JP6188236B2 - Liquid detergent and method for producing the same - Google Patents

Description

  The present invention relates to a liquid cleaning agent and a method for producing the same.

In recent years, in detergents used for washing clothes and the like, the use ratio of liquid detergents is increasing. And this liquid cleaning agent is calculated | required by the high cleaning power with respect to the stain | pollution | contamination adhering to to-be-washed | cleaned material.
Some liquid detergents contain a cationic base such as a long-chain amine in order to improve the sterilizing effect on the object to be washed.
For example, a disinfectant / antibacterial agent composition in which a water-soluble silver salt, a water-soluble copper salt or a water-soluble zinc salt and a long-chain amine represented by a specific general formula are used in combination is disclosed (Patent Document 1). reference).
Also disclosed is a liquid bleaching composition containing hydrogen peroxide, a nonionic surfactant, and a long-chain amine represented by a specific general formula (see Patent Document 2).

JP 2009-235058 A JP2013-136696A

However, long-chain amines blended in the compositions described in Patent Documents 1 and 2 have low solubility in water. For this reason, when a long-chain amine is used in the liquid detergent, the long-chain amine is not sufficiently dispersed, and precipitation and precipitation are likely to occur with time, and it is difficult to ensure appearance stability. The occurrence of precipitation and precipitation with the passage of time is remarkable particularly in the case of a composition where the concentration of the surfactant is not so high (about 30% by mass or less), and it is difficult to obtain a sterilizing effect on the washing object.
This invention is made | formed in view of the said situation, and makes it a subject the liquid detergent which is excellent in external appearance stability, and was excellent in the disinfection effect with respect to to-be-washed | cleaned object.

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.
That is, the liquid detergent of the present invention comprises 30% by mass or less of the surfactant (A) containing the anionic surfactant (a1), the compound (B) represented by the following general formula (b1), and the following: And a compound (C) represented by the general formula (c1).

［式中、ｎは１〜６の整数である。Ｒ^１は直鎖状若しくは分岐鎖状のアルキル基、又は直鎖状若しくは分岐鎖状のアルケニル基である。Ｒ^２は水素原子又は（ＣＨ_２）_ｍＮＨ_２である。ｍは１〜６の整数である。］

[Wherein, n is an integer of 1 to 6. R ¹ is a linear or branched alkyl group, or a linear or branched alkenyl group. R ² is a hydrogen atom or (CH ₂ ) _m NH ₂ . m is an integer of 1-6. ]

［式中、Ｒ^３はフェニル基又はベンジル基である。ｕはＰＯの平均繰返し数、ｖはＥＯの平均繰返し数を表し、ｕは０〜３の数、ｖは０〜３の数であり、１≦ｕ＋ｖ≦６である。ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基を表し、ＥＯとＰＯとは混在して配列してもよい。］

[Wherein R ³ represents a phenyl group or a benzyl group. u represents the average number of repetitions of PO, v represents the average number of repetitions of EO, u is a number from 0 to 3, v is a number from 0 to 3, and 1 ≦ u + v ≦ 6. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO may be mixed and arranged. ]

  In the liquid cleaning agent of the present invention, it is preferable that the surfactant (A) further includes a nonionic surfactant (a2).

  Moreover, the manufacturing method of the liquid cleaning agent of this invention is a manufacturing method of the said liquid cleaning agent of this invention, Comprising: The said surfactant (A), the said compound (B), and the said compound (C) are mixed. It is characterized by that. Among them, the step (i) of obtaining a mixture (BC) of the compound (B) and the compound (C), and the mixture (BC) obtained in the step (i) and the surfactant (A) A production method comprising the step (ii) of mixing the

The liquid detergent of the present invention has good appearance stability and is excellent in the sterilizing effect on the object to be washed.
According to the method for producing a liquid detergent of the present invention, it is possible to produce a liquid detergent having good appearance stability and excellent sterilizing effect on an object to be washed.
In the present invention, “sterilization” refers to reducing the number of bacteria present in the cleaning liquid or on the surface of the object to be cleaned.

(Liquid cleaning agent)
The liquid detergent of the present invention comprises 30% by mass or less of the surfactant (A) containing the anionic surfactant (a1), the compound (B) represented by the general formula (b1), and the general formula (c1). And a compound (C) represented by:
In the present invention, these components are also referred to as component (a1), component (A), component (B), and component (C), respectively. In addition, (B) component and (C) component shall not be contained in (A) component in this invention.
The liquid detergent of the present invention can be used for household and industrial applications, and can be suitably used for household use, and is particularly suitable for clothing.
Examples of the types of items to be cleaned include those similar to those to be cleaned by washing at home, and examples thereof include textiles such as clothes, cloths, towels, and sheets.

<Surfactant (A)>
Surfactant (A) contains anionic surfactant (a1).
As the surfactant other than the component (a1), a surfactant usually used for liquid detergents for clothing and the like can be used, and a nonionic surfactant (a2) (hereinafter referred to as “component (a2)”). Also a cationic surfactant, an amphoteric surfactant, and the like.
In addition to the component (a1), the component (A) preferably includes the component (a2) because the appearance stability of the liquid detergent and the effect of removing oily stains on the object to be cleaned are further improved.
In the liquid detergent, the content of the component (A) (total amount of the surfactant including the component (a1)) is 30% by mass or less, preferably less than 30% by mass, more preferably 2 to 22% by mass. Yes, and particularly preferably 5 to 22% by mass.
If content of (A) component is 30 mass% or less, the effect of this invention will be exhibited notably. On the other hand, if it is more than a preferable lower limit, the cleaning effect is easily exhibited.

≪Anionic surfactant (a1) ≫
As the component (a1), alkylbenzene sulfonate (preferably one having an alkyl group having 10 to 18 carbon atoms, or one having an alkenyl group having 10 to 18 carbon atoms), polyoxyalkylene alkyl ether sulfate ester salt, Examples thereof include alkyl sulfate ester salts, α-olefin sulfonates, α-sulfo fatty acid salts, α-sulfo fatty acid lower (preferably having 1 to 5 carbon atoms) alkyl ester salts, secondary alkane sulfonates, and the like.
Among these, alkylbenzene sulfonates, polyoxyalkylene alkyl ether sulfates, alkyl sulfates, α-olefin sulfonates and secondary alkane sulfonates are preferred, alkyl benzene sulfonates and secondary alkane sulfonates. Is more preferable.
(A1) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
The proportion of the component (a1) in the component (A) is preferably 4% by mass or more, more preferably 4 to 50% by mass, or 100% by mass. If the proportion of the component (a1) in the component (A) is equal to or higher than the preferred lower limit, the oil stain removal effect on the article to be washed is further enhanced, while the proportion of the component (a1) is less than the preferred upper limit, An appropriate viscosity is maintained, and the usability when applied to an object to be washed is improved.
In the liquid detergent, the content of the component (a1) is preferably 15% by mass or less, more preferably 0.5 to 10% by mass, and particularly preferably 1 to 5% by mass.
If content of (a1) component is more than a preferable lower limit, the external appearance stability of a liquid detergent will be more easily ensured. In addition, the effect of removing oily stains on the object to be washed is further increased. On the other hand, if the content of the component (a1) is less than or equal to the preferable upper limit value, an appropriate viscosity is maintained, the usability when applied to an object to be washed is improved, and the appearance stability of the liquid detergent is also improved. improves.

≪Nonionic surfactant (a2) ≫
As the component (a2), for example, a nonionic surfactant represented by the following general formula (a2-1) is preferably exemplified.

［式中、Ｒ^４は炭素数９〜１８の直鎖状もしくは分岐鎖状のアルキル基、又は炭素数９〜１８の直鎖状もしくは分岐鎖状のアルケニル基である。ｐはオキシエチレン基の平均繰返し数を示し、４〜３０の数である。］

[Wherein, R ⁴ represents a linear or branched alkyl group having 9 to 18 carbon atoms, or a linear or branched alkenyl group having 9 to 18 carbon atoms. p shows the average repeating number of an oxyethylene group, and is a number of 4-30. ]

In the formula (a2-1), R ⁴ is a linear or branched alkyl group having 9 to 18 carbon atoms, or a linear or branched alkenyl group having 9 to 18 carbon atoms, Of these, a linear or branched alkyl group having 9 to 18 carbon atoms is preferable.
The number of carbon atoms in the alkyl group or alkenyl group of R ⁴ is preferably 10 to 16, and more preferably 12 to 14, because the oil stain removal effect and appearance stability are further enhanced.
p is preferably a number of 4 to 20 and more preferably a number of 4 to 10 because the oily spot removal effect and appearance stability are further enhanced.

As the component (a2), nonionic surfactants having an HLB (hydrophilic lipophilic balance) of HLB of 9.5 to 13.5 are preferable, those of HLB of 10 to 13 are more preferable, and those of HLB 11 to 13 are preferable. Is more preferable. When the HLB of the component (a2) is not less than the preferred lower limit, the storage stability as a preparation becomes better and the permeability to the washing object to which oily stains are attached is increased, whereas the preferred upper limit is not more than When it is, the oil-based stain stain removal effect with respect to a to-be-washed object increases more.
Here, “HLB” is a value obtained by the Griffin method (see Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Kogyoshosho Co., Ltd., 1991, page 234).

  Further, as the component (a2), polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether, polyoxyethylene alkyl (or alkenyl) phenyl ether, fatty acid alkyl ester alkoxylate, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit Examples also include fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene hydrogenated castor oil, glycerin fatty acid esters, fatty acid alkanolamides, alkyl glycosides, and alkyl amine oxides.

(A2) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
When the liquid detergent contains the component (a2), the proportion of the component (a2) in the component (A) is preferably 50% by mass or more, more preferably 50 to 95% by mass. If the proportion of the component (a2) in the component (A) is not less than the preferred lower limit value, the effect of removing oily stains is further enhanced. On the other hand, if the proportion of the component (a2) is not more than the preferred upper limit value, appearance stability is improved. Rise.
When the liquid detergent contains the component (a2), the content of the component (a2) in the liquid detergent is preferably 30% by mass or less, more preferably 3 to 20% by mass. If content of (a2) component is more than a preferable lower limit, the appearance stability of the liquid detergent and the effect of removing oily stains on the article to be washed will be further enhanced. On the other hand, if the content of the component (a2) is equal to or less than the preferable upper limit value, an appropriate viscosity is maintained, and the usability when applied to an object to be washed is further improved.

When the component (a1) and the component (a2) are used in combination, the mixing ratio of the component (a1) and the component (a2) in the liquid detergent is a mass ratio represented by (a2) component / (a1) component. Is preferably 0.5 to 20, and more preferably 1 to 20.
If the mass ratio represented by (a2) component / (a1) component is equal to or greater than the preferred lower limit, an appropriate viscosity can be easily obtained, while the mass ratio represented by (a2) component / (a1) component. If it is below the preferable upper limit value, the appearance stability is further increased.

<< Surfactant other than (a1) component and (a2) component >>
Examples of the cationic surfactant include various quaternary ammonium salts such as a mono long chain hydrocarbon type quaternary ammonium salt and a di long chain hydrocarbon type quaternary ammonium salt, and an amidoamine salt type surfactant. Among these, amidoamine salt type surfactants are preferable.
Examples of the amidoamine salt type surfactant include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylamino. Examples include salts of long-chain aliphatic amide alkyl tertiary amines such as propylamide, behenic acid dimethylaminopropylamide, and oleic acid dimethylaminopropylamide; palmitic acid diethanolaminopropylamide salts, stearic acid diethanolaminopropylamide salts, and the like.
Examples of amphoteric surfactants include alkyl betaine type, alkyl amide betaine type, imidazoline type, alkyl amino sulfone type, alkyl amino carboxylic acid type, alkyl amide carboxylic acid type, amide amino acid type or phosphoric acid type amphoteric surfactant. Etc.

<Compound (B)>
The compound (B) is a compound represented by the following general formula (b1). In the liquid detergent of this invention, disinfection property is mainly provided by containing (B) component.

［式中、ｎは１〜６の整数である。Ｒ^１は直鎖状若しくは分岐鎖状のアルキル基、又は直鎖状若しくは分岐鎖状のアルケニル基である。Ｒ^２は水素原子又は（ＣＨ_２）_ｍＮＨ_２である。ｍは１〜６の整数である。］

[Wherein, n is an integer of 1 to 6. R ¹ is a linear or branched alkyl group, or a linear or branched alkenyl group. R ² is a hydrogen atom or (CH ₂ ) _m NH ₂ . m is an integer of 1-6. ]

In said formula (b1), n is an integer of 1-6, and since the disinfection effect with respect to a to-be-washed object increases more, it is preferable that it is an integer of 1-4, Most preferably, it is 3. When n exceeds 6, it is difficult to obtain a sufficient sterilizing effect.
R ¹ is preferably a linear or branched alkyl group. The number of carbon atoms in the alkyl group or alkenyl group of R ¹ is preferably 8 to 18 carbon atoms, more preferably 8 to 16 carbon atoms, and even more preferably 10 to 14 carbon atoms, because the affinity with bacteria increases.
Specific examples of R ¹ include a group derived from cocoalkyl (coconut oil), a group derived from beef tallow, a lauryl group, a myristyl group, a palmityl group, and an oleyl group. Among these, cocoalkyl (coconut oil) derived And a lauryl group are preferred, and a lauryl group is particularly preferred.
R ² is preferably (CH ₂ ) _m NH ₂ , since the sterilizing effect on the article to be washed is further increased. m is an integer of 1 to 6, and is preferably an integer of 1 to 4, particularly preferably 3, because the sterilization effect on the washing object is further enhanced.
Among the components (B), N, N-bis (3-aminopropyl) alkylamine with m = n = 3 is particularly preferable because the sterilizing effect on the article to be washed is further enhanced.

(B) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
In the liquid detergent, the content of the component (B) is preferably 0.1 to 10% by mass, more preferably 0.1 to 3% by mass, and particularly preferably 0.3 to 3% by mass.
If the content of the component (B) is not less than the preferred lower limit value, it becomes easy to obtain a sterilizing effect on the object to be washed. On the other hand, if the content of the component (B) is not more than the preferred upper limit value, the liquid detergent. It is easy to keep the appearance of (good separation or white turbidity).

In the present invention, “mass ratio represented by component (a1) / component (B)” means the ratio (mass ratio) of the content of component (a1) to the content of component (B) in the liquid detergent. Represents.
The mixing ratio of the component (a1) and the component (B) is preferably such that the mass ratio represented by the component (a1) / component (B) is 0.1 to 50, and is 0.2 to 20. Is more preferable, and it is further more preferable that it is 0.5-10.
If the mass ratio represented by (a1) component / (B) component is equal to or greater than the preferred lower limit value, the appearance stability of the liquid detergent is further increased, whereas if the mass ratio is equal to or less than the preferred upper limit value, it is high. Bactericidal power is easily obtained.

<Compound (C)>
The compound (C) is a compound represented by the following general formula (c1).

［式中、Ｒ^３はフェニル基又はベンジル基である。ｕはＰＯの平均繰返し数、ｖはＥＯの平均繰返し数を表し、ｕは０〜３の数、ｖは０〜３の数であり、１≦ｕ＋ｖ≦６である。ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基を表し、ＥＯとＰＯとは混在して配列してもよい。］

[Wherein R ³ represents a phenyl group or a benzyl group. u represents the average number of repetitions of PO, v represents the average number of repetitions of EO, u is a number from 0 to 3, v is a number from 0 to 3, and 1 ≦ u + v ≦ 6. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO may be mixed and arranged. ]

In the formula (c1), R ³ is a phenyl group or a benzyl group.
Only one of EO and PO in (EO) v / (PO) u may exist, or they may be mixed and arranged. In (EO) v / (PO) u, EO and PO may be added randomly or may be added in blocks.
Specific examples of the component (C) include polyoxyethylene monophenyl ether, polyoxypropylene monophenyl ether, polyoxyethylene polyoxypropylene monophenyl ether, polyoxyethylene monobenzyl ether, polyoxypropylene monobenzyl ether, polyoxy And ethylene polyoxypropylene monobenzyl ether.
Among these, polyoxyethylene monophenyl ether is preferable, and polyoxyethylene monophenyl ether (v = 1 to 4, u = 0) is more preferable because appearance stability and sterilization power are further improved.

(C) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
In the liquid detergent, the content of the component (C) is preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass.
If the content of the component (C) is at least the preferred lower limit, the appearance stability, the sterilizing effect, and the oil stain removal effect are further improved, while the content of the (C) component is less than the preferred upper limit. The moderate viscosity is maintained, and the usability when applied to the object to be washed is further improved.

In the present invention, “mass ratio represented by (C) component / (B) component” means the ratio (mass ratio) of the content of (C) component to the content of (B) component in the liquid detergent. Represents.
The mixing ratio of the component (B) and the component (C) is preferably such that the mass ratio represented by the component (C) / component (B) is 0.1-50, and is 0.2-20. Is more preferable, and it is further more preferable that it is 1-15.
When the mass ratio represented by component (C) / component (B) is within the above preferred range, high sterilizing power is easily obtained, and appearance stability is also better.
If the mass ratio represented by (C) component / (B) component is at least the preferred lower limit value, the appearance stability of the liquid cleaning agent is further increased, while if the mass ratio is at most the preferred upper limit value, it is high. Bactericidal power is easily obtained.

<Solvent: Water>
The liquid detergent of the present invention preferably contains water as a solvent from the viewpoints of ease of preparation, solubility in water when used, and the like.
The content of water in the liquid detergent is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and still more preferably 70 to 85% by mass with respect to the total amount of the liquid detergent.
If the water content is at least the preferred lower limit, the liquid stability of the liquid detergent with time will be better. On the other hand, if the water content is less than the preferred upper limit, the liquid viscosity will be reasonably low, and the viewpoint of usability Is good.

<Optional component>
In the liquid cleaning agent of the present invention, other components other than the components (A) to (C) described above may be blended as necessary within a range not impairing the effects of the present invention.
As other components, liquid detergents for clothing, liquid bleach detergents, liquid bleaches, and the like can be blended. Specifically, hydrogen peroxide, bleach activator, chelate Agents, radical trapping agent components, hydrotropes, inorganic salts, boric acid compounds, polyol compounds, fragrances, pH adjusters and the like.

≪Hydrogen peroxide≫
In the liquid detergent of this invention, bleaching performance is provided by mix | blending hydrogen peroxide.
When the liquid detergent contains hydrogen peroxide, the content of hydrogen peroxide in the liquid detergent is preferably 0.1 to 10% by mass, more preferably 0.5 to 6% by mass, particularly preferably. Is 1-6 mass%.
When the content of hydrogen peroxide is at least the preferred lower limit, the bleaching effect is more easily exhibited, and in addition, the sterilization effect is further enhanced. On the other hand, when it is not more than the preferable upper limit value, the liquid stability of the liquid cleaning agent with time is further improved.

≪Bleach activator≫
Examples of the bleach activator include tetraacetylethylenediamine, pentaacetylglucose, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium undecanoyloxybenzenesulfonate, and dodeca Sodium noyloxybenzenesulfonate, octanoyloxybenzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid, octanoyloxybenzene, nonanoyloxybenzene, decanoyloxybenzene And organic peracid precursors such as undecanoyloxybenzene and dodecanoyloxybenzene. Among these, sodium nonanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate, and decanoyloxybenzoic acid are preferable.
These bleach activators may be used individually by 1 type, and may use 2 or more types together.
When the liquid detergent contains a bleach activator, the content of the bleach activator in the liquid detergent is 0.1 to 5% by mass from the viewpoints of improvement in bleaching power, storage stability, economy, and the like. Is preferable, and 0.1 to 2 mass% is more preferable.

≪Chelating agent≫
The chelating agent is a chelate having a logarithmic value (log K) of the chelate stabilization constant for Fe ³⁺ and Cu ²⁺ of 10 or more and a logarithm value of the chelate stabilization constant (log K) for Ca ²⁺ of 5.5 or more, respectively. It is preferable to use an agent. The logarithmic values (log K) of the chelate stabilization constant for Fe ³⁺ and Cu ²⁺ are each preferably 12 or more.
Examples of such chelating agents include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonate, 1-hydroxyethane-1,1-diphosphonic acid, ethanehydroxy-1,1,2 -Organic phosphonic acid derivatives such as triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, nitrilotrimethylenephosphonic acid, and ethylenediaminetetrakismethylenephosphonic acid. Among these, 1-hydroxyethane-1,1-diphosphonic acid and ethylenediaminetetrakismethylenephosphonic acid are preferable, and 1-hydroxyethane-1,1-diphosphonic acid is particularly preferable.
As 1-hydroxyethane-1,1-diphosphonic acid, commercially available products can be used. For example, “Feliox 115” manufactured by Lion Corporation, “BRIQUEST ADPA” manufactured by Albright Wilson Corporation, PH-210 ”,“ DEQUEST 2010 ”manufactured by Monsanto, and the like.

≪Radical trapping agent ingredient≫
As the radical trapping agent, a phenol radical trapping agent is preferably used. In particular, when the liquid cleaning agent contains hydrogen peroxide, when the pH of the liquid cleaning agent is 5 or more, decomposition of hydrogen peroxide may not be sufficiently suppressed only by adding the above-described chelating agent. In such a case, it is preferable to use a phenol radical trapping agent together with a chelating agent. In addition, when the liquid cleaning agent is applied to clothing and left for a long time, components such as metals that are highly reactive with hydrogen peroxide cause abnormal decomposition of hydrogen peroxide, which damages the object to be cleaned. There is also a case. In such a case, if a phenol radical trapping agent is added to the liquid cleaning agent, damage to the object to be cleaned can be suppressed.
The phenol radical trapping agent is phenol or a phenol derivative, and preferred examples of the phenol derivative include a compound having a phenolic OH group, an ester derivative of a phenolic OH group, an ether derivative, and the like. The substitution position may be any of the ortho, meta, and para positions. Among these, a compound having a phenolic OH group is more preferable. Among them, compounds having an oxidation-reduction potential (OP) ₀ of 1.25 V or less described in “GE Penketh, J. Appl. Chem”, pages 7,512 to 521 (1957) are preferable. More preferred is a compound of .75V or less. Among these, dimethoxyphenol, catechol, hydroquinone, 4-methoxyphenol, dibutylhydroxytoluene (BHT) and the like are more preferable, and 4-methoxyphenol is particularly preferable.
When the liquid cleaning agent contains a radical trapping agent component, the content of the radical trapping agent component in the liquid cleaning agent is 0.01 to 6% by mass from the viewpoint of the hydrogen peroxide decomposition inhibitory effect and economy. Preferably, 0.05-1 mass% is more preferable.

≪Hydrotrope agent≫
Examples of the hydrotrope include water-miscible organic solvents such as alcohols having 2 to 4 carbon atoms, glycols, polyglycols, and alkyl ethers; paratoluenesulfonic acid, benzoate, urea, and the like.
When the liquid detergent contains a hydrotrope, the content of the hydrotrope in the liquid detergent is preferably 0.01 to 15% by mass.

≪Inorganic salts≫
Examples of inorganic salts include sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium carbonate and the like.

≪Boric acid compounds≫
Examples of the boric acid compound include orthoboric acid (H ₃ BO ₃ ); a salt formed by borate ion (BO ₃ ³⁻ ) or (BO ₄ ⁵⁻ ), or an anion salt obtained by condensing them (condensed boric acid). Salt). Examples of the salt include alkali metal salts such as sodium salt and potassium salt; alkanolamine salts such as monoethanolamine salt and diethanolamine salt; ammonium salt and the like. Among these, alkali metal salts are preferable, and sodium salts and potassium salts are more preferable.
Among the boric acid compounds described above, orthoboric acid, sodium borate, potassium borate, ammonium borate, sodium tetraborate, potassium tetraborate, ammonium tetraborate and the like are preferable, and orthoboric acid and sodium tetraborate are more preferable. preferable.
These boric acid compounds may be used alone or in combination of two or more.
When the liquid detergent contains a boric acid compound, the content of the boric acid compound in the liquid detergent is preferably 0.2 to 10% by mass, and more preferably 1 to 5% by mass. When the content of the boric acid compound is equal to or more than the preferred lower limit, the removal efficiency of the liquid detergent with respect to aqueous stains is improved. On the other hand, if the content of the boric acid compound is equal to or less than the preferable upper limit, the storage stability at low temperatures is improved.

≪Polyol compound≫
A polyol compound is a compound in which one or more sites each having one hydroxy group exist on both adjacent carbon atoms. As specific examples of such a compound, compounds shown in the following (1) to (4) are preferably exemplified.
(1) Glycerin, diglycerin, triglycerin, alkyl (C1-10) polyglyceryl ether (for example, alkyl (C1-10) diglyceryl ether, alkyl (C1-10) triglyceryl ether).
(2) Sugar alcohols selected from sorbitol, mannitol, maltose, inositol and phytic acid.
(3) A reducing saccharide selected from glucose, apiose, arabinose, galactose, lyxose, mannose, galose, aldose, idose, talose, xylose and fructose, or a derivative thereof (alkyl (poly) glycoside, etc.).
(4) A polysaccharide selected from starch, dextran, xanthan gum, guar gum, curdlan, pullulan, amylose and cellulose.
When the liquid detergent contains a polyol compound, the content of the polyol compound in the liquid detergent is preferably 0.3 to 35% by mass, more preferably 1 to 30% by mass, It is especially preferable that it is 20 mass%. If content of a polyol compound is in this range, the cleaning power of a liquid cleaning agent will improve.

≪Perfume≫
A fragrance | flavor may be mix | blended with a liquid detergent for the purpose of the added value improvement of goods, etc.
The fragrance includes a fragrance raw material alone or a fragrance composition composed of a fragrance raw material, a fragrance solvent, a fragrance stabilizer, and the like, and is a liquid detergent for clothes, a liquid bleach detergent, a liquid bleach. The fragrance | flavor normally used for etc. can be mix | blended.
When a liquid detergent contains a fragrance | flavor, content of a fragrance | flavor in a liquid detergent becomes like this. Preferably it is 0.0001-15 mass%, More preferably, it is 0.001-10 mass%.

≪pH adjuster≫
Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid, citric acid and phosphonic acid derivatives; sodium borate, sodium hydroxide, potassium hydroxide and sodium carbonate Sodium bicarbonate, monoethanolamine, diethanolamine, triethanolamine, ammonia and the like.

The pH of the liquid detergent at 25 ° C. is preferably pH 2-7. If pH is in the said range, the storage stability of a liquid detergent can be maintained favorable. If the pH exceeds 7, decomposition of each component (particularly hydrogen peroxide) may occur, and the effects of the present invention may not be sufficiently obtained. The pH of the liquid cleaning agent may be adjusted appropriately using the various pH adjusting agents described above so that a predetermined pH is obtained.
The pH at 25 ° C. of the liquid detergent is a value measured by adjusting the sample to 25 ° C. and using a pH meter (for example, using a product name “HM-30G” manufactured by Toa DKK Corporation). .

The viscosity of the liquid detergent at 25 ° C. is preferably 10 to 300 mPa · s. If the viscosity is within the above range, the liquid detergent can be easily measured on a measuring cap or the like.
Adjustment of the viscosity of the liquid detergent may be performed using, for example, the inorganic salts described above as appropriate.
The viscosity of the liquid cleaning agent at 25 ° C. is a value measured using a B-type viscometer (manufactured by TOKIMEC) after adjusting the sample to 25 ° C. (an example of measurement conditions: rotor NO. 2, Measure the viscosity after 10 revolutions at 30 rpm).

  The liquid cleaning agent of this invention can be accommodated in the container generally used. As this container, for example, a nozzle type container or an inner stopper type container provided with a measuring cap, a squeeze container or a pump container provided with an automatic measuring mechanism or a simple measuring mechanism, a trigger container or a squeeze for spraying liquid or applying in a foam form Examples include containers, application containers having an application surface for applying liquid, and refill containers (pouches, thin bottles, replacement bottles, etc.).

  Examples of the method of using the liquid cleaning agent of the present invention include a method in which the liquid cleaning agent is poured into water together with the laundry at the time of washing, a method in which the liquid cleaning agent is preliminarily dissolved in water and so on. In the case of a liquid cleaning agent having bleaching performance, the liquid cleaning agent may be applied as appropriate after being applied to the object to be washed, and then ordinary washing may be performed.

(Method for producing liquid detergent)
The liquid cleaning agent of this invention can be manufactured by mixing said (A) component, (B) component, and (C) component. For example, it can be produced by dissolving the components (A), (B), (C) and, if necessary, optional components in water as a solvent and adjusting to a predetermined pH using a pH adjuster. .
In particular, the step (i) of obtaining a mixture (BC) of the component (B) and the component (C), and the mixture (BC) obtained in the step (i) and the component (A) are mixed. The manufacturing method provided with the process (ii) to perform is preferable, and according to this manufacturing method, (B) component can be disperse | distributed favorably and the external appearance stability of a liquid detergent increases more.

The liquid detergent of the present invention described above has good appearance stability and is excellent in the sterilizing effect on the object to be cleaned.
The liquid detergent of the present invention comprises 30% by mass or less of the surfactant (A) containing the anionic surfactant (a1), the compound (B) represented by the general formula (b1), and the general formula (c1). And a compound (C) represented by:
As described above, the component (B) (long-chain amine) has a low solubility in water, and particularly contains a component (B) in a composition where the concentration of the surfactant is not so high (about 30% by mass or less). Conventionally, the liquid cleaning agent is likely to precipitate and precipitate with time, and it has been difficult to ensure the appearance stability.
In the liquid cleaning agent of the present invention, at least the component (a1) is used as a cleaning component and the component (C) is used as a solvent. It is sufficiently dispersed and maintained in a good dispersion state, and the appearance stability of the liquid detergent is excellent. In addition, since the affinity of the liquid cleaning agent to the bacteria and the permeability to the bacteria increase, the sterilizing effect on the object to be cleaned is improved. It is considered that these effects are obtained because the synergistic action of the components (A) to (C) works well due to the good balance between the hydrophilicity and hydrophobicity of the component (C).

In addition, the liquid cleaning agent of the present invention has a good oil stain removal effect on the object to be cleaned.
Furthermore, the liquid cleaning agent of the present invention can increase the dispersibility of the component (B) and the permeability to the oily spot in the article to be washed by using the nonionic surfactant (a2) in combination. And oily stain removal effect are further improved.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In this example, “%” indicates “% by mass” unless otherwise specified.
The composition of the liquid cleaning agent in each example is shown in Tables 1-3.
The raw materials used in this example are as follows.

<Surfactant (A)>
≪Anionic surfactant (a1) ≫
a1-1: Linear alkyl (C10-14) benzenesulfonic acid sodium salt. At the time of production of the liquid detergent, linear alkyl (10 to 14 carbon atoms) benzene sulfonic acid [manufactured by Lion Corporation, pure mass 96 mass%, trade name Raipon LH-200] is added by sodium hydroxide which is a pH adjuster. Neutralized to sodium salt.
a1-2: Secondary alkane sulfonate sodium [manufactured by Clariant Japan Ltd., trade name SAS30].
≪Nonionic surfactant (a2) ≫
a2-1: A mixture of an alcohol having 12 carbon atoms (C12OH) and an alcohol having 14 carbon atoms (C14OH) (mass ratio C12OH / C14OH = 75/25) with an average of 6 moles of ethylene oxide, HLB11.6 [Product name Leox CL-60, manufactured by Lion Corporation]. In the general formula (a2-1), R ⁴ = an alkyl group having 12 and 14 carbon atoms, p = 6.
a2-2: A mixture of alcohol having 12 carbon atoms (C12OH) and alcohol having 14 carbon atoms (C14OH) (mass ratio C12OH / C14OH = 75/25) with an average of 8 mol of ethylene oxide, HLB12.9 [Product name Leox CL-80, manufactured by Lion Corporation]. R ⁴ in the general formula (a2-1) = an alkyl group having 12 or 14 carbon atoms, p = 8.

<Compound (B)>
b-1: N, N-bis (3-aminopropyl) laurylamine [manufactured by Lion Akzo Co., Ltd., trade name: triamine Y12D]. In the general formula (b1), n = 3, R ¹ = a linear alkyl group having 12 or 14 carbon atoms, R ² = (CH ₂ ) ₃ NH ₂ , m = 3.
b-2: Lion Akzo Co., Ltd., trade name duomin CD. In the general formula (b1), n = 3, R ¹ = coconut oil-derived (C12, 14) alkyl group, R ² = hydrogen atom.
b-3: n = 1 in the general formula (b1), R ¹ = alkyl group derived from coconut oil (carbon number 12, 14), R ² = hydrogen atom; synthetic product.
b-4: n = 6 in the general formula (b1), R ¹ = alkyl group derived from coconut oil (carbon number 12, 14), R ² = hydrogen atom; synthetic product.

<Comparison component (B ′) of compound (B)>
b′-1: n = 8 in the general formula (b1), R ¹ = alkyl group derived from coconut oil (carbon number 12, 14), R ² = hydrogen atom; synthetic product.
b′-2: n = 3 in formula (b1), R ¹ = hydrogen atom, R ² = hydrogen atom; synthetic product.

<Compound (C)>
c-1: Phenyl polyoxyethylene alcohol [manufactured by Sanyo Chemical Industries, Ltd., 90% by mass pure, trade name Sunfine PH-20]. R ³ in the general formula (c1) = phenyl group, u = 0, v = 2.
c-2: benzyl polyoxyethylene polyoxypropylene alcohol. R ³ in formula (c1) = benzyl group, u = 1, v = 2, u + v = 3; synthetic product.
c-3: Phenyl polyoxyethylene alcohol. R ³ in the general formula (c1) = phenyl group, u = 0, v = 1, u + v = 1; synthetic product.
c-4: Phenyl polyoxyethylene polyoxypropylene alcohol. ^{R 3} = phenyl group in Formula (c1), u = 1, v = 5, u + v = 6; synthetic.

<Comparison component (C ′) of compound (C)>
c′-1: Butyl carbitol [manufactured by Nippon Emulsifier Co., Ltd., pure content: 84 mass%, trade name: butyl diglycol (84)]. R < ³ > = n-butyl group in general formula (c1), u = 0, v = 2.
c'-2: Phenyl polyoxyethylene polyoxypropylene alcohol. R ³ in the general formula (c1) = phenyl group, u = 8, v = 2, u + v = 10; synthetic product.

<Optional component>
Hydrogen peroxide: Mitsubishi Gas Chemical Co., Ltd., pure content 35% by mass.
HEDP: 1-hydroxyethane-1,1-diphosphonic acid [manufactured by Lion Corporation, trade name Ferriox 115].
MQ: 4-methoxyphenol [made by Kawaguchi Chemical Co., Ltd., trade name MQ-F].
Fragrance: Fragrance composition A described in Tables 7 to 14 of JP-A No. 2003-268398.
pH adjuster: sulfuric acid (manufactured by Toho Zinc Co., Ltd.), sodium hydroxide (manufactured by Tsurumi Soda Co., Ltd.).

<Manufacture of liquid detergent>
According to the composition shown in Tables 1 to 3 (compounding components, content (mass%)), the liquid detergents of each example were produced by the following production methods.
In the table, when there is a blank blending component, the blending component is not blended.
In the table, the content of the compounding component indicates a pure equivalent amount.
The “appropriate amount” indicating the content of the pH adjusting agent indicates the total amount of the pH adjusting agent (sulfuric acid, sodium hydroxide) added to adjust the pH (25 ° C.) of the liquid cleaning agent to 6.0.
“Balance” indicating the content of purified water means the balance added so that the total amount (mass%) of all the ingredients contained in the liquid detergent is 100 mass%.
“Mass ratio (a1) / (B)” means the mass ratio of the content of the component (a1) to the content of the component (B) in the liquid detergent.
“Mass ratio (C) / (B)” means the mass ratio of the content of the component (C) to the content of the component (B) in the liquid detergent.
The pH of the liquid detergent is a value obtained by adjusting the sample to 25 ° C. and measuring with a pH meter (product name “HM-30G” manufactured by Toa DKK Co., Ltd.).
“X” indicating a method for producing a liquid detergent is a step (i) for obtaining a mixture (BC) of the component (B) and the component (C), and the mixture (BC) obtained in the step (i). It means that the production method comprises the step (ii) of mixing the surfactant (A).
“Y” indicating a method for producing a liquid detergent means a method for producing a mixture (BC) of the component (B) and the component (C) without preparing in advance.

Example 1
Step (i):
The component (B) was dissolved in the component (C) to obtain a mixture (BC).
Step (ii):
The mixture (BC) obtained in step (i), the component (a1), hydrogen peroxide, HEDP, MQ, and fragrance are dissolved in purified water, and the pH is adjusted to 6.0 using a pH adjuster. To obtain a liquid detergent.

(Examples 2 to 14)
Step (i):
The component (B) was dissolved in the component (C) to obtain a mixture (BC).
Step (ii):
A pH adjuster obtained by dissolving the mixture (BC) obtained in step (i), the component (a1), the component (a2), hydrogen peroxide, HEDP, MQ, and a fragrance in purified water. Was used to adjust the pH to 6.0 to obtain a liquid detergent.

(Example 15)
A liquid cleaning agent was obtained in the same manner as in Example 1 except that hydrogen peroxide was not blended.

(Example 16)
A liquid detergent was obtained in the same manner as in Example 2 except that b-3 was used as the component (B).

(Example 17)
A liquid detergent was obtained in the same manner as in Example 2 except that b-4 was used as the component (B).

(Example 18)
A liquid detergent was obtained in the same manner as in Example 2 except that c-3 was used as the component (C).

(Example 19)
A liquid detergent was obtained in the same manner as in Example 2 except that c-4 was used as the component (C).

(Example 20)
The component (a1), the component (a2), the component (C), hydrogen peroxide, HEDP, MQ, and a fragrance were dissolved in purified water. Then, (B) component was mixed and the liquid cleaning agent was obtained by adjusting to pH 6.0 using a pH adjuster.

(Comparative Example 1)
(A1) The component, hydrogen peroxide, HEDP, MQ, and a fragrance | flavor were melt | dissolved in purified water, and the liquid cleaning agent was obtained by adjusting to pH 6.0 using a pH adjuster.

(Comparative Example 2)
Liquid detergent by dissolving component (B), component (a1), hydrogen peroxide, HEDP, MQ, and fragrance in purified water and adjusting the pH to 6.0 using a pH adjuster. Got.

(Comparative Example 3)
Liquid detergent by dissolving component (C), component (a1), hydrogen peroxide, HEDP, MQ, and perfume in purified water and adjusting the pH to 6.0 using a pH adjuster Got.

(Comparative Example 4)
(B) Component, (a1) component, (a2) component, hydrogen peroxide, HEDP, MQ, and fragrance | flavor are melt | dissolved in purified water, and it adjusts to pH 6.0 using a pH adjuster. As a result, a liquid detergent was obtained.

(Comparative Example 5)
A liquid cleaning agent was obtained in the same manner as in Example 1 except that c′-1 was used instead of c-1.

(Comparative Example 6)
A liquid detergent was obtained in the same manner as in Example 2 except that b′-1 was used instead of b-1.

(Comparative Example 7)
A liquid detergent was obtained in the same manner as in Example 1 except that c′-2 was used instead of c-1.

(Comparative Example 8)
A liquid detergent was obtained in the same manner as in Example 2 except that b′-2 was used instead of b-1.

(Reference Example 1)
(B) Component, (a1) component, (a2) component, hydrogen peroxide, HEDP, MQ, and fragrance | flavor are melt | dissolved in purified water, and it adjusts to pH 6.0 using a pH adjuster. As a result, a liquid detergent was obtained.

<Evaluation of liquid detergent>
With respect to the liquid detergents of the respective examples, “appearance stability”, “sanitizing power”, and “oil stain removal effect” were evaluated by the following evaluation methods. These results are shown in Tables 1-3.

[Evaluation of appearance stability]
The appearance of each of the liquid detergents was observed immediately after the production and after standing for 24 hours immediately after the production, and the appearance stability of the liquid detergent was evaluated according to the following evaluation criteria.
A: No turbidity is observed immediately after the production of the liquid detergent, and no change in appearance is observed after standing for 24 hours.
○: Slight turbidity was observed immediately after the production of the liquid detergent, but even after being left for 24 hours, it was evenly dispersed and no precipitation or precipitation occurred.
(Triangle | delta): Turbidity was recognized immediately after manufacture of a liquid detergent, and precipitation and precipitation had arisen after leaving for 24 hours.
X: Precipitation and precipitation had already occurred immediately after production of the liquid detergent.

[Evaluation of sterilizing power]
Staphylococcus aureus NBRC12732 was inoculated with a platinum loop in an SCD agar medium manufactured by Daigo and cultured at 37 ° C. for 24 hours. Colonies grown using platinum ears were collected, suspended in sterilized water, and adjusted to 1 × 10 ⁸ / mL, which was used as a staphylococcal suspension.
JIS Kanaki No. 3 was cut into a 1 cm square, and about 0.3 g was put into a 50 mL capacity centrifuge tube and sterilized by high-pressure steam. Here, 10 mL of an aqueous solution obtained by diluting the liquid detergent of each example with sterilized water to a concentration (mass standard) of 666 ppm was added and stirred, and then 0.01 mL of staphylococcal suspension was added, and 25 Left at 10 ° C. for 10 minutes. After standing, 0.3 mL was extracted and added to 2.7 mL of Daigo SCDLP medium. 0.3 mL of this was diluted sequentially with 2.7 mL of Japanese Pharmacopoeia phosphate buffer, 1 mL of each was mixed with SCDLP agar medium manufactured by Daigo, and then pour-cultured at 37 ° C. The number of bacteria (V1) was determined.
Similarly, the viable cell count (VO) was determined using purified water instead of the treatment liquid, and the sterilization activity value (ΔLOG) was determined by the following equation.
Bactericidal activity value (ΔLOG) = log ₁₀ (V0) −log ₁₀ (V1)

[Evaluation of oily stain removal effect]
1) Preparation of model dirt cloth Prepared a plurality of cotton cloths (face cloth) with the same amount of rubbing on the face, and divided into 4 pieces per sheet to prepare a model dirt cloth with a collar stain. .
2) Cleaning treatment After directly applying 0.2 mL of the liquid cleaning agent to 5 pieces of the model dirt cloth and leaving it for 5 minutes, it was cleaned with a Terg-O-Tometer (manufactured by U.S. Testing) for 10 minutes ( 120 rpm, 25 ° C., 4 ° DH tap water, bath ratio 30, no detergent), then dehydrated for 1 minute, rinsed with running water for 2 minutes, and dehydrated for 1 minute.
3) Calculation of washing rate After washing the model dirt cloth after washing with an iron, the reflectance (Z value) was measured using a reflectometer (Σ90 manufactured by Nippon Denshoku). And the oil-based spot removal effect was evaluated by calculating | requiring the washing | cleaning rate (%) by the following formula.
Cleaning rate (%) = (Z value of model dirt cloth before washing−Z value of model dirt cloth after washing) / (Z value of model dirt cloth before washing−cotton cloth before rubbing facial stains) Z value) x 100
The oily stain removal effect was evaluated based on the average value of the washing rate of 5 model soiled cloths.

  From the results shown in Tables 1 to 3, it can be seen that the liquid detergents of Examples 1 to 20 to which the present invention is applied have good appearance stability and an excellent sterilizing effect on the object to be washed.

Claims (4)

2 to 30 % by mass of the surfactant (A) containing the anionic surfactant (a1),
0.1 to 10% by mass of the compound (B) represented by the following general formula (b1),
0.5 to 15% by mass of the compound (C) represented by the following general formula (c1),
A liquid cleaning agent comprising:

[Wherein, n is an integer of 1 to 6. R ¹ is a linear or branched alkyl group, or a linear or branched alkenyl group. R ² is a hydrogen atom or (CH ₂ ) _m NH ₂ . m is an integer of 1-6. ]

[Wherein R ³ represents a phenyl group or a benzyl group. u represents the average number of repetitions of PO, v represents the average number of repetitions of EO, u is a number from 0 to 3, v is a number from 0 to 3, and 1 ≦ u + v ≦ 6. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO may be mixed and arranged. ]   The liquid detergent according to claim 1, wherein the surfactant (A) further comprises a nonionic surfactant (a2). It is a manufacturing method of the liquid detergent according to claim 1 or 2,
A method for producing a liquid detergent, comprising mixing the surfactant (A), the compound (B), and the compound (C).   Step (i) for obtaining a mixture (BC) of the compound (B) and the compound (C), and mixing the mixture (BC) obtained in the step (i) with the surfactant (A) The method for producing a liquid detergent according to claim 3, further comprising a step (ii) of: