CN108699493B - Detergent composition - Google Patents

Abstract

A detergent composition comprising an alkylene oxide adduct of a polyalkyleneamine (A), a surfactant (B) comprising a nonionic surfactant (B1) and an anionic surfactant (B2), and a perfume (C), wherein the mass ratio of component (B1)/component (B2) is 1.0 or more.

Description

Detergent composition

Technical Field

The present invention relates to detergent compositions.

The present application claims priority based on japanese patent application No. 2016-.

Background

In recent years, a detergent composition is desired to have high fragrance retention (a property that fragrance remains on a washed object) in addition to a stain removal function as a basic function.

In response to such a demand, fragrance retention has been improved by adding a perfume component which tends to remain in the object to be washed, or adding a cationic surfactant or the like.

For example, patent document 1 discloses a perfume delivery-system suitable for delivering a perfume to a surface using a composition comprising polyethyleneimine and a perfume.

Documents of the prior art

Patent document

Patent document 1: japanese patent application laid-open No. 2010-31285

Disclosure of Invention

Problems to be solved by the invention

However, in the conventional techniques, the usable perfume is limited, or the effect is insufficient.

The present invention has been made in view of the above circumstances, and relates to a detergent composition having high fragrance retention. Further, the recontamination preventing performance (performance of preventing the dirt from being reattached to the washed object) of the present invention is also excellent.

Means for solving the problems

The inventor finds that: the following detergent compositions can solve the above problems.

That is, the present invention has the following aspects.

[1] A detergent composition comprising:

alkylene oxide adducts (A) of polyalkyleneamines,

A surfactant (B) comprising a nonionic surfactant (B1) and an anionic surfactant (B2), and

a fragrance (C) which is a perfume,

the mass ratio represented by component (B1)/component (B2) is 1.0 or more.

[2] The detergent composition according to [1], wherein the component (B1) contains a fatty acid methyl ester ethoxylate, and the content of the fatty acid methyl ester ethoxylate is 10% by mass or more relative to the total mass of the component (B).

[3] The detergent composition according to [1] or [2], further comprising:

component (D): a polymer having at least one repeating unit (d1) selected from an alkylene terephthalate unit and an alkylene isophthalate unit, and an oxyalkylene unit (d 2).

[4] The detergent composition according to any one of [1] to [3], further comprising:

component (E): at least 1 kind selected from carboxylic acids represented by the following general formula (VII) and salts thereof, and

component (F): an enzyme.

X－R¹－COOH···(VII)

Wherein, in the formula (VII), R¹Is C1-4 divalent alkyl or arylene, X is-H, -OH, -CH₃or-COOH.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a detergent composition having high fragrance retention can be provided.

Detailed Description

Detergent composition

The detergent composition of the present invention contains the following components (a) to (C).

< ingredient (A) >

The component (A) is an alkylene oxide adduct of a polyalkyleneamine.

Examples of the component (A) include the following component (a1) and component (a 2).

[ component (a1) ]

The component (a1) is an alkylene oxide adduct of polyalkyleneimine.

The polyalkyleneimine of the component (a1) is represented by, for example, the following general formula (I).

NH₂－R²¹－(NA－R²¹)_n－NH₂···(I)

In the formula (I), R²¹Independently represents an alkylene group having 2 to 6 carbon atoms, A represents a hydrogen atom or a branched polyamine chain, and n is an integer of 1 or more. Wherein the A is not all hydrogen atoms.

That is, the polyalkyleneimine represented by formula (I) has a branched polyamine chain in the structure.

R²¹Is a C2-C6 linear alkylene group or a C3-C6 branched alkylene group. R²¹Preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 carbon atoms.

The polyalkyleneimine can be obtained by polymerizing 1 or 2 or more species of alkyleneimines having 2 to 6 carbon atoms by a conventional method. Examples of the alkyleneimine having 2 to 6 carbon atoms include ethyleneimine, propyleneimine, 1, 2-butyleneimine, 2, 3-butyleneimine, and 1, 1-dimethylethyleneimine.

The polyalkyleneimine is preferably a polyethyleneimine (hereinafter, also referred to as "PEI") (in the formula (I), R is R²¹Represents an ethylene group), a polypropyleneimine (in the formula (I), R²¹Representing propylene) and more preferably PEI. PEI is obtained by polymerizing ethyleneimine and has a branched structure containing nitrogen atoms of primary, secondary, and tertiary amines in its structure.

n is an integer of 1 or more.

The mass average molecular weight of the polyalkyleneimine is preferably 200 to 2000, more preferably 300 to 1500, further preferably 400 to 1000, and particularly preferably 500 to 800.

The polyalkyleneimine is preferably a polyalkyleneimine having 5 to 30 active hydrogen atoms in 1 molecule thereof, more preferably a polyalkyleneimine having 7 to 25 active hydrogen atoms in 1 molecule thereof, and still more preferably a polyalkyleneimine having 10 to 20 active hydrogen atoms in 1 molecule thereof. Here, "active hydrogen" refers to a highly reactive hydrogen atom, specifically, a hydrogen atom bonded to a nitrogen atom.

The component (a1) is obtained by adding alkylene oxide to polyalkyleneimine. Examples of the method include the following methods: a method of adding an alkylene oxide such as ethylene oxide to a polyalkyleneimine as a starting material in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, or sodium methoxide at 100 to 180 ℃.

The alkylene oxide includes alkylene oxides having 2 to 4 carbon atoms. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide, with ethylene oxide and propylene oxide being preferred, and ethylene oxide being more preferred.

Examples of the component (a1) include an ethylene oxide adduct of polyalkyleneimine, a propylene oxide adduct of polyalkyleneimine, and an ethylene oxide-propylene oxide adduct of polyalkyleneimine. The ethylene oxide-propylene oxide adduct of polyalkyleneimine is obtained by adding ethylene oxide and propylene oxide to polyalkyleneimine, and the order of addition of ethylene oxide and propylene oxide to polyalkyleneimine and the form of addition (block form, random form) may be arbitrary.

The component (a1) is preferably an ethylene oxide adduct of polyalkyleneimine or an ethylene oxide-propylene oxide adduct of polyalkyleneimine, and more preferably an ethylene oxide adduct of polyalkyleneimine.

The component (a1) is preferably an adduct in which 5 to 40 alkylene oxide atoms are added on average to 1 atom of active hydrogen in the raw material polyalkyleneimine, and more preferably an adduct in which 10 to 30 alkylene oxide atoms are added on average. That is, the adduct in which 5 to 40 moles of alkylene oxide are added on the average, and more preferably 10 to 30 moles of alkylene oxide are added on the average to 1 mole of active hydrogen in the polyalkyleneimine as the raw material.

The mass average molecular weight of the component (a1) is preferably 1000 to 80000, more preferably 2000 to 50000, still more preferably 5000 to 30000, and particularly preferably 10000 to 20000.

The mass average molecular weight is a value obtained by converting a value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent based on a calibration curve of PEG (polyethylene glycol).

As the component (a1), for example, a compound represented by the formula (I-a) can be mentioned.

[ solution 1]

In the formula (I-a), R²²Each independently an alkylene group having 2 to 6 carbon atoms, and m is a number of 1 or more.

R²²Preferably an alkylene group having 2 or 3 carbon atoms, more preferably an alkylene group having 2 carbon atoms. m is (R)²²O), preferably 5 to 40, more preferably 10 to 30.

In the formula (I-a), - (R)²²O)_min-H, -R²²The O-may be bonded randomly or in blocks.

As the component (a1), a synthetic product or a commercially available product can be used.

Examples of commercially available products include "Sokalan HP 20" manufactured by BASF corporation.

< ingredient (a2) >

The component (a2) is an alkylene oxide adduct of a polyalkyleneamine represented by the following formula (II).

NH₂(R³¹NH)_lH···(II)

In the formula (II), R³¹Is an alkylene group having 2 to 6 carbon atoms, and l is a number of 1 or more.

R³¹Is a C2-C6 linear alkylene group or a C3-C6 branched alkylene group. R³¹Preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 carbon atoms.

As the polyalkyleneamine, polyethyleneamine is preferable. Examples of the polyethylene amine include ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, and pentaethylene hexamine. In addition, these polyethyleneamines can be obtained by a known production method such as reacting ammonia and ethylene dichloride.

l is a number of 1 or more.

The polyalkylene amine preferably has a mass average molecular weight of 60 to 1800, more preferably 60 to 1000, and still more preferably 60 to 800.

The polyalkyleneamine is preferably a polyalkyleneamine having 6 to 30 active hydrogens in 1 molecule thereof, and more preferably a polyalkyleneamine having 7 to 20 active hydrogens in 1 molecule thereof.

The component (a2) is obtained by adding alkylene oxide to polyalkyleneamine. The reaction can be carried out in the same manner as the component (a 1). The alkylene oxide includes alkylene oxides having 2 to 4 carbon atoms. Examples of the alkylene oxide include ethylene oxide, propylene oxide and butylene oxide, preferably ethylene oxide and propylene oxide, and more preferably ethylene oxide.

Examples of the component (a2) include an ethylene oxide adduct of polyalkyleneimine, a propylene oxide adduct of polyalkyleneimine, and an ethylene oxide-propylene oxide adduct of polyalkyleneimine.

The alkylene oxide adduct of the polyalkyleneamine is preferably an ethylene oxide adduct of polyalkyleneamine or an ethylene oxide-propylene oxide adduct of polyalkyleneamine, and more preferably an ethylene oxide adduct of polyalkyleneamine.

The component (a2) is preferably an adduct in which 5 to 40 alkylene oxide atoms are added on average to 1 atom of active hydrogen in the polyalkyleneamine as the raw material, and more preferably an adduct in which 10 to 30 alkylene oxide atoms are added on average. That is, the adduct in which 5 to 40 moles of alkylene oxide are added on the average, and more preferably 10 to 30 moles of alkylene oxide are added on the average to 1 mole of active hydrogen in the polyalkylene amine as the raw material.

The mass average molecular weight of the component (a2) is preferably 1000 to 80000, more preferably 2000 to 50000, still more preferably 5000 to 30000, and particularly preferably 10000 to 20000.

The component (a) is preferably the component (a 1). Among the components (a1), an ethylene oxide adduct of polyethyleneimine represented by the formula (I-a) is particularly preferred.

The component (A) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The content of the component (a) is preferably 0.01 to 5% by mass, preferably 0.05 to 3% by mass, and more preferably 0.1 to 2% by mass, based on the total mass of the detergent composition.

When the content of the component (a) is not more than the above upper limit, the degree of freedom in mixing other components can be easily maintained.

When the content of the component (a) is not less than the above lower limit, the fragrance retention property is easily improved and the storage stability is easily improved.

< ingredient (B) >

The component (B) is a surfactant containing a nonionic surfactant (hereinafter, also referred to as a component (B1)) and an anionic surfactant (hereinafter, also referred to as a component (B2)).

[ component (B1) ]

The component (B1) is a nonionic surfactant.

The components (B1) include, for example, the following (1) to (8).

(1) A polyoxyalkylene alkyl (or alkenyl) ether obtained by adding 3 to 30 moles (preferably 3 to 20 moles, more preferably 5 to 20 moles) of a C2-4 alkylene oxide on average to a C6-22 (preferably 8 to 18) 1-membered aliphatic alcohol. Among them, polyoxyethylene alkyl (or alkenyl) ethers, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ethers are suitable. As the 1-membered aliphatic alcohol used herein, primary alcohols and secondary alcohols are exemplified. In addition, the alkyl group may have a branch or not. As the aliphatic alcohol, primary alcohols are preferred.

(2) Polyoxyethylene alkyl (or alkenyl) phenyl ethers.

(3) An alkylene oxide-containing fatty acid alkyl ester alkoxylate is added between ester bonds of long-chain fatty acid alkyl esters.

(4) Polyoxyethylene sorbitan fatty acid esters.

(5) Polyoxyethylene sorbitol fatty acid esters.

(6) Polyoxyethylene fatty acid esters.

(7) Polyoxyethylene hydrogenated castor oil.

(8) Glycerin fatty acid ester.

The nonionic surfactant is preferably the nonionic surfactant of the above (1) or (3), and among them, preferred is a nonionic surfactant represented by the following general formula (III) or (IV).

R²－C(＝O)O－[(EO)_s/(PO)_t]－(EO)_u－R³···(III)

R⁴－O－[(EO)_v/(PO)_w]－(EO)_x－H···(IV)

(in the formula (III), R²Is a C7-22 hydrocarbon group; r³An alkyl group having 1 to 6 carbon atoms; s represents an average number of EO repeats and is a number of 6 to 20; t represents the average number of repetitions of PO and is a number of 0 to 6; u represents the average number of EO repeats, and is a number of 0 to 20; EO represents an oxyethylene group; PO represents an oxypropylene group.

In the formula (IV), R⁴Is a C6-22 hydrocarbon group; v represents an average number of EO repeats, and is a number of 3 to 20; w represents the average number of repetitions of PO and is a number of 0 to 6; x represents the average repeating number of EO, and is a number of 0 to 20; EO represents an oxyethylene group; PO represents an oxypropylene group. )

In the formula (III), R²Is a C7-22 hydrocarbon group. R²The carbon number of (b) is preferably 9 to 21, more preferably 11 to 21.

R²Alkyl and alkenyl groups are preferred.

R²May be either linear or branched.

From the viewpoint of further improving the washing power, R²Preferably, the alkyl group has 7 to 22 carbon atoms and is linear or branched, or the alkenyl group has 7 to 22 carbon atoms and is linear or branched.

R³The alkyl group has 1 to 6 carbon atoms and may be either a straight chain or a branched chain.

Among them, methyl and ethyl are preferred.

In the formula (III), s and u are each independently a number representing the average number of EO repeats.

s + u is preferably 6 to 20, more preferably 6 to 18, further preferably 11 to 18, and particularly preferably 14 to 18. When the amount is not less than the lower limit, the liquid stability is more easily improved. When the amount is equal to or less than the upper limit, the washing power can be more easily increased.

In the formula (III), t represents the number of average repetition numbers of PO.

t is a number of 0 to 6, preferably 0 to 3, and more preferably 0. When the content is not more than the above upper limit, the liquid stability is more easily improved.

When t is 1 or more, [ (EO)_s/(PO)_t]In the above, the oxyethylene group and oxypropylene group may be bonded randomly or in a block form.

In the present specification, the average number of repetitions can be measured by gas chromatography (gas chromatography) or the like.

In the formula (IV), R⁴Is a C6-22 hydrocarbon group.

In the formula (IV), R is a group represented by formula (IV) in view of further improving detergency⁴The carbon number of (b) is preferably 10 to 22, more preferably 10 to 20, and still more preferably 10 to 18.

R⁴And may be straight chain or branched.

As preferred R⁴O-is represented by the following general formula (V)A group of (1).

(R¹⁰¹)(R¹⁰²)CH－O－···(V)

(in the formula (V), R¹⁰¹And R¹⁰²Each independently represents a hydrogen atom or a chain hydrocarbon group; r¹⁰¹And R¹⁰²The total number of carbon atoms is 5 to 21. )

R¹⁰¹And R¹⁰²The total number of carbon atoms of (A) is preferably 9 to 21, more preferably 9 to 19, and still more preferably 9 to 17.

R¹⁰¹And R¹⁰²And may be straight chain or branched.

As R⁴Specifically, the alkyl group is preferably an alkyl group derived from a secondary alcohol having 12 to 14 carbon atoms.

In the formula (IV), v and x are each independently a number representing the average number of EO repeats.

v + x is preferably 3 to 20, more preferably 5 to 18, further preferably 6 to 18, particularly preferably 11 to 18, and further preferably 14 to 18. When the amount is not less than the lower limit, the liquid stability is more easily improved. When the amount is equal to or less than the upper limit, the washing power can be more easily increased.

In the formula (IV), w represents the number of average repetition numbers of PO.

w is a number of 0 to 6, preferably 0 to 3, and more preferably 0. When the content is not more than the above upper limit, the liquid stability is more easily improved.

when w is 1 or more, [ (EO)_v/(PO)_w]In the above, the oxyethylene group and oxypropylene group may be bonded randomly or in a block form.

The distribution of EO or PO in the formula (III) varies depending on the reaction method at the time of production. For example, when ethylene oxide or propylene oxide is added to the raw material using sodium hydroxide or potassium hydroxide, which is a common alkali catalyst, the distribution of v or w becomes wide. Use of Al additive described in Japanese patent publication No. 6-15038³⁺、Ga³⁺、In³⁺、Tl³⁺、Co³⁺、Sc³⁺、La³⁺、Mn²⁺Specific alkoxylation catalyst such as magnesium oxide with metal ion, ethylene oxide, propylene oxideWhen added to the starting material, the distribution of v or w becomes narrower.

The narrowing ratio of the nonionic surfactant represented by the formula (III) (hereinafter, also referred to as component (b11)) and the nonionic surfactant represented by the formula (IV) (hereinafter, also referred to as component (b12)) is preferably 20 mass% or more, and more preferably 25 mass% or more.

The higher the narrowing rate, the better the washing power can be obtained. When the above-mentioned narrowing rate is 20% by mass or more, particularly 25% by mass or more, a detergent composition with less odor of the raw material of the surfactant can be easily obtained.

When the component (b11) is produced by a conventional method, a component which does not contribute to detergency (for example, a fatty acid ester which is a raw material of the component (b11) or an ethylene oxide adduct having s of 1 or 2 of a nonionic surfactant represented by the formula (III)) coexists with the component (b11 in the product, and the narrowing rate is reduced. Therefore, when the narrowing rate is high, the amount of the component to be coexisted is sufficiently small, and problems such as reduction in washing power and generation of raw material odor are difficult to occur. The same applies to the component (b 12).

The upper limit of the above-mentioned narrowing rate is not particularly limited, but is preferably substantially 80 mass% or less.

The narrowing rate is more preferably 20 to 50% by mass, and still more preferably 20 to 40% by mass, from the viewpoint of improving the liquid stability and solubility.

In the present specification, the term "narrowing rate" refers to the ratio of the distribution of ethylene oxide adducts having different numbers of moles of EO added, and is represented by the following formula (S).

[ number 1]

[ in the formula, p_maxRepresents the number of addition mols of EO of the ethylene oxide adduct present at the maximum in the whole ethylene oxide adduct. i represents the number of EO addition mols. Yi represents an ethylene oxide adduct in which the number of EO addition moles is i, which is present in the entire ethylene oxide adductRatio (mass%).]

The narrowing rate can be controlled by, for example, the method for producing the component (b11) or the component (b 12). The method for producing the component (b11) is not particularly limited, and can be easily produced, for example, by a method of addition polymerization of ethylene oxide to a fatty acid alkyl ester using a surface-modified complex metal oxide catalyst (see Japanese patent application laid-open No. 2000-144179). The component (b12) can be produced, for example, by a method of addition-polymerizing ethylene oxide to an alcohol having 6 to 22 carbon atoms using a surface-modified composite metal oxide catalyst.

As suitable materials for the surface-modified composite metal oxide catalyst used in the related method, there can be specifically mentioned: metal ion (Al) added by surface modification with metal hydroxide or the like³⁺、Ga³⁺、In³⁺、T1³⁺、Co^{3 +}、Sc³⁺、La³、Mn²⁺Etc.) and a calcined product catalyst of hydrotalcite surface-modified with a metal hydroxide and/or a metal alkoxide.

In the surface modification using the composite metal oxide catalyst, it is preferable to use a composite metal oxide in combination with a metal hydroxide and/or a metal alkoxide. In this case, the ratio of the metal hydroxide and/or the metal alkoxide is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, based on 100 parts by mass of the composite metal oxide.

In addition, as a method for producing the other component (b11), there is a method of adding alkylene oxide to fatty acid alkyl ester by an alkoxylation catalyst prepared from a mixture of an alkaline earth metal compound and an oxygen acid or the like. As the above-mentioned alkoxylation catalyst, for example, an alkoxylation catalyst prepared from a mixture of an alkaline earth metal salt of a carboxylic acid and/or an alkaline earth metal salt of a hydroxycarboxylic acid and sulfuric acid or the like is disclosed in japanese patent No. 04977609, international publication No. WO1993004030, international publication No. WO2002038269, international publication No. WO2012028435 or the like.

As the nonionic surfactant, commercially available products or products obtained by a known synthesis method can be used. As a known production method, the component (b11) can be produced, for example, by a method of addition-polymerizing ethylene oxide and/or propylene oxide to a fatty acid alkyl ester. The component (b12) can be produced, for example, by a method of addition-polymerizing ethylene oxide and/or propylene oxide to an alcohol having 6 to 22 carbon atoms.

The component (B1) may be used alone in 1 kind or in combination of 2 or more kinds.

The component (B1) is preferably the component (B11), more preferably a compound of the formula (III) in which t is 0 (i.e., polyoxyethylene fatty acid alkyl ester), and particularly preferably R in the formula (III)³Polyoxyethylene fatty acid methyl ester (fatty acid methyl ester ethoxylate) (hereinafter, referred to as "MEE").

The content of the fatty acid methyl ester ethoxylate is preferably 10% by mass or more, more preferably 15 to 90% by mass, and still more preferably 20 to 80% by mass, based on the total mass of the component (B).

When the content of the fatty acid methyl ester ethoxylate is less than the above upper limit, the fragrance retention property is easily improved.

When the content of the fatty acid methyl ester ethoxylate is not less than the lower limit value, the fragrance retention property is easily improved, and the anti-redeposition performance is easily improved.

In the detergent composition of the present invention, the component (b11) is preferably used in combination with the component (b 12).

The mass ratio (hereinafter, also referred to as b11/b12 ratio) represented by component (b 11)/component (b12) is preferably 0.1 to 65, and more preferably 0.5 to 50.

When the b11/b12 ratio is within the above numerical range, the fragrance retention property is easily improved, and the recontamination preventing performance is easily improved.

The content of the component (B1) is preferably 20 to 90% by mass, more preferably 25 to 80% by mass, and still more preferably 30 to 70% by mass, based on the total mass of the component (B).

When the content of the component (B1) is not more than the above upper limit, the fragrance retention property is easily improved.

When the content of the component (B1) is not less than the lower limit, the fragrance retention property and the anti-redeposition performance can be easily improved.

The content of the component (B1) is preferably 20 to 70% by mass, more preferably 20 to 60% by mass, even more preferably 35 to 60% by mass, and particularly preferably 40 to 60% by mass, based on the total mass of the detergent composition.

When the content of the component (B1) is not more than the above upper limit, the fragrance retention property is easily improved.

When the content of the component (B1) is not less than the lower limit, the fragrance retention property and the anti-redeposition performance can be easily improved.

The mass ratio (hereinafter, also referred to as a ratio A/B1) represented by component (A)/component (B1) is preferably 0.001 to 1.0, more preferably 0.005 to 0.5, and still more preferably 0.01 to 0.25.

When the a/B1 ratio is not more than the above upper limit, the fragrance retention property is easily improved and the recontamination preventing performance is easily improved.

When the A/B1 ratio is not less than the above lower limit, the fragrance retaining property is easily improved.

[ component (B2) ]

The component (B2) is an anionic surfactant.

Examples of the anionic surfactant include the following (1) to (12).

(1) Methyl ester, ethyl ester or propyl ester salt of saturated or unsaturated alpha-sulfo fatty acid with 8-20 carbon atoms.

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

(2) Alkane sulfonate with 10-20 carbon atoms.

(4) Alpha-olefin sulfonate (AOS) having 10 to 20 carbon atoms.

(5) An alkyl sulfate or Alkenyl Sulfate (AS) having 10 to 20 carbon atoms.

(6) Polyoxyalkylene alkyl (or Alkenyl) Ether Sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms, wherein the polyoxyalkylene alkyl (or alkenyl) ether sulfate is obtained by adding 0.5 to 10 moles of any of 2 to 4 carbon atoms alkylene oxides or Ethylene Oxide (EO) and Propylene Oxide (PO) (molar ratio EO/PO 0.1/9.9 to 9.9/0.1) on average.

(7) An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms, wherein the alkyl (or alkenyl) phenyl ether sulfate is obtained by adding 3 to 30 moles of any of 2 to 4 carbon atoms alkylene oxides or ethylene oxide and propylene oxide (molar ratio EO/PO 0.1/9.9 to 9.9/0.1) on average.

(8) An alkyl (or alkenyl) ether carboxylate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms, wherein 0.5 to 10 moles of any of alkylene oxides having 2 to 4 carbon atoms or ethylene oxide and propylene oxide (molar ratio EO/PO 0.1/9.9 to 9.9/0.1) are added on average.

(9) Alkyl polyol ether sulfates such as C10-20 alkyl glyceryl ether sulfonic acid.

(10) A long-chain (C8-20) monoalkyl, dialkyl or sesquialkyl phosphate.

(11) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphates.

(12) Higher fatty acids or salts thereof. A higher fatty acid having an average carbon number of 10 to 20 (preferably 12 to 18) or a salt thereof.

Anionic surfactants other than those exemplified above may be used. There may be exemplified carboxylic acid type anionic surfactants such as alkyl ether carboxylate, polyoxyalkylene ether carboxylate, alkylamide ether carboxylate or alkenylamide ether carboxylate, acylamino carboxylate and the like; phosphate ester type anionic surfactants such as alkyl phosphate ester salts, polyoxyalkylene alkylphenyl phosphate ester salts, and glycerin fatty acid ester monophosphates.

The anionic surfactant (2) or (6) is preferred.

The polyoxyalkylene alkyl ether sulfate salt of (6) is particularly preferably a compound represented by the general formula (VI).

R⁴⁰－O－[(EO)_m/(PO)_n]–SO₃ ^﹣M⁺···(VI)

[ in the formula (VI), R⁴⁰Is a C8-20 linear chain orA branched alkyl group. EO represents an oxyethylene group, and PO represents an oxypropylene group. m represents the average number of EO repeats and is a number of 1 or more. n represents the average number of repetitions of PO and is a number of 0 to 6. M⁺Is a counter cation (counter cation). When n exceeds 0, [ (PO)_m(EO)_n]The PO and EO in (1) may be arranged in a block form or in a random form. Further, with respect to PO and EO, PO may be bonded to "R⁴⁰-O- ", EO may be bonded to" R "⁴⁰－O－”。]

The polyoxyalkylene alkyl ether sulfate is preferably a polyoxyalkylene alkyl ether sulfate having a linear or branched alkyl group of 10 to 20 carbon atoms and containing 1 to 5 moles of alkylene oxide added on average.

The number of carbon atoms in the alkyl group is preferably 10 to 20, more preferably 12 to 14. Specific examples thereof include dodecyl group, tridecyl group, and tetradecyl group. Among them, dodecyl group is preferable.

The average number of EO repeats is preferably 1 to 5, more preferably 1 to 3.

The average number of repetitions of PO is preferably 0 to 3, more preferably 0.

Preferably, the polyoxyalkylene alkyl ether sulfate represented by the formula (VI) contains 35 to 55 mass% of the compound of the formula (VI) wherein m is 0 and n is 0, based on the whole polyoxyalkylene alkyl ether sulfate represented by the formula (VI).

Examples of the salt form of the anionic surfactant include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salts; alkanolamine salts such as monoethanolamine salt and diethanolamine salt; ammonium salts, and the like. Among them, alkali metal salts are preferred.

As a method for producing an anionic surfactant, for example, in the case of LAS, it can be produced by the following method: a process comprising sulfonating an alkylbenzenesulfonate with sulfuric anhydride and neutralizing with a base. For example, in the case of AES, it can be manufactured by the following method: a method of reacting sulfuric anhydride with polyoxyalkylene alkyl ether or reacting chlorosulfonic acid with polyoxyalkylene alkyl ether, sulfonating, and neutralizing with a base.

In the detergent composition of the present invention, AES is preferably used in combination with LAS and a higher fatty acid or a salt thereof.

The component (B2) may be used alone in 1 kind or in combination of 2 or more kinds.

The content of the component (B2) is preferably 2 to 50 mass%, more preferably 5 to 45 mass%, and still more preferably 10 to 40 mass% with respect to the total mass of the component (B).

When the content of the component (B2) is not more than the above upper limit, the fragrance retention property is easily improved.

When the content of the component (B2) is not less than the lower limit, the fragrance retention property and the anti-redeposition performance can be easily improved.

The content of the component (B2) is preferably 1 to 40% by mass, more preferably 2 to 35% by mass, and still more preferably 5 to 30% by mass, based on the total mass of the detergent composition.

When the content of the component (B2) is not more than the above upper limit, the fragrance retention property is easily improved.

When the content of the component (B2) is not less than the lower limit, the fragrance retention property and the anti-redeposition performance can be easily improved.

The mass ratio (hereinafter, also referred to as A/B2 ratio) represented by component (A)/component (B2) is preferably 0.01 to 5, more preferably 0.05 to 2, and still more preferably 0.1 to 1.

When the a/B2 ratio is not more than the above upper limit, the fragrance retention property is easily improved, and the recontamination prevention performance is easily improved.

When the A/B2 ratio is not less than the lower limit value, the fragrance retaining property is easily improved.

The mass ratio represented by component (B1)/component (B2) (hereinafter also referred to as B1/B2 ratio) is 1.0 or more, preferably more than 1.0, more preferably 1.5 or more, and particularly preferably 2.0 or more. The ratio of B1/B2 is preferably 30 or less, more preferably 15 or less, and still more preferably 10 or less. Specifically, the B1/B2 ratio is preferably 1.0 to 30, more preferably more than 1.0 and 15 or less, and still more preferably 1.5 to 10.

When the ratio B1/B2 is less than the above upper limit, the fragrance retention property can be easily improved, and the recontamination preventing performance can be easily improved.

When the ratio B1/B2 is not less than the lower limit, the fragrance retention property is easily improved.

[ cationic surfactant ]

Examples of the cationic surfactant include cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salts. Examples of such salts include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; alkanolamine salts such as monoethanolamine and diethanolamine.

The cationic surfactant may be used alone in 1 kind, or in combination of 2 or more kinds.

The content of the cationic surfactant is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, based on the total mass of the detergent composition.

[ amphoteric surfactant ]

Examples of the amphoteric surfactant include alkyl betaine type, alkylamide betaine type, imidazoline type, alkylaminosulfonic acid type, alkylaminocarboxylic acid type, alkylamide carboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric surfactants.

The amphoteric surfactant may be used alone in 1 kind, or in combination of 2 or more kinds.

The content of the amphoteric surfactant is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, based on the total mass of the detergent composition.

The content of the component (B) is 15 to 70% by mass, more preferably 20 to 65% by mass, based on the total mass of the detergent composition.

When the content of the component (B) is not more than the above upper limit, the fragrance retention property is easily improved.

When the content of the component (B) is not less than the above lower limit, the fragrance retention property and the anti-redeposition performance can be easily improved.

< ingredient (C) >

Component (C) is a perfume.

Component (C) is a perfume. The "perfume" is a product containing at least 1 perfume component, and a solvent (solvent for perfume) may be added as needed. The perfume component may be appropriately selected depending on the desired fragrance, and a plurality of perfume components are usually combined.

The perfume component is not particularly limited, and may be a perfume component generally used in detergents, fiber processing agents, hair cosmetics, and the like. Specific examples of such perfume components include phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, ketones, lactones, musks, natural perfumes, animal perfumes, and the like as described below.

The carboxylic acids are not particularly limited and may be suitably selected according to the purpose, and examples thereof include geranic acid, citronellac acid, phenylpropionic acid, cinnamic acid, 2-methyl-2-pentenoic acid, anthranilic acid, benzoic acid, and phenylacetic acid.

The phenol is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include eugenol, isoeugenol, methyl isoeugenol, ethyl eugenol, benzyl isoeugenol, acetyl eugenol, acetyl isoeugenol, methyl eugenol, raspberry ketone, vanillin propylene glycol acetal, ethyl salicylate, benzyl salicylate, and the like.

The alcohols are not particularly limited and may be suitably selected according to the purpose, and examples thereof include, for example, santalol (Bacdanol), citronellol, dihydromyrcenol, dihydrolinalool, geraniol, linalool, nerol, santalol (Sandalore), Santalex, terpineol, tetrahydrolinalool, phenethyl alcohol, trans-2-hexenol, trans-3-hexenol, myrcenol, dihydromyrcenol, tetrahydromyrcenol, terpineol, farnesol (farnesol), nerolidol (nerolidol), 1-octanol, 1-nonanol, leaf alcohol (leaf alcohol), menthol, matsutake alcohol (matsutake alcohol), 1, 8-cineol (cineol), chavicol (chavicol), carvacrol (carvacrol), cuminol (cuminol), anisol, thymol, tetrahydrolinalool, benzyl alcohol, beta-phenylethyl alcohol, and the like, Styryl alcohol (styrylalcohol), cinnamyl alcohol, phenoxyethanol, linalool oxide (linalool oxide), guaiacol (guaiacol), hydroxycitronellal, nerol (nerol), cedrol (cedrol), 2-buten-1-ol (Santalinol), ambroil (Ambrinol), Timberol (Timberol), borneol, isoborneol, santalol (Polysantol), vanillin, maltol, ethyl maltol, vetanol (vetiverol), patchouli alcohol (patcholi alcohol), neroli, anethole, 4-damascol (4-damascol), galbanum resinoid (galbanum resinoid), and the like.

The aldehyde is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include undecylenic aldehyde, lauric aldehyde, 2-methylundecylenic aldehyde (aldehyde C-12MNA), myrac aldehyde (myrac aldehyde), α -amyl cinnamic aldehyde, cyclamenal aldehyde, citral, citronellal, ethyl vanillin, piperonal (heliotropin), anisaldehyde, α -hexyl cinnamic aldehyde, caprylic aldehyde, ligastral, Lilial (Lilial), lyral (lyral), Ligustral (triplane), vanillin (vanillin), heliotropin (Helional), nonanal, decanal, undecylic aldehyde, dodecanal, cis-3-hexanal, benzaldehyde, muguel aldehyde (muguet aldehyde), Dupical (Dupical), p-tert-butylbenzaldehyde (Bourgeonal), cinnamic aldehyde, hexyl ketone (Jasmal), Jasmal (ligral), etc.

The ethers are not particularly limited and may be suitably selected according to the purpose, and examples thereof include cedryl methyl ether (cedramber), ambergris ether (grisalava), β -naphthyl methyl ether, β -naphthyl ethyl ether, herboxide (trans-5-isopropenyl-2-methyl-2-vinyl tetrahydrofuran), rose oxide, and the like.

The ester is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include: cis-3-hexenyl acetate, cis-3-hexenyl PROPIONATE, cis-3-hexenyl salicylate, p-cresyl acetate, p-tert-butylcyclohexyl acetate, pentyl acetate, methyl dihydrojasmonate, pentyl salicylate, benzyl benzoate, benzyl acetate, cedryl acetate, citronellyl acetate, decahydro-beta-naphthyl acetate, dimethylbenzylortho acetate, tricyclodecenyl PROPIONATE (ERICA PROPIONATE), ethyl acetoacetate, tricyclodecenyl acetate (ERICA ACETATE), geranyl acetate, geranyl formate, citronellyl formate, neryl formate, methyl dihydrojasmonate (Hedione), linalyl acetate, beta-phenylethyl acetate, tricyclodecenyl acetate, cinnamyl acetate, hexyl salicylate, styryl acetate (styrylalacetate), terpinyl acetate, p-naphthylmethyl acetate, p-butylcyclohexyl acetate, p-butylbenzyl acetate, p-butylsalicylate, p-butylmethacrylate, p-ethyl methacrylate, p-butylmethacrylate, p-ethyl acrylate, p-butyl acrylate, p-ethyl acrylate, p-butyl acrylate, p-ethyl acrylate, p-butyl acrylate, methyl acrylate, p-ethyl acrylate, p-butyl acrylate, p-ethyl acrylate, p-butyl acrylate, p-ethyl acrylate, p-butyl acrylate, p-ethyl acrylate, p-, Vetiveryl acetate, o-tert-butylcyclohexyl acetate, Manzanate (ethyl 2-methylpentanoate), allyl heptanoate, allyl amyl glycolate, ethyl acetate, neryl acetate, isobornyl acetate, methyl anthranilate, cis-3-hexenyl anthranilate, phenylethyl anthranilate, cinnamyl anthranilate, methyl N-methyl anthranilate, tricyclodecenyl propionate, benzyl propionate, methyl jasmonate, methyl cinnamate, ethyl-2, 2, 6-trimethylcyclohexane carbonate, and fruit flavor esters (FRTATUIE).

The hydrocarbon is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include d-limonene, α -pinene, β -pinene, myrcene, 3-carene, β -caryophyllene, p-cymene, cedrene, citronellonitrile, citral (Lemonile), indole, 6-isopropylquinoline, isobutylquinoline, 2-isobutylquinoline, benzothiazole, and Mint sulfide (Mint sulfofide).

The ketone is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include α -ionone, β -ionone, methyl- β -naphthylketone, α -damascone, β -damascone, δ -dihydrodamascone (δ -damascone), cis-jasmone, methyl ionone, allyl ionone, kestomean ketone (Cashmeran), dihydrojasmone, methyl cedryl ketone (Vertofix), isolongifolanone (isolongifolanone), gomisione (Koavone), rose crystalline (rosephenone), Dynarone (DYNASCONE), Nootkatone (Nootkatone), carvone, menthone, trazone (Floralozone), damascone (damascone), watermelon ketone (Calone), isojasmone, ionone, methylionone, musk, tonne (Tonalide), and verdoe.

The lactone is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include γ -decalactone, γ -undecalactone, γ -nonalactone, γ -dodecalactone, coumarin, Ambroxan (Ambroxan), pelargonide (ambrettolide), cyclopentadecanolide (Pentalide), cyclopentadecanolide (Habanolide), and musk tese (Traseolide).

The musk is not particularly limited and may be suitably selected according to the intended purpose, and examples thereof include cyclopentadecanolide (cyclopentadecanolide), ethylene glycol brassylate (ethylene brassylate), Galaxolide (Galaxolide), musk ketone (musk ketone), tonalid (tonalide), nitromusk (nitromusk), musky ambroxide (musk ambrette), tibetan musk (musky diene), musk ketone (musone), abelmonolide (ambrettolide), cyclohexadecanolide (cyclohexadecanolide), and Galoxolide (Galoxolide).

The natural perfume is not particularly limited, and may be suitably selected according to the purpose, and examples thereof include orange oil, lemon oil, lime oil (lime oil), orange leaf oil (petitgrain oil), grapefruit oil, neroli oil (neroli oil), bergamot oil (bergamot oil), lavender oil (lavandin oil), lavandin oil (lavandin oil), anise oil (pine oil), bay oil (bay oil), rosewood oil (Bois de Rose oil), ylang-ylang oil (ylang-ylang oil), citronella oil (citronella oil), geranium oil (geranium oil), peppermint oil (peppermint oil), peppermint oil (ハッカ oil), spearmint oil (eucalyptus oil), lemongrass oil, patchouli oil, Rose oil, jasmine oil (cedarwood oil), spearmint oil (ylang oil), and oak oil (oak oil), lemon oil (geranium oil), spearmint oil (peppermint oil), spearmint oil (geranium oil), spearmint oil (oak oil), lemon oil (oak oil (bergamot oil), lavender oil (geranium oil), and peppermint oil (oak oil (geranium oil), Pine oil, camphor oil, white sandalwood oil, linaloe oil, turpentine oil (turpentine oil), clove oil, clove leaf oil, cinnamon oil (cassia oil), nutmeg oil (nutmeg oil), caraway oil (cananga oil), thyme oil, orange oil (orange oil), basil oil, fennel oil (fennel oil), clary sage oil (critical sage oil), rosemary oil, caraway seed oil (caraway seed oil), coriander oil, sandalwood oil (sandwood oil), abelmoschus seed oil (ambrette seed oil), elemi oil (elemi oil), elemi oil resin (elemi oil), elemi absolute oil (elemi absolute oil), guaiacum oil (guaiac wood oil), benzoin oil (absolute oil), sesame oil (sthopax), patchouli oil (pauli oil), jasmine oil (jasmine oil), rose wax (rose oil), rose oil extract (rose oil), rose oil (rose oil extract, rose oil extract (rose oil, rose oil extract), rose oil (rose oil extract, rose oil extract, rose oil (rose oil, rose oil extract, rose oil (rose oil, rose oil, Castor absolute, iris resinoid (iris resinoid), olibanum resinoid (olibanum resinoid), copaiba balm (copaiba balsam), Tuolu balm, vanilla absolute, benzoin resin, and the like.

The animal-based perfume is not particularly limited, and may be suitably selected according to the purpose, and examples thereof include musk, civet, castoreum, ambergris, and the like.

Examples of the solvent for perfume include ethanol, triacetin (triacetin), MMB acetate (3-methoxy-3-methylbutyl acetate), sucrose hexaisobutyrate diacetate, ethylene glycol dibutyrate, hexylene glycol, dibutyl sebacate, deltylextratra (isopropyl myristate), methyl carbitol (methyl carbitol) (diethylene glycol monomethyl ether), carbitol (carbitol) (diethylene glycol monoethyl ether), TEG (triethylene glycol), benzyl benzoate, propylene glycol, diethyl phthalate, tripropylene glycol, Avolin (dimethyl phthalate), Deltyl Prime (isopropyl palmitate), dipropylene glycol DPG-FC (dipropylene glycol), farnesene (farnesene), dioctyl adipate, Tributyrin (glyceryl tributyrate), hydroe-5 (1, 2-pentanediol), propylene glycol diacetate, and the like, Cetyl acetate (cetyl acetate), ethyl abietate, ablyn (methyl abietate), Citroflex a-2 (acetyl triethyl citrate), Citroflex a-4 (acetyl tributyl citrate), Citroflex No.2 (triethyl citrate), Citroflex No.4 (tributyl citrate), Durafix (methyl dihydroabietate), MITD (isotridecyl myristate), poly (limonene) (limonene polymers), 1, 3-butanediol, dibutyl hydroxytoluene, hydrogenated methyl pinoleate (Hercolyn), and the like.

The component (C) preferably contains 30 to 75 mass%, more preferably 40 to 50 mass%, of a compound having at least 1 functional group selected from a hydroxyl group and a carboxyl group, based on the total mass of the component (C).

The compound having at least 1 functional group selected from a hydroxyl group and a carboxyl group includes carboxylic acids, phenols, alcohols, and the like among the above perfume components.

The component (C) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The content of the component (C) is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and still more preferably 0.1 to 2% by mass, based on the total mass of the detergent composition.

When the content of the component (C) is within the above numerical range, the fragrance retention property is easily improved.

The mass ratio (hereinafter, also referred to as the A/C ratio) represented by component (A)/component (C) is preferably 0.01 to 100, and preferably 0.1 to 50.

When the A/C ratio is within the above numerical range, the fragrance retaining property is easily improved.

The total of components (A) to (C) is not more than 100% by mass.

< ingredient (D) >

Component (D) is a polymer having the following units: at least one repeating unit (d1) selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit, and an alkylene oxide unit (d 2).

The liquid detergent of the present invention can further improve the effect of easily removing stains adhering to the object to be washed (Soil Release effect, hereinafter also referred to as "SR effect") by using the component (a) and the component (D) in combination.

In the present specification, the term "repeating unit" refers to a monomer unit constituting a polymer.

With respect to a particular repeating unit (d1)

Among the specific repeating units (D1), as an alkylene terephthalate unit (hereinafter, this repeating unit is also referred to as "repeating unit (D11)"), a repeating unit represented by the following general formula (D1-1) can be exemplified.

[ solution 2]

In the above formula (D1-1), R⁴¹Is lower alkylene. R⁴¹The carbon number of the lower alkylene group in (1) is preferably 1 to 5, more preferably 1 to 4, and further preferably 2 to 4.

Specific examples of the repeating unit (d11) include an ethylene terephthalate unit, an n-propylene terephthalate unit, an isopropylidene terephthalate unit, an n-butylene terephthalate unit, an isobutylene terephthalate unit, a sec-butylene terephthalate unit, a tert-butylene terephthalate unit, and the like. Among them, an isopropylidene terephthalate unit is preferable.

The repeating unit (d11) may be used alone in 1 kind or in combination of 2 or more kinds.

Among the specific repeating units (D1), as an alkylene isophthalate unit (hereinafter, this repeating unit is also referred to as "repeating unit (D12)"), a repeating unit represented by the following general formula (D1-2) can be exemplified.

[ solution 3]

In the above formula (D1-2), R⁴²Is lower alkylene. R⁴²The carbon number of the lower alkylene group in (1) is preferably 1 to 5, more preferably 1 to 4, and further preferably 2 to 4.

Specific examples of the repeating unit (d12) include an ethylene isophthalate unit, an n-propylene isophthalate unit, an isopropylidene isophthalate unit, an n-butylene isophthalate unit, a sec-butylene isophthalate unit, a tert-butylene isophthalate unit, and the like. Among them, isopropylidene isophthalate units are preferable.

The repeating unit (d12) may be used alone in 1 kind or in combination of 2 or more kinds.

Component (D) may have only 1 repeating unit (D1) or 2 or more repeating units (D1). That is, the component (D) may have only the repeating unit (D11), only the repeating unit (D12) or both the repeating unit (D11) and the repeating unit (D12) as the repeating unit (D1) in 1 molecule thereof.

In addition, there may be 2 or more repeating units (d11), and/or 2 or more repeating units (d 12).

The repeating unit (d1) may be introduced as a1 unit or 2 or more units (i.e., in a block form) in a1 molecule.

The number of repeating units (D1) in the 1 molecule in the component (D) is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4.

When the number of the repeating unit (d1) is within the above preferred range, the washing effect is easily improved.

With respect to the oxyalkylene unit (d2)

As the oxyalkylene unit (hereinafter, this repeating unit is also referred to as "repeating unit (D2)"), a repeating unit represented by the following general formula (D2-1) can be mentioned.

[ solution 4]

In the above formula (D2-1), R⁴³Is lower alkylene. R⁴³The carbon number of the lower alkylene group in (1) is preferably 1 to 4, more preferably 2 to 4, and further preferably 2 or 3.

Examples of the repeating unit (d2) include an oxyethylene unit, an oxypropylene unit, and an oxybutylene unit. Among them, oxyethylene units and oxypropylene units are preferable.

Component (D) may have only 1 repeating unit (D2) or 2 or more repeating units (D2). That is, the component (D) may have, for example, only an oxyethylene unit, only an oxypropylene unit, or both an oxyethylene unit and an oxypropylene unit as the repeating unit (D2) in 1 molecule thereof.

The component (D) may have an oxyalkylene group (the number of repetitions of the repeating unit (D2) is 1), a polyoxyalkylene group (the number of repetitions of the repeating unit (D2) is 2 or more), or both an oxyalkylene group and a polyoxyalkylene group in 1 molecule as the repeating unit (D2).

The number of repeating units (D2) in the 1 molecule in the component (D) is 1 or more, preferably 1 to 100, more preferably 1 to 80, and still more preferably 1 to 50.

When the number of repeating units (d2) is in the above preferred range, the effect of cleaning oily stains is easily improved.

The component (D) may be a polymer obtained by polymerizing the repeating unit (D1) and the repeating unit (D2) in a block form, or a polymer obtained by polymerizing the repeating unit (D1) and the repeating unit (D2) in a random form. Among these, as the component (D), a block-polymerized polymer is preferable.

Component (D) may have other repeating units in addition to the repeating unit (D1) and the repeating unit (D2). Examples of the other repeating unit include a repeating unit derived from a polymerization initiator, a polymerization inhibitor, and the like, a repeating unit derived from a monomer copolymerizable with the monomer providing the repeating unit (d1) or the repeating unit (d2), and the like.

When the component (D) has another repeating unit, the total of the repeating unit (D1) and the repeating unit (D2) is preferably 80 mol% or more, more preferably 90 mol% or more, and may be 100 mol% based on the total of all repeating units constituting the component (D). When the total of the repeating unit (d1) and the repeating unit (d2) is equal to or higher than the above preferable lower limit, the detergency can be more easily improved.

The component (D) is preferably a water-soluble polymer from the viewpoint of solubility of the component (D) itself and stability of the liquid when the component (D) is prepared into a liquid detergent.

The "water-soluble polymer" as used herein means a water-soluble polymer dissolved in a1 liter beaker by adding 10g of the polymer to 1000g of water at 40 ℃ and stirring the mixture with a stirrer (thickness: 8mm, length: 50mm) for 12 hours (200 rpm).

The weight average molecular weight of the component (D) is preferably 500 to 10000. When the weight average molecular weight is within the above range, the dispersibility in water is improved, and the SR effect and the recontamination preventing effect are more likely to be further improved. In addition, it becomes easy to improve the low-temperature stability of the liquid detergent. The lower limit of the weight average molecular weight is more preferably 800 or more, and still more preferably 1000 or more. On the other hand, the upper limit of the weight average molecular weight is more preferably 9000 or less, and still more preferably 8000 or less. The weight average molecular weight of the component (D) is more preferably 800 to 9000, and still more preferably 1000 to 8000.

The weight average molecular weight of the component (D) is a value obtained by converting a value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent based on a calibration curve of PEG (polyethylene glycol).

The component (D) can be produced by synthetic methods disclosed in various documents, textbooks, patent documents, etc., for example, by Journal of Polymer Science, Vol.3, p.609 to 630 (1948); journal of Polymer Science, volume 8, pages 1-22 (1951); the method described in Japanese patent laid-open No. 61-218699.

Suitable specific examples of the component (D) include a polymer compound represented by the following general formula (D1), a polymer compound represented by the general formula (D2), and a component containing a mixture thereof.

[ solution 5]

In the above formulae (D1), (D2), R⁴⁰And R⁵⁰Each independently is a hydrogen atom or a methyl group, preferably each methyl group, more preferably each methyl group.

R⁴⁴And R⁴⁷Each is a methyl group or a hydrogen atom, and each is preferably a methyl group.

R⁴⁵、R⁴⁶、R⁴⁸And R⁴⁹Each independently an alkylene group having 2 to 4 carbon atoms.

s1 and s2 are each 0 to 10, preferably 0.5 to 5, and more preferably 0.5 to 2.5. t1, t2, u1 and u2 are each independently 1 to 100, preferably 1 to 80, more preferably 1 to 50, still more preferably 10 to 50, and particularly preferably 20 to 30. When s1, s2, t1, t2, u1 and u2 are in the above preferable ranges, the effect of blending the component (D) can be easily exerted sufficiently. Further, the solubility in water is further improved, and a liquid detergent having excellent transparency can be easily obtained when the detergent is blended into a liquid detergent.

(D1) Of (a), the ratio of s1 to (t1+ u1) [ s 1: (t1+ u1) ] is preferably 1: 5-1: 20, more preferably 1: 8-1: 18. when the ratio of s1 to (t1+ u1) is within the above preferable range, the detergency can be further improved and the solubility in water can be further improved.

(D2) Ratio of s2 to (t2+ u2) [ s 2: (t2+ u2) ] is preferably a compound of the formula [ s 1: (t1+ u1) ].

The component (D) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

Further, as the component (D), a synthetic product or a commercially available product may be used.

Commercially available products of the component (D) include a product name of TexCare SRN-100 (manufactured by Clariant, Inc., having a weight average molecular weight of 2000 to 3000), a product name of TexCare SRN-300 (manufactured by Clariant, Inc., having a weight average molecular weight of 7000), a product name of Reel-O-Tex Crystal (manufactured by Rhodia, Inc.), and a product name of Reel-O-Tex QC (manufactured by Rhodia, Inc.).

Among these, TexCare SRN-100 is preferable in view of high solubility in water and excellent storage stability. Further, from the viewpoint of excellent workability, it is preferable to use TexCare SRN-170 (manufactured by Clarian) which is a commercially available 70% aqueous solution of the TexCare SRN-100.

The content of the component (D) is preferably 0.1 to 1.5% by mass, more preferably 0.5 to 1% by mass, based on the total mass of the detergent. When the content of the component (D) is not less than the lower limit, the SR effect is easily further improved. In addition, it becomes easy to further improve the recontamination prevention effect. When the content of the component (D) is not more than the above upper limit, the blending stability in a liquid detergent is easily improved, and the low-temperature stability is easily improved.

The total content [ hereinafter, also referred to as "(a + D) total content" ] of the component (a) and the component (D) in the liquid detergent is preferably 0.1 to 3.5% by mass, more preferably 0.6 to 3.3% by mass, and still more preferably 1 to 3% by mass. When the total content of (a + D) in the liquid detergent is not less than the lower limit, the SR effect is easily further improved. In addition, it becomes easy to further improve the recontamination prevention effect. When the total content of (a + D) in the liquid detergent is not more than the above upper limit, it becomes easy to further improve the low-temperature stability.

The mass ratio [ mass ratio of the content of the component (A) to the content of the component (D), "A/D ratio" hereinafter also referred to as "mass ratio" represented by the component (A)/the component (D) is preferably 0.5 to 4, more preferably 1 to 3. When the A/D ratio is in the above preferred range, the SR effect can be easily further improved.

When the average number of EO added moles of the nonionic surfactant (B1) is 10 or more, the SR effect is further improved.

< ingredient (E) >

Component (E) is at least 1 selected from carboxylic acids represented by the following general formula (VII) and salts thereof.

X－R¹－COOH···(VII)

Wherein, in the formula (VII), R¹Is a C1-4 divalent hydrocarbon group or arylene group, X is-H, -OH, -CH₃or-COOH.

In the liquid detergent of the present invention, the enzyme stability can be improved by using the component (B) and the component (E) in combination.

In the formula (VII), R¹Is a C1-4 divalent hydrocarbon group or arylene group. These C1-4 divalent hydrocarbon groups and arylene groups may or may not have a substituent. Examples of the substituent include a hydroxyl group.

The C1-4 divalent hydrocarbon group may be saturated, unsaturated, linear, branched, or cyclic. Examples of the divalent hydrocarbon group having 1 to 4 carbon atoms include a divalent group obtained by removing 1 hydrogen atom from an alkyl group having 1 to 4 carbon atoms, a divalent group obtained by removing 1 hydrogen atom from an alkenyl group having 1 to 4 carbon atoms, and a divalent group obtained by removing 1 hydrogen atom from an alkynyl group having 1 to 4 carbon atoms.

As the arylene group, a phenylene group is exemplified.

X is-H, -OH, -CH₃or-COOH.

Examples of the carboxylic acid represented by the formula (VII) include benzoic acid, acetic acid, propionic acid, butyric acid, hydroxybutyric acid, hydroxyisobutyric acid, lactic acid, adipic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, malic acid, glutaric acid, and the like.

Examples of the salt of the carboxylic acid include sodium salt, potassium salt, calcium salt, monoethanolamine salt, diethanolamine salt, and triethanolamine salt.

Among these, as the component (E), benzoic acid, lactic acid or a salt thereof is preferable, and lactic acid or a salt thereof is more preferable, from the viewpoint of further improving the enzyme stability. In addition, from the viewpoint of further improving the appearance stability, sodium salt is preferable as the component (E).

As the component (E), sodium lactate is preferable from the viewpoint of further improving the enzyme stability and the appearance stability.

The component (E) may be used alone or in combination of 1 or more than 2.

The content of the component (E) is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, and still more preferably 0.2 to 2% by mass, based on the total mass of the liquid detergent.

< ingredient (F) >

The component (F) is an enzyme.

The liquid detergent of the present invention can further improve the detergency by containing the component (F).

As the component (F), enzymes used in laundry detergent applications and the like can be used, and examples thereof include protease (protease), amylase, lipase (lipase), cellulase, mannanase (mannanase) and the like.

In the present specification, "enzyme" refers to an enzyme preparation.

Examples of proteases include protease preparations commercially available from Novozymes (Novozymes) under the trade names Savinase 16L, Savinase Ultra16XL, Everase 16L TypeEX, Everase Ultra16L, Esperase 8L, Alcalase 2.5.5L, Alcalase Ultra 2.5L, Liquanase 2.5.5L, Liquase Ultra 2.5XL, Coronase 48L, and Jenenaceae (Genencor) under the trade names of "rafect L", Purafect, and "Properase L".

As the amylase, there may be mentioned, as amylase preparations, a product name of Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, a product name of Maxamamyl, a product name of Pullulanase Amano, a product name of DB-250, a product name of Biochemical industries, and the like, which are available from Novoxin.

Examples of the lipase include lipase preparations commercially available from Novixin under the trade name Lipex 100L, Lipolase 100L.

Examples of the cellulase include Endolase5000L and Celluzyme 0.4L, Carzyme 4500L, which are commercially available from Novoxin as a cellulase preparation.

The mannanase may be exemplified by mannanase enzyme available from novicent under the trade name Mannaway 4L, and the like.

Component (F) preferably contains a protease. By adding protease, the detergency against protein stains can be further improved.

Among the above proteases, preferred are those having tradenames of Savinase 16L, Savinase Ultra16XL, Everlase16L, Everlase Ultra16L, Alcalase 2.5.5L, Alcalase Ultra 2.5L, Liquanase 2.5.5L, Liquanase Ultra 2.5XL, and Coronase 48L, and particularly preferred are Alcalase 2.5L, Everlase16L and Savinase 16L, Coronase 48L. The component (F) may be used alone or in combination of 1 or more than 2.

The content of the component (F) is preferably 0.01 to 3% by mass, more preferably 0.05 to 2% by mass, and still more preferably 0.1 to 1.5% by mass, based on the total mass of the liquid detergent. When the content of the component (D) is not less than the lower limit of the above preferable range, the detergency can be further improved. When the content of the component (D) is not more than the upper limit of the above preferable range, precipitation of the enzyme is suppressed, and the appearance stability can be further improved.

In the present specification, the amount of enzyme added to a liquid detergent is the amount added as a preparation. The amount of the above-mentioned enzyme can be determined by a usual method, for example, by calculating the amount of the raw material used or the amount of the enzyme protein in the liquid detergent in reverse.

The mass ratio [ mass ratio of the content of the component (a) to the content of the component (E) ], represented by the above component (a)/the above component (E), is hereinafter also referred to as "a/E ratio". 0.1 to 20.

When the A/E ratio is less than 0.1 or exceeds 20, the appearance stability is impaired.

The A/E ratio is preferably 0.3 to 10, more preferably 0.5 to 7, and further preferably 1 to 5.

The total content of the component (a) and the component (E) is preferably 0.1 to 4% by mass, more preferably 0.5 to 3% by mass, and still more preferably 1 to 2.5% by mass, based on the total mass of the liquid detergent. When the total content of the component (a) and the component (E) is not less than the lower limit, the a/E ratio can be easily adjusted to the specific range of the present application, and a liquid detergent having excellent appearance stability can be easily obtained. When the total content of the component (a) and the component (E) is not more than the upper limit, the degree of freedom in mixing other components can be easily maintained.

< optional Components >

In the detergent composition of the present invention, components generally used in detergent compositions may be used according to the purpose, within the range not to impair the effects of the present invention.

The detergent composition of the present invention may contain an enzyme such as protease, a water-miscible organic solvent such as ethanol, an alkaline agent such as monoethanolamine, an antioxidant such as dibutylhydroxytoluene, a preservative such as sodium benzoate, an enzyme stabilizer such as calcium chloride or sodium lactate, a coloring agent such as a pigment, zeolite (zeolite), a detergency builder (builder), and the like.

Preferably, in the detergent composition of the present invention, the component (a) is at least 1 selected from the compounds represented by the above general formula (I) and the compounds represented by the above general formula (II), the component (B1) is at least 1 selected from the compounds represented by the above general formula (III) and the compounds represented by the above general formula (IV), the component (C) is at least 1 selected from the group consisting of phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, ketones, lactones, musks, natural perfumes and animal perfumes, and the mass ratio represented by the component (B1)/the component (B2) is 1.0 or more.

Preferably, in the detergent composition of the present invention, the component (a) is at least 1 selected from the compounds represented by the above general formula (I) and the compounds represented by the above general formula (II), the component (B1) contains a fatty acid methyl ester ethoxylate, the component (C) is at least 1 selected from the group consisting of phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, ketones, lactones, musks, natural perfumes and animal perfumes, and the mass ratio represented by the component (B1)/the component (B2) is 1.0 or more.

Preferably, in the detergent composition of the present invention, the component (a) is at least 1 selected from the group consisting of the compound represented by the above general formula (I) and the compound represented by the above general formula (II), the component (B1) contains a fatty acid methyl ester ethoxylate, the component (C) is at least 1 selected from the group consisting of phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, ketones, lactones, musks, natural perfumes and animal perfumes, the mass ratio represented by the component (B1)/the component (B2) is 1.0 or more, and the content of the fatty acid methyl ester ethoxylate is 10% by mass or more relative to the total mass of the component (B).

Preferably, in the detergent composition of the present invention, the component (a) is at least 1 selected from the compounds represented by the general formula (I) and the compounds represented by the general formula (II), the component (B1) is at least 1 selected from the compounds represented by the general formula (III) and the compounds represented by the general formula (IV), the component (B2) is at least 1 selected from the compounds represented by the formula (VI) and linear or branched alkylbenzene sulfonates having an alkyl group having 8 to 18 carbon atoms, the component (C) is at least 1 selected from phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, ketones, lactones, musks, natural perfumes, and animal perfumes, and the mass ratio represented by the component (B1)/the component (B2) is 1.0 or more.

Preferably, in the detergent composition of the present invention, the component (a) is a compound represented by the above general formula (I-a), the component (B1) is at least 1 selected from a compound represented by the above general formula (III) and a compound represented by the above general formula (IV), the component (B2) is at least 1 selected from a compound represented by the above general formula (VI) and a linear or branched alkylbenzene sulfonate having an alkyl group with 8 to 18 carbon atoms, the component (C) is at least 1 selected from phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, ketones, lactones, musks, natural perfumes and animal perfumes, and the mass ratio represented by the component (B1)/the component (B2) is 1.0 or more.

Preferably, in the detergent composition of the present invention, the component (a) is a compound represented by the general formula (I-a), the component (B1) is at least 1 selected from a compound represented by the general formula (III) and a compound represented by the general formula (IV), the component (B2) is at least 1 selected from a compound represented by the formula (VI) and a linear or branched alkylbenzene sulfonate having an alkyl group with 8 to 18 carbon atoms, the component (C) is at least 1 selected from phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydrocarbons, ketones, lactones, musks, natural perfumes, and animal perfumes, the mass ratio represented by the component (B1)/the component (B2) is 1.0 to 30, and the mass ratio represented by the component (a)/the component (B2) is 0.01 to 5.

Process for producing detergent composition

When the detergent composition of the present invention is a liquid, it can be produced by mixing the components (a) to (C) with optional components as required by a conventionally known method.

When the detergent composition of the present invention is in the form of granules, it can be produced by a conventionally known method, for example, a dry blend (dry blend) method in which the respective raw materials are powder-mixed; a dry granulation method in which a powder raw material is granulated while being mixed and fluidized; a stirring granulation method in which a liquid adhesive is sprayed and granulated while the powder raw material is mixed and fluidized; an extrusion granulation method in which a raw material is kneaded and extruded by an extruder; a pulverization granulation method in which the raw materials are kneaded and pulverized; spray drying method of spray drying slurry containing raw material, and the like.

Method for Using detergent composition

The detergent composition of the present invention can be used in a conventional manner.

When the detergent composition of the present invention is used for washing a textile product, for example, a method of washing an object to be washed with a washing machine using 30L of a washing liquid to which 5 to 30mL of the detergent composition is added; and a method of immersing the object to be washed in the washing liquid. In addition, it can be used by the following method: the detergent composition is directly applied to an object to be washed, left for a certain period of time, and then subjected to a usual washing method (coating washing).

When the detergent composition of the present invention is used for washing hard surfaces, the following methods may be exemplified: a method in which a detergent composition is dissolved in water to prepare a cleaning solution, the cleaning solution is applied by spraying or the like to a hard surface to be cleaned, and then the cleaning solution is scrubbed with a cleaning implement such as a sponge.

When the detergent composition of the present invention is used for washing dishes, the following methods may be mentioned: a method for containing the detergent composition in a sponge, washing dishes, etc.; a method of dissolving a detergent composition in water to prepare a thin washing solution, immersing tableware or the like in the washing solution, and wiping the tableware or the like with a sponge.

Examples

The present invention will be described in further detail with reference to examples below, but the present invention is not limited to these examples.

The compositions (contents (% by mass)) of the detergent compositions of the respective examples are shown in tables 6 to 7.

In the table, when the formulation ingredient is blank, the formulation ingredient is not added.

In the table, "balance" means the remainder added so that the total amount of all formulation components contained in the detergent composition is 100 mass%.

The raw materials used in this example are as follows.

< ingredient (A) >

A-1: ethylene oxide adduct of polyethyleneimine, manufactured by BASF corporation, under the trade name of "SokalanHP20 ". In the above formula (I-a), R²²Is a compound of ethylene and m is 20.

A-2: polyethyleneimine, a comparative product of component (A) having a weight average molecular weight of about 75000, under the trade name "Lupasol P" manufactured by BASF.

< ingredient (B) >

[ component (B1) ]

B1-1: fatty acid Methyl Ester Ethoxylate (MEE) (fatty acid having 12 to 14 carbon atoms and an average EO molar number of addition of 15) in the general formula (III), wherein R is²Alkyl group having 11 carbon atoms and alkyl group having 13 carbon atoms, R³Methyl, s-15, t-0, and u-0. Synthesized by the following synthesis method.

(Synthesis of B1-1)

Synthesized according to the synthesis method described in Japanese patent laid-open No. 2000-144179.

Under the condition of 600 ℃, the composition is 2.5 MgO. Al₂O₃·zH₂O aluminum/magnesium hydroxide (KYOWARD 300 (trade name), available from Kyowa chemical industries, Ltd.) was calcined in a nitrogen atmosphere to obtain a calcined aluminum/magnesium hydroxide (unmodified) catalyst. 2.2g of calcined aluminum-magnesium hydroxide (unmodified) catalyst, 2.9mL of 0.5N ethanol potassium hydroxide solution, 280g of methyl laurate and 70g of methyl myristate were charged into a 4L autoclave, and the catalyst was modified in the autoclave. Subsequently, the inside of the autoclave was replaced with nitrogen, and 1052g of ethylene oxide was introduced while maintaining the temperature at 180 ℃ and the pressure at 0.3MPa, and the reaction was carried out while stirring.

The obtained reaction solution was cooled to 80 ℃, 159g of water was added, and 5g of activated clay and diatomaceous earth were added as filter aids, respectively, and the mixture was mixed, followed by filtration of the catalyst to obtain B1-1. The stenosis rate of B1-1 was 30% by mass.

B1-1': fatty acid Methyl Ester Ethoxylate (MEE) (fatty acid having 12 to 14 carbon atoms and an average EO molar number of addition of 15) in the general formula (III), wherein R is²Alkyl group having 11 carbon atoms and alkyl group having 13 carbon atoms, R³Methyl, s-15, t-0, and u-0. Synthesized by the following synthesis method.

(Synthesis of B1-1')

B1-1' was synthesized according to the following synthesis method.

137g of 2-ethylhexanol (first-grade reagent, manufactured by Kanto chemical Co., Ltd.) and 41.7g of calcium acetate monohydrate (special-grade reagent, manufactured by Kanto chemical Co., Ltd.) were placed in a 500mL beaker, and the mixture was mixed at room temperature (25 ℃ C.) with a paddle-type stirring blade to obtain a dispersion (dispersing step). While the dispersion was stirred, 20.9g of sulfuric acid (special grade reagent, manufactured by kanto chemical corporation) was added and mixed through a dropping funnel over 10 minutes (mixing step). Since the addition of sulfuric acid in the mixing step generates heat, the beaker is cooled in a water bath, and the reaction temperature is controlled to 30 to 50 ℃. After the addition of sulfuric acid, the mixture was further stirred for 2 hours while being maintained at 50 ℃ (catalyst aging step), thereby obtaining an alkoxylation catalyst.

12.5g of the above alkoxylation catalyst, 462g of methyl laurate (PASTE M12, manufactured by Shiwang chemical Co., Ltd.), and 166g of methyl myristate (PASTE M14, manufactured by Shiwang chemical Co., Ltd.) were placed in an autoclave and stirred. While stirring, the autoclave was purged with nitrogen, heated to 100 ℃ and dehydrated under reduced pressure of 1.3kPa or less for 30 minutes. Then, the temperature was raised to 160 ℃ and Ethylene Oxide (EO)1876g (15 times by mol of the total of methyl laurate and methyl myristate) was introduced under a pressure of 0.1 to 0.5MPa, followed by stirring (addition reaction step). Further, the mixture was stirred at the addition reaction temperature for 0.5 hour (aging step), and then cooled to 80 ℃ to obtain 2516g of a crude reaction product (fatty acid Methyl Ester Ethoxylate (MEE), average molar number of EO added ═ 15). The crude reaction product was filtered to remove the catalyst, and the obtained product was designated as B1-1'.

B1-2: alcohol Ethoxylate (AE) obtained by adding 15 molar equivalents of ethylene oxide to a natural alcohol. In the general formula (IV), R⁴Alkyl group having 12 carbon atoms and alkyl group having 14 carbon atoms, v 15, w 0, and x 0. Synthesized by the following synthesis method.

(Synthesis of B1-2)

224.4g of CO-1214 (trade name) manufactured by Procter & Gamble, and 2.0g of a 30 mass% NaOH aqueous solution were charged into a pressure-resistant reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. Then, the mixture was dehydrated at 100 ℃ under a pressure of 2.0kPa or less for 30 minutes, and the temperature was raised to 160 ℃. Then, 760.6g of ethylene oxide (gaseous) was slowly added to the reaction solution while stirring the reaction solution. At this time, the addition rate was adjusted so that the reaction temperature did not exceed 180 ℃ while feeding ethylene oxide with a blowing tube.

After the addition of ethylene oxide was completed, the mixture was aged at a temperature of 180 ℃ and a pressure of 0.3MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ℃ and a pressure of 6.0kPa or less for 10 minutes.

Next, the temperature was cooled to 100 ℃ or lower, and then, 70 mass% of p-toluenesulfonic acid was added to neutralize so that the pH of a1 mass% aqueous solution of the reactant became about 7, to obtain B1-2.

B1-3: alcohol Ethoxylate (AE) obtained by adding 7 molar equivalents of ethylene oxide to a natural alcohol. In the general formula (IV), R⁴Alkyl group with 12 carbon atoms and alkyl group with 14 carbon atoms, v is 7, w is 0, and x is 0. Synthesized by the following synthesis method.

(Synthesis of B1-3)

224.4g of CO-1214 (trade name) manufactured by Procter & gamble and 2.0g of a 30 mass% aqueous NaOH solution were charged into a pressure-resistant reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. Then, the mixture was dehydrated at 100 ℃ under a pressure of 2.0kPa or less for 30 minutes, and the temperature was raised to 160 ℃. Then, 355.0g of ethylene oxide (gaseous) was slowly added to the reaction solution while stirring the reaction solution. At this time, the addition rate was adjusted so that the reaction temperature did not exceed 180 ℃ while adding ethylene oxide with a blowing tube.

After the addition of ethylene oxide was completed, the mixture was aged at a temperature of 180 ℃ and a pressure of 0.3MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ℃ and a pressure of 6.0kPa or less for 10 minutes.

Next, the temperature was cooled to 100 ℃ or lower, and then, 70 mass% of p-toluenesulfonic acid was added to neutralize so that the pH of a1 mass% aqueous solution of the reactant became about 7, to obtain B1-3.

B1-4: the alcohol block copolymer is obtained by sequentially adding 8 molar equivalents of ethylene oxide, 2 molar equivalents of propylene oxide, and 8 molar equivalents of ethylene oxide to a natural alcohol (7/3 carbon 12 alcohol/14 carbon 14 alcohol in terms of mass ratio). In the above general formula (IV), R⁴Alkyl group with 12 carbon atoms and alkyl group with 14 carbon atoms, v is 8, w is 2, and x is 8.

B1-5: and ethylene oxide of 7 molar equivalents is added to the secondary alcohol of 12 carbon atoms and the secondary alcohol of 14 carbon atoms. The trade name is "Softanol 70", manufactured by Nippon catalyst K.K.. In the above general formula (IV), R⁴Secondary alkyl group having 12 carbon atoms and secondary alkyl group having 14 carbon atoms, v is 7, w is 0, and x is 0.

[ component (B2) ]

B2-1: sodium polyoxyethylene Alkyl Ether Sulphate (AES). In the formula (VI), R40 is a C12-14 straight-chain alkyl group, M is 1.0, n is 0, and M is sodium. Synthesized by the following synthesis method.

(Synthesis of B2-1)

400G of a raw alcohol having a trade name of CO 1270 alcohol (a mixture of an alcohol having 12 carbon atoms and an alcohol having 14 carbon atoms in a mass ratio of 75/25) manufactured by Procter & gamble (P & G) was charged into an autoclave having a capacity of 4L, 0.8G of potassium hydroxide was charged as a reaction catalyst, the inside of the autoclave was replaced with nitrogen gas, and then the temperature was raised with stirring. Subsequently, 91g of ethylene oxide was introduced while maintaining the temperature at 180 ℃ and the pressure at 0.3MPa or less, and the mixture was reacted to obtain an alcohol ethoxylate.

Using a gas chromatography-mass spectrometer: GC-5890 manufactured by Hewlett-Packard, detector: hydrogen Flame Ionization Detector (FID), chromatography column: when the analysis was carried out in Ultra-1 (manufactured by HP, L25m X. phi.0.2 mm X T0.11. mu.m), the average molar number of addition of ethylene oxide of the obtained alcohol ethoxylate was 1.0. In addition, the compound to which ethylene oxide was not added was 43 mass% with respect to the total mass of the alcohol ethoxylate obtained.

Then, 237g of the alcohol ethoxylate obtained above was taken into a 500mL flask equipped with a stirrer, and after replacing it with nitrogen, 96g of liquid sulfuric anhydride (sulfuric anhydride) was slowly added dropwise while maintaining the reaction temperature at 40 ℃. After the end of the dropwise addition, stirring was continued for 1 hour (sulfation reaction), and polyoxyethylene alkyl ether sulfuric acid was obtained. Then, it was neutralized by using an aqueous sodium hydroxide solution to obtain B2-1.

B2-2: sodium Linear alkyl benzene sulfonate (LAS), manufactured by Shiwang corporation, under the trade name "Lipon LH-200".

B2-3: monoethanolamine salt of polyoxyalkylene alkyl ether sulfate (AEPS). In the formula (VI), R⁴⁰A compound of monoethanolamine, wherein m is 2.0, n is 1.0, and m is a linear alkyl group having 12 carbon atoms. Synthesized by the following synthesis method.

(Synthesis of B2-3)

A linear primary alcohol having 12 carbon atoms [ manufactured by tokyo chemical industry co., ltd., trade name: 1-dodecanol (molecular weight 186.33), purity > 99% ]640g, and KOH 1.0g were charged into an autoclave equipped with a stirrer, a temperature controller, and an automatic inlet, and dehydrated at 110 ℃ under 1.3kPa for 30 minutes. After dehydration, nitrogen gas was replaced, and after the temperature was raised to 120 ℃, 199g of propane-1, 2-diyl oxide (propane-1, 2-diyl oxide) was charged. Subsequently, the reaction mixture was subjected to addition reaction and aging at 120 ℃ and then heated to 145 ℃ to charge 303g of ethylene oxide. Subsequently, the reaction mixture was subjected to addition reaction and aging at 145 ℃ and then cooled to 80 ℃ to remove unreacted ethylene oxide under 4.0 kPa. After removing unreacted ethylene oxide, 1.0g of acetic acid was charged into the autoclave, stirred at 80 ℃ for 30 minutes, and then subjected to extraction to obtain an alkoxylate in which the alkyl group was dodecyl, the average molar number of addition of PO was 1.0, and the average molar number of addition of EO was 2.0.

Using SO₃The alkoxylate obtained is sulfated by passing the gas through a descending membrane reactor. The obtained sulfate was neutralized with monoethanolamine to obtain a composition containing monoethanolamine salt (AEPS) of polyoxyethylene polyoxypropylene-1, 2-diyl alkyl ether sulfate.

B2-4: coconut fatty acid (coco fatty acid) is a product name of "coconut fatty acid", manufactured by Nichikoku K.K.

< ingredient (C) >

C-1: fragrances as shown in tables 1 to 5.

[ Table 1]

	Spice (mass%)
		Orange leaf oil	0.5
Orange oil	3
		Clove oil	0.002
Citronella oil	0.2
		Pine oil	0.02
Bergamot oil	1
		Orange oil	0.5
Lime oil	1
		LemonOil	1.3
Lemongrass oil	1
		Glassy resin	0.1
Alpha-pinene	0.001
		Beta-pinene	0.003
Limonene	1
		3-carene	0.002
Beta-caryophyllene	0.03
		Myrcene	0.05
P-cymene	0.001
		Orange Terpene (Orange Terpene)	5
Trans-2-hexenol	0.005
		Trans-3-hexenol	0.005
Neroli absolute	0.001
		Chrysanthemum oil	0.001
Violet absolute	0.001
		Basil oil	0.001
Myrcenol	2
		Dihydromyrcenol	2
Tetrahydromyrcenol	0.1
		Terpineol	3
Farnesol	0.1
		Nerolidol	2
1-octanol	1
		1-nonanol	1
Leaf of Qingyechun	1
		Tricholoma matsutake alcohol	0.01
Citral	1
		N-octanal aldehyde	0.3
N-nonanal	0.3
		1-decanol	0.5
Undecanal aldehyde	0.001
		Dodecanol	0.001
Cis-3-hexanal	0.2
		Triplal	0.001
Benzaldehyde	0.001
		Nootkatone (Nootkatone)	0.001
Alpha-dynasty ketone (alpha-Dainasukon)	0.001
		Acetic acid cis-3-hexenyl ester	0.1
Amyl glycolate allyl ester	0.01
		Ethyl acetate	0.02
Linalyl acetate	2
		Neryl acetate	0.002
Terpinyl acetate	0.05
		Isobornyl acetate

[ Table 2]

	Spice (mass%)
		Verdox	0.001
Fruit fragrant ester(FRUITATE)	0.05
		Manzanate (2-methyl ethyl valerate)	1
Salicylic acid ethyl ester	0.1
		Salicylic acid benzyl ester	2
Ethyl-2, 2, 6-trimethylcyclohexane carbonate	2
		Gamma-nonanolide	0.01
Gamma-decalactone	0.01
		Gamma undecalactones	1
Anthranilic acid methyl ester	1
		Anthranilic acid cis-3-hexenyl ester	0.001
Phenylethyl anthranilate	0.001
		Anthranilic acid cinnamyl ester	0.001
N-methyl anthranilic acid methyl ester	0.5
		Neroli essence	0.1
Citronellyl nitrile	1
		Lemon nitrile	1.5
Fennel oil	0.001
		Perilla oil	0.5
Mint oil	0.005
		Eucalyptus oil	0.1
Lavender oil	0.1
		Mixed lavender absolute	0.1
Rosemary oil	0.03
		Mint terpenes	0.02
Menthol	0.5
		Carvone
Menthones
		Camphor
1, 8-cineole	1
		Jiawei phenol (chavicol)	0.1
Carvacrol (carvacrol)	0.1
		Benzothiazole 0.1 ethanol solution	0.001
Peppermint sulfide 0.1 ethanol solution	0.001
		Artemisia leaf seed oil	0.5
Cuminchol	1
		Coriander oil	0.5
Nutmeg oil	0.5
		Anethol	1
Anisaldehyde	1
		Acetyl eugenol	0.3
Acetyl isoeugenol	0.3
		Anethole	0.3
Methyl eugenol	0.3
		Thymol	0.3
Eugenol	0.3
		Isoeugenol	0.3
Methyl isobutyl phenol	0.1
		Ethyl isoeugenol	0.1
Benzyl eugenol	0.1
		Benzyl isobutyl phenol	0.3
Mimosa pudica extract
		Jasmine extract	0.1
Geranium oil	0.2
		Ylang oil (ylang-ylang oil)	0.01
Rose wood oil	0.02

[ Table 3]

	Spice (mass%)
		Rose extract	0.2
Rose wax	0.007
		Jasmine wax	0.001
Geraniol	3
		Citronellol	5
Nerol	1
		Linalool	3
Tetrahydrolinalool	1
		Benzyl alcohol	1
Beta-phenylethyl alcohol	1
		Storax alcohol	1
Cinnamyl alcohol	0.5
		Phenoxyethyl alcohol	0.5
Citronellal	0.005
		Hydroxycitronellal
Convallaria aldehyde	0.001
		Dupical (Dupical)	0.1
P-tert-butylbenzaldehyde (Bourgeonal)	0.1
		Cyclamen aldehyde	0.05
Sea breeze aldehyde (Florazone)
		Cinnamyl alcohol
Helional (Helonal)	0.05
		New lilial (Lyral)	1
Lilial aldehyde (Lilial)	1
		Alpha-amyl cinnamic aldehyde	0.2
Alpha-hexyl cinnamic aldehyde	1
		Cis-jasmone	0.001
Isojasmone
		4-damascol	0.07
Damascenone	0.2
		Dihydrodamascone (damascone)	0.3
Watermelon ketone (Calone)	0.001
		Citronellyl formate	0.001
Geranyl formate
		Neryl formate
Citronellyl acetate	0.1
		Geraniyl acetate	0.2
Tricyclodecenyl acetate	0.3
		Acetic acid benzyl ester	0.2
Phenylethyl acetate	0.1
		Styracin acetate
Crystalline rose (rosephenone)	0.02
		Acetic acid cinnamyl ester	0.1
Acetic acid dimethyl benzyl ortho ester	0.05
		Jasmal
Tricyclic decene propanoates	0.1
		Propionic acid benzyl ester	0.001
Jasmonic acid methyl ester	0.001
		Hedione	2
Aldehyde C-16
		Cinnamic acid methyl ester
Cinnamic acid ethyl ester	0.002
		Linalool oxide	0.1
herboxide
		Rose ether	0.001

[ Table 4]

	Spice (mass%)
		Beta-naphthyl methyl ether	0.003
Beta-naphthyl ethyl ether	0.001
		Guaiacol	0.1
Anthranilic acid	0.1
		Benzoic acid	0.1
Phenylacetic acid	0.001
		Glossy privet acetal (Ligantral)	0.001
Indoles	0.01
		6-isopropylquinoline 1% dipropylene glycol solution	0.01
1% ethanol solution of isobutylquinoline	0.01
		2-Isobutylquinoline 1% benzyl benzoate solution	0.001
Abelmoschus esculentus seed oil
		Iris resin
Elemi oil resin
		Elemi absolute oil	2
Oak oil	0.005
		Mastic gum	0.001
Guaiac wood oil	0.5
		Guba balsam (copaiba balsam)
Storax sesame oil	0.03
		Tuolu balsam	0.3
Patchouli oil	0.006
		Vanilla essential oil	0.001
Vetiver oil	0.1
		Benzoin resin
Cistus oil
		Cedrene	0.1
Cedarol	0.001
		2-Buten-1-ol (Santalinol)	0.005
Santanol (Bacdanol)	0.5
		Santalore (Sandalore)	0.001
Ambroxol (Ambrinol)	0.1
		Temuchun (Timberol)	0.02
Borneol (borneol)	0.01
		Isoborneol	0.05
Poly santalol (Polysantol)	0.05
		Vanillin	0.05
Ethyl vanillin	0.05
		Piperonal	0.5
Maltol	0.05
		Ethyl maltol	0.05
Raspberry ketone	0.3
		Zixiang ketone	0.5
Methyl Zixiang ketone	1
		Methyl cedryl ketone (Vertofix)	1
Kescomide (Cashmeran)	0.1
		Muscone (muscone)	0.5
Tetrakis musk (Traseolide)	0.1
		Tunai musk (Tonalide)	1
Iso·E·Super	1
		Vetiverol	0.1
Patchouli alcohol	0.1
		Cyclopentadecanolide (Habanolide)	0.5
Okra lactone	0.001
		Cyclohexadecanolide (cyclohexadecanolide)	0.001
Resin of red myrrh	0.1

[ Table 5]

< ingredient (D) >

D-1: a polymer having a specific repeating unit (d1) and an oxyalkylene unit (d 2). The polymer compound is manufactured by Clariant, has a trade name of TexCare SRN-170, a weight average molecular weight of 2000-3000, and contains a polymer compound represented by the general formula (D1). D-1 satisfied the conditions for the "water-soluble polymer" described above (i.e., dissolved after 10g of the polymer was added to 1000g of water at 40 ℃ in a 1-liter beaker and stirred (200rpm) for 12 hours with a stirrer (thickness: 8mm, length: 50 mm)).

< ingredient (E) >

Sodium lactate (stabilizer), manufactured by kanto chemical corporation, under the trade name "sodium lactate".

< ingredient (F) >

Alcalase (protease), manufactured by Novitin corporation, under the trade name "Alcalase 2.5L".

< optional Components >

MEA: monoethanolamine (alkaline agent) manufactured by japan catalyst, ltd., trade name "monoethanolamine".

BHT: dibutylhydroxytoluene (antioxidant), manufactured by Sumitomo chemical Co., Ltd., trade name "SUMILZER BHT-R".

Ethanol (water-miscible organic solvent), manufactured by Japan Alcohol Trading co., LTD., under the trade name "specific ethanol (Alcohol)95 degree synthesis".

Sodium benzoate (preservative) manufactured by Toyo chemical Co., Ltd, trade name "sodium benzoate".

Calcium chloride (enzyme stabilizer), manufactured by kanto chemical corporation, under the trade name "calcium chloride (extra)".

Pigment (colorant), manufactured by Kaihua corporation, under the trade name "Green No. 3".

< Process for producing detergent composition >

(examples 1 to 13, comparative examples 1 to 5)

The detergent compositions of examples 1 to 13 and comparative examples 1 to 5 were obtained by adding the respective components to water and mixing them, according to the compositions shown in tables 6 to 7.

The detergent compositions of examples 1 to 13 and comparative examples 1 to 5 were evaluated for their anti-redeposition performance, fragrance retention property, and storage stability in the following manner.

< evaluation of anti-redeposition Property >

Washing treatment was performed by repeating the following washing step, rinsing step, and drying step in this order 3 times using the detergent compositions of the respective examples.

A washing procedure:

as the object to be washed, the following cotton cloth, wet-type artificially contaminated cloth, and shirts were used.

Cotton cloth: 5 pieces of cotton knit fabric (manufactured by Kokusho Co., Ltd.) of 5cm × 5cm were used as the recontamination determining cloths.

Wet artificially soiled cloth: 20 pieces of soiled cloth (cloth to which stains having a composition of 28.3% by mass of oleic acid, 15.6% by mass of triolein, 12.2% by mass of cholesterol oleate, 2.5% by mass of paraffin wax, 2.5% by mass of squalene, 1.6% by mass of cholesterol, 7.0% by mass of gelatin, 29.8% by mass of mud, and 0.5% by mass of carbon black were attached) manufactured by the society of finance and law.

A shirt: 150 shirts (LL size, manufactured by DVD company) were cut out in small pieces (about 3 cm. times.3 cm).

In a Terg-O-meter (manufactured by United states test (United STATES TESTING)), 900mL of 3 ℃ DH hard water was put at 25 ℃, 0.6g of a detergent composition was added thereto, and then the above-mentioned object was added to adjust the bath ratio to 20 times, and the mixture was washed at 25 ℃ for 10 minutes at 120 rpm.

Rinsing:

the washed matter was dehydrated for 1 minute, then placed in 900mL of 25 ℃ 3 ℃ DH hard water, and rinsed at 120rpm at 25 ℃ for 3 minutes. This operation (dehydration, rinsing) was repeated 2 times. In the 2 nd time, a predetermined amount of softener was added to 900mL of 3 ℃ DH hard water at 25 ℃ and rinsed. The softener was dried in the shade in a room to obtain Soflan (partially dried room しソフラン) (available from Shiwang corporation).

A drying procedure:

the washed matter was dehydrated for 1 minute, and then only the recontaminated determination cloth (cotton cloth) was taken out, sandwiched between filter papers, and dried with an iron.

The reflectance (Z value) of the recontamination cloth before and after the washing treatment was measured using a reflectance meter (spectroscopic color difference meter SE2000, manufactured by japan electro-chromic co., ltd.) and Δ Z was obtained by the following equation.

Δ Z is (Z value before washing) - (Z value after washing)

Regarding Δ Z in the recontamination cloth of cotton cloth, an average value of 5 pieces was obtained. Then, the effect of preventing the recontamination of the cotton cloth by the detergent composition was evaluated according to the following criteria using the average value as an index. In the following evaluation criteria, x and o are acceptable. The evaluation results are shown in tables 6 to 7.

[ evaluation standards ]

Very good: Δ Z is less than 5.

O: Δ Z is 5 or more and less than 7.

And (delta): Δ Z is 7 or more and less than 9.

X: Δ Z is 9 or more.

< evaluation of fragrance Retention >

(1) Treatment of cotton towels using detergent compositions

(pretreatment of evaluation cloth)

A commercially available cotton towel (manufactured by Toshiba Co., Ltd.) was pretreated 3 times with a commercially available detergent "Top Plastic Clear" (manufactured by Shiwang Co., Ltd.) by using a two-tub washing machine (VH-30S manufactured by Toshiba Co., Ltd.).

Pretreatment: the cycle of detergent standard usage, bath ratio 30 times, washing with tap water at 45 ℃ for 10 minutes and then rinsing with water for 10 minutes was performed 2 times.

(treatment with a detergent composition in rinsing step at washing time)

1.0kg of cotton towels (manufactured by Toshiba Co., Ltd.) after the pretreatment washing was washed (using tap water at 25 ℃ C. and a standard usage amount, a standard recipe, a bath ratio 30 times) for 10 minutes using a two-tank washing machine (VH-30S manufactured by Toshiba) with the detergent composition described in tables 6 to 7, and then dehydrated for 1 minute, followed by rinsing for 1 st time for 3 minutes. After the 1 st rinse, 1 minute of dewatering was performed, followed by a 3 minute 2 nd rinse, followed by 1 minute of dewatering.

(2) Evaluation of treated Fabric

The fragrance intensity of the treated fabric (cotton towel) after drying for 18 hours and storage for 5 days at 20 ℃ and 40RH was evaluated organoleptically according to the following 6-stage odor intensity expression method. The fragrance persistence was evaluated by the average score of 8 persons (1 st decimal place) by the professional team according to the following criteria. From the viewpoint of commercial value, it is acceptable to set O or more. The evaluation results are shown in tables 6 to 7.

< 6-stage odor intensity representation >

0: without bad smell

1: barely detectable fragrance

2: fragrance to know what degree of fragrance

3: easily perceivable fragrance

4: strong fragrance

5: strong fragrance

[ evaluation standards ]

Very excellent-: 3.0 min or more

Very excellent: 2.9 to 2.5 points

Very good: 2.4 to 2.0 minutes

O: 1.9 to 1.5 points

And (delta): 1.4 to 1.0 minutes

X: 0.9 min or less

< evaluation of storage stability >

Each example of the detergent composition (100 mL) was filled in a transparent glass bottle (jar, PS-No.11), and the lid was closed and sealed. In this state, the mixture was stored in a thermostatic bath at 5 ℃ or 25 ℃ for 7 days.

After the storage, the liquid appearance was visually observed, and the storage stability of the detergent composition was evaluated according to the following evaluation criteria. And the product is qualified when the delta is more than delta. The evaluation results are shown in tables 6 to 7.

[ evaluation standards ]

O: no precipitated material was seen at the bottom of the vial, which was liquid-flowable.

And (delta): although the precipitated substance was seen at the bottom of the glass bottle, the precipitated substance disappeared (dissolved) upon gentle shaking of the glass bottle.

X: the precipitate was observed at the bottom of the glass bottle, and even if the glass bottle was shaken gently, the precipitate did not disappear, or gelation or cloudiness occurred immediately after the production of the detergent composition.

< evaluation of SR Effect >

TETO cotton cloth (テト cloth) (cotton/polyester 40/60) for evaluation and a cotton knitted fabric were put into a full-automatic electric washing machine (AW-80VC, manufactured by Toshiba, Ltd.) and blended at a bath ratio of 20 times. The liquid detergent 12g of examples 1 and 12 was added thereto, and washing, rinsing, and spin-drying were performed in this order according to the standard recipe. The washing time, rinsing, dewatering, and water amount (set to 36L) were all not adjusted, and the standard settings of the washing machine were used. The temperature of the tap water used was 15 ℃. This washing operation was repeated 5 times. After completion of 5 washing operations, the test cloth was dried overnight, and the dried test cloth was cut into 5 × 5cm pieces. To this evaluation cloth, 50 μ L of a stain-forming fat (a mixture of oleic acid, palmitic acid, myristic acid, lauric acid, triolein, tripalmitin, cetyl palmitate, squalene, and carbon black) was applied, and the applied cloth was dried for 24 hours to prepare a stained cloth.

For this soiled cloth, a washing test was carried out in the following manner.

As the washing tester, a Terg-O-meter (manufactured by American test Co.) was used. The following preparations were used as washing solutions: to 900mL of water was added 300. mu.L of the liquid detergent of comparative example 4, and the mixture was stirred for 30 seconds to prepare a suspension. 900mL of the cleaning solution, 5 pieces of the soiled cloth, and the cleaning woven cloth were put into the cleaning tester, mixed at a bath ratio of 20 times, and washed at 120rpm and 15 ℃ for 20 minutes. Subsequently, the mixture was transferred to a two-tank washing machine (product name: CW-C30A 1-H1, Mitsubishi Motor), dehydrated for 1 minute, washed with tap water (15 ℃ C., 4 ℃ DH)30L for 3 minutes, and air-dried. The reflectance of non-soiled cloth (cloth for evaluation), soiled cloth before washing, and soiled cloth after washing were measured by a color difference meter (product name SE200, manufactured by Nippon Denshoku Co., Ltd.), and the washing rate (%) was calculated by the following equation.

Washing rate (%) - (K/S of soiled cloth before washing-K/S of soiled cloth after washing)/(K/S of soiled cloth before washing-K/S of unsoiled cloth) × 100

Wherein K/S is (1-R/100)²(2R/100) (R represents the reflectance of the soiled Fabric before washing and the reflectance of the soiled Fabric after washing)Rate or reflectance (%) of the non-soiled cloth. The average value of the washing rates of 5 pieces of the soiled cloths was obtained, and the SR effect of the liquid detergents of examples 1 and 12 was evaluated according to the following evaluation criteria using the average value as an index. X and O are acceptable.

[ evaluation criteria for SR effect ] <' > x: the washing rate is more than 10%.

O: the washing rate is more than 7% and less than 10%.

And (delta): the washing rate is more than 4% and less than 7%.

X: the washing rate is less than 4%.

< evaluation of enzyme stability (enzyme Activity residual Rate) >

After the liquid detergents of example 1, example 13 and comparative example 1 were produced, they were stored at 37 ℃ and 4 ℃ for 4 weeks, respectively. The following protease activity measurements were performed on a liquid detergent (37 ℃ storage product) stored at 37 ℃ for 4 weeks and a liquid detergent (4 ℃ storage product) stored at 4 ℃ for 4 weeks.

Determination of protease Activity:

milk Casein (Casein, bone Milk, Carbohydrate and fat Acid Free/Calbiochem (registered trademark)) was dissolved in 1N sodium hydroxide (1mol/L sodium hydroxide solution (1N), manufactured by Kanto chemical Co., Ltd.), the pH was adjusted to 10.5, and the solution was diluted with 0.05M boric Acid (special grade), manufactured by Kanto chemical Co., Ltd.) aqueous solution so that the Milk Casein concentration became 0.6%, thereby preparing a protease substrate.

The obtained liquid detergent was diluted 25-fold by 1g with 3 ° DH hard water (calcium chloride (extra grade), manufactured by kanto chemical corporation), and the obtained diluted solution was used as a sample solution.

5g of the protease substrate was added to 1g of the sample solution, stirred with a vortex mixer for 10 seconds, and then allowed to stand at 37 ℃ for 30 minutes to carry out an enzymatic reaction. Then, 5g of a 0.44M aqueous solution of TCA (trichloroacetic acid (Special grade), manufactured by Kanto chemical Co., Ltd.) as an enzyme reaction terminator was added to the solution, and the mixture was stirred with a vortex mixer for 10 seconds. Then, the solution was allowed to stand at 20 ℃ for 30 minutes to precipitate an unreacted substrate, and the precipitated unreacted substrate was removed with a 0.45 μm filter to collect a filtrate.

The absorbance (absorbance A) of the collected filtrate at a wavelength of 275nm was measured using an ultraviolet-visible spectrophotometer UV-160 manufactured by Shimadzu corporation. The greater the absorbance A, the greater the amount of tyrosine (produced by protease cleavage of the protease substrate) present in the filtrate.

In order to eliminate the influence of absorption other than the target components, 5g of TCA as an enzyme reaction terminator was added to 1g of each sample solution, the mixture was stirred with a vortex mixer for 10 seconds, 5g of the protease substrate was added thereto, the mixture was stirred with a vortex mixer for 10 seconds, and the mixture was removed with a 0.45 μm filter to collect a filtrate. Then, the absorbance of the filtrate at a wavelength of 275nm (absorbance B) was measured using UV-160.

The protease activity residual ratio (%) was calculated from the measurement results of the protease activity by the following formula.

Further, the absorbance value at 275nm of each sample substituted into the following formula was used except for the absorbance value at 600nm measured at the same time because scattered light such as bubbles was excluded from the absorbance.

The protease activity residual rate was (absorbance of 37 ℃ storage A-absorbance of 37 ℃ storage B)/(absorbance of 4 ℃ storage A-absorbance of 4 ℃ storage B). times.100

The enzyme stability was evaluated based on the following criteria using the protease activity residual rate (%) as an index, and the results were "good", and "Δ" as good as possible.

Very good: more than 80 percent.

O: more than 70% and less than 80%.

And (delta): more than 60% and less than 70%.

X: less than 60%.

[ Table 6]

[ Table 7]

As is clear from the results in tables 6 to 7, examples 1 to 13 using the present invention are excellent in the anti-redeposition performance and the fragrance retention property.

In comparative example 1 containing no component (A), the fragrance retention was poor.

B1/B2 was inferior to those of comparative examples 2 and 5, which are outside the range of the present invention, in fragrance retention.

The fragrance retention was inferior to that of comparative example 3 which contained no component (A) and in which B1/B2 was outside the numerical range of the present invention.

In comparative example 4 using polyethyleneimine instead of the component (a), the recontamination prevention performance and fragrance retention were poor.

Industrial applicability of the invention

According to the present invention, a detergent composition having high fragrance retention can be provided.

Claims (6)

1. A detergent composition comprising, in total mass of the detergent composition:

0.01 to 5 mass% of alkylene oxide adduct A of polyalkyleneamine,

A surfactant B comprising 20 to 70 mass% of a nonionic surfactant B1 and 1 to 40 mass% of an anionic surfactant B2, and

the fragrance (C) is added to the perfume (A),

the component B1 contains a nonionic surfactant B11 represented by the following general formula (III) and a nonionic surfactant B12 represented by the following general formula (IV),

the content of the component B11 is 10-80 mass% based on the total mass of the component B,

the mass ratio of component B1/component B2 is 1.0 or more,

R²－C(＝O)O－[(EO)_s/(PO)_t]－(EO)_u－R³…(III)

in the formula (III), R²Is a C7-22 hydrocarbon group; r³An alkyl group having 1 to 6 carbon atoms; s represents an average number of EO repeats of 6 to 2A number of 0; t represents the average number of repetitions of PO and is a number of 0 to 6; u represents the average number of EO repeats, and is a number of 0 to 20; EO represents an oxyethylene group; PO represents an oxypropylene group, and PO represents an oxypropylene group,

R⁴－O－[(EO)_v/(PO)_w]－(EO)_x－H…(IV)

in the formula (IV), R⁴Is a C6-22 hydrocarbon group; v represents an average number of EO repeats, and is a number of 3 to 20; w represents the average number of repetitions of PO and is a number of 0 to 6; x represents the average repeating number of EO, and is a number of 0 to 20; EO represents an oxyethylene group; PO represents an oxypropylene group, and v + x is 14 to 18.

2. The detergent composition according to claim 1, wherein the mass ratio of component b 11/component b12 is 0.1-65,

the content of the component A is 0.05-3 mass%,

the content of the component B1 is 20-60 mass%, the content of the component B2 is 2-35 mass%,

the mass ratio of component B1/component B2 is 1.5 or more.

3. The detergent composition according to claim 1,

the ingredient B1 contains fatty acid methyl ester ethoxylate,

the content of the fatty acid methyl ester ethoxylate is 10% by mass or more with respect to the total mass of the component B.

4. The detergent composition according to claim 1 or 2, wherein the detergent composition further comprises:

component D: a polymer having at least one repeating unit d1 selected from alkylene terephthalate units and alkylene isophthalate units, and an oxyalkylene unit d 2.

5. The detergent composition according to claim 1 or 2, wherein the detergent composition further comprises:

component E: at least 1 kind selected from carboxylic acids represented by the following general formula (VII) and salts thereof, and

component F: an enzyme(s) is (are),

X－R¹－COOH…(VII)

in the formula (VII), R¹Is C1-4 divalent alkyl or arylene, X is-H, -OH, -CH₃or-COOH.

6. The detergent composition of claim 4, further comprising:

component E: at least 1 kind selected from carboxylic acids represented by the following general formula (VII) and salts thereof, and

component F: an enzyme(s) is (are),

X－R¹－COOH…(VII)

in the formula (VII), R¹Is C1-4 divalent alkyl or arylene, X is-H, -OH, -CH₃or-COOH.