JP2002129189A - Solubilizing process of surfactant, surfactant solubilized solution obtained by it, liquid detergent composition using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solubilizing process by which an anionic surfactant and a cationic surfactant can be uniformly solubilized without losing their effects as surfactants and to provide a solubilized solution obtained by it and a liquid detergent composition using it. SOLUTION: A transparent and uniform solubilized solution is obtained by adding an anionic surfactant (b) and a cationic surfactant (c) to a liquid (a) comprising water or water and an aqueous solvent and stirring it in the presence of a solubilizing agent (d). As the solubilizing agent (d), a carboxylic acid salt selected from the group consisting of an aliphatic dicarboxylic acid salt having a 7-16C alkyl or alkenyl group and a 7-12C aliphatic carboxylic acid salt is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for solubilizing an anionic surfactant and a cationic surfactant, a surfactant solubilizing solution obtained by the method, and a liquid detergent composition using the same. It is about.

[0002]

2. Description of the Related Art Conventionally, for cleaning foods, clothing, etc., a cleaning agent containing an anionic surfactant as a main component, which is excellent in penetrating power, emulsifying power, detergency, etc. into a stained portion, has been widely used. .
Further, for the dry finish after washing, a finish mainly composed of a cationic surfactant having excellent sterilizing power and antistatic performance is widely used. Therefore, in order to perform washing and drying in one step, development of a treating agent in which the above-described anionic surfactant and cationic surfactant are simultaneously blended is being studied.

[0003]

However, when an anionic surfactant and a cationic surfactant are blended in the same solution, both easily form a complex, and the effects of the respective surfactants are lost. Problem. In other words, due to complex formation, in the case of anionic surfactants, the surfactant and cleaning performance such as osmotic power and emulsifying power are lost, and in the case of cationic surfactants, such as bactericidal power and antistatic The effect disappears.

[0004] Therefore, a specific nonionic surfactant such as an alkylamine oxide is blended, a soap and a non-soap-based anionic surfactant are used in combination as anionic surfactants, or a specific anionic surfactant is used. By various measures such as combining a surfactant and a specific cationic surfactant, without losing the effect of each other,
A method of blending an anionic surfactant and a cationic surfactant has been proposed.

For example, JP-A-54-157109 discloses an alkaline earth metal salt of an anionic surfactant,
There is disclosed a detergent composition containing a quaternary ammonium salt type cationic surfactant and an alkaline earth metal inorganic salt, and capable of imparting a soft finishing effect to clothes simultaneously with washing. JP-A-54-108814 also contains a cationic surfactant, an anionic surfactant, and an alkoxylated nonionic surfactant, and has improved cleaning performance against oil and dirt, In addition, a granular detergent composition which is not sensitive to free hardness and builder is disclosed. Japanese Patent Application Laid-Open No. 55-106299 discloses that a cationic amine softener and a soap in the components are made to have a specific weight ratio, thereby making the composition relatively soft. There is disclosed a detergent composition which softens a treated fabric in the presence of a low-concentration softener, and imparts a washing / antistatic property and a stain re-adhesion preventing property.

Further, Japanese Patent Application Laid-Open No. 57-137396 discloses a cleaning material excellent in finishing effect and detergency, which is obtained by blending a detergent fabric with a powdered cationic surfactant by a spray cooling method in an after blend. An agent composition is disclosed,
JP-A-6-330090 discloses an anionic functional group-containing surfactant and a specific guanidine derivative,
There is disclosed a detergent composition which forms a cation-anion complex to improve mildness and the like on hand skin and hair. And, in Japanese Patent Application Laid-Open No. 11-286699,
Disclosed is a liquid detergent composition for a hard body containing an anionic surfactant, a specific cationic surfactant, and a water-soluble polymer, which is less likely to damage a cleaning surface, and has excellent detergency, anti-redeposition properties, and finished feeling. Have been.

On the other hand, it has been reported that various properties such as cleaning performance are improved by blending a dicarboxylic acid derivative, and various dicarboxylic acid derivatives are used together with a surfactant. For example, JP-A-58-196296
Japanese Patent Application Publication No. JP-A-2003-175, discloses a low-viscosity tableware containing a specific anionic surfactant, a specific tertiary amine oxide, and a succinic acid derivative in a specific ratio, having excellent foaming power, detergency and low-temperature stability. A liquid detergent composition for cooking utensils and the like is disclosed. Japanese Patent Application Laid-Open No. 58-196299 discloses a liquid light cleaning which contains an anionic surfactant and a specific succinic acid derivative as essential components, does not contain an alkaline builder, and is excellent in low-temperature stability and excellent ability to prevent film formation. An agent composition is disclosed. Further, Japanese Patent Laid-Open No. 2-11
Japanese Patent No. 3100 contains a sulfate or sulfonate type anionic surfactant, a nonionic surfactant or an amphoteric surfactant, a succinic acid derivative and a lower alkylbenzene sulfonate in a specific ratio, and has a low-temperature stability. Disclosed are concentrated liquid detergent compositions that are excellent and maintain a uniform phase upon freeze reconstitution.

However, each of the above-mentioned various detergent compositions has a problem that there are many restrictions on the selection of anionic surfactants and cationic surfactants that can be combined, and other surfactants and detergents. There is a problem that the compatibility with the components is poor and the performance may be reduced. In addition, in the case of liquid detergents, it is difficult to obtain a completely homogeneous liquid unless the mixing ratio of each component is sufficiently examined, and there is also a problem that cloudiness or separation occurs during storage. .

The present invention has been made in view of such circumstances, and an anionic surfactant and a cationic surfactant can be used without losing the effect of each other's surfactants.
A solubilization method that can be solubilized uniformly, and has a wide range of types of anionic surfactant and cationic surfactant that can be solubilized, and both can be easily solubilized at any ratio. It is an object of the present invention to provide a surfactant solubilizing solution obtained thereby and a liquid detergent composition using the same.

[0010]

In order to achieve the above-mentioned object, the present invention relates to a method comprising the steps of: adding water or a liquid (a) comprising water and a water-soluble solvent to an anionic surfactant (b); A method of obtaining a transparent and uniform solubilizing solution by adding a surfactant (c) and stirring in the presence of a solubilizing agent (d). ,
An interface in which at least one carboxylate selected from the group consisting of an aliphatic dicarboxylate having 7 to 16 carbon atoms and an aliphatic carboxylate having 7 to 12 carbon atoms of an alkyl group or an alkenyl group is used. The first aspect is a method of solubilizing an activator.

[0011] The present invention, among others,
The mixing ratio of the solubilizer (d) to the anionic surfactant (b) and the cationic surfactant (c) [d /
(B + c)] has, as a second gist, a method for solubilizing a surfactant set to 2/1 to 1/3 on a mass basis, wherein the solubilizing agent (d) has a carbon number of an alkenyl group. Is 7-16
A third aspect of the present invention is a method for solubilizing a surfactant that is an alkenyl disuccinate, wherein the solubilizing agent (d) includes an alkenyl disuccinate having an alkenyl group having 7 to 16 carbon atoms; A fourth gist of the present invention is a method for solubilizing a surfactant, which is a combination of two or more kinds including an aliphatic carboxylate having 7 to 12 carbon atoms.

Further, the present invention provides a method for solubilizing a surfactant, wherein an anionic surfactant (b) and a cationic surfactant are added to water or a liquid (a) comprising water and a water-soluble solvent. A fifth aspect of the present invention is a surfactant solubilizing solution in which the agent (c) is solubilized and the entire solution is a transparent and uniform solution, and a liquid detergent composition containing the surfactant solubilizing solution is provided. This is the sixth gist.

Further, the present invention relates to the above-mentioned liquid detergent composition, in which the nonionic surfactant (e) is contained in an amount of 0.1 to 95.0% by mass based on the whole composition. Wherein the nonionic surfactant (e) is a polyoxyethylene alkyl ether, a polyoxyalkylene dialkyl ether, a polyoxyalkylene alkyl phenyl ether, a pluronic block polymer, or a tetronic. An eighth subject is a substance which is at least one kind of nonionic surfactant selected from a mold block polymer, a reverse pluronic block polymer, and a reverse stetronic block polymer.

[0014] Of these liquid detergent compositions, a ninth aspect is that the detergent builder (f) contains 1 to 50% by mass based on the whole composition.
The whole is diluted to a concentration of 0.05 to 0.3% by mass and used for an automatic dishwasher, and the pH at the diluted concentration is in the range of 7.0 to 9.5. What is set as such is the tenth gist.

[0015]

Next, an embodiment of the present invention will be described.

First, in the method for solubilizing a surfactant of the present invention, a liquid (a) comprising water or water and a water-soluble solvent is used.
, An anionic surfactant (b) and a cationic surfactant (c) are added thereto, and the mixture is solubilized by stirring in the presence of a specific solubilizing agent (d). This is a method for obtaining a suitable solubilizing solution.

In the above-mentioned solubilization method, the liquid (a) serving as a solvent is water or water and a water-soluble solvent.

Examples of the water include tap water, soft water, ion-exchanged water, pure water, purified water, and the like.
Ion exchange water and pure water are used. In addition, the water shown here does not include water derived from each component constituting the liquid detergent composition and water of crystallization, and refers to water added from outside. The mixing ratio of the water is not particularly limited, and the total amount of the solubilizing solution obtained by solubilizing the anionic surfactant (b) and the cationic surfactant (c) is 100% by mass.
As a balance, the remaining mass% is blended.

When a water-soluble solvent is used together with the water as the liquid (a), examples of the water-soluble solvent include glycols such as propylene glycol, ethylene glycol and polyethylene glycol, and lower grades such as ethyl alcohol, isopropyl alcohol and methanol. Alcohols,
Glycerin, ethylene glycol monobutyl ether,
Glycol ethers such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

One or more of these water-soluble solvents are appropriately selected and used depending on the use and purpose of the solubilizing solution. In particular, when the solubilizing solution is prepared as a liquid detergent composition, the water-soluble solvent has a function of accelerating the emulsification and dispersion of grease stains.

Therefore, for example, in the use of detergents for dishwashers, propylene glycol, polyethylene glycol and lower alcohols are preferably used from the viewpoint of economy and storage stability. Among them, propylene glycol and ethyl alcohol are preferably used in terms of odor and safety. Further, in applications to oil stains such as gas ranges and ventilation fans, glycol ethers are preferably used in terms of cleaning performance, odor, and ease of wiping.

The water-soluble solvent is usually used as a mixture of water and a water-soluble solvent in an amount of 3.0 to 7 with respect to the whole solubilized solution.
It is preferable to mix 5.0 mass% (hereinafter abbreviated as “%”). If it is 3.0% or less, the effect of the water-soluble solvent such as the effect of promoting emulsification and dispersion of oil and fat stains and the storage stability of the composition is poor. If it exceeds 75.0%, the balance with other components becomes poor, and separation occurs. -This is because problems such as separation and turbidity are likely to occur.

The mixing ratio of water and the water-soluble solvent is as follows:
It is set appropriately according to the use and purpose of the solubilizing solution,
Usually, when water is 1, the water-soluble solvent is preferably set to be 4 or less on a mass basis. If the proportion of water is too small, the dissolution balance with other components is lost, and the components are separated / separated, turbid, or gelled.

In the present invention, the anionic surfactant (b) to be added to the liquid (a) includes alkanesulfonic acid salts, alkylbenzenesulfonic acid salts, α-
Alkyl sulfates such as olefin sulfonate and sodium lauryl sulfate, alkyl sulfates such as sodium lauryl sulfate and triethanolamine lauryl sulfate, and polyoxyalkylene alkyl ether sulfates such as polyoxyethylene (3) sodium lauryl ether sulfate Amide ether sulfates such as sodium polyoxyethylene (3) coconut fatty acid amide sulfate; aliphatic phosphorus such as sodium monododecyl ether phosphate; di- (polyoxyethylene (6) coconut fatty acid amide) -sodium phosphate; Aromatic phosphoric acid ester salts such as acid ester salts, polyoxyethylene alkyl phenyl ether phosphoric acid ester salts, polyoxyalkylene alkyl phenyl ether phosphoric acid ester salts, sodium cocoyl methyl taurate, lauroy Acyl isethionates such as methyltaurine salt, sodium lauroylisethionate, disodium lauryl sulfosuccinate, disodium lauryl disoxysulfonate, polyoxyethylene (1-4) disodium lauryl sulfosuccinate, polyoxyethylene (5) disodium monoethanolamide sulfosuccinate And the like, a sulfosuccinic acid type surfactant, an alkyl ether carboxylate, an N-acyl glutamate, an amide carboxylic acid type surfactant and the like. These may be used alone or in combination of two or more.

Of these, alkyl sulfates such as alkane sulfonates, alkyl benzene sulfonates, α-olefin sulfonates, sodium lauryl sulfate, etc. are particularly preferred from the viewpoints of cleaning performance and economy (cost). Salts, alkyl sulfates such as sodium lauryl sulfate and triethanolamine lauryl sulfate, and polyoxyalkylene alkyl ether sulfates such as polyoxyethylene (3) sodium lauryl ether sulfate are preferably used.

The above anionic surfactant (b)
Is preferably 0.1 to 50.0% based on the whole solubilizing solution.

Next, the above anionic surfactant (b)
Examples of the cationic surfactant (c) to be added together with the above include dialkyldimethylammonium halides such as didecyldimethylammonium chloride, octyldecyldimethylammonium chloride, dioctyldimethylammonium chloride, distearyldimethylammonium chloride, and alkyls such as stearyltrimethylammonium chloride. Alkyldimethylbenzylammonium halides such as trimethylammonium halide and alkyldimethylbenzylammonium chloride;
Examples include biguanide compounds such as polyhexamethylene biguanidine hydrochloride and chlorhexidine gluconate, and quaternary ammonium salts such as benzalkonium chloride and benzethonium chloride. Among them, didecyldimethylammonium chloride, alkyltrimethylammonium chloride, benzalkonium chloride, polyhexamethylene biguanidine hydrochloride, etc. are preferably used from the viewpoint of compatibility with other components, bactericidal effect, and economy. These may be used alone or in combination of two or more.

It is preferable that the component (c) is incorporated in an amount of 0.1 to 20.0% based on the whole solubilized solution.

The above anionic surfactant (b)
The mixing ratio of the and the cationic surfactant (c) is appropriately determined depending on the purpose, application, cost, and the like of the solubilizing solution, and is not particularly limited.
It is preferable to set it in the range of 1/1/1 to 500/1. If the proportion of the anionic surfactant (b) is larger than the above range, the surfactant activity and the cleaning effect become saturated, foaming is easy, and it is economically disadvantageous, and the storage stability of the solubilizing solution is poor. It will be. Conversely, if the proportion of the cationic surfactant (c) is large, the bactericidal activity and the antistatic effect become saturated, and depending on the object to be washed, stickiness may occur in washing, and it is economically disadvantageous. Yes,
The storage stability of the solubilized solution is poor, which is not preferable. However, a large feature of the present invention is that the selection range and combination of the anionic surfactant (b) and the cationic surfactant (c) are wide.

Next, the solubilizer (d) used in the present invention includes an aliphatic dicarboxylate having 7 to 16 carbon atoms in an alkyl group or an alkenyl group, and having 7 to 1 carbon atoms.
And aliphatic carboxylate (2).

As the aliphatic dicarboxylate having 7 to 16 carbon atoms of the alkyl group or alkenyl group, succinic acid, alkyl group or alkenyl group having 7 to 16 carbon atoms of the alkyl group or alkenyl group has the same number of carbon atoms. 7-16
Maleic acid, an alkali metal salt such as fumaric acid having an alkyl group or an alkenyl group having 7 to 16 carbon atoms, an alkanolamine salt or the like can be used. As the alkali metal salt, alkali metal salts such as sodium and potassium,
Examples of the alkanolamine salts include alkanolamine salts such as monoethanolamine, diethanolamine, and triethanolamine.

Among them, its solubilizing performance, storage stability,
In light of the combination with the surfactant, an aliphatic succinate having 7 to 16 carbon atoms in the alkyl group or the alkenyl group is preferably used.
An alkali metal salt such as a potassium salt is preferably used.
Among them, dipotassium alkenyl succinate having 7 to 16 carbon atoms is preferable, and particularly, its solubilizing performance,
From the viewpoint of storage stability, dipotassium alkenyl succinate having 9 to 14 carbon atoms is preferably used.

Examples of the aliphatic carboxylate having 7 to 12 carbon atoms include saturated or unsaturated aliphatic carboxylate, such as caprylic acid, heptyl acid, pelargonic acid, capric acid, and undecane. Acid, lauric acid,
Aliphatic carboxylic acids such as obsuccinic acid, caproleic acid, undecylenic acid and lindelic acid, or alkali metal salts and alkanolamine salts thereof are preferably used. Above all, from the viewpoint of cleaning performance, odor and storage stability,
Sodium heptylate and potassium heptylate are preferably used.

The aliphatic carboxylate having 7 to 12 carbon atoms and the aliphatic dicarboxylate having 7 to 16 carbon atoms in the alkyl or alkenyl group may be used alone.
Alternatively, two or more kinds may be used in combination.

The component (d) accounts for 1.0 to 13.0% of the total solubilized solution in which the anionic surfactant (b) and the cationic surfactant (c) are solubilized. It is preferred to mix. That is, at 1.0% or less,
This is because the solubilizing performance and storage stability are poor, and if it exceeds 13.0%, it is not preferable in terms of cost, balance with other components, and concentration (enhancement) of the active ingredient of the composition.

From the viewpoint of the washing performance and storage stability of the composition, the content ratio of the component (d) and the sum (b + c) of the components (b) and (c) is 2 / (mass basis). 1-1 /
It is preferably in the range of 3.

In the solubilizing solution thus obtained, the anionic surfactant (b) and the cationic surfactant (c) are homogeneously dissolved in the same solution. The characteristics as have not been impaired. Therefore, it has both surfactant properties such as penetrating power and emulsifying power, cleaning performance, bactericidal power, antistatic power and the like, and can be widely used as a detergent composition and the like.

When the solubilizing solution is used as a liquid detergent composition, it can be used as it is, but in order to further enhance the performance as a detergent, it is necessary to mix various components as described below. Can be.

For example, in addition to adjusting foaming during use according to the use and purpose of the various liquid detergent compositions, a nonionic surfactant (e) is used for the purpose of further improving dirt penetration performance and cleaning performance. Can be blended.

As the nonionic surfactant (e),
Polyoxyethylene alkyl ether, polyoxyalkylene dialkyl ether, polyoxyethylene alkenyl ether, polyoxyalkylene alkyl phenyl ether, pluronic block polymer, tetronic block polymer, reverse pluronic block polymer, reverse stetronic block polymer, sucrose Fatty acid esters, sorbitan fatty acid esters,
Fatty acid esters such as polyethylene glycol fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polypropylene glycol fatty acid ester, coconut fatty acid diethanolamide (1: 1), coconut fatty acid diethanolamide (1: 2), lauric acid Fatty acid alkanolamides such as diethanolamide, lauric myristic acid diethanolamide, myristic acid diethanolamide, oleic acid diethanolamide, palm kernel fatty acid diethanolamide, alkyl glucosides, amine oxides and the like. These nonionic surfactants (e) may be used alone or in combination of two or more.

Of these, polyoxyethylene alkyl ethers, polyoxyalkylene dialkyl ethers, polyoxyalkylene alkyl phenyl ethers, and
A pluronic block polymer, a tetronic block polymer, a reverse pluronic block polymer, or a reverse stetronic block polymer is used. In particular, a pluronic block polymer and a polyoxyalkylene alkyl ether are preferably used from the viewpoints of cleaning performance, low foamability, and economy.

The amount of the nonionic surfactant (e) is from 0.1 to 95.% based on the whole liquid detergent composition.
It is preferable to set within the range of 0%. That is,
If it is less than 0.1%, it is difficult to obtain a foaming adjustment effect,
On the other hand, if it exceeds 95.0%, it is not preferable from the viewpoint of balance with other cleaning components and economy.

In addition, the liquid detergent composition of the present invention includes a cleaning builder (f) in terms of cleaning performance and ion-sealing performance.
Can be blended. The washing builder (f) includes nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycoletherdiaminetetraacetic acid, triethylenetetraminehexaacetic acid, bis (2-hydroxyphenyl Acetic acid) Examples thereof include aminopolyacetic acids such as ethylenediamine, diencoric acid, iminodiacetic acid, hydroxyethyliminodiacetic acid and salts thereof, and alkali metal salts, alkaline earth metal salts, ammonium salts, and alkanolamine salts thereof.

Further, orthophosphoric acid, polyphosphoric acid, pyrophosphoric acid, metaphosphoric acid, hexametaphosphoric acid and alkali metal salts thereof are used. Examples of the alkali metal to be combined with these include sodium and potassium.

Further, ethane-1,1-diphosphonate, ethane-1,1,2-triphosphonate, ethane-
1-hydroxy-1,1-diphosphonic acid salt and derivatives thereof, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, amino Phosphonic acid compounds such as trimethylenephosphonic acid, or alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts thereof, 2-phosphonobutane-
1,2-dicarboxylic acid, 1-phosphonobutane-2,3
Examples thereof include phosphonocarboxylic acid compounds such as 4-tricarboxylic acid and α-methylphosphonosuccinic acid, and alkali metal salts, alkaline earth metal salts, ammonium salts and alkanolamine salts thereof.

Further, polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, poly-α-hydroxyacrylic acid, polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride diamine Isobutylene copolymer, maleic anhydride styrene copolymer, maleic anhydride methylvinyl ether copolymer, maleic anhydride ethylene copolymer, maleic anhydride ethylene crosslink copolymer, maleic anhydride vinyl acetate copolymer, anhydrous Maleic acrylonitrile copolymer, maleic anhydride acrylate copolymer, maleic anhydride butadiene copolymer, maleic anhydride isoprene copolymer, poly-β-ketocarboxylic acid derived from maleic anhydride and carbon monoxide , Itaconic acid, d Tylene copolymer, itaconic acid aconitic acid copolymer, itaconic acid maleic acid copolymer, itaconic acid acrylic acid copolymer, methylene malonate copolymer, itaconic acid fumaric acid copolymer, ethylene glycol ethylene terephthalate copolymer And vinylpyrrolidone vinyl acetate copolymer.

Also, citric acid, malic acid, gluconic acid,
Organic acids such as heptonic acid, maleic acid, tartaric acid, fumaric acid, lactic acid, diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, carboxymethyltartaric acid or alkali metal salts, alkaline earth metal salts, ammonium salts or alkanols thereof In addition to amine salts, sulfates such as sodium sulfate and potassium sulfate, amino acids such as aspartic acid and glutamic acid, and alkali metal salts, alkaline earth metal salts, ammonium salts and alkanolamine salts thereof can be used.

In addition, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and silicic acid, orthosilicic acid, metasilicic acid, and alkali metal salts thereof are used. Examples of the alkali metal to be combined with these include sodium and potassium.

Among them, from the viewpoint of washing performance and ion sequestering performance, trisodium nitrilotriacetate, tetrasodium ethylenediaminetetraacetate, sodium gluconate, sodium heptanoate, potassium hydroxide, potassium carbonate, sodium tripolyphosphate, sodium metasilicate It is preferred to use

And these washing builders (f) are:
They may be used alone or in combination of two or more.

It is preferable that these cleaning builders (f) are incorporated in the liquid detergent composition in an amount of 0.1 to 50.0%. That is, when the amount is less than 0.1%, it is difficult to obtain the cleaning performance and the ion-sequestering performance, and 50.0%
If the amount exceeds the above range, it is not preferable in terms of balance with other cleaning components and economic efficiency.

The liquid detergent composition of the present invention may contain a fragrance, a dye, a metal corrosion inhibitor, an antioxidant, an amphoteric surfactant, a dispersant, a bactericide, and the like, if necessary. Can be.

Examples of the amphoteric surfactant include alkyl betaine-type amphoteric surfactants such as lauryl betaine, amidobetaine-type amphoteric surfactants such as lauroylamidopropyl betaine, and 2-alkyl-N-carboxymethylimidazolinium. Betaine and imidazoline-type amphoteric surfactants such as 2-alkyl-N-carboxyethylimidazolinium betaine, alkylsulfobetaine-type zwitterionic surfactants, and amido-sulfobetaine-type amphoteric such as coconut fatty acid amide dimethylhydroxypropyl sulfobetaine Surfactant, N-alkyl-β-aminopropionate, N-alkyl-β-iminodipropionate, β-alanine type amphoteric surfactant,
Glycine-type zwitterionic surfactants such as alkyl diaminoethyl glycine and alkyl polyaminoethyl glycine are exemplified.

As the dispersant, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, xanthan gum, guar gum, carrageenan and the like can be used.

Further, as a bactericide, triclosan (2,4,4'trichloro-2'-hydroxydiphenyl ether), PCMX (parachloromethaxinol)
And aldehyde compounds such as glutaraldehyde, alcohol compounds such as ethanol and isopropyl alcohol, iodine compounds such as iodohole, and natural products such as hinokitiol and Wasaolo.

The liquid detergent composition of the present invention can be suitably used for cleaning hard surfaces such as tableware, glass, ceramics, metals, plastics, tiles, floors, etc. In addition, the detergent composition having a bactericidal activity, The present invention can also be provided as a special detergent composition to which specific performance is added, such as a detergent composition having a preventive property and a detergent composition having a soft finishing property.

The liquid detergent composition of the present invention does not impair the bactericidal properties of the solubilized cationic surfactant. Can provide sterilization power. Therefore, for example, a dilution concentration of 0.05 to 0.3%
When used in a degree, the pH of the diluent is adjusted to 7.0 to 9.
It can be set as low as 5 and the load on the environment can be reduced. It is also preferable for workers involved in the cleaning operation.

[0058]

As described above, according to the present invention, it is possible to easily solubilize an anionic surfactant and a cationic surfactant, and to provide a cleaning agent or the like utilizing the respective properties. In addition, compared with the conventional art, the range of usable anionic surfactants and cationic surfactants is wide, and they are highly practical in that they can be mixed at an arbitrary ratio. Then, the obtained solubilized solution is transparent without causing turbidity or precipitation, and is excellent in storage stability. Therefore,
Based on the solubilizing solution of the present invention, a cleaning composition having various properties, such as a cleaning composition having a bactericidal effect, a cleaning composition having a soft finishing effect, a cleaning composition having an antistatic property, and the like. High quality can be obtained. Further, according to the present invention, since the bactericidal power derived from the cationic surfactant can be utilized, it is possible to provide a detergent composition for a dishwasher which can suppress the occurrence of various bacteria with a low alkali.

Hereinafter, examples of the present invention will be described together with comparative examples. Note that the present invention is not limited by these examples.

[0060]

Examples 1 to 10 and Comparative Examples 1 and 2 Liquids having the compositions shown in the following Tables 1 to 3 (units are% and the same in other tables) were prepared, and the appearance was visually observed. The bactericidal activity was evaluated by the following method. The results are shown in Tables 1 to 3 below.

[Appearance] The appearance of the solubilized solution one day after its preparation was visually observed.・Evaluation criteria transparent: transparent, no separation / separation was observed. Slightly separated: Transparent, but very slightly separated and separated. Separation… Transparent, but clearly separated and separated. Precipitation: A precipitate was observed.

[Evaluation method 1 of sterilizing power] Liquid NB was placed in a test tube.
Put 10 ml of culture medium, and add 0.02 m
l and 10 ³ cells / ml (1 ml) shown below were added, and cultured at 37 ° C. for 48 hours in a static place. After 48 hours, 100 µl of the above culture solution was spread on NA agar medium, and the number of colonies after static culture at 37 ° C for 48 hours was counted.・Strain Escherichia coli IFO12734 Staphylococcus aureus IFO
12712 ・Evaluation criteria ○: The number of colonies is less than 10 ² ×: The number of colonies is 10 ² or more

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

Examples 11 to 23 As shown in Tables 4 to 6 below,
A liquid having a composition in which a nonionic surfactant (e) and a cleaning builder (f) were added as optional components to the solubilizing solution was prepared, and the state was visually observed. The results are shown in Tables 4 to 6 below.

[0067]

[Table 4]

[0068]

[Table 5]

[0069]

[Table 6]

[0070]

Examples 24 to 28 As shown in Table 7 below, a liquid detergent composition was prepared by blending a nonionic surfactant (e) and a washing builder (f) based on a solubilizing solution.
The appearance was visually observed. In addition, the pH of the stock solution and the dilution concentration (0.2%) suitable for use as a washing solution
PH was measured. Further, the cleaning properties, dispersibility, bactericidal properties and stability of this cleaning solution were measured and evaluated. The results are shown in Table 7 below. In addition, each evaluation method is as follows.

[Method for Evaluating Detergency] First, the above-mentioned cleaning liquid was put into an automatic dishwasher for business use (model: DW-RD61, manufactured by Sanyo Electric Co., Ltd.) and operated, and a ceramic dish as a cleaning object shown below was placed. Washing and evaluation were performed as a set of 10 sheets. For the evaluation, the degree of dirt removal was confirmed by visual observation.・Washing conditions Detergent concentration: 0.20% Washing temperature: 60 ° C Rinsing temperature: 80 ° C Washing course: Standard washing cycle (washing time 43 seconds, rinsing time 15 seconds) ・Adjustment of standard dirt 70 parts by mass of margarine (hereinafter “parts”) Is heated and dissolved, and then 15 parts of powdered milk, 5 parts of non-fat milk, 1 part of flour
0 parts was added to make it uniform, and 30 parts of water was added to make a paste, which was used as a standard soil. -Preparation of the object to be washed The above-mentioned standard stain was attached to a ceramic dish having a diameter of 20 cm so as to be 8 g / sheet, and dried at room temperature for 1 hour. Evaluation criteria ◎: Removal of stains of 90% or more ○: Removal of stains of 70% to less than 90% △: Removal of stains of 50% to less than 70% ×: Removal of stains of less than 50%

[Dispersibility evaluation method] In the above-mentioned method for evaluating the detergency, 100 ml of the washing liquid in the washing tank was immediately transferred to the colorimetric tube immediately after the operation of the automatic dishwasher, and the dispersion state of the stain when left for 10 minutes. Was visually observed. Evaluation Criteria : Stable dispersion of stains was observed even after 10 minutes of standing. X: Soil was separated from the cleaning solution in less than 10 minutes.

[Evaluation Method 2 for Bactericidal Activity] Liquid NB was placed in a test tube.
The medium was placed 10 ml, and 0.02ml liquid detergent composition which is a sample serially diluted, strain 10 ³ shown below / m
l (1 ml) was added, and the cells were cultured in an incubator (model: IN61, manufactured by Yamato Scientific Co., Ltd.) set at 37 ° C. for 48 hours. After a lapse of 48 hours, the maximum dilution factor that hindered the growth of the cells was searched.・Strain Escherichia coli IFO12734 Staphylococcus aureus IFO
12712

[Evaluation Method of Appearance Stability] A liquid detergent composition as a sample was put in a 100 ml plastic container, and a 50 ° C. incubator (model: DN-41, manufactured by Yamato Scientific Co., Ltd.) and a −5 ° C. freezer (model: MDF) -U332, manufactured by Sanyo Electric Co., Ltd.) for 3 months
Evaluation was made according to the following evaluation criteria. Evaluation criteria ○: Good storage stability without precipitation or separation (no change). X: Precipitation, separation, etc. were observed.

[Method of Evaluating Low Foaming Property] A prepared automatic dishwasher (model: DW-RD61,
(Manufactured by Sanyo Electric Co., Ltd.) and operated under the following operating conditions.
Then, the foaming of the cleaning liquid was visually evaluated according to the evaluation criteria described below.・Operating conditions Detergent concentration: 0.15% Washing temperature: 60 ° C Washing course: Standard washing cycle (washing time: 43 seconds,
Rinse time: 15 seconds) Hardness of tap water: 70 to 80 ppm (as CaCO ₃ ) Evaluation criteria ○: Foam is less than 50 mm from the liquid level during operation, and the foam disappears immediately after the operation is completed. ×: Foam is 50 mm or more from the liquid level during operation, or the foam remains without disappearing even after 1 minute from the end of operation.

[0076]

[Table 7]

[0077]

Example 29 A disinfecting detergent for hand washing having the composition (present) shown in Table 8 below was obtained. Then, the detergency and the bactericidal effect of this detergent were evaluated according to the following methods.
The results are shown in Table 8 below.

[Method of Evaluating Detergency] The above-mentioned detergent was put into a tester for improving the detergency of a leaf nut, and the prepared slide glass pieces to be washed shown below were washed and evaluated as a set of 6 slides. The evaluation was carried out by measuring the weight difference between before and after contamination of the slide glass. Washing efficiency = (Rw−Ro) / (Ro−Rs) × 100
(%) Ro: Weight of slide glass Rs: Weight of prepared slide glass Rw: Weight of prepared slide glass after washing・Washing conditions Washing concentration: 100% Washing temperature: 30 ° C. Washing time: 3 minutes Washing speed: 250 rotations / Min Hardness of water used: 70 ppm (as CaCO ₃ ) ・Preparation of test glass pieces 20 g of a 1: 1 mixed oil of beef tallow and soybean oil and 0.25 g of monoolein were dissolved in 60 ml of chloroform.
The slide glass was immersed in a 25 ° C. soil bath for 2 seconds to a point of 55 mm, and excess stain was sucked out on a clean filter paper, made uniform, air-dried, and weighed.・Evaluation criteria ○: Cleaning efficiency of 80% or more ×: Cleaning efficiency of less than 80%

[Evaluation Method 3 of Bactericidal Activity] The following bacterial species were plated on NA agar medium and cultured in a static place until colonies appeared. A clean filter paper was placed on the colony, and the above-mentioned detergent (concentration: 100%) was impregnated on the filter paper, and the removal of colonies was evaluated.・Bacterium species Escherichia coli Pseudomonas aeruginosa ・Evaluation standard ○: Complete colony removal ×: Colony remaining

[0080]

[Table 8]

[0081]

Example 30 A laundry detergent containing a softening agent having a composition (present) shown in Table 9 below was obtained. Then, the cleaning power and the soft finishing effect of this detergent were evaluated according to the following method. The results are shown in Table 9 below.

[Method for Evaluating Detergency] Home Washing Machine (Model:
A612, manufactured by Matsushita Electric Industrial Co., Ltd.), and a set of three artificially contaminated cloths to be cleaned as shown below was fixed and washed. Evaluation is whiteness reflectance (model: TC-1800M)
KII, manufactured by Tokyo Denshoku Co., Ltd.), the whiteness difference before and after the contamination of the artificially stained cloth was measured. Washing efficiency = (Rw−Ro) / (Ro−Rs) × 100
(%) Ro: reflectivity of white contaminated cloth Rs: reflectivity of contaminated cloth Rw: reflectivity of contaminated cloth after cleaning・Cleaning conditions Detergent concentration: 0.08 w / v% Cleaning temperature: 25 ° C. Rinsing temperature: 25 ° C. Cleaning course: Standard cleaning cycle Hardness of water used: 70 to 80 ppm (as CaCO ₃ ) ・Adjustment of artificially contaminated cloth 1 g of tallow extremely hardened oil, 3 g of liquid paraffin, 0.8 g of carbon black dissolved in 800 ml of carbon tetrachloride It was turbid and prepared. A 30 mm x 30 mm white cloth for white contamination was immersed in this at 25 ° C for 2 seconds, and carbon tetrachloride was completely dried and removed in a fume hood.・Evaluation criteria ○: Cleaning efficiency of 90% or more ×: Cleaning efficiency of less than 90%

[Soft Finishing Effect Evaluation Method] Home Washing Machine
(Model: A612, manufactured by Matsushita Electric Industrial Co., Ltd.) was charged with the above-mentioned cleaning agent to wash the polyester fiber cloth. For the evaluation, the surface charge was measured using an electrostatic meter (model: SV-5, manufactured by Nippon Statec). Antistatic efficiency = (Ro−Rs) / Ro × 100 (%) Ro: Charge before cleaning Rs: Charge after cleaning ・Evaluation criteria ○: Antistatic efficiency of 80% or more ×: Antistatic efficiency of less than 80%

[0084]

[Table 9]

[0085]

Example 31 An antistatic agent-containing hard surface detergent having the composition (present) shown in Table 10 below was obtained. Then, the detergency and antistatic effect of this detergent were evaluated according to the following methods. The results are shown in Table 10 below.

[Evaluation Method of Detergency] The above-mentioned cleaning agent is completely impregnated into a Kimwipe, and dirt on a test piece to be cleaned shown below is wiped on both sides. Evaluation is by weight measurement,
The weight difference before and after contamination of the test piece was measured. Washing efficiency = (Rw−Ro) / (Rs−Ro) × 100
(%) Ro: Weight of the test piece material before being stained Rs: Weight of the test piece Rw: Weight of the test piece after washing・Washing conditions Washing temperature: 25 ° C. Number of times of wiping: 5 reciprocations ・Adjusting tallow for the test piece 1 g of extremely hardened oil, 3 g of liquid paraffin, and 0.8 g of carbon black were dissolved and suspended in 800 ml of carbon tetrachloride. In addition, 2 pieces of polyethylene, which is a test piece material,
It was immersed at 5 ° C for 2 seconds, and carbon tetrachloride was completely dried and removed in a fume hood. Evaluation criteria ○: Cleaning efficiency of 80% or more ×: Cleaning efficiency of less than 80%

[Method of Evaluating Antistatic Effect] With respect to the test piece after cleaning used in the above-described evaluation of detergency, the charge on the surface was measured using an electrostatic meter (model: SV-5, manufactured by Nippon Statec). . Antistatic efficiency = (Ro−Rs) / Ro × 100 (%) Ro: Charge on the surface of the test piece material before applying dirt Rs: Charge on the test piece surface after washing ・Evaluation standard ○: Antistatic efficiency of 80% or more ×: Antistatic efficiency of less than 80%

[0088]

[Table 10]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 1/04 C11D 1/04 1/72 1/72 1/722 1/722 3/20 3/20 17 / 08 17/08 F term (reference) 4H003 AB07 AB14 AB27 AB31 AB44 AB46 AC08 AC11 AC23 AE05 BA12 DA01 DA19 EA16 EA21 EB04 EB07 EB12 EB15 EB19 ED02 FA10 FA16 FA19 FA21 FA22 FA28 FA34 4H011 AA02 BA05 BA06 BB04 BB07 BC06

Claims (10)

[Claims] 1. An anionic surfactant (b) and a cationic surfactant (c) are added to water or a liquid (a) comprising water and a water-soluble solvent, and a solubilizing agent (d) is added. A) a method of obtaining a transparent and uniform solubilizing solution by stirring in the presence of the solubilizing agent (d),
At least one carboxylate selected from the group consisting of an aliphatic dicarboxylate having 7 to 16 carbon atoms and an aliphatic carboxylate having 7 to 12 carbon atoms in an alkyl group or an alkenyl group is used. A method for solubilizing a surfactant. 2. The compounding ratio [d / (b + c)] of the solubilizer (d) to the anionic surfactant (b) and the cationic surfactant (c) is 2/1 by mass. ~ 1
The method for solubilizing a surfactant according to claim 1, wherein the ratio is set to / 3. 3. The method for solubilizing a surfactant according to claim 1, wherein the solubilizer (d) is an alkenyl disuccinate having an alkenyl group having 7 to 16 carbon atoms. 4. The at least two solubilizers (d) include an alkenyl disuccinate having an alkenyl group having 7 to 16 carbon atoms and an aliphatic carboxylate having 7 to 12 carbon atoms. The method for solubilizing a surfactant according to claim 1, which comprises a combination of the following. 5. An anionic surfactant (b) is added to water or a liquid (a) comprising water and a water-soluble solvent by the solubilization method according to any one of claims 1 to 4.
And the cationic surfactant (c) are solubilized to form a transparent and uniform solution as a whole. 6. A liquid detergent composition comprising the surfactant solubilizing solution according to claim 5. 7. The liquid detergent composition according to claim 6, wherein the nonionic surfactant (e) is contained in an amount of 0.1 to 95.0% by mass based on the whole composition. 8. The nonionic surfactant (e) is a polyoxyethylene alkyl ether, a polyoxyalkylene dialkyl ether, a polyoxyalkylene alkyl phenyl ether, a pluronic block polymer,
The liquid detergent composition according to claim 7, which is at least one nonionic surfactant selected from a tetronic block polymer, a reverse pluronic block polymer, and a reverse stetronic block polymer. 9. The liquid cleaning composition according to claim 6, wherein the cleaning builder (f) is contained in an amount of 1 to 50% by mass based on the whole composition. 10. The whole is diluted to a concentration of 0.05 to 0.3% by mass and used for an automatic dishwasher, and the pH at the above-mentioned diluted concentration is 7.0 to 9.5.
The liquid detergent composition according to any one of claims 6 to 9, which is set so as to be within the range of.