JP2016216543A - Liquid detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent for washing having good detergency to protein stains and excellent sterilization performance.SOLUTION: The liquid detergent for washing is provided which contains a semi-polar surfactant or an ampholytic surfactant represented by an amine oxide type surfactant (A), a nonionic surfactant represented by poly(oxyethylene-oxypropylene)-alkyl ether and (C) a cationic surfactant represented by alkyl trimethyl chloride, and in which content of the nonionic surfactant (C) is 10 mass% or more and a mass ratio of (B)/(A) is less than 10.SELECTED DRAWING: None

Description

  The present invention relates to a liquid cleaning agent.

In recent years, due to an increase in hygiene awareness, excellent sterilization performance is demanded in laundry detergents. The frequency of laundry drying in the room has increased in recent years, and a laundry detergent having a higher sterilizing effect has been demanded. As a bactericidal agent imparting bactericidal performance, for example, a cationic surfactant is used.
Conventionally, an anionic surfactant has been used to improve the detergency against protein stains, but there is a disadvantage that the bactericidal performance of the cationic surfactant is lowered by adding the anionic surfactant.
That is, it has been difficult to achieve both a cleaning ability against protein soil and an excellent sterilization performance.
On the other hand, although amine oxide which is a semipolar surfactant is known to have bactericidal performance (for example, Patent Document 1), its effect is not necessarily sufficient.

JP 2013-227257 A

  An object of this invention is to provide the liquid detergent which has the favorable detergency with respect to protein soil, and the outstanding sterilization performance.

  The liquid cleaning agent of the present invention comprises an amine oxide surfactant (A) represented by the following formula (I), a nonionic surfactant (B) represented by the following formula (II), and the following formula (III) ) And a nonionic surfactant (B) content of 10% by mass or more, and the content of the amine oxide surfactant (A) is (B) / (A) representing the mass ratio of the content of the nonionic surfactant (B) is less than 10.

[Wherein, R ¹ is a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, and R ² and R ³ are each independently an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms. is there. R ⁴ is an alkylene group having 1 to ⁴ carbon atoms, A is —CO—NH—, —NHCO—, —C (O) O—, —OCO— or —O—, and m is 0 or 1 is there. ]

[Wherein, R ⁵ represents a hydrocarbon group having 8 to 18 carbon atoms, X represents —O— or —C (O) O—, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, Or it is a C2-C6 alkenyl group. s represents the average number of repetitions of EO and is a number from 3 to 20. t represents the average number of repetitions of PO and is a number from 0 to 6. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO may be mixed and arranged. ]

[Wherein, one or two of R ^{20 to} R ²³ are an alkyl group or an alkenyl group having 8 to 20 carbon atoms, and the others are independently an alkyl group or a benzyl group having 1 to 3 carbon atoms. is there. Z ⁻ represents a counter ion. ]

  According to the present invention, a liquid detergent composition having good detergency against protein soil and excellent sterilization performance can be obtained.

The liquid cleaning agent of the present invention comprises an amine oxide surfactant (A) represented by the above formula (I) (hereinafter referred to as component A) and a nonionic surfactant represented by the above formula (II) ( B) (hereinafter referred to as B component) and a cationic surfactant (C) (hereinafter referred to as C component) represented by the above formula (III).
The liquid detergent of the present invention can be used for household, commercial, and industrial applications, and can be suitably used for household use, and is particularly suitable as a liquid detergent for clothing.
Examples of types of objects to be cleaned (objects to be cleaned) include those that are the objects to be cleaned in laundry at home, and examples include textiles such as clothes, cloths, towels, sheets, and curtains. The

<A component>
The component A is represented by the above formula (I). A component may be 1 type and may use 2 or more types together. The compound represented by the formula (I) is a semipolar surfactant and / or an amphoteric surfactant.
In the formula (I), R ¹ is a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, preferably a linear or branched alkyl group having 10 to 18 carbon atoms.
R ² and R ³ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, preferably an alkyl group, more preferably an alkyl group having 1 carbon atom.
R ⁴ is an alkylene group having 1 to ⁴ carbon atoms, preferably an alkylene group having 3 carbon atoms.
-A- is a group selected from -CO-NH-, -NHCO-, -COO-, -OCO- or -O-, and -CO-NH- is preferred.
m is 0 or 1, and 0 is preferable.

Specific examples of the component A include alkyl dimethylamine oxide, alkylamidopropyl dimethylamine oxide, and the like.
From the viewpoint of excellent detergency, alkyldimethylamine oxide with m = 0 in formula (I) is desirable. Among the alkyldimethylamine oxides, the following C12 amine oxide, C14 amine oxide, 16 amine oxide, or C18 amine oxide is preferable, and C14 amine oxide is particularly preferable from the viewpoint of excellent bactericidal activity.
C12 amine oxide: a compound in which m = 0, R ¹ is a linear alkyl group having 12 carbon atoms, and R ² and R ³ are both alkyl groups having 1 carbon atom.
C14 amine oxide: a compound in which m = 0, R ¹ is a linear alkyl group having 14 carbon atoms, and R ² and R ³ are both alkyl groups having 1 carbon atom.
C16 amine oxide: a compound in which m = 0, R ¹ is a linear alkyl group having 16 carbon atoms, and R ² and R ³ are both alkyl groups having 1 carbon atom.
C18 amine oxide: a compound in which m = 0, R ¹ is a linear alkyl group having 18 carbon atoms, and R ² and R ³ are both alkyl groups having 1 carbon atom.
Examples of the alkylamidopropyldimethylamine oxide include lauric acid amidopropylamine oxide and myristic amidopropyldimethylamine oxide. From the viewpoints of detergency and appearance stability, lauric acid amidopropylamine oxide (described below) is preferable.
Lauric acid amidopropylamine oxide: m = 1, -A- is -CO-NH-, R ¹ is a linear alkyl group having 11 carbon atoms, R ² and R ³ are alkyl groups having 1 carbon atom, A compound in which R ⁴ is an alkylene group having 3 carbon atoms.

The content of the component A is preferably 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, further preferably 5 to 20% by mass, and 10 to 20% by mass with respect to the total mass of the liquid detergent. % Is particularly preferred.
Sufficient sterilization performance is easily obtained when the content of the component A is not less than the lower limit of the above range. Moreover, the effect of improving the protein soil cleaning power by using both the A component and the B component is easily obtained. When the amount is not more than the upper limit of the above range, sufficient appearance stability during low-temperature storage is easily obtained.

<B component>
Component B is a nonionic surfactant represented by the above formula (II). One type of B component may be used, or two or more types may be used in combination.
In the above formula, the number of carbon atoms of the hydrocarbon group is R ⁵ is from 8 to 18, 10 to 18 is preferred especially good detergency is likely that the obtained. R ⁵ may be linear or branched. R ⁵ is preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, or a linear or branched alkenyl group.
Examples of the hydrocarbon group as R ⁵ include those derived from raw materials such as primary or secondary higher alcohols, higher fatty acids and higher fatty acid amides. Specifically, residues obtained by removing OH groups from primary or secondary higher alcohols, residues obtained by removing C (O) OH groups from higher fatty acids, and C (O) NH groups removed from higher fatty acid amides. Residue, etc.
The carbon number of the alkyl group as R ⁶ is 1-6, 1-3 are preferred. The number of carbon atoms of the alkenyl group as R ⁶ is 2 to 6, preferably 2 to 3.
X is —O— or —C (O) O—. When X is —O—, the component (B) is an alcohol alkoxylate. In this case, since the detergency is good, it is preferable that the carbon number of R ⁵ is 10 to 18, R ⁵ may have an unsaturated bond. In this case, R ⁶ is preferably a hydrogen atom.
When X is -C (O) O-, the component (B) is a fatty acid ester type nonionic surfactant. In this case, since the detergency is good, it is preferable that the carbon number of ^{R 5} is 9 to 18, more preferably from 11 to 18. R ⁵ may have an unsaturated bond. In this case, R ⁶ is preferably an alkyl group having 1 to 3 carbon atoms.

In the formula, s is the average number of repetitions of EO (oxyethylene group), and t is the average number of repetitions of PO (oxypropylene group). s and t mean weighted average values, respectively. s and t can be measured using, for example, a gas chromatograph mass spectrometer.
s is 3-20, Preferably it is a number of 5-18, More preferably, it is a number of 14-18. When s exceeds 20, the HLB value becomes too high and the cleaning power tends to decrease. On the other hand, when s is less than 3, the raw material odor of the B component itself tends to deteriorate.
t is 0 to 6, preferably 0 to 3. When t exceeds 6, the storage stability of the liquid detergent at high temperature tends to be lowered.
EO and PO may be mixed and arranged, and (EO) _s / (PO) _t may be added in a random form or in a block form.

Further, for example, as represented by the following formula (IIa), it may be added in the order of EO block chain-PO block chain-EO block chain, or in the order of EO and PO random chain-EO block chain. It may be added.
^{_{R 7 -O - [(EO)}} p / (PO) q] - (EO) r -H (IIa)
In formula (IIa), R ⁷ is a hydrocarbon group having 8 to 18 carbon atoms. p represents the average number of repetitions of EO, q represents the average number of repetitions of PO, r represents the average number of repetitions of EO, p, q, r are p> 1, r> 1, 0 <q ≦ 3, p + r = 10-20. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO in (EO) p / (PO) q may be arranged randomly or in blocks.
R ⁷ is the same as R ^{5 in} formula (II), including preferred embodiments.
The component represented by the formula (IIa) can be produced by a known method. For example, it can be produced by adding ethylene oxide to an alcohol having a hydrocarbon group after addition reaction in the order of ethylene oxide and propylene oxide, or after adding and mixing ethylene oxide and propylene oxide (random addition).
When the component B represented by the formula (IIa) is used, an appropriate viscosity is easily obtained in the liquid cleaning agent, and gelation is also suppressed. Moreover, foamability improves and biodegradability also becomes better.
In particular, the ratio of EO and PO in the formula (IIa) is preferably 0.1 to 0.5, more preferably 0.1 to 0.3 in terms of q / (p + r). . When the ratio represented by q / (p + r) is equal to or higher than the lower limit value, bubbles are not excessively formed and foaming is easily optimized. When it is at most the upper limit value, an appropriate viscosity is easily obtained, and gelation is easily suppressed.

In the B component represented by the formula (II), the distribution of the average number of repetitions of EO or PO easily varies depending on the reaction method in producing the B component, and is not particularly limited. For example, using a general alkali catalyst such as sodium hydroxide or potassium hydroxide, ethylene oxide or propylene oxide is converted to a starting compound having a hydrocarbon group (primary or secondary higher alcohol, higher fatty acid, higher fatty acid amide, etc. ), The distribution tends to be relatively wide. On the other hand, 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 the starting compound having a hydrocarbon group using a catalyst, the distribution tends to be relatively narrow.

Specific examples of the component B include Mitsubishi Chemical's trade name Diadol (C13, C represents the number of carbon atoms; the same shall apply hereinafter), Shell's trade name Neodol (a mixture of C12 and C13), and Sasol. A product obtained by adding 12 mole equivalent or 15 mole equivalent of ethylene oxide to alcohol such as Safol 23 (mixture of C12 and C13);
A product obtained by adding 12 moles or 15 moles of ethylene oxide to a natural alcohol such as trade name CO-1214 or CO-1270 manufactured by P &G;
7 mol equivalent of ethylene oxide added to C13 alcohol obtained by subjecting C12 alkene obtained by trimerization of butene to oxo method (trade name Lutensol TO7 manufactured by BASF);
A product obtained by adding 9 moles of ethylene oxide to C10 alcohol obtained by subjecting pentanol to gerbet reaction (trade name Lutensol XP90 manufactured by BASF);
A product obtained by adding 7 moles of ethylene oxide to C10 alcohol obtained by subjecting pentanol to garvet reaction (trade name Lutensol XL70 manufactured by BASF);
A product obtained by adding 6 moles of ethylene oxide to C10 alcohol obtained by subjecting pentanol to garvet reaction (trade name Lutensol XA60 manufactured by BASF);
Examples include those obtained by adding 9 mol or 15 mol of ethylene oxide to a secondary alcohol having 12 to 14 carbon atoms (trade names Softanol 90, Softanol 150 manufactured by Nippon Shokubai Co., Ltd.).
Furthermore, to the palm fatty acid methyl (lauric acid / myristic acid = 8/2), using an alkoxylation catalyst, 15 mol equivalent of ethylene oxide was added (polyoxyethylene palm fatty acid methyl ester (EO 15 mol)) Also mentioned.

  (B) As a component, especially in terms of detergency, in formula (II), X is —O—, polyoxyethylene alkyl ether (AE), polyoxyethylene polyoxypropylene alkyl ether (EOPO type nonion), etc. Or a fatty acid ester type nonionic surfactant in which X is —C (O) O— in formula (II). A fatty acid ester type nonionic surfactant is more preferable.

Content of B component is 10 mass% or more with respect to the total mass of a liquid detergent, and 15 mass% or more is preferable. If B component is 10 mass% or more, sufficient cleaning power can be imparted to the liquid detergent. The upper limit of the amount of component B is preferably less than 60% by weight, more preferably less than 50% by weight, and even more preferably less than 40% by weight from the viewpoint of the appearance stability of the liquid detergent.
Moreover, the protein dirt cleaning power by using together A component and B component can be improved effectively. The value of (B) / (A) representing the mass ratio of the B component content to the A component content is less than 10, preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less. Within this range, the effect of the combined use of the A component and the B component is easily obtained.
On the other hand, the lower limit of (B) / (A) is preferably 0.01 or more, more preferably 0.1 or more, and further preferably 0.5 or more, from the viewpoint of the stability of the liquid cleaning body.
10-60 mass% is preferable and, as for the total amount of A component and B component with respect to the total mass of a liquid detergent, 20-50 mass% is more preferable.

<C component>
Component C is a cationic surfactant represented by the above formula (III). C component may be used alone or in combination of two or more.
In the formula (II), one or two of R ^{2 to} R ⁵ are an alkyl group having 8 to 20 carbon atoms or an alkenyl group having 8 to 20 carbon atoms, and other than that, each independently represents 1 to 2 carbon atoms. 3 alkyl groups or benzyl groups. The alkyl group having 8 to 20 carbon atoms is preferably an alkyl group having 12 to 18 carbon atoms. The alkyl group may be linear or branched. The alkenyl group having 8 to 20 carbon atoms is preferably an alkenyl group having 12 to 18 carbon atoms. The alkenyl group may be linear or branched. In particular, an alkyl group having 14 or 16 carbon atoms is excellent in sterilization performance.
The alkyl group having 1 to 3 carbon atoms is a methyl group, an ethyl group, or a propyl group. Of these, a methyl group is preferred from the viewpoint of easy availability of raw materials.
Z ⁻ is a counter ion, preferably a halogen ion or an alkyl sulfate ion. Examples of the halogen ion include fluorine ion, chlorine ion, bromine ion and iodine ion, and chlorine ion is preferable from the viewpoint of versatility. As an alkyl sulfate ion, what has a C1-C3 alkyl group is preferable, for example, a methyl sulfate ion etc. are mentioned.

The content of the component C is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, and further preferably 1 to 5% by mass with respect to the liquid detergent. When the amount is not less than the lower limit of the above range, the effect of improving the sterilization performance is easily obtained, and when it is not more than the upper limit, the stability of the liquid detergent is excellent.
The value of (A) / (C) representing the mass ratio of the content of the A component to the content of the C component is preferably 0.005 to 250, more preferably 0.05 to 20, and more than 2 and 20 or less. Further preferred. When (A) / (C) is not less than the above lower limit value, the bactericidal property is excellent, and when it is not more than the above upper limit value, the stability of the liquid detergent is excellent.

<D component: anionic surfactant>
The liquid detergent of the present invention does not contain an anionic surfactant or, if included, is limited to one or more anionic surfactants selected from the group consisting of fatty acids or salts thereof, and linear alkylbenzene sulfonic acids or salts thereof. Is done. Examples of these salts include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; alkanolamine salts such as monoethanolamine and diethanolamine.
Preferably, it is a fatty acid salt having 8 to 20 carbon atoms. Even when a fatty acid salt is added to the liquid detergent of the present invention, the protein cleaning performance can be improved without reducing the bactericidal effect.
When the anionic surfactant (D) is contained in the liquid detergent of the present invention, the content thereof is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 6% by mass or less with respect to the liquid detergent. preferable. When the amount is not more than the above upper limit value, excellent sterilization performance is easily obtained.
The lower limit of the content in the case of containing the anionic surfactant (D) is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, and more preferably 3% by mass or more in terms of easily obtaining the effect of addition. Is more preferable.

<E component: other surfactant>
As long as the effects of the present invention are not impaired, the liquid detergent contains one or more of other surfactants (E) that are not included in any of the A component, B component, C component, and D component. Also good.
For example, when a fatty acid ester having a fatty acid residue of 4 to 10 carbon atoms (for example, 2-ethylhexyl 2-ethylhexanoate), which is a nonionic surfactant other than the component B, is included, the defoaming property at the time of use is improved. To do.
10 mass% or less is preferable, as for the total content of other surfactant (E) with respect to a liquid washing body, 8 mass% or less is more preferable, and 5 mass% or less is further more preferable.

<F component: enzyme>
The liquid detergent may contain the enzyme (F). Protease is preferred as the enzyme (F). By blending protease, it is possible to further improve the detergency against protein stains and further enhance the bactericidal effect.
For example, a commercially available protease preparation can be used. Specific examples include Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type EX, Everase Ultra 16L, Esperse 8L, Alcalase 2.5L, Alcalase 2.5L, Alcale 2.5L 2.5XL, Coronase 48L (all are trade names, manufactured by Novozymes), Purefect L, Perfect OX, Properase L (all are trade names, manufactured by Genencor).
An enzyme may be used individually by 1 type and may be used in combination of 2 or more type.
When the enzyme (F) is contained in the liquid detergent of the present invention, the total content is preferably 0.01 to 4% by mass, more preferably 0.05 to 2% by mass with respect to the liquid detergent. More preferably, the content is 1-1. When the content of the enzyme (F) is not less than the above lower limit, the effect of improving the protein dirt cleaning power is excellent. Even if it contains more enzyme (F) than the said upper limit, the effect commensurate economically will not be acquired.

<G component: Water-miscible organic solvent>
In addition to water, the liquid detergent may contain one or more water-miscible organic solvents (G). The “water-miscible organic solvent” is an organic solvent that dissolves 50 g or more in 1 liter of ion-exchanged water at 25 ° C., and a known liquid detergent can be used.
For example, C2-C4 monohydric alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol;
A C2-C4 polyhydric alcohol such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having an average molecular weight of about 200 to 5000, methoxypolyethylene glycol, glycerin; and ethylene glycol monobutyl ether; Examples thereof include glycol ether solvents such as ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and Celltor EDGAC (diethylene glycol monoethyl ether acetate) manufactured by Daicel Corporation.
When the water-miscible organic solvent (G) is contained in the liquid detergent of the present invention, the content thereof is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and 6 to 25% with respect to the liquid detergent. More preferred is mass%. When it is at least the lower limit of the above range, good stability of the liquid detergent can be easily obtained. Even if it contains more than the upper limit of the said range, the effect commensurate economically will not be acquired.

<Other optional components>
In addition to the above components and water, the liquid detergent of the present invention can appropriately contain known components used for liquid detergents.
For example, pH adjusters, solubilizers (or thickeners), metal ion scavengers, antioxidants, preservatives, texture improvers, dye transfer inhibitors, recontamination inhibitors, pearl agents, soil release agents, wear Arbitrary components, such as a fragrance | flavor, a coloring agent, an emulsion agent, a fluorescent agent, and an extract, are mentioned.
The total content of other optional components is not particularly limited. For example, in 100% by mass of the liquid detergent, 10% by mass or less is preferable, 7% by mass or less is more preferable, and 5% by mass or less is more preferable.

  Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as polyvalent carboxylic acids and hydroxycarboxylic acids; sodium hydroxide, potassium hydroxide, alkanolamine and ammonia. Among these, sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamine are preferable, and sulfuric acid and sodium hydroxide are preferable from the viewpoint of the temporal stability of the liquid detergent. A pH adjuster may be used individually by 1 type, and may use 2 or more types together.

<Manufacturing method>
A liquid detergent can be manufactured according to the manufacturing method of a conventionally well-known liquid detergent. For example, after adding and mixing each component excluding the pH adjuster to a part of the water as the dispersion medium, adding the pH adjuster to adjust to an arbitrary pH, and then adding the remainder of the water to adjust the total amount Let it be a liquid cleaning agent as 100 mass%.

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.
Tables 1 and 2 show the composition of the liquid cleaning agent in each example. In the table, the unit of the content of each compounding component is “mass%”, and all indicate the amount in terms of pure content. In the table, when there is a blank blending component, the blending component is not blended.

<A component>
a1: C12 alkyl dimethylamine oxide, manufactured by Lion Specialty Chemicals Co., Ltd., trade name “Aromox DM12D-W”.
a2: C14 alkyl dimethylamine oxide, manufactured by Lion Specialty Chemicals Co., Ltd., trade name “Aromox DM14D-N”.
a3: C16 alkyl dimethylamine oxide, manufactured by Lion Specialty Chemicals Co., Ltd., trade name “Aromox DM16D-M”.
a4: C18 alkyl dimethylamine oxide, manufactured by Lion Specialty Chemicals, Inc., trade name “Aromox DM18D-M”.
a5: Lauric acid amidopropylamine oxide, manufactured by Oji Kogyo Co., Ltd., trade name “Aromox (APA-12W)”.
These components were used after adjusting the pure content according to the blending amount.

<B component>
b1 (MEE): A coconut fatty acid methyl ester (a mixture of methyl laurate / methyl myristate = 8/2 in mass ratio) added with 15 moles of ethylene oxide using an alkoxylation catalyst. In Formula (II), R ⁵ is an alkyl group having 11 or 12 carbon atoms, -R ⁶ is -CH ₃ , -X- is -C (O) O-, s is 15, and t is 0 It is.
b2 (LMAO): A compound obtained by adding 15 moles of ethylene oxide to natural alcohol (Procter & Gamble, trade name “CO-1214”). In the formula (II), R ⁵ is an alkyl group having 12 carbon atoms or an alkyl group having 14 carbon atoms, R ⁶ is H, —X— is —O—, s is 15, and t is 0.

<C component>
c1: Alkyl chloride (carbon number 12) trimethylammonium, manufactured by Lion Akzo Corporation, trade name “ARCARD 12-37W”.
c2: Alkyl chloride (14 carbon atoms) trimethylammonium, manufactured by Tokyo Chemical Industry Co., Ltd.
c3: Alkyl chloride (16 carbon atoms) trimethylammonium, manufactured by Lion Akzo Co., Ltd., trade name “Arcade 16”.
c4: Alkyl chloride (16 to 18 carbon atoms) trimethylammonium, manufactured by Lion Akzo, trade name “ARCARD T-800”.
c5: Benzalkonium chloride, manufactured by Lion Akzo, trade name “ARCARD CB”.
c6: Didecyldimethylammonium chloride, product name “Arcade 210” manufactured by Lion Akzo Corporation.

<D component: anionic surfactant>
d1 (LAS): linear alkylbenzene sulfonic acid, manufactured by Lion Corporation, trade name “Lypon LS-200”.
d2: Trade name “Zushi fatty acid”, manufactured by NOF Corporation.
<E component: other surfactant>
[Nonionic surfactant other than B component]
e1: 2-ethylhexyl 2-ethylhexanoate (2H-2EH), fatty acid alkyl ester synthesized in Synthesis Example 1 below.
<F component: enzyme>
f1: Protease, manufactured by Novozymes, trade name “Coronase 48L”.
f2: Protease, manufactured by Novozymes, trade name “Alcalase 2.5L”.
<G component: Water-miscible organic solvent>
g1: Polyethylene glycol, manufactured by Lion Corporation, trade name “PEG1000”.
g2: Ethanol, manufactured by Nippon Alcohol Sales Co., Ltd., trade name “specific alcohol 95 degree synthesis”.
<PH adjuster>
MEA: monoethanolamine.
PTS: p-toluenesulfonic acid (Kyowa Hakko Kogyo Co., Ltd., trade name: PTS acid).
NaOH: manufactured by Tsurumi Soda Co., Ltd., trade name: sodium hydroxide.

[Synthesis Example 1: Synthesis of 2-ethylhexyl 2-ethylhexanoate]
A 5 L four-necked flask was charged with 1700 g of 2-ethylhexanoic acid, 1425 g of 2-ethylhexanol, and 17 g of p-toluenesulfonic acid (manufactured by Kanto Chemical Co., Inc.) as a catalyst, and was purged with nitrogen. Then, while flowing nitrogen at a flow rate of 1 mL / second, the liquid temperature was raised to 140 ° C. to carry out an esterification reaction, and water produced by the reaction was removed by distillation. After removing water, the temperature was raised to 200 ° C. while gradually reducing the pressure to 0.6 kPa to obtain a crude product. Next, 21.5 g (1.5 parts by mass with respect to 100 parts by mass of the crude product) of Hyflo Supercell (trade name, manufactured by Nacalai Tesque Co., Ltd.) as a filter aid is added to 1500 g of the crude product and stirred for 10 minutes. And uniformly dispersed, and then filtered under pressure at 80 ° C. to obtain 2-ethylhexyl 2-ethylhexanoate.

<Preparation of liquid detergent>
According to the composition shown in Tables 1 and 2 (blending components, content (mass%)), liquid detergents of respective examples were prepared by the following production methods. The content shown in the table indicates the content of the compounding component (pure equivalent amount). In the table, a blank means that the blending component is not blended.
In the table, “(A + B) total” means the total amount of the A component and the B component. “B / A mass ratio” means the ratio of the content (mass%) of the component B to the content (mass%) of the component A. “A / C mass ratio” means the ratio of the content (mass%) of the A component to the content (mass%) of the C component.

(Examples 1-19, Comparative Examples 1-3)
Each component except the pH adjuster was added to ion-exchanged water and mixed. A liquid detergent was obtained by adding an appropriate amount of a pH adjuster so that the pH value (25 ° C.) was 7.
“Balance” indicating the content of ion-exchanged water means that an appropriate amount of water was added and adjusted so that the total of all components contained in the liquid detergent was 100% by mass.

<Evaluation of liquid detergent>
About the liquid detergent of each example, the bactericidal performance and protein cleaning power were evaluated by the following method. The evaluation results are shown in Tables 1 and 2.
[Evaluation of protein stain cleaning power]
A protein soiled cloth was obtained by cutting EMPA117 (EMPA Testmateliaien), which is a protein soiled cloth, into 5 cm × 5 cm. As the liquid detergent, the liquid detergent of each example immediately after production was used. The washing liquid was prepared by adding 10 mL of liquid detergent to 30 L of water and stirring both for 30 seconds.
Next, using a Terg-O-meter (manufactured by UNITED STATES TESTING) as a cleaning tester, 10 protein soiled cloths, a cleaning knitted cloth, and the washing liquid are put into the cleaning tester, and a bath ratio of 30 is used. Washing was performed at 120 rpm and 15 ° C. for 10 minutes.
Thereafter, it was transferred to a two-tub washing machine (Mitsubishi Electric Corp., product number: CW-C30A1-H1), dehydrated for 1 minute, rinsed in 30 L of tap water (15 ° C., 4 ° DH) for 3 minutes, and air-dried. .
The reflectance was measured with a color difference meter (product name: SE200 type) manufactured by Nippon Denshoku Co., Ltd. for the unwashed and washed cloths, and the washing rate (%) was calculated by the following formula.
Washing rate (%) = (K / S of contaminated cloth before washing−K / S of contaminated cloth after washing) / (K / S of contaminated cloth before washing−K / S of unsoiled cloth) × 100.
However, K / S is a value calculated | required by type | formula: (1-R / 100) ² / (2R / 100), R is the reflectance (%) of a non-contaminated cloth, a contaminated cloth, or a washing cloth.
In addition, the cleaning rate (%) was calculated for five contaminated cloths, and the average value was used to make a determination based on the following criteria, and ◯ and ◎ were regarded as acceptable.
◎: 55% or more ○: 50 or more and less than 55% △: 45% or more and less than 50% ×: less than 45%

[Evaluation of sterilization performance]
E. coli was inoculated into an SCD agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.) and cultured at 37 ° C. for 24 hours, and then the colonies on the agar surface were scraped off and suspended in sterile water. What was adjusted with the sterilized water so that the light absorbency of 650 nm might be set to 30 was used as the microbial solution.
A liquid detergent to be evaluated was added at a rate of 0.33 mL to 1 L of sterilized water at 3 ° DH to obtain a test liquid, and 0.01 mL of the above bacterial liquid and 9.99 mL of the test liquid were mixed to obtain a test bacterial liquid. Three pieces of sterilized cotton kanakin cloth of 2 cm square were put into this test bacterial solution and allowed to stand at room temperature for 10 minutes. Ten minutes later, 0.3 mL of the test bacterial solution was added to 2.7 mL of SCDLP liquid medium (manufactured by Nippon Pharmaceutical Co., Ltd.) to reduce the action of the bactericide on the bacteria, and further diluted 100 to 1000 times with the SCDLP medium. The solution was subjected to pour culture in SCD medium. After culturing at 37 ° C. for 24 hours, the number of colonies was counted.
A comparative test solution was prepared using Tween 80 (product name, manufactured by Tokyo Chemical Industry Co., Ltd., polyoxyethylene sorbitan monooleate) as a comparative cleaning agent. That is, Tween 80 was added at a rate of 0.5 mL to 1 L of sterilized water of 3 ° DH to obtain a comparative test solution, and the above bacterial solution 0.01 mL and 9.9 mL of the comparative test solution were mixed to obtain a test bacterial solution. The same operation as described above was performed using this test bacterial solution.
Bactericidal properties were evaluated by the difference between the number of bacteria in the comparative test solution added with Tween 80 and the number of bacteria in the test solution added with a liquid detergent. The difference in the number of bacteria was converted to LOG (CFU / ml), and ○ and ◎ were accepted.
A: 4 or more
○: 3 or more and less than 4
Δ: 2 or more and less than 3
X: Less than 2

From the results of Tables 1 and 2, in Examples 1 to 19, liquid detergents excellent in protein soil cleaning power and sterilization performance were obtained.
On the other hand, in Comparative Example 1 in which the A component was not blended, the protein stain detergency was slightly inferior to that of Example 12 because the B component was increased, but the bactericidal performance was greatly reduced.
Comparing Examples 2, 12, 13 and Comparative Example 1, it can be seen that component A contributes to sterilization performance and protein soil cleaning power.
Moreover, when Example 12 and Comparative Example 1 are compared, it can be seen that the combined use of the component A and the component B can efficiently improve the protein soil cleaning power with a small addition amount.
When Examples 7-11 are compared, it turns out that C component contributes to sterilization performance.
Further, comparing Comparative Example 2 in which the A component is not blended or Comparative Example 3 in which the C component is not blended with Example 2, it can be seen that the bactericidal performance can be synergistically improved by using the A component and the C component together. .
Comparing Examples 2 and 14, it can be seen that the addition of protease as the component (F) improves the protein soil cleaning power and sterilization performance.

Claims (1)

An amine oxide type surfactant (A) represented by the following formula (I):
A nonionic surfactant (B) represented by the following formula (II):
Containing a cationic surfactant (C) represented by the following formula (III):
Content of the said nonionic surfactant (B) is 10 mass% or more,
A liquid detergent, wherein (B) / (A) representing a mass ratio of the content of the nonionic surfactant (B) to the content of the amine oxide surfactant (A) is less than 10.

[Wherein, R ¹ is a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, and R ² and R ³ are each independently an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms. is there. R ⁴ is an alkylene group having 1 to ⁴ carbon atoms, A is —CO—NH—, —NHCO—, —C (O) O—, —OCO— or —O—, and m is 0 or 1 is there. ]

[Wherein, R ⁵ represents a hydrocarbon group having 8 to 18 carbon atoms, X represents —O— or —C (O) O—, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, Or it is a C2-C6 alkenyl group. s represents the average number of repetitions of EO and is a number from 3 to 20. t represents the average number of repetitions of PO and is a number from 0 to 6. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO may be mixed and arranged. ]

[Wherein, one or two of R ^{20 to} R ²³ are an alkyl group or an alkenyl group having 8 to 20 carbon atoms, and the others are independently an alkyl group or a benzyl group having 1 to 3 carbon atoms. is there. Z ⁻ represents a counter ion. ]