JP3441261B2 - Aqueous liquid cleaner - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
Is extremely small, and the
An aqueous liquid detergent that can be easily extruded. [0002] 2. Description of the Related Art Foamed cleaning agents usually have a relatively low viscosity.
Fill the former solution with the surfactant solution, and then
By extruding, the foam is discharged and used.
It is excellent in convenience, ease of use, etc.
It is applied to hair shampoos, facial cleansers, etc. this
Cleansing agents used in the form of foam are particularly suitable for personal cleansing
Can be washed without straining the skin
Can be compared to liquid, paste, solid and other forms
It has a very good form in terms of mildness.
You. [0003] However, such foamed detergents are usually used.
At high temperatures a uniform foam can be obtained, but at low temperatures
Increases the viscosity of the cleaning liquid filled in the former container
When the foam becomes uneven or extrusion becomes impossible
There was a problem. [0004] SUMMARY OF THE INVENTION Accordingly, an object of the present invention is as follows.
Has no viscosity increase at low temperature
Provide a liquid detergent that is easy to extrude and provides uniform foam
It is to be. [0005] In such a situation, the book
The present inventors have conducted intensive studies and found that amino acid-based surfactants
If the agent and salt are used in a specific ratio, the viscosity increase at low temperature
Easy to push out of container even at low temperature, uniform foam
That an aqueous liquid detergent that can obtain
And completed the present invention. That is, the present invention relates to (A) an amino acid system
Surfactant 5 to 50% by weight, and (B) salt 0.1 to 5
The cleaning solution containing the weight% was filled in the former container.
An aqueous liquid detergent characterized by that
You. [0007] BEST MODE FOR CARRYING OUT THE INVENTION The component (A) used in the present invention
Amino acid surfactants include primary to tertiary amino groups
Is particularly limited as long as it has a surfactant and a carboxyl group.
Not specifically, (a) N-acylamino acid-based interface
Activator, (b) amide amino acid (imidazoline) field
Surfactants, (c) aminodiacetic acid-based surfactants and the like.
It is. (A) N-acylamino acid surfactants
For this reason, those represented by the following formula (1) are preferable. [0009] Embedded image [Wherein, R¹Is a linear or branched carbon number 7
To 21 alkyl groups or alkenyl groups;^TwoIs water
Represents an alkyl or alkenyl group having 1 to 4 carbon atoms.
Then R ^ThreeIs-(CH_Two)_pR^Four(R^FourIs hydrogen, hydroxyl group or
-COOM¹M)¹Is hydrogen, alkali metal or
Alkanolamine) In the equation (1), R¹Has 6 to 18 carbon atoms
Are preferred, and especially an alkyl group having 10 to 14 carbon atoms.
Kill groups are preferred. R^TwoAs hydrogen, carbon number 1-4
Alkyl groups are preferred, and hydrogen and methyl groups are particularly preferred.
No. R^ThreeAs hydrogen,-(CH_Two)_pR^FourIs preferred. M¹
Potassium and triethanolamine are preferred
No. N-acyl amino acid represented by formula (1)
Among the surfactants, N-lau is preferable.
Loylglutamic acid, N-myristoylglutamic acid,
N-lauroyl-N-methylglycine, N-lauroyl
-Β-alanine, N-myristoyl-β-alanine, N
-Lauroyl aspartic acid, N-lauroyl serine
And alkali gold such as sodium and potassium
Genus salt; monoethanolamine, diethanolamine,
Alkanolamine salts such as liethanolamine;
Can be The compound represented by the formula (1) has an L-form,
Although there are D-form and racemic-form, in the present invention, these
Either can be used. (B) Amidoamino acid surfactants
Is preferably represented by the following formulas (2) and (3).
