TW201529836A - Liquid detergent - Google Patents

Abstract

A liquid detergent containing component (A): a surfactant, component (B): a carbohydrate degrading enzyme preparation and component (C): hydroxy carboxylic acid or a salt thereof, and in which a mass ratio of the component (B) / the component (C) is 1 or less.

Description

Liquid detergent

This invention relates to a liquid detergent.

The present application is based on Japanese Patent Application No. 2013-253646, filed on Jan.

Due to the improvement of cleaning awareness, liquid detergent for clothing, in addition to requirements In addition to the stain (cleaning effect) attached to the clothing or the like (the laundry), it is also required to remove the unpleasant odor generated from the laundry or to prevent an unpleasant odor from being caused by the laundry.

The unpleasant odor generated from the laundry is mainly caused by the proliferation of microorganisms adhering to the fibers during drying or storage of the laundry.

In response to this, a detergent having a cationic cation surfactant having a bactericidal effect or an antibacterial effect has been previously proposed. Patent Document 1 discloses a liquid detergent containing a cationic surfactant, a nonion surfactant, and benzoic acid and/or a salt thereof.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-316130

In other words, with the recent changes in the lifestyle, the number of households that wash at night and dry the laundry after drying in the room, that is, indoors, is increasing. Drying in the house is difficult to dry due to poor ventilation and the laundry is not easily dried.

Therefore, it is desirable to suppress the generation of an unpleasant odor (hereinafter, also referred to as an indoor drying odor) from the laundry when it is dried in the house. The liquid detergent described in Patent Document 1 has an insufficient effect of suppressing the occurrence of the indoor dryness. Further, if only the cationic surfactant having a bactericidal effect or an antibacterial effect is increased, the washing effect is deteriorated, and accordingly, it is difficult to obtain an effect of suppressing the occurrence of the indoor drying odor.

The inventors of the present invention have focused on the method of decomposing and removing a biofilm which is attached to the back surface of the laundry or the washing tank, in particular, in order to improve the effect of suppressing the drying of the interior. Further, it has been found that by effectively utilizing a glycolytic enzyme such as mannanase, it is possible to effectively suppress the dryness in the house.

However, when a saccharide-decomposing enzyme is formulated, it is difficult to ensure the storage stability (for example, transparency uniformity and fluidity) of the liquid detergent.

The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a liquid detergent which has a high effect of suppressing generation of a dryness in a house and which has excellent storage stability.

The inventors discovered by further research that by living in the interface The present invention can be solved by using a saccharide-degrading enzyme preparation such as mannanase in combination with a saccharide-degrading enzyme preparation such as mannanase and a hydroxycarboxylic acid or a salt thereof in an amount equal to or higher than the saccharide-decomposing enzyme preparation. That is, the liquid detergent of the present invention relates to a liquid detergent comprising (A) a component: a surfactant, (B) a component: a saccharide-decomposing enzyme preparation, and (C) a component: a hydroxycarboxylic acid or The salt and the mass ratio represented by the component (B)/(C) are 1 or less.

In the liquid detergent of the present invention, it is preferred that the component (A) contains a cationic surfactant.

That is, the present invention relates to the following.

[1] A liquid detergent comprising: (A) component: a surfactant, (B) component: a saccharide-decomposing enzyme preparation, and (C) component: a hydroxycarboxylic acid or a salt thereof, and (B) component/ The mass ratio represented by the component (C) is 1 or less.

[2] The liquid detergent according to [1], wherein the component (A) comprises a cationic surfactant.

According to the liquid detergent of the present invention, the effect of suppressing the occurrence of the indoor drying odor is high, and the storage stability is good.

The liquid detergent of the present invention contains the component (A): a surfactant, the component (B): a saccharide-decomposing enzyme preparation, and the component (C): a hydroxycarboxylic acid or a salt thereof.

The liquid detergent of the present invention can be used for household, commercial, industrial use, and can be preferably used for household use, and can be preferably used as a liquid detergent for clothing.

The type of the object to be washed (the object to be washed) is the same as the object to be cleaned which is to be washed in the household, and examples thereof include clothes, rags, towels, sheets, and curtains. (curtain) and other fiber products.

<(A) component: surfactant]

The liquid detergent of the present invention has detergency by containing the component (A).

As the component (A), a surfactant which is usually used in a liquid detergent such as a clothing can be used, and examples thereof include a nonionic surfactant, an anion surfactant, a cationic surfactant, and an amphoteric surfactant. Wait.

In the present specification, the nonionic surfactant is also referred to as (A-1) component, the anionic surfactant is referred to as (A-2) component, and the cationic surfactant is referred to as (A-3) component.

((A-1) component: nonionic surfactant)

Examples of the component (A-1) include the nonionic surfactants (1) to (9) shown below.

(1) A polyoxyalkylene alkyl (or alkenyl) ether.

(2) A polyoxyethylene alkyl (or alkenyl) phenyl ether.

(3) A fatty acid alkyl ester alkoxylate obtained by adding an alkylene oxide to an ester bond of a long-chain fatty acid alkyl ester.

(4) Polyoxyethylene sorbitan fatty acid ester.

(5) Polyoxyethylene sorbitan fatty acid ester.

(6) Polyoxyethylene fatty acid ester.

(7) Polyoxyethylene hydrogenated castor oil.

(8) Glycerol fatty acid ester.

(9) An alkylamine alkoxylate obtained by adding an alkylene oxide to a long-chain alkyl (or alkenyl) amine.

Among the components (A-1), the above (1), (3), and (9) are preferred. its Among them, the storage stability and the effect of suppressing the formation of a film on the liquid surface are further improved, and the above (3) is further preferable. Further, in the case where the component (A-2) described later is the main washing component, the effect of the present invention is more easily obtained, and the above (1) is preferably used.

Preferred examples of the above (3) include those represented by the following formula (a-1-1). A polyoxyalkylene type nonionic surfactant (hereinafter also referred to as "(a-1-1) component").

In addition, the polyoxyalkylene type nonionic surfactant represented by the following general formula (a-1-2) is exemplified (hereinafter, also referred to as "(a-1-) 2) Component ") A polyoxyalkylene type nonionic surfactant represented by the formula (a-1-3) (hereinafter also referred to as "(a-1-3) component").

In addition, the polyoxyalkylene alkylamine type nonionic surfactant represented by the following general formula (a-1-4) is exemplified (hereinafter, also referred to as "(a) -1-4) ingredient").

. About (a-1-1) ingredients

The component (a-1-1) is a polyoxyalkylene type nonionic surfactant represented by the following formula (a-1-1).

R ¹ -CO-[(EO')s/(PO')t]-R ² (a-1-1)

[wherein, R ¹ is an alkyl group having 7 to 18 carbon atoms or an alkenyl group having 7 to 18 carbon atoms; R ² is an alkyl group having 1 to 3 carbon atoms; and s represents an average repeat number of EO', which is 6~ The number of 20; t indicates the average number of repetitions of PO', which is a number from 0 to 6; EO' indicates oxygen extended ethyl, PO' indicates oxygen extended propyl; so-called [(EO')s/(PO')t] In the formula (a-1-1), R ^{1 is} preferably an alkyl group having a carbon number of 9 to 18 or a carbon number in terms of detergency. The alkenyl group of 9 to 18 may be linear or branched.

R ¹ may, for example, be an alkyl group or an alkenyl group derived from a raw material such as a higher alcohol, a higher fatty acid or a higher fatty acid decylamine of the first or second stage.

In the formula (a-1-1), R ² is an alkyl group having 1 to 3 carbon atoms, preferably a methyl group.

In the formula (a-1-1), s is a number of 6 to 20, preferably a number of 6 to 18, more preferably a number of 11 to 18, and particularly preferably a number of 14 to 16. In addition, s can be an integer or a decimal.

If s exceeds 20, there is a hydrophilic-lipophile balance (Hydrophile-Lipophile) The balance, HLB) value becomes too high, and the detergency tends to decrease. On the other hand, when s is less than 6, the raw material odor of the component (a-1-1) itself tends to be easily deteriorated.

t is a number from 0 to 6, preferably a number from 0 to 3. In addition, t can be an integer or a decimal.

When t exceeds 6, the storage stability of the liquid detergent at a high temperature tends to decrease.

In addition, the so-called "average repetition number" in this specification and the scope of patent application, Refers to the molar number of ethylene oxide or propylene oxide reacted with respect to the alcohol 1 mole used.

The so-called [(EO')s/(PO')t] means that EO' and PO' can be mixed and arranged, and EO' and PO' can be added in a random manner, or can be added in a block form. to make.

In the component (a-1-1), the distribution of the number of repetitions of EO' or PO' is not particularly limited, and it is easy to vary depending on the reaction method in the case of producing the component (a-1-1). For example, the repeat number distribution of EO' or PO' is such that an alkali catalyst such as sodium hydroxide or potassium hydroxide is used to add ethylene oxide or propylene oxide to the hydrophobic base material (ie, primary or secondary). When a higher alcohol, a higher fatty acid, a higher fatty acid decylamine or the like is used, there is a tendency to be relatively broadly distributed. Further, Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^{2+ ,} etc. are added as described in Japanese Patent Publication No. 6-15038. A specific alkoxylation catalyst such as magnesium oxide of metal ion, in which ethylene oxide or propylene oxide is added to the hydrophobic base material, the repeat number distribution of EO' or PO' exists. The tendency to become a relatively narrow distribution.

Preferable examples of the component (a-1-1) include, for example, an epoxy resin having a carbon number of 10 to 18 (preferably 12 to 14) of a fatty acid methyl ester addition of 11 to 18 (preferably 15) molar equivalent. A polyoxyalkylene type nonionic surfactant such as ethane.

. About (a-1-2) component and (a-1-3) component

The component (a-1-2) is a polyoxyalkylene-type nonionic surfactant represented by the following formula (a-1-2), and the component (a-1-3) is represented by the following formula (a). -1-3) A polyoxyalkylene type nonionic surfactant represented.

R ^3a -O-(EO') _u -H (a-1-2)

R ^3b -O-[(EO') _p /(PO') _q ]-(EO') _r -H (a-1-3)

[wherein R ^3a and R ^3b are each independently an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms; u represents an average number of repetitions of EO', and is a number of 5 to 20; p represents EO 'the average number of repetitions, q represents the average number of repetitions of PO', r represents the average number of repetitions of EO', and p, q, r satisfy 17>p>1, 17>r>1, 0<q≦3, and p+r=10~20; EO' means oxygen extended ethyl, PO' means oxygen extended propyl; [(EO') _p /(PO') _q ] means that EO' and PO' may also be mixed ]

In the formula (a-1-2) and the formula (a-1-3), R ^3a and R ^3b are each independently an alkyl group having 10 to 18 carbon atoms from the viewpoint of x washability. Or an alkenyl group having 10 to 18 carbon atoms, which may be linear or branched.

In the formula (a-1-2), u is a number of 5 to 20, preferably a number of 8 to 18, more preferably a number of 10 to 16, and particularly preferably a number of 14 to 16. If u exceeds 20, it exists The HLB value becomes too high and the detergency tends to decrease. On the other hand, when u is less than 5, the raw material odor of the component (a-1-2) itself tends to be easily deteriorated.

In the formula (a-1-3), the so-called [(EO') _p /(PO') _q ] means that EO' and PO' can be mixed and arranged, and EO' and PO' can be random. Addition of ground can also be added in the form of a block.

In the formula (a-1-3), the ratio of EO' to PO' is preferably from 0.1 to 0.5, more preferably from 0.1 to 0.3, in terms of q/(p+r). When q/(p+r) is at least the lower limit value, excessive foaming is not caused, and foaming is easily made appropriate. When the amount is preferably at most the upper limit, it is easy to obtain an appropriate viscosity and it is easy to suppress gelation.

The component (a-1-2) and the component (a-1-3) can be produced by a conventionally known method. The component (a-1-2) can be produced, for example, by adding ethylene oxide to an alcohol having R ^3a derived from natural fats and oils. The component (a-1-3) can be produced, for example, by subjecting an alcohol having R ^3b derived from natural fats and oils to ethylene oxide and propylene oxide in an orderly addition reaction or a mixture thereof. After ethylene oxide and propylene oxide are formed (random addition), ethylene oxide is added again.

When the component (a-1-2) or the component (a-1-3) is used, the liquid detergent can easily obtain an appropriate viscosity and the gelation can be easily suppressed. In addition, the foaming property is improved and the biodegradability is also improved.

Preferred examples of the component (a-1-2) and the component (a-1-3) include Diadol (trade name, alcohol (C13) having a carbon number of 13) and Shell (manufactured by Mitsubishi Chemical Corporation). Neodol (trade name, a mixture of carbon 12 (C12) and C13) manufactured by Shell), Safol23 manufactured by Sasol (trade name, a mixture of C12 and C13), a nonionic surfactant obtained by adding 12 moles or 15 moles of ethylene oxide to an alcohol; CO-1214 manufactured by Procter & Gamble (trade name) or a nonionic surfactant obtained by adding a natural alcohol such as CO-1270 (trade name) to 12 moles or 15 moles of ethylene oxide; A nonionic surfactant obtained by adding a C13 alcohol obtained by an oxo method to an oxo method to form 7 moles of ethylene oxide (for example, trade name: Lutensol TO7, BASF) Manufactured; a nonionic surfactant obtained by adding 9 moles of ethylene oxide to a C10 alcohol obtained by supplying pentanol to a Guerbet reaction (for example, trade name: Lutensol XP90) , manufactured by BASF Corporation; a nonionic surfactant obtained by adding 7 moles of ethylene oxide to a C10 alcohol obtained by supplying pentanol to a Guerbet reaction (for example, trade name: Lutensol XL70, Manufactured by BASF Corporation; added to a 6 molar equivalent ring of C10 alcohol obtained by supplying pentanol to the Guerbet reaction A nonionic surfactant obtained by ethane (for example, trade name: Lutensol XA60, manufactured by BASF Corporation); 9 mole equivalent or 15 mole equivalent of ethylene oxide added to a secondary alcohol having 12 to 14 carbon atoms The obtained nonionic surfactant (for example, trade name: Softanol 90, Softanol 150, manufactured by Nippon Shokubai Co., Ltd.); sequential addition of natural alcohol (mixture of carbon number 12 alcohol and carbon number 14 alcohol, etc.) A nonionic surfactant obtained by adding 8 molar equivalents of ethylene oxide to 2 molar equivalents of propylene oxide and then adding 8 moles of ethylene oxide.

. About (a-1-4) ingredients

The component (a-1-4) is a polyoxyalkylene alkyl group represented by the following formula (a-1-4) Amine type nonionic surfactant.

[wherein, R ⁰ is an alkyl group having 10 to 20 carbon atoms or an alkenyl group having 10 to 20 carbon atoms; and A ¹ O and A ² O each independently represent an oxygen alkyl group having 2 to 3 carbon atoms; i represents The average number of repetitions of A ¹ O; j represents the average number of repetitions of A ² O; i>0, j>0, and i+j is a number of 10 to 50]

In the formula (a-1-4), R ^{0 has} a carbon number of 10 to 20, and from the viewpoint of detergency, an alkyl group having 10 to 18 carbon atoms or an alkyl group having 10 to 18 carbon atoms is preferable. The base may be linear or branched.

When the carbon number of R ⁰ is 10 or more, good washing performance can be obtained, and if it is 20 or less, good solubility can be obtained.

In the formula (a-1-4), (A ¹ O) _i and (A ² O) _j represent a repeating structure of an oxygen-extended alkyl group having 2 to 3 carbon atoms, and each of them may be an oxygen-extended ethyl group (EO). The repeating structure of ') may be a repeating structure of only oxygen-extended propyl (PO'), or a structure in which EO' and PO' are mixed and arranged. In the case where the two are mixed and arranged, EO' and PO' may be added in a random manner or may be added in a block form. Among them, (A ¹ O) _i and (A ² O) _{j are} preferably repeating structures of only EO', respectively, in terms of high detergency for sebum stains.

In the formula (a-1-4), i and j are 40>i>0, 40>j>0, and i+j is a number of 10~50. The i+j is preferably 10 to 40, more preferably 10 to 30. When i+j is at least the lower limit of the range, the washing performance is further improved, and when i+j is equal to or less than the upper limit of the range, the storage stability of the liquid detergent is further improved.

Preferable examples of the component (a-1-4) include polyoxyalkylene which is obtained by adding 20 (i.e., i + j = 20) molar equivalent of ethylene oxide to an alkylamine having 16 carbon atoms. Alkylamine type nonionic surfactant and the like.

The component (A-1) may be used alone or in combination of two or more.

Among the components (A-1), the above (1), (3), and (9) are preferable, and the above (1) and (3) are more preferable, wherein the detergency and the liquid wash are used. Further, in terms of better low-temperature stability of the detergent, it is further preferably a component (a-1-1), a component (a-1-2), or a component (a-1-3), and particularly preferably (a- 1-1) Ingredients. Among the components (a-1-1), a fatty acid ester type nonionic surfactant in the case of t=0 in the above formula (a-1-1) is more preferable.

The proportion of the component (A-1) in the total amount of the component (A) is not particularly limited, and is preferably 10% by mass to 96% by mass, and more preferably 30% by mass based on the total mass of the component (A). 90% by mass, further preferably 50% by mass to 90% by mass, particularly preferably 70% to 90%. When the ratio of the component (A-1) is within the above preferred range, the detergency of the stain adhering to the object to be washed is further improved.

((A-2) component: anionic surfactant)

Examples of the component (A-2) include the anionic surfactants (11) to (22) shown below.

(11) A linear or branched alkylbenzenesulfonate (LAS) having an alkyl group having 8 to 18 carbon atoms (A(alkylbenzene sulfonate) or ABS (alkylbenzene sulfonate)).

(12) an alkane sulfonate having 10 to 20 carbon atoms.

(13) α-olefin sulfonate (AOS) having a carbon number of 10 to 20.

(14) an alkyl sulfate having 10 to 20 carbon atoms or an alkyl sulfate/alkenyl sulfate (AS) having 10 to 20 carbon atoms.

(15) Adding an average of 2 to 4 carbon oxides or averaging ethylene oxide (EO) and propylene oxide (PO) (Morby EO/PO = 0.1/9.9 to 9.9/0.1) a linear or branched alkyl (or alkenyl) alkyl group having 10 to 20 carbon atoms (ie, an average number of repeats of 0.5 to 10) Aether (alkyl ether sulfate, AEPS).

(16) Adding an average of 2 to 4 carbon oxides or averaging ethylene oxide (EO) and propylene oxide (PO) (Morby EO/PO = 0.1/9.9 to 9.9/0.1) 3 to 30 moles (ie, an average repeat number of 3 to 30) having a linear or branched alkyl (or alkenyl) alkyl group (or alkenyl group) having 10 to 20 carbon atoms Phenyl ether sulfate.

(17) Adding an average of 2 to 4 carbon oxides or averaging ethylene oxide (EO) and propylene oxide (PO) (Morby EO/PO = 0.1/9.9 to 9.9/0.1) a linear or branched alkyl (or alkenyl) alkyl group having 10 to 20 carbon atoms (ie, an average number of repeats of 0.5 to 10) Base) ether carboxylate.

(18) Alkyl polyether ether sulfuric acid such as alkyl glyceryl ether sulfonate having a carbon number of 10 to 20 salt.

(19) Long-chain monoalkyl, dialkyl or sesquialkyl phosphates.

(20) a polyoxyethylene monoalkyl group, a polyoxyethylene dialkyl group or a polyoxyethylene sesquialkyl phosphate salt.

(21) Alpha-sulfo fatty acid methyl ester salt (MES) having a carbon number of 14 to 18.

(22) A fatty acid salt (soap) having a carbon number of 10 to 22.

As the component (A-2), an alkali metal salt such as sodium or potassium; an alkaline earth metal salt such as magnesium; an alkanolamine salt such as monoethanolamine or diethanolamine; an ammonium salt or the like can be used.

The component (A-2) may be used alone or in combination of two or more.

Among the components (A-2), the above (11), (15), (21), and (22) are preferable, and the above (11) is particularly preferable.

The proportion of the component (A) in the total amount of the component (A) is not particularly limited, and is preferably from 1% by mass to 30% by mass, and more preferably 2% by mass based on the total mass of the component (A). 20% by mass, and more preferably 3% by mass to 15% by mass. When the ratio of the component (A-2) is within the above preferred range, the detergency of the stain adhering to the laundry is further improved.

((A-3) component: cationic surfactant)

The (A-3) component may, for example, be a cationic surfactant of (31) to (33) shown below.

(31) A di-long chain alkyl di-short alkyl type quaternary ammonium salt.

(32) A single long chain alkyl tris short chain alkyl type quaternary ammonium salt.

(33) A three-long chain alkyl single short chain alkyl type quaternary ammonium salt.

The "long-chain alkyl group" in the above (31) to (33) represents an alkyl group having 10 to 26 carbon atoms. The alkyl group of the long-chain alkyl group preferably has a carbon number of 10 to 18. Specific examples thereof include C12 alkyltrimethylammonium chloride and dimercaptodimethylammonium chloride as preferred cationic surfactants.

The "short-chain alkyl group" means an alkyl group having 1 to 4 carbon atoms which may have a substituent. The alkyl group of the short-chain alkyl group preferably has 1 or 2 carbon atoms. Examples of the substituent which the alkyl group of the short-chain alkyl group may have include a phenyl group, a benzyl group, a hydroxyl group, a hydroxyalkyl group, a polyoxyalkylene group, and the like. The hydroxyalkyl group preferably has 2 to 4 carbon atoms, more preferably 2 or 3. The carbon number of the oxygen alkyl group in the polyoxyalkylene group is preferably from 2 to 4, more preferably 2 or 3.

The component (A-3) may be used alone or in combination of two or more.

Among the components (A-3), it is particularly preferable to use the above (32).

The proportion of the component (A-3) in the total amount of the component (A) is not particularly limited, and is preferably 0.01% by mass to 30% by mass, and more preferably 0.1% by mass based on the total mass of the component (A). 20% by mass, particularly preferably 0.5% by mass to 10% by mass. When the ratio of the component (A-3) is within the above-mentioned preferred range, when the interior is dried, it is possible to further suppress an unpleasant odor (dryness in the house) from the laundry.

Examples of the amphoteric surfactant include an imidazoline-based amphoteric surfactant, a guanamine-beta-based amphoteric surfactant, an alkyl dimethylamine oxide, and a alkylguanamine dimethylamine oxide. Specific examples thereof include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, guanamine propyl betaine laurate, and C12 amine oxide in alkyl dimethyl amine oxide. And C14 amine oxide, etc. as a preferred amphoteric interface Active agent.

The amphoteric surfactant may be used alone or in combination of two or more.

The proportion of the amphoteric surfactant in the total amount of the component (A) is not particularly limited, and is preferably from 0% by mass to 60% by mass, more preferably from 0% by mass to 30% by mass based on the total mass of the component (A). %. When the ratio of the amphoteric surfactant is within the above preferred range, the detergency of the stain adhering to the object to be washed is further improved.

In the liquid detergent, the component (A) may be used alone or in combination of two or more.

The component (A) is preferably a combination of the component (A-1) and the component (A-2).

When the component (A-1) and the component (A-2) coexist, the cleaning power of various stains such as sebum stains, protein stains, and sugar stains adhering to the laundry is further improved, and thus it is easy to remarkably express the present invention. The effect of the invention.

The mass ratio (also referred to as "mass ratio (A-1) / (A-2)") expressed by the component (A-1)/(A-2) is preferably 0.1 to 20, more preferably 0.5 to 0.5. 10.

When the mass ratio (A-1)/(A-2) is more than the preferred lower limit value, the detergency of the sebum stain is further improved, and on the other hand, if the mass ratio (A-1)/(A-2) When it is below the upper limit of the preferable value, the detergency of the protein stain is further improved.

In the present invention, the "mass ratio represented by the component (A-1) / (A-2)" means the content of the component (A-1) in the liquid detergent relative to (A-2). The mass ratio of the content of the ingredients.

Further, the mass ratio represented by the component (A-1) / (A-2) may be 5 to 20.

Further, in the liquid detergent of the present invention, the component (A) preferably contains (A-3) ingredients. When the component (A-3) is contained and dried in the house, the effect of suppressing the occurrence of the dryness in the house is further improved.

In addition, in order to improve the detergency of various stains and to easily suppress the effect of drying the inside of the house, the component (A) is preferably used in combination with the component (A-1), the component (A-2), and A-3) ingredients.

Mass ratio expressed by [(A-1) component + (A-2) component] / (A-3) component (also referred to as "mass ratio [(A-1) + (A-2)] / (A -3)") is preferably from 1 to 50, more preferably from 5 to 30, and still more preferably from 18 to 46.

When the mass ratio [(A-1) + (A-2)] / (A-3) is at least the lower limit value, the storage stability (transparency uniformity and fluidity) is further improved. When the mass ratio [(A-1) + (A-2)] / (A-3) is preferably at least the upper limit value, the effect of suppressing the occurrence of the indoor drying odor is further improved.

In the present invention, the "mass ratio represented by the component [(A-1) component + (A-2) component] / (A-3)" means the component (A-1) in the liquid detergent. The mass ratio of the total content of the component (A-2) to the content of the component (A-3).

The content of the component (A) in the liquid detergent is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more based on the total mass of the liquid detergent. When the content of the component (A) is at least the lower limit value, it is easy to obtain a cleaning effect on the stain adhering to the laundry, and the higher the content of the component (A), the more easily the invention can be obtained. Effect.

On the other hand, the upper limit of the content of the component (A) is preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less. If component (A) When the content is preferably at most the upper limit value, it becomes easier to ensure transparency uniformity and fluidity of the appearance.

In other words, the content of the component (A) is preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% by mass or less, and still more preferably 40% by mass or less based on the total mass of the liquid detergent. The above is 60% by mass or less.

Further, the content of the component (A) may be 27% by mass to 48% by mass based on the total mass of the liquid detergent.

<(B) component: saccharide-degrading enzyme preparation>

The component (B) is an enzyme preparation containing a saccharide-decomposing enzyme.

In the liquid detergent of the present invention, the component (B) is contained, and the effect of suppressing the occurrence of the indoor dryness is mainly exhibited.

Examples of the saccharide-degrading enzyme include cellulase, amylase, mannanase, pectinase, xylanase, glucoamylase, and glucosidase ( Glucosidase, glucanase, hextranase, chitinase, sialidase, mannosidase, saccharase, Fucosidase, alginate lyase, pectinlyase, and the like. Among these, it is more preferable to obtain an effect of suppressing the drying odor in the house, and it is preferably a cellulase, an amylase, or a mannanase, and particularly preferably an amylase or a mannanase.

Specific commercially available products for the component (B), and enzyme preparations containing cellulase include Endolase available from Novozymes. 5000 L, Celluzyme 0.4 L, Carezyme Premium 4500 L (above, trade name), and the like. Examples of the enzyme preparation containing amylase include Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, and Stainzyme Plus 12L (trade names above) available from Novozymes; and products available from Genencor. Maxamyl, trade name Pullulanase Amano available from Amano Enzyme Co., Ltd., and DB-250 available from Biosei Chemical Co., Ltd. Examples of the enzyme preparation containing the mannanase include Mannaway 4L available from Novozymes, Inc., and the like.

The component (B) may be used alone or in combination of two or more.

The content of the component (B) in the liquid detergent is preferably 0.01% by mass based on the total mass of the liquid detergent in terms of the cleaning effect and the effect of suppressing the occurrence of the indoor drying odor. The above is more preferably 0.03 mass% or more, further preferably 0.05 mass% or more.

On the other hand, the upper limit of the content of the component (B) is washed with respect to the liquid in terms of ensuring storage stability (inhibition of enzyme precipitation, etc.) and saturation of the compounding effect of the component (B). The total mass of the detergent is preferably 2% by mass or less, more preferably 1.5% by mass or less, still more preferably 1% by mass or less. In other words, the content of the component (B) is preferably 0.01% by mass or more and 2% by mass or less, more preferably 0.03% by mass or more and 1.5% by mass or less, and further preferably 0.05% by mass or less based on the total mass of the liquid detergent. The above is 1% by mass or less.

Further, the content of the component (B) is preferably from 0.1% by mass to 0.5% by mass based on the total mass of the liquid detergent.

<(C) component: hydroxycarboxylic acid or its salt>

The component (C) is at least one compound selected from the group consisting of a hydroxycarboxylic acid or a salt thereof, that is, a hydroxycarboxylic acid, and a hydroxycarboxylic acid salt.

In the present invention, the "hydroxycarboxylic acid" means a compound having a carboxyl group (-COOH) and an alcoholic hydroxyl group (-OH) in one molecule.

In the liquid detergent of the present invention, by containing the component (C), the appearance of the liquid detergent can be maintained to be transparent and uniform, and the fluidity of the liquid detergent can be ensured, and the storage stability is excellent.

Examples of the hydroxycarboxylic acid salt include an alkali metal salt such as a sodium salt or a potassium salt of the hydroxycarboxylic acid; an alkaline earth metal salt such as a calcium salt or a magnesium salt; and an alkanolamine salt such as an ammonium salt or an ethanolamine salt.

A preferred example of the component (C) is a compound represented by the following formula (c-1).

In the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group which may have a substituent, a nitro group (-NO ₂ ), an ester group, and an ether group. An amine group (-NH ₂ ) or an amine derivative group which may have a substituent; R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; v is an integer of 0 to 4; M ⁺ is Counter ion

In the formula (c-1), the alkyl group in R ⁴ and R ⁵ has a carbon number of 1 to 10, preferably a carbon number of 1 to 5, more preferably a methyl group, an ethyl group or a propyl group. , isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl; further preferably methyl, ethyl, propyl, and isopropyl; It is a methyl group and an ethyl group; the most preferred is a methyl group. The aryl group in R ⁴ and R ⁵ preferably has a carbon number of 6 to 15, more preferably 6 to 10 carbon atoms, and more preferably a phenyl group and a naphthyl group.

The ester group in R ⁴ and R ⁵ may preferably be, for example, -COOR ⁸ .

The ether group in R ⁴ and R ⁵ may preferably be, for example, -R ⁴ -OR ⁵ .

In the case of R ⁴ and R ⁵ , the "alkyl group having a substituent, the aryl group having a substituent, and the amine group having a substituent" mean a hydrogen atom constituting an alkyl group, a hydrogen atom constituting an aryl group, and an amine. An alkyl group, an aryl group or an amine group in which at least one hydrogen atom of each of the hydrogen atoms of the group is substituted with a substituent.

Examples of the substituent which the alkyl group having 1 to 10 carbon atoms may include an aryl group, a nitro group, a nitro derivative group, a hydroxyl group (-OH), a hydroxy derivative group, an ester group, an ether group, an amine group, and an amine group. A derivative group, a guanamine group, a decylamine derivative group, a halogen atom or the like.

Examples of the substituent which the aryl group may have include an alkyl group, a nitro group, a nitro derivative group, a hydroxyl group, a hydroxy derivative group, an ester group, an ether group, an amine group, an amine derivative group, a decylamino group, a decylamine group. Derivative group, halogen atom, and the like.

Examples of the substituent which the amino group may have include an alkyl group, an aryl group, a nitro group, a nitro derivative group, a hydroxyl group, a hydroxy derivative group, an ester group, an ether group, an amine derivative group, and an anthracene group. An amine group, a guanamine derivative group, a halogen atom or the like.

Examples of the alkyl group, the aryl group and the ester group in the substituent include the same groups as the alkyl group, the aryl group and the ester group in the above R ⁴ and R ⁵ .

The guanamine group in the substituent may preferably be, for example, -C(=O)NH-R ⁹ .

The halogen atom in the substituent may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom.

In the above, each of R ⁴ and R ^{5 is} preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, and an aryl group which may have a substituent.

Further, each of R ⁴ and R ⁵ is preferably a hydrogen atom, and one of R ⁴ and R ⁵ is a hydrogen atom and the other is a C 1 to 10 alkyl group which may have a substituent, R ^{One of 4} and R ⁵ is a hydrogen atom and the other is an aryl group which may have a substituent.

In the formula (c-1), the alkyl groups in R ⁶ and R ⁷ are each independently a carbon number of 1 to 5, and more preferably a methyl group, an ethyl group, a propyl group or an isopropyl group. It is a methyl group or an ethyl group, and more preferably a methyl group.

Further, it is preferred that both of R ⁶ and R ⁷ are each a hydrogen atom, and one of R ⁶ and R ⁷ is a hydrogen atom and the other is a methyl group.

v is an integer of 0 to 4, preferably 0, 1, or 2, more preferably 0 or 1, and particularly preferably 0.

M ⁺ is a relative ion as long as it is a relative ion which can form a water-soluble salt together with -COO ^- . Examples of the counter ion include an alkali metal ion, an alkaline earth metal ion (in this case, a counter ion is a divalent ion), a protonized amine, an ammonium, a proton, and the like. Further, when M ⁺ is a proton, the compound represented by the formula (c-1) represents a hydroxycarboxylic acid.

Examples of the alkali metal which can be the relative ion include sodium, potassium, and the like.

Examples of the alkaline earth metal which can be the relative ion include calcium, magnesium, and the like.

The amine which can be the relative ion can be any of a primary amine to a tertiary amine, and preferably has a total carbon number of 1 to 6. The amine may have a hydroxyl group, and such an amine may be an alkanolamine, and the alkanol group preferably has a carbon number of 1 to 3. Specific examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine.

The amine that can become the opposite ion is protonated to become a relative ion.

In terms of easy availability and further improvement in solubility, M ^{+ is} preferably an alkali metal ion, preferably a sodium ion or a potassium ion, and particularly preferably a sodium ion.

Preferred examples of the component (C) include, for example, glycolic acid, lactic acid (α-hydroxypropionic acid, and β-hydroxypropionic acid), hydroxybutyric acid (2-hydroxybutyric acid, 3-hydroxyl group). Butyric acid, and γ-hydroxybutyric acid), hydroxyisobutyric acid (2-hydroxyisobutyric acid, and 3-hydroxyisobutyric acid), mandelic acid, optical isomers, or Some salt and so on.

Among the above, in particular, the storage component (C) is preferably an α-hydroxycarboxylic acid or a salt thereof, more preferably an α-hydroxy-monocarboxylic acid or a salt thereof, and particularly preferably The compound represented by the formula (c-1-1).

[wherein R ⁴ ' and R ⁵ ' are each independently a hydrogen atom, a C 1-10 alkyl group which may have a substituent, an aryl group which may have a substituent, a nitro group (-NO ₂ ), an ether group, may have a substituted amino group (-NH ₂₎ or an amine derivative group; and M ⁺ (c-1) ⁺ M in the same formula]

In the formula (c-1-1), the alkyl group having 1 to 10 carbon atoms and the aryl group in R ⁴ ' and R ⁵ ' may be the same as the carbon number in the above R ⁴ and R ⁵ . The alkyl group of 10 and the same group of the aryl group.

R ⁴ ' and R ⁵ ' are preferably both a hydrogen atom, one of R ⁴ ' and R ⁵ ' is a hydrogen atom and the other is a C 1-10 alkyl group which may have a substituent, or One of R ⁴ ' and R ⁵ ' is a hydrogen atom and the other is an aryl group which may have a substituent; more preferably, one of R ⁴ ' and R ⁵ ' is a hydrogen atom and the other may have a substitution. The alkyl group having 1 to 10 carbon atoms or one of R ⁴ ' and R ⁵ ' is a hydrogen atom and the other is an aryl group which may have a substituent; and particularly preferably one of R ⁴ ' and R ⁵ ' The one is a hydrogen atom and the other is an alkyl group having 1 to 10 carbon atoms which may have a substituent.

Preferable examples of the compound represented by the formula (c-1-1) include glycolic acid, α-hydroxypropionic acid, 2-hydroxybutyric acid, 2-hydroxyisobutyric acid, phenylglycolic acid, and the like. An optical isomer, or a salt thereof, etc.; preferably α-hydroxypropionic acid, phenylglycolic acid, or a salt thereof; more preferably α-hydroxypropionic acid, phenylglycolic acid, or a salt thereof; More preferably, it is α-hydroxypropionic acid or a salt thereof.

The component (C) may be used alone or in combination of two or more.

The content of the component (C) in the liquid detergent is relative to the total amount of the liquid detergent The mass is preferably from 0.1% by mass to 5% by mass, more preferably from 0.5% by mass to 4% by mass, still more preferably from 1% by mass to 3% by mass, even more preferably from 1% by mass to 2% by mass.

When the content of the component (C) is within the above preferred range, the stability of the component (B) in the liquid detergent is improved. Further, it becomes easier to obtain an effect of suppressing the formation of a film on the liquid surface.

When the content of the component (C) is at least the lower limit value, the transparency uniformity and fluidity of the appearance of the liquid detergent are further improved. On the other hand, when the content of the component (C) is preferably at most the upper limit value, precipitation or the like becomes less likely to occur when the liquid detergent is prepared.

In the present invention, the "mass ratio represented by the component (B)/(C)" means the mass ratio of the content of the component (B) in the liquid detergent to the content of the component (C).

The mass ratio (also referred to as "mass ratio (B) / (C)") expressed by the component (B) / (C) is 1 or less, preferably 0.001 to 1, more preferably 0.01 to 0.75, and further preferably It is 0.1~0.25.

When the mass ratio (B)/(C) is at most the above upper limit value, transparency uniformity and fluidity of the appearance of the liquid detergent can be ensured, and storage stability is excellent. Further, it is easy to obtain an effect of suppressing the formation of a film on the liquid surface. When the mass ratio (B)/(C) exceeds the above upper limit value, precipitation or the like occurs when the liquid detergent is prepared.

On the other hand, when it is more than a preferable lower limit, the detergency is improved, and the effect of suppressing the occurrence of the indoor drying odor is also improved.

[(D) ingredient]

The component (D) in the present invention is selected from the group consisting of isopropyl methyl phenol (IPMP) and 3-iodo-2-propynylbutylcarbamate (IPBC). At least one of a group consisting of thiabendazole (TBZ), polylysine, polyhexamethylene biguanide, and acid salts thereof. By containing the component (D), the antibacterial property is mainly imparted.

<<Polyacyl acid or its acid salt>>

As the polyaminic acid, any of α-poly-L-lysine, ε-poly-L-lysine, α-poly-D-lysine, and ε-poly-D-lysine can be used. Among these, from the viewpoint of safety, α-poly-L-isoamine acid and ε-poly-L-lysine are preferred, and ε-poly-L-lysine is more preferred. Among them, in terms of safety, ε-poly-L-lysine represented by the following formula (d1) is particularly preferable.

[where r is an integer from 5 to 100]

In the formula (d1), r is an integer of 5 to 100, preferably an integer of 10 to 50, and more preferably an integer of 13 to 27.

ε-poly-L-lysine is a microorganism that genus Streptomyces It is obtained as a polypeptide formed by condensation of an amino acid which is essential for the human body. When the poly-amino acid is hydrolyzed by an enzyme or the like in the body, it becomes an L-deaminic acid which is an original constituent component, and thus the safety is very high.

As the poly-aminic acid, any of polyisoguanylic acid in the form of a free polyaminic acid and an acid salt of an inorganic acid or an organic acid can be used.

In the case of the form of the acid salt, a hydrochloride, a gluconate or an acetate is preferred, and a hydrochloride is more preferred.

Further, in order to facilitate handling, a polylysine which is processed by an excipient or an extender may also be used.

<<Polyhexamethylene biguanide or its acid salt>>

The polyhexamethylene biguanide or the acid salt thereof is, for example, a compound represented by the following formula (d2) (hereinafter referred to as "(d2) component").

[wherein m is an integer of 2 to 14; HR ⁴ represents an organic acid or a mineral acid; n represents the number of HR ⁴ and is an integer of 0 to 5 m]

In the formula (d2), m is an integer of 2 to 14, preferably an integer of 10 to 14, more preferably an integer of 11 to 13, and particularly preferably 12.

In the formula (d2), HR ⁴ represents an organic acid or an inorganic acid, preferably hydrochloric acid, gluconic acid, acetic acid, more preferably hydrochloric acid.

n is an integer from 0 to 5 m. Further, the term "5m" means 5 x m.

In the case where n is 0, the component (d2) is polyhexamethylene biguanide. In the case where n is not 0, the component (d2) is a partial acid salt or a total acid salt of polyhexamethylene biguanide. n is preferably an integer of 1 to 5 m, more preferably an integer of 2 to 3 m, further preferably an integer of m to 2 m, and particularly preferably m.

Further, 3 m and 2 m mean 3 × m and 2 × m, respectively.

The component (D) may be used alone or in combination of two or more.

In terms of easier to ensure the appearance stability, the component (D) is preferably IPMP, IPBC, and a combination of IPMP and IPBC, more preferably IPMP.

The content of the component (D) in the liquid detergent is preferably 0.01% by mass to 2% by mass, and more preferably 0.1% by mass to 1% by mass based on the total mass of the liquid detergent. When the component (D) is at least the lower limit value, the effect of suppressing the indoor drying odor is more excellent, and when it is at most the upper limit, the storage stability of the liquid detergent is further improved.

In the present invention, the "mass ratio represented by the component (B)/(D)" means the mass ratio of the content of the component (B) in the liquid detergent to the content of the component (D).

The mass ratio (also referred to as "mass ratio (B) / (D)") expressed by the component (B) / (D) is preferably 0.2 to 100, more preferably 2.5 to 20.

When the mass ratio (B)/(D) is at least the above lower limit, transparency uniformity and fluidity of the appearance of the liquid detergent can be ensured, and storage stability is excellent. Further, it is easy to obtain an effect of suppressing the formation of a film on the liquid surface. If the mass ratio (B) / (D) is the above When the value is less than the limit, the detergency is improved, and the effect of suppressing the occurrence of the dryness in the room is also improved.

<solvent>

The liquid detergent of the present invention preferably contains water as a solvent, and more preferably ion-exchanged water, from the viewpoints of ease of preparation, solubility in water, and the like at the time of use.

The content of the water in the liquid detergent is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less based on the total mass of the liquid detergent. The smaller the content of water, the easier it is to obtain the effects of the present invention remarkably. In addition, it is easy to prepare a concentrated lotion.

On the other hand, the lower limit of the water content is preferably 30% by mass or more. When the content of water is preferably at least the lower limit value, the storage stability of the liquid detergent over time is further improved.

In other words, when water is used as the solvent, the content of water in the liquid detergent is preferably 30% by mass or more and 70% by mass or less, more preferably 30% by mass or more and 60% by mass or less, and further preferably 30% by mass or more and 50% by mass or less.

Further, the content of water in the liquid detergent may be 40% by mass to 70% by mass.

<Other ingredients>

In the liquid detergent of the present invention, components (other components) other than the components (A) to (C) may be contained as needed within the range in which the effects of the present invention are not impaired.

The other components are not particularly limited, and examples of the components generally used in the liquid detergents such as the adjustable coating materials include enzyme preparations other than the component (B) (hereinafter sometimes referred to as any enzyme preparation), and the enzyme is stable. Agent, preservative, alkali agent, antioxidant, water mixed organic solvent, flavoring agent, viscosity reducing agent or cosolvent (solubilizing agent), coloring agent, detergent builder, defoamer, pH adjuster, silicone, fluorescent whitening agent, anti-leveling agent, recontamination inhibitor, pearlescent agent ( A pearl agent), a soil release agent, a foam control agent, a chelate agent, an opacifying agent, an extract, and the like.

The enzyme preparation (any enzyme preparation) other than the component (B) can be a liquid preparation obtained by dispersing an enzyme component in a liquid, a powder preparation obtained by fixing an enzyme to a stabilizer of a powder, or the like. The enzyme component may be an enzyme component which is previously applicable to a liquid detergent for clothing. Examples of the enzyme preparation include a protease preparation, a lipase preparation, and the like.

Protease preparations include Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L TypeEX, Everlase Ultra 16L, Esperase 8L, Alcalase 2.5L, Alcalase Ultra 2.5L, Liquanase 2.5L, Liquanase Ultra 2.5 available from Novozymes. L, Liquanase Ultra 2.5XL, Coronase 48L (above trade name); Purafect L, Purafect OX, Properase L (above trade name) available from Genencor.

Examples of the lipase preparation include Lipex 100L and Lipolase 100L (above, trade names) available from Novozymes.

Any of the enzyme preparations may be used alone or in combination of two or more.

By using at least one of any of the enzyme preparations in combination with the component (B), the effect of suppressing the generation of the indoor drying odor is further improved.

The quality of "(B) component / any enzyme preparation" is preferably 0.2 to 1, more Good is 0.5~1. When the mass ratio is within the above preferred range, the effect of suppressing the occurrence of the indoor drying odor is further improved.

In the present invention, the "mass ratio expressed by (B) component / any enzyme preparation" means the mass of the component (B) in the liquid detergent relative to the content of the enzyme preparation other than the component (B). proportion.

Among any of the enzyme preparations, a protease preparation is preferred, and more preferably Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L, Everlase Ultra 16L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, and Coronase 48L; further preferably Everlase 16L, Savinase 16L, and Coronase 48L.

In the liquid detergent, the content of any enzyme preparation is preferably 0.01 to 2% by mass, more preferably 0.01 to 1% by mass, still more preferably 0.03 to 0.8% by mass, based on the total mass of the liquid detergent. When the content of any of the enzyme preparations is preferably at least the lower limit value, the enzyme preparation effect is easily exhibited. When the content is preferably at most the upper limit value, the enzyme preparation is less likely to be precipitated even in a composition having a small water content.

Examples of the enzyme stabilizer include boric acid, borax, formic acid or a salt thereof; and calcium salts such as calcium chloride and calcium sulfate. The content of the enzyme stabilizer is preferably 0.001% by mass or more and 2% by mass or less based on the total mass of the liquid detergent.

Examples of the preservative include Kathon CG manufactured by Rohm and Haas Co., Ltd., and the like. The content of the preservative is preferably from 0.001% by mass to 1% by mass based on the total mass of the liquid detergent.

In addition, in order to improve storage stability, it may also contain an effect as a preservative. Benzoic acid or its salt. The content of the benzoic acid or a salt thereof is preferably from 0.1% by mass to 5% by mass, and more preferably from 0.15% by mass to 2% by mass based on the total mass of the liquid detergent.

The alkali agent may, for example, be monoethanolamine, diethanolamine or triethanolamine. The content of the alkali agent is preferably from 0.5% by mass to 5% by mass based on the total mass of the liquid detergent.

The antioxidant is not particularly limited, and is preferably a phenolic antioxidant in terms of maintaining the detergency and liquid stability more satisfactorily. Among them, monophenols such as dibutylhydroxytoluene and butylhydroxyanisole are more preferred. An antioxidant; a bisphenol-based antioxidant such as 2,2'-methylenebis(4-methyl-6-tert-butylphenol); and a polymeric phenolic antioxidant such as dl-α-tocopherol; Further, a monophenolic antioxidant and a polymeric phenolic antioxidant are preferable. The content of the antioxidant is preferably from 0.01% by mass to 2% by mass based on the total mass of the liquid detergent.

The water-miscible organic solvent means that 50 g or more of an organic solvent is dissolved in 1 L of ion-exchanged water at 25 °C. The water-miscible organic solvent may be a solvent which becomes a homogeneous solution when mixed with water, and examples thereof include alcohols such as ethanol, 1-propanol, 2-propanol, and 1-butanol; propylene glycol and butanediol; a glycol such as hexanediol; diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having an average molecular weight of about 200, polyethylene glycol having an average molecular weight of about 400, and an average molecular weight of about Polyethylene glycol such as polyethylene glycol or dipropylene glycol of 1,000; alkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol dimethyl ether; and the like. The content of the water-miscible organic solvent is preferably from 0.1% by mass to 15% by mass based on the total mass of the liquid detergent.

Examples of the viscosity reducing agent or the co-solvent include toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, toluenesulfonate, and xylene. Sulfonate, cumene sulfonate, substituted or unsubstituted naphthalene sulfonate. Examples of the salt of the aromatic sulfonic acid include a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an ammonium salt, and an alkanolamine salt.

The viscosity reducing agent or the co-solvent may be used singly or in combination of two or more. The content of the viscosity reducing agent or the co-solvent is preferably from 0.01% by mass to 15% by mass based on the total mass of the liquid detergent. When the content of the viscosity reducing agent or the co-solvent is within this preferred range, the effect of suppressing the formation of a film formed by gelation of the liquid detergent on the liquid surface of the liquid detergent is further improved.

As the detergency adjuvant, any of an inorganic adjuvant or an organic adjuvant can be used. The content of the detergency aid is preferably from 0.01% by mass to 20% by mass based on the total mass of the liquid detergent.

Further, the liquid detergent of the present invention may contain a short-chain fatty acid which is preferably from 0% by mass to 5% by mass based on the total mass of the liquid detergent.

The liquid detergent of the present invention preferably has a pH of 4 to 9 at 25 ° C, more preferably a pH of 6 to 9. When the pH is in this range, the storage stability of the liquid detergent can be maintained more satisfactorily.

The pH of the liquid detergent can be adjusted by adding a pH adjusting agent. Examples of the pH adjuster include hydrochloric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, and an alkanolamine. These pH adjusters may be used alone or in combination of two or more.

In the present invention, the pH of the liquid detergent is a value measured by adjusting the liquid detergent to 25 ° C and using a pH meter (product name: HM-30G, manufactured by Toray Corporation (TOADKK)). . In addition, even the pH outside the range specified in this manual is corrected to the pH at 25 ° C for this specification. The pH of the specified range is included in the scope of the present invention.

The viscosity of the liquid detergent of the present invention at 25 ° C is preferably 10 mPa from the viewpoint of the discharge property of the container and the like. s~1000mPa. s or so, more preferably 80mPa. s~500mPa. s or so.

In the present invention, the viscosity of the liquid detergent means a value measured by adjusting the liquid detergent to 25 ° C and measured by a B type viscometer. Further, even if the value outside the range specified in the present specification is corrected to a value at 25 ° C, the value of the viscosity in the range specified in the present specification is included in the scope of the present invention.

The liquid detergent of the present invention is prepared by mixing a solvent (preferably water), a component (A), a component (B), a component (C), and optionally other components.

For example, after the solvent and the component (A) are mixed, the component (B) and the component (C) are added thereto, and then the pH adjuster is added to adjust the pH, and when the solvent remains, the solvent is added. The remainder is mixed to thereby obtain the target liquid detergent.

That is, one aspect of the method for adjusting the liquid detergent of the present invention includes: mixing a part or all of the solvent with the component (A); and further adding the component (B) and the component (C) to the mixed solution. mixing. Further, it may be further included by adding other components to the mixed solution and mixing, and in the case where the remaining portion of the solvent is present, the remaining portion of the solvent may be added to the mixed solution to be mixed.

The method of using the liquid detergent of the present invention may be the same as the method of using a usual liquid detergent. For example, a method of introducing the liquid detergent of the present invention into the water together with the laundry at the time of washing, and straightening the liquid detergent of the present invention A method of applying a stain applied to a laundry, a method of dissolving the liquid detergent of the present invention in water in advance, and immersing clothes. Further, it is also preferred to apply the liquid detergent of the present invention to a laundry and then suitably place it, followed by a normal washing using a usual washing liquid. At this time, the liquid detergent of the present invention is used in an amount of 10 g / 30 L.

As described above, in the liquid detergent of the present invention, a specific mass ratio (mass ratio expressed by (B) component / (C) component is 1 or less) in the liquid containing the component (A) is used in combination (B). The component and the component (C) have a high effect of suppressing the occurrence of the indoor drying odor, and an effect of good storage stability can be obtained.

In other words, by blending the component (B), it is possible to decompose and remove the saccharide formed by the structure of the biofilm which is adhered to the back surface of the laundry or the washing tub, and the number of bacteria adhering to the laundry after washing is reduced. Therefore, even when the interior is dried, it is possible to suppress an unpleasant odor (drying in the house) from the laundry.

In addition, when the component (B) and the component (C) are combined in a specific mass ratio, the component (C) is sufficiently adsorbed on the surface of the component (B), and the solubility of the component (B) in the liquid detergent is improved. Thereby, the storage stability (transparency uniformity, fluidity) becomes good.

Further, since the liquid detergent according to the present invention has an effect of decomposing and removing the biofilm, it is difficult to form a biofilm in the object to be washed or the washing tub by repeated washing.

Further, in the liquid detergent of the present invention, it is less likely to occur in the liquid surface forming film. Therefore, the liquid detergent of the present invention is useful in the preparation of a high concentration of a surfactant, a so-called concentrated lotion.

Another embodiment of the liquid detergent of the present invention may cite a liquid a detergent comprising: (A) component: a surfactant, (B) component: a saccharide-decomposing enzyme preparation, and (C) component: a group selected from the group consisting of hydroxycarboxylic acids and salts thereof At least one compound or solvent: preferably water, more preferably ion-exchanged water, and optionally other components; and the content of the component (A) is 20% by mass or more based on the total mass of the liquid detergent. 80% by mass or less, preferably 27% by mass to 48% by mass, and the content of the component (B) is 0.01% by mass or more and 2% by mass or less, preferably 0.1% by mass to 0.5% by mass, based on the content of the component (C). 0.1% by mass to 5% by mass, preferably 1% by mass to 2% by mass, and the solvent content is 30% by mass or more and 70% by mass or less, preferably 48% by mass to 70% by mass, and all the components are The total content is not more than 100% by mass; the mass ratio of the component (B)/(C) is 0.001 to 1, preferably 0.1 to 0.25.

Still another embodiment of the liquid detergent of the present invention may be a liquid detergent comprising: (A) a component selected from the group consisting of (A-1) nonionic surfactant, (A-2) At least one surfactant in the group consisting of an anionic surfactant, (A-3) cationic surfactant, and (B) component: selected from the group consisting of cellulase, amylase, and mannanase At least one saccharide-degrading enzyme preparation in the group, (C) component: a compound represented by the following formula (c-1), a solvent: preferably water, more preferably ion-exchanged water, and other components as necessary; The content of the component (A) is 20% by mass or more and 80% by mass or less, preferably 27% by mass to 48% by mass based on the total mass of the liquid detergent, and the content of the component (B) is 0.01% by mass. The content is preferably 2% by mass or less, preferably 0.1% by mass to 0.5% by mass, and the content of the component (C) is 0.1% by mass to 5% by mass, preferably 1% by mass to 2% by mass, and the solvent content is 30% by mass. % or more and 70% by mass or less, preferably 48% by mass to 70% by mass, and the total content of all the components is not more than 100% by mass; (B) component / (C) component The mass ratio is 0.001 to 1, preferably 0.1 to 0.25 (in the range of ○ evaluation of the example), and when the component (A-1) and the component (A-2) are contained, (A-1) The mass ratio represented by the component / (A-2) component is 0.1 to 20, preferably 5 to 20; and the component (A-1), (A-2), and (A-3) are contained. Next, the mass ratio represented by the [(A-1) component + (A-2) component] / (A-3) component is 1 to 50, preferably 18 to 46:

In the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group which may have a substituent, a nitro group (-NO ₂ ), an ester group, and an ether group. An amine group (-NH ₂ ) or an amine derivative group which may have a substituent; R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; v is an integer of 0 to 4; M ⁺ is Relative ion].

Still another embodiment of the liquid detergent of the present invention may be a liquid detergent comprising: (A) a component selected from the group consisting of (A-1) nonionic surfactant, (A-2) At least one surfactant in the group consisting of an anionic surfactant, (A-3) cationic surfactant, and (B) component: at least one selected from the group consisting of amylase and mannanase A saccharide-degrading enzyme preparation and a component (C): a compound represented by the following formula (c-1-1): a solvent: preferably water, more preferably ion-exchanged water, and optionally other components; The component A-1) is a polyoxyalkylene type nonionic surfactant represented by the following formula (a-1-1), and a polyoxygen extension represented by the following formula (a-1-2) The alkyl type nonionic surfactant, the polyoxyalkylene type nonionic surfactant represented by the following formula (a-1-3), and the following formula (a-1-4) At least one of the group consisting of polyoxyalkylene alkylamine type nonionic surfactants; the component (A-2) being selected from a linear or branched group having an alkyl group having 8 to 18 carbon atoms Chain alkyl benzene sulfonate, Adding any alkylene oxide having a carbon number of 2 to 4, or adding an average of 0.5 moles of ethylene oxide (EO) to propylene oxide (PO) (Morby EO/PO = 0.1/9.9 to 9.9/0.1) ~10 moles of alkyl (or alkenyl) ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms, and α-sulfon having a carbon number of 14 to 18 At least one of a group consisting of a base fatty acid methyl ester salt and a fatty acid salt having a carbon number of 10 to 22; the (A-3) component is a single long-chain alkyl tri-short chain alkyl type quaternary ammonium salt; The content of the component (A) is 20% by mass or more and 80% by mass or less, preferably 27% by mass to 48% by mass based on the total mass of the liquid detergent, and the content of the component (B) is 0.01% by mass. The content is preferably 2% by mass or less, preferably 0.1% by mass to 0.5% by mass, and the content of the component (C) is 0.1% by mass to 5% by mass, preferably 1% by mass to 2% by mass, and the solvent content is 30% by mass. % or more and 70% by mass or less, preferably 48% by mass to 70% by mass, and the total content of all the components is not more than 100% by mass; and the mass ratio represented by the component (B)/(C) is 0.001. ~1, preferably 0.1 to 0.25 (the range of the evaluation of ○ in the example), including the component (A-1) and (A-2) In the case of a component, the mass ratio represented by the component (A-1) / (A-2) is 0.1 to 20, preferably 5 to 20, and the component (A-1) and (A-2) are contained. In the case of the component (A-3), the mass ratio represented by the [(A-1) component + (A-2) component] / (A-3) component is 1 to 50, preferably 18 to 46. :R ¹ -CO-[(EO')s/(PO')t]-R ² (a-1-1)

[wherein, R ¹ is an alkyl group having 7 to 18 carbon atoms or an alkenyl group having 7 to 18 carbon atoms; R ² is an alkyl group having 1 to 3 carbon atoms; and s represents an average repeat number of EO', which is 6~ The number of 20; t indicates the average number of repetitions of PO', which is a number from 0 to 6; EO' indicates oxygen extended ethyl, PO' indicates oxygen extended propyl; so-called [(EO')s/(PO')t] , meaning that EO' and PO' may also be mixed]; R ^3a -O-(EO')uH (a-1-2)

R ^3b -O-[(EO')p/(PO')q]-(EO')rH (a-1-3)

[wherein R ^3a and R ^3b are each independently an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms; u represents an average number of repetitions of EO', and is a number of 5 to 20; p represents EO 'The average number of repetitions, q represents the average number of repetitions of PO', r represents the average number of repetitions of EO', and p, q, r satisfy p>1, r>1, 0<q≦3, and p+r= Number of 10~20; EO' means oxygen extended ethyl, PO' means oxygen extended propyl; [(EO')p/(PO')q] means that EO' and PO' may also be mixed];

[wherein, R ⁰ is an alkyl group having 10 to 20 carbon atoms or an alkenyl group having 10 to 20 carbon atoms; and A ¹ O and A ² O each independently represent an oxygen alkyl group having 2 to 3 carbon atoms; i represents The average number of repetitions of A ¹ O; j represents the average number of repetitions of A ² O; i>0, j>0, i+j is a number of 10 to 50];

[wherein R ⁴ ' and R ⁵ ' are each independently a hydrogen atom, a C 1-10 alkyl group which may have a substituent, an aryl group which may have a substituent, a nitro group (-NO ₂ ), an ether group, An amine group (-NH ₂ ) or an amine derivative group which may have a substituent; M ⁺ is a relative ion].

Still another embodiment of the liquid detergent of the present invention may be a liquid detergent comprising: (A) component: surfactant, (B) component: saccharide-decomposing enzyme preparation, (C) Ingredient: at least one compound selected from the group consisting of hydroxycarboxylic acids and salts thereof, (D) component selected from the group consisting of isopropylmethylphenol (IPMP), 3-iodo-2-propynyl carbamic acid At least one of a group consisting of butyl ester (IPBC), carbendazim (TBZ), polylysine, polyhexamethylene biguanide, and acid salts thereof, preferably: water, more preferably The ion-exchanged water and other components as necessary; the content of the component (A) is 20% by mass or more and 80% by mass or less, preferably 27% by mass to 48% by mass based on the total mass of the liquid detergent. The content of the component (B) is 0.01% by mass or more and 2% by mass or less, preferably 0.1% by mass to 0.5% by mass, and the content of the component (C) is 0.1% by mass to 5% by mass, preferably 1% by mass. ~2% by mass, the content of the component (D) is 0.1% by mass to 2% by mass, and the content of the solvent is 30% by mass or more and 70% by mass or less, preferably 48% by mass. The amount is % to 70% by mass, and the total content of all the components is not more than 100% by mass; and the mass ratio of the component (B) and the component (C) is 0.001 to 1, preferably 0.1 to 0.25.

Still another embodiment of the liquid detergent of the present invention may be a liquid detergent comprising: (A) a component selected from the group consisting of (A-1) nonionic surfactant, (A-2) At least one surfactant in the group consisting of an anionic surfactant, (A-3) cationic surfactant, and (B) component: selected from the group consisting of cellulase, amylase, and mannanase At least one saccharide-degrading enzyme preparation in the group, (C) component: a compound represented by the following formula (c-1), a solvent: preferably water, more preferably ion-exchanged water, or (D) component: selected from At least one of the group consisting of the compound represented by the following formula (d1) and the compound represented by the following formula (d2), and optionally other components; and the total amount of the liquid detergent The content of the component (A) is 20% by mass or more and 80% by mass or less, preferably 27% by mass to 48% by mass, and the content of the component (B) is 0.01% by mass or more and 2% by mass or less, preferably 0.1% by mass to 0.5% by mass, the content of the component (C) is 0.1% by mass to 5% by mass, preferably 1% by mass to 2% by mass, and the solvent content is 30% by mass. 70% by mass or less, preferably 48% by mass to 70% by mass, and the total content of all the components is not more than 100% by mass; and the mass ratio represented by the component (B)/(C) is 0.001~ 1, preferably 0.1 to 0.25 (in the range of ○ evaluation of the example of the example), and when the component (A-1) and the component (A-2) are contained, the component (A-1) / (A-2) The mass ratio represented by the component is 0.1 to 20, preferably 5 to 20; and when the component (A-1), the component (A-2), and the component (A-3) are contained, [(A-1) The mass ratio represented by the component + (A-2) component / / (A-3) component is 1 to 50, preferably 18 to 46:

In the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group which may have a substituent, a nitro group (-NO ₂ ), an ester group, and an ether group. An amine group (-NH ₂ ) or an amine derivative group which may have a substituent; R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; v is an integer of 0 to 4; M ⁺ is Relative ion]; [10]

[where r is an integer from 5 to 100];

[wherein, m is an integer of 2 to 14; HR ⁴ represents an organic acid or a mineral acid; and n represents the number of HR ⁴ and is an integer of 0 to 5 m].

Still another embodiment of the liquid detergent of the present invention may be a liquid detergent comprising: (A) a component selected from the group consisting of (A-1) nonionic surfactant, (A-2) At least one surfactant in the group consisting of an anionic surfactant, (A-3) cationic surfactant, and (B) component: at least one selected from the group consisting of amylase and mannanase A saccharide-degrading enzyme preparation, (C) component: a compound represented by the following formula (c-1-1), and a component (D) selected from the group consisting of isopropylmethylphenol (IPMP), 3-carbamic acid amide- 2-propynyl butyl acrylate (IPBC), bismuth benzoic acid (TBZ), and the poly(amino) acid represented by the above formula (d1) or an acid salt thereof, and the polyhexamethylene group represented by the formula (d2) At least one of a group consisting of a biguanide, a combination of the polylysine represented by the formula (d1) and the polyhexamethylene biguanide represented by the formula (d2), a solvent: preferably water, More preferably, it is ion-exchanged water, and other components as needed; and the (A-1) component is a polyoxyalkylene type nonionic surfactant selected from the following formula (a-1-1), Expressed by the following general formula (a-1-2) a polyoxyalkylene type nonionic surfactant, a polyoxyalkylene type nonionic surfactant represented by the following formula (a-1-3), and the following formula (a-1-4) At least one selected from the group consisting of polyoxyalkylene alkylamine type nonionic surfactants; the component (A-2) is selected from a linear chain having an alkyl group having 8 to 18 carbon atoms a branched or branched alkylbenzene sulfonate, any alkylene oxide having a carbon number of 2 to 4, or ethylene oxide (EO) and propylene oxide (PO) (mole ratio EO/PO = 0.1) /9.9~9.9/0.1) A linear (or alkenyl) alkyl (or alkenyl) group having a linear or branched alkyl group having 10 to 20 carbon atoms and having an average of 0.5 moles to 10 moles. At least one of a group consisting of an ether sulfate, an α-sulfo fatty acid methyl ester having 14 to 18 carbon atoms, and a fatty acid salt having 10 to 22 carbon atoms; the (A-3) component being single long The chain alkyl tris-chain alkyl type quaternary ammonium salt; the content of the component (A) is 20% by mass or more and 80% by mass or less, preferably 27% by mass or less based on the total mass of the liquid detergent. 48% by mass, the content of the component (B) is 0.01% by mass or more and 2% by mass or less, preferably 0.1% by mass to 0.5% by mass, and (C) is formed. The content of the fraction is 0.1% by mass to 5% by mass, preferably 1% by mass to 2% by mass, and the content of the solvent is 30% by mass or more and 70% by mass or less, preferably 48% by mass to 70% by mass, and The total content of all the components is not more than 100% by mass; the mass ratio of the component (B)/(C) is 0.001 to 1, preferably 0.1 to 0.25 (in the range of ○ evaluation of the example), When the component (A-1) and the component (A-2) are contained, the mass ratio represented by the component (A-1)/(A-2) is 0.1 to 20, preferably 5 to 20; (A-1) component, (A-2) component, and (A-3) component, [(A-1) component + (A-2) component] / (A-3) component The mass ratio is 1~50, preferably 18~46: R ¹ -CO-[(EO')s/(PO')t]-R ² (a-1-1)

[wherein, R ¹ is an alkyl group having 7 to 18 carbon atoms or an alkenyl group having 7 to 18 carbon atoms; R ² is an alkyl group having 1 to 3 carbon atoms; and s represents an average repeat number of EO', which is 6~ The number of 20; t indicates the average number of repetitions of PO', which is a number from 0 to 6; EO' indicates oxygen extended ethyl, PO' indicates oxygen extended propyl; so-called [(EO')s/(PO')t] , meaning that EO' and PO' may also be mixed]; R ^3a -O-(EO')uH (a-1-2)

R ^3b -O-[(EO')p/(PO')q]-(EO')rH (a-1-3)

[wherein R ^3a and R ^3b are each independently an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms; u represents an average number of repetitions of EO', and is a number of 5 to 20; p represents EO 'The average number of repetitions, q represents the average number of repetitions of PO', r represents the average number of repetitions of EO', and p, q, r satisfy p>1, r>1, 0<q≦3, and p+r= Number of 10~20; EO' means oxygen extended ethyl, PO' means oxygen extended propyl; [(EO')p/(PO')q] means that EO' and PO' may also be mixed];

[wherein, R ⁰ is an alkyl group having 10 to 20 carbon atoms or an alkenyl group having 10 to 20 carbon atoms; and A ¹ O and A ² O each independently represent an oxygen alkyl group having 2 to 3 carbon atoms; i represents The average number of repetitions of A ¹ O; j represents the average number of repetitions of A ² O; i>0, j>0, i+j is the number of 10 to 50]; [Chem. 13]

[wherein R ⁴ ' and R ⁵ ' are each independently a hydrogen atom, a C 1-10 alkyl group which may have a substituent, an aryl group which may have a substituent, a nitro group (-NO ₂ ), an ether group, An amine group (-NH ₂ ) or an amine derivative group which may have a substituent; M ⁺ is a relative ion].

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. In the present embodiment, "%" means "% by mass" unless otherwise specified.

The composition of each of the liquid detergents is shown in Tables 1 to 3.

The raw materials used in this example are as follows.

<(A) component: surfactant] (A-1) Ingredients: Nonionic surfactant

A-1-1: Alkoxylated catalyst was added to 15 molar equivalents relative to coconut oil fatty acid methyl ester (mixture of methyl laurate/methyl myristate = 8/2 by mass ratio) Ethylene oxide (MBE). In the above formula (a-1-1), R ¹ = an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms, R ² = methyl group, and s = 15, t = 0. Synthesized by the following synthesis methods.

[Synthesis method of MEE]

It is synthesized according to the synthesis method described in JP-A-2000-144179.

Will be composed of 2.5MgO. Al ₂ O ₃ . wH ₂ O aluminum hydroxide. Magnesium (Kyoward 300 (trade name), manufactured by Kyowa Chemical Industry Co., Ltd.) was calcined at 600 ° C for 1 hour under a nitrogen atmosphere to obtain calcined aluminum hydroxide. Magnesium (unmodified) catalyst. Will roast aluminum hydroxide. Magnesium (unmodified) catalyst 2.2g, 2.9mL of 0.5N potassium hydroxide ethanol solution, 280g of methyl laurate, and 70g of methyl myristate were added to a 4L autoclave and touched in an autoclave. Media modification. Then, after replacing the inside of the autoclave with nitrogen gas, while maintaining the temperature at 180 ° C and maintaining the pressure at 0.3 MPa, 1052 g of ethylene oxide was introduced and reacted while stirring.

The obtained reaction liquid was cooled to 80 ° C, and 159 g of water, 5 g of activated clay as a filter aid, and 5 g of diatomaceous earth were mixed, and the catalyst was separated by filtration to obtain MEE.

A-1-2: The addition of 15 moles of ethylene oxide to natural alcohol (LMAO). In the above formula (a-1-2), R ^3a = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, and u = 15. Synthesized by the following synthesis method.

[Synthesis method of LMAO]

861.2 g of CO-1214 (trade name) manufactured by Procter & Gamble, and 2.0 g of a 30% by mass aqueous NaOH solution were placed in a pressure-resistant reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Next, after dehydrating the reaction liquid in the reactor at a temperature of 100 ° C and a pressure of 2.0 kPa or less for 30 minutes, the temperature in the reactor is raised. Warm to 160 ° C. Then, while stirring the reaction liquid, 760.6 g of ethylene oxide (gas) was slowly added to the reaction liquid. At this time, ethylene oxide was added by a blowing tube while adjusting the addition rate so that the reaction temperature of the reaction liquid did not exceed 180 °C.

After the completion of the addition of ethylene oxide, the reaction liquid was aged at a temperature of 180 ° C and a pressure of 0.3 MPa or less for 30 minutes, and then the unreacted ring was passed from the reaction liquid at a temperature of 180 ° C and a pressure of 6.0 kPa or less for 10 minutes. Oxyethane is removed by distillation.

Next, after cooling the temperature of the reaction liquid to 100 ° C or lower, 70% by mass of p-toluenesulfonic acid was added to neutralize the pH of the 1 mass % aqueous solution of the reactant to be about 7, and LMAO was obtained.

A-1-3: sequential addition of 8 moles of ethylene oxide, 2 moles of propylene oxide to natural alcohol (carbon number 12 alcohol / carbon number 14 alcohol = 7 / 3 by mass ratio) A nonionic surfactant obtained with 8 moles of ethylene oxide. In the above formula (a-1-3), R ^3b = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, p = 8, q = 2, and r = 8.

[Synthesis method of nonionic surfactant represented by formula (a-1-3)]

Nitrogen replacement was carried out by adding 194.5 g of CO-1214 (trade name) manufactured by Procter & Gamble Company and 1.1 g of potassium hydroxide, and dehydrating at 110 ° C and 1.3 kPa for 30 minutes. After nitrogen substitution, the temperature was raised to 140 ° C, and 352 g of ethylene oxide was introduced to carry out an addition reaction. Ripening operation. Then, it was cooled to 120 ° C, and 116 g of propylene oxide was introduced to carry out an addition reaction. Ripening operation. Thereafter, the temperature was raised again to 140 ° C, and 352 g of ethylene oxide was introduced to carry out an addition reaction. Ripening operation. After completion of the reaction, after cooling to 80 ° C, 1.2 g of acetic acid was added to the autoclave, and the mixture was stirred at 80 ° C for 30 minutes, and then extracted to obtain (a-1-3).

A-1-4: Synthetic by the following synthesis method (Ethomeen). In the above formula (a-1-4), R ⁰ = alkyl group having 16 carbon atoms, A ¹ O = oxygen-extended ethyl group, A ² O = oxygen-extended ethyl group, and i + j = 20.

[Synthesis method of Ethomeen]

Fatty acid amine (manufactured by Tokyo Chemical Industry Co., Ltd., n-hexadecylamine) was added to an autoclave (manufactured by Pressure-resistant Industrial Co., Ltd.), and the inside of the system was replaced with nitrogen, and then heated to 150 ° C, successively. A small amount of ethylene oxide (EO) was added until a predetermined amount was reached, and the average addition mole number of the synthesized EO (i.e., the average number of repetitions) was 2 moles of the tertiary amine (first stage).

Next, the obtained tertiary amine and alkaline catalyst (NaOH; 0.8 parts by mass, 40% by mass aqueous NaOH solution based on 100 parts by mass of the tertiary amine) were added to the autoclave, and the system was purged with nitrogen. After the replacement, the mixture was dehydrated by heating and depressurization, and then heated to 150 ° C, and EO was added in small amounts until a predetermined amount was reached, and a product having an average addition mole number of EO (that is, an average number of repetitions) of 20 mol was obtained. (second stage).

After the addition reaction of EO, the product was subjected to neutralization treatment with acetic acid to obtain Ethomeen. The molecular weight was calculated by measurement of an amine value and found to be 1121.

(A-2) Ingredients: Anionic surfactant

A-2-1: LAS, linear alkyl group (carbon number 10 to 14) benzenesulfonic acid [Manufactured by Lion Co., Ltd., trade name: Lipon LH-200 (LAS-H, purity = 96% by mass) Sodium salt, average molecular weight 322 (in the preparation of liquid detergent, will be in LAS-H And become a sodium salt).

A-2-2: MES, α-sulfo fatty acid methyl ester salt, manufactured by Lion Eco Chemicals Co., Ltd., trade name "MIZULAN FL-80".

A-2-3: AES, polyoxyethylene lauryl ether sulfate, manufactured by New Japan Physical and Chemical Co., Ltd., trade name "Cinnoline SPE-1350".

A-2-4: AEPS, polyoxyalkylene alkyl ether sulfate monoethanolamine salt (alkyl group is a linear alkyl group having 10 to 14 carbon atoms, and the average addition mole number of propylene oxide (ie, The average number of repetitions is 1, and the average addition mole number of ethylene oxide (i.e., the average number of repetitions) is 3).

A-2-5: Coconut oil fatty acid sodium (combined with sodium neutralized coconut oil fatty acid (trade name, manufactured by Nippon Oil Co., Ltd.)).

(A-3) Ingredients: Cationic surfactant

A-3-1: alkyl chloride (carbon number 12) trimethylammonium, manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Arquad 12-37W".

A-3-2: Alkyl chloride (carbon number 14) trimethylammonium, manufactured by Tokyo Chemical Industry Co., Ltd. (reagent).

A-3-3: Alkyl chloride (carbon number 16~18) trimethylammonium, manufactured by Lion King Refinery Co., Ltd., trade name "Arquad T-800".

A-3-4: Dimethyl dimethyl ammonium chloride, manufactured by Lion King Refinery Co., Ltd., trade name "Arquad 210".

<(B) component: saccharide-degrading enzyme preparation>

B-1: Mannanase preparation, manufactured by Novozymes, under the trade name "Mannaway" 4L".

B-2: Amylase preparation, manufactured by Novozymes, under the trade name "Termamyl 300L".

<(B') component: Proteolytic enzyme preparation, and comparative component of (B) component>

B'-1: Protease preparation, manufactured by Novozymes, under the trade name "Coronase 48L".

B'-2: Protease preparation, manufactured by Novozymes, under the trade name "Everlase 16L".

<Component (C): at least one compound selected from the group consisting of α-hydroxy-monocarboxylic acids and salts thereof>

C-1: Sodium lactate, manufactured by Kanto Chemicals. In the above formula (c-1-1), R ⁴ = methyl group and R ⁵ = hydrogen atom.

C-2: phenylglycolic acid, manufactured by Kanto Chemicals. In the above formula (c-1-1), R ⁴ = phenyl group and R ⁵ = hydrogen atom.

<(D) component: selected from the group consisting of isopropylmethylphenol (IPMP), 3-iodo-2-propynyl butyl amide (IPBC), bismuth (TBZ), polylysine, poly six At least one of a group consisting of methylene biguanide and the acid salts thereof >

D-1: Poly-aminic acid, trade name "Polyamino acid 25% aqueous solution", manufactured by Chisso Co., Ltd.

D-2: Polyhexamethylene biguanide, trade name "PROXEL IB", manufactured by Lonza Japan Co., Ltd.

D-3: 2-isopropyl-5-methylphenol (IPMP), trade name "BIOSOL", manufactured by Osaka Chemical Industry Co., Ltd.

D-4: 3-iodo-2-propynyl butyl amide (IPBC), trade name "GLYCACIL", manufactured by Lonza Japan Co., Ltd.

<Other ingredients>

Common ingredient: sodium benzoate: manufactured by East Asia Synthetic Co., Ltd.

Monoethanolamine: manufactured by Nippon Shokubai Co., Ltd.

Dibutylhydroxytoluene: manufactured by Sumitomo Chemical Co., Ltd., trade name "SUMILZER BHT-R".

Ethanol: manufactured by Japan Alcohol Trading Co., Ltd., trade name "Specific alcohol 95 degree synthesis".

Fatty acid 2-ethylhexyl ester: manufactured by Lion King Co., Ltd., trade name "Pastel 2H-08".

Perfume: The fragrance composition A described in Tables 11 to 18 of JP-A-2002-146399.

P-toluenesulfonic acid: manufactured by Xiehe Yeast Industry Co., Ltd., trade name "PTS".

Pigment: manufactured by Suihuacheng Co., Ltd., trade name "Green No.3".

pH adjuster: sodium hydroxide (manufactured by Tsurumi Soda Co., Ltd.), sulfuric acid (manufactured by Toho Asian Lead Co., Ltd.).

Ion exchange water.

<Preparation of liquid detergent> (Examples 1 to 35, Comparative Examples 1 to 4)

According to the composition (mixing component, content (% by mass)) shown in Tables 1 to 3, the liquid detergents of the respective examples were prepared by the following production methods.

In the table, in the case where there is a blending component of the blank, the blending component is not formulated.

In the table, the content of the compounding component indicates the amount of purity conversion.

The "appropriate amount" indicating the content of the pH adjuster is the total amount of the pH adjuster (sodium hydroxide, sulfuric acid) added to adjust the pH (25 ° C) of the liquid detergent to 7.0.

The "balance" indicating the content of the ion-exchanged water means the remainder added so that the total amount (% by mass) of all the components contained in the liquid detergent is 100% by mass.

In the table, "mass ratio (B) / (C)" means the mass ratio of the content of the component (B) in the liquid detergent to the content of the component (C). Comparative Example 2 shows the mass ratio of the content of the (B') component in the liquid detergent to the content of the component (C).

The "mass ratio (A-1) / (A-2)" means the mass ratio of the content of the component (A-1) in the liquid detergent to the content of the component (A-2).

"mass ratio [(A-1) + (A-2)] / (A-3)" means the total content of (A-1) component and (A-2) component in a liquid detergent with respect to ( A-3) The mass ratio of the content of the ingredients.

In the table, the composition of the common ingredients is as follows. The content (% by mass) of each compounding component means the ratio in the liquid detergent. The total content of the shared components was 11.55553 mass% with respect to the total mass of the liquid detergent.

Sodium benzoate 0.5% by mass, monoethanolamine 1% by mass, dibutylhydroxytoluene 0.05% by mass, ethanol 7 mass%, fatty acid 2-ethylhexyl ester 1.5% by mass, perfume 0.5% by mass, p-toluenesulfonic acid 1% by mass, The pigment was 0.0005 mass%.

[Method for producing liquid detergent]

According to the composition shown in Tables 1 to 4, ethanol and (A) components were added to a 500 mL beaker, and the mixture was thoroughly stirred by a magnetic stirrer (manufactured by MITAMURA KOGYO INC.). .

Then, a pH adjusting agent (sodium hydroxide or sulfuric acid) was added so as to have a pH of 7 (25 ° C) while adding a common component other than ethanol and ion-exchanged water. At this time, ion-exchanged water was added so that the total amount of the point at this time became 95 mass% of the total amount of the liquid detergent finally obtained.

After adjusting the pH to 7, the component (B) or the component (B') and the component (C) are added and stirred. Then, a pH adjuster (sodium hydroxide or sulfuric acid) was added so that the pH became 7 (25 ° C), and ion-exchange water was added so that the total amount might become 100 mass %, and the liquid detergent was obtained.

The pH of the liquid detergent was measured by adjusting the sample to 25 ° C and using a pH meter (product name "HM-30G" manufactured by TOADDK Co., Ltd.).

<Evaluation of liquid detergent>

For each of the liquid detergents, evaluation of the effect of suppressing the generation of the indoor dryness, evaluation of the storage stability, and evaluation of the effect of suppressing the formation of the liquid film were performed.

[Evaluation of the effect of suppressing the drying of the inside of the house]

The 10 hand towels that were repeatedly used and washed in the home for half a year were used (usually not washed) for about 2 days in normal life. For each of the ten hand towels, a liquid detergent of each example was used, and a washing process (JW-Z23A type, manufactured by Haier Co., Ltd.) was used for washing treatment (injection water temperature was about 20 ° C, hardness was about 3° DH tap water, bath ratio 20 times). At this time, the amount of the liquid detergent to be supplied to the washing machine was set to 10 mL/30 L of tap water, and the washing treatment was performed.

In addition, the clothing that meets the bath ratio is washed by a washing machine using a fully automatic washing machine (manufactured by Matsushita Electric Co., Ltd., NA-F70SD1) with a 100% cotton shirt (manufactured by BVD). (Injection of tap water with a water temperature of about 20 ° C and a hardness of about 3 ° DH). In this case, the lotion was prepared by using a commercially available synthetic lotion Top (manufactured by Lion Co., Ltd.), and the amount of the lotion used per washing treatment was 25 g/30 L of tap water.

After the washing treatment of the hand towel was completed, the hand towel was air-dried at room temperature (about 23 ° C) and a relative humidity of 90% RH and dried for 5 hours (to dry in the house).

Thereafter, six professional panel inspectors separately performed a sensory evaluation of the odor of 10 hand towels after drying for 5 hours (drying in the house).

The sensory evaluation was performed based on the following evaluation criteria score. Specifically, the professional sensation inspector smelled the scent of each of the ten hand towels which were dried in the house, and evaluated according to the odor intensity indication of the six levels in the following evaluation criteria. Then, the average score of the ten hand towels was calculated, and the average score was used as an index to evaluate the effect of suppressing the occurrence of the indoor dryness. The average scores are shown in Tables 1 to 3. Divide the average into 2.5 points The following are set to pass.

Evaluation criteria for sensory evaluation (intensity indication)

0 points: completely odorless.

1 point: I feel the odor with a barely perceptible degree.

2 points: Weakly felt the odor.

3 points: I feel the odor slightly.

4 points: Strong feeling of odor.

5 points: I feel strong odor.

[Evaluation of preservation stability]

30 mL of each of the liquid detergents of each example was filled in a glass bottle, and the lid was closed to seal it.

In this state, it was left to stand in a constant temperature bath at 5 ° C and stored for 24 hours.

Thereafter, a cylindrical glass bottle filled with a liquid detergent was taken out from the constant temperature bath, and the transparency uniformity and fluidity of the liquid detergent at 5 ° C were observed, and the liquids of the respective examples were washed based on the following evaluation criteria. The storage stability of the detergent was evaluated. The result of the evaluation was A and B was set as pass.

Evaluation basis

A: Transparent and uniform and showing fluidity.

B: Gelation was confirmed in a part, but fluidity was obtained.

C: Curing without fluidity, or precipitation was confirmed.

[Evaluation of the effect of inhibiting the formation of a film on the liquid surface]

Take 5g of liquid detergent of each case separately and put it in length 5.3cm × width 3.3cm × height 1.5 cm container (manufactured by Maruemu, MAJY Case, model SS).

The cover of the length and width was not allowed to stand at 5 ° C for 24 hours in a state of being directly opened, and the liquid level after the observation was observed, and the liquid detergent of each example was suppressed based on the following evaluation criteria. The effect of forming a film on the liquid surface was evaluated. The result of the evaluation was A and B was set as pass.

Evaluation basis

A: It was not confirmed that a film was formed on the liquid surface, and the liquid detergent had fluidity.

B: It was confirmed that a film was formed on the liquid surface, but the liquid detergent had fluidity.

C: The liquid detergent is gelled or solidified as a whole.

From the results shown in Tables 1 to 4, it was confirmed that the liquid detergents of Examples 1 to 35 of the present invention have a high effect of suppressing generation of indoor dryness and have good storage stability.

Further, it was found that the liquid detergents of Examples 1 to 35 were also excellent in suppressing the formation of a film on the liquid surface.

[Industrial availability]

The liquid detergent of the present invention is highly useful in the industry because it has a high effect of suppressing the drying of the inside of the house and has good storage stability.

Claims (3)

A liquid detergent comprising: (A) component: a surfactant, (B) component: a saccharide-decomposing enzyme preparation, and (C) component: a hydroxycarboxylic acid or a salt thereof, and (B) component / (C) The mass ratio represented by the component is 1 or less. The liquid detergent according to claim 1, wherein the component (A) comprises a cationic surfactant. The liquid detergent according to claim 1 or 2, further comprising (D) component selected from the group consisting of isopropylmethylphenol (IPMP), 3-iodo-2-propylidene amide At least one of a group consisting of butyl butyl ester (IPBC), carbendazim (TBZ), polylysine, polyhexamethylene biguanide, and acid salts thereof.