CN108699493A - Detergent composition - Google Patents

Abstract

A kind of detergent composition, its surfactant (B) and fragrance (C) for containing the alkylene oxide addition product of polyalkylene amine (A), containing nonionic surfactant (B1) and anion surfactant (B2), the mass ratio indicated by ingredient (B1)/ingredient (B2) is 1.0 or more.

Description

Detergent composition

Technical field

The present invention relates to detergent compositions.

This application claims based on 2 16th, 2016 Japan submit Japanese patent application 2016-027293 priority, And its content is quoted herein.

Background technology

In recent years, for detergent composition, other than the dirt-removing functions as basic function, also it is desirable to have high lasting Property (property of substrate of the flavor residue after washing).

For such expectation, so far, it is easy to remain on the fragrance component of substrate by addition or addition cationic surface is lived Property agent etc. improves fragrance retention.

For example, patent document 1 discloses a kind of composition of the use comprising polyethyleneimine and fragrance, it is suitable for fragrance It is delivered to the fragrance conveying-system on surface.

Existing technical literature

Patent document

Patent document 1:Japanese Patent Laid-Open 2010-31285 bulletins

Invention content

Problem to be solved by the invention

However, in conventional art, workable fragrance is limited or effect aspect is also and insufficient.

The present invention is completed in view of above-mentioned item, is related to the detergent composition with high fragrance retention.Further, this hair It is also excellent that bright recontamination, which prevents performance (performance for the substrate for preventing dirt to be attached to again after washing),.

To the means solved the problems, such as

The present inventor is found that after further investigation:Detergent composition below can solve the above problems.

That is, the present invention has following manner.

[1]A kind of detergent composition, contains:

Alkylene oxide addition product (the alkylen oxide adducts of polyalkylene amine;alkylene oxide adduct)(A),

Including the surfactant (B) of nonionic surfactant (B1) and anion surfactant (B2) and

Fragrance (C),

The mass ratio indicated by ingredient (B1)/ingredient (B2) is 1.0 or more.

[2]Gen Ju [1]The detergent composition, wherein the ingredient (B1) contains fatty acid methyl ester ethoxylate, phase For the gross mass of the ingredient (B), the content of the fatty acid methyl ester ethoxylate is more than 10 mass %.

[3]Gen Ju [1]Huo [2]The detergent composition, wherein the detergent composition also contains:

Ingredient (D):With at least one in terephthalic acid (TPA) alkylene ester unit and alkylene isophthalate unit The polymer of kind repetitive unit (d1) and oxyalkylene units (d2).

[4]Gen Ju [1]~[3]Any one of described in detergent composition, wherein the detergent composition also contains:

Ingredient (E):At least one kind of in the carboxylic acid and its salt indicated by the following general formula (VII) and

Ingredient (F):Enzyme.

X-R¹-COOH···(VII)

Wherein, in formula (VII), R¹For the bivalent hydrocarbon radical or arlydene of carbon number 1~4, X is-H ,-OH ,-CH₃Or-COOH.

The effect of invention

According to the present invention, it is possible to provide the detergent composition with high fragrance retention.

Specific implementation mode

"Detergent composition"

The detergent composition of the present invention contains following compositions (A)~(C).

<Ingredient (A)s >

Ingredient (A) is the alkylene oxide addition product of polyalkylene amine.

As ingredient (A), it can be exemplified below and state ingredient (a1), ingredient (a2).

&#91;Ingredient (a1)s &#93;

Ingredient (a1) is the alkylene oxide addition product of polyalkyleneimine.

The polyalkyleneimine of ingredient (a1) is for example indicated by the following general formula (I).

NH₂-R²¹-(NA-R²¹)_n-NH₂···(I)

In formula (I), R²¹It is separately the alkylidene of carbon number 2~6, A indicates hydrogen atom or the other polyamines based on branch Chain, the integer that n is 1 or more.Wherein, the A will not all hydrogen atoms.

That is, there is branch's polyamines chain in the structure by the polyalkyleneimine that formula (I) indicates.

R²¹For the straight-chain alkyl-sub of carbon number 2~6 or the branched alkylene groups of carbon number 3~6.R²¹The preferably Asia of carbon number 2~4 The alkylidene that alkyl, more preferably carbon number are 2.

Polyalkyleneimine can by conventional method by one kind or two or more polymerize of the alkylene imine of carbon number 2~6 and .As the alkylene imine of carbon number 2~6, ethylenimine, propylidene imines, 1,2- butyleneimines, 2,3- can be enumerated Butyleneimine, 1,1- dimethylethylene imines etc..

As polyalkyleneimine, preferably polyethylene imine (hereinafter also referred to as " PEI ") (in formula (I), R²¹Indicate sub- second Base), polypropylneimine (in formula (I), R²¹Indicate propylidene), more preferably PEI.PEI can be by the way that ethylenimine to polymerize And obtain, in structure, there is the branched structure for including primary, secondary and tertiary amine nitrogen atom.

The integer that n is 1 or more.

The matter average molecular weight of polyalkyleneimine is preferably 200~2000, and more preferably 300~1500, further preferably It is 400~1000, particularly preferably 500~800.

As polyalkyleneimine, the polyalkyleneimine with 5~30 reactive hydrogens preferably in its 1 molecule, more Preferably in its 1 molecule with 7~25 reactive hydrogens polyalkyleneimine, more preferably in its 1 molecule have 10~ The polyalkyleneimine of 20 reactive hydrogens.Herein, " reactive hydrogen " refer to hydrogen atom with high reactivity, in particular to be bonded to nitrogen original The hydrogen atom of son.

Ingredient (a1) can obtain alkylene oxide addition in polyalkyleneimine.As this method, the method for stating can be exemplified below Deng:In the presence of the basic catalysts such as sodium hydroxide, potassium hydroxide, sodium methoxide, make epoxy under conditions of 100~180 DEG C The addition of the alkylene oxides such as ethane is in the method for the polyalkyleneimine as initial substance.

As alkylene oxide, the alkylene oxide of carbon number 2~4 can be enumerated.As the alkylene oxide, ethylene oxide, epoxy can be enumerated Propane, epoxy butane, optimization ethylene oxide and propylene oxide, more preferable ethylene oxide.

As ingredient (a1), the ethylene oxide adduct of polyalkyleneimine, the epoxy of polyalkyleneimine can be enumerated The epoxy ethane-epoxy propane addition product etc. of propane addition product, polyalkyleneimine.In addition, the ring of the polyalkyleneimine Oxidative ethane-propylene oxide adduct is obtained by by ethylene oxide and propylene oxide addition in polyalkyleneimine, epoxy second Alkane can be arbitrary for addition sequence, the addition form (block-wise, random shape) of polyalkyleneimine with propylene oxide.

As ingredient (a1), preferably ethylene oxide-ring of the ethylene oxide adduct of polyalkyleneimine, polyalkyleneimine Ethylene Oxide addition product, the more preferably ethylene oxide adduct of polyalkyleneimine.

It is preferably average for 1 atom of reactive hydrogen possessed by the polyalkyleneimine as raw material as ingredient (a1) Addition has an addition product of 5~40 alkylene oxides, and more preferably averagely addition has the addition products of 10~30 alkylene oxides.That is, for Every 1 mole of reactive hydrogen possessed by polyalkyleneimine as raw material, preferably averagely addition has 5~40 moles of alkylene oxide Addition product, more preferably averagely addition have 10~30 moles alkylene oxide addition product.

The matter average molecular weight of ingredient (a1) is preferably 1000~80000, and more preferably 2000~50000, further preferably It is 5000~30000, particularly preferably 10000~20000.

In addition, matter average molecular weight indicates, it is based on the calibration curve of PEG (polyethylene glycol), THF (tetrahydrofuran) will be used as molten Agent, the value to be converted by GPC (gel permeation chromatography) values measured.

As ingredient (a1), can illustrate the compound such as indicated by formula (I-a).

&#91;Change 1&#93;

In formula (I-a), R²²It is separately the alkylidene of carbon number 2~6, m is separately 1 or more number.

R²²The alkylidene that the alkylidene that preferably carbon number is 2 or 3, more preferably carbon number are 2.M is (R²²O averaged repeating numbers), Preferably 5~40, more preferably 10~30.

In formula (I-a) ,-(R²²O)_mIn-H ,-R²²O- both can be in that random shape is bonded, and also can be in that block-wise is bonded.

As ingredient (a1), composite both can be used, it is possible to use commercially available product.

As commercially available product, the trade name " Sokalan HP20 " for such as BASF AG's manufacture that can illustrate.

<Ingredient (a2)s >

Ingredient (a2) is the alkylene oxide addition product of the polyalkylene amine indicated by lower formula (II).

NH₂(R³¹NH)_lH···(II)

In formula (II), R³¹For the alkylidene of carbon number 2~6, the number that l is 1 or more.

R³¹For the straight-chain alkyl-sub of carbon number 2~6 or the branched alkylene groups of carbon number 3~6.R³¹The preferably Asia of carbon number 2~4 The alkylidene that alkyl, more preferably carbon number are 2.

As polyalkylene amine, preferably poly- ethylene amines.As poly- ethylene amines, can enumerate ethylenediamine, diethylenetriamines, Trien, tetren, penten etc..In addition, these poly- ethylene amines can pass through well known manufacture Method for example makes ammonia and ethylene dichloride react and obtain.

The number that l is 1 or more.

The matter average molecular weight of polyalkylene amine is preferably 60~1800, more preferably 60~1000, more preferably 60~ 800。

As polyalkylene amine, the polyalkylene amine with 6~30 reactive hydrogens preferably in its 1 molecule, more preferably For the polyalkylene amine with 7~20 reactive hydrogens in its 1 molecule.

Ingredient (a2) can obtain alkylene oxide addition in polyalkylene amine.The reaction can equally be carried out with ingredient (a1). As alkylene oxide, the alkylene oxide of carbon number 2~4 can be enumerated.As the alkylene oxide, ethylene oxide, propylene oxide, epoxy can be enumerated Butane, optimization ethylene oxide and propylene oxide, more preferable ethylene oxide.

As ingredient (a2), the ethylene oxide adduct of polyalkyleneimine, the epoxy third of polyalkyleneimine can be enumerated The epoxy ethane-epoxy propane addition product etc. of alkane addition product, polyalkyleneimine.

As the alkylene oxide addition product of polyalkylene amine, the preferably ethylene oxide adduct of polyalkylene amine, polyalkylene amine Epoxy ethane-epoxy propane addition product, the ethylene oxide adduct of more preferable polyalkylene amine.

It is preferably average to add for 1 atom of reactive hydrogen possessed by the polyalkylene amine as raw material as ingredient (a2) At the addition product for having 5~40 alkylene oxides, more preferably averagely addition has the addition products of 10~30 alkylene oxides.That is, for making Every 1 mole of reactive hydrogen possessed by polyalkylene amine for raw material, preferably averagely addition have 5~40 moles alkylene oxide plus At object, more preferably averagely addition have 10~30 moles alkylene oxide addition product.

The matter average molecular weight of ingredient (a2) is preferably 1000~80000, and more preferably 2000~50000, further preferably It is 5000~30000, particularly preferably 10000~20000.

As ingredient (A), preferred component (a1).In ingredient (a1), the poly- ethylidene particularly preferably indicated by formula (I-a) is sub- The ethylene oxide adduct of amine.

Ingredient (A) both can be used alone a kind, but also two or more is applied in combination.

Relative to the gross mass of detergent composition, the content of ingredient (A) is preferably 0.01~5 mass %, and preferably 0.05~3 Quality %, more preferably 0.1~2 mass %.

When the content of ingredient (A) is below above-mentioned upper limit value, the mixing degree of freedom for keeping other ingredients is become easy.

When the content of ingredient (A) is more than above-mentioned lower limiting value, raising fragrance retention is become easy, and becomes easy raising stable storing Property.

<Ingredient (B)s >

Ingredient (B) be containing nonionic surfactant (hereinafter also referred to as ingredient (B1)) and anion surfactant (with Under, also referred to as ingredient (B2)) surfactant.

&#91;Ingredient (B1)s &#93;

Ingredient (B1) is nonionic surfactant.

As ingredient (B1), for example following (1)~(8) can be arranged.

(1) being averaged on 1 yuan of aliphatic alcohol of carbon number 6~22 (preferably 8~18), (preferably 3~20 rub for 3~30 moles of addition You, further preferred 5~20 moles) carbon number 2~4 alkylene oxide obtained by polyoxyalkylene alkyl (or alkenyl) ether.Wherein, it fits Suitable is polyxyethylated (or alkenyl) ether, polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether.As used herein 1 First aliphatic alcohol can enumerate primary alconol, secondary alcohol.In addition, its alkyl is with or without branch.As aliphatic alcohol, preferably primary alconol.

(2) polyxyethylated (or alkenyl) phenyl ether.

(3) addition has the fatty acid alkyl esters alcoxylates of alkylene oxide between the ester bond of long-chain fat acid alkyl ester.

(4) polyoxyethylene sorbitan fatty acid ester.

(5) polyoxyethylene sorbitol aliphatic ester.

(6) polyoxyethylene fatty acid ester.

(7) Crodaret.

(8) fatty acid glyceride.

As nonionic surfactant, the nonionic surfactant of preferably above-mentioned (1) or (3), wherein preferably The nonionic surfactant indicated by the following general formula (III) or (IV).

R²- C (=O) O-&#91;(EO)_s/(PO)_t&#93;-(EO)_u-R³···(III)

R⁴-O-&#91;(EO)_v/(PO)_w&#93;-(EO)_x-H···(IV)

(in formula (III), R²It is the alkyl of carbon number 7~22;R³For the alkyl of carbon number 1~6;S indicates the averaged repeating numbers of EO, is 6 ~20 number;T indicates the averaged repeating numbers of PO, is 0~6 number;U indicates the averaged repeating numbers of EO, is 0~20 number;EO tables Show oxygen (change) vinyl;PO indicates oxygen (change) acrylic.

In formula (IV), R⁴It is the alkyl of carbon number 6~22;V indicates the averaged repeating numbers of EO, is 3~20 number;W indicates that PO's is flat Equal repeat number is 0~6 number;X indicates the averaged repeating numbers of EO, is 0~20 number;EO indicates oxygen (change) vinyl;PO is indicated Oxygen (change) acrylic.)

In formula (III), R²For the alkyl of carbon number 7~22.R²Carbon number be preferably 9~21, more preferably 11~21.

R²Preferably alkyl, alkenyl.

R²It can be any one of linear chain or branched chain.

From the point of view of further raising washing force, R²The preferably alkyl or straight chain of the carbon number 7~22 of linear chain or branched chain Or the alkenyl of the carbon number 7~22 of branch.

R³Can be any one of linear chain or branched chain for the alkyl of carbon number 1~6.

Wherein, preferably methyl and ethyl.

In formula (III), s, u are separately the number for the averaged repeating numbers for indicating EO.

S+u is preferably 6~20, more preferably 6~18, further preferably 11~18, particularly preferably 14~18.It is above-mentioned When more than lower limiting value, become easier to improve liquid stability.When it is below above-mentioned upper limit value, become easier to improve washing Power.

In formula (III), t is the number for the averaged repeating numbers for indicating PO.

The number that t is 0~6, preferably 0~3, more preferably 0.When it is below above-mentioned upper limit value, become easier to improve liquid Stability.

, &#91 when t is 1 or more;(EO)_s/(PO)_t&#93;In, oxygen (change) vinyl can be both bonded with oxygen (change) acrylic in random shape, Can be in that block-wise is bonded.

In addition, in this specification, averaged repeating numbers can pass through the measurement such as gas chromatography (gas chromatography).

In formula (IV), R⁴For the alkyl of carbon number 6~22.

In formula (IV), from the point of view of further raising washing force, R⁴Carbon number be preferably 10~22, more preferably 10~ 20, more preferably 10~18.

R⁴It can be linear chain or branched chain.

As preferred R⁴- O- can enumerate the group indicated by the following general formula (V).

(R¹⁰¹)(R¹⁰²)CH-O-···(V)

(in formula (V), R¹⁰¹And R¹⁰²Separately indicate the alkyl of hydrogen atom or chain;R¹⁰¹With R¹⁰²Total carbon number be 5~21.)

R¹⁰¹With R¹⁰²Total carbon number be preferably 9~21, more preferably 9~19, more preferably 9~17.

R¹⁰¹And R¹⁰²It can be linear chain or branched chain.

As R⁴, it is preferably specifically the alkyl of the secondary alcohol from carbon number 12~14.

In formula (IV), v, x are separately the number for the averaged repeating numbers for indicating EO.

V+x is preferably 3~20, more preferably 5~18, further preferably 6~18, particularly preferably 11~18, further excellent It is selected as 14~18.When it is more than above-mentioned lower limiting value, become easier to improve liquid stability.It is below above-mentioned upper limit value When, it becomes easier to improve washing force.

In formula (IV), w is the number for the averaged repeating numbers for indicating PO.

The number that w is 0~6, preferably 0~3, more preferably 0.When it is below above-mentioned upper limit value, become easier to improve liquid Stability.

, &#91 when w is 1 or more;(EO)_v/(PO)_w&#93;In, oxygen (change) vinyl can be both bonded with oxygen (change) acrylic in random shape, Can be in that block-wise is bonded.

The distribution of EO or PO in formula (III) are changed according to reaction method when manufacturing.For example, being urged used as common alkali Sodium hydroxide, potassium hydroxide of agent etc., by ethylene oxide, propylene oxide addition when the raw material, the distribution of v or w become wider. Use described in Japanese Patent Laid-fair 6-15038 bulletins is added with Al³⁺,Ga³⁺,In³⁺,Tl³⁺,Co³⁺,Sc³⁺,La³⁺, Mn²⁺The specific alkoxylating catalysts such as the magnesia of equal metal ions, by ethylene oxide, propylene oxide addition when the raw material, v or The distribution of w becomes narrow.

It is indicated by the nonionic surfactant (hereinafter also referred to as ingredient (b11)) of formula (III) expression and by formula (IV) Nonionic surfactant (hereinafter also referred to as ingredient (b12)), stenosis rate preferably more than 20 mass %, more preferably exists 25 mass % or more.

The stenosis rate is higher, more available good washing force.In addition, the stenosis rate is more than 20 mass %, especially exist When 25 mass % or more, the few detergent composition of the raw material foul smell of acquisition surfactant is become easy.

When manufacturing ingredient (b11) by conventional method, in product, and ingredient (b11) while coexisting and be helpless to washing force Ingredient is (for example, the aliphatic ester of raw material, the s of the nonionic surfactant indicated by formula (III) as ingredient (b11) are 1 Or 2 ethylene oxide adduct), so that stenosis rate is reduced.Therefore, when stenosis rate is high, the ingredient coexisted is fully few, becomes difficult Declined with leading to the problem of washing force, raw material foul smell.The case where ingredient (b12) is also same.

The upper limit value of the stenosis rate is not particularly limited, but is preferably essentially 80 mass % or less.

As the stenosis rate, from the point of view of improving liquid stability and dissolubility, more preferably 20~50 mass %, more Preferably 20~40 mass %.

Herein, in this specification, " stenosis rate " refers to the ratio of the distribution of the different ethylene oxide adduct of addition molal quantity of EO Example is indicated by following mathematical expressions (S).

&#91;Number 1&#93;

&#91;In formula, p_maxIndicate in whole ethylene oxide adducts most the EO's of existing ethylene oxide adduct plus At molal quantity.I indicates the addition molal quantity of EO.Yi is indicated present in whole ethylene oxide adducts, the addition mole of EO Number is the ratio (quality %) of the ethylene oxide adduct of i.&#93;

The stenosis rate can be controlled according to the manufacturing method etc. of such as ingredient (b11) or ingredient (b12).To as at The manufacturing method of (b11) is divided to be not particularly limited, such as can be by using surface-modified O composite metallic oxide catalyst Ethyleneoxide addition is set to polymerize in the method (referring to Japanese Patent Laid-Open 2000-144179 bulletins) of fatty acid alkyl esters, To be easily manufactured.As the manufacturing method of ingredient (b12), such as can be by using surface-modified metal composite oxide Catalyst makes ethyleneoxide addition polymerization in the method for the alcohol of carbon number 6~22, to manufacture.

As the suitable substance of the surface-modified O composite metallic oxide catalyst used in correlation technique, can specifically arrange It lifts:By metal hydroxides etc. carried out surface modification be added with metal ion (Al³⁺,Ga³⁺,In³⁺,T1³⁺,Co³⁺,Sc^{3 +},La³,Mn²⁺Deng) the O composite metallic oxide catalysts such as magnesia, pass through metal hydroxides and/or metal alkoxide Etc. the burned material catalyst for the hydrotalcite for having carried out surface modification.

In having used the surface of the O composite metallic oxide catalyst to be modified, preferably by metal composite oxide and metallic hydrogen Oxide and/or metal alkoxide are used in combination.In this case, relative to 100 mass parts of metal composite oxide, preferably make metal The ratio of hydroxide and/or metal alkoxide is 0.5~10 mass parts, more preferably 1~5 mass parts.

In addition, the manufacturing method as other ingredients (b11), has by by the mixtures tune such as alkaline earth metal compound and oxyacid The alkoxylating catalyst of system, by alkylene oxide addition in the method for fatty acid alkyl esters.About above-mentioned alkoxylating catalyst, such as No. 04977609 bulletin of Japanese Patent No., International Publication WO1993004030 bulletins, International Publication WO2002038269 public affairs It discloses, can be illustrated such as by the alkali salt of carboxylic acid and/or hydroxycarboxylic acid in report, International Publication WO2012028435 bulletins etc. Alkali salt and sulfuric acid etc. mixture modulation alkoxylating catalyst etc..

As nonionic surfactant, commercially available product both can be used, it is possible to use be made by well known synthetic method Product.As well known manufacturing method, about ingredient (b11), such as can be by making ethylene oxide and/or propylene oxide addition It polymerize the method in fatty acid alkyl esters to manufacture.About ingredient (b12), such as can be by making ethylene oxide and/or epoxy third Alkane addition polymerization is manufactured in the method for the alcohol of carbon number 6~22.

Ingredient (B1) both can be used alone a kind, but also two or more is applied in combination.

As ingredient (B1), preferred component (b11), the compound that the t in further preferred formula (III) is 0 is (that is, polyoxyethylene Fatty acid alkyl esters), the R in particularly preferred formula (III)³For polyoxyethylene fatty acid methyl esters (the fatty acid methyl ester ethoxy of methyl Glycolylate) (hereinafter, being designated as " MEE ".).

Relative to the gross mass of ingredient (B), the content of fatty acid methyl ester ethoxylate is preferably more than 10 mass %, more preferably For 15~90 mass %, more preferably 20~80 mass %.

When the content of fatty acid methyl ester ethoxylate is below above-mentioned upper limit value, raising fragrance retention is become easy.

When the content of fatty acid methyl ester ethoxylate is more than above-mentioned lower limiting value, raising fragrance retention is become easy, is become simultaneously Being easy raising recontamination prevents performance.

In the detergent composition of the present invention, preferably ingredient (b11) and ingredient (b12) are applied in combination.

The mass ratio indicated by ingredient (b11)/ingredient (b12) is preferably 0.1~65 (hereinafter also referred to as b11/b12 ratios), more excellent It is selected as 0.5~50.

When b11/b12 ratios are in above-mentioned numberical range, raising fragrance retention is become easy, while becoming easy raising recontamination to prevent Performance.

Relative to the gross mass of ingredient (B), the content of ingredient (B1) is preferably 20~90 mass %, and more preferably 25~80 Quality %, more preferably 30~70 mass %.

When the content of ingredient (B1) is below above-mentioned upper limit value, raising fragrance retention is become easy.

When the content of ingredient (B1) is more than above-mentioned lower limiting value, raising fragrance retention is become easy, while it is dirty again to become easy raising Dye prevents performance.

Relative to the gross mass of detergent composition, the content of ingredient (B1) is preferably 20~70 mass %, more preferably 20~60 mass %, further preferably 35~60 mass %, particularly preferably 40~60 mass %.

When the content of ingredient (B1) is below above-mentioned upper limit value, raising fragrance retention is become easy.

When the content of ingredient (B1) is more than above-mentioned lower limiting value, raising fragrance retention is become easy, while it is dirty again to become easy raising Dye prevents performance.

The mass ratio indicated by ingredient (A)/ingredient (B1) is preferably 0.001~1.0 (hereinafter also referred to as A/B1 ratios), more Preferably 0.005~0.5, more preferably 0.01~0.25.

When A/B1 ratios are below above-mentioned upper limit value, fragrance retention is easy to improve, while the easy recontamination that improves prevents performance.

When A/B1 ratios are more than above-mentioned lower limiting value, it is easy to improve fragrance retention.

&#91;Ingredient (B2)s &#93;

Ingredient (B2) is anion surfactant.

As anion surfactant, it can be exemplified below and state (1)~(12).

(1) methyl esters, ethyl ester or the propyl ester salt of the saturation of carbon number 8~20 or unsaturated alpha-sulfo-fatty acid.

(2) alkylbenzene sulfonate (LAS or ABS) of the straight-chain or branched of the alkyl with carbon number 8~18.

(2) alkane sulfonate of carbon number 10~20.

(4) alpha-alkene sulfonate (AOS) of carbon number 10~20.

(5) alkyl sulfate of carbon number 10~20 or alkenyl sulfate (AS).

(6) be averaged any one of 0.5~10 mole alkylene oxide of carbon number 2~4 of addition or ethylene oxide (EO) and ring The alkane of the straight-chain or branched with carbon number 10~20 of Ethylene Oxide (PO) (molar ratio EO/PO=0.1/9.9~9.9/0.1) Polyoxyalkylene alkyl (or alkenyl) ether sulfate (AES) of base (or alkenyl).

(7) be averaged any one of 3~30 moles alkylene oxide of carbon number 2~4 of addition or ethylene oxide and propylene oxide The alkyl (or alkenyl) of the straight-chain or branched with carbon number 10~20 of (molar ratio EO/PO=0.1/9.9~9.9/0.1) Alkyl (or alkenyl) phenyl ether sulfate.

(8) be averaged any one of 0.5~10 mole alkylene oxide of carbon number 2~4 of addition or ethylene oxide and epoxy third Alkyl (or the alkene of the straight-chain or branched with carbon number 10~20 of alkane (molar ratio EO/PO=0.1/9.9~9.9/0.1) Base) alkyl (or alkenyl) ether carboxylate.

(9) the alkyl polyols ether sulfate as the alkyl glycerol ether sulfonic acid of carbon number 10~20.

(10) long-chain (carbon number 8~20) monoalkyl, dialkyl group or sesquialter alkylphosphonic.

(11) polyoxyethylene monoalkyl, dialkyl group or sesquialter alkylphosphonic.

(12) higher fatty acids or its salt.Average carbon number be 10~20 (preferably carbon numbers 12~18) higher fatty acids or its Salt.

The anion surfactant other than above-mentioned illustration can be used.It can illustrate such as alkyl ether carboxy acid salt, polyoxyalkylene ether The carboxylic acid types anionic surface such as carboxylate, alkyl carboxylates or eneamide ether carboxylate, acyl amino carboxylate is lived Property agent;Alkyl phosphate salt, polyoxyalkylene alkyl phosphate ester salt, polyoxyalkylene alkyl phenyl phosphate ester salt, fatty acid glyceride Phosphate types anion surfactant such as monophosphates etc..

As anion surfactant, the anion surfactant of preferably above-mentioned (2) or (6).

As the polyoxyalkylene alkyl sulfate of (6), specifically preferably by the compound of logical formula (VI) expression.

R⁴⁰-O-&#91;(EO)_m/(PO)_n]–SO₃ ^﹣M⁺···(VI)

&#91;In formula (VI), R⁴⁰For the linear or branched alkyl group of carbon number 8~20.EO indicates that oxygen (change) vinyl, PO indicate oxygen (change) Acrylic.M indicates the averaged repeating numbers of EO, is 1 or more number.N indicates the averaged repeating numbers of PO, is 0~6 number.M⁺It is anti- Counter cation (counter cation)., &#91 when n is more than 0;(PO)_m(EO)_n&#93;In PO and EO, both can be in block-wise arrange, also may be used It is arranged in random shape.In addition, about PO and EO, PO is bonding in " R⁴⁰- O- ", EO are bonding in " R⁴⁰-O-".&#93;

As polyoxyalkylene alkyl sulfate, it is however preferred to have the linear or branched alkyl group of carbon number 10~20, average addition have 1 The polyoxyalkylene alkyl sulfate of~5 moles of alkylene oxide.

As the carbon number of alkyl, preferably 10~20, more preferably 12~14.Specifically, dodecyl, tridecane can be enumerated Base, myristyl etc..Wherein, preferred dodecyl.

The averaged repeating numbers of EO are preferably 1~5, and more preferably 1~3.

The averaged repeating numbers of PO are preferably 0~3, and more preferably 0.

Preferably, whole relative to the polyoxyalkylene alkyl sulfate indicated by formula (VI), contain 35~55 mass %'s The compound of m=0, n=0 in above-mentioned formula (VI).

The form of salt as anion surfactant can enumerate the alkali metal salts such as sodium salt, sylvite;The alkaline earths such as magnesium salts gold Belong to salt;The alkanolamines such as monoethanolamine salt, diethanolamine salt;Ammonium salt etc..Wherein, preferred as alkali salt.

As the manufacturing method of anion surfactant, such as in the case of LAS, can be made by following methods It makes:Using sulfuric anhydride by alkylbenzene sulfonation, the method neutralized using alkali.For example, in the case of AES, it can be by following Method manufactures:So that sulfuric anhydride is reacted with polyoxyalkylene alkyl, or chlorosulfonic acid is made to be reacted with polyoxyalkylene alkyl, carries out sulphur Change, the method neutralized using alkali.

In the detergent composition of the present invention, preferably AES and LAS and higher fatty acids or its salt are applied in combination.

Ingredient (B2) both can be used alone a kind, but also two or more is applied in combination.

Relative to the gross mass of ingredient (B), the content of ingredient (B2) is preferably 2~50 mass %, more preferably 5~45 matter Measure %, more preferably 10~40 mass %.

When the content of ingredient (B2) is below above-mentioned upper limit value, raising fragrance retention is become easy.

When the content of ingredient (B2) is more than above-mentioned lower limiting value, raising fragrance retention is become easy, while it is dirty again to become easy raising Dye prevents performance.

Relative to the gross mass of detergent composition, the content of ingredient (B2) is preferably 1~40 mass %, and more preferably 2 ~35 mass %, more preferably 5~30 mass %.

When the content of ingredient (B2) is below above-mentioned upper limit value, raising fragrance retention is become easy.

When the content of ingredient (B2) is more than above-mentioned lower limiting value, raising fragrance retention is become easy, while it is dirty again to become easy raising Dye prevents performance.

The mass ratio indicated by ingredient (A)/ingredient (B2) is preferably 0.01~5 (hereinafter also referred to as A/B2 ratios), more preferably It is 0.05~2, more preferably 0.1~1.

When A/B2 ratios are below above-mentioned upper limit value, raising fragrance retention is become easy, while becoming easy and improving preventing property of recontamination Energy.

When A/B2 ratios are more than above-mentioned lower limiting value, raising fragrance retention is become easy.

The mass ratio (hereinafter also referred to as B1/B2 ratios) indicated by ingredient (B1)/ingredient (B2) is 1.0 or more, preferably greater than 1.0, further preferably 1.5 or more, particularly preferably 2.0 or more.In addition, B1/B2 ratios are preferably 30 hereinafter, more preferably 15 Hereinafter, further preferably below 10.Specifically, B1/B2 ratios be preferably 1.0~30, more preferably above 1.0 and 15 hereinafter, Further preferably 1.5~10.

When B1/B2 ratios are below above-mentioned upper limit value, raising fragrance retention is become easy, while becoming easy and improving preventing property of recontamination Energy.

When B1/B2 ratios are more than above-mentioned lower limiting value, raising fragrance retention is become easy.

&#91;Yang Lizibiaomianhuoxingji &#93;

As cationic surfactant, can illustrate such as alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl benzyl diformazan The cationic surfactant etc. of base ammonium salt, Fixanol.As these salt, the alkali metal salts such as sodium, potassium can be enumerated;Magnesium Equal alkali salts;Alkanolamines such as monoethanolamine, diethanol amine etc..

Cationic surfactant both can be used alone a kind, but also two or more is applied in combination.

Relative to the gross mass of detergent composition, the content of cationic surfactant is preferably 0~10 mass %, more preferably For 0~5 mass %.

&#91;Liang Xingbiaomianhuoxingji &#93;

As amphoteric surfactant, can illustrate such as alkyl betaine-type, alkyl amido betaine type, imidazoline type, alkyl ammonia Base sulfonic acid type, alkyl aminocarboxylic acid's type, alkylamide carboxylic acid type, amidoamino acid type, phosphatic type amphoteric surfactant etc..

Amphoteric surfactant both can be used alone a kind, but also two or more is applied in combination.

Relative to the gross mass of detergent composition, the content of amphoteric surfactant is preferably 0~10 mass %, more preferably 0~5 mass %.

Relative to the gross mass of detergent composition, the content of ingredient (B) is 15~70 mass %, more preferably 20~65 Quality %.

When the content of ingredient (B) is below above-mentioned upper limit value, raising fragrance retention is become easy.

When the content of ingredient (B) is more than above-mentioned lower limiting value, raising fragrance retention is become easy, while becoming easy raising recontamination Prevent performance.

<Ingredient (C)s >

Ingredient (C) is fragrance.

Ingredient (C) is fragrance." fragrance " is the product containing at least one kind of fragrance component, and being added as needed on solvent, (fragrance is used Solvent).Fragrance component can suitably be selected according to desirable fragrance, usually combine a variety of fragrance components.

It as fragrance component, is not particularly limited, maying be used at detergent, fiber processing agent, hair cosmetic composition etc. usually makes Fragrance component.As the specific example of such fragrance component, can illustrate as phenols as described below, alcohols, carboxylic acids, Aldehydes, ethers, esters, hydro carbons, ketone, lactone, Moschus class, natural perfume material, animal spice etc..

As above-mentioned carboxylic acids, there is no particular restriction, can suitably be selected, can be illustrated such as geranic acid, lemongrass according to purpose Acid, phenylpropionic acid, cinnamic acid, 2- methyl -2- penetenoic acids, ortho-aminobenzoic acid, benzoic acid, phenylacetic acid etc..

As above-mentioned phenols, there is no particular restriction, can suitably be selected, can be illustrated such as eugenol, isobutyl according to purpose Eugenol, methyl iso eugenol, ethyl isobutyl eugenol, ethyl eugeno, benzyl eugenol, the different clove tree of benzyl Phenol, eugenyl acetate, acetyl group isoeugenol, methyleugenol, raspberry ketone, vanillin propylene glycol acetal, water Poplar acetoacetic ester, benzyl salicylate etc..

As above-mentioned alcohols, there is no particular restriction, can suitably be selected, can be illustrated such as Asiatic sweet leaf alcohol according to purpose (Bacdanol), citronellol, dihydromyrcenol, dihydro linalool, geraniol, linalool, nerol, santalol (Sandalore), Santalex, terpinol, tetrahydrolinalool, benzyl carbinol, trans- -2- hexenols, trans- -3- hexenols, the moon Osmanthus enol, dihydromyrcenol, 2,6-Dimethyl-2-octanol, terpinol, farnesol (farnesol), nerolidol (nerolidol), 1- octanols, 1 nonyl alcohol, leaf alcohol (leaf alcohol), menthol, matsutakealcohol (matsutakeol), 1,8- cineols (cineol), in chavicol (chavicol), carvacrol (carvacrol), cuminyl alcohol (cumin alcohol), anise alcohol, hundred Phenol, tetrahydrolinalool, benzylalcohol, beta-phenyl alcohol, bata-phenethyl alcohol, styracitol (styralyl alcohol), cinnamyl alcohol, phenoxy group Ethyl alcohol, linalool oxide (linalool oxide), guaiacol (guaiacol), laurine, nerol (nerol), Cedrol (cedrol), 2- butene-1-ols (Santalinol), imperial saliva alcohol (Ambrinol), timberol (Timberol), ice Piece, isoborneol, polysantalol (Polysantol), vanillic aldehyde, maltol, ethylmaltol, vetiverol (vetiverol), Patchoulicalcohol (patchouli alcohol), aurantiol, anethole, 4- damascols (4-damascol), the fluffy botany bar gum of lattice (galbanum resinoid) etc..

As above-mentioned aldehydes, there is no particular restriction, can suitably be selected, can be illustrated such as undecylene aldehyde, bay according to purpose Aldehyde, the 2- methyl hendecanals (aldehyde C-12MNA), Myracaldehyde (myrac aldehyde), jasminal, cyclamen aldehyde, lemon Aldehyde, citronellal, ethyl vanillin, piperonal (heliotropin), anisaldehyde, jasmonal H, octanal, Ligustral, Lilial (Lilial), lyral (lyral), ligustral (Triplal), vanillic aldehyde (vanillin), helional (Helional), aldehyde C-9, capraldehyde, the hendecanal, lauric aldehyde, cis- -3- hexanals, benzaldehyde, flores convallariae aldehyde (muguet Aldehyde), Du's pik aldehyde (Dupical), bougeonal (Bourgeonal), cinnamic acid, hexyl jasmone (Jasmal), glossy privet acetal (Ligantraal) etc..

As above-mentioned ethers, there is no particular restriction, can suitably be selected, can be illustrated such as cedrol methyl ether according to purpose (cedramber), ambergris ether (Grisalva), β-naphthol methyl ether, bromelia, herboxide (trans- 5- isopropenyls -2- Methyl -2- vinyl tetrahydrofuran), rose oxide etc..

As above-mentioned esters, there is no particular restriction, can suitably be selected, can be illustrated such as according to purpose:Cis- -3- hexenyls Acetic acid esters, cis- -3- hexenyls propionic ester, cis- -3- hexenyl salicylates, narceol, acetic acid are to tertiary butyl ring Own ester, pentyl acetate, jessamona, amyl salicylate, Ergol, benzyl acetate, cedryl acetate, second Sour citronellyl acrylate, decahydronaphthalene-betanaphthyl acetic acid esters, dimethyl benzyl carbinyl acetate, tricyclo decenyl propionate (ERICA PROPIONATE), ethyl acetoacetate, cyclacet (ERICA ACETATE), geranyl acetate, geranyl formate, Citronellyl formate, neryl formate, dihydrojasmonate (Hedione), bergamio, beta-phenyl ethylhexoate, Cyclacet, cinnamyl acetate, 1-Hexyl salicylate, methyl phenyl carbinyl acetate (styralyl acetate), acetic acid pine tar Ester, vetacetyl, verdox, Manzanate (2 methyl valeric acid ethyl ester), allyl heptanoate, amyl Glycol allyl propionate (allyl amyl glycolate), ethyl acetate, neryl acetate, isobornyl acetate, adjacent aminobenzene Cis- -3- the hexene esters of methyl formate, ortho-aminobenzoic acid, ortho-aminobenzoic acid phenyl chlorocarbonate, ortho-aminobenzoic acid cinnamic ester, N- Methyl anthranilic acid methyl esters, tricyclo decenyl propionate, benzyl propionate, methyl jasmonate, methyl cinnamate, cinnamic acid second Ester, ethyl -2,2,6- trimethyl-cyclohexanes carbonic ester, fruity ester (FRUITATE) etc..

As above-mentioned hydro carbons, there is no particular restriction, can suitably be selected, can be illustrated such as (R)-4-isopropenyl-1-methyl-1-cyclohexene, australene according to purpose Alkene, nopinene, laurene, 3- carenes, β-carypohyllene, p-cymene, cedrene, citronellyl nitrile, lemonile (Lemonile), Yin Diindyl, 6- isopropyl quinolines, isobutyl quinoline, 2- isobutyl quinolines, benzothiazole, peppermint sulfide (Mint sulfide) etc..

As above-mentioned ketone, there is no particular restriction, can suitably be selected, can be illustrated such as α-ionone, β-according to purpose Irisone, methyl-betanaphthyl ketone, α-damascone, β-damascone, δ-damascone (δ-damascone), cis- jasmine Ketone, methylionone, allyl ionone, cashmeran (Cashmeran), dihydro jasmone, vertofix coeur (Vertofix), isolongitolanone (isolongifolanone), can end ketone (Koavone), rosalin (rosephenone), imperial court's ketone (DYNASCONE), nootkatone (Nootkatone), carvol, menthones, Hai Feng Quan " (Floralozone), damascenone (damascenone), watermelon ketone (Calone), isojasmone, ionone, crystal violet are fragrant Ketone, tonalid (Tonalide), Verdox, IsoESuper etc..

As above-mentioned lactone, there is no particular restriction, can suitably be selected according to purpose, can illustrate as γ-decalactone, Gamma-undecalactone, nonyl lactone, γ-dodecalactone, cumarin, ambrox (Ambroxan), ambrettolide (ambrettolide), pentadacanolide (Pentalide), cyclopentadecylene lactone (Habanolide), Te Lasi Moschus (Traseolide) etc..

As above-mentioned Moschus class, there is no particular restriction, can suitably be selected, can be illustrated such as pentadacanolide according to purpose (cycropentadecanolide), brazilic acid glycol ester (ethylene brassylate), Jiale muskiness (Galaxolide), muskone (musk ketone), tonalid (tonalide), nitro musk (nitro musk), certain herbaceous plants with big flowers Moschus (musk ambrette), musk tibetene (musk tibetene), muskone (muscone), ambrettolide (ambrettolide), cyclohexadecanolide (cyclohexadecanolide), Jiale muskiness (Galoxolide) class etc..

As above-mentioned natural perfume material, there is no particular restriction, can suitably be selected, can be illustrated such as orange oil, lemon according to purpose Oil, limette oil (lime oil), petit grain oil (petitgrain oil), shaddock oil, neroli oil (neroli oil), bergamot oil (bergamot oil), lavender oil, lavandin oil (lavandin oil), abies oil (abies oil), fennel oil, the moon Bay leaves 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 (Ha ッ カ oil), Spearmint oil, eucalyptus oil (eucalyptus oil), lemongrass oil, patchouli oil, jasmine oil, attar of rose, cedar oil (cedar Oil), vetiver oil (vetiver oil), galbanum oil (galbanum oil), oak moss oil (oak moss oil), pine tar, camphor tree Cerebrol, Oleum Ligni Santali, shiu oil, turpentine oil (turpentine oil), caryophyllus oil, clove leaf oil, cinnamon oil (cassia oil), Mace oil (nutmeg oil), cananga oil (cananga oil), thyme linaloe oil, mandarin oil (mandarin oil), sweet basil Oil, ennel oil (fennel oil), sage clary oil (clary sage oil), rosemary oil, caraway seed oil (caraway Seed oil), coriander oil, sandalwood oil (sandalwood oil), yellow seed oil of sunflower (ambretteseed oil), elemi oil Resin (elemi oleoresin), guaiac wood oil (guaiac wood oil), is rested in peace at elemi absolute oil (elemi absolute) Sesame oil (styrax oil), patchouli oil (patchouli oil), labdanum oil (labdanum oil), sensitive plant medicinal extract (mimosa concrete), concrete of jasmine, rose medicinal extract, oleoptene, jasmine wax, flores aurantii absolute oil, violet absolute, opopanax Botany bar gum (opopanax resinoid), castoreum absolute oil, iris botany bar gum (iris resinoid), frankincense botany bar gum (olibanum resinoid), copaiba balsam (copaiba balsam), tolu balsam, vanilla absolute, styrax botany bar gum Etc. essential oil.

As above-mentioned animal spice, there is no particular restriction, can suitably be selected, can be illustrated such as Moschus, spirit according to purpose Cat perfume, beaver perfume, ambergris etc..

As pices solvent, can illustrate such as ethyl alcohol, acetin (glyceryl triacetate (triacetin)), MMB acetic acid esters (3- methoxies Base -3- Methylbutyl acetates), six isobutyric acid sucrose ester of oxalic acid, ethylene glycol dibutyrate, hexylene glycol, dibutyl sebacate, Deltylextra (isopropyl myristate), methyl carbitol (methyl carbitol) (diethylene glycol monomethyl ether), card must Alcohol (carbitol) (diethylene glycol monoethyl ether), TEG (triethylene glycol), Ergol, propylene glycol, phthalic acid diethyl Ester, tripropylene glycol, Avolin (repefral), Deltyl Prime (isopropyl palmitate), dipropylene glycol DPG- FC (dipropylene glycol (dipropylene glycol)), farnesene (farnesene), dioctyl adipate, Tributyrin (three Glycerol monobutyralte), Hydrolite-5 (1,2- pentanediol), propylene-glycol diacetate, acetic acid cetyl (acetic acid cetyl Ester), ethyl abietate, Abalyn (methyl abietate), Citroflex A-2 (acetyl triethyl citrate), Citroflex A-4 (citroflex A-4), Citroflex No.2 (triethyl citrate), Citroflex No.4 (tributyl citrate), Durafix (dihydro methyl abietate), MITD (myristic acid isotridecyl ester), poly- limonene (lemon Lemon alkene polymer), 1,3-BDO, dibutyl hydroxy toluene, hydrogenation Methyl pinolenate (Hercolyn) etc..

It is that having for 30~75 mass % is selected from hydroxyl and carboxylic that ingredient (C), which is preferably comprised relative to the gross mass of ingredient (C), The compound of at least one kind of functional group in base, further preferably 40~50 mass %.

As the compound at least one kind of functional group in hydroxyl and carboxyl, among above-mentioned fragrance component, carboxylic can be enumerated Acids, phenols, alcohols etc..

Ingredient (C) both can be used alone a kind, but also two or more is applied in combination.

Relative to the gross mass of detergent composition, the content of ingredient (C) is preferably 0.01~5 mass %, and more preferably 0.05 ~3 mass %, further preferably 0.1~2 mass %.

When the content of ingredient (C) is in above-mentioned numberical range, raising fragrance retention is become easy.

The mass ratio indicated by ingredient (A)/ingredient (C) is preferably 0.01~100 (hereinafter also referred to as A/C ratios), preferably 0.1~50.

When A/C ratios are in above-mentioned numberical range, raising fragrance retention is become easy.

The total of ingredient (A)~(C) is no more than 100 mass %.

<Ingredient (D)s >

Ingredient (D) is the polymer with following units:Selected from terephthalic acid (TPA) alkylene ester unit and M-phthalic acid alkylene At least one of base ester unit repetitive unit (d1) and oxyalkylene units (d2).

The liquid detergent of the present invention, by using ingredient (A) and ingredient (D), can further improve makes to be attached on substrate The effect (soil-releasing finiss (Soil Release) effect, hereinafter also referred to " SR effects ") that easily removes of spot.

In addition, in this specification, " repetitive unit " refers to the monomeric unit for constituting polymer.

About specific repetitive unit (d1)

Among specific repetitive unit (d1), as terephthalic acid (TPA) alkylene ester unit (hereinafter, being also known as the repetitive unit " repetitive unit (d11) "), the repetitive unit indicated by the following general formula (D1-1) can be enumerated.

&#91;Change 2&#93;

In above formula (D1-1), R⁴¹For low-grade alkylidene.R⁴¹In the carbon number of low-grade alkylidene be preferably 1~5, more preferably It is 1~4, further preferably 2~4.

As repetitive unit (d11), terephthalic acid (TPA) ethylidene ester units, terephthalic acid (TPA) n-propylene ester can be specifically enumerated Unit, terephthalic acid (TPA) isopropylidene ester units, the positive butylidene ester units of terephthalic acid (TPA), terephthalic acid (TPA) isobutylene ester list Member, terephthalic acid (TPA) sec-butylidene ester units, the tertiary butylidene ester units of terephthalic acid (TPA) etc..Wherein, preferably terephthalic acid (TPA) is different Propylidene ester units.

Repetitive unit (d11) both can be used alone a kind, but also two or more is applied in combination.

Among specific repetitive unit (d1), as alkylene isophthalate unit (hereinafter, also by the repetitive unit Referred to as " repetitive unit (d12) "), the repetitive unit indicated by the following general formula (D1-2) can be enumerated.

&#91;Change 3&#93;

In above formula (D1-2), R⁴²For low-grade alkylidene.R⁴²In the carbon number of low-grade alkylidene be preferably 1~5, more preferably It is 1~4, further preferably 2~4.

As repetitive unit (d12), M-phthalic acid ethylidene ester units, M-phthalic acid n-propylene ester can be specifically enumerated Unit, M-phthalic acid isopropylidene ester units, the positive butylidene ester units of M-phthalic acid, M-phthalic acid sec-butylidene ester list Member, the tertiary butylidene ester units of M-phthalic acid etc..Wherein, preferred M-phthalic acid isopropylidene ester units.

Repetitive unit (d12) both can be used alone a kind, but also two or more is applied in combination.

Ingredient (D) both can only have a kind of repetitive unit (d1), can also have two or more repetitive unit (d1).That is, ingredient (D) in its 1 molecule, as repetitive unit (d1), can only have repetitive unit (d11), can only have repetitive unit (d12), Also can have both repetitive unit (d11) and repetitive unit (d12).

In addition, can have two or more repetitive unit (d11), and/or two or more repetitive unit (d12).

About repetitive unit (d1), in 1 molecule, can be both imported into Unit 1, it can also be with more than Unit 2 (i.e. blocks Shape) it is imported into.

The repeat number of repetitive unit (d1) possessed by 1 molecule is preferably 1~10 in ingredient (D), and more preferably 1~6, into One step is preferably 1~4.

The quantity of repetitive unit (d1) becomes easy raising washing effect in above-mentioned preferred scope.

About oxyalkylene units (d2)

As oxyalkylene units (hereinafter, the repetitive unit is also known as " repetitive unit (d2) "), can enumerate by the following general formula (D2-1) repetitive unit indicated.

&#91;Change 4&#93;

In above formula (D2-1), R⁴³For low-grade alkylidene.R⁴³In the carbon number of low-grade alkylidene be preferably 1~4, more preferably It is 2~4, further preferably 2 or 3.

As repetitive unit (d2), oxygen (change) ethylene unit, oxygen (change) propylene units, oxygen (change) butene units etc. can be enumerated.Its In, preferably oxygen (change) ethylene unit, oxygen (change) propylene units.

Ingredient (D) both can only have a kind of repetitive unit (d2), can also have two or more repetitive unit (d2).That is, ingredient (D) in its 1 molecule, as repetitive unit (d2), such as can only have oxygen (change) ethylene unit, can only have oxygen (change) propylene Unit can have both oxygen (change) ethylene unit and oxygen (change) propylene units.

In addition, ingredient (D) in its 1 molecule, as repetitive unit (d2), can have the oxyalkylene group (weight of repetitive unit (d2) Plural number is 1), can also have polyoxyalkylenes (repeat number of repetitive unit (d2) is 2 or more), can also have oxyalkylene group and gather Both oxyalkylene groups.

The repeat number of repetitive unit (d2) possessed by 1 molecule is 1 or more, preferably 1~100 in ingredient (D), more preferably It is 1~80, further preferably 1~50.

The repeat number of repetitive unit (d2) becomes easy the washing effect improved to oil-dirt in above-mentioned preferred scope.

Ingredient (D) may be either the polymer that repetitive unit (d1) polymerize with repetitive unit (d2) in block-wise, or again Multiple unit (d1) and the polymer that repetitive unit (d2) is in that random shape polymerize.Preferably it is in block as ingredient (D) among these The polymer of shape polymerization.

Ingredient (D) can also have other repetitive units other than with repetitive unit (d1) and repetitive unit (d2).Make For other repetitive units, the repetitive unit derived from polymerization initiator, polymerization inhibitor etc. can be enumerated, is derived from and can repeat list with providing The repetitive unit etc. of the monomer of the monomer of first (d1) or repetitive unit (d2) copolymerization.

When there is other repetitive units in ingredient (D), total, the repetition of whole repetitive units relative to constituent (D) Total preferably 80 moles of % or more, the more preferably 90 moles of % or more of unit (d1) and repetitive unit (d2), can rub for 100 You are %.Repetitive unit (d1) and when being aggregated in above-mentioned preferred lower limit value or more of repetitive unit (d2) become easier to improve and wash Wash power.

About ingredient (D), from the point of view of liquid stability when from the dissolubility of its own and liquid detergent is made, Preferably water-soluble polymer.

" water-soluble polymer " described herein refers to, in 1 liter of beaker, under conditions of 40 DEG C, 10g polymer is added to In 1000g water, after stirring 12 hours (200rpm) by blender (thickness 8mm, length 50mm), the water-soluble polymeric that is dissolved Object.

The weight average molecular weight of ingredient (D) is preferably 500~10000.Weight average molecular weight within the above range when, in water Dissolution dispersity improves, and SR effects and recontamination prevent from effect from becoming easy further increasing.In addition, becoming easy raising liquid The low-temperature stability of detergent.The lower limiting value of weight average molecular weight is more preferably 800 or more, further preferably 1000 or more.Separately On the one hand, the upper limit value of weight average molecular weight is more preferably 9000 hereinafter, further preferably below 8000.The weight of ingredient (D) is equal Molecular weight is more preferably 800~9000, further preferably 1000~8000.

In addition, the weight average molecular weight of ingredient (D) indicates, it is based on the calibration curve of PEG (polyethylene glycol), THF (tetrahydrochysene furans will be used Mutter) value that is converted as solvent, by GPC (gel permeation chromatography) values measured.

Ingredient (D) can be manufactured by synthetic method disclosed in various documents, textbook and patent document etc., such as can be led to Cross Journal of Polymer Science, volume 3, page 609~630 (1948);Journal of Polymer Science, volume 8, page 1~22 (nineteen fifty-one);The systems such as the method described in Japanese Patent Laid-Open No. Sho 61-218699 bulletins It makes.

As the suitable specific example of ingredient (D), can enumerate the high-molecular compound indicated by the following general formula (D1), by The high-molecular compound that general formula (D2) indicates or the ingredients of a mixture comprising them.

&#91;Change 5&#93;

In above-mentioned formula (D1), (D2), R⁴⁰And R⁵⁰It is separately hydrogen atom or methyl, preferably respectively methyl, it is more excellent Choosing is methyl.

R⁴⁴And R⁴⁷Respectively methyl or hydrogen atom, preferably respectively methyl.

R⁴⁵,R⁴⁶,R⁴⁸And R⁴⁹It is separately the alkylidene of carbon number 2~4.

S1 and s2 is respectively 0~10, preferably respectively 0.5~5, more preferably respectively 0.5~2.5.T1, t2, u1 and u2 distinguish It independently is 1~100, is preferably separately 1~80, is more preferably separately 1~50, it is further preferably only respectively It is on the spot 10~50, is particularly preferably separately 20~30.When s1, s2, t1, t2, u1 and u2 are above-mentioned preferred scope, become It must be easy to give full play to the compound effects of ingredient (D).In addition, dissolubility in water further increases, compounding to liquid scrubbing Become to be easy to get transparent feel excellent liquid detergent when agent.

(D1) in, s1 and (t1+u1) Zhi Bi &#91;s1:(t1+u1)&#93;Preferably 1:5~1:20, more preferably 1:8~1:18. When the ratio between s1 and (t1+u1) are above-mentioned preferred scope, washing force is can further improve, and can further improve dissolving in water Property.

(D2) s2 and (t2+u2) the Zhi Bi &#91 in;s2:(t2+u2)&#93;Preferably with Shang Shu &#91;s1:(t1+u1)&#93;The ratio between identical model It encloses.

Ingredient (D) both can be used alone a kind, but also two or more is applied in combination.

In addition, as ingredient (D), composite both can be used, it is possible to use commercially available product.

As the commercially available product of ingredient (D), can enumerate trade name TexCare SRN-100 (Clariant (Clariant) company manufactures, Weight average molecular weight 2000~3000), trade name TexCare SRN-300 (Clariant Corporation manufacture, weight average molecular weight 7000), quotient (Rhodia is public by name of an article Repel-O-Tex Crystal (manufacture of Rhodia (Rhodia) company), trade name Repel-O-Tex QC Department's manufacture) etc..

Among these, from the point of view of from dissolubility in water, high, storage stability is also excellent, preferably TexCare SRN- 100.In addition, from operability it is excellent from the point of view of, it is preferable to use as above-mentioned TexCare SRN-100 70% aqueous solution and Commercially available trade name TexCare SRN-170 (Clariant Corporation manufacture).

Relative to the gross mass of detergent, the content of ingredient (D) is preferably 0.1~1.5 mass %, and more preferably 0.5~1 Quality %.When the content of ingredient (D) is above-mentioned lower limiting value or more, becomes easy and further increase SR effects.In addition, becoming easy Further increasing recontamination prevents effect.When the content of ingredient (D) is above-mentioned upper limit value or less, becomes easy raising and washed in liquid The compounding stability in agent is washed, raising low-temperature stability is become easy.

Total Han Liang &#91 of ingredient (A) and ingredient (D) in liquid detergent;Hereinafter also referred to as " (A+D) adds up to content " &#93; Preferably 0.1~3.5 mass %, more preferably 0.6~3.3 mass %, further preferably 1~3 mass %.Liquid detergent In (A+D) add up to content be above-mentioned lower limiting value more than when, become easy and further increase SR effects.In addition, become easy into One step, which improves recontamination, prevents effect.When (A+D) in liquid detergent adds up to content for below above-mentioned upper limit value, become easy Further increase low-temperature stability.

The Zhi Liangbi &#91 indicated by ingredient (A)/ingredient (D);Quality of the content of ingredient (A) relative to the content of ingredient (D) Than, hereinafter also referred to " A/D ratios " is preferably 0.5~4, and more preferably 1~3.When A/D ratios are above-mentioned preferred scope, become easy Further increase SR effects.

In addition, the EO of nonionic surfactant (B1) is averaged, addition molal quantity further increases SR effects at 10 or more.

<Ingredient (E)s >

Ingredient (E) is selected from least one kind of in the carboxylic acid and its salt indicated by the following general formula (VII).

X-R¹-COOH···(VII)

Wherein, in formula (VII), R¹For the bivalent hydrocarbon radical or arlydene of carbon number 1~4, X is-H ,-OH ,-CH₃Or-COOH.

In the liquid detergent of the present invention, by and with mentioned component (B) and ingredient (E), enzyme stability can be improved.

In formula (VII), R¹For the bivalent hydrocarbon radical or arlydene of carbon number 1~4.The bivalent hydrocarbon radical of these carbon numbers 1~4 and Asia Aryl can have or can not have substituent group.As substituent group, hydroxyl etc. can be enumerated.

In addition, the bivalent hydrocarbon radical of carbon number 1~4 can be saturation, can be unsaturated, it can be straight-chain, can be branched, can be ring Shape.As the bivalent hydrocarbon radical of such carbon number 1~4, the divalent that 1 hydrogen atom is eliminated from the alkyl of carbon number 1~4 can be enumerated Group, from eliminating the bivalent group of 1 hydrogen atom in the alkenyl of carbon number 1~4, eliminate 1 from the alkynyl of carbon number 1~4 The bivalent group etc. of hydrogen atom.

As arlydene, phenylene can be enumerated.

X is-H ,-OH ,-CH₃Or-COOH.

As the carboxylic acid indicated by formula (VII), can illustrate as benzoic acid, acetic acid, propionic acid, butyric acid, hydroxybutyric acid, hydroxyl are different Butyric acid, lactic acid, adipic acid, maleic acid, fumaric acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), malic acid, glutaric acid Deng.

In addition, the salt as carboxylic acid, can enumerate sodium salt, sylvite, calcium salt, monoethanolamine salt, diethanolamine salt, triethanolamine salt Deng.

Among these, as ingredient (E), from the point of view of further increasing enzyme stability, preferably benzoic acid, lactic acid or they Salt, more preferable lactic acid or its salt.In addition, from the point of view of further increasing appearance stability, as ingredient (E), preferably Sodium salt.

As ingredient (E), from the point of view of further increasing enzyme stability and appearance stability, preferred sodium lactate.

Ingredient (E) both can be used alone wantonly a kind, but also two or more is applied in combination.

Relative to the gross mass of liquid detergent, the content of ingredient (E) is preferably 0.1~5 mass %, and more preferably 0.1 ~3 mass %, further preferably 0.2~2 mass %.

<Ingredient (F)s >

Ingredient (F) is enzyme.

In the liquid detergent of the present invention, by containing ingredient (F), washing force can further improve.

As ingredient (F), using the enzyme for being used for clothing detergent purposes etc., such as the protease (protease) that can illustrate forms sediment Powder enzyme, lipase (lipase), cellulase, mannase (mannanase) etc..

In addition, in this specification, " enzyme " refers to enzyme preparation.

As protease, can enumerate can believe trade name that (Novozymes) company buys as protease preparation from Novi Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L TypeEX, Everlase Ultra16L,Esperase 8L,Alcalase 2.5L,Alcalase Ultra 2.5L,Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, can be from Jie Neng sections (Genencor) trade name Purafect L, the Purafect OX that company buys, Properase L etc..

As amylase, can enumerate trade name Termamyl 300L that can be bought from Novozymes Company as diastase, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, can be from Jie Neng sections Trade name Maxamyl that company buys, trade name Pullulanase Amano that can be bought from amano pharmaceutical company, can be from life The trade name DB-250 etc. that chemical industrial company buys.

As lipase, can enumerate trade name Lipex 100L that can be bought from Novozymes Company as lipase preparation, Lipolase 100L etc..

As cellulase, the trade name that can be bought from Novozymes Company as cellulase preparation can be enumerated Endolase5000L, Celluzyme 0.4L, Carzyme 4500L etc..

As mannase, the trade name Mannaway that can be bought from Novozymes Company as mannase preparation can be enumerated 4L etc..

Ingredient (F) preferably comprises protease.By adding protease, the washing force to protein stain can further improve.

As protease, among above-mentioned, preferably trade name Savinase 16L, Savinase Ultra 16L, Savinase Ultra16XL,Everlase 16L,Everlase Ultra 16L,Alcalase 2.5L,Alcalase Ultra 2.5L, Liquanase 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, it is especially excellent Select Alcalase 2.5L, Everlase16L, Savinase 16L, Coronase 48L.Ingredient (F) both can be used alone wantonly 1 Kind, but also two or more is applied in combination.

Relative to the gross mass of liquid detergent, the content of ingredient (F) is preferably 0.01~3 mass %, more preferably 0.05~2 mass %, further preferably 0.1~1.5 mass %.The content of ingredient (D) is the lower limiting value of above-mentioned preferred scope When above, washing force can further improve.When the content of ingredient (D) is the upper limit value of above-mentioned preferred scope or less, the precipitation of enzyme It is inhibited, can further improve appearance stability.

In addition, in this specification, the additive amount of the enzyme in liquid detergent is the additive amount as preparation.Above-mentioned additive amount, can It is sought, such as can be acquired from the zymoprotein amount inverse operator in the usage amount of raw material or liquid detergent by usual way.

The Zhi Liangbi &#91 indicated by mentioned component (A)/mentioned component (E);Content containing relative to ingredient (E) of ingredient (A) The mass ratio of amount, hereinafter also referred to " A/E ratios ".&#93;It is 0.1~20.

When A/E ratios are less than 0.1 or more than 20, appearance stability is impaired.

A/E ratios are preferably 0.3~10, more preferably 0.5~7, further preferably 1~5.

Relative to the gross mass of liquid detergent, ingredient (A) and total content of ingredient (E) are preferably 0.1~4 matter Measure %, more preferably 0.5~3 mass %, further preferably 1~2.5 mass %.Total content of ingredient (A) and ingredient (E) It when to be more than above-mentioned lower limiting value, is easy to adjust A/E ratios to the particular range of the application, it is excellent to become easy acquisition appearance stability Different liquid detergent.In addition, when ingredient (A) and total content of ingredient (E) are above-mentioned upper limit value or less, holding is become easy The compounding degree of freedom of other ingredients.

<Ren Yichengfen >

In the detergent composition of the present invention, in the range for the effect for not interfering the present invention, detergent can be used according to purpose Usually used ingredient in composition.

The detergent composition of the present invention can contain the alkali such as water Combination organic solvent, the monoethanolamine such as enzymes, the ethyl alcohol such as protease The enzyme stabilizers such as the preservatives such as the antioxidants such as agent, dibutyl hydroxy toluene, sodium benzoate, calcium chloride, sodium lactate, pigment are waited Toner, zeolite (zeolite), washing performance builder (builder) etc..

Preferably, in detergent composition of the invention, ingredient (A) be selected from the compound that above-mentioned logical formula (I) indicates and It is at least one kind of in the compound indicated by above-mentioned logical formula (II), ingredient (B1) be selected from the compound that above-mentioned logical formula (III) indicates with And by least one kind of in the compound of above-mentioned logical formula (IV) expression, ingredient (C) is selected from phenols, alcohols, carboxylic acids, aldehydes, ether It is at least one kind of in class, esters, hydro carbons, ketone, lactone, Moschus class, natural perfume material and animal spice, by ingredient (B1)/ The mass ratio that ingredient (B2) indicates is 1.0 or more.

Preferably, in detergent composition of the invention, ingredient (A) be selected from the compound that above-mentioned logical formula (I) indicates and At least one kind of in the compound that above-mentioned logical formula (II) indicates, ingredient (B1) contains fatty acid methyl ester ethoxylate, ingredient (C) Selected from phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydro carbons, ketone, lactone, Moschus class, natural perfume material and animal Property fragrance in it is at least one kind of, the mass ratio indicated by ingredient (B1)/ingredient (B2) is 1.0 or more.

Preferably, in detergent composition of the invention, ingredient (A) be selected from the compound that above-mentioned logical formula (I) indicates and At least one kind of in the compound indicated by above-mentioned logical formula (II), ingredient (B1) contains fatty acid methyl ester ethoxylate, ingredient (C) phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydro carbons, ketone, lactone, Moschus class, natural perfume material are selected from and is moved At least one kind of in physical property fragrance, the mass ratio indicated by ingredient (B1)/ingredient (B2) is 1.0 or more, relative to mentioned component (B) gross mass, the content of above-mentioned fatty acid methyl ester ethoxylate is more than 10 mass %.

Preferably, in detergent composition of the invention, ingredient (A) be selected from the compound that above-mentioned logical formula (I) indicates and It is at least one kind of in the compound indicated by above-mentioned logical formula (II), ingredient (B1) be selected from the compound that above-mentioned logical formula (III) indicates with And it is at least one kind of in the compound indicated by above-mentioned logical formula (IV), ingredient (B2) be selected from the compound that above-mentioned formula (VI) indicates, with And it is at least one kind of in the alkylbenzene sulfonate of the straight or branched of the alkyl with carbon number 8~18, ingredient (C) be selected from phenols, In alcohols, carboxylic acids, aldehydes, ethers, esters, hydro carbons, ketone, lactone, Moschus class, natural perfume material and animal spice At least one kind of, the mass ratio indicated by ingredient (B1)/ingredient (B2) is 1.0 or more.

Preferably, in detergent composition of the invention, ingredient (A) is the compound indicated by above-mentioned general formula (I-a), at At least 1 in compound that point (B1) is indicated selected from above-mentioned logical formula (III) and the compound indicated by above-mentioned logical formula (IV) Kind, ingredient (B2) is selected from the straight or branched of the compound that above-mentioned formula (VI) indicates and the alkyl with carbon number 8~18 It is at least one kind of in alkylbenzene sulfonate, ingredient (C) be selected from phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydro carbons, ketone, Quality that is at least one kind of in lactone, Moschus class, natural perfume material and animal spice, being indicated by ingredient (B1)/ingredient (B2) Than 1.0 or more.

Preferably, in detergent composition of the invention, ingredient (A) is the compound that above-mentioned general formula (I-a) indicates, ingredient (B1) at least one kind of in the compound that the compound and above-mentioned logical formula (IV) indicated selected from above-mentioned logical formula (III) indicates, at Divide (B2) alkyl for being selected from the straight or branched of compound that above-mentioned formula (VI) indicates and the alkyl with carbon number 8~18 At least one kind of in benzene sulfonate, ingredient (C) is selected from phenols, alcohols, carboxylic acids, aldehydes, ethers, esters, hydro carbons, ketone, lactone At least one kind of in class, Moschus class, natural perfume material and animal spice, the mass ratio indicated by ingredient (B1)/ingredient (B2) is 1.0~30, it is 0.01~5 by the mass ratio that ingredient (A)/ingredient (B2) indicates.

"The manufacturing method of detergent composition"

It, can be by known method, by by ingredient (A)~(C) and root when the detergent composition of the present invention is liquid It is mixed according to any ingredient of needs to manufacture.

When the detergent composition of the present invention is granular, it can be manufactured, can be lifted for example, by each raw material by known method Carry out dry blending (dry blend) method of powder mixing;The dry type being granulated while powder material mixed flow is set to make Grain method;While making powder material mixed flow, liquid adhesive is sprayed, the stirring-granulating method being granulated;Raw material is mediated, The extruding pelletization method squeezed out with extruder;Raw material is mediated, the crushing comminution granulation crushed;By the slurry containing raw material The spray drying process etc. of spray drying.

"The application method of detergent composition"

The application method of detergent composition as the present invention, can enumerate common application method.

By the detergent composition of the present invention for that when washing fibre, can lift for example, being added to using relative to water 30L The cleaning solution of 5~30mL of detergent composition, the method for cleaning substrate with washing machine;Substrate is impregnated in above-mentioned cleaning solution Method etc..In addition, can be used by following methods:Detergent composition is directly coated at substrate, places certain time, Then, the method (coating washing) of common washing is carried out.

When the detergent composition of the present invention is used for washed hardened surface, following methods can be enumerated:Detergent composition is molten Xie Yushui prepares cleaning solution, in as the hard surface of washing object spray etc. and after being coated with, with washing implements such as sponges The method cleaned.

When being used for the detergent composition of the present invention to wash tableware etc., following methods etc. can be enumerated:Make detergent composition It is contained in sponge, the method for washing tableware etc.;Detergent composition is dissolved in water, modulates thin cleaning solution, by leachings such as tablewares In the cleaning solution, the method that is wiped with sponge.

Embodiment

Hereinafter, illustrate the present invention in further detail with embodiment, but the present invention is not limited to these embodiments.

The composition (content (quality %)) of the detergent composition of each example is as shown in table 6~7.

In table, when formula components are empty column, which is not added.

In table, " aequum (balance) " refers to, so that total addition of all formula components contained in detergent composition Measure the remainder added as the mode of 100 mass %.

The raw material used in the present embodiment is as follows.

<Ingredient (A)s >

·A-1:The ethylene oxide adduct of polyethyleneimine, BASF AG's manufacture, trade name " Sokalan HP20 ".Above-mentioned formula (I-a) in, R²²The compound for being 20 for ethylidene, m.

·A-2:Polyethyleneimine, BASF AG's manufacture, trade name " Lupasol P ", weight average molecular weight about 75000, ingredient (A) Comparison product.

<Ingredient (B)s >

&#91;Ingredient (B1)s &#93;

·B1-1:Fatty acid methyl ester ethoxylate (MEE) (carbon number 12~14 of aliphatic acid, the average addition molal quantity of EO 15), lead in formula (III), R²The alkyl of=carbon number 11 and the alkyl of carbon number 13, R³=methyl, s=15, t=0, u=0.Pass through Following synthetic methods and synthesize.

(synthesis of B1-1)

It is synthesized according to the synthetic method described in Japanese Patent Laid-Open 2000-144179 bulletins.

Under conditions of 600 DEG C, group is become into 2.5MgOAl₂O₃·zH₂Aluminum magnesium hydroxide (300 (the commodity of KYOWARD of O Name), Kyowa Chemical Industry Co., Ltd's manufacture) it is burnt into a nitrogen atmosphere, it obtains firing aluminum magnesium hydroxide (unmodified) and urges Agent.It will firing aluminum magnesium hydroxide (unmodified) catalyst 2.2g, 0.5N potassium hydroxide-ethanol solution 2.9mL, lauric acid first Ester 280g and methyl myristate 70g is added into 4L autoclaves, and the modification of catalyst is carried out in autoclave.Then, nitrogen is used After gas is replaced in autoclave, temperature is maintained 180 DEG C on one side, pressure is maintained to 0.3MPa, imports ethylene oxide on one side 1052g is allowed to react while stirring.

The reaction solution obtained is cooled to 80 DEG C, addition water 159g, adds atlapulgite and silicon respectively as filtration adjuvant Diatomaceous earth 5g, is mixed, and catalyst is then filtered out, and obtains B1-1.The stenosis rate of B1-1 is 30 mass %.

·B1-1':Fatty acid methyl ester ethoxylate (MEE) (carbon number 12~14 of aliphatic acid, the average addition molal quantity of EO 15), lead in formula (III), R²The alkyl of=carbon number 11 and the alkyl of carbon number 13, R³=methyl, s=15, t=0, u=0.Pass through Following synthetic methods and synthesize.

(synthesis of B1-1 ')

B1-1 ' is synthesized according to following synthetic methods.

By 2-Ethylhexyl Alcohol (extra pure reagent, Kanto Kagaku K. K. manufacture) 137g, calcium acetate monohydrate (special grade chemical, Kanto Kagaku K. K. manufactures) 41.7g is put into 500mL beakers, by oar blade type stirring wing, in the condition of room temperature (25 DEG C) Under be mixed, obtain dispersion (dispersion step).It is by dropping funel, sulfuric acid is (special while stirring above-mentioned dispersion Grade reagent, Kanto Kagaku K. K.'s manufacture) time-consuming 10 minutes of 20.9g adds and mixes (mixed processes).Due in mixing work It generates heat because adding sulfuric acid in sequence, so by beaker water-bath cooling, reaction temperature is controlled at 30~50 DEG C.Add sulfuric acid it Afterwards, it while being maintained at 50 DEG C, futher stirs 2 hours (catalyst curing step), obtains alkoxylating catalyst.

By above-mentioned alkoxylating catalyst 12.5g, methyl laurate (PASTEL M12, the manufacture of lion king's Chemical Co., Ltd.) 462g, it is put into autoclave, stirs with methyl myristate (PASTEL M14, the manufacture of lion king's Chemical Co., Ltd.) 166g. While stirring, nitrogen displacement will be carried out in autoclave, be warming up to 100 DEG C, taken off under 1.3kPa reduced pressures below Water 30 minutes.Then, 160 DEG C are warming up to, under conditions of 0.1~0.5MPa, imports ethylene oxide (EO) 1876g (lauric acid Total 15 times moles of methyl esters and methyl myristate), it stirs (addition reaction process).Further, in addition reaction temperature Under conditions of degree, after stirring 0.5 hour (curing step), 80 DEG C are cooled to, obtains and reacts crude object (fatty acid methyl ester ethyoxyl Compound (MEE), EO are averaged addition molal quantity=15) 2516g.By the crude object filtering of above-mentioned reaction, catalyst, products therefrom are removed As B1-1 '.

·B1-2:Alcohol ethoxylate (AE), in natural alcohol addition have 15 molar equivalents ethylene oxide and person.General formula (IV) in, R⁴The alkyl of=carbon number 12 and the alkyl of carbon number 14, v=15, w=0, x=0.It is closed by following synthetic methods At.

(synthesis of B1-2)

By P&G (Procter&Gamble) CO-1214 (trade name) 224.4g, water-soluble with 30 mass %NaOH of company's manufacture Liquid 2.0g is added to pressure resistant type reaction vessel, and nitrogen displacement will be carried out in above-mentioned reaction vessel.Then, in 100 DEG C of temperature, pressure Under the conditions of power 2.0kPa is below, it is dehydrated 30 minutes, temperature is warming up to 160 DEG C.It then, will while being stirred to react liquid Ethylene oxide (gas shape) 760.6g is slowly added into reaction solution.At this point, adjusting adding speed so that reaction temperature does not surpass 180 DEG C are crossed, while ethylene oxide is added with pipe is blown into.

After the addition of ethylene oxide, under the conditions of 180 DEG C of temperature, pressure 0.3MPa are below, cure 30 minutes, then exist Under the conditions of 180 DEG C of temperature, pressure 6.0kPa are below, unreacted ethylene oxide is distilled off 10 minutes.

Then, temperature is cooled to 100 DEG C hereinafter, then, 70 mass % p-methyl benzenesulfonic acid of addition are neutralized, so that reaction The pH of 1 mass % aqueous solutions of object becomes about 7, obtains B1-2.

·B1-3:Alcohol ethoxylate (AE), in natural alcohol addition have 7 molar equivalents ethylene oxide and person.General formula (IV) in, R⁴The alkyl of=carbon number 12 and the alkyl of carbon number 14, v=7, w=0, x=0.It is closed by following synthetic methods At.

(synthesis of B1-3)

It is added to pressure resistance by CO-1214 (trade name) 224.4g of Procter & Gamble's manufacture, with 30 mass %NaOH aqueous solutions 2.0g In type reaction vessel, nitrogen displacement will be carried out in above-mentioned reaction vessel.Then, in 100 DEG C of temperature, pressure 2.0kPa items below Under part, it is dehydrated 30 minutes, temperature is warming up to 160 DEG C.Then, while being stirred to react liquid, by ethylene oxide (gas shape) 355.0g is slowly added into reaction solution.At this point, adjusting adding speed so that reaction temperature is no more than 180 DEG C, while with blowing Enter pipe addition ethylene oxide.

After the addition of ethylene oxide, under the conditions of 180 DEG C of temperature, pressure 0.3MPa are below, cure 30 minutes, then exist Under the conditions of 180 DEG C of temperature, pressure 6.0kPa are below, unreacted ethylene oxide is distilled off 10 minutes.

Then, temperature is cooled to 100 DEG C hereinafter, then, 70 mass % p-methyl benzenesulfonic acid of addition are neutralized, so that reaction The pH of 1 mass % aqueous solutions of object becomes about 7, obtains B1-3.

·B1-4:To natural alcohol (12 alcohol of carbon number/carbon number, 14 alcohol=7/3 by quality ratio) successively 8 molar equivalent of block addition Ethylene oxide, the propylene oxide of 2 molar equivalents, 8 molar equivalents ethylene oxide and obtain.In above-mentioned logical formula (IV), R⁴=carbon number 12 alkyl and the alkyl of carbon number 14, v=8, w=2, x=8.

·B1-5:The ethylene oxide of 7 molar equivalent of secondary alcohol addition of secondary alcohol and carbon number 14 to carbon number 12 and obtain.Trade name " Softanol 70 ", Nippon Shokubai Co., Ltd's manufacture.In above-mentioned logical formula (IV), R⁴The secondary alkyl and carbon number of=carbon number 12 14 secondary alkyl, v=7, w=0, x=0.

&#91;Ingredient (B2)s &#93;

·B2-1:Polyoxyethylene alkyl ether sodium sulphate (AES).In formula (VI), the straight chained alkyl of R40=carbon numbers 12~14, m= The compound of 1.0, n=0, M=sodium.It is synthesized by following synthetic methods.

(synthesis of B2-1)

In the autoclave of capacity 4L, it is packed into P&G (P&G) 1270 alcohol of the trade name CO (alcohol and carbon of carbon number 12 of company's manufacture The mixture that the mass ratio of the alcohol of number 14 is 75/25) 400g is as raw alcohol, and potassium hydroxide 0.8g is as anti-applied catalysis for loading Agent, with nitrogen by built in above-mentioned autoclave alternatively after, warming while stirring.Then, temperature is being maintained into 180 DEG C, pressure dimension It holds while 0.3MPa or less, imports ethylene oxide 91g, be allowed to react, obtain alcohol ethoxylate accordingly.

Use gas chromatography-mass spectrometry:GC-5890, the detector of Hewlett-Packard (Hewlett-Packard) company manufacture:Hydrogen flame Ionization type detector (FID), chromatographic column:Ultra-1 (Hewlett-Packard Corporation manufactures, L25m × Φ 0.2mm × T0.11 μm) is divided The average addition molal quantity of analysis, the ethylene oxide of the alcohol ethoxylate as a result obtained is 1.0.In addition, non-addition has epoxy second Gross mass of the compound of alkane relative to the alcohol ethoxylate obtained is 43 mass %.

Then, in the 500mL flasks that the alcohol ethoxylate 237g of above-mentioned acquisition is extracted to additional agitating device, with nitrogen into Then line replacement keeps 40 DEG C of reaction temperature, liquid sulfuric anhydride (Sulfan) 96g is slowly added dropwise on one side on one side.Completion of dropwise addition Later, 1 hour (sulfating reaction) persistently is stirred, obtains polyoxyethylene alkyl ether sulfuric acid.Then, by using sodium hydroxide water Solution is neutralized, and B2-1 is obtained.

·B2-2:Sodium n-alkylbenzenesulfonate (LAS), Lion Corporation's manufacture, trade name " Lipon LH-200 ".

·B2-3:The monoethanolamine salt (AEPS) of polyoxyalkylene alkyl sulfuric ester.In formula (VI), R⁴⁰The straight chain of=carbon number 12 Alkyl, m=2.0, n=1.0, the compound of m=monoethanolamine.It is synthesized by following synthetic methods.

(synthesis of B2-3)

By the Bai Chun &#91 of the straight chain of carbon number 12;Tokyo Chemical Industry Co., Ltd manufactures, trade name:DODECANOL, 1- (molecular weight 186.33), Chun Du >99%&#93;640g, it is packed into equipped with agitating device, control and temperature device and leads automatically with KOH 1.0g Enter in the autoclave of device, under conditions of 110 DEG C, 1.3kPa, carries out dehydration 30 minutes.After dehydration, nitrogen displacement is carried out, is risen Temperature is put into bis- base oxide of propane -1,2- (propan-1,2-diyl oxide) 199g to after 120 DEG C.Then, at 120 DEG C Under conditions of carry out addition reaction curing, then heat to 145 DEG C, be packed into ethylene oxide 303g.Then, in 145 DEG C of conditions Lower progress addition reaction curing, is subsequently cooled to 80 DEG C, unreacted ethylene oxide is removed under conditions of 4.0kPa.It removes After unreacted ethylene oxide, acetic acid 1.0g is added to autoclave, stirs 30 minutes under conditions of 80 DEG C, then into Row extraction, obtain alkyl be dodecyl, PO average addition molal quantity be 1.0, the alkane that the average addition molal quantity of EO is 2.0 Oxygroup compound.

Use SO₃The alcoxylates obtained are carried out sulphation by gas by falling film formula reactor.Use monoethanol Amine neutralizes the hydrosulphate obtained, obtains and contains polyoxyethylene polyoxygenated propane -1,2- diyl alkyl ether sulphate Monoethanolamine salt (AEPS) composition.

·B2-4:Coconut fatty acid (coco fatty acid), trade name " coconut fatty acid ", Japan Oil Co's manufacture.

<Ingredient (C)s >

·C-1:Fragrance shown in table 1~5.

&#91;Table 1&#93;

	Fragrance (quality %)
		Petit grain oil	0.5
Orange oil	3
		Caryophyllus oil	0.002
Citronella oil	0.2
		Pine tar	0.02
Bergamot oil	1
		Mandarin oil	0.5
Limette oil	1
		Lemon oil	1.3
Lemongrass oil	1
		The fluffy botany bar gum of lattice	0.1
Australene	0.001
		Nopinene	0.003
Limonene	1
		3- carenes	0.002
β-carypohyllene	0.03
		Laurene	0.05
P-cymene	0.001
		Sweet orange terpene (Orange Terpene)	5
Trans- -2- hexenols	0.005
		Trans- -3- hexenols	0.005
Flores aurantii absolute oil	0.001
		Chamomile oil	0.001
Violet absolute	0.001
		Basil	0.001
Myrcenol	2
		Dihydromyrcenol	2
2,6-Dimethyl-2-octanol	0.1
		Terpinol	3
Farnesol	0.1
		Nerolidol	2
1- octanols	1
		1 nonyl alcohol	1
Leaf alcohol	1
		Matsutakealcohol	0.01
Citral	1
		N-octaldehyde	0.3
N-nonyl aldehyde	0.3
		1- decyl alcohol	0.5
The hendecanal	0.001
		Dodecanol	0.001
Cis- -3- hexanals	0.2
		Triplal	0.001
Benzaldehyde	0.001
		Nootkatone (Nootkatone)	0.001
α-imperial court's ketone (α-Dainasukon)	0.001
		Acetate cis -3- hexene esters	0.1
Allyl amyl glycolate	0.01
		Ethyl acetate	0.02
Bergamio	2
		Neryl acetate	0.002
Terpinyl acetate	0.05
		Isobornyl acetate

&#91;Table 2&#93;

	Fragrance (quality %)
		Verdox	0.001
Fruity ester (FRUITATE)	0.05
		Manzanate (2 methyl valeric acid ethyl ester)	1
Salethyl	0.1
		Benzyl salicylate	2
Ethyl -2,2,6- trimethyl-cyclohexane carbonic esters	2
		Nonyl lactone	0.01
γ-decalactone	0.01
		Gamma-undecalactone	1
Methyl anthranilate	1
		Cis- -3- the hexene esters of ortho-aminobenzoic acid	0.001
Ortho-aminobenzoic acid phenylethylester	0.001
		Ortho-aminobenzoic acid cinnamic ester	0.001
N- methyl anthranilic acid methyl esters	0.5
		Aurantiol	0.1
Citronellyl nitrile	1
		Lemonile	1.5
Ennel oil	0.001
		Sage clary oil	0.5
Peppermint oil	0.005
		Eucalyptus oil	0.1
Lavender oil	0.1
		Miscellaneous lavender absolute oil	0.1
Rosemary oil	0.03
		Peppermint terpenes	0.02
Menthol	0.5
		Carvol
Menthones
		Camphor
1,8- cineole	1
		Chavicol (chavicol)	0.1
Carvacrol (carvacrol)	0.1
		0.1 ethanol solution of benzothiazole	0.001
0.1 ethanol solution of peppermint sulfide	0.001
		Caraway seed oil	0.5
Cuminyl alcohol	1
		Coriander oil	0.5
Mace oil	0.5
		Anise alcohol	1
Anisaldehyde	1
		Eugenyl acetate	0.3
Acetyl group isoeugenol	0.3
		Anethole	0.3
Methyleugenol	0.3
		Thymol	0.3
Eugenol	0.3
		Isoeugenol	0.3
Methyl iso eugenol	0.1
		Ethyl isobutyl eugenol	0.1
Benzyl eugenol	0.1
		Benzylisoeugenol	0.3
Sensitive plant medicinal extract
		Concrete of jasmine	0.1
Geranium oil	0.2
		Ylang ylang oil (ylang-ylang oil)	0.01
Rosewood oil	0.02

&#91;Table 3&#93;

	Fragrance (quality %)
		Rose medicinal extract	0.2
Oleoptene	0.007
		Jasmine wax	0.001
Geraniol	3
		Citronellol	5
Nerol	1
		Linalool	3
Tetrahydrolinalool	1
		Benzylalcohol	1
Bata-phenethyl alcohol	1
		Styracitol	1
Cinnamyl alcohol	0.5
		Phenoxyethyl alcohol	0.5
Citronellal	0.005
		Laurine
Flores convallariae aldehyde	0.001
		Du's pik aldehyde (Dupical)	0.1
Bougeonal (Bourgeonal)	0.1
		Cyclamen aldehyde	0.05
Hai Feng Quan " (Floralozone)
		Cinnamyl alcohol
Helional (Helional)	0.05
		Lyral (Lyral)	1
Lilial (Lilial)	1
		Jasminal	0.2
Jasmonal H	1
		Cis-jasmone	0.001
Isojasmone
		4- damascols	0.07
Damascenone	0.2
		Damascone (damascone)	0.3
Watermelon ketone (Calone)	0.001
		Citronellyl formate	0.001
Geranyl formate
		Neryl formate
Citronellyl acetate	0.1
		Geranyl acetate	0.2
Cyclacet	0.3
		Benzyl acetate	0.2
Phenethyl acetate	0.1
		Methyl phenyl carbinyl acetate
Rosalin (rosephenone)	0.02
		Cinnamyl acetate	0.1
Dimethyl benzyl carbinyl acetate	0.05
		Jasmal
Tricyclo decenyl propionate	0.1
		Benzyl propionate	0.001
Methyl jasmonate	0.001
		Hedione	2
Aldehyde C-16
		Methyl cinnamate
Ethyl cinnamate	0.002
		Linalool oxide	0.1
herboxide
		Rose oxide	0.001

&#91;Table 4&#93;

	Fragrance (quality %)
		β-naphthol methyl ether	0.003
Bromelia	0.001
		Guaiacol	0.1
Ortho-aminobenzoic acid	0.1
		Benzoic acid	0.1
Phenylacetic acid	0.001
		Glossy privet acetal (Ligantraal)	0.001
Indoles	0.01
		1% dipropylene glycol solution of 6- isopropyl quinolines	0.01
1% ethanol solution of isobutyl quinoline	0.01
		1% Benzyl Benzoate ester solution of 2- isobutyl quinolines	0.001
Yellow seed oil of sunflower
		Iris botany bar gum
Elemi oleoresin
		Elemi absolute oil	2
Oak moss absolute	0.005
		Frankincense botany bar gum	0.001
Guaiac wood oil	0.5
		Copaiba balsam (copaiba balsam)
Levant storax oil	0.03
		Tolu balsam	0.3
Patchouli oil	0.006
		Vanilla absolute	0.001
Vetiver oil	0.1
		Styrax botany bar gum
Labdanum oil
		Cedrene	0.1
Cedrol	0.001
		2- butene-1-ols (Santalinol)	0.005
Asiatic sweet leaf alcohol (Bacdanol)	0.5
		Santalol (Sandalore)	0.001
Imperial saliva alcohol (Ambrinol)	0.1
		Timberol (Timberol)	0.02
Borneol	0.01
		Isoborneol	0.05
Polysantalol (Polysantol)	0.05
		Vanillic aldehyde	0.05
Ethyl vanillin	0.05
		Piperonal	0.5
Maltol	0.05
		Ethylmaltol	0.05
Raspberry ketone	0.3
		Ionone	0.5
Methyl ionone	1
		Vertofix coeur (Vertofix)	1
Cashmeran (Cashmeran)	0.1
		Muskone (muscone)	0.5
Special Lars Moschus (Traseolide)	0.1
		Tonalid (Tonalide)	1
Iso·E·Super	1
		Vetiverol	0.1
Patchoulicalcohol	0.1
		Cyclopentadecylene lactone (Habanolide)	0.5
Ambrettolide	0.001
		Cyclohexadecanolide (cyclohexadecanolide)	0.001
Opopanax botany bar gum	0.1

&#91;Table 5&#93;

<Ingredient (D)s >

D-1:Polymer with specific repetitive unit (d1) Yu oxyalkylene units (d2).Clariant (Clariant) corporation It makes, trade name " TexCare SRN-170 ", weight average molecular weight 2000~3000, contain the high score indicated by above-mentioned general formula (D1) Sub- compound.In addition, the condition that D-1 meets above-mentioned " water-soluble polymer " (that is, in 1 liter of beaker, is incited somebody to action under conditions of 40 DEG C Polymer 10g is added in water 1000g, after blender (thickness 8mm, length 50mm) stirring (200rpm) 12 hours, Dissolving).

<Ingredient (E)s >

Sodium lactate (stabilizer), Kanto Kagaku K. K.'s manufacture, trade name " sodium lactate ".

<Ingredient (F)s >

Alcalase (protease), Novozymes Company's manufacture, trade name " Alcalase 2.5L ".

<Ren Yichengfen >

·MEA:Monoethanolamine (alkaline agent), Nippon Shokubai Co., Ltd's manufacture, trade name " monoethanolamine ".

·BHT:Dibutyl hydroxy toluene (antioxidant), Sumitomo Chemical Co's manufacture, trade name " SUMILZER BHT- R"。

Ethyl alcohol (water Combination organic solvent), Japanese alcohol peddle Co., Ltd. (Japan Alcohol Trading CO., LTD. it) manufactures, trade name " the 95 degree of synthesis of specific ethyl alcohol (alcohol) ".

Sodium benzoate (preservative), Toagosei Co., Ltd's manufacture, trade name " sodium benzoate ".

Calcium chloride (enzyme stabilizers), Kanto Kagaku K. K.'s manufacture, trade name " calcium chloride (superfine) ".

Pigment (colorant), the sixth of the twelve Earthly Branches in the last of the ten Heavenly stems are melted into Co., Ltd.'s manufacture, trade name " green 3 ".

<The Zhi Zaofangfa &gt of detergent composition;

(embodiment 1~13, the Comparative Examples 1 to 5)

It is formed according to shown in table 6~7, adds each ingredient in water, mixed, obtain embodiment 1~13, the Comparative Examples 1 to 5 Detergent composition.

To the detergent composition of embodiment 1~13, the Comparative Examples 1 to 5, in the following manner, evaluate its recontamination prevent performance, Fragrance retention, storage stability.

<Recontamination prevents the Ping Jia &gt of performance;

Using the detergent composition of each example, into being about to washing procedure as described below, rinsing process, drying process with such The washing processing that sequence is repeated 3 times.

Washing procedure:

As substrate, following cottons, wet type artificial contamination cloth and personal shirt are used.

Cotton:Judge cloth using 5 cotton braids (manufacture of valley head shop) 5cm × 5cm as recontamination.

Wet type artificial contamination's cloth:The pollution cloth that juridical person washs scientific institution's manufacture (is attached with 28.3 mass % of oleic acid, three 15.6 mass % of olein (triolein), 12.2 mass % of cholesteryl oleate, 2.5 mass % of Liquid Paraffin, 2.5 matter of squalene Measure the spot of the composition of %, 1.6 mass % of cholesterine, 7.0 mass % of gelatin, 29.8 mass % of mud, 0.5 mass % of carbon black Cloth) 20 pieces.

Personal shirt:Personal shirt (LL sizes, the manufacture of DVD companies) (3cm × 3cm or so) fine crushing is cut out and is obtained by 150 Person.

In Terg-O-tometer (U.S. tests the manufacture of (UNITED STATES TESTING) company), it is put into 3 ° of 25 DEG C DH hard water 900mL, detergent composition 0.6g is added thereto, and then, adds above-mentioned substrate, and bath raio is adjusted to 20 times, It is washed 10 minutes under conditions of 120rpm, 25 DEG C.

Rinsing process:

Substrate after washing is dehydrated 1 minute, 25 DEG C of 3 ° of DH hard water 900mL are then placed in, in 120rpm, 25 DEG C of condition Lower rinsing 3 minutes.Repeat the operation (dehydration, rinsing) 2 times.At the 2nd time, the softening agent of specified amount is added to 25 DEG C of 3 ° of DH In hard water 900mL, rinsed.Softening agent is dried in the shade Soflan (portion room do ソ Off ラ Application) (Lion Corporation using interior Manufacture).

Drying process:

Substrate after rinsing is dehydrated 1 minute, then, recontamination judgement cloth (cotton) is only taken out, is sandwiched in filter paper, uses flatiron It is dry.

Using albedometer (beam splitting type colour difference meter SE2000, electricity Se Industrial Co., Ltd of Japan system makes), measure at washing The reflectivity (Z values) of the front and back recontamination judgement cloth of reason, Δ Z is found out by following formula.

Δ Z=(washing processing before Z values)-(washing treated Z values)

About the Δ Z in the recontamination judgement cloth of cotton, 5 average value is sought.Then, according to using the average value as index Following determinating references, evaluation prevent effect by the recontamination to cotton that detergent composition is brought.In following evaluation criteria, ◎ And zero for qualification.Evaluation result is as shown in table 6~7.

&#91;Ping Jiajizhun &#93;

◎:Δ Z is less than 5.

○:Δ Z is 5 less than 7.

△:Δ Z is 7 less than 9.

×:Δ Z is 9 or more.

<The Ping Jia &gt of fragrance retention;

(1) processing of the cotton towel of detergent composition has been used

(pre-treatment of evaluation cloth)

With commercial detergent " Top Platinum Clear " (manufacture of lion princes and dukes department), using two slot type washing machines, (Toshiba manufactures VH-30S), 3 following pre-treatments are carried out to commercially available cotton towel (east is manufactured into company).

Pre-treatment:Detergent standard usage amount, 30 times of bath raio, will be with 45 DEG C of originally water washing 10 minutes and next note The cycle that water rinses 10 minutes carries out 2 times.

(processing based on detergent composition when washing in rinsing process)

Using two slot type washing machines (Toshiba manufacture VH-30S), with the detergent composition described in table 6~7, by premenstrual Treatment of Washing Cotton towel (east is manufactured into company) 1.0kg after washing is washed (using standard usage amount, standard formula, 30 times, 25 DEG C of bath raio Tap water) 10 minutes, then carry out dehydration in 1 minute, then carry out the 1st rinsing in 3 minutes.In the 1st rinsing Afterwards, dehydration in 1 minute is carried out, the 2nd rinsing in 3 minutes is and then carried out, then carries out dehydration in 1 minute.

(2) evaluation for the treatment of cloth

According to following 6 stage odor strength representations, to being taken care of 5 after drying in above-mentioned 18 hours, under conditions of 20 DEG C, 40RH The aroma strength for the treatment of cloth (cotton towel) afterwards carries out sensory evaluation.It (is calculated to decimal point the by the average mark of 8 people of professional group 1), according to following judgement benchmark, evaluate fragrance last.From the point of view of commodity value, if zero or more is qualified.Evaluation As a result as shown in table 6~7.

<6 stage odor strength Biao Shifa >

0:It is odorless

1:The fragrance of detectable degree reluctantly

2:Know the fragrance of the degree of which kind of fragrance

3:Fragrance that can be easily perceivable

4:Qiang Xiang

5:Strong fragrance

&#91;Ping Jiajizhun &#93;

◎◎◎:3.0 points or more

◎◎:2.9~2.5 points

◎:2.4~2.0 points

○:1.9~1.5 points

△:1.4~1.0 points

×:0.9 point or less

<The Ping Jia &gt of storage stability;

Each example detergent composition 100mL is filled in transparent vial (wide-mouth specification bottle, PS-No.11), lid is closed Son, sealing.In this state, it stands and preserves 7 in 5 DEG C or 25 DEG C of thermostat.

After preserving in this way, liquid appearance is visually observed, according to following evaluation criteria, evaluates the stable storing of detergent composition Property.If △ or more is qualified.Evaluation result is as shown in table 6~7.

&#91;Ping Jiajizhun &#93;

○:Do not see deposit in vial bottom, there is liquid fluidity.

△:Although deposit is seen in the bottom in vial, it is light shake vial when, which disappears (dissolving).

×:See deposit in the bottom of vial, though gently shake the vial deposit if do not disappear, alternatively, rigid It manufactures detergent composition and just generates gelation or gonorrhoea later.

<The Ping Jia &gt of SR effects;

By evaluation TETO cotton (テ ト Cotton cloth) (cotton polyester=40/60) and cotton braid input full-automatic electric washing machine (AW-80VC, Toshiba Corporation manufacture), blending to 20 times of bath raio.Add embodiment 1 thereto, the liquid of embodiment 12 is washed Agent 12g is washed, the washing being washed, rinsed successively according to standard formula, is dehydrated operation is carried out.About wash time, rinsing, take off Water, water (being set as 36L), all without adjustment, use the standard setting of washing machine.The temperature of used tap water It is 15 DEG C.Repeat 5 washings operation.After completing 5 washing operations, evaluation is made to be carried out with a TETO cottons flat dry evening It is dry, use TETO cottons to be cut into 5 × 5cm person as evaluation cloth the evaluation after drying.By as the fat of spot (oleic acid, The mixture of palmitic acid, myristic acid, lauric acid, triolein, glyceryl tripalmitate, cetyl palmitate, squalene, carbon black) 50 μ L are coated on the evaluation cloth, make it dry 24 hours, make dirt cloth.

For the dirt cloth, decantation test is carried out in the following manner.

As decantation test device, use Terg-O-tometer (U.S. tests company and manufactures).As cleaning solution, following tune are used Object processed:The 300 μ L of liquid detergent that comparative example 4 is added into water 900mL, stir 30 seconds kinds, are modulated.By above-mentioned cleaning solution 900mL, above-mentioned dirt cloth 5 are put into washing woven cloth into above-mentioned decantation test device, are reconciled to 20 times of bath raio, 120rpm, it washs 20 minutes under conditions of 15 DEG C.Then, being transferred to two slot type washing machines, (Mitsubishi Electric Corporation manufactures:Product name CW-C30A1-H1), after being dehydrated 1 minute, in tap water (15 DEG C, 4 ° of DH) 30L, wash 3 minutes, air-dry.For non-dirt The dirt cloth after dirt cloth and washing before cloth (evaluation cloth), washing, uses colour difference meter (Japanese electricity Se Co., Ltd. respectively Manufacture:Product name SE200 types) reflectivity is measured, Washing ratio (%) is calculated by following formula.

Washing ratio (%)=(K/S of the pollution cloth after the K/S- washings of the pollution cloth before washing)/(pollution cloth before washing The K/S of the non-dirt cloth of K/S-) × 100

Wherein, K/S is (1-R/100)²(R indicates the dirt cloth after the reflectivity of the dirt cloth before washing, washing to/(2R/100) Reflectivity or non-dirt cloth reflectivity (%)).The average value for seeking the Washing ratio of dirt cloth 5, according to the average value For following evaluation criteria of index, the SR effects of the liquid detergent of embodiment 1, embodiment 12 are evaluated.If ◎, zero are qualification.

&#91;The Ping Jiajizhun &#93 of SR effects;◎:Washing ratio is 10% or more.

○:Washing ratio is 7% less than 10%.

△:Washing ratio is 4% less than 7%.

×:Washing ratio is less than 4%.

<The Ping Jia &gt of enzyme stability (enzymatic activity residue rate);

After the liquid detergent for manufacturing embodiment 1, embodiment 13 and comparative example 1, respectively under conditions of 37 DEG C and 4 DEG C It preserves 4 weeks.For after being saved 4 weeks under conditions of 37 DEG C liquid detergent (37 DEG C preservation product) and under conditions of 4 DEG C The liquid detergent after 4 weeks (4 DEG C of preservation product) is saved, the measurement of proteinase activity as follows is carried out.

The measurement of proteinase activity:

By milk casein (Casein, Bovine Milk, Carbohydrate and Fatty Acid Free/Calbiochem (registered trademark)) it is dissolved in 1N sodium hydroxides (1mol/L sodium hydroxide solutions (1N), the manufacture of Northeast chemical company), by pH tune To 10.5, be diluted with 0.05M boric acid (boric acid (superfine), Northeast chemical company manufacture) aqueous solution so that milk casein it is dense Degree becomes 0.6%, and protease matrix is made.

The liquid detergent 1g dilutions that will be obtained with 3 ° of DH hard water of calcium chloride (calcium chloride (superfine), Northeast chemical company manufacture) 25 times, using obtained dilute solution as sample solution.

Above-mentioned protease matrix 5g is added into sample solution 1g, is stirred 10 seconds with eddy mixer, then in 37 DEG C of condition It is lower to stand 30 minutes, carry out enzyme reaction.Then, the TCA (trichloroacetic acid (spies of enzyme reaction stopping agent are added into above-mentioned solution Grade), the Northeast chemical company manufacture) 0.44M aqueous solution 5g, with eddy mixer stir 10 seconds.Then, by the solution 20 30 minutes are stood under conditions of DEG C, unreacted matrix is precipitated, is removed the unreacted matrix of precipitation with 0.45 μm of filter, recycling Filtrate.

The ultraviolet-uisible spectrophotometer UV-160 manufactured using company of Shimadzu Seisakusho Ltd. measures the filtrate of recycling in wavelength Absorbance (absorbance A) at 275nm.Absorbance A is bigger, then it represents that tyrosine present in filtrate (passes through proteases for decomposing Protease matrix and generate) amount it is more.

In order to exclude the influence of the absorption other than purpose ingredient, in addition into each sample solution 1g, addition is used as enzyme reaction stopping agent TCA 5g, with eddy mixer stir 10 seconds, then add 5g protease matrix, with eddy mixer stir 10 seconds Clock is removed with 0.45 μm of filter, recycles filtrate.Then, using UV-160, suction of the above-mentioned filtrate at wavelength 275nm is measured Luminosity (absorbance B).

By following formula, proteinase activity residual rate (%) is calculated from the measurement result of above-mentioned proteinase activity.

In addition, substitute into the value of absorbance of each sample 275nm at of following formula, due to from absorbance by the scattering light such as bubble It excludes, so the absorbance value at removing while the 600nm measured, and use.

Proteinase activity residual rate=(the absorbance B of -37 DEG C of preservation product of absorbance A of 37 DEG C of preservation product)/(4 DEG C preserve product The absorbance B of -4 DEG C of preservation product of absorbance A) × 100

With such proteinase activity residual rate (%) for index, following benchmark are based on, enzyme stability are evaluated, if ◎, zero And △ is qualification.

◎:80% or more.

○:70% less than 80%.

△:60% less than 70%.

×:Less than 60%.

&#91;Table 6&#93;

&#91;Table 7&#93;

From the result of table 6~7 it is found that using in the embodiment of the present invention 1~13, recontamination prevents from haveing excellent performance, and stays Fragrance is also excellent.

In comparative example 1 without ingredient (A), fragrance retention is poor.

B1/B2 than the present invention numberical range outside comparative example 2 and comparative example 5 in, fragrance retention is poor.

Without ingredient (A) and B1/B2 is than in the comparative example 3 outside the numberical range of the present invention, fragrance retention is poor.

In the comparative example 4 for replacing ingredient (A) using polyethyleneimine, recontamination prevents performance and fragrance retention poor.

Industrial utilizability

According to the present invention, it is possible to provide the detergent composition with high fragrance retention.

Claims (4)

1. a kind of detergent composition, contains:

The alkylene oxide addition product A of polyalkylene amine,

Including the surfactant B of nonionic surfactant B1 and anion surfactant B2 and

Fragrance C,

The mass ratio indicated by ingredient B1/ ingredients B2 is 1.0 or more.

2. detergent composition according to claim 1, wherein

The ingredient B1 contains fatty acid methyl ester ethoxylate,

Relative to the gross mass of the ingredient B, the content of the fatty acid methyl ester ethoxylate is more than 10 mass %.

3. detergent composition according to claim 1 or 2, wherein the detergent composition also contains:

Ingredient D:With selected from least one of terephthalic acid (TPA) alkylene ester unit and alkylene isophthalate unit The polymer of repetitive unit d1 and oxyalkylene units d2.

4. detergent composition described in any one of claim 1 to 3, wherein the detergent composition also contains:

Ingredient E:At least one kind of in the carboxylic acid and its salt indicated by the following general formula (VII) and

Ingredient F:Enzyme,

X-R¹-COOH···(VII)

In formula (VII), R¹For the bivalent hydrocarbon radical or arlydene of carbon number 1~4, X is-H ,-OH ,-CH₃Or-COOH.