No. [0014] Embedded image [Wherein R^FiveAnd R⁷Is the number of carbon atoms respectively
Represents a saturated or unsaturated hydrocarbon group of 7 to 19;⁶Passing
And R⁸Is -CH_TwoCOOM^TwoOr -CH_TwoCH_TwoCOOM^Two(M^Two
Represents hydrogen, alkali metal or alkanolamine)
And R⁹Is hydrogen, -CH_TwoCOOM ^TwoOr -CH_TwoCH_TwoCOOM^Two(M
^TwoHas the same meaning as described above) In the formulas (2) and (3), R^FiveAnd R⁷As
Is preferably an acyl group having 10 to 14 carbon atoms;⁶And R
⁸As -CH_TwoCH_TwoCOOM^TwoIs preferred, and R⁹As the water
Elementary, -CH_TwoCH_TwoCOOM^TwoIs preferred. The amidoamido represented by the formulas (2) and (3)
Among the surfactants, N-lac
Uroyl-N'-carboxymethyl-N '-(2-hydr
Roxyethyl) ethylenediamine, N-lauroyl-
N'-carboxyethyl-N '-(2-hydroxyethyl
G) ethylenediamine, N-myristoyl-N'-cal
Boxymethyl-N '-(2-hydroxyethyl) ethyl
Diamine, N-lauroyl-N- (2-hydroxy
Tyl) -N'-carboxymethylethylenediamine, N
-Lauroyl-N- (2-hydroxyethyl) -N ',
N'-bis (carboxymethyl) ethylenediamine, etc.
Is mentioned. (C) As aminodiacetate surfactant
Is preferably represented by the following formula (4). [0019] Embedded image[Wherein, R^TenIs alkyl having 8 to 24 carbon atoms
Group, alkenyl group, aryl group, aralkyl group, alk
Represents an aryl group or an alkenyl aryl group, and X represents water
Elementary or-(CH_Two)_qCOOM^ThreeAnd M^ThreeIs hydrogen, alkali gold
Genus, ammonium or hydroxyalkyl having 2 to 3 carbon atoms
Represents an alkanolamine having a thiol group, wherein q is 1 to 4
Show the number) In the formula (4), R^TenHas 8 to 14 carbon atoms
Is preferably an alkyl group, and X is preferably hydrogen;
M^ThreePotassium and alkanolamines are preferred
In addition, q is preferably 1 or 2. The aminodiacetic acid-based interface represented by the formula (4)
Among the activators, preferred are laurylamino
Propionic acid, myristylaminopropionic acid, etc.
Can be Among these surfactants, the following formula
(5): [0024] [Formula 5] R¹¹CONH (CH_Two)_nCOOM^Four... (5) [Wherein R¹¹CO- is a straight chain having 10 to 16 carbon atoms
An acyl group; n is a number of 1 or 2;^FourIs n
When 1, sodium, potassium or alkanolan
Monium, potassium or alkanol when n is 2
Ammonium amide]
Silamino acid salts are preferred. The above secondary amide type N-acyl amino acid salt
In equation (5), R¹¹Of a linear acyl group represented by CO-
Carbon number is 10-16, especially 12-14
Are preferable, and specifically, a caprinoyl group, a lauroyl group
Or a myristoyl group is preferred. Also, M^FourIndicated by
As alkanol ammonium, for example, monoethano
Ammonium, diethanol ammonium, triet
Tanol ammonium, especially triethanol
Ammonium is preferred. In addition, in Formula (5), n is 2 and
Yes, M^FourIs sodium, the craft point is high
Is poor in water solubility, so when used in liquid skin cleanser
Is not preferred. Secondary amide N represented by the formula (5)
-Among the acyl amino acid salts, particularly preferred
Is N-lauroyl-β-alanine, N-myristoyl
-Β-alanine and the like. These are
Less irritating to use as a cleaning agent
No. These amino acid-based surfactants may be used alone or in combination.
Can be used in combination of two or more, and
5 to 50% by weight (hereinafter simply referred to as%), preferably
The content is 2 to 30%, particularly preferably 5 to 20%. 1
%, Sufficient detergency cannot be obtained, and if it exceeds 50%,
It is preferable because it may cause clogging of the former container
Absent. The salt of the component (B) used in the present invention
May be any of an inorganic salt and an organic acid salt.
As, for example, hydrochloric acid, sulfuric acid, sulfurous acid, carbonic acid, phosphoric acid,
Sodium, potassium, lithium of inorganic acids such as boric acid
Etc., alkali metal salts, alkaline earth metal salts, ammonium
Salts, alkylamine salts, alkanolamine salts, etc.
Examples of the organic acid salt include acetic acid and propion.
Acid, oxalic acid, malonic acid, succinic acid, glutaric acid,
Pinic acid, citric acid, maleic acid, fumaric acid, glycol
Acid, lactic acid, 2-hydroxybutyric acid, glyceric acid, hydro
Organics such as xymalonic acid, malic acid, tartaric acid and citric acid
Alkali metal salts, alkaline earth metal salts of acid, ammonium
Salt, alkylamine salt, alkanolamine salt, and
Glycine, alanine, arginine, glutamic acid, seri
Amino acid salts such as N, N, N-trimethylglycine
Betaine (with quaternary amine and carboxyl group in the molecule)
Compounds). Of these salts, organic acid salts are preferred,
Especially oxalic acid, malonic acid, succinic acid, glutaric acid, etc.
Polyvalent such as tricarboxylic acid such as dicarboxylic acid and citric acid
Carboxylic acid, glycolic acid, lactic acid, 2-hydroxybutyric acid
Hydroxy acid salts such as succinic acid
Lium, sodium succinate, triethanol succinate
Amine, potassium citrate, sodium citrate, que
Triethanolamine acid, potassium lactate, sodium lactate
Um, diethanolamine lactate, triethanolamine lactate
Min is preferred. As inorganic salts, sodium phosphate
And triethanolamine phosphate. The salt of component (B) is not necessarily a salt.
It is not necessary to mix them with each other
To form a salt in the composition. These salts may be used alone or in combination of two or more.
0.1 to 5% in the total composition, preferably
Or 0.2 to 5%, particularly preferably 1 to 4%
You. If it is less than 0.1%, prevent viscosity increase at low temperature
If it exceeds 5%, the viscosity of the system will be too high
Not good. The species of the bases of component (B) and component (A)
Classes may be the same or different.
Are preferably the same. The washing liquid is obtained by mixing the above components (A) and (B) with water.
Manufactured by dissolving in a neutral medium. Used here
The aqueous medium used is, for example, water, or water and glycerol.
And mixed systems with ethanol and the like.
50 to 94.9%, preferably 60 to 85% in the total composition
Be blended. Higher fat of component (C) used in the present invention
The acid salt may be either saturated or unsaturated.
And those having 8 to 22 carbon atoms, particularly 10 to 18 carbon atoms, are preferred.
No. Specific examples of preferred ones include lauric acid, milliliter
Stinic acid, palmitic acid, stearic acid, isostearic
Acid, oleic acid, hydroxydecenoic acid, coconut oil fat
Acid, reduced coconut oil fatty acid, tallow fatty acid, reduced tallow fatty acid,
Alkali such as sodium and potassium such as palm kernel fatty acids
Potassium metal salt, ammonium salt, monoethanolamine
Salt, diethanolamine salt, triethanolamine salt,
2-amino-2-methylpropanol, 2-amino-2
Alkanolamines such as methylpropanediol
Salts, basic amino acid salts such as lysine, arginine, etc.
I can do it. Of these, especially triethanolamine laurate
Luamine, potassium laurate, myristate trieta
Nolamine, potassium myristate, coconut oil fatty acid
Lium is preferred. Also, the higher fatty acid triethanol
When the amine salt is used, the pH of the composition is 6.5 to 8.5.
It is low irritation and is particularly preferred for skin cleansing. Further, these higher fatty acid salts are not necessarily
It is not necessary to mix it in the washing solution as a fatty acid salt.
Fatty acids and bases are added separately,Anti-standard
Let me respondFatty acid salts may be formed in the composition. One or more of these higher fatty acid salts may be used.
The above can be used in combination, and 5 to 5
0% by weight, preferably 5 to 30%, particularly preferably 5 to
20% is blended. If it is less than 5%, sufficient detergency can be obtained.
If it exceeds 50%, skin irritation occurs, which is not preferable.
No. The washing solution contains the amino acid-based surfactant.
In addition to surfactants, other additives commonly used in liquid cleaners
On, amphoteric, nonionic surfactants can impair the effectiveness of the present invention.
It is possible to mix within the range not to be mentioned. This
Specific examples of these surfactants include the following:
Can be (1) An alkyl group having an average of 10 to 16 carbon atoms
Or branched alkylbenzene sulfonic acid having
salt. (2) Linear or branched alkyl having an average of 10 to 20 carbon atoms
Having an average of 0.5 to 1 in one molecule.
8 moles of ethylene oxide, propylene oxide,
Butylene oxide, ethylene oxide and propylene
Oxide in a ratio of 0.1 / 9.9 to 9.9 / 0.1,
Or ethylene oxide and butylene oxide
Alkyl added at a ratio of 0.1 / 9.9 to 9.9 / 0.1
Or alkenyl ether sulfate. (3) an alkyl group or alkenyl having an average of 10 to 20 carbon atoms
Alkyl or alkenyl sulfate having a phenyl group. (4) O having an average of 10 to 20 carbon atoms in one molecule
Refin sulfonate. (5) A compound having an average of 10 to 20 carbon atoms in one molecule.
Lucane sulfonate. (6) an alkyl group having an average of 10 to 20 carbon atoms
Or an alkenyl group, having an average of 0.5 to 8
Ethylene oxide, propylene oxide, butyral
Len oxide, ethylene oxide and propylene oxide
The side has a ratio of 0.1 / 9.9 to 9.9 / 0.1
Or 0.1% ethylene oxide and butylene oxide
Alkyl added at a ratio of /9.9 to 9.9 / 0.1 or
Alkenyl ether carboxylate. (7) an alkyl group or alkenyl having an average of 10 to 20 carbon atoms
Α-sulfofatty acid salts or esters having a phenyl group. (8) Higher alcohol having 8 to 22 carbon atoms or its alcohol
Sulfosuccinates such as toxylates or higher fats
Sulfosuccinate derived from fatty amide. Pairs of anionic residues of these surfactants
As ions, alkali gold such as sodium and potassium
Alkaline earths such as genus ions, calcium and magnesium
Metal ion, ammonium ion, C2 or C3
Alkanolamine having 1 to 3 lucanol groups (eg
For example, monoethanolamine, diethanolamine, triethanolamine
Ethanolamine, triisopropanolamine, etc.)
Can be mentioned. Also counter ion of cationic residue
As halogen ions such as chlorine, bromine, iodine, etc.
Tosulfate, saccharinate ion
it can. (9) C8 to C20 represented by the following formula:
A fatty acid amide derivative having an alkyl group of the formula: [0041] Embedded image [Wherein, R¹²Is alkyl having 8 to 20 carbon atoms
A group represented by R¹³And R¹⁴Are the same or different, and
, An alkyl group having 1 to 3 carbon atoms, a hydro group having 1 to 3 carbon atoms
Xyalkyl group or-(C_TwoH_FourO)_mH group (m represents a number of 2 to 4)
Show) (10) Alkyl sacchar represented by the following formula:
Ride surfactant. [0044] Embedded image R^Fifteen-O- (R¹⁶O)_a-G_b [Where R^FifteenIs a straight chain having 8 to 18 carbon atoms or
Branched alkyl, alkenyl, or alkylphenyl
And R represents¹⁶Represents an alkylene group having 2 to 4 carbon atoms
A represents a number of 0 to 10, and G represents a reduction of 5 to 6 carbon atoms.
Represents a sugar, and b represents a number from 1 to 10] (11) an alkyl group having 8 to 24 carbon atoms,
Carbobetaine having a kenyl group or an acyl group,
Dobetaine, sulfobetaine, hydroxysulfobe
Tyne or amido sulfobetaine amphoteric surfactants. Among these surfactants, especially fatty acids
Salt, alkyl saccharide surfactant, fatty acid amide
Derivatives and betaine amphoteric surfactants are preferred. Further washing
Higher fatty acid salt for freshness and foaming
It is preferred to add. Further, in the cleaning solution, in addition to the surfactant,
Ingredients used in normal cleaning compositions, such as oils,
Wetting agents, high molecular compounds, preservatives, chelating agents, drugs, colors
Elements, fragrances, antioxidants, pH adjusters, etc.
It can be appropriately compounded within the range not to be described. The washing solution thus obtained is used.
At 5 ° C, a B-type viscometer (East
The viscosity when measured by Kyo Keiki Co., Ltd. is 30 cps or less.
It is preferably 1 to 15 cps.
It can be adjusted by selecting. 5 ° C of cleaning solution
If the viscosity exceeds 30 cps, a uniform foam can be obtained.
Tend to be difficult to extrude. [0050] The obtained washing liquid is a foam having a porous membrane.
Is filled in a steam container. As a porous membrane, for example,
Ponges, sintered bodies, nets and the like can be mentioned. These many
Of the porous membrane, the cleaning liquid remaining on the membrane is dried and solidified.
If clogging occurs due to
Therefore, the solidified material can be immediately dissolved to eliminate clogging.
Therefore, a thin net is preferable. As a net
Is preferably 50 to 500 mesh, especially 20 mesh
Because the thing of 0-400 mesh produces a good foam
preferable. Also preferred as a material for such meshes
Nylon, polyester, etc.
It is. The container must have a plurality of such membranes.
It is preferable to use two sheets especially from the viewpoints of economy, foam stability, etc.
Preferably it is. Also, as a former container,
Mix a certain amount of cleaning solution with a certain amount of air
Any one can be used as long as it can be put out.
JP-A-8-174272, JP-A-62-42787
And Japanese Patent Publication No. 52-16567.
Press the torso of the flexible container with your fingers to use
Quiz former; for example, Japanese Utility Model Laid-Open No. 3-7963,
Japanese Patent Application Laid-Open No. 62-103458 and the like
Pressing the head of a cap with a pump mechanism with fingers
More commonly used pump formers. As the former container used in the present invention
Preferred examples include those shown in FIG.
It is. In FIG. 1, the former container 10 is
A cap is attached to the opening 11A of the container body 11 having a quiz property.
Screw the cap 12 and mix gas and liquid
A joint 13 is provided. The gas-liquid mixing unit 13 is
And a porous membrane 13B. Ma
In addition, the former container 10 cares about the dip tube 14.
A certain gap is provided between the tube connecting portion 13A of the liquid mixing portion 13 and the tube connecting portion 13A.
In the state of being connected to the gas-liquid mixing section 13, and
While supporting the dip tube 14
It is inserted into the container body 11. The former container 10 has a cap
12 on the discharge side (upper side in the figure) of the gas-liquid mixing unit 13.
The existing nozzle portion 15 is screwed. The nozzle 15 is
Closed position and open position rotated 90 degrees with respect to cap 12
In the closed position, the nozzle portion 15 is set in an annular shape.
Put the protruding seal ring part 16 above the gas-liquid mixing part 13
Adhere to the plug part 17 located, seal at the open position
Discharge path is formed by separating ring portion 16 from plug portion 17
I do. In addition, the discharge port 18 of the nozzle portion 15 has many
A porous membrane is provided with a porous membrane fixture 18A and a porous membrane 18B.
The porous membrane 18B is fitted and fixed by the fixture 18A.
You. The former container 10 includes the cap 1
The second air return path 21 is provided with a ball valve 22. baud
The valve 22 is a seal above the air return path 21 when discharging bubbles.
Pressure inside the container body 11 due to squeezing in close contact with the part 21A
To rise. Then, the ball valve 22 finishes discharging bubbles.
After that, it is locked by the protrusion 21B below the air return path 21,
Due to the container restoring force of the container body 11 from which the squeeze has been removed
External air is introduced into the container body 11 by the negative pressure inside the container.
Enter. The former container 10 operates in the following manner.
Therefore, foam is discharged. (1) By rotating the nozzle portion 15, the nozzle portion 15
The seal ring portion 16 of the plug 12 of the cap 12
1 and form a bubble discharge path indicated by arrow A in FIG. (2) By manually squeezing the container body 11
And the air directly introduced into the gas-liquid mixing section 13 of the cap 12.
Gas (or liquid) and gas-liquid via dip tube 14
By mixing with the liquid (or air) introduced into the mixing section 13
Forming bubbles passing through the porous membrane 13B, and
Through the bubble discharge path A described above, the discharge port 18 of the nozzle 15
Through the porous film 18B provided at the end, the discharge port 18
And discharge it. At this time, the ball valve 22 is connected to the air return path 21.
And the pressure inside the container body 11 is increased
Raise it. (3) After discharging the foam, the ball valve 22 returns to the air.
The squeeze is removed by the projection 21B of the road 21 and the squeeze is removed.
To the negative pressure inside the container caused by the container restoring force of the container body 11
From the air return path indicated by arrow B in FIG.
It is introduced into the container body 11. At this time, the external air
While trying to go through the reverse path of the bubble discharge path A of the above (2),
Since the residual bubbles of the porous film 13B become resistance, the air
Take the return route B. Also, the residual bubbles of the porous film 18B are
When the air is slowly introduced into the air return path B
Is replaced with an air return path 21 and a boa.
Valve 22 at a position that directly communicates with the outside of the cap 12.
A girder former container may be used. In the aqueous liquid cleaning agent of the present invention, the cleaning liquid forms a film.
A bubble is generated by passing, but the generated foam bubble
A density of 0.03 to 0.25 g / ml, especially 0.06 to 0.
It is preferably 15 g / ml. In this range of bubble density
Cleaning power, especially when used for skin cleaning
It is preferable because it has excellent properties. The foam density is 100ml
The foam is discharged from the former into the measuring cylinder of
Can be determined by measuring The aqueous liquid detergent of the present invention comprises
System, cleansing foam, shaving foam,
For skin cleansing agents such as D-foam and hair foam
Can be suitably used. [0060] The aqueous liquid detergent of the present invention has a low viscosity at low temperatures.
Extremely small rise in temperature
Can be easily extruded from and obtain a uniform foam
it can. [0061] Next, the present invention will be further described with reference to examples.
However, the present invention is not limited to these examples. [0062] [0063] [0064] Example1 table1The cleaning liquid having the composition shown in was produced by a conventional method, and the obtained cleaning liquid was obtained.
Cleaning solutionThe former container shown in FIG. 1 (200 mesh
2 polyester screens (manufactured by NBC Industries) (13
B, 18B))And extruded at 5 ° C
NatureToWas evaluated.For evaluation, use the container containing the cleaning solution.
After storing at 5 ° C. for 24 hours, it was extruded at 5 ° C.
Sometimes it is easy to extrude and ○ is hard to extrude.
I went.Table of results1Shown in [0066] [Table 1] Table1As is clear from the results, the product of the present invention
All have no viscosity increase at 5 ° C and are easy to extrude
And a uniform foam could be obtained. Example2 [Table 2] (Ingredient) (%) N-lauroyl-β-alanine 5.0 Lauric acid 4.0 Potassium hydroxide 2.5 Potassium succinate 2.0 Glycerin 5.0 Polyoxyethylene (5) monolaurate 0.5 Cocoylamide propyl betaine 0.3 Isopropyl methylphenol 0.2 Fragrance 0.2 Water balance A cleaning solution having the above composition was prepared by a conventional method, and
It was used by filling it into the same former container as in Example 1.
Roasted and foamed, good massage, low temperature
No exudation at 5 ° C
It was good.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing an example of a former container used in the present invention. [Description of Signs] 13 Gas-liquid mixing section 13B Porous membrane 14 Dip tube 15 Nozzle section 18 Discharge port 18B Porous membrane

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Yasushi Kajiwara 666-1 Kasubeka, Kasukabe-shi, Saitama (56) References JP-A-48-10107 (JP, A) JP-A-58-1885697 (JP, A) Japanese Patent Laid-Open No. 47-42809 (JP, A) JP-A-6-158089 (JP, A) JP-A-63-91311 (JP, A) JP-A-5-156281 (JP, A) JP, A) Technical News, Ajinomoto Co., 1982, No. 2 (58) Field surveyed (Int. Cl. ⁷ , DB name) C11D 1/00-17/08 A61K 7/075 A61K 7/50

Claims (1)

(57) [Claims 1] (A) the following formula: ## STR1 ## ^{_{R 11 CONH (CH 2) n}} COOM 4 ( wherein, R ¹¹ CO- is a straight of 10 to 16 carbon atoms Chain acyl group
And n is a number of 1 or 2, and M ⁴ is when n is 1.
Is sodium, potassium or alkanol ammonium
And when n is 2, potassium or alkanol ammonium
Amino acid-based surfactant represented by 5)
50% by weight , (B) oxalic acid, malonic acid, succinic acid, glutaric acid,
Enoic acid, glycolic acid, lactic acid, and 2-hydroxybutyric acid
An aqueous liquid detergent, characterized by filling a former container with a detergent containing 0.1 to 5% by weight of a salt of an organic acid selected from salts and (C) a higher fatty acid salt .