodium polyacrylate: weight average molecular weight 1000
0-Enzyme: Durazyme 16.0L (protease, manufactured by Novo Nordisk Bioindustry Co., Ltd.)-Fluorescent dye: Chinopearl CBS-X (manufactured by Ciba Specialty Chemicals)

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C11D 3/33 C11D 3/33 3/48 3/48 (72) Inventor Hiroshi Nishimura 1334 Minato, Wakayama, Wakayama Prefecture Kao Corporation Research Laboratory (72) Inventor Kazutoshi Ide 1334 Minato Wakayama Prefecture Wakayama City F Term (Reference) 4H003 AB03 AB19 AC08 AC09 AE06 AE08 BA12 DA01 EA12 EA21 EB04 EB06 EB12 EB14 EB17 EB30 EB22 EB22 EB22 EB36 EC02 FA16 FA34

Claims (3)

[Claims] 1. A liquid detergent composition containing (a) 10 to 60% by weight of a nonionic surfactant of the general formula (I) and (b) 0.1 to 20% by weight of an antibacterial agent. R—O—(R ¹ O) _n —H (I) [In the formula, R is a hydrocarbon group having 8 to 18 carbon atoms, and R ¹
Is an alkylene group having 2 to 4 carbon atoms, and the average value of n (n
_AV ) is 5 to 15. Further, when the addition mole number having the highest weight% is n _MAX , the total weight of the components having the addition mole number of (n _MAX +3) or more is 20 weight% or less. ] 2. The antibacterial agent (b) is the following (b-1) to (b-
The liquid detergent composition according to claim 1, which is one or more selected from the antibacterial compounds of 3). (B-1) A water-insoluble antibacterial compound having a molecular weight of 100 to 420, containing no quaternary ammonium group, and having a melting point of 40° C. or higher (excluding organic peracid or organic peroxide). ) (B-2) at least one alkyl group having 8 to 16 carbon atoms
Water-soluble quaternary ammonium type antibacterial compound (b-3) one or more antibacterial compounds selected from 2-(4-thiocyanomethylthio)benzimidazole, polylysine, polyhexamethylene biguanide and chlorhexidine glucuronate 3. The antibacterial compound (b-2) has the following general formula:
A contract which is one or more compounds selected from (II) to (IV)
The liquid detergent composition according to claim 2. [Chemical 1][In the formula, R²And R⁷Is an alkyl group having 5 to 19 carbon atoms or
An alkenyl group, R ³, R^FourIs an alky having 1 to 3 carbon atoms
Group or hydroxyalkyl group. X is -COO
-, -OCO-, -CONH-, -NHCO- orIs. R^FiveIs an alkylene group having 1 to 3 carbon atoms, R⁶
Is an alkylene group having 1 to 6 carbon atoms or -(OR⁸)_n−
It Where R⁸Is an alkylene group having 2 to 4 carbon atoms,
n is a number from 1 to 10. m is 0 or 1. Y^-Is
It is an anionic group. ] [Chemical 3][In the formula, R⁹~R¹²2 or more of which have 8 to 10 carbon atoms
Alkyl group, otherwise alkyl having 1 to 3 carbon atoms
Or a hydroxyalkyl group. Y^-Is an anionic group
Is. ]