CN105793410A

CN105793410A - Liquid detergent

Info

Publication number: CN105793410A
Application number: CN201480066690.9A
Authority: CN
Inventors: 星田善行; 寺林刚; 森圭辅
Original assignee: Lion Corp
Current assignee: Lion Corp
Priority date: 2013-12-06
Filing date: 2014-12-04
Publication date: 2016-07-20
Anticipated expiration: 2034-12-04
Also published as: HK1226436A1; KR102305050B1; MY176485A; SG11201604459SA; TW201529836A; JPWO2015083800A1; JP6504710B2; KR20160093613A; CN105793410B; WO2015083800A1; TWI663252B

Abstract

A liquid detergent that contains: a component (A) that is a surfactant; a component (B) that is a saccharide-degrading-enzyme preparation; and a component (C) that is a hydroxycarboxylic acid or a salt thereof. The mass ratio of component (B)/component (C) is 1 or less.

Description

Liquid detergent

Technical field

The present invention relates to liquid detergent.

The application is by December in 2013 CLAIM OF PRIORITY based on the Patent 2013-253646 of Japanese publication on the 6th, and its content is incorporated herein.

Background technology

Due to the raising that cleaning is required, liquid detergent for dress material, except requiring removing to be attached to the spot (clean result) of (substrates) such as dress materials, also require remove the undesirable abnormal smells from the patient produced by substrate and prevent substrate from producing undesirable abnormal smells from the patient.

Substrate produces undesirable abnormal smells from the patient mainly due to caused by the microbial growth drying or being attached in keeping fiber of substrate.

To this, proposed the detergent being mixed with the cationic surfactant with bactericidal effect or antibacterial effect in the past.Patent Document 1 discloses the liquid detergent containing cationic surfactant, nonionic surfactant and benzoic acid and/or its salt.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open 2006-316130 publication

Summary of the invention

The problem that invention to solve

But, along with the change of recent life style, carry out washing at night and the substrate after washing is dried in indoor such a dry the family of operation within doors and increase.For drying within doors, owing to ventilating, poor, substrate is difficult to dry, thus, the microorganism being attached to fiber is easily bred.

Therefore, it is desirable to following detergent: even if dry within doors, the generation of undesirable abnormal smells from the patient (following, otherwise referred to as drying taste within doors) from substrate also can be suppressed.In above-mentioned patent documentation 1 record liquid detergent suppress this dry within doors taste produce effect insufficient.Additionally, only increase when having the content of cationic surfactant of bactericidal effect or antibacterial effect, clean result is deteriorated, and consequently also becomes that being difficult to is inhibited dries the effect that taste produces within doors.

As improving the method suppressing to dry the effect that taste produces within doors, the present inventor is newly conceived to will attach to the aspect of the particularly biofilm breakup of inner side, the removing of substrate or sink, and has studied.It was found that by effectively utilizing the carbohydrate degradation enzymes such as mannase, it is possible to effectively taste is dried in suppression within doors.

But, during mixing saccharide digestive enzyme, the problem that there is the storage stability (such as, transparent homogeneity and mobility) being difficult to ensure that liquid detergent.

The present invention completes in view of the foregoing, its problem be in that to provide a kind of suppression to dry within doors taste produces effective and liquid detergent that storage stability is good.

The means of solution problem

By further research, the inventors discovered that by surfactant solution by the carbohydrate degradation enzyme preparation such as mannase simultaneously with hydroxy carboxylic acid or its salt use, wherein, the consumption of hydroxy carboxylic acid or its salt is and carbohydrate degradation enzyme preparation equivalent or above, thus solving the problems referred to above, complete the present invention.Namely, the liquid detergent of the present invention relates to following liquid detergent: described liquid detergent contains the surfactant as (A) composition, the carbohydrate degradation enzyme preparation as (B) composition and the hydroxy carboxylic acid as (C) composition or its salt, and with the mass ratio represented by (B) composition/(C) composition for less than 1.

In the liquid detergent of the present invention, it is preferable that above-mentioned (A) composition contains cationic surfactant.

That is, the present invention relates to herein below.

[1] a kind of liquid detergent, it contains:

(A) composition: surfactant；

(B) composition: carbohydrate degradation enzyme preparation；And

(C) composition: hydroxy carboxylic acid or its salt；

And with the mass ratio represented by (B) composition/(C) composition for less than 1.

[2] such as the liquid detergent that [1] is recorded, wherein, described (A) composition contains cationic surfactant.

The effect of invention

Liquid detergent according to the present invention, the effective of taste generation is dried in its suppression within doors and storage stability is good.

Detailed description of the invention

The liquid detergent of the present invention contains the surfactant as (A) composition, the carbohydrate degradation enzyme preparation as (B) composition and the hydroxy carboxylic acid as (C) composition or its salt.

The liquid detergent of the present invention can be used for home-use, business use, industrial purposes, wherein, is suitable for home-use, the particularly suitable liquid detergent as dress material.

The kind of washing object (substrate), can enumerate and wash the identical washing object of object with home washings as washing object, for instance, the fibres etc. such as clothes, rag, towel class, sheet, curtain can be enumerated.

<(A) composition: surfactant>

The liquid detergent of the present invention has washing performance by containing (A) composition.

As (A) composition, it is possible to use commonly used surfactant in the liquid detergents such as dress material use, nonionic surfactant, anion surfactant, cationic surfactant and amphoteric surfactant etc. can be enumerated.

In this specification, nonionic surfactant is also referred to as (A-1) composition, and anion surfactant is also referred to as (A-2) composition, and cationic surfactant is also referred to as (A-3) composition.

((A-1) composition: nonionic surfactant)

As (A-1) composition, for instance, the nonionic surfactant of (1)～(9) shown below can be enumerated.

(1) polyoxyalkylene alkyl (or thiazolinyl) ether.

(2) polyxyethylated (or thiazolinyl) phenyl ether.

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

(4) polyoxyethylene sorbitan fatty acid ester.

(5) polyoxyethylene sorbitol fatty acid ester.

(6) polyoxyethylene fatty acid ester.

(7) polyoxyethylene hydrogenated Oleum Ricini.

(8) fatty acid glyceride.

(9) addition alkylene oxide and the alkylamine alkoxylates that obtains on chain alkyl (or thiazolinyl) amine.

(A-1) in composition, it is preferable that above-mentioned (1), (3) and (9).Wherein, from improving storage stability further and suppressing liquid level to form epithelium effect, it is preferred that above-mentioned (3).Additionally, during using aftermentioned (A-2) composition as main wash composition, obtain effect of the present invention from being more easy to, it is preferred to use above-mentioned (1).

As the preferred thing of above-mentioned (3), the poly (oxyalkylene) fundamental mode nonionic surfactant (hereinafter also referred to " (a-1-1) composition ") shown in following formula (a-1-1) can be enumerated.

Additionally, as the preferred thing of above-mentioned (1), the poly (oxyalkylene) fundamental mode nonionic surfactant (hereinafter also referred to " (a-1-2) composition ") shown in following formula (a-1-2) and the poly (oxyalkylene) fundamental mode nonionic surfactant (hereinafter also referred to " (a-1-3) composition ") shown in formula (a-1-3) can be enumerated.

Additionally, as the preferred thing of above-mentioned (9), the amines type nonionic surfactant (hereinafter also referred to " (a-1-4) composition ") shown in following formula (a-1-4) can be enumerated.

About (a-1-1) composition

(a-1-1) composition is the poly (oxyalkylene) fundamental mode nonionic surfactant shown in following formula (a-1-1).

R¹-CO-[(EO’)s/(PO’)t]-R²(a-1-1)

[in formula, R¹It it is the thiazolinyl of the alkyl of carbon number 7～18 or carbon number 7～18；R²It it is the alkyl of carbon number 1～3；S represents the averaged repeating numbers of EO ', and is the number of 6～20；T represents the averaged repeating numbers of PO ', and is the number of 0～6；EO ' represents oxyethylene group, and PO ' represents oxypropylene group；[(EO ') and s/ (PO ') t] mean that EO ' and PO ' can be mixed.]

In above-mentioned formula (a-1-1), from the viewpoint of washing performance, R¹The alkyl of preferred carbon number 9～18 or the thiazolinyl of carbon number 9～18, it can be straight-chain or containing branched.

As R¹, the alkyl or alkenyl from raw materials such as the higher alcohol of one-level or two grades, higher fatty acids, higher fatty acid amides can be enumerated.

In above-mentioned formula (a-1-1), R²It it is the alkyl of carbon number 1～3, it is preferable that methyl.

In above-mentioned formula (a-1-1), s is the number of 6～20, it is preferable that the number of 6～18, more preferably the number of 11～18, it is particularly preferred to the number of 14～16.It addition, s can be integer, it is also possible to containing decimal.

When s is more than 20, HLB value becomes too high, has washing performance downward trend.On the other hand, when s is less than 6, there is the trend of the raw material abnormal smells from the patient mutability difference of (a-1-1) composition self.

T is the number of 0～6, it is preferable that the number of 0～3.It addition, t can be integer, it is also possible to containing decimal.

When t is more than 6, there is storage stability downward trend under the high temperature of liquid detergent.

It addition, " averaged repeating numbers " in this specification and claims means the molal quantity of ethylene oxide or the propylene oxide reacted relative to 1 mol of alcohol used.

[(EO ') s/ (PO ') t] means that EO ' and PO ' can be mixed arrangement, EO ' and PO ' and also can add and become random shape or add and become block-wise.

(a-1-1), in composition, the repeat number distribution of EO ' or PO ' is not particularly limited, it is easy to change according to reaction method when manufacturing (a-1-1) composition.Such as, repeat number for EO ' or PO ' is distributed, the base catalysts such as common sodium hydroxide, potassium hydroxide are used to make ethylene oxide or propylene oxide addition in hydrophobic group raw material (namely, the higher alcohol of one-level or two grades, higher fatty acids, higher fatty acid amides etc.) time, have and become more eurytopic trend.Additionally, the use recorded in Japanese Patent Laid-fair 6-15038 publication is added with Al³⁺、Ga³⁺、In³⁺、Tl³⁺、Co³⁺、Sc³⁺、La³⁺And Mn²⁺The specific alkoxylating catalyst such as the magnesium oxide Deng metal ion and make ethylene oxide or propylene oxide addition when above-mentioned hydrophobic group raw material, the repeat number of EO ' or PO ' distribution has the trend becoming relatively narrow ditribution.

Preference as (a-1-1) composition, such as can enumerating the fatty acid methyl ester relative to carbon number 10～18 (preferably 12～14), addition is equivalent to the ethylene oxide of 11～18 (preferably 15) mole and the poly (oxyalkylene) fundamental mode nonionic surfactant etc. that obtains.

About (a-1-2) composition and (a-1-3) composition

(a-1-2) composition is the poly (oxyalkylene) fundamental mode nonionic surfactant shown in following formula (a-1-2), and (a-1-3) composition is the poly (oxyalkylene) fundamental mode nonionic surfactant shown in following formula (a-1-3).

R^3a-O-(EO’)_u-H(a-1-2)

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

[in formula, R^3aAnd R^3bIndependently represent the alkyl of carbon number 8～18 or the thiazolinyl of carbon number 8～18；U represents the averaged repeating numbers of EO ', and is the number of 5～20；P represents the averaged repeating numbers of EO ', and q represents the averaged repeating numbers of PO ', and r represents the averaged repeating numbers of EO ', and p, q, r are the number meeting 17>p>1,17>r>1,0<q 3 and p+r=10～20；EO ' represents oxyethylene group, and PO ' represents oxypropylene group；[(EO’)_p/(PO’)_q] mean that EO ' and PO ' can be mixed.]

In above-mentioned formula (a-1-2) and formula (a-1-3), from the viewpoint of x washing performance, R^3aAnd R^3bThe separately thiazolinyl of the preferably alkyl of carbon number 10～18 or carbon number 10～18, it can be straight-chain or containing branched.

In above-mentioned formula (a-1-2), u is the number of 5～20, it is preferable that the number of 8～18, more preferably the number of 10～16, it is particularly preferred to the number of 14～16.When u is more than 20, HLB value becomes too high, has washing performance downward trend.On the other hand, when u is less than 5, there is the trend that the raw material abnormal smells from the patient of (a-1-2) composition self is easily deteriorated.

In above-mentioned formula (a-1-3), [(EO ')_p/(PO’)_q] mean that EO ' and PO ' can be mixed arrangement, EO ' and PO ' and can add and become random shape or add and become in block-wise.

In above-mentioned formula (a-1-3), for the ratio of EO ' and PO ', with the ratio meter represented by q/ (p+r), it is preferred to 0.1～0.5, more preferably 0.1～0.3.When q/ (p+r) is more than preferred lower limit value, will not excess foam formation, it is easy to seek the optimization bubbled.When q/ (p+r) is below preferred upper limit value, becomes prone to obtain suitable viscosity, and be prone to suppress gelation.

(a-1-2) composition and (a-1-3) composition can manufacture respectively through known method.(a-1-2) composition, for instance, can by derived by natural oil obtain there is R^3aAlcohol on addition ethylene oxide and manufacture.(a-1-3) composition, for instance, can by derived by natural oil obtain there is R^3bAlcohol on, after carrying out after being sequentially carried out the additive reaction of ethylene oxide and propylene oxide or with ethylene oxide and propylene oxide mixing addition (random addition), again addition ethylene oxide and manufacture.

When using (a-1-2) composition or (a-1-3) composition, liquid detergent becomes to be readily obtained suitable viscosity, also becomes easily to suppress gelation.Additionally, foaming characteristic improves, biological degradability also becomes better.

Preference as (a-1-2) composition and (a-1-3) composition, such as, Diadol (the trade name that Mitsubishi chemical Co., Ltd is manufactured can be enumerated, the alcohol (C13) of carbon number 13), shell (Shell) company manufacture Neodol (trade name, the alcohol (C12) of carbon number 12 and the mixture of C13), the ethylene oxide of alcohol addition 12 molar equivalent such as the Safol23 (trade name, the mixture of C12 and C13) that manufactures of husky rope (Sasol) company or 15 molar equivalents and the nonionic surfactant that obtains；The CO-1214 (trade name) that P&G's (プロ Network タア Application De ギャ Application Block Le) company is manufactured or the ethylene oxide of natural alcohol addition 12 molar equivalent such as CO-1270 (trade name) or 15 molar equivalents and the nonionic surfactant that obtains；For the C12 alkene of butylene trimerizing gained is supplied in oxo synthesis and to the ethylene oxide of C13 alcohol addition 7 molar equivalent and the nonionic surfactant (such as, trade name: LutensolTO7, BASF AG manufactures) that obtains；The nonionic surfactant that obtains for amylalcohol being supplied in the ethylene oxide of C10 alcohol addition 9 molar equivalent that Guerbet (Guerbet) is obtained by reacting (such as, trade name: LutensolXP90, BASF AG manufactures)；The nonionic surfactant that obtains for amylalcohol being supplied in the ethylene oxide of C10 alcohol addition 7 molar equivalent that Guerbet reaction obtains (such as, trade name: LutensolXL70, BASF AG manufactures)；The nonionic surfactant that obtains for amylalcohol being supplied in the ethylene oxide of C10 alcohol addition 6 molar equivalent that Guerbet reaction obtains (such as, trade name: LutensolXA60, BASF AG manufactures)；Nonionic surfactant that secondary alcohol addition 9 molar equivalent of carbon number 12～14 or the ethylene oxide of 15 molar equivalents are obtained (such as, trade name: Softanol90, Softanol150, Nippon Catalyst K. K. manufactures)；After propylene oxide to natural alcohol (mixture etc. of the alcohol of the alcohol of carbon number 12 and carbon number 14) ethylene oxide of addition 8 molar equivalent, 2 molar equivalents successively, the ethylene oxide of addition 8 molar equivalent and the nonionic surfactant etc. that obtains again.

About (a-1-4) composition

(a-1-4) composition is the amines type nonionic surfactant that following formula (a-1-4) represents.

[changing 1]

[in formula, R⁰It it is the thiazolinyl of the alkyl of carbon number 10～20 or carbon number 10～20；A¹O and A²O separately represents the oxyalkylene of carbon number 2～3；I represents A¹The averaged repeating numbers of O；J represents A²The averaged repeating numbers of O；I > 0, j > 0, and i+j is the number of 10～50.]

In above-mentioned formula (a-1-4), R⁰Carbon number be 10～20, from the viewpoint of washing performance, it is preferable that the alkyl of carbon number 10～18 or the thiazolinyl of carbon number 10～18, it can be straight-chain or containing branched.

R⁰Carbon number when being more than 10, it is possible to obtain good washing performance；R⁰Carbon number when being less than 20, it is possible to obtain good dissolubility.

In above-mentioned formula (a-1-4), (A¹O)_iAnd (A²O)_jRepresent the repetitive structure of the oxyalkylene of carbon number 2～3, it can be merely the repetitive structure of oxyethylene group (EO ') respectively, the repetitive structure of oxypropylene group (PO ') can also be merely, the structure that also can obtain for EO ' and PO ' be mixed arrangement.When both are mixed arrangement, EO ' and PO ' can add to be become random shape or add and becomes in block-wise.Wherein, in there is high washing force for sebum spot, (A¹O)_iAnd (A²O)_jIt is preferably only the repetitive structure of EO ' respectively.

In above-mentioned formula (a-1-4), i, j are 40 > i > 0,40 > j > 0 and i+j be the number of 10～50.I+j preferably 10～40, more preferably 10～30.When i+j is more than the lower limit of above-mentioned scope, scourability becomes more good, and when i+j is below the higher limit of above-mentioned scope, the storage stability of liquid detergent improves further.

Preference as (a-1-4) composition, for instance, the ethylene oxide of alkylamine addition 20 (that is, the i+j=20) molar equivalent for carbon number 16 can be enumerated and the amines type nonionic surfactant etc. that obtains.

(A-1) composition can be used alone or two or more kinds may be used.

(A-1) in composition, preferably above-mentioned (1), (3) and (9), more preferably above-mentioned (1) and (3), wherein, better from the viewpoint of the low-temperature stability of washing performance, liquid detergent, it is preferred that (a-1-1) composition, (a-1-2) composition and (a-1-3) composition, it is particularly preferred to (a-1-1) composition.(a-1-1) in composition, the more preferably fatty acid ester type nonionic surfactant during t=0 in above-mentioned formula (a-1-1).

In whole (A) composition, the ratio shared by (A-1) composition is not particularly limited, relative to the gross mass of (A) composition, it is 10～96 mass % preferably, more preferably 30～90 mass %, it is preferred that 50～90 mass %, it is particularly preferred to 70～90%.If (A-1) ratio of composition is in above-mentioned preferable range, then improve the washing performance for the spot being attached to substrate further.

((A-2) composition: anion surfactant)

As (A-2) composition, for instance, the anion surfactant of (11)～(22) shown below can be enumerated.

(11) there is the straight-chain of the alkyl of carbon number 8～18 or the alkylbenzenesulfonate (LAS or ABS) containing branched.

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

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

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

(15) by alkyl (or thiazolinyl) ether sulfate (AES, AEPS) of any one or the straight-chain with atomic number 10～20 that ethylene oxide (EO) and average 0.5～10 mole of propylene oxide (PO) (mol ratio EO/PO=0.1/9.9～9.9/0.1) addition (that is, averaged repeating numbers is 0.5～10) are obtained or the alkyl (or thiazolinyl) containing branched of the epoxyalkane of carbon number 2～4.

(16) by alkyl (or thiazolinyl) the phenyl ether sulfate of any one in the epoxyalkane of carbon number 2～4 or the straight-chain with carbon number 10～20 that ethylene oxide (EO) and average 3～30 moles of propylene oxide (PO) (mol ratio EO/PO=0.1/9.9～9.9/0.1) addition (that is, averaged repeating numbers is 3～30) are obtained or the alkyl (or thiazolinyl) containing branched.

(17) by alkyl (or thiazolinyl) ether carboxylate of any one or the straight-chain with carbon number 10～20 that ethylene oxide (EO) and propylene oxide (PO) (mol ratio EO/PO=0.1/9.9～9.9/0.1) addition average 0.5～10 mole (that is, averaged repeating numbers 0.5～10) are obtained or the alkyl (or thiazolinyl) containing branched of the epoxyalkane of carbon number 2～4.

(18) the alkyl polyols ether sulfate such as alkyl glyceryl ether sulfonate of carbon number 10～20.

(19) phosphate of long-chain monoalkyl, dialkyl group or sesquialter alkyl.

(20) phosphate of polyoxyethylene monoalkyl, polyoxyethylene dialkyl group or polyoxyethylene sesquialter alkyl.

(21) α-sulfofattyacidmethylestersalt (MES) of carbon number 14～18.

(22) soap (soap) of carbon number 10～22.

(A-2), in composition, alkanolamine, the ammonium salts etc. such as the alkali earth metal salts such as the alkali metal salt such as sodium and potassium, magnesium, monoethanolamine and diethanolamine can be used.

(A-2) composition can be used alone or two or more kinds may be used.

(A-2) in composition, it is preferable that above-mentioned (11), (15), (21) and (22), it is particularly preferred to above-mentioned (11).

In whole (A) composition, the ratio shared by (A-2) composition is not particularly limited, and relative to the gross mass of (A) composition, it is 1～30 mass % preferably, more preferably 2～20 mass %, it is preferred that 3～15 mass %.If (A-2) ratio of composition is in above-mentioned preferable range, then improve the washing performance for the spot being attached on substrate further.

((A-3) composition: cationic surfactant)

As (A-3) composition, for instance the cationic surfactant of (31)～(33) shown below can be enumerated.

(31) two chain alkyl two short-chain alkyl type quaternary ammonium salts.

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

(33) tri-long-chain alkyl list short-chain alkyl type quaternary ammonium salt.

" chain alkyl " in these (31)～(33) represents the alkyl of carbon number 10～26.The carbon number of the abovementioned alkyl of chain alkyl preferably 10～18.Specifically, C12 alkyl trimethyl ammonium chloride, DDAC etc. can be enumerated as suitable cationic surface active agent.

" short-chain alkyl " represents the alkyl of the carbon number 1～4 can with substituent group.The carbon number of the abovementioned alkyl of short-chain alkyl preferably 1 or 2.As the substituent group that the abovementioned alkyl of short-chain alkyl can have, phenyl, benzyl, hydroxyl, hydroxyalkyl, polyoxy alkylidene etc. can be enumerated.The carbon number of hydroxyalkyl preferably 2～4, more preferably 2 or 3.The carbon number of the oxyalkylene in polyoxy alkylidene preferably 2～4, more preferably 2 or 3.

(A-3) composition can be used alone or two or more kinds may be used.

(A-3) in composition, it is particularly preferred to use above-mentioned (32).

In whole (A) composition, the ratio shared by (A-3) composition is not particularly limited, and relative to the gross mass of (A) composition, it is 0.01～30 mass % preferably, more preferably 0.1～20 mass %, it is particularly preferred to 0.5～10 mass %.If (A-3) ratio of composition is in above-mentioned preferable range, then when drying within doors, it is possible to suppress the generation of the undesirable abnormal smells from the patient (drying taste within doors) from substrate further.

As amphoteric surfactant, for instance, imidazoline system amphoteric surfactant, amide betaine system amphoteric surfactant, alkyl dimethyl amine oxide, alkyl amidopropyldimethyl amine oxide etc. can be enumerated.Specifically, the C12 amine oxide in 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazole quinoline glycine betaine, lauric amide CAB, alkyl dimethyl amine oxide and C14 amine oxide etc. can be enumerated as suitable amphoteric surfactant.

Amphoteric surfactant can be used alone or two or more kinds may be used.

In whole (A) composition, the ratio shared by amphoteric surfactant is not particularly limited, and relative to the gross mass of (A) composition, it is 0～60 mass % preferably, more preferably 0～30 mass %.If the ratio of amphoteric surfactant is in above-mentioned preferred scope, then the washing performance for the spot being attached to substrate improves further.

In liquid detergent, (A) composition can be used alone or two or more kinds may be used.

As (A) composition, it is preferable that and with (A-1) composition and (A-2) composition.(A-1), when composition and (A-2) composition coexist, improve further for the washing performance being attached to the various spots such as the sebum spot of substrate, protein contaminants, saccharide spot, thus, it is easy to significantly show the effect of the present invention.

(A-1) mass ratio (also being indicated as " mass ratio (A-1)/(A-2) ") that composition/(A-2) composition represents preferably 0.1～20, more preferably 0.5～10.

If mass ratio (A-1)/(A-2) is more than preferred lower limit, then the washing performance especially for sebum spot improves further；On the other hand, if mass ratio (A-1)/(A-2) is below preferred higher limit, then the washing performance especially for protein contaminants improves further.

In the present invention, " mass ratio that (A-1) composition/(A-2) composition represents " means the mass ratio relative to (A-2) component content of (A-1) component content in liquid detergent.

It addition, the mass ratio that (A-1) composition/(A-2) composition represents can be 5～20.

Additionally, in the liquid detergent of the present invention, it is preferable that (A) composition contains (A-3) composition.By containing (A-3) composition, when drying within doors, can improve further and suppress to dry the effect that taste produces within doors.

Additionally, as (A) composition, from improving the washing performance for various spots and being easily obtained and suppress to dry the effect that taste produces within doors, it is preferable that and with (A-1) composition, (A-2) composition and (A-3) composition.

The mass ratio (also being indicated as " mass ratio [(A-1)+(A-2)]/(A-3) ") that [(A-1) composition+(A-2) composition]/(A-3) composition represents preferably 1～50, more preferably 5～30, it is preferred that 18～46.

If mass ratio [(A-1)+(A-2)]/(A-3) is more than preferred lower limit, then improve storage stability (transparent homogeneity and mobility) further；On the other hand, if mass ratio [(A-1)+(A-2)]/(A-3) is below preferred higher limit, then improves further and suppress to dry the effect that taste produces within doors.

In the present invention, the total content of (A-1) composition that " mass ratio that [(A-1) composition+(A-2) composition]/(A-3) composition represents " means in liquid detergent and (A-2) composition is relative to the mass ratio of (A-3) component content.

Relative to the gross mass of aforesaid liquid detergent, content preferably more than the 20 mass %, more preferably more than 30 mass %, it is particularly preferred to more than 40 mass % of (A) composition in liquid detergent.If (A) content of composition is more than preferred lower limit, then becoming prone to obtain for the good clean result of the spot being attached to substrate, the content of (A) composition becomes more high, more easy obtains effect produced by the present invention significantly.

On the other hand, the higher limit of the content of (A) composition is preferably in below 80 mass %, and more preferably below 70 mass %, it is preferred that below 60 mass %.If (A) content of composition is below preferred higher limit, then can guarantee transparent homogeneity and the mobility of outward appearance more easily.

That is, relative to the gross mass of liquid detergent, the content of (A) composition preferably more than 20 mass %, below 80 mass %, more preferably more than 30 mass %, below 70 mass %, it is preferred that more than 40 mass %, below 60 mass %.

Additionally, relative to the gross mass of liquid detergent, the content of (A) composition can be 27～48 mass %.

<(B) composition: carbohydrate degradation enzyme preparation>

(B) composition is the enzyme preparation containing carbohydrate degradation enzyme.

In the liquid detergent of the present invention, by containing (B) composition, main suppression is dried the effect of taste generation within doors and is played.

As carbohydrate degradation enzyme, cellulase, amylase, mannonase pectase, xylanase, saccharifying enzyme, glucosidase, glucanase, dextranase, chitinase, sialidase, mannosidase, saccharase, fucosidase, algin catenase and pectin lyase etc. can be enumerated.In these, suppress to dry the effect that taste produces within doors from the viewpoint of being more readily available, it is preferable that cellulase, amylase and mannase, it is particularly preferred to amylase and mannase.

The commercially available product that can specifically obtain for (B) composition, as the enzyme preparation containing cellulase, Endolase5000L, Celluzyme0.4L, the CarezymePremium4500L (more than, trade name) that can believe (Novozymes) company from Novi and obtain etc. can be enumerated.As containing diastatic enzyme preparation, Termamyl300L, TermamylUltra300L, Duramyl300L, Stainzyme12L, the StainzymePlus12L (above, trade name) that can obtain can be enumerated from Novozymes Company；Can from Jie Neng section (Genencor) company obtain trade name Maxamyl, can from Amano Enzyme Inc. obtain trade name pullulanaseamano, can from Seikagaku Kogyo Co. Ltd. obtain trade name DB-250 etc..As the enzyme preparation containing mannase, the trade name Mannaway4L etc. that can obtain can be enumerated from Novozymes Company.

(B) composition can be used alone or two or more kinds may be used.

From the viewpoint of improving clean result further and suppressing to dry the effect that taste produces within doors, gross mass relative to aforesaid liquid detergent, (B) component content preferably more than 0.01 mass % in liquid detergent, more preferably more than 0.03 mass %, it is preferred that more than 0.05 mass %.

On the other hand, saturated from the viewpoint of the mixed effect guaranteeing (inhibitory enzyme precipitation etc.) and (B) composition of storage stability, gross mass relative to aforesaid liquid detergent, (B) the upper content limit value of composition preferably below 2 mass %, more preferably below 1.5 mass %, it is preferred that below 1 mass %.That is, relative to the gross mass of liquid detergent, the content of (B) composition preferably more than 0.01 mass %, below 2 mass %, more preferably more than 0.03 mass %, below 1.5 mass %, it is preferred that more than 0.05 mass %, below 1 mass %.

Additionally, relative to the gross mass of liquid detergent, content particularly preferably 0.1～0.5 mass % of (B) composition.

<(C) composition: hydroxy carboxylic acid or its salt>

(C) composition is hydroxy carboxylic acid or its salt, i.e. it is chosen from least one compound in the group being made up of hydroxy carboxylic acid and hydroxycarboxylate.

In the present invention, " hydroxy carboxylic acid " refers to the compound in 1 molecule with carboxyl (-COOH) and alcohol hydroxyl group (-OH).

In the liquid detergent of the present invention, by containing (C) composition, mainly the outward appearance of liquid detergent can be remained transparent homogeneous, furthermore it is possible to guarantee the mobility of liquid detergent, make excellent storage stability.

As hydroxycarboxylate, the alkali metal salt such as sodium salt and the potassium salt that can enumerate above-mentioned hydroxy carboxylic acid；The alkali earth metal salt such as calcium salt and magnesium salt；The alkanolamine such as ammonium salt and ethanolamine salt etc..

As the preference of (C) composition, the compound shown in following formula (c-1) can be enumerated.

[changing 2]

[in formula, R⁴And R⁵Separately represent hydrogen atom, can have the alkyl of the carbon number 1～10 of substituent group, can have the aryl of substituent group, nitro (-NO₂), ester group, ether, can have the amino (-NH of substituent group₂) or amine derivative group；R⁶And R⁷Separately represent the alkyl of hydrogen atom or carbon number 1～5；V is the integer of 0～4；M⁺It it is counter ion.]

In above-mentioned formula (c-1), R⁴And R⁵In the carbon number of alkyl be 1～10, it is preferable that carbon number is 1～5, wherein, more preferably methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, amyl group, isopentyl and neopentyl；It is preferred that methyl, ethyl, propyl group and isopropyl；Particularly preferably methyl and ethyl；Most preferable.R⁴And R⁵In aryl, it is preferable that carbon number is 6～15, and more preferably carbon number is 6～10, wherein, it is preferred that phenyl and naphthyl.

As R⁴And R⁵In ester group, for instance, can suitably enumerate-COOR⁸.As R⁴And R⁵In ether, for instance, can suitably enumerate-R⁴-O-R⁵。

R⁴And R⁵In, " alkyl with substituent group, the aryl with substituent group, have the amino of substituent group " means to constitute the hydrogen atom of alkyl, the hydrogen atom constituting aryl, respective at least 1 hydrogen atom of constituting in the hydrogen atom of amino are replaced the replaced alkyl of base, aryl and amino.

As the substituent group that the alkyl of carbon number 1～10 can have, such as, aryl, nitro, nitro-derivative group, hydroxyl (-OH), hydroxyl derivative groups, ester group, ether, amino, amine derivative group, amide groups, amide derivatives group and halogen atom etc. can be enumerated.

As the substituent group that aryl can have, for instance, alkyl, nitro, nitro-derivative group, hydroxyl, hydroxyl derivative groups, ester group, ether, amino, amine derivative group, amide groups, amide derivatives group and halogen atom etc. can be enumerated.

As the substituent group that amino can have, for instance, alkyl, aryl, nitro, nitro-derivative group, hydroxyl, hydroxyl derivative groups, ester group, ether, amine derivative group, amide groups, amide derivatives group and halogen atom etc. can be enumerated.

As the alkyl in above-mentioned substituent group, aryl and ester group, can enumerate and above-mentioned R⁴And R⁵In alkyl, group that aryl is identical with ester group.

As the amide groups in above-mentioned substituent group, for instance, can suitably enumerate-C (=O) NH-R⁹。

As the halogen atom in above-mentioned substituent group, for instance, fluorine atom, chlorine atom, bromine atoms and atomic iodine can be enumerated, it is preferable that fluorine atom.

In above-mentioned, R⁴And R⁵Respectively preferably hydrogen atom, can have the alkyl of the carbon number 1～10 of substituent group, can have the aryl of substituent group.

Additionally, the preferred R of difference⁴And R⁵Both of which is hydrogen atom, R⁴And R⁵A side be hydrogen atom and the opposing party can have the alkyl of carbon number 1～10 of substituent group, R⁴And R⁵A side be hydrogen atom and the opposing party is the aryl can with substituent group.

In above-mentioned formula (c-1), R⁶And R⁷In alkyl separately represent the alkyl of carbon number 1～5, wherein, it is preferable that methyl, ethyl, propyl group or isopropyl, more preferably methyl or ethyl, it is preferred that methyl.

Additionally, the preferred R of difference⁶And R⁷Both of which is hydrogen atom, R⁶And R⁷A side be hydrogen atom and the opposing party is methyl.

V is the integer of 0～4, it is preferable that 0,1 or 2, more preferably 0 or 1, it is particularly preferred to 0.

M⁺It is counter ion, as long as can with-COO^-Together form the counter ion of water soluble salt.As above-mentioned counter ion, alkali metal ion, alkaline-earth metal ion (in this case, counter ion is divalent ion), protonated amines, ammonium and proton etc. can be enumerated.It addition, M⁺When being proton, the compound shown in formula (c-1) represents hydroxy carboxylic acid.

As the alkali metal that can obtain above-mentioned counter ion, sodium and potassium etc. can be enumerated.

The alkaline-earth metal of above-mentioned counter ion can be obtained, calcium and magnesium etc. can be enumerated.

The amine of above-mentioned counter ion can be obtained, it is possible to be any one in primary amine, secondary amine, tertiary amine, it is preferable that total carbon atom number is 1～6.Above-mentioned amine can have hydroxyl, as such amine, can enumerate alkanolamine, it is preferable that the carbon number of above-mentioned silane alcohol base is 1～3.As the object lesson of alkanolamine, monoethanolamine, diethanolamine and triethanolamine etc. can be enumerated.

The amine that can obtain above-mentioned counter ion becomes counter ion through protonation.

As M⁺, from the viewpoint of the difficulty obtained and further raising dissolubility, it is preferable that alkali metal ion, it is preferable that sodium ion and potassium ion, it is particularly preferred to sodium ion.

Preference as (C) composition, specifically, glycolic, lactic acid (α-hydracrylate and ethylene lactic acid), hydroxybutyric acid (2-hydroxybutyric acid, 3-hydroxybutyrate and gamma-hydroxybutyric acid), hydroxy-iso-butyric acid (2-hydroxy-iso-butyric acid and 3-HIB), mandelic acid and their optical isomer or their salt etc. can be enumerated.

In above-mentioned, as (C) composition, particularly become good from the viewpoint of storage stability, it is preferable that alpha-hydroxy carboxylic acid compounds or its salt, more preferably Alpha-hydroxy-monocarboxylic acid or its salt, it is particularly preferred to the compound that following formula (c-1-1) represents.

[changing 3]

[in formula, R⁴' and R⁵' separately represent hydrogen atom, can have the alkyl of the carbon number 1～10 of substituent group, can have the aryl of substituent group, nitro (-NO₂), ether, can have substituent group amino (-NH₂) or amine derivative group；M⁺With the M in above-mentioned formula (c-1)⁺Identical.]

In above-mentioned formula (c-1-1), R⁴' and R⁵' in the alkyl of carbon number 1～10 and aryl, can enumerate and above-mentioned R⁴And R⁵The alkyl of middle carbon number 1～10 and the identical group of aryl.

Preferred R⁴' and R⁵' both of which is hydrogen atom, R⁴' and R⁵' a side is hydrogen atom and alkyl or R that the opposing party is the carbon number 1～10 can with substituent group⁴' and R⁵' a side be hydrogen atom and the opposing party is the aryl can with substituent group；More preferably R⁴' and R⁵' a side is hydrogen atom and alkyl or R that the opposing party is the carbon number 1～10 can with substituent group⁴' and R⁵' a side be hydrogen atom and the opposing party is the aryl can with substituent group；Particularly preferably R⁴' and R⁵' a side is hydrogen atom and alkyl that the opposing party is the carbon number 1～10 can with substituent group.

As the preference of compound shown in above-mentioned formula (c-1-1), glycolic, α-hydracrylate, 2-hydroxybutyric acid, 2-hydroxy-iso-butyric acid, mandelic acid and their optical isomer or their salt etc. can be enumerated；Preferred α-hydracrylate, mandelic acid or their salt；More preferably α-hydracrylate, mandelic acid or their salt；Particularly preferably α-hydracrylate or its salt.

(C) composition can be used alone or two or more kinds may be used.

Relative to the gross mass of aforesaid liquid detergent, content preferably 0.1～5 mass %, more preferably 0.5～4 mass % of (C) composition in liquid detergent, it is preferred that 1～3 mass %, it is particularly preferred to 1～2 mass %.

If (C) content of composition is in above-mentioned preferred scope, then the stability of (B) composition in liquid detergent improves.Additionally it is possible to be inhibited more easily, liquid level forms the effect of epithelium.

If (C) content of composition is more than preferred lower limit, then improve appearance transparent homogeneity and the mobility of liquid detergent further.On the other hand, if the content of (C) composition is below preferred higher limit, then more it is difficult to when making liquid detergent produce precipitation etc..

In the present invention, " mass ratio that (B) composition/(C) composition represents " means the mass ratio relative to (C) component content of (B) component content in liquid detergent.

(B) mass ratio (also being indicated as " mass ratio (B)/(C) ") that composition/(C) represents is less than 1, it is preferable that 0.001～1, more preferably 0.01～0.75, it is preferred that 0.1～0.25.

If mass ratio (B)/(C) is below above-mentioned higher limit, then liquid detergent appearance transparent homogeneity and mobility is guaranteed and excellent storage stability.Additionally, be also easily available the effect suppressing liquid level to form epithelium.When mass ratio (B)/(C) exceedes above-mentioned higher limit, the situations such as precipitation when making liquid detergent, may be produced.

On the other hand, if more than preferred lower limit, then washing performance improves and suppresses the effect drying taste generation within doors also to improve.

<(D) composition>

(D) composition in the present invention selects at least one in the group that free isopropyl methyl phenol (IPMP), the iodo-2-propynyl ester (IPBC) of butylamino formic acid 3-, probenazole (TBZ), polylysine, poly hexamethylene biguanide and their hydrochlorate are constituted.By containing (D) composition, mainly can endowing antibacterial.

" polylysine and hydrochlorate thereof "

As polylysine, it is possible to use α-poly-L-Lysine, epsilon-poly-L-lysine, α-poly-D-Lys and any one in ε-poly-D-Lys.In these, from the viewpoint of safety, it is preferable that α-poly-L-Lysine and epsilon-poly-L-lysine, more preferably epsilon-poly-L-lysine.Wherein, from the viewpoint of safety, it is particularly preferred to the epsilon-poly-L-lysine shown in following formula (d1).

[changing 4]

[in formula, r is the integer of 5～100.]

In above-mentioned formula (d1), r is the integer of 5～100, it is preferable that the integer of 10～50, more preferably the integer of 13～27.

Epsilon-poly-L-lysine can obtain by cultivating streptomycete (Streptomyces) microorganism that belongs to, and it is the polypeptide by the lysine condensation as human body institute essential amino acids being obtained.Can be changed into the 1B of constituent originally when this polylysine is by hydrolysis such as internal enzymes, therefore, safety is very high.

As polylysine, it is possible to use any one in the free polylysine of shape and the polylysine of mineral acid or organic acid hydrochlorate form.

When hydrochlorate form, it is preferable that hydrochlorate, gluconate and acetate, more preferably hydrochlorate.

Additionally, for processing ease, it is possible to use the polylysine after excipient or filler are processed.

" poly hexamethylene biguanide or its hydrochlorate "

As poly hexamethylene biguanide or its hydrochlorate, for instance, the compound shown in following formula (d2) can be enumerated (hereinafter referred to as " (d2) composition ".).

[changing 5]

[in formula, m is the integer of 2～14；HR⁴Represent organic acid or mineral acid；N means HR⁴Number, and be the integer of 0～5m.]

In above-mentioned formula (d2), m is the integer of 2～14, it is preferable that the integer of 10～14, more preferably the integer of 11～13, it is particularly preferred to 12.

In above-mentioned formula (d2), HR⁴Represent organic acid or mineral acid, it is preferable that hydrochloric acid, gluconic acid and acetic acid, more preferably hydrochloric acid.

N is the integer of 0～5m.It addition, " 5m " means 5 × m.

When n is 0, (d2) composition is poly hexamethylene biguanide.When n is not 0, (d2) composition is the part hydrochlorate of poly hexamethylene biguanide or whole hydrochlorate.The integer of n preferably 1～5m, the more preferably integer of 2～3m, it is preferred that the integer of m～2m, it is particularly preferred to m.

It addition, 3m, 2m mean 3 × m, 2 × m respectively.

(D) composition can be used alone or two or more kinds may be used.

As (D) composition, from the viewpoint of guaranteeing appearance stability more easily, it is preferable that the combination of IPMP, IPBC and IPMP and IPBC, more preferably IPMP.

Relative to the gross mass of aforesaid liquid detergent, content preferably 0.01～2 mass %, more preferably 0.1～1 mass % of (D) composition in liquid detergent.If (D) composition is more than preferred lower limit, then can obtain better suppression and dry the effect of taste within doors；If below higher limit, then the storage stability of liquid detergent becomes better.

In the present invention, " mass ratio that (B) composition/(D) composition represents " means the mass ratio relative to (D) component content of (B) component content in liquid detergent.

(B) mass ratio (also being indicated as " mass ratio (B)/(D) ") that composition/(D) represents preferably 0.2～100, more preferably 2.5～20.

If mass ratio (B)/(D) is more than above-mentioned lower limit, then liquid detergent appearance transparent homogeneity and mobility is guaranteed and excellent storage stability.Additionally, be also easily available the effect suppressing liquid level to form epithelium.If mass ratio (B)/(D) is below above-mentioned higher limit, then washing performance improves and suppresses the effect drying taste generation within doors also to improve.

The liquid detergent of the present invention, from the difficulty of preparation, use time water the viewpoint such as dissolubility consider, it is preferable that containing the water as solvent, more preferably contain ion exchange water.

Relative to the gross mass of aforesaid liquid detergent, the content of the water in liquid detergent is below 70 mass % preferably, more preferably below 60 mass %, it is preferred that below 50 mass %.The content of water becomes more few, more easy obtains effect produced by the present invention significantly.Additionally, be also easy to prepare concentrated cleaning.

On the other hand, the lower limit of the content of water preferably more than 30 mass %.If the content of water is more than preferred lower limit, then the storage stability of the liquid detergent passed in time becomes better.

That is, when containing the water as solvent, the content of the water in liquid detergent preferably more than 30 mass %, below 70 mass %, more preferably more than 30 mass %, below 60 mass %, it is preferred that more than 30 mass %, below 50 mass %.

Additionally, the content of the water in liquid detergent can be 40 mass %～70 mass %.

In the liquid detergent of the present invention, in the scope not damaging effect of the present invention, as required, the composition (other composition) beyond above-mentioned (A)～(C) composition can also be contained.

As other composition, it is not particularly limited, commonly used composition in the liquid detergent of dress material use etc. can be mixed into, the enzyme preparation beyond (B) composition can be enumerated (following, there is also the situation being called any enzyme preparation), enzyme stabilizers, preservative, alkaline agent, antioxidant, miscible organic solvents, spice, viscosity reductant or solubilizing agent, coloring agent, washing performance builder, defoamer, pH adjusting agent, silicone, fluorescent whitening agent, dye transfer inhibitor, recontamination inhibitor, pearling agent, detergent, foam control agent, chelating agen, opacifiers and extract class etc..

For the enzyme preparation (any enzyme preparation) beyond (B) composition, it is possible to use enzyme component is scattered in the liquid preparation of liquid, enzyme is fixed on the powder formulation etc. of the stabilizer etc. of powder.As enzyme component, as long as the enzyme component of the liquid detergent of conventional dress material can be used for.As any enzyme preparation, for instance, protease preparation and lipase preparation etc. can be enumerated.

As protease preparation, can enumerate can obtain from Novozymes Company Savinase16L, SavinaseUltra16L, SavinaseUltra16XL, Everlase16LTypeEX, EverlaseUltra16L, Esperase8L, Alcalase2.5L, AlcalaseUltra2.5L, Liquanase2.5L, LiquanaseUltra2.5L, LiquanaseUltra2.5XL and Coronase48L (more than, trade name)；PurafectL, PurafectOX, the ProperaseL (more than, trade name) etc. that can obtain from Genencor Company.

As lipase preparation, Lipex100L and the Lipolase100L (more than, trade name) etc. that can obtain from Novozymes Company can be enumerated.

Any enzyme preparation can be used alone or two or more kinds may be used.

By by least one in any enzyme preparation and (B) composition use, improving further and suppress to dry the effect that taste produces within doors.

The mass ratio that " (B) composition/arbitrarily enzyme preparation " represents preferably 0.2～1, more preferably 0.5～1.If this mass ratio is in above-mentioned preferred scope, then improves further and suppress to dry the effect that taste produces within doors.

In the present invention, (B) component content that " mass ratio that (B) composition/arbitrarily enzyme preparation represents " means in liquid detergent is relative to the mass ratio of the enzyme preparation content beyond (B) composition.

In any enzyme preparation, optimization protein enzyme preparation, wherein, more preferably Savinase16L, SavinaseUltra16L, SavinaseUltra16XL, Everlase16L, EverlaseUltra16L, Liquanase2.5L, LiquanaseUltra2.5L, LiquanaseUltra2.5XL and Coronase48L；It is preferred that Everlase16L, Savinase16L and Coronase48L.

In liquid detergent, relative to the gross mass of aforesaid liquid detergent, the content of any enzyme preparation preferably 0.01～2 mass %, more preferably 0.01～1 mass %, it is preferred that 0.03～0.8 mass %.If arbitrarily the content of enzyme preparation is more than preferred lower limit, then easily play the mixed effect of enzyme；If below preferred higher limit, even if being then also difficult to precipitate out enzyme preparation in the composition that moisture is few.

As enzyme stabilizers, for instance, boric acid, Borax, formic acid or their salt can be enumerated；And the calcium salt such as calcium chloride and calcium sulfate.Relative to the gross mass of liquid detergent, the content of enzyme stabilizers preferably more than 0.001 mass %, below 2 mass %.

As preservative, for instance, the trade name KathonCG etc. of ROHM AND HAAS (RohmandHaas) company can be enumerated.Relative to the gross mass of liquid detergent, the content of preservative preferably 0.001～1 mass %.

Additionally, in order to improve storage stability, also can contain and there is the benzoic acid as preservative effectiveness or its salt.Content preferably 0.1～5 mass %, more preferably 0.15～2 mass % relative to the gross mass of liquid detergent, benzoic acid or its salt.

As alkaline agent, monoethanolamine, diethanolamine and triethanolamine etc. can be enumerated.Relative to the gross mass of liquid detergent, the content of alkaline agent preferably 0.5～5 mass %.

As antioxidant, it is not particularly limited, but from the viewpoint of maintaining washing performance and liquid stability more well, preferred phenol system antioxidant, wherein, more preferably bis-phenol system antioxidant and the dl-alpha-tocopherol etc. such as single phenol system such as dibenzylatiooluene and butylated hydroxyanisole (BHA) antioxidant, 2,2'-di-2-ethylhexylphosphine oxides (4-methyl-6-tert-butylphenol) polymer electrolyte phenol system antioxidant, it is preferred that single phenol system antioxidant and polymer electrolyte phenol system antioxidant.Relative to the gross mass of liquid detergent, the content of antioxidant preferably 0.01～2 mass %.

Miscible organic solvents refers to the organic solvent dissolving more than 50g in the ion exchange water 1L of 25 DEG C.As miscible organic solvents, as long as the solvent of uniform solution can be formed with water when mixing, for instance, the alcohols such as ethanol, 1-propanol, 2-propanol and n-butyl alcohol can be enumerated；The glycolss such as propylene glycol, butanediol and hexanediol；Diethylene glycol, triethylene glycol, TEG, mean molecule quantity be about 200 Polyethylene Glycol, mean molecule quantity be about 400 Polyethylene Glycol, the polyethylene glycols such as mean molecule quantity Polyethylene Glycol, dipropylene glycol of being about 1000；The alkyl ether such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether etc..Relative to the gross mass of liquid detergent, the content of miscible organic solvents preferably 0.1～15 mass %.

As viscosity reductant or solubilizing agent, for instance, toluenesulfonic acid, xylene monosulfonic acid, isopropyl sulfonic acid, substituted or unsubstituted LOMAR PWA EINECS 246-676-2, toluene fulfonate, xylenesulfonate, cumene sulfonate, substituted or unsubstituted naphthalene sulfonate can be enumerated.As the salt of aromatic sulphonic acid, sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, alkanolamine etc. can be enumerated.

Viscosity reductant or solubilizing agent can be used alone or two or more kinds may be used.Content preferably 0.01～15 mass % relative to the gross mass of liquid detergent, viscosity reductant or solubilizing agent.When the content of viscosity reductant or solubilizing agent is in this preferred scope, improve the formation effect suppressing to pass through the epithelium that aforesaid liquid detergent gels is formed in liquid detergent liquid level further.

As washing performance builder, it is possible to use inorganic builders or any one in organic washing-assisting detergent.Relative to the gross mass of liquid detergent, the content of washing performance builder preferably 0.01～20 mass %.

Additionally, for froth breaking, the liquid detergent of the present invention also can contain short-chain fatty acid, wherein, relative to the gross mass of liquid detergent, it is preferable that containing 0～5 mass % short-chain fatty acid.

The liquid detergent of the present invention preferably 25 DEG C time pH be 4～9, more preferably pH6～9.When pH is in above-mentioned scope, it is possible to maintain the storage stability of liquid detergent more well.

The pH of liquid detergent can be adjusted by interpolation pH adjusting agent.As pH adjusting agent, hydrochloric acid, sulphuric acid, sodium hydroxide, potassium hydroxide and alkanolamine etc. can be enumerated.These pH adjusting agents can be used alone or two or more kinds may be used.

In the present invention, the pH of liquid detergent represented and adjusted by liquid detergent to 25 DEG C and the numerical value that measured by pH meter (name of product: HM-30G, DKK Toa Corp. manufactures) etc..Even it addition, pH value beyond the scope of regulation in this specification, as long as be the pH value of the scope of regulation in this specification during pH value when being modified to 25 DEG C, then it is included within the scope of the present invention.

The liquid detergent of the present invention, considers from viewpoints such as the discharges of container, it is preferable that viscosity when 25 DEG C is 10～1000mPa about s, more preferably 80～500mPa about s.

In the present invention, the viscosity of liquid detergent is represented and is adjusted by liquid detergent to 25 DEG C and the numerical value that measured by Brookfield viscometer.Even if it addition, the value beyond the scope that this specification specifies, as long as value when being modified to 25 DEG C is that then it is contained within the scope of the invention at the viscosity number of this specification prescribed limit.

The liquid detergent of the present invention is prepared by mixed solvent (preferred water), (A) composition, (B) composition and (C) composition and other composition as required.

Such as, after mixed solvent and (A) composition, mix (B) composition and (C) composition wherein further, then, add pH adjusting agent and adjust pH, have in remaining situation at solvent, add its remainder, mixing, thus obtaining the liquid detergent as object.

That is, a mode of the preparation method of the liquid detergent of the present invention includes the one of solvent or all mixes with (A) composition；The solution of above-mentioned mixing adds (B) composition further mix with (C) composition.Further, it is also possible to include in above-mentioned mixed solution, add other composition and mix, and when solvent has remainder, it may include add solvent remainder in above-mentioned mixed solution and mix.

The using method of the liquid detergent of the present invention can be identical with the using method of liquids in general detergent.Such as, the method, the method being directly coated in the spot of washings by the liquid detergent of the present invention that put in water together with washings by the liquid detergent of the present invention when washing can be enumerated and in advance the liquid detergent of the present invention be dissolved in the water and impregnate the method etc. of clothing.Furthermore it is preferred that following method: after the liquid detergent of the present invention is coated washings, suitably place, then, use usual cleaning mixture to carry out common washing.Now, the consumption that makes of the liquid detergent of the present invention is 10g/30L.

As mentioned above, in the liquid detergent of the present invention, by will (B) composition and (C) composition use with specific mass ratio (mass ratio that (B) composition/(C) composition represents is below 1) in the solution containing (A) composition, it is possible to obtain following effect: improve the effect suppressing to dry taste generation within doors and storage stability is good.

Namely, mixing by (B) composition, the carbohydrate breakdown that the particularly biofilm structure body inside it being attached to substrate or sink formed can be will assist in remove, thus reducing the substrate bacterial number after being attached to washing, therefore, even if dry within doors, also can suppress the generation of the undesirable abnormal smells from the patient from substrate (drying taste within doors).

In addition, by combining (B) composition and (C) composition with specific mass ratio, (C) composition is made fully to be adsorbed in the surface of (B) composition, the dissolubility of (B) composition in raising liquid detergent, thus storage stability (transparent homogeneity, mobility) becomes good.

Additionally, the liquid detergent according to the present invention, owing to there is decomposition, removing biomembranous effect, therefore, pass through cyclic washing, it is difficult in substrate or sink, form biomembrane.

Further, in the liquid detergent of the present invention, it is difficult to produce the epithelium on liquid level and formed.Therefore, the liquid detergent of the present invention is useful when preparing the high so-called concentrated cleaning of surfactant concentration.

As the alternate manner of the liquid detergent of the present invention, following liquid detergent can be enumerated:

Described liquid detergent contains: (A) composition: surfactant；(B) composition: carbohydrate degradation enzyme preparation；(C) composition: select at least one compound in the group of free hydroxy carboxylic acid and salt composition thereof；Solvent (preferred water, more preferably ion exchange water)；And other compositions as required；

Relative to the gross mass of described liquid detergent, the content of (A) composition is more than 20 mass %, below 80 mass %, it is preferable that 27～48 mass %；(B) content of composition is more than 0.01 mass %, below 2 mass %, it is preferable that 0.1～0.5 mass %；(C) content of composition is 0.1～5 mass %, it is preferable that 1～2 mass %；The content of solvent is more than 30 mass %, below 70 mass %, it is preferable that 48～70 mass %；And the total of the content of above-mentioned total composition is less than 100 mass %；

(B) mass ratio that composition/(C) composition represents is 0.001～1, it is preferable that 0.1～0.25.

Described liquid detergent contains: (A) composition: at least one surfactant in the group that choosing freely (A-1) nonionic surfactant, (A-2) anion surfactant, (A-3) cationic surfactant are constituted；(B) composition: select at least one carbohydrate degradation enzyme preparation in the group of free cellulase, amylase and mannase composition；(C) composition: the compound that following formula (c-1) represents；Solvent (preferred water, more preferably ion exchange water)；And other composition as required；

Relative to the gross mass of described liquid detergent, the content of (A) composition is more than 20 mass %, below 80 mass %, it is preferable that 27～48 mass %；(B) content of composition is more than 0.01 mass %, below 2 mass %, it is preferable that 0.1～0.5 mass %；(C) content of composition is 0.1～5 mass %, it is preferable that 1～2 mass %；The content of solvent is more than 30 mass %, below 70 mass %, it is preferable that 48～70 mass %；And the content of above-mentioned total composition adds up to less than 100 mass %；

(B) mass ratio that composition/(C) composition represents is 0.001～1, it is preferable that 0.1～0.25 (zero range of value of ← embodiment)；

During containing (A-1) composition and (A-2) composition, the mass ratio that (A-1) composition/(A-2) composition represents is 0.1～20, it is preferable that 5～20；

During containing (A-1) composition with (A-2) composition and (A-3) composition, the mass ratio that [(A-1) composition+(A-2) composition]/(A-3) composition represents is 1～50, it is preferable that 18～46.

[changing 6]

[in formula, R⁴And R⁵Separately represent hydrogen atom, can have the alkyl of the carbon number 1～10 of substituent group, can have the aryl of substituent group, nitro (-NO₂), ester group, ether, can have the amino (-NH of substituent group₂) or amine derivative group；R⁶And R⁷It is each independently hydrogen atom or the alkyl of carbon number 1～5；V is the integer of 0～4；M⁺It it is counter ion.]

As the liquid detergent alternate manner of the present invention, following liquid detergent can be enumerated:

Described liquid detergent contains: (A) composition: at least one surfactant in the choosing group that freely (A-1) nonionic surfactant, (A-2) anion surfactant and (A-3) cationic surfactant are constituted；(B) composition: select at least one carbohydrate degradation enzyme preparation in the group of free amylase and mannase composition；(C) composition: the compound that following formula (c-1-1) represents；Solvent (preferred water, more preferably ion exchange water)；And other composition as required；

Above-mentioned (A-1) composition selects at least one in the group of poly (oxyalkylene) fundamental mode nonionic surfactant that poly (oxyalkylene) fundamental mode nonionic surfactant that free following formula (a-1-1) the poly (oxyalkylene) fundamental mode nonionic surfactant that represents, following formula (a-1-2) represent, following formula (a-1-3) represent and the amines type nonionic surfactant composition that following formula (a-1-4) represents；

The choosing of above-mentioned (A-2) composition freely has the straight-chain of the alkyl of carbon number 8～18 or the alkylbenzenesulfonate containing branched, any one in the epoxyalkane of carbon number 2～4, or by average to ethylene oxide (EO) and propylene oxide (PO) (mol ratio EO/PO=0.1/9.9～9.9/0.1) addition 0.5～10 mole and alkyl (or thiazolinyl) ether sulfate of the straight chain with carbon number 10～20 that obtains or the alkyl (or thiazolinyl) containing side chain, at least one in the group of the α-sulfofattyacidmethylestersalt of carbon number 14～18 and the Fatty acid compositions of carbon number 10～22；

Above-mentioned (A-3) composition is single-long-chain alkyl three short-chain alkyl type quaternary ammonium salt；

(B) mass ratio that composition/(C) composition represents is 0.001～1, it is preferable that 0.1～0.25 (scope that the zero of ← embodiment evaluates)；

During containing (A-1) composition with (A-2) composition and (A-3) composition, the mass ratio that [(A-1) composition+(A-2) composition]/(A-3) composition represents is 1～50, it is preferable that 18～46；

R¹-CO-[(EO’)s/(PO’)t]-R²(a-1-1)

[in formula, R¹It it is the thiazolinyl of the alkyl of carbon number 7～18 or carbon number 7～18；R²It it is the alkyl of carbon number 1～3；S represents the averaged repeating numbers of EO ', and is the number of 6～20；T represents the averaged repeating numbers of PO ', and is the number of 0～6；EO ' represents oxyethylene group, and PO ' represents oxypropylene group；[(EO ') and s/ (PO ') t] mean that EO ' and PO ' can be mixed.]；

R^3a-O-(EO’)u-H(a-1-2)

R^3b-O-[(EO’)p/(PO’)q]-(EO’)r-H(a-1-3)

[in formula, R^3aAnd R^3bIt is each independently the alkyl of carbon number 8～18 or the thiazolinyl of carbon number 8～18；U represents the averaged repeating numbers of EO ', and is the number of 5～20；P represents the averaged repeating numbers of EO ', and q represents the averaged repeating numbers of PO ', and r represents the averaged repeating numbers of EO ', and p, q, r meet p>1, r>1,0<q 3 and the number of p+r=10～20；EO ' represents oxyethylene group, and PO ' represents oxypropylene group；[(EO ') and p/ (PO ') q] mean that EO ' and PO ' can be mixed.]；

[changing 7]

[in formula, R⁰It it is the thiazolinyl of the alkyl of carbon number 10～20 or carbon number 10～20；A¹O and A²O separately represents the oxyalkylene of carbon number 2～3；I represents A¹The averaged repeating numbers of O；J represents A²The averaged repeating numbers of O；I > 0, j > 0 and i+j be 10～50 number.]；

[changing 8]

[in formula, R⁴' and R⁵' separately represent hydrogen atom, can have the alkyl of the carbon number 1～10 of substituent group, can have the aryl of substituent group, nitro (-NO₂), ether, can have the amino (-NH of substituent group₂) or amine derivative group；M⁺It it is counter ion.].

Described liquid detergent contains: (A) composition: surfactant；(B) composition: carbohydrate degradation enzyme preparation；(C) composition: select at least one compound in the group of free hydroxy carboxylic acid and salt composition thereof；(D) composition: select at least one in the group of the iodo-2-propynyl ester (IPBC) of free isopropyl methyl phenol (IPMP), butylamino formic acid 3-, probenazole (TBZ), polylysine, poly hexamethylene biguanide and their hydrochlorate composition；Solvent (preferred water, more preferably ