JP3179629B2 - Liquid detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid detergent composition, and more particularly, to a liquid detergent composition having excellent detergency, foaming properties and rinsing properties, and having no deterioration in performance even when stored for a long time at a low temperature. .

[0002]

2. Description of the Related Art
Soaps, which are natural anionic surfactants, have been used as detergents, but recently, in addition to these, various synthetic surfactants have also been used. Among them, phosphate ester surfactants are used in body cleansing agents, shampoos, etc. because they cause less skin irritation than alkyl sulfates, alkyl ether sulfates, etc. (JP-B-55-9033, JP-B) 57-47
No. 959).

[0003] However, calcium-sensitive anionic surfactants such as phosphate ester surfactants and soaps readily bind to divalent metal ions such as calcium ions in water and form insoluble salts (scum). It forms and leads to a reduction in foaming properties. As a countermeasure, ethylenediaminetetraacetic acid (E
DTA) (US Pat. No. 4,303,55)
No. 6) and a method of adding a branched amine oxide-based surfactant (Japanese Patent Application Laid-Open No. 62-124194), etc., but none of them provide satisfactory effects.

[0004] Therefore, even when used with hard water, detergency,
It has been desired to develop a liquid detergent composition which is excellent in foaming properties and rinsing properties and which does not cause performance deterioration even during long-term storage at a low temperature.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above circumstances, and as a result, have found that liquid washing containing specific components such as betaines, fatty acids, alkylphosphoric acids, and aliphatic alkanolamides described below, respectively. The present inventors have found that the agent composition is excellent in detergency, foaming power, rinsing property, etc., and can maintain good performance even under long-term storage at a low temperature, thereby completing the present invention.

That is, the present invention provides the following component (a):
(B), (c) and (d); (a) a betaine-type amphoteric surfactant, (b) the following general formula (1) RCOOM (1) (wherein R is a straight chain having 8 to 24 carbon atoms or A branched-chain alkyl group or alkenyl group, and M represents a hydrogen atom, an alkali metal, ammonium or an alkanolamine), a fatty acid or a salt thereof, or a phosphoric ester-type surfactant; (c) an aliphatic alkanolamide 0.1 to 10% by weight, (d) 0.1 to 50% by weight of a solvent, and the sum of the contents of the components (a) and (b) is 0.1.
The present invention provides a neutral to basic liquid detergent composition having a weight ratio of 20/1 to 1/1 and a weight ratio of 20/1 to 1/1.

The betaine-type amphoteric surfactant of component (a) used in the present invention is not particularly limited as long as it is an alkylcarbobetaine, an alkylsulfobetaine, an alkylhydroxysulfobetaine, or an alkylimidazoline-type betaine. Betaine-type amphoteric surfactants represented by (2), (3) or (4) are preferred.

[0008]

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(Wherein, R ¹ represents a saturated or unsaturated linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms, and R ² and R ³ are the same or different and are substituted by a hydroxyl group. X represents a hydrogen atom or a hydroxyl group, m represents an integer of 0 to 5, n represents an integer of 1 or more, and p and q represent 0 ≤
An integer satisfying p + q ≦ 4 is shown. )

The betaine-type amphoteric surfactant used in the present invention
R of the active agent (2), (3) or (4) ¹Is detergency or activation
A saturated alkyl group having 10 to 16 carbon atoms is preferred in terms of foaming power.
No. For similar reasons, R^TwoAnd R^ThreeRepresents a methyl group,
A tyl group or a hydroxyethyl group, m is 2 or 3,
In addition, n, p, and q are all preferably 1. Examples of these
As alkylamidopropyl-N, N-dimethyl
Betaine acetate, alkylamidopropyl-N, N-dimethyl
Tyl-2-hydroxypropylsulfobetaine, alkyl
Luamidopropyl-N, N-dimethyl-propylsulfo
Betaine, dodecyl-N, N-dimethyl acetate betaine
Etc., detergency, foaming, rinsing
And lauric acid represented by the above general formulas (2) and (3)
Amidopropyl-N, N-dimethyl-betaine acetate,
Amidopropyl listinate-N, N-dimethyl-acetate
Tyne, cocamidoamidopropyl-N, N-dimethyl vinegar
Acid betaine and the like are preferred.

Formula (1) of component (b) used in the present invention
As the fatty acid represented by or a derivative thereof, a fatty acid having a linear or branched alkyl group or alkenyl group having an average carbon number of 8 to 24, preferably 10 to 18 or an alkali metal salt or an ammonium salt or a mono,
And alkanolamine salts such as di and tri. Specific examples include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, cocoic acid,
"Emazol 871" and "Emazol 875" (manufactured by Emery), which are palm nucleic acid, tallow acid, and methyl branched acid, or a water-soluble salt thereof.

The phosphate type surfactant (b) used in the present invention has a linear or branched alkyl or alkenyl group having 8 to 24 carbon atoms, and if necessary, has a water solubility. In order to increase the amount, monoalkyl phosphates having an ethylene oxide group or a propylene oxide group, alkali metal salts thereof, ammonium salts, and alkanolamine salts such as mono, di, and tri are exemplified. Further, a dialkyl phosphate or an alkali metal salt, an ammonium salt or a monoalkyl phosphate thereof having a linear or branched alkyl group or alkenyl group having 1 to 24 carbon atoms and optionally having an ethylene oxide group or a propylene oxide group. And alkanolamine salts such as di, tri and the like.

Specific examples include linear or branched undecyl phosphate, dodecyl phosphate, tridecyl phosphate, tetradecyl phosphate, pentadecyl phosphate, hexadecyl phosphate, dodecyloxydiethylene glycol phosphate. , Didodecyl phosphate, 9-octadecene phosphate or a salt thereof.

As the component (b), a fatty acid or a salt thereof or a phosphate ester type surfactant may be used alone, or a mixture thereof may be used.

The sum of the contents of the components (a) and (b) is 0.1 to 40% in the composition of the present invention, preferably 1 to 3%.
0%. If it is less than 0.1%, sufficient detergency and foaming power cannot be obtained, while if it exceeds 40%, the effect is saturated and it is not economical.

The use ratio of components (a) and (b) is from 20/1 to 1/1 by weight, preferably from 10/1.
/ 1 to 2/1. If it exceeds 20/1, rinsability deteriorates, while if it is less than 1/1, sufficient detergency cannot be obtained.

The aliphatic alkanolamide of component (c) used in the present invention includes, for example, monoethanolamide cocoate, monoethanolamide palm nucleic acid, monoethanolamide laurate, diethanolamide cocoate,
Palm nucleic acid diethanolamide, lauric acid diethanolamide and the like.

The content of the component (c) is 0.1 to 10% in the composition of the present invention, preferably 0.5 to 5%. If it is less than 0.1%, the effect of preventing performance deterioration during long-term storage at a low temperature is poor, while if it exceeds 10%, the rinsing property is deteriorated.

The solvent (d) used in the present invention includes:
Although not particularly limited, the following general formulas (5) to (5)
Those represented by (8) are preferred.

[0020]

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(Wherein, R ⁴ represents a saturated or unsaturated linear or branched alkyl, phenyl or benzyl group having 3 to 8 carbon atoms, and r and s each represent an integer of 0 to 4) And 1 ≦ r + s ≦ 4, where r ×
When s ≠ 0, the added ethylene oxide group and propylene oxide group are arbitrarily arranged. Specific examples of the solvent represented by the general formula (5) include diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, di- (propylene ethylene glycol) -monobutyl ether, phenyl glycol, phenyl diglycol, and benzyl. Glycol and benzyldiglycol. These may be used alone or in combination of two or more.

[0022]

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(In the formula, R ⁵ and R ⁶ may be the same or different and each represent an alkyl group having 1 to 6 carbon atoms.) Specific examples thereof include 1,3-dimethyl-2-imidazo Preferred are lydinone, 1,3-diethyl-2-imidazolidinone and the like.

[0024]

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(In the formula, R ⁷ represents an alkyl group having 1 to 6 carbon atoms.) Specific examples thereof include 3-methoxy-3
-Methylbutanol and 3-ethoxy-3-methylbutanol are preferred.

[0026]

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(In the formula, R ⁸ represents a hydrocarbon group having 4 to 12 carbon atoms.) Examples of these are 3-methyl-
1,3-butanediol, 2,2,4-trimethyl-
Preferred examples thereof include 1,3-pentanediol, 2-ethyl-1,3-hexanediol, 1,9-nonanediol, and 1,8-octanediol. Component (d) may be used alone or in combination of two or more.

The content of the component (d) in the composition of the present invention is from 0.1 to 50%, preferably from 0.5 to 20%, particularly preferably from 3 to 20%. If it is less than 0.1%, a sufficient detergency cannot be obtained, while if it exceeds 50%, it becomes difficult to mix.

It is particularly preferable that the composition of the present invention contains a sequestering agent (e) in addition to the components (a), (b), (c) and (d) from the viewpoint of improving detergency. . Any sequestering agent can be used as long as it is commonly used, but is not particularly limited. Examples thereof include the following.

(1) Alkali metal salts or alkanolamine salts of phosphoric acid compounds such as orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, hexametaphosphoric acid and phytic acid. (2) ethane-1,1-diphosphonic acid, ethane-1,
1,2-triphosphonic acid, ethane-1-hydroxy-
Alkali metal salts of phosphonic acids such as 1,1-diphosphonic acid and derivatives thereof, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid Or alkanolamine salts. (3) 2-phosphonobutane-1,2-dicarboxylic acid, 1
-Phosphonobutane-2,3,4-tricarboxylic acid, α-
Alkali metal salts or alkanolamine salts of phosphonocarboxylic acids such as methylphosphonosuccinic acid; (4) Alkali metal salts or alkanolamine salts of amino acids such as aspartic acid, glutamic acid and glycine. (5) Alkali metals of aminopolyacetic acid such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, hydroxyethylenediamineacetic acid, diethylenetriaminepentaacetic acid, glycoletherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraminehexaacetic acid and diencoric acid Salt or alkanolamine salt. (6) Alkali metals of organic acids such as diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid, carboxymethyltartaric acid Salt or alkanolamine salt. (7) Aminopoly (methylenephosphonic acid) and its alkali metal salt or alkanolamine salt, polyethylenepolyaminepoly (methylenephosphonic acid) and its alkali metal salt or alkanolamine salt. In particular, hydroxycarboxylic acids such as citric acid or malic acid, condensed phosphoric acids such as pyrophosphoric acid, aminocarboxylic acids such as ethylenediaminetetraacetic acid or hydroxyethylenediamineacetic acid, or alkali metal salts such as sodium salts, potassium salts or ammonium salts thereof, or Preferred are alkanolamine salts and the like and their water-soluble salts.

The above sequestering agents may be used alone or in combination of two or more. The content of the sequestering agent (e) is preferably 0.1 to 5 in the composition of the present invention.
0%, more preferably 0.5 to 20%, particularly preferably 3 to 20%. If it is less than 0.1%, sufficient improvement in detergency cannot be obtained, while if it exceeds 50%, it becomes difficult to mix the composition components, which is not preferable.

In order to further enhance the detergency of the composition of the present invention, component (f) may be used, if necessary, as component (a),
Surfactants other than (b) can be added. The surfactant used here is not particularly limited, but one or more selected from the group consisting of a nonionic surfactant and an anionic surfactant can be used.

Examples of the anionic surfactant include alkyl benzene sulfonates, alkylene oxide-added alkyl or alkenyl ether sulfates, olefin sulfonates, alkane sulfonates, alkylene oxide-added alkyl or alkenyl ether carboxylates, α- Salts of sulfo fatty acids and esters thereof are exemplified. Examples of the counter ion of the anionic surfactant include alkali metal ions such as sodium and potassium, and ammonia or alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine.

Examples of the nonionic surfactant include polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxypropylene alkyl or alkenyl ethers, polyoxybutylene alkyl or alkenyl ethers, and alkylene oxide addition. Alkyl or alkenyl group-containing nonionic surfactant mixture, sucrose fatty acid esters, fatty acid glycerin monoesters, amine oxides, ethylene oxide condensed surfactants, or alkyl glycosides represented by the following general formula (9) And the like.

[0035] ^{R 9 (OR 10) xGy (} 9) ( wherein, R ⁹ is alkyl or alkenyl having 8 to 18 carbon atoms in total a linear or branched chain alkyl phenyl group, R ¹⁰ is the number of carbon atoms 2 to 4 alkylene groups;
Is a residue derived from a reducing sugar having 5 to 7 carbon atoms such as glucose. In addition, x (average value) shown by alkyl glycosides is 0-5. y (average value) is 1 to 10.
The alkyl glycoside represented by the general formula (9) will be further described. In the general formula (9), x has an average value of 0 to 5, and by changing this value, the liquid used in the present invention is changed. The water solubility and crystallinity of the detergent composition can be adjusted. That is, the larger the value of x, the higher the water solubility and the lower the crystallinity. Preferred values of x are 0 to 2, and particularly preferably 0. On the other hand, when the average value of y is larger than 1, that is, when a nonionic surfactant having a sugar group of two or more saccharides as a hydrophilic group is contained, the sugar chain binding mode is 1-2 or 1-. 3, 1-
It is possible to include any mixture having 4, 1-6 linkages, as well as α-, β-pyranoside linkages or furanoside linkages and mixed modes of binding thereof. Also,
The average value of y is 1 to 5, preferably 1 to 1.5, more preferably 1.1 to 1.4. In addition, the measuring method of y is based on a proton NMR method.

R ⁹ in the general formula (9) is preferably an alkyl group having 10 to 14 carbon atoms from the viewpoint of solubility and detergency. Further, R ¹⁰ is preferably an alkylene group having 2 to 3 carbon atoms from the viewpoint of water solubility. G is a monosaccharide or 2
The structure is determined by the raw materials of sugars or more. Examples of the raw materials of G include glucose, fructose, galactose, xylose, mannose, lyxose, arabinose, and mixtures thereof in the case of monosaccharides.
For sugars or more, maltose, xylobiose, isomaltose, cellobiose, gentibiose, lactose, sucrose, nigerose, turanose, raffinose, gentianose, melezitose, and mixtures thereof, and the like. Among these, preferred raw materials are glucose and fructose for monosaccharides, and maltose and sucrose for disaccharides or more, in view of their availability and cost. Of these, glucose is particularly preferred from the viewpoint of availability. Among them, alkylbenzene sulfonates, alkylene oxide-added alkyl or alkenyl ether sulfates, polyoxyethylene alkyl or alkenyl ethers, and alkyl glycosides are preferred from the viewpoint of cleaning performance and foaming power.

Component (f) is used to increase the foaming power.
(A) / [(a) + (b) + (f)] is 0.5 by weight ratio.
Or more, preferably 0.6 or more, particularly preferably 0.7
It is desirable to mix so as to be as described above.

The liquid detergent composition of the present invention may contain an amine compound such as ammonia or alkanolamine in order to maintain product stability. As the alkanolamine, any of mono-, di- or trialkanolamine can be used, and among them, monoethanolamine and diethanolamine are particularly preferable in terms of detergency and odor.

The amount of the alkanolamine in the composition of the present invention is 0.5 to 20%, preferably 1 to 10%. If it is less than 0.5%, the stabilizing effect is insufficient, while if it exceeds 10%, the effect does not increase.

The liquid detergent composition of the present invention contains a low-temperature stabilizer such as a lower alcohol such as ethyl alcohol, a lower glycol such as ethylene glycol, a lower alkylbenzene sulfonate such as benzenesulfonate or toluenesulfonate. Can be blended. Further, the liquid detergent composition of the present invention, as a viscosity modifier, a swelling clay mineral known as montmorillonite, hectorite, permiculite, attapulgite, sepiolacto and a smectite-type clay mineral containing a mixture thereof as a main component, Acrylic homopolymers or copolymers such as sodium acrylate, cross-linked polyacrylic acid, and poly (alkyl acrylate), polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl pyrrolidone, and maleic anhydride polymer can be blended. Further, fragrances, dyes, preservatives, antioxidants, thickeners, and the like can be arbitrarily added in order to increase the added value of the product.

The liquid detergent composition of the present invention is neutral or basic, but its pH is adjusted to, for example, 6.1 or more, especially from 6.5 to 8.5 in terms of detergency and mixability. Is preferred. Under acidic conditions, the compoundability of the components deteriorates, and when mixed with a chlorine bleach used as a mold remover, toxic chlorine gas is easily generated, which is not preferable.

The liquid detergent composition of the present invention can be prepared as an aqueous solution by blending the essential components (a), (b), (c) and (d) and, if necessary, the above-mentioned optional components according to a conventional method. Can be prepared.

[0043]

Industrial Applicability The liquid detergent composition of the present invention has excellent detergency and foaming power even when used with hard water, has good rinsing properties after washing, and has good performance even during long-term storage at low temperatures. It does not cause deterioration and is particularly suitable as a detergent for dwelling, bathroom, kitchen, tableware and the like.

[0044]

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

Examples 1-4, Comparative Examples 1-4 Liquid detergent compositions having the compositions shown in Tables 1 (Examples 1-4) and (Comparative Examples 1-4) were prepared according to a conventional method. The obtained composition was evaluated for detergency, foaming power, rinsing property and storage stability according to the following measurement methods.

(Detergency) About 500 g of a cast iron enamel bath tub (using a zircon-based glaze) to which a bath dirt that cannot be removed by rubbing is adhered to a urethane sponge containing a cleaning agent for evaluation. The state of removal of dirt on the bathtub surface after rubbing 5 times with a load of 5 is visually evaluated in the following 5 stages. 5: Very good stain removal. 4: Good stain removal. 3: There is unevenness in dirt removal. 2: Degree of dirt being slightly removed. 1: Almost no dirt is removed.

(Foaming power) The detergent composition was heated to a German hardness of 4 °.
After diluting to 5.0% with DH water and keeping the temperature at 25%, Ross and Miles (Ross and Miles)
s) The height of the generated foam was measured (based on JIS K 3362) using a foaming force measuring device (unit: mm).

(Rinseability) Detergent concentration 0.25% (Temperature 2
500 cc of 100 cc of 0 ° C German hardness 4 ° DH) aqueous solution
Take in a separatory funnel and shake a certain number of times. Pour out the liquid and measure the amount of foam. Then rinse water 50cc (temperature 20 ° C 4 °
DH), the separation funnel is slowly rotated 10 times, and then the liquid is poured out. This is repeated, and the number of times until the bubble disappears is determined as the number of times of rinsing.

(Storage stability) After storing each sample at -5 ° C for 10 days, the appearance of precipitation was observed. Result is,
○: no change in appearance, △: slight precipitation
The case where a clear white precipitate was formed was indicated by x. The results are shown in Table 1.

[0050]

[Table 1]

As is clear from the results shown in Table 1, the products of the present invention (Examples 1 to 4) were all comparative products (Comparative Examples 1 to 4).
Compared with 4), the washing properties, foaming properties, rinsing properties after washing and storage stability were excellent.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ identification code FI C11D 1:04 1:34) (58) Investigated field (Int.Cl. ⁷ , DB name) C11D 17/08 C11D 1/94 A61K 7/50

Claims (4)

(57) [Claims] 1. The following components (a), (b), (c) and (d): (a) a betaine-type amphoteric surfactant, (b) the following general formula (1) RCOOM (1) , R represents a linear or branched alkyl or alkenyl group having 8 to 24 carbon atoms, and M represents a hydrogen atom, an alkali metal, ammonium or an alkanolamine), a fatty acid or a salt thereof, or a phosphate ester type. A surfactant, (c) 0.1 to 10% by weight of an aliphatic alkanolamide, (d) 0.1 to 50% by weight of a solvent, and the sum of the contents of the components (a) and (b) is 0.1
A neutral to basic liquid detergent composition having a weight ratio of 20/1 to 1/1 and a weight ratio of 20/1 to 1/1. 2. The method according to claim 1, wherein the sequestering agent (e) is used in an amount of 0.1 to 50.
The liquid detergent composition according to claim 1, which is contained by weight. 3. The betaine-type amphoteric surfactant of the component (a) is represented by the following general formula (2), (3) or (4). (Wherein, R ¹ represents a saturated or unsaturated linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms, and R ² and R ³ are the same or different and are substituted with a hydroxyl group. Represents an alkyl group having 1 to 5 carbon atoms, X represents a hydrogen atom or a hydroxyl group, m represents an integer of 0 to 5,
n represents an integer of 1 or more, and p and q represent integers satisfying 0 ≦ p + q ≦ 4. 3. The liquid detergent composition according to claim 1, which is a betaine-type amphoteric surfactant represented by the formula: 4. The liquid detergent composition according to claim 1, which has a pH of 6.1 or more.