JP3236704B2 - 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 for bathrooms, and more particularly to a liquid detergent composition having excellent detergency and foaming properties, good rinsing properties after washing, and long-term storage at low temperatures. The present invention relates to a bathroom liquid detergent composition that does not deteriorate.

[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, a liquid detergent for bathrooms which has excellent detergency and foaming property even when used with hard water, has good rinsing properties after washing, and does not cause performance deterioration even during long-term storage at low temperatures. Development of compositions has been desired.

[0005]

The inventors of the present invention have conducted intensive studies in view of the above circumstances, and as a result, have found that a liquid detergent for bathroom containing specific components such as betaines, fatty acids, organic amines, and inorganic alkalis described below, respectively. The present inventors have found that the composition is excellent in detergency, foaming power, etc., has good rinsing properties after washing, and can maintain good performance even under long-term storage, and has completed the present invention.

That is, the present invention provides the following component (a):
(B), (c), (d), (e) and (f); (a) a synthetic surfactant in which at least 50% by weight is a betaine-type amphoteric surfactant; (b) the following general formula (1)

[0007]

Embedded image RCOOM (1)

Wherein R represents a linear or branched alkyl or alkenyl group having 10 to 18 carbon atoms, and M represents a hydrogen atom, an alkali metal, ammonia or an alkanolamine. (C) 0.1 to 50% by weight of a sequestering agent, (d) 0.1 to 50% by weight of a solvent, (e) an organic amine compound, and (f) an inorganic alkali. The sum of the contents with b) is 0.1
~ 40% by weight, and the weight ratio is 20/1 ~ 1/1,
Furthermore, the sum of the contents of the components (e) and (f) is 0.01
A neutral to alkaline liquid detergent composition for bathrooms, characterized in that the amount of the component (e) is at least 25% by mole with respect to the component (f). is there.

The betaine-type amphoteric surfactant of the component (a) used in the present invention is not particularly limited, but an amidobetaine-type amphoteric surfactant represented by the following general formula (2) or (3) is preferred.

[0010]

Embedded image

(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. )

R ¹ of the amidobetaine type amphoteric surfactant (2) or (3) used in the present invention is preferably a saturated alkyl group having 10 to 16 carbon atoms from the viewpoint of detergency or foaming power. For the same reason, R ² and R ³ each represent a methyl group, an ethyl group or a hydroxyethyl group; m represents 2 or 3;
Is preferably 1, p is 1, and q is 1. Specific examples thereof include alkylamidopropyl-N, N-dimethylacetate betaine, alkylamidopropyl-N, N-dimethyl-2-hydroxypropylsulfobetaine, alkylamidopropyl-N, N-dimethyl-propylsulfobetaine and the like. In terms of detergency, foaming power, and rinsing properties, amide laurate-N, N-dimethyl acetate betaine, amidopropyl myristate-
N, N-dimethyl acetate betaine, cocamidoamidopropyl-N, N-dimethyl acetate betaine and the like are preferred.

The synthetic surfactant other than the above which can be used as the component (a) in the present invention is not particularly limited.
One or two or more selected from the group consisting of nonionic surfactants and anionic surfactants 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, alkyl phosphorus Examples thereof include acids or salts thereof, salts of α-sulfofatty acids, and esters thereof.

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. Examples of the mixture include a nonionic surfactant mixture containing an alkyl group or an alkenyl group, sucrose fatty acid esters, fatty acid glycerin monoesters, amine oxides, ethylene oxide condensed surfactants, and alkyl glycosides.

The betaine-type amphoteric surfactant accounts for at least 50% by weight (hereinafter simply referred to as “%”), preferably 60% or more, particularly preferably 70%, of the total synthetic surfactant.
% Or more. If it is less than 50%, sufficient foaming power cannot be obtained, which is not preferable.

The formula (1) of the 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 alkanol-substituted ammonium salts such as di and tri. Specific examples include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid,
Examples include "Emazol 871" and "Emazol 875" (manufactured by Emery), which are cocoic acid, palm nucleic acid, tallow acid, and methyl branched acid, or water-soluble salts thereof.

The most preferred fatty acid or salt thereof from the viewpoint of rinsing properties and ease of blending is a fatty acid having 12 to 16 carbon atoms in a saturated alkyl chain or a salt thereof. Specific examples include linear or branched myristic acid, and the myristic acid content in the total fatty acid composition is more preferably 30% or more, and particularly preferably 60% or more.

The fatty acid or its salt (b) is incorporated in the composition of the present invention in an amount of 0.1 to 5%, preferably 0.3 to 4%, particularly preferably 0.5 to 3%. If it is less than 0.1%, the foaming power and rinsing properties cannot be satisfied, while if it exceeds 5%, the effect is saturated and the compounding becomes difficult.

As the component (b), fatty acids may be used alone or in combination.

The sum of the contents of the components (a) and (b) in the composition of the present invention is 0.1 to 40%, preferably 1 to 30%, particularly preferably 3 to 15%. . 0.
If it is less than 1%, sufficient detergency cannot be obtained, while if it exceeds 40%, the effect is saturated and it is not economical.

The ratio of the components (a) and (b) used is 20/1 to 1/1 by weight, preferably 20/1 to 2 /
It is one. If it exceeds 20/1, the rinsability deteriorates, while if it is less than 1/1, the detergency decreases.

The sequestering agent of component (c) used in the present invention is not particularly limited as long as it is commonly used, and examples thereof include the following. .

(1) Alkali metal salts or alkanolamine salts of phosphoric 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 singly or as a mixture of two or more. The content of the sequestering agent is preferably 0.1 to 50 in the composition of the present invention.
%, More preferably 0.5 to 20%, particularly preferably 3 to 20%. If it is less than 0.1%, sufficient detergency cannot be obtained, while if it exceeds 50%, it becomes difficult to mix the composition components.

The solvent (d) used in the present invention includes:
Although not particularly limited, the following general formulas (4) to (4)
Those represented by (7) are preferred.

[0028]

Embedded image

(Wherein, R ⁴ represents a saturated or unsaturated linear or branched alkyl group having 3 to 8 carbon atoms, a phenyl group or a benzyl group, 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. ) General formula (4)
Specific examples of the solvent represented by are diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, di- (propylene ethylene glycol) -monobutyl ether, phenyl glycol, phenyl diglycol, benzyl glycol, benzyl diglycol, and the like. Is mentioned. These may be used alone or in combination of two or more.

[0030]

Embedded image

(In the formula, R ⁵ and R ⁶ may be the same or different and 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.

[0032]

Embedded image

(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.

[0034]

HO-R ⁸ -OH (7)

(In the formula, R ⁸ represents a hydrocarbon group having 4 to 12 carbon atoms.) Specific examples thereof include 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 0.1 to 50%, preferably 0.5 to 20%, and particularly preferably 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.

As the organic amine compound of the component (e) used in the present invention, ammonia, alkanolamine and the like can be mentioned. Among them, mono-, di- and trialkanolamine are preferable, and monoethanolamine and diethanolamine are particularly preferable. .

The inorganic alkali of component (f) used in the present invention includes alkali metal hydroxide salts, alkali metal phosphate salts, alkali metal carbonate salts and the like. Of these, sodium hydroxide and potassium hydroxide are preferred.

The sum of the contents of the components (e) and (f) is 0.1.
It is from 0.1 to 10%, preferably from 0.1 to 5%. Further, the content of the component (e) is at least 25% by mol based on the component (f). If it is less than 25%, the storage stability of the composition of the present invention cannot be improved.

The present invention relates to a neutral or alkaline hard surface detergent composition, for example, having a pH of 6.1 or more, particularly adjusted to 6.5 to 8.5 from the viewpoint of detergency and compoundability. Is preferred. Under acidic conditions, the compoundability of the components deteriorates,
Further, when mixed with a chlorine bleach used for kitchen and mold removal, toxic chlorine gas is easily generated, which is not preferable.

The liquid detergent composition for bathrooms of the present invention comprises a low-temperature stabilizer such as a lower alcohol such as ethyl alcohol, a polyol such as ethylene glycol or glycerin,
A lower alkylbenzenesulfonate such as benzenesulfonate and toluenesulfonate can be blended. In addition, the liquid detergent composition for bathrooms 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 polyacrylate, cross-linked polyacrylic acid, and alkyl polyacrylate, polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl pyrrolidone, and maleic anhydride polymer can be blended. . In addition, fragrances to increase the added value of products,
Dyes, preservatives, antioxidants, thickeners and the like can be optionally added.

The liquid detergent composition for bathrooms of the present invention comprises the essential components (a) to (f), and
An aqueous solution can be prepared by mixing the above optional components.

[0043]

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 a long-term storage at low temperatures. It does not cause deterioration and is particularly suitable for bathroom use.

[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 to 3 and Comparative Examples 1 to 3 Bathroom cleaning compositions having the compositions shown in Table 1 (Examples 1 to 3) and Table 2 (Comparative Examples 1 to 3) were prepared according to a conventional method. About the obtained composition, the cleaning power, the foaming power, and the rinsing property were each evaluated according to the following measuring methods.

(Detergency) About 500 g of a cast iron enamel tub (using a zircon-based glaze) to which a bath dirt that does not fall off by rubbing is adhered to a urethane sponge containing a detergent 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 ° C, 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
100 cc of an aqueous solution of 0 ° C, German hardness 4 ° DH)
Take in a cc separating funnel and shake for a certain number of times. Pour out the liquid and measure the amount of foam. Next, rinse water 50cc (temperature 20 ℃,
4 ° DH), slowly rotate the separating funnel 10 times, and then drain the liquid. This is repeated, and the number of times until the bubble disappears is determined as the number of times of rinsing.

(Storage Stability) Each sample was stored at -5 ° C. for 10 days and 3 months, and the appearance of precipitation was observed. The results were shown as ○ when there was no change in appearance, as 白 when white turbidity or slightly white precipitate was formed, and as X when white precipitate was formed. The results are shown in Table 1.

[0050]

[Table 1]

As is clear from the results shown in Table 1, all of the present invention (Examples 1 to 3) are comparative products (Comparative Examples 1 to 3).
It can be seen that the cleaning power, the foaming power, the rinsing property after cleaning and the storage stability are superior to 3).

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-103299 (JP, A) JP-A-6-116135 (JP, A) JP-A-7-11291 (JP, A) JP-A-7-107 18294 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C11D 1/94 C11D 1/92 C11D 1/90 C11D 1/04

Claims (2)

(57) [Claims] 1. The following components (a), (b), (c),
(D), (e) and (f); (a) a synthetic surfactant in which at least 50% by weight is a betaine-type amphoteric surfactant; (b) RCOOM (1) (Wherein, R represents a straight-chain or branched-chain alkyl or alkenyl group having 10 to 18 carbon atoms, and M represents a hydrogen atom, an alkali metal, ammonia or an alkanolamine). 0.1 to 50% by weight of a sequestering agent, 0.1 to 50% by weight of a solvent (d), (e) an organic amine compound, and (f) an inorganic alkali, and the components (a) and (b) Is 0.1
~ 40% by weight, and the weight ratio is 20/1 ~ 1/1,
Furthermore, the sum of the contents of the components (e) and (f) is 0.01
A neutral to alkaline liquid detergent composition for bathrooms, characterized in that the amount is from 10 to 10% by weight and the component (e) is contained in a molar fraction of at least 25% with respect to the component (f). 2. Component (a) is represented by the following general formula (2) or (3): (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. The liquid detergent composition for bathrooms according to claim 1, which is an amidobetaine-type amphoteric surfactant represented by the formula: