JP2010184987A - Liquid detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition capable of exhibiting an excellent sterilizing or antibacterial effect while maintaining preservation stability. <P>SOLUTION: This liquid detergent composition contains the following components (A), (B) and (C): component (A) is a water soluble zinc salt, water soluble copper salt or water soluble silver salt; component (B) is polyethyleneimine or a long chain alkylamine compound and/or an anion formed from the long chain alkylamine compound, provided that the long chain alkylamine compound is at least one selected from the group consisting of compounds expressed by general formula (I): R<SP>1</SP>-(A<SP>1</SP>-)N-(CH<SB>2</SB>)<SB>n</SB>-COOX<SP>1</SP>, etc.; and component (C) is a surfactant. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a liquid detergent composition.

In recent years, due to the increase in cleanliness, as a result of washing textile products, not only the degree of visible stain removal but also a cleaning effect (deodorizing effect) against odor stains has been demanded.
As one of the causes of odor generation from clothes after washing, it is known that dirt such as sebum remaining without being completely removed by washing is decomposed by microorganisms.

Then, the method of making it act on microbes, such as microorganisms, using the inorganic metal compound which has microbe elimination and antibacterial property, and obtaining the deodorizing effect is examined (for example, refer patent documents 1-4). .
As the inorganic metal compound, it is common to use a compound containing metals such as silver, copper, and zinc, or a complex (metal complex) of these metals with a polydentate ligand.

JP 2007-176985 A JP 2006-151907 A Japanese Patent Application Laid-Open No. 9-1332797 JP-A-3-141205

However, when an inorganic metal compound is blended in a detergent for textile products, since the detergent is diluted with a large amount of water during washing, a large amount of inorganic metal is required to exhibit a sufficient sterilizing effect and antibacterial effect. It was necessary to add a compound, which was costly.
In addition, particularly in the case of a liquid cleaning agent, it is required to stably mix a cleaning agent component such as an inorganic metal compound in the liquid and maintain the storage stability of the cleaning agent.
However, the sterilization effect and the antibacterial effect cannot always be satisfied by simply adding an inorganic metal compound to the cleaning agent.

  This invention is made | formed in view of the said situation, and it aims at providing the liquid detergent composition which can express the outstanding microbe elimination effect or antimicrobial effect, maintaining storage stability.

  As a result of intensive studies, the present inventors need to adsorb the inorganic metal compound on the textile after washing in order to obtain a deodorizing effect by utilizing the sterilization / antibacterial effect of the inorganic metal compound by washing. Focused on that. However, most of the inorganic metal compounds in the cleaning agent are easily washed away in the washing process such as rinsing, and as a result, the inorganic metal compounds are difficult to be adsorbed and remained on the textile after washing. Thus, it has been found that by adding a specific component to the cleaning agent, the adsorption residual property of the inorganic metal compound to the textile after washing can be improved, and the present invention has been completed.

That is, the liquid detergent composition of the present invention is characterized by containing the following component (A), component (B), and component (C).
(A) component: Water-soluble zinc salt, water-soluble copper salt, or water-soluble silver salt.
Component (B): Polyethyleneimine, or a long-chain alkylamine compound and / or an anion generated from the long-chain alkylamine compound (however, the long-chain alkylamine compound has the following general formulas (I) and (II)) One or more selected from the group consisting of:
(C) Component: Surfactant.

In formula (I), R ¹ represents an alkyl group having 8 to 22 carbon atoms. A ¹ represents any ^one of a hydrogen atom and (CH ₂ ) _m —COOX ² . X ¹ and X ² may be the same or different and represent one selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group. n represents any of 1 to 3, and m represents any of 1 to 3.

In formula (II), R ² represents either an alkyl group having 8 to 22 carbon atoms or an acyl group having 8 to 22 carbon atoms. Q is (NH— (CH ₂ ) _m ), and r represents 1 or 0. When r is 0, A ² and A ³ may be the same or different and are selected from a hydrogen atom and a methyl group. When r is 1, one of A ² and A ³ is a hydrogen atom, and the other is either a hydrogen atom or CH ₂ COOX ³ . X ³ represents one selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group. n represents any of 1 to 3, and m represents any of 1 to 3.

  According to the liquid detergent composition of the present invention, an excellent sterilization effect or antibacterial effect can be exhibited while maintaining storage stability.

Hereinafter, the present invention will be described in detail.
The liquid detergent composition of the present invention comprises the following component (A), component (B), and component (C).
(A) component: Water-soluble zinc salt, water-soluble copper salt, or water-soluble silver salt.
Component (B): polyethyleneimine, or a long-chain alkylamine compound and / or an anion generated from the long-chain alkylamine compound (wherein the long-chain alkylamine compound is represented by the general formulas (I) and (II)) One or more selected from the group consisting of:
(C) Component: Surfactant.

[(A) component]
The component (A) is used for imparting a sterilizing effect or an antibacterial effect to the liquid detergent composition.
The sterilization effect indicates an effect of reducing the number of bacteria present in the cleaning liquid or on the surface of the object to be cleaned, and the antibacterial effect indicates an effect of suppressing the growth of bacteria attached to the surface of the object to be cleaned.

(A-1) Water-soluble zinc salt;
The water-soluble zinc salt is not particularly limited as long as it dissolves in water and releases zinc ions at that time. Examples of water-soluble zinc salts include zinc nitrate, zinc sulfate, zinc sulfide, zinc chloride, zinc acetate, zinc cyanide, zinc chloride zinc, zinc tartrate, zinc perchlorate, etc. Zinc sulfate is preferred from the standpoint of raw material supply.
The blending amount of the water-soluble zinc salt in the liquid detergent composition is not particularly limited, but is preferably blended so as to be 0.2% by mass or more, more preferably 0.7% by mass or more, It is especially preferable that it is 1.0 mass% or more. If 0.2 mass% or more of water-soluble zinc salts are mix | blended in a cleaning composition, sufficient disinfection effect or antibacterial effect will be acquired. On the other hand, the upper limit of the amount of the water-soluble zinc salt is not particularly limited, but is preferably 5% by mass or less, and more preferably 3% by mass or less. If the amount of the water-soluble zinc salt is 5% by mass or less, a composition having good stability can be obtained. In addition, even if the blending amount of the water-soluble zinc salt exceeds 5% by mass, it is difficult to obtain a sterilization or antibacterial improvement effect commensurate with it, which is economically disadvantageous.

(A-2) Water-soluble copper salt;
The water-soluble copper salt is not particularly limited as long as it dissolves in water and releases copper ions at that time. Examples of water-soluble copper salts include silver nitrate, copper sulfate, copper sulfide, copper chloride, copper acetate, copper cyanide, copper chloride ammonium, copper tartrate, copper perchlorate, etc. Copper sulfate is preferable in terms of supply ability and the like.
The blending amount of the water-soluble copper salt in the liquid detergent composition is not particularly limited, but is preferably blended so as to be 0.1% by mass or more, more preferably 0.3% by mass or more, It is especially preferable that it is 0.5 mass% or more. If the water-soluble zinc salt is added in an amount of 0.1% by mass or more in the cleaning composition, a sufficient sterilizing effect or antibacterial effect can be obtained. On the other hand, the upper limit of the amount of the water-soluble copper salt is not particularly limited, but is preferably 5% by mass or less, and more preferably 3% by mass or less. If the amount of the water-soluble copper salt is 5% by mass or less, a composition having good stability can be obtained. In addition, even if the blending amount of the water-soluble copper salt exceeds 5% by mass, it is difficult to obtain a sterilization or antibacterial improvement effect commensurate with it, which is economically disadvantageous.

(A-3) Water-soluble silver salt;
The water-soluble silver salt is not particularly limited as long as it is soluble in water and releases silver ions at that time. Examples of the water-soluble silver salt include silver sulfate, silver nitrate, silver acetate, silver fluoride, and silver perchlorate. Silver sulfate is preferred from the viewpoint of handleability and odor.
The blending amount of the water-soluble silver salt in the liquid detergent composition is not particularly limited, but is preferably blended so as to be 0.01% by mass or more, more preferably 0.05% by mass or more, It is especially preferable that it is 0.09 mass% or more. If the water-soluble silver salt is blended in an amount of 0.01% by mass or more in the cleaning composition, a sufficient sterilizing effect or antibacterial effect can be obtained. On the other hand, the upper limit of the amount of the water-soluble silver salt is not particularly limited, but is preferably 5% by mass or less, and more preferably 3% by mass or less. If the amount of the water-soluble silver salt is 5% by mass or less, a composition having good stability can be obtained. In addition, even if the blending amount of the water-soluble silver salt exceeds 5% by mass, it is difficult to obtain a sterilization or antibacterial improvement effect commensurate with it, which is economically disadvantageous.

[Component (B)]
The component (B) is used to improve the adsorption residual property of the component (A) on the textile product after washing (hereinafter sometimes referred to as “clothing”).

(B-1) polyethyleneimine;
As the polyethyleneimine, commercially available products can be used, and examples thereof include “Epomin (P-1000), molecular weight 70000” manufactured by Nippon Shokubai Co., Ltd.
The blending amount of polyethyleneimine is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and particularly preferably 0.09 to 3% with respect to the total mass of the liquid detergent composition. % By mass. If the blending amount of polyethyleneimine is 0.01% by mass or more, sterilization and antibacterial properties can be imparted to the clothes after washing. On the other hand, even if polyethyleneimine is added in an amount of more than 10% by mass, it is difficult to obtain an effect of improving the sterilization and antibacterial properties, which is economically disadvantageous.

(B-2) a long-chain alkylamine compound and / or an anion generated from the long-chain alkylamine compound;
The long chain alkylamine compound is a compound selected from the group consisting of the general formulas (I) and (II).

In the general formula (I), R ¹ is an alkyl group having 8 to 22 carbon atoms, and more preferably 12 to 18 carbon atoms. If the number of carbon atoms in the alkyl group is 8 or more, the alkyl group tends to be adsorbed to the bacteria, and the metal ions tend to come into contact with the bacteria. On the other hand, when the number of carbon atoms in the alkyl group is 22 or less, there is no problem of solubility in water, and sterilization ability and antibacterial ability are maintained. In particular, when R ¹ is an alkyl group having 12 to 18 carbon atoms, the balance between hydrophobicity (that is, adsorptivity to bacteria) and hydrophilicity (that is, solubility in water) becomes better, and therefore, more It can effectively exhibit sterilizing ability and antibacterial ability.
A ¹ is any ^one of a hydrogen atom and (CH ₂ ) _m —COOX ² .
X ¹ and X ² may be the same or different and are one selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group. Examples of the alkali metal atom include sodium and potassium, examples of the alkaline earth metal atom include magnesium and calcium, and examples of the cationic ammonium group include trimethylammonium and tetramethylammonium.
n is any one of 1 to 3, and if n is within this range, it is considered that the complex formed by the component (A) and the component (B) is stably present in the liquid detergent composition. Further, m is any one of 1 to 3, and if m is within this range, it is considered that the complex is more stably present in the liquid detergent composition.

  The general formula (I) can be represented by the following general formula (I-1) and general formula (I-2). The symbols in each formula are the same as those in the general formula (I).

Specific examples represented by the general formula (I-1) include sodium octyliminodiacetate, sodium lauryliminodiacetate, sodium myristyliminodiacetate, sodium palmitateiminodiacetate and the like, octyliminodiacetate Examples thereof include alkyliminodipropionates such as sodium propionate, sodium lauryliminodipropionate, sodium myristyliminodipropionate, sodium palmityliminodipropionate.
Specific examples represented by the general formula (I-2) include sodium laurylaminoacetate, sodium myristylaminoacetate, sodium palmitylaminoacetate, sodium laurylaminopropionate, sodium myristylaminopropionate, sodium palmitylaminopropionate and the like. Is mentioned.
Of these, alkyliminodiacetate is preferred in view of the stability of the complex.

In the general formula (II), R ² is any one of an alkyl group having 8 to 22 carbon atoms and an acyl group having 8 to 22 carbon atoms. In addition, in both an alkyl group and an acyl group, the number of carbon atoms is more preferably 12-18. If the alkyl group or acyl group has 8 or more carbon atoms, the alkyl group is adsorbed to the bacterium, and the metal ions tend to come into contact with the bacterium. On the other hand, when the number of carbon atoms in the alkyl group or acyl group is 22 or less, there is no problem of solubility in water, and sterilization ability and antibacterial ability are maintained. In particular, when R ² is any one of an alkyl group having 12 to 18 carbon atoms and an acyl group having 12 to 18 carbon atoms, it is hydrophobic (that is, adsorptive to bacteria) and hydrophilic (that is, dissolved in water). Therefore, the sterilization ability and antibacterial ability can be expressed more effectively.
Q is (NH— (CH ₂ ) _m ), where r is 1 or 0 (single bond). If r is 1 or less, it is considered that metal ions tend to come into contact with bacteria.
When r is 0 (single bond), A ² and A ³ may be the same or different and are selected from a hydrogen atom and a methyl group.
On the other hand, when r is 1, one of A ² and A ³ is a hydrogen atom, and the other is either a hydrogen atom or CH ₂ COOX ³ . At this time, X ³ is one selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group. Specific examples of the alkali metal atom, alkaline earth metal atom and cationic ammonium include the same as those in the general formula (I).
n is any one of 1 to 3, and if n is within this range, it is considered that the complex is stably present in the liquid detergent composition.
m is any one of 1 to 3, and if m is within this range, it is considered that the complex is present more stably in the liquid detergent composition.

  The general formula (II) can be represented by the following general formula (II-1) and general formula (II-2). In addition, the symbol in each formula shows the same thing as said general formula (II).

Specific examples of the general formula (II-1) include cocoalkylpropylenediamine, beef tallow alkylpropylenediamine, laurylethylenediamine, myristylethylenediamine, palmitylethylenediamine, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmiticin. And acid dimethylaminopropylamide.
Specific examples of the general formula (II-2) include lauryl diethylene triamine, myristyl diethylene triamine, palmityl diethylene triamine, lauryl dipropylene triamine, myristyl dipropylene triamine, palmityl dipropylene triamine, alkyldiaminoethyl glycine, and the like.
Of these, alkyldiaminoethylglycine is preferred in view of the stability of the complex.

The long-chain alkylamine compound represented by the general formula (II) and the long-chain alkylamine compound represented by the general formula (II) are more preferable than the long-chain alkylamine compound represented by the general formula (II). There is a tendency that the disinfection effect or the antibacterial effect is large. This is considered to be due to the following reason.
In the long-chain alkylamine compound represented by the general formula (I), the charge of the metal ion is reduced or canceled by the carboxyl group of the terminal group. On the other hand, the long-chain alkylamine compound represented by the general formula (II) maintains the charge of the metal ion as it is because the amino group interacts with the metal ion. It is thought to show.

  The compounding amount of the long-chain alkylamine compound and / or the anion generated from the long-chain alkylamine compound (hereinafter sometimes referred to as “component (B-2)”) is the total amount of the liquid detergent composition. 0.01-10 mass% is preferable with respect to mass, More preferably, it is 0.05-7 mass%, Most preferably, it is 0.09-5 mass%. (B-2) If the compounding quantity of a component is 0.01 mass% or more, disinfection and antibacterial property can be provided to the clothes after washing. On the other hand, even if it contains more than 10 mass% of (B-2) component, the improvement effect of disinfection and antibacterial property corresponding to it is difficult to be acquired, and it becomes economically disadvantageous.

  The mass ratio of the component (A) and the component (B) in the liquid detergent composition is preferably (B) component / (A) component = 1.75 / 1 to 10/1. / 1 to 10/1 is more preferable. When the mass ratio is less than 1.75 / 1, the proportion of the component (A) present alone is increased without forming a complex with the component (B) in the liquid detergent composition. As a result, the hydration state of the hydrophilic group of the component (C) described later is adversely affected (that is, the hydration water near the hydrophilic group is dehydrated, so that it is difficult to ensure the stability as a preparation). The storage stability of the cleaning composition tends to decrease. On the other hand, even if the mass ratio exceeds 10/1, it is difficult to obtain an effect of improving sterilization and antibacterial properties, which is economically disadvantageous.

  In the liquid detergent composition, at least a part of the component (A) and the component (B) inevitably forms a complex. By forming a complex between the component (A) and the component (B), the adsorptivity of the metal ions derived from the component (A) to clothing and fungi can be improved by the component (B). Therefore, a more excellent sterilization effect or antibacterial effect can be exhibited with a small amount of metal.

[Component (C)]
Component (C) is a surfactant and is used for imparting detergency to the liquid detergent composition.
It is preferable to use a nonionic surfactant and / or an anionic surfactant as the surfactant.

(C-1) a nonionic surfactant;
Although it does not specifically limit as a nonionic surfactant, For example, the polyoxyalkylene type nonionic surfactant represented by the following general formula (III) is used suitably.
^{R 3 -X 2 - (EO)} s (PO) t -R 4 ··· (III)

In the formula (III), R ³ is a hydrophobic group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, and may be linear or branched. Examples of the hydrophobic group include those derived from primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides and the like.
—X ² — is a functional group such as —O—, —COO— or —CONH—.
EO is ethylene oxide and PO is propylene oxide.
s and t represent an average added mole number, s is an integer of 3 to 20, preferably 5 to 18, and t is an integer of 0 to 6, preferably 0 to 3.
R ⁴ is a hydrogen atom, or an alkyl group or alkenyl group having 1 to 6 carbon atoms, preferably a hydrogen atom, or an alkyl group or alkenyl group having 1 to 3 carbon atoms.

If the average added mole number s of EO exceeds 20, the HLB value becomes too high, which is disadvantageous for sebum cleaning, and the cleaning function tends to be lowered. On the other hand, when the average added mole number s of EO is less than 3, the effect of preventing odor deterioration tends to be reduced.
When the average added mole number t of PO exceeds 6, the storage stability of the liquid detergent composition at a high temperature tends to be lowered.

The added mole number distribution of EO or PO is not particularly limited and is likely to vary depending on the reaction method in producing the nonionic surfactant. For example, the addition mole number distribution of EO or PO is relatively wide when ethylene oxide or propylene oxide is added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide. It tends to be distributed. Also, specific alkoxylation such as magnesium oxide to which metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ and the} like described in Japanese Patent Publication No. 6-15038 are added. When ethylene oxide or propylene oxide is added to a hydrophobic group raw material using a catalyst, the distribution tends to be relatively narrow.

Further, in the equation (III), -X 2 ^- when is -O-, non-ionic surfactants are alcohol ethoxylates. In this case, the carbon number of the linear or branched alkyl group or alkenyl group of R ³ is 10 to 22, preferably 10 to 20, and more preferably 10 to 18. R ³ may have an unsaturated bond. In this case, R ⁴ is preferably a hydrogen atom.
Further, -X 2 in formula (III) ^- when is -COO-, non-ionic surfactant is a fatty acid ester type nonionic surface active agents. In this case, the carbon number of the linear or branched alkyl group or alkenyl group of R ³ is 9 to 21, preferably 11 to 21. R ³ may have an unsaturated bond. In this case, R ⁴ is preferably an alkyl group having 1 to 3 carbon atoms.

  Specific examples of the nonionic surfactant represented by the formula (III) include: Mitsubishi Chemical Co., Ltd .: trade name Diadol (C13, C represents the number of carbons, the same applies hereinafter), Shell: Trade name: Neodol (C12 / C13), manufactured by Sasol: a product obtained by adding 12 moles or 15 moles of ethylene oxide to an alcohol such as the trade name Safol23 (C12 / C13), manufactured by P & G: trade names CO-1214 and CO An ethylene oxide equivalent to 7 moles of a C13 alcohol obtained by subjecting a C12 alkene obtained by subjecting a C12 alkene obtained by trimerizing butene to a natural alcohol such as -1270 or the like to a 12 mole equivalent or 15 mole equivalent of ethylene oxide. (Product name: Lutensol TO7, manufactured by BASF), obtained by subjecting pentanol to a garbed reaction 7 alcohol equivalent of 7 moles of ethylene oxide (BASF, trade name: Lutensol XL70), 6 moles of ethylene oxide added to C10 alcohol obtained by subjecting pentanol to gerbet reaction (BASF) Manufactured by trade name: Lutensol XA60), or a secondary alcohol having 12 to 14 carbon atoms added with 9 mole equivalent or 15 mole equivalent ethylene oxide (made by Nippon Shokubai Co., Ltd .: trade names Softanol 90 or Softanol 150). Can be mentioned. Furthermore, what added 15 mol equivalence ethylene oxide to the palm fatty acid methyl (lauric acid / myristic acid = 8/2) using the alkoxylation catalyst is mentioned.

  As the nonionic surfactant, a single type of nonionic surfactant may be used alone, or a plurality of types of nonionic surfactants may be used in combination.

  As for the compounding quantity of a nonionic surfactant, 10-60 mass% is preferable with respect to the total mass of a liquid detergent composition, More preferably, it is 10-50 mass%. When the blending amount of the nonionic surfactant is 10% by mass or more, a high detergency can be imparted to the liquid detergent composition. When the blending amount of the nonionic surfactant is 60% by mass or less, high storage stability can be imparted to the liquid detergent composition.

(C-2) an anionic surfactant;
As an anionic surfactant, a well-known anionic surfactant can be used and it can obtain easily in a market.
Examples of the anionic surfactant include linear alkylbenzene sulfonic acid or a salt thereof; α-olefin sulfonate; linear or branched alkyl sulfate ester salt; alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt; Examples include alkane sulfonates having an alkyl group; α-sulfo fatty acid ester salts and the like.
Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.

Moreover, as these anionic surfactants, the following are specifically preferable.
As the linear alkylbenzene sulfonic acid or a salt thereof, one having 8 to 16 carbon atoms in the linear alkyl group is preferable, and one having 10 to 14 carbon atoms is particularly preferable.
The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms.
As the alkyl sulfate ester salt, those having 10 to 20 carbon atoms are preferable.
The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms, and an average of 1 to 10 moles of ethylene oxide added (that is, Polyoxyethylene alkyl ether sulfate ester salt or polyoxyethylene alkenyl ether sulfate ester salt) is preferable.
As the alkanesulfonate, a secondary alkanesulfonate having an alkyl group having 10 to 20 carbon atoms, preferably 14 to 17 carbon atoms, is particularly preferable.
The α-sulfo fatty acid ester salt is preferably one having 10 to 20 carbon atoms.
Among these, linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyethylene alkyl ether sulfate, and α-olefin sulfonate are particularly preferable.

  As the anionic surfactant, a single type of anionic surfactant may be used alone, or a plurality of types of anionic surfactants may be used in combination.

It is preferable that the compounding quantity of an anionic surfactant is 0-20 mass% with respect to the total mass of a liquid detergent composition.
Moreover, when mix | blending anionic surfactant, the value of the mass ratio (C-2) / (B) component of (B) component and anionic surfactant has preferable 1.05 or more. 10 or more is preferable. If the value of the mass ratio is 1.05 or more, the hydrophilicity is maintained without losing the anionic charge of the anionic surfactant, so that the storage stability of the liquid detergent composition is further improved. The upper limit of the mass ratio value is preferably 6000 or less, and more preferably 1000 or less.

[Other ingredients]
In the liquid detergent composition of the present invention, components usually used in the liquid detergent can be blended as necessary within a range not impairing the effects of the present invention.
Examples of other components include those shown below.

(Surfactant)
The liquid detergent composition of the present invention includes a nonionic surfactant other than (C-1), an anionic surfactant other than (C-2), a cationic surfactant, and amphoteric. Surfactant can be mix | blended according to a use.

  Examples of nonionic surfactants other than (C-1) include alkylene oxide adducts such as alkylphenols, higher fatty acids or higher amines, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, and polyvalent surfactants. Alcohol fatty acid ester or its alkylene oxide adduct, polyhydric alcohol fatty acid ether, alkyl (or alkenyl) amine oxide, alkylene oxide adduct of hydrogenated castor oil, sugar fatty acid ester, N-alkyl polyhydroxy fatty acid amide, alkyl glycoside, etc. It is done.

Examples of the anionic surfactant other than (C-2) include higher fatty acid salts, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, and acylaminocarboxylic acids. Phosphate-type anionic surface activity such as carboxylic acid type such as salt, alkyl phosphate ester salt, polyoxyalkylene alkyl phosphate salt, polyoxyalkylene alkylphenyl phosphate salt, glycerin fatty acid ester monophosphate ester salt Agents and the like.

  Examples of the cationic surfactant include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salt cationic surfactants.

  Examples of amphoteric surfactants include alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric surfactant. Can be mentioned.

(Water-miscible organic solvent)
Examples of the water-miscible organic solvent include alcohols such as ethanol, 1-propanol, 2-propanol, and 1-butanol, glycols such as propylene glycol, butylene glycol, and hexylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. Polyethylene glycol having an average molecular weight of about 200, polyethylene glycol having an average molecular weight of about 400, polyethylene glycol having an average molecular weight of about 1000, polyglycols such as dipropylene glycol, and alkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol dimethyl ether.
As for the compounding quantity of a water-miscible organic solvent, 0.1-15 mass% is preferable with respect to the total mass of a liquid detergent composition.

(Optional component)
The liquid detergent composition of the present invention may contain the components exemplified below as optional components.
As a thinning agent and a solubilizer, paratoluenesulfonic acid, a benzoate (which also has an effect as a preservative), urea, and the like can be contained, for example, in an amount of 0.01 to 30% by mass.
As a metal ion sparsely capturing agent, malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid and the like can be contained, for example, in an amount of 0.1 to 20% by mass.
As the antioxidant, for example, 0.01 to 2% by mass of butylhydroxytoluene, distyrenated cresol, sodium sulfite, sodium hydrogensulfite and the like can be contained.
As an antiseptic | preservative, for example, Rohm & House company make: Brand name Kaison CG etc. can be included, for example, 0.001-1 mass%.

  Furthermore, the liquid detergent composition of the present invention is an enzyme (protease, lipase, cellulase, etc.), texture improver, alkali builder such as alkanolamine, pH adjuster, etc., for the purpose of improving cleaning performance and storage stability. A hydrotrope agent, a fluorescent agent, a dye transfer inhibitor, a recontamination inhibitor, a pearl agent, a soil release agent and the like may be contained.

In addition, the liquid detergent composition of the present invention may contain flavoring agents, coloring agents, emulsifying agents, extracts such as natural products, and the like for the purpose of improving the added value of products.
As a flavoring agent, the fragrance | flavor composition A, B, C, D etc. of Table 11-18 of Unexamined-Japanese-Patent No. 2002-146399 can be used as a typical example. The blending amount of the flavoring agent is preferably 0.1 to 1% by mass with respect to the total mass of the liquid detergent composition.

  General-purpose dyes and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, Turquoise P-GR (all trade names) Is mentioned. The blending amount of the colorant is preferably about 0.00005 to 0.005% by mass with respect to the total mass of the liquid detergent composition.

  Examples of the emulsion include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is suitably used. Specific examples include polystyrene emulsion (manufactured by Syden Chemical Co., Ltd .: trade name Cybinol RPX-196 PE-3, solid content 40% by mass) and the like. As for the compounding quantity of an emulsion, 0.01-0.5 mass% is preferable with respect to the total mass of a liquid detergent composition.

  Examples of extracts such as natural products include Inuenju, Uwaurushi, Echinacea, Koganebana, Yellowfin, Ouren, Allspice, Oregano, Enju, Chamomile, Honeysuckle, Clara, Keigai, Kay, Bay bay, Honoki, Burdock, Comfrey, Jasho, Waremokou, Peonies, Ginger, Solidago, Elderberry, Sage, Mistletoe, Prunus, Thyme, Prunus, Clove, Satsuma Mandarin, Tea Tree, Barberry, Dokudami, Nanten, Nyuko, Yorigusa, Shirogaya, Bow Fu, Dutch Hyu, Mountain, Gray , Murasakitagayasan, yamahakka, cypress, yamajiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gilead balsamno , Ringworm, kochia, Polygonum aviculare, Jingyou, sealed and Adenophortriphylla, Yamabishi, cayratia japonica, licorice, plant extracts, such as St. John's Wort. The blending amount of extracts such as natural products is preferably about 0 to 0.5% by mass relative to the total mass of the liquid detergent composition.

[Physical properties of liquid detergent composition]
The liquid detergent composition of the present invention preferably has a pH at 25 ° C. of 4 to 9, more preferably pH 4 to 8. When the pH is in such a range, the storage stability of the liquid detergent composition can be maintained well.
The pH of the liquid detergent composition can be adjusted using a pH adjuster. The pH adjuster is optional as long as the effects of the present invention are not impaired, but sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are preferable from the viewpoint of stability.

[Preparation of liquid detergent composition]
The liquid detergent composition of the present invention further comprises the above-described components (A), (B), (C), and other components dissolved or dispersed as necessary in a solvent such as water. Accordingly, it is obtained by adjusting the pH to a desired value with a pH adjusting agent. The blending order of each component is not particularly limited.

  Since the liquid detergent composition of the present invention described above contains specific (A) component, (B) component, and (C) component, (A) for a textile product while maintaining storage stability. The adsorption residual property of the component (inorganic metal compound) can be improved. Therefore, the liquid detergent composition of the present invention can exhibit an excellent sterilizing effect or antibacterial effect. Since the sterilizing effect or antibacterial effect acts on microorganisms such as microorganisms, degradation by microorganisms can be suppressed even if dirt such as sebum remains on clothes after washing. Therefore, the liquid detergent composition of the present invention can reduce the generation of odor and can be expected to have an excellent deodorizing effect.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

[Raw materials]
As the component (A), the following reagents were used.
(A-1): Zinc sulfate heptahydrate (manufactured by Junsei Chemical Co., Ltd., special grade).
(A-2): Copper sulfate pentahydrate (manufactured by Kanto Chemical Co., Ltd., special grade).
(A-3): Silver sulfate (manufactured by Wako Pure Chemical Industries, special grade).

As the component (B), the following reagents and compounds were used.
(B-1): Polyethyleneimine (Nippon Shokubai Co., Ltd., “Epomin P-1000”, molecular weight 70,000).
(B-2): Alkyldiaminoethylglycine represented by formula (1) (manufactured by Wako Pure Chemical Industries, for antibacterial and antifungal research, 30% by mass solution) (the alkyl group (R) in formula (1) is the number of carbon atoms) 12 and 14 are mainly).

(B-3): Octylamine (Wako Pure Chemical Industries, special grade) 2.5 g (19.5 mmol), monochloroacetic acid (Wako Pure Chemical Industries, special grade) 5.0 g (52.9 mmol) which is alkylamine ) Was added to a mixed solution of 5 mL of water and 32 mL of ethanol (manufactured by Kanto Chemical Co., Ltd., special grade) and stirred at reflux for 6 hours. During this reflux stirring, 7.8 mL of an aqueous sodium hydroxide solution (5.0 mol / L) prepared from sodium hydroxide (manufactured by Kanto Chemical Co., Ltd., special grade) was added to adjust the pH. Thereafter, the solution was cooled to 4 ° C. to form a precipitate. The generated precipitate was washed with ethanol, filtered, and dried under reduced pressure to collect a solid, to obtain sodium octyliminodiacetate (carbon number of alkyl group (R): 8 in formula (2)). .

(B-4): Except for using 3.6 g (19.5 mmol) of laurylamine (manufactured by Wako Pure Chemical Industries, Ltd., primary) as the alkylamine, the same operation as in compound (b-3) was performed, The following sodium lauryliminodiacetate (carbon number of alkyl group (R): 12 in formula (2)) was obtained.

(B-5): Other than using myristylamine (manufactured by Tokyo Chemical Industry Co., Ltd., special grade) 4.2 g (19.5 mmol) as the alkylamine, the same formulation as compound (b-3) was used, and The sodium myristyliminodiacetate (carbon number of the alkyl group (R): 14 in the formula (2)) was obtained.

(B-6): The same operation as in the compound (b-3) was carried out except that 4.7 g (19.5 mmol) of palmitylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the alkylamine. The obtained sodium palmiticiminodiacetate (carbon number of alkyl group (R): 16 in formula (2)) was obtained.

(B-7): The same operation as in the compound (b-3) was carried out except that 5.3 g (19.5 mmol) of stearylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the alkylamine. Sodium stearyliminodiacetate (carbon number of alkyl group (R): 18 in formula (2)) was obtained.

(B-8): Eicosylamine as an alkylamine (synthetic product; based on Langmuir, 1994, No. 10, page 1226, arachidic acid is reacted with thionyl chloride to give carboxylic acid chloride, and ammonia is added thereto. In addition, eicosanamide was obtained and then reduced with lithium aluminum hydride to synthesize eicosylamine. Except for using 5.8 g (19.5 mmol), the same composition as compound (b-3) was used. Operation was performed to obtain sodium eicosyliminodiacetate (carbon number of alkyl group (R): 20 in formula (2)) shown below.

(B-9) 55.5 g (0.3 mol) of laurylamine (manufactured by Wako Pure Chemical Industries, Ltd., first grade), which is an alkylamine, was dissolved in 100 mL of ethanol, and 40.4 g of sodium monochloroacetate dissolved in 50 mL of water there. (0.33 mol) was added to obtain a mixed solution. The mixture was heated to 60 ° C., and an aqueous sodium hydroxide solution (12.5 mol / L) was added dropwise while adjusting the pH so as not to be 9 or less. After the dropwise addition, the reaction was allowed to proceed for 5 hours, and the precipitated sodium chloride was filtered and removed by washing. The obtained filtrate was distilled off under reduced pressure, and sodium laurylaminoacetate represented by the formula (3) (carbon number of alkyl group: 12 )

(B-10): A cocoalkylpropylenediamine represented by the formula (4) (manufactured by Lion Akzo, Duomine) (the alkyl group (R) in the formula (4) is mainly having 12 and 14 carbon atoms) is used. It was.

(B-11): Lauric acid (manufactured by Tokyo Chemical Industry Co., Ltd., special grade) 224 g (1.1 mol) was charged into a four-necked flask, and nitrogen substitution was performed twice at 80 ° C. Thereafter, the temperature was raised to 170 ° C., and 173 g (1.7 mol) of dimethylaminopropylamine (manufactured by Kanto Chemical Co., Ltd., deer special grade) was added dropwise over 2 hours while distilling off the replicating water. Furthermore, it was kept at 170 ° C. to 180 ° C. and aged for 7 hours.
After aging, the pressure was reduced and unreacted amine and water were distilled off to obtain dimethylaminopropylamide laurate (carbon number of acyl group: 12) represented by the formula (5).

(B-12): 10.3 g (100 mmol) of diethylenetriamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.0 g (10 mmol) of 1-iodododecane (manufactured by Wako Pure Chemical Industries, Ltd.) were stirred at 40 ° C. for 5 hours. Thereafter, 2.4 mL of an aqueous sodium hydroxide solution (5.0 mol / L) was added, and the mixture was further stirred for a while. After allowing to cool, extraction operation was performed 5 times with diethyl ether / water using a separatory funnel, and the organic layer was distilled off under reduced pressure. The obtained organic layer is a column (manufactured by Nacalai Tesque, silica gel 60, spherical, neutral), eluent: chloroform (manufactured by Kanto Chemical Co., special grade) / methanol (manufactured by Kanto Chemical Co., special grade) = 1/1, or more After being purified by column chromatography under the conditions of (2), the solid was recovered by drying under reduced pressure to obtain lauryldiethylenetriamine (carbon number of alkyl group: 12) represented by formula (6).

(B-13 (comparative product)): Iminodiacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd., special grade) represented by the formula (7) was used.

(B-14 (Comparative product)): Lauroyl lysine (Ajinomoto Co., Amihope) (carbon number of acyl group: 12) represented by formula (8) was used.

(B-15 (comparative product)): Lauroyl aspartic acid (aminoformer manufactured by Asahi Kasei Chemicals Corporation) (carbon number of acyl group: 12) represented by formula (9) was used.

(B-16 (comparative product)): Lauroyl sarcosine (Saipon, manufactured by Kawaken Fine Chemical Co., Ltd.) (carbon number of acyl group: 12) represented by the formula (10) was used.

As the component (C), the following reagents were used.
(C-1): A product obtained by adding 15 moles of ethylene oxide to P & G natural alcohol CO-1214.
(C-2): A product obtained by adding 15 moles of ethylene oxide to natural alcohol CO-1270 manufactured by P & G.
(C-3): A product obtained by adding 12 moles of ethylene oxide to natural alcohol CO-1214 manufactured by P & G.
(C-4): A product obtained by adding 12 moles of ethylene oxide to P & G natural alcohol CO-1270.
(C-5): A product obtained by adding 15 mol of ethylene oxide to Safol 23 alcohol manufactured by Sasol.
(C-6): 12 mol of ethylene oxide added to Sasol 23 alcohol manufactured by Sasol.
(C-7): “Sobutanol 150” manufactured by Nippon Shokubai Co., Ltd.
(C-8): “Sophanol 90” manufactured by Nippon Shokubai Co., Ltd.
(C-9): A synthetic product obtained by adding 15 moles of ethylene oxide to a palm fatty acid methyl (lauric acid / myristic acid = 8/2) using an alkoxylation catalyst.
(C-10): “Lutensol TO7” manufactured by BASF Corporation.
(C-11): “Lutensol XL70” manufactured by BASF Corporation.
(C-12): “Lutensol XA60” manufactured by BASF Corporation.
(C-13): Sodium linear alkylbenzene sulfonate (LAS) (manufactured by Lion Corporation, alkyl group carbon chain length of 10 to 14).
(C-14): Secondary alkane sulfonate sodium (SAS) (manufactured by Clariant Japan, “HOSTAPUR SAS30A”).
(C-15): C12-13 alkyl ethoxysulfate sodium (AES) [average EO chain length of 2 mol, raw alcohol: Saffol 23 (manufactured by Sasol, C12 / C13 = 55% / 45%, linearity: 50%) ]].
(C-16): C14-18 alpha-olefin sodium sulfonate (AOS) (manufactured by Lion Corporation, “Lipolane LB-840”).

As other components, the following reagents were used.
-Sodium benzoate: "Sodium benzoate" manufactured by Toa Gosei Co., Ltd.
Trisodium citrate: “Sodium citrate” manufactured by Miles (USA).
-95% ethanol: "Special alcohol 95 degree synthesis" manufactured by Nippon Alcohol Sales Co., Ltd.
Paratoluenesulfonic acid: “PTS acid” manufactured by Kyowa Hakko Kogyo Co., Ltd.
Polyethylene glycol: “PEG # 1000” manufactured by Lion Corporation.
-Isothiazolone solution: manufactured by Rohm and House, "Caisson CG (5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one / magnesium salt / water mixed solution ) "
-Fragrance | flavor: The fragrance | flavor composition A of Tables 11-18 of Unexamined-Japanese-Patent No. 2002-146399.
-Dye: “Kasumi Kasei”, “Green 3”.
-Sodium hydroxide: manufactured by Tsurumi Soda Co., Ltd.
・ Sulfuric acid: Toho Zinc Co., Ltd.

[Examples 1 to 52, Comparative Examples 1 to 4]
<Preparation of liquid detergent composition>
In a 500 mL beaker, 6.0% by mass of 95% ethanol, 4.0% by mass of polyethylene glycol, 2.0% by mass of paratoluenesulfonic acid, types and blending amounts (% by mass) shown in Tables 1-7. ) Component (C) was added and sufficiently stirred with a magnetic stirrer (MITAMURA KOGYO INC.).
Next, a balanced amount of water heated to 40 ° C. was added, and 0.5% by mass of sodium benzoate, 0.2% by mass of citric acid, 0.01% by mass of isothiazolone solution, and 0% of fragrance. .2% by mass and 0.0001% by mass of the dye were added and stirred to dissolve these components, and then the type and blending amount (% by mass) of component (B) shown in Tables 1 to 7 were added. Stir.
Next, an aqueous solution in which the components (A) shown in Tables 1 to 7 are dissolved in water so that the concentration is 10% by mass is used as a blending amount of the component (A) in the liquid detergent composition (solid content: (Mass%) is adjusted to a value shown in Tables 1 to 7, and then adjusted with sodium hydroxide and sulfuric acid as a pH adjuster so that the pH of the solution becomes 7, to obtain a liquid detergent composition It was.
The balance amount of water is water whose blending amount is adjusted so that the total amount of the liquid detergent composition as the final product is 100% by mass.

<Preparation of liquid cleaning composition for evaluation comparison>
A liquid cleaning composition for evaluation and comparison was prepared in the same manner as in Example 1 except that the components (A) and (B) were not blended.

<Evaluation>
(Evaluation of storage stability)
100 mL of the obtained liquid detergent composition was added to a transparent glass bottle (wide-mouth standard bottle PS-NO.11), and the lid was closed and sealed. In this state, it was placed in a thermostatic bath at -5 ° C. and stored for one month, and then the appearance of the liquid was visually observed and evaluated according to the following criteria. The results are shown in Tables 1-7.
○: No precipitated substance is observed at the bottom of the bottle.
Δ: A precipitate was observed at the bottom of the bottle, but the precipitate disappeared (dissolved) by heating to 40 ° C.
X: Precipitated substance was observed at the bottom of the bottle, and the precipitate did not disappear even when heated at 40 ° C.

(Evaluation of antibacterial effect)
Fully automatic electric washing machine (manufactured by Haier, “JW-Z23A”), cotton knitted fabric (manufactured by Nisshinbo Co., Ltd., “CK43202”, purchased from Tanigami Shoten), about 100 g, and cotton shirt (BVD Corporation) The product was adjusted and added so that the total mass of the entire cloth to be washed was about 800 g [bath ratio (washing water / total mass of the cloth to be washed): 15 times].
Next, 10 mL of a liquid detergent composition was added, and a washing operation was performed in which washing, rinsing, and dehydration were sequentially performed using a standard course. With regard to washing time, rinsing, dehydration, and water volume (set to a low water level, water volume of about 12 L), the standard course setting of the washing machine was used without any adjustment.
After the washing, the taken-out cotton knitted fabric was left to dry in a constant temperature and humidity chamber at 25 ° C. and a humidity of 65% RH. After drying, it was cut into 5 × 5 cm, and this was used as a test cloth for evaluation of antibacterial effect.
Moreover, the cotton knitted fabric which has not performed the process of washing | cleaning operation was used as an untreated cloth.

Evaluation method of antibacterial effect; Evaluation of antibacterial effect against Staphylococcus aureus The instruments, water, and the like used in this evaluation were used after sterilization by an autoclave in advance.
In this evaluation, Staphylococcus aureus was used as the bacterium.
A Staphylococcus aureus mother solution was prepared using Staphylococcus aureus cultured according to JIS L1902, so that the nutrient medium was diluted 20 times and the number of bacteria was 1 ± 0.3 × 10 ⁵ cells / mL. .
The test cloth (5 × 5 cm) was inoculated with 0.1 mL of Staphylococcus aureus mother liquor at four locations, cultured in a thermostatic bath at 37 ° C. for 18 hours, and grown or bacteriostatic on the test cloth. Thereafter, bacteria were extracted from the test cloth with an extract (washing saline described in JIS L1902), and the extract was diluted 10-fold with saline. The operation of further diluting the obtained diluted solution 10 times was repeated 4 times to obtain a 100000 times diluted solution. Note that “washing saline” refers to 8.5 g of sodium chloride per 1000 mL of purified water, which is placed in a flask and sufficiently dissolved, and polyoxyethylene sorbitan as a nonionic surfactant. 2 g of monooleate (manufactured by Kanto Chemical Co., Ltd., “Polysorbate 80, Tween 80”) was added and dissolved, followed by high-pressure steam sterilization (autoclave treatment).
100 μL was collected from the obtained diluted solution, placed on a standard agar medium (manufactured by Akt), and uniformly applied with a congeal rod, cultured in a thermostatic bath at 37 ° C. for 1 to 2 days, and then the number of colonies was counted. The number of viable bacteria was determined.
For the untreated cloth, the number of viable bacteria was measured by performing the same operation as that of the test cloth, and the antibacterial activity value (A) was calculated from the following formula (i) from these measured values.
Antibacterial activity value = log (viable cell count of untreated cloth / viable cell count of test cloth) (i)

Subsequently, the number of viable bacteria was measured for the test cloth and the untreated cloth except that a liquid detergent composition for evaluation and comparison was used instead of the liquid detergent composition, and the antibacterial activity value was measured. (B) was calculated.
From the calculated antibacterial activity value (A) and the antibacterial activity value (B), the difference between the antibacterial activity values {antibacterial activity value (A) -antibacterial activity value (B)} was determined and evaluated according to the following criteria. The results are shown in Tables 1-7.
A: The difference in antibacterial activity value is 2.2 digits or more.
A: The difference in antibacterial activity value is 1.0 digit or more and less than 2.2 digits.
Δ: Difference in antibacterial activity value is 0.5 digits or more and less than 1.0 digit.
X: The difference in antibacterial activity value is less than 0.5 digits.

Evaluation method of antibacterial effect; evaluation of antibacterial effect against Escherichia coli Escherichia coli cultured according to JIS L1902 is used instead of Staphylococcus aureus, a nutrient medium is diluted 20 times, and the number of bacteria is 1 An Escherichia coli mother liquor was prepared so as to be ± 0.3 × 10 ⁵ cells / mL.
The difference in the antibacterial activity value was determined in the same manner as the evaluation of the antibacterial effect against the Staphylococcus aureus except that the Escherichia coli mother liquor was used instead of the Staphylococcus aureus mother liquor, and the evaluation was performed according to the same evaluation criteria. The results are shown in Tables 1-7.

As is clear from Tables 1 to 7, the liquid detergent composition obtained in each example had good storage stability. In particular, the mass ratio {(B) / (A)} of the component (A) to the component (B) is in the range of 1.75 to 10, and the mass ratio of the component (B) to the component (C-2) { In Examples 1 to 48, (C-2) / (B)} was 1.05 or more, the storage stability was remarkably excellent.
Moreover, the liquid detergent composition obtained in each Example had an excellent antibacterial effect. Furthermore, it is also suggested that the liquid detergent composition obtained in each example has an excellent sterilizing effect.

On the other hand, since the liquid detergent composition obtained in Comparative Example 1 used iminodiacetic acid having no terminal alkyl group as the component (B), an antibacterial effect on Staphylococcus aureus was not particularly obtained. In addition, the antibacterial effect on Escherichia coli was also lower than in each example.
Since the liquid detergent composition obtained in Comparative Example 2 used lauroyllysine that did not conform to the formulas (I) and (II) as the component (B), the antibacterial effect on Staphylococcus aureus was not particularly obtained. In addition, the antibacterial effect on Escherichia coli was also lower than in each example.
Since the liquid detergent composition obtained in Comparative Example 3 used lauroyl aspartic acid that does not match the formulas (I) and (II) as the component (B), the antibacterial effect on Staphylococcus aureus was not particularly obtained. . In addition, the antibacterial effect on Escherichia coli was also lower than in each example.
Since the liquid detergent composition obtained in Comparative Example 4 used lauroyl sarcosine that does not match the formulas (I) and (II) as the component (B), the antibacterial effect on S. aureus was not particularly obtained. In addition, the antibacterial effect on Escherichia coli was also lower than in each example.

Claims (1)

A liquid detergent composition comprising the following component (A), component (B), and component (C).
(A) component: Water-soluble zinc salt, water-soluble copper salt, or water-soluble silver salt.
Component (B): Polyethyleneimine, or a long-chain alkylamine compound and / or an anion generated from the long-chain alkylamine compound (however, the long-chain alkylamine compound has the following general formulas (I) and (II)) One or more selected from the group consisting of:
(C) Component: Surfactant.

[In the formula (I), R ¹ represents an alkyl group having 8 to 22 carbon atoms. A ¹ represents any ^one of a hydrogen atom and (CH ₂ ) _m —COOX ² . X ¹ and X ² may be the same or different and represent one selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group. n represents any of 1 to 3, and m represents any of 1 to 3. ]

[In Formula (II), R ² represents either an alkyl group having 8 to 22 carbon atoms or an acyl group having 8 to 22 carbon atoms. Q is (NH— (CH ₂ ) _m ), and r represents 1 or 0. When r is 0, A ² and A ³ may be the same or different and are selected from a hydrogen atom and a methyl group. When r is 1, one of A ² and A ³ is a hydrogen atom, and the other is either a hydrogen atom or CH ₂ COOX ³ . X ³ represents one selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, and a cationic ammonium group. n represents any of 1 to 3, and m represents any of 1 to 3. ]