JP3532333B2 - 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 detergent composition, and more particularly, it contains an amide ether carboxylate, an amide ether and a water-soluble divalent metal salt and does not contain glycerin or a specific glyceryl ether. Alternatively, the present invention relates to a cleansing composition which contains a small amount and is excellent in foaming property and feeling in use and mild to the skin.

[0002]

2. Description of the Related Art Nowadays, the awareness of safety for the human body is increasing more and more, and the detergent for clothes, the detergent for kitchen, the detergent for home, the detergent for hair, and the detergent for body are provided. With respect to detergents that are often exposed to humans, various attempts have been made to moderate the action on the skin. For example, the pH of the cleaning composition is 5 to 6
It is adjusted to (weakly acidic) to bring it closer to the pH of human skin so that its action on the skin is mild, and the main washing base is one that is as mild as possible. ing.

Amino acid type surfactants and alkylphosphoric acid type surfactants are used as such mild detergent bases (Japanese Examined Patent Publication No. 50-40125 and Japanese Examined Patent Publication No. 55-90335). Publication, JP-B-58-27319
No. However, although these surfactants are mildly irritating, they cannot exhibit sufficient foaming power and detergency alone, and have drawbacks such as poor solubility.

Further, in the kitchen cleaner, sodium alkylbenzene sulfonate has been widely known as a base having excellent cleaning performance, but it has a strong degreasing power from the skin and is apt to cause rough hands. There are difficulties.

Therefore, recently, kitchen detergents containing sodium alkylethoxysulfate, which is less irritating to the skin, as the main washing base have become mainstream, and further, tertiary amine oxides and higher fatty acids. By using a co-surfactant such as diethanolamide together, various properties are improved, and at the same time, the action on the skin is becoming milder.

However, although the effects of various detergents on the skin have become milder than in the past, the present situation is that they have not yet reached a sufficiently satisfactory level. In addition, it is difficult to say that all of them have a strong squeakiness during use and have a good feeling in use.

On the other hand, the alkyl glycoside, which is a sugar derivative surfactant, is not only a mild surfactant but also a nonionic surfactant, it not only produces stable bubbles, but also It is known to act as a foam stabilizer against other anionic surfactants, and has been attracting attention in recent years. For example, JP-A-58-104625
JP-A No. 58-186429 discloses a foaming surfactant composition containing an alkyl glycoside and an anionic / amphoteric surfactant. A foaming surfactant composition containing an agent and an amide / amine oxide is described. Further, JP-A-64-69695 discloses a detergent composition containing an alkyl glycoside and an amphoteric surfactant in a specific ratio.

However, although the surfactant composition and detergent composition described in these publications are superior in performance to conventional polyoxyethylene alkyl ether-based detergents, they do not affect the skin. It also has a problem in that it does not reach a sufficiently satisfactory level in terms of mildness. Particularly, for alkyl glycosides, sulfate groups such as alkylbenzene sulfonate, α-olefin sulfonate, alkyl sulfate, alkyl ethoxy sulfate, α-sulfo fatty acid ester salt,
Alternatively, when an anionic surfactant having a sulfonate group is used in combination, it is preferable in terms of detergency, foaming power or economy, but a decrease in mildness to the skin is an unavoidable problem.

This decrease in skin mildness is considered to be caused by the exacerbation of the denaturing action on the proteins constituting the skin, and has been a problem for some time. Further, although alkyl glycosides have high foaming properties, they have strong creases during washing and rinsing, and it is not technically easy to mix them into shampoos in large amounts.

Amide ether carboxylate is also known as a mild surfactant, and is known as CHE in Germany.
It is marketed by the company MY under the Akipo brand name. The use feeling of amide ether carboxylate does not have a squeaky feeling unlike alkyl glycosides. However, it is difficult to say that the anionic surfactant is strong, and when it is mixed with a dishwashing detergent or the like, the dish is slippery and difficult to wash, and is not necessarily good. Further, the foaming property is poor by itself, and the application to the detergent is limited to the use as the cosurfactant.

[0011] As a technique known so far regarding application of an amide ether carboxylic acid type surfactant to a detergent, amide ether carboxylic acid, polyoxyethylene alkyl sulfuric acid ester, fatty acid diethanol amide, higher alcohol alkylene oxide are known. Detergent combined with an adduct, acyl sarcosinate, etc. (European Patent No. 102118), a method in which an amide ether carboxylic acid surfactant and a polyoxyethylene alkyl sulfate are used in combination (European Patent No. 215504). ), Amide ether carboxylic acid starting from fat and oil, lauryl sulfate ester, lauryl ether sulfate ester, alkyl ether carboxylic acid, lauric acid and glycidyl trimethyl ammonium chloride were reacted 4
Foam bath agents, shampoo agents, shower agents, etc. in combination with graded products (Japanese Patent Publication No. 63-291996, European Patent No. 219893), amide ether carboxylic acids and alkyl ethers containing soap as a main component. Detergent containing carboxylic acid salt (US Pat. No. 4,865)
757 specification) and the like. However, none of these detergents is still satisfactory in terms of foamability.

Therefore, an object of the present invention is to provide a mild detergent composition having sufficient detergency and foaming ability even in the presence of a large amount of oily stains and having a low denaturing effect on skin proteins and having a good feeling of use. To do.

[0013]

Means for Solving the Problems The present inventors have paid attention to the mildness of amide ether carboxylate salts to the skin, and as a result of intensive studies to overcome the drawbacks, as a result, a specific amide ether carboxylate salt, A detergent composition containing a specific amide ether and a water-soluble divalent metal ion in a specific ratio and containing no or a small amount of glycerin or the specific glyceryl ether can achieve the above object. I found out.

The present invention has been made based on the above findings and contains the following components (a), (b) and (c):
The weight ratio [(a) / (b)] between the content of the component (a) and the content of the component (b) is 0.1 to 100, and the total divalent amount of the component (c) in the entire composition. The molar ratio (X / Y) between the metal ion (denoted as X) and the total anionic surfactant (denoted as Y) containing the component (a) is 0.025 to 10, and the following component (x) The present invention provides a detergent composition which does not substantially contain or the content of the component (x) is 10% by weight or less based on the total content of the components (a) and (b). .

(A) An amide ether carboxylate represented by the following formula (5) (same as the above-mentioned formula 1) represented by the general formula (I).

[0016]

[Chemical 5]

(B) An amide ether represented by the general formula (II) of the following [Chemical formula 6] (the same as the above-mentioned [Chemical formula 2]).

[0018]

[Chemical 6]

(C) Water-soluble divalent metal salt. (X) The following general formula (I)
Glycerin or glyceryl ether represented by II).

[0020]

[Chemical 7]

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The detergent composition of the present invention will be described in detail below.

The amide ether carboxylate represented by the above general formula (I), which is the component (a) used in the present invention, is used for improving the mildness to the skin. In the above general formula (I), R ₂
As the alkyl group or alkenyl group represented by, an alkyl group, particularly a linear alkyl group is preferable, and further,
From the viewpoint of foamability and detergency, carbon number is 9 to 17, especially 10
Those of -14 are preferable. Further, n is 1 to 1 in terms of foaming property.
7, more preferably 2 to 5, especially 2 to 3 are preferable. Also,
m is preferably 0 to 5, more preferably 0 to 2, and most preferably 0 in terms of foamability. Further, A is particularly preferably a hydrogen atom from the viewpoint of foaming property. K in the group represented by A is 0 to 0 in terms of foaming property.
5 is preferable, and j is 0 to 2, particularly 0 in terms of foaming property.
Are preferred. The alkali metals represented by M are sodium and potassium, the alkaline earth metals are magnesium and calcium, and the alkanol ammonium is monoethanol ammonium (H
^{_{OCH 2 CH 2 NH 3 +)}} , diethanolammonium _{((HOCH 2 CH 2) 2} NH 2 +), triethanolammonium _{((HOCH 2 CH 2) 3} NH +) is preferable, and alkaline earth metals, particularly magnesium , Calcium, and magnesium is more preferable.

The content of the component (a) in the composition of the present invention is preferably 3 to 70% by weight, more preferably 5 to 70% by weight.
It is 40% by weight. If the content is less than 3% by weight, the foaming power is insufficient, and if it exceeds 70% by weight, it is difficult to produce the composition, and in the case of a liquid detergent, the solution stability is deteriorated, which is not preferable.

The amide ether represented by the general formula (II) which is the component (b) used in the present invention is used as a foaming agent. In the general formula (II),
The alkyl group or alkenyl group represented by R ₂ is preferably an alkyl group, particularly a linear alkyl group, and further has 9 to 17 carbon atoms, particularly 10 to 10 carbon atoms from the viewpoint of solubility, foaming property and detergency.
14 is preferable. Further, n is 2 to 5 in terms of foaming property.
It belongs to

The content of the component (b) in the composition of the present invention is preferably 1 to 70% by weight, more preferably 3 to.
It is 40% by weight. When the content is less than 1% by weight, sufficient foaming power cannot be obtained, and when it exceeds 70% by weight, it is difficult to produce a composition, and in the case of a liquid detergent, solution stability is deteriorated, which is preferable. Absent.

The weight ratio [(a) / (b)] of the content of the component (a) to the content of the component (b) is
It is 0.1 to 100, preferably 0.1 to 20, more preferably 0.1 to 10, most preferably 0.5 to 3.
If the weight ratio is less than 0.1, a tingling sensation occurs, and if it exceeds 100, the foaming force is insufficient, which is not preferable.

The sum of the contents of the components (a) and (b) [(a) + (b)] is preferably 1 to
It is 80% by weight, more preferably 5 to 40% by weight. If the total content is less than 1% by weight, the foaming power is insufficient, and if it exceeds 80% by weight, the production becomes difficult, and in the case of a liquid detergent, the solution stability deteriorates, which is not preferable.

The amide ether carboxylic acid salt (hereinafter sometimes referred to as "amido ether carboxylic acid salt (a)") which is the component (a) used in the present invention is, for example,
It can be produced by the method described in European Patent No. 219893. The method for producing a mixture of the component (a) and the component (b) (hereinafter sometimes referred to as “amide ether derivative mixture”) is not particularly limited, and the amide which is the component (b) is not particularly limited. It can also be produced directly by reacting a part of ether [hereinafter sometimes referred to as "amide ether (b)"] with halogen acetic acid, and the above amide ether carboxylate (a) can be converted to the above amide ether (b). Can also be added later.

As a method for synthesizing the amide ether (b) which is an intermediate for producing the amide ether carboxylate (a), a fatty acid lower alcohol ester such as a fatty acid methyl ester is used as a starting material to react an alkanolamine, Next, a method of polyoxyethylenating and / or polyoxypropylene, reacting an alkanolamine with a fat or oil as a starting material, and then a method of polyoxyethylenating and / or polyoxypropylene, reacting an alkanolamine with a fatty acid as a starting material Let
Next, a method of converting to polyoxyethylenation and / or polyoxypropylene, and the like can be mentioned. Among them, the method of producing a fatty acid lower alcohol ester such as fatty acid methyl ester as a starting material is preferable because it is less colored and does not substantially contain impurities such as glycerin or a glycerin derivative.

In another method for synthesizing the amide ether (b), for example, a method in which a fat or oil having a coconut oil fatty acid composition is used as a starting material and a alkanolamine is directly reacted and then polyoxyethylenated, the fat or oil is derived. General formula of the following [Chemical formula 8] (same as the above-mentioned [Chemical formula 3] and [Chemical formula 7])
A large amount of glycerin or glyceryl ether [component (x)] represented by (III) is produced, and the yield of component (b) and thus component (a) is low, which is not preferable in practice. In the method for producing the amide ether derivative mixture, the ratio of the amide ether carboxylate (a) and the amide ether (b) in the obtained amide ether derivative mixture is such that the amide ether (b) is a monohaloacetic acid alkali salt. It can be adjusted by selecting reaction conditions such as a molar ratio and a mixing method when the above are reacted.

[0031]

[Chemical 8]

The detergent composition of the present invention contains substantially no glycerin or glyceryl ether represented by the general formula (III) which is the component (x), or the content of the glycerin or glyceryl ether. Is 10% by weight or less, preferably 5% by weight or less, and more preferably 0% by weight (substantially not contained) with respect to the total content of the components (a) and (b). When the content exceeds 10% by weight, the foaming power of the composition is significantly reduced, and the low temperature stability when used as a liquid detergent is significantly deteriorated.

Further, for example, in the method of directly reacting an alkanolamine with an oil or fat having a coconut oil fatty acid composition as a starting material and then polyoxypropylene-forming or polyoxyethylenating and polyoxypropylene-forming, Glyceryl ether [(y) component] represented by the general formula (IV) of the following [Chemical Formula 9] (the same as the above-mentioned [Chemical Formula 4]) is produced, and the yield of the above-mentioned component (b) and thus the above-mentioned component (a) is obtained. The rate may be lower. Therefore, in the detergent composition of the present invention, the general formula (I
V) does not substantially contain the glyceryl ether, or the total content of the glyceryl ether and the component (x) is relative to the total content of the component (a) and the component (b). It is desirable that the content is 10% by weight or less, preferably 5% by weight or less, more preferably 0% by weight (substantially not contained). If the total content of the component (y) and the component (x) exceeds 10% by weight, the foaming power of the composition may be reduced, and the low temperature stability when used as a liquid detergent is low. There is a fear of falling.

[0034]

[Chemical 9]

Examples of the amide ether carboxylate as the component (a) include those sold under the trade name of "Akipo" by CHEM-Y of Germany. Since it contains glycerin or glyceryl ether as the component (x), it cannot be used for the purpose of the present invention.

The water-soluble divalent metal salt which is the component (c) used in the present invention suppresses the feeling of sliminess and improves the feeling of use. Examples of the water-soluble divalent metal salt include inorganic salts of alkaline earth metals, for example, magnesium chloride, magnesium sulfate, magnesium iodide, magnesium nitrate, magnesium bromide, calcium chloride, calcium iodide, bromide. A water-soluble magnesium salt such as calcium or calcium nitrate or a water-soluble calcium salt, especially a water-soluble magnesium salt, is preferable in terms of solubility and storage stability. In particular, magnesium chloride, magnesium sulfate and calcium chloride are preferable, and among these, magnesium chloride and magnesium sulfate are particularly preferable. These water-soluble divalent metal salts can be used alone or in combination of two or more.

The content of component (c) in the composition of the present invention is preferably 0.05 to 40% by weight, more preferably 0.1 to 10% by weight. If the above content is less than 0.05% by weight, a tingling sensation will occur, and if it exceeds 40% by weight, salt will precipitate and the stability of the composition will deteriorate, such being undesirable.

Further, the above-mentioned component (c) (metal ion constituting the water-soluble divalent metal salt) in the whole composition of the present invention
The molar ratio (X / Y) of all divalent metal ions containing (containing X) to the total anionic surfactant containing containing (a) component (containing Y) is 0.025 to 10, preferably. Is 0.05
~ 1. When the above molar ratio is less than 0.025, a tingling sensation occurs, and when it exceeds 10, the production becomes difficult, and in the case of a liquid detergent, solution stability deteriorates.

The composition of the present invention further comprises, as component (d), 0.1 to 10% by weight, preferably 0.1 to 10% by weight, of a linear or branched fatty acid salt having 5 to 23 carbon atoms, preferably 8 to 16 carbon atoms. 5
Further high foaming performance can be obtained by containing ~ 7%. As the fatty acid constituting the fatty acid salt, beef tallow fatty acid, coconut oil fatty acid, palm oil fatty acid and the like, coconut oil fatty acid is preferable, and as the salt constituting the fatty acid salt, sodium salt, alkali metal salt such as potassium salt, Alkanol ammonium salts such as monoethanol ammonium salt, diethanol ammonium salt and triethanol ammonium salt, or ammonium salts such as alkali metal salts such as sodium salt and potassium salt are preferable.

In addition, the composition of the present invention may further comprise (e)
As a minute, alkyl (C₈~ C₁₈) Sulfate, polyoxy
Ethylene (average addition mole number 1-10) Alkyl (C₈~
C₁₈) Ether sulfate, straight chain alkyl (C₈~ C₁₈)
Benzene sulfonate, α-olefin (C₈~ C₁₈) Su
Ruphonate, alkane (C₈~ C₁₈) Sulfonate, α
-Sulfo fatty acid (C₈~ C₁₈) Methyl ester salt, poly
Oxyethylene (average addition mole number 1-10) alkyl
(C₈~ C₁₈) Ether acetate, alkyl (C₈~
C₁₈) Glyceryl ether sulfate, α-sulfo fatty acid
(C₈~ C₁₈) Salt and polyoxyethylene glycol
(Average added mole number 1 to 10) α-sulfo fatty acid (C ₈~
C₁₈) 1 type or 2 types selected from the group consisting of ester salts
1-30% by weight of the above anionic surfactants, preferably
Content of 3 to 10% by weight,
Foam performance can be obtained. Among the components (e) above,
Polyoxyethylene (average addition mole number 1-10) alk
Le (C₈~ C₁₈) Ether sulfate, α-sulfo fatty acid
(C₈~ C₁₈) Methyl ester salt, α-sulfo fatty acid
(C₈~ C₁₈) Salt and polyoxyethylene glycol
(Average added mole number 1 to 10) α-sulfo fatty acid (C₈~
C₁₈) Ester salts are preferred, especially polyoxyethylene
(Average addition mole number 1 to 10) alkyl (C₈~ C₁₈) D
Ether sulfate, α-sulfo fatty acid (C₈~ C₁₈) Salt and
Polyoxyethylene glycol (average addition mole number 1 to 1
0) α-sulfo fatty acid (C₈~ C₁₈) Ester salt is preferred
Good

If desired, other known surfactants for detergents may be appropriately added to the composition of the present invention for the purpose of improving detergency and foaming ability. As the other surfactant, a nonionic surfactant and an amphoteric surfactant are particularly preferable.

Examples of the nonionic surfactants include polyoxyethylene (average added mole number: 2 to 20) alkyl (linear or branched chain having 8 to 20 carbon atoms) ether, alkyl (directly having 8 to 18 carbon atoms). (Chain or branched) glyceryl ether, fatty acid (C8-18) alkanolamide, alkyl (straight or branched C8-18) glycoside, and the like, among which alkyl glyceryl ether is preferable.

Examples of the amphoteric surfactant include tertiary amine oxide, carbobetaine, sulfobetaine, imidazolinium betaine and the like (all having 8 carbon atoms).
(Having 18 to 18 alkyl groups or alkenyl groups), among them, tertiary amine oxides are preferable.

In addition, the composition of the present invention contains, in a range that does not impair the separation stability, cleaning performance and foaming performance of the composition,
Other optional ingredients can be added. Examples of the other optional components include lower aliphatic alcohols such as ethyl alcohol, solubilizing agents such as sodium salts and potassium salts of toluenesulfonic acid and xylenesulfonic acid, urea, and clay minerals and water-soluble polymer substances. Viscosity modifiers, calcite, silica, calcium phosphate, zeolite, polyethylene, nylon, water-insoluble abrasives such as polystyrene, glycerin, moisturizers such as sorbitol, feel improvers such as cationized cellulose, other enzymes, fragrances, pigments, antiseptic, Examples include antifungal agents.

According to a conventional method, the composition of the present invention comprises the above-mentioned essential components (a), (b) and (c), and if necessary, the above-mentioned component (d) and the above-mentioned component (e), which are known. Prepared as an aqueous solution [usually selected from the concentration of the active ingredient (component other than water) of 5 to 80% by weight depending on the purpose] by adding a surfactant and other optional ingredients and adding water thereto. . (At this time, the component (x), preferably the component (x) and the component (y) are not substantially contained, or the total content of the component (a) and the component (b) is added. To 10% by weight or less.)

The composition of the present invention is preferably in liquid form, and the pH of the composition stock solution is 4 to 10,
It is particularly preferably adjusted to have a pH of 5-8. Further, water in the composition of the present invention is 20 to 80% by weight.
It is preferably blended.

The detergent composition of the present invention can be used in various detergent compositions such as clothing detergent compositions, kitchen detergent compositions, residential detergent compositions, hair detergent compositions, and personal detergent compositions. Used in applications, among others, kitchen, hair or body cleaning compositions,
It is particularly preferable to use it as a kitchen cleaning composition.

[0048]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Synthesis Example 1 (Synthesis of Amido Ether Carboxylate Containing Amido Ether) 214.4 g (1 mol) of methyl laurate, 61.7 g (1.02 mol) of monoethanolamine and 30% by weight of sodium methoxide. Methanol solution 15.3g 9
The product obtained by heating at 0 ° C. and 50 mmHg for 5 hours was added with 88.2 g (2 mol) of ethylene oxide in an amount of 100 to 1
It was introduced at 10 ° C. and a gauge pressure of 0 to 3.5 atm. 331 g of the reaction mixture was heated to 70-75 ° C., and 174.8 g (1.5 mol) of sodium monochloroacetate (SMCA) and 65.2 g of solid sodium hydroxide were added over 4 hours. SMCA and sodium hydroxide were divided into 5 portions, and added at the start of the reaction and at 1, 2, 3, and 4 hours after the start of the reaction.
After the addition at the 4th hour, the mixture was aged for 1 hour. Next, the reaction temperature was set to 85 ° C., 5.3 g of water was added, and the mixture was aged for 1 hour to obtain 592 g of a reaction mixture. Water is added to the reaction mixture.
Add 00 g and add 36% aqueous hydrochloric acid at 90 ° C to adjust the pH.
The mixture was adjusted to 2.8, stirred for 1 hour, and allowed to stand for 1 hour to perform layer separation to obtain 545 g of an acid product. The acid type compound was adjusted to pH 7 with a 30% sodium hydroxide aqueous solution, and water was added to form a transparent solution to obtain an amide ether derivative mixture shown below. According to this method, glycerin or glyceryl ether represented by the general formula (III) is not included.

[Amide Ether Derivative Mixture] Content / Amide Ether Carboxylate (a) [In the General Formula (I), R ₂ = C ₁₁ H ₂₃ , n = 3, m = 0, A = H, M = Compound of Na] 82% by weight Amide ether (b) [Compound of the general formula (II) wherein R ₂ = C ₁₁ H ₂₃ , n = 3, m = 0, and B = H] 14% by weight ─────────── (a) and (b) [(a) :( b) = 85: 15] 96% by weight in total ・ Others (sodium chloride, glycolates) 4% by weight

[Test Method and Evaluation Criteria] (1) Detergency Test 0.1% by weight of Sudan III (red dye) as an indicator was added to beef tallow, and 2.5 g of this was applied to a porcelain dish (diameter 25 cm). To do. Rubbing this with a sponge soaked with 3 g of detergent and 27 g of water (water with a hardness of 3.5 ° DH) at 40 ° C., the number of dishes that can be washed until the beef fat can no longer be removed from the dishes Is represented by.

(2) Foaming power test Detergent aqueous solution with a detergent concentration of 1.0% by weight (water hardness 3.5 °
DH, 40 ° C.) with commercially available butter as a stain component.
The foaming when adding 0% by weight is measured. As a measuring method, 40 ml of the detergent solution containing butter was put in a glass cylindrical container having a diameter of 5 cm and a height of 12 cm, and the mixture was rotatively stirred for 10 minutes, and the foam height immediately after stopping was measured.

(3) Enzyme Inhibitory Test As a measure of the protein denaturing action of the surfactant, the enzyme activity inhibiting action on acid phosphatase was measured.
The measuring method is the method of Imokawa et al. [Oil Chemistry, Vol. 25, No. 1
No. 24 to 30 (1976)]. According to this method, the lower the enzyme inhibition rate, the lower the protein denaturing action.

(4) Hand Roughness Test Detergent aqueous solution having a detergent concentration of 5% by weight (water hardness 3.5 ° D
H, 40 ° C.). 1 liter of this detergent aqueous solution is placed in a 2 liter beaker, the hand is immersed in the wrist for 20 minutes, and then the hand is thoroughly rinsed with running water at 40 ° C. Subject 10
Repeat this operation once a day for 4 days for 5 people
The condition of the hands after the day was visually judged according to the following criteria and shown as an average point. In this test, the average score is preferably 1 or less. No hand roughness is observed ..... 0 Hand roughness is slightly recognized ..... 1 Hand roughness is considerably recognized ........ 2

(5) Usability test Detergent aqueous solution having a detergent concentration of 5% by weight (water hardness 3.5 ° D
H, 40 ° C.). 1 liter of this detergent aqueous solution is placed in a 2 liter beaker, and a porcelain crucible is immersed in the aqueous solution. One hand was dipped in a sample aqueous solution and the other hand was dipped in 3.5 ° DH hard water at the same time, and the difference in the slimyness of the crucible surface was evaluated by 5 expert panelists, and the average was shown. 1 for the average score in this test
It is desirable that it is below the point. There is no difference .... 0 There is a slight sliminess ..... 1 There is a large sliminess ..... 2.

Example 1 A detergent composition having the composition shown in the following [Table 1] to [Table 5] was prepared, and the cleaning power, foaming power, enzyme inhibitory property, hand roughening property and feeling of use were evaluated by the above evaluation method. An evaluation was made. The results are also shown in the following [Table 1] to [Table 5]. As the components (a) / (b) in each table, those prepared by the same method as in Synthesis Example 1 were used. As the component (a) which does not substantially contain the component (b), one obtained by separating and removing the component (b) by column separation was used. Below [table
1] to [Table 3] among the cleaning composition having the composition shown in No.
Washing 1, 3, 7, 9, 11, 13, 19, 23 and 24
The cleaning composition is a reference product .

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

[0060]

[Table 4]

[0061]

[Table 5]

From the results of [Table 1] to [Table 5] described above, the detergent composition of the present invention exhibits excellent detergency, foaming ability, enzyme inhibition, hand roughening and feeling of use. You know that you have. The cleaning composition of the present invention is another cleaning composition (comparative products 1 to 14).
It can be seen that, in particular, the foaming power and the feeling of use are superior to those of the above.

[0063]

The cleaning composition of the present invention (claim 1) is
It has sufficient detergency and foaming power even in the presence of a large amount of oily stains, has a mild denaturing effect on skin proteins, and has a good feeling in use. The detergent composition of the present invention (claim 2) is excellent in foamability and low-temperature stability when used as a liquid detergent. The detergent composition of the present invention (claims 3 and 4) has further high foaming performance. The detergent composition of the present invention (claims 5 and 6) is more excellent in foamability and solubility. The cleaning composition of the present invention (claims 7, 8 and 9) is more excellent in the above effects.

─────────────────────────────────────────────────── ─── Continuation of front page (31) Priority claim number Japanese Patent Application No. 7-287614 (32) Priority date November 6, 1995 (November 6, 1995) (33) Priority claim country Japan (JP) (72) Inventor Masaki Tosaka 2606, Akabane, Kaigai, Haga-gun, Tochigi Prefecture Kao Institute of Stock Companies (56) References JP-A-60-158298 (JP, A) JP-A-5-132699 (JP, A) JP-A 6-340891 (JP, A) JP-A-3-31398 (JP, A) US Pat. No. 4818440 (US, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C11D 1 / 00-19 / 00

Claims (9)

(57) [Claims] 1. A weight ratio [(a) / (b)] containing the following components (a), (b) and (c), the content of the component (a) and the content of the component (b): Is 0.1 to 100, and all divalent metal ions (X
And the total anionic surfactant containing component (a) (denoted as Y) is 0.025 to 10 in molar ratio (X / Y).
And the following (x) component is not substantially contained, or the content of the (x) component is 10% by weight or less based on the total content of the (a) component and the (b) component. Agent composition. (A) An amide ether carboxylate represented by the following general formula (I). [Chemical 1] (B) An amide ether represented by the general formula (II) of the following [Chemical Formula 2]. [Chemical 2] (C) Water-soluble divalent metal salt. (X) Glycerin or glyceryl ether represented by the general formula (III) of the following [Chemical Formula 3]. [Chemical 3] 2. The following (y) component is not substantially contained, or the total content of the (y) component and the above (x) component is the content of the above (a) component and the above (b) component. The cleaning composition according to claim 1, which is 10% by weight or less based on the total of the above. (Y) A glyceryl ether represented by the general formula (IV) of the following [Chemical Formula 4]. [Chemical 4] 3. Further, the component (d) has 5 to 2 carbon atoms.
The cleaning composition according to claim 1 or 2, which contains 0.1 to 10% by weight of the linear or branched fatty acid salt of 3. 4. Further, as the component (e), alkyl (C
_{8 to} C ₁₈ ) sulfate, polyoxyethylene (average addition mole number 1 to 10) alkyl (C _{8 to} C ₁₈ ) ether sulfate,
Linear alkyl (C ₈ ~C ₁₈₎ benzenesulfonate, alpha
- olefins (C ₈ -C ₁₈₎ sulfonate, alkane (C ₈ -C ₁₈₎ sulfonate, alpha-sulfo fatty acid (C ₈
To C ₁₈ ) methyl ester salt, polyoxyethylene (average addition mole number 1 to 10) alkyl (C _{8 to} C ₁₈ ) ether acetate, alkyl (C _{8 to} C ₁₈ ) glyceryl ether sulfate, α-sulfo fatty acid ( C _{8 to} C ₁₈ ) salt and polyoxyethylene glycol (average addition mole number 1 to 10) α-
Sulfo fatty acid (C ₈ ~C ₁₈₎ 1 or more kinds of anionic surfactants 1 selected from the group consisting of an ester salt
The cleaning composition according to any one of claims 1 to 3, which contains 30% by weight. Wherein definitive by the general formula (I) m and j,
All are 0, The cleaning composition in any one of Claims 1-4. 6. A detergent composition according to any one of claims 1 to 4 A is a hydrogen atom, m is 0 in formula (I). 7. The weight ratio [(a) / (b)] is 1 to 2.
The cleaning composition according to claim 1, wherein the cleaning composition is 0 and the molar ratio (X / Y) is 0.05 to 1. 8. The cleaning composition according to claim 1, wherein the component (c) is a water-soluble magnesium salt or a water-soluble calcium salt. 9. The water-soluble magnesium salt or water-soluble calcium salt is magnesium chloride, magnesium sulfate,
The cleaning composition according to claim 8, which is one or more selected from the group consisting of magnesium iodide, magnesium nitrate, magnesium bromide, calcium chloride, calcium iodide, calcium bromide and calcium nitrate.