JPH04164016A - Cleaning agent composition - Google Patents

Abstract

PURPOSE:To obtain a cleaning composition containing a surfactant, polymer and fluorine based lubricant, having excellent cleaning force and conditioning effect and suitable as shampoo, cleaning agent for body, cleaning agent for soft clothing, etc. CONSTITUTION:The objective composition containing (A) 5-50wt.% one kind or two or more kinds of surfactants selected from an anionic surfactant and amphoteric surfactant, (B) 0.01-5wt.% one kind or two or more kinds of polymers selected from a cationic polymer and amphoteric polymer and (C) 0.01-5wt.% fluorine based lubricant (e.g. perfluoropolyether) and obtained by properly blending these ingredients with other ingredients normally used in cleaning composition and preparing the blend according an ordinary method. The resultant composition is suitable for shampoo and has excellent finger- passing property of hair in washing and combing smoothness after drying and softness, free from sticking and has excellent conditioning effects.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a detergent composition that can be suitably used as a shampoo, a body cleansing agent, a light laundry detergent, and the like.

[Issues to be solved by conventional techniques and inventions] In detergents such as shampoo, in addition to the basic function of detergents, which is detergency, there are also important factors such as ease of rinsing and the quality of finished hair. Conditioning effects such as good feel are very important points. For this reason, water-soluble polymers such as cationic polymers such as cationized cellulose and amphoteric polymers are widely used as conditioning agents.

These water-soluble polymers form a complex with a surfactant, and this complex is deposited on the hair during rinsing to exert a high conditioning effect. However, there are problems such as the composite remaining in the hair becomes unpleasantly sticky as it dries, and it hardens and becomes stiff after sufficiently drying, so it is not possible to obtain an ideal hair feel. .

Furthermore, JP-A-56-72095 discloses a shampoo composition to which a silicone derivative is added for the purpose of improving the drawbacks of the above-mentioned cationic polymer. This shampoo composition contains an anionic surfactant, a cationic polymer, and a silicone derivative. Although polyether-modified silicone is cited as a preferred silicone derivative, it still does not have sufficient conditioning effects. There wasn't.

Furthermore, perfluoropolyether is known as a compound that can impart lubricity and flexibility to hair, and its application to shampoos is also known.

Rigano, S., 5avonalli and P.
, L., Bencini.

International Journal o
f Cosmetic 5science ll.

259-282 (1989)). However, although this perfluoropolyether improves the slippage of hair after drying, it has little effect on improving the smoothness of the hair during rinsing, and depending on the amount added, it may cause stickiness, and its conditioning effect is insufficient. there were.

Therefore, there has been a desire for a detergent composition that does not have the above drawbacks and exhibits excellent conditioning effects from rinsing to drying.

[Means to solve the problem]

Under such circumstances, the present inventors conducted extensive research and found that one or more selected from anionic surfactants and amphoteric surfactants, and one or more selected from cationic polymers and amphoteric polymers. By containing the above-mentioned polymer and fluorine-based oil, a cleaning composition having good conditioning effects from rinsing to drying can be obtained, and furthermore, this cleaning composition can also be used as a body cleansing agent and a light clothing cleaning agent. The present invention was completed after discovering that the present invention can be suitably used.

That is, the present invention provides the following components (A), (B) and (C) (A) one or more surfactants selected from anionic surfactants and amphoteric surfactants (B) cationic surfactants The present invention provides a cleaning composition containing a fluorine-based oil (C) and one or more polymers selected from polymers and amphoteric polymers.

The surfactant of component (A) is an anionic surfactant or an amphoteric surfactant, and specific examples thereof include the following.

Anionic surfactant: (1) A straight or branched alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16.

(2) Contains a linear or branched alkyl group or alkenyl group with an average of 10 to 20 carbon atoms, with an average of 0.5 to 20 carbon atoms per molecule.
8 moles of ethylene oxide, propylene oxide,
Butylene oxide, ethylene oxide and propylene oxide in a ratio of 0.1/9.9 to 9.910.1,
Or ethylene oxide and butylene oxide are O
,], an alkyl or alkenyl ether sulfate added in a ratio of /9.9 to 9.910.1.

(3) An alkyl or alkenyl sulfate having an alkyl group or alkenyl group having an average carbon number of 10 to 20.

(4) Olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule.

(5) Alkanesulfonate having an average of 10 to 20 carbon atoms in one molecule.

(6) A saturated or unsaturated fatty acid salt having an average of 10 to 24 carbon atoms in one molecule.

(7) It has an alkyl group or an alkenyl group having an average carbon number of 10 to 20, and has an average of 0.5 to 8 moles of ethylene oxide, propylene oxide, butylene oxide, ethylene oxide and propylene oxide in one molecule.
The ratio of 1/9.9 to 9.910.1 or ethylene oxide and butylene oxide is 0.1/9.9 to 9.
．． gamma alkyl or alkenyl ether carboxylate added in a ratio of 910.1.

(8) α-Sulfo fatty acid salts or esters having an alkyl or alkenyl group having an average of 10 to 20 carbon atoms.

(9) N-acylamino acid type surfactant having a C8-C24 acyl group and a free carboxylic acid residue.

αQ A phosphoric acid mono- or diester type surfactant having an alkyl group or an alkenyl group having 8 to 24 carbon atoms.

(Company) Sulfosuccinate esters such as higher alcohols having 8 to 22 carbon atoms or their ethoxylates and propoxylates, or sulfosuccinates derived from higher fatty acid amides.

Amphoteric surfactant: An α-position addition type, secondary amide, or tertiary T-mide type imidacillin-based amphoteric surfactant having an alkyl group, alkenyl group, or acyl group having 8 to 24 carbon atoms.

Carbobetaine type, amidobetaine type, sulfobetaine type, hydroxysulfobetaine type, having an alkyl group, alkenyl group or acyl group having 8 to 24 carbon atoms,
or amidosulfobetaine type amphoteric surfactant.

Counter ions for the anionic residues of these surfactants include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium and magnesium,
Examples include ammonium ions and alkanolamines having 1 to 3 alkanol groups having 2 or 3 carbon atoms (eg, monoethanolamine, jetanolamine, triethanolamine, triisopropanolamine, etc.). Examples of counter ions for cationic residues include halogen ions such as chlorine, bromine, and iodine, and methosulfate and saracalinate ions.

Among these surfactants, (2) alkyl ether sulfates, (3) alkyl sulfates, (6) saturated or unsaturated fatty acid salts, (9) acylated amino acids, αl) IJ acid monoester type interfaces Active agent, sulfosuccinic acid ester, 02- and tertiary-amide type imidacillin-based amphoteric surfactants, especially amide-amino acid-type amphoteric surfactants that have been desalted to improve polymer solubility (Japanese Patent Application Laid-Open No. 1983-1998) 128
No. 100) is preferred as the main activator.

Suitable examples include sodium polyoxyethylene lauryl ether sulfate (average addition of 2 to 3 moles of ethylene oxide), triethanolamine lauryl sulfate, sodium salt of coconut fatty acid, lauroyl-N-methyltaurine, lauroyl-N- Methyl-β-alanine, polyoxyethylene sulfosuccinate lauryl disodium (3-7
B, O,), lauryl phosphate, N-lauroyl-N
'-hydroxymethyl-N'12-hydroxyethyl)
Ethylenediamine triethanolamine salt, N-lauroyl-N-(2-hydroxyethyl)-N'.

Examples include N'-bis(carboxymethyl)ethylenediamine sodium salt and the like. These surfactants are (B
) It has the property of forming a complex with the polymer of the component, and this complex deposits in large quantities on the hair and remains when the shampoo is rinsed.

These surfactants can be used singly or in combination of two or more, and are preferably blended in an amount of 5 to 50% by weight (hereinafter simply expressed as %), particularly 10 to 40%, in the total composition.

Among the components (B) used in the present invention, examples of cationic polymers include cationic cellulose derivatives, cationic starches, cationic guar gum derivatives, diallyl-4
Examples include quaternary ammonium salts, diallyl quaternary ammonium salt/acrylamide copolymers, and quaternized polyvinylpyrrolidone derivatives.

As a cationized cellulose derivative, the following general formula (n
) is preferred.

(n) In the formula, A represents a residue of anhydroglucose unit, a is an integer of 50 to 20,000, and each R6 represents a substituent represented by the following general formula (III).

-(R'0)b-([H,["HD)c-(R'
D) d-) 1 (III) In formula R', R': Alkylene group having 2 or 3 carbon atoms b: Integer from 0 to 10 c: Integer from 0 to 3 d: Integer from 0 to 10 R/// , an alkylene group or hydroxyalkylene group having 1 to 3 carbon atoms Rt, Rs, Re, which are the same or different and have up to 20 carbon atoms, an alkyl group, an aryl group, an aralkyl group, or a heterocyclic ring containing a nitrogen atom in the formula may be formed.

xl: represents an anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfate, phosphoric acid, nitric acid, etc.).

The degree of cation substitution of cationized cellulose is from 0.01 to
1, ie the average value of C per anhydroglucose unit is between 0.01 and 1, preferably between 0.02 and 0.5. Further, the average sum of b+d is 1 to 3. The degree of substitution is 0
．． A value of 0.01 or less is not sufficient, and a value of 1 or more is acceptable, but from the viewpoint of reaction yield, 1 or less is preferable. For example, R',
RB and R9 are all CH3 groups, or two are C1 (
Short chain alkyl group, such as 3 groups, with the remaining one having 10 carbon atoms
~20 long chain alkyl groups are preferred. The cationized cellulose molecular weight used here is about 100,000 to
Between 8,000,000 and 8,000,000.

As the cationic starch, those represented by the following general formula (IV) are preferred.

l3 (rV) in the formula, B: starch residue R10: alkylene group or hydroxyalkylene group RI I, R12, R13, the same or different, alkyl group, aryl group, aralkyl group having 10 or less carbon atoms, or in the formula may contain a nitrogen atom to form a heterocycle.

X2: Anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfate, phosphoric acid, nitric acid, etc.) e: Positive integer The degree of cation substitution of cationic starch is 0.01 to 1, that is, 0 per anhydroglucose unit. .01~1, especially 0.02~
Preferably, 0.5 cationic groups are introduced. A degree of substitution of 0.01 or less is not sufficient, and a degree of substitution of 1 or more is acceptable, but from the viewpoint of reaction yield, 1 or less is preferable.

As the cationized guar gum derivative, the following general formula (V) is used.
Those represented by are preferred.

(V) In the formula, D=gum residue RI4, alkylene group or hydroxyalkylene group RIs, RIs, Rat are the same or different and have 10 or less carbon atoms, an alkyl group, an aryl group, an aralkyl group, or in the formula may contain a nitrogen atom to form a heterocycle.

x,: Anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfate, phosphoric acid, nitric acid, etc.) f: Positive integer The degree of cation substitution of the cationized guar gum derivative is 0.0
Preferably, 1 to 1, especially 0.02 to 0.5, cationic groups are introduced into the sugar unit. This type of cationic polymer is disclosed in Japanese Patent Publication No. 58-35640 and Japanese Patent Publication No. 6
0-46158 and Japanese Patent Application Laid-Open No. 58-53996, and is commercially available, for example, from Celanese-Stein-Hall under the trade name Jaguar.

The diallyl quaternary ammonium salt polymer or diallyl quaternary ammonium salt/acrylamide copolymer is preferably one represented by the following general formula (VI) or (■).

In the following margins (VI) (■) (VI) and (■), RII, RII, are the same or different, hydrogen, alkyl group (1 to 18 carbon atoms), phenyl group, aryl group, hydroxyalkyl group , amidoalkyl group, cyanoalkyl group, alkoxyalkyl group, carboalkoxyalkyl R20. lli21. R22. R23, same or different, hydrogen atom, lower alkyl group (1 to 3 carbon atoms), phenyl group x 4: anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfate, nitric acid, etc.) g: Integer h from 1 to 50: Integer i from 0 to 50: Integer from 150 to 8000 The molecular weight of the diallyl quaternary ammonium salt/acrylamide' copolymer is approximately 30,000 to 2 million, preferably 1
A range of 00,000 to 1,000,000 is good).

As the quaternized polyvinylpyrrolidone derivative, those represented by the following general formula (■) are preferred.

(■) In the formula, R24: hydrogen atom or alkyl group having 1 to 3 carbon atoms R25
．． l (26. R2'l, same or different, hydrogen atom, alkyl group having 1 to 4 carbon atoms, hydroxyalkyl group, amidoalkyl group, cyanoalkyl group, alkoxyalkyl group, carboalkoxyalkyl group Y: oxygen atom or NH group x in amide bond: anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, carbon number 1-4
alkyl sulfuric acid, phosphoric acid, nitric acid, etc.) 1: integer j+ of 1 to 10 = integer of 20 to 8000 The molecular weight of the quaternized polyvinylpyrrolidone derivative is 1
Especially good is 50,000 to 2,000,000, preferably 50,000 to 1,500,000.

The content of cationic nitrogen derived from the cationic polymer contained in the vinyl polymer is 0.0% relative to the vinyl polymer. 004-0.2%, preferably 0.01-0.1
It is 5%. 0. If it is less than 0.04%, it will not be sufficiently effective, and if it is more than 0.2%, it will be good in terms of performance but will cause coloring of the vinyl polymer and will also be economically disadvantageous.

Among these cationic polymers, cationized cellulose, diallylammonium salt polymers, diallylammonium salt/acrylamide copolymers, and the like are particularly preferred.

Examples of amphoteric polymers include copolymers of acrylic esters or methacrylic esters and betaine-type amphoteric compounds of acrylic esters or methacrylic esters, polymers of methacrylic esters, polymers of acrylic esters, etc. Can be mentioned. Specifically, for example, each of the following groups (i) to (iii): (i) dimethyl esterminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, N,N-dimethylethylmethacrylamide, 4-vinylpyridine; etc., (ii) stearyl (meth)
Acrylate, lauryl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, allyl (meth)acrylate, ethyl (meth)acrylate
Acrylate, 2-ethylhexyl acrylate, etc. (
iii) A'/IJ lonitrile, dia7ton, acrylamide, styrene, chlorostyrene, vinyltoluene, vinyl acetate, hydroxyalkyl (meth)acrylate, ester of polyethylene glycol or polypropylene glycol with (meth)acrylic acid, N-
Copolymerizing monomers selected from vinylpyrrolidone, etc.
This can be treated with halogenated acetic acid to make it amphoteric (Japanese Unexamined Patent Publication No. 104209/1983).

These cationic polymers and amphoteric polymers can be used alone or in combination of two or more, and there is no
．． It is preferably blended in an amount of 0.05 to 2%, particularly 0.1 to 1.0%.

(C) The fluorine-based oil used as the Jlli component is an organic compound containing a fluorine atom that is liquid at room temperature, such as perfluorodecalin, perfluoroadamantane, perfluorobutyltetrahydrofuran,
Perfluorooctane, perfluorononane, perfluoropencune, perfluorotecan, perfluorooctane, perfluoropolyether, etc. are mentioned, and in particular, the following general formula [wherein R1, R3, R4 and R5 are the same or different] a fluorine atom, a perfluoroalkyl group, or a perfluoroalkyloxy group, respectively.
Lt fluorine atom or perfluoroalkyl group, plq
and r represents a number of 0 or more such that the molecular weight is 500 to 100.000. However, p=q=r=0 is never satisfied. ] Perfluoropolyethers represented by these are preferred.

Note that the perfluoro groups shown in parentheses do not need to be arranged in this order, and random polymerization or block polymerization may be used. Such perfluoropolyethers are preferably liquid ones with a viscosity of 5 to 5.000 cSt, such as those of the following general formula (■) CF3 CF30-(CFCF20)T-(cF, Kano, CF,
[:IX:] (wherein, X and y have a molecular weight of 50
0-10.000 indicates tonal number, x/y is 0.2-2
It is. ) FOMBLIN HClO4
(average molecular weight 11.500), HC/25 (average molecular weight 3.2
00) and HC/R (6,600) (manufactured by Montefluos), and the following general formula (X)F-(CF2CP
Demnum S-20 (weight average molecular weight 25.000) represented by 2CF20h-CF2CF3 (X) (in the formula, 2 represents a number from 4 to 500), the same S-
65 (4.500), S-100 (5.600)
Commercially available products such as and S-200 (8.400) (manufactured by Daikin Industries, Ltd.) can be used.

Fluorine-based oils can be used alone or in combination of two or more, and these fluorine-based oils may be present in the total composition in an amount of 0.01 to
It is preferable to add 5%, especially 0.1 to 1%. 0.0
If it is less than 1%, the conditioning effect will be low.
If it exceeds 5%, disadvantages such as decreased foaming and stickiness after drying are observed, which is not preferable.

The fluorine-based oil used in the present invention is insoluble in water and has a higher specific gravity than hydrocarbon-based oils. Therefore, depending on the form of cleaning agents containing fluorine-based oils,
A technique to stabilize this dispersion may be required. For this dispersion, it is effective to add a generally used thickener such as an anionic polymer or a nonionic polymer in addition to the conditioning polymer that is component (B) of the present application. For example, anionic polymers include xanthan gum, carboxyvinyl polymer, carboxymethylcellulose, etc., and nonionic polymers include methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc., but xanthan gum and carboxyvinyl polymer are preferable. be.

These thickeners may be added in an amount of 0.1 to 5% in the total composition, especially 0.
．． Preferably, it is blended in an amount of 1 to 2%. If it is less than 0.05%, the stabilizing effect will not be sufficient, and if it exceeds 5%, there will be disadvantages such as an adverse effect on the conditioning effect, which is not preferable.

Furthermore, if the cleaning agent according to the present invention is not a homogeneous liquid phase system,
For example, when mixed with a propellant and used as an aerosol type, or when shaken before use, these thickeners are not necessarily required.

Furthermore, the cleaning composition of the present invention may contain components commonly used in cleaning compositions, such as nonionic surfactants, alkylamine oxides, foam boosters such as fatty acid alkanolamide, etc., to the extent that the effects of the present invention are not impaired. , squalene, lanolin, silicone derivatives, cationic surfactants, etc.; humectants such as propylene glycol, glycerin, diethylene glycol monoethyl ether, sorbitol; viscosity modifiers such as polyoxyethylene glycol distearate, ethanol; Pearlizing agents, fragrances, pigments, ultraviolet absorbers, antioxidants, disinfectants such as triclosan and trichlorocarpan; anti-inflammatory agents such as potassium glycyrrhizinate and tocopherol acetate; anti-dandruff agents such as zinc pyrithione and octopirox; methylparaben , preservatives such as butylparaben, etc., Encyclopedia・
of Shampoo Ingredients [BNCYCL
OPBDIAOFS)IAMPOOINGRBDIB
NTS (MICBLLB PRBS3.1985)]
Components etc. described in can be added as desired.

〔Effect of the invention〕

The detergent composition of the present invention has excellent conditioning effects such as ease of combing through the hair during rinsing, ease of combing after drying, and no stickiness, and can be suitably used as a shampoo. Furthermore, when used on the body, the skin does not feel sticky and has a smooth feel, making it useful as a body cleansing agent such as body shampoo or face wash. It is also useful as a detergent for light clothing.

〔Example〕

Next, the present invention will be explained by giving examples.

Example 1 Shampoo compositions having the compositions shown in Table 1 were prepared according to a conventional method, and the feel of the hair during rinsing and after drying was evaluated using the following evaluation method. The results are shown in Table 1.

Evaluation method: Apply 1 g of shampoo to 20 g (15 cm) of hair of a healthy Japanese woman, lather for 1 minute, and evaluate how easily the shampoo runs through your fingers when rinsing, how well you can comb the hair after drying it with a hair dryer, stickiness, and softness. Evaluation was made by 15 expert panelists according to the following criteria.

When rinsing, the comb A: Squeak is weak and the comb runs well B: The squeak is a little strong and it is difficult to comb the comb C: The squeak is strong and the comb is difficult to comb after drying A: The comb runs smoothly B : Slightly gets caught when combing C: Difficult to comb the ends of hair, etc. A: Smooth without stickiness B: Slightly sticky C: Sticky Softness after drying A: Soft B: Slightly soft C: Soft As is clear from Table 1, the shampoo composition of the present invention has good combability after rinsing, good combability after drying,
It is non-sticky and has excellent softness.

Examples 2 to 5 The shampoo compositions having the compositions shown below all had a good feel after rinsing and drying, and had excellent conditioning effects.

(Example 2) (%) (FOMBLIN HClO4: Montefluos) Preservative 0.1 Flavor, pigment, pH adjuster (appropriate amount) Water
balance total
100.0 (Example 3) (%) Lauryl sulfate triethanolamine 4 Lauric acid diethanolamide 5 Preservative 0
．． 1 Fragrance, pigment, pH adjuster (appropriate amount) water
balance total
100.0 (Example 4) (%)Polyoxyethylene laurylny 10Tyl sulfate triethanolamine (3B, O,)Lauryldimethylamino-2-hydro 5Xypropylsulfobetaine Lauric acid monoethanolamide 4Cationic polymer 0 .3 (Marko)
100: Merck & Co.) Preservatives 0.1 Fragrances, pigments, pH adjusters (appropriate amount) Water
balance total
ioo,.

(Example 5) (%) Polyoxyethylene lauryl ether 8 Triethanolamine sulfate (3B, O,”) (Amizole υ
tl: Yoken Fine Chemicals Q@) Preservatives 0.1 Fragrances, pigments, pH adjusters (appropriate amount) Water
balance total
100.0 Example 6 A body cleansing composition having the composition shown below has an excellent feel such that the skin is not sticky and smooth after drying.

(%) Triethanolamine lauryl phosphate 18 Triethanolamine laurate 2 Monoethanolamide laurate 2 Xanthan gum
l (Echo Gum: Dainippon Pharmaceutical @) Preservative 0.1 Fragrance, pigment, PI + regulator (appropriate amount) Water Balance total i 00.0 Test Example 1 Regarding Example 4, stored in a constant temperature bath at 30°C for 20 days,
The presence or absence of precipitate was observed.

As a result, no precipitate was observed, and it was confirmed that the fluorine-based oil was stably dispersed.

that's all

Claims (1)

[Claims] 1. The following components (A), (B) and (C) (A) One or more surfactants selected from anionic surfactants and amphoteric surfactants (B ) A cleaning composition containing one or more polymers selected from cationic polymers and amphoteric polymers (C) a fluorine-based oil agent. 2. The fluorine-based oil agent (C) has the following general formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] [In the formula, R^1, R^3, R^4 and R^5 may be the same or different, and each represents a fluorine atom, a perfluoroalkyl group, or a perfluoroalkyloxy group, and R^2
represents a fluorine atom or a perfluoroalkyl group, and p, q and r represent a number of 0 or more such that the molecular weight is 500 to 100,000. However, p=q=r=0 is never satisfied. ] The cleaning composition according to claim 1, which is a perfluoropolyether represented by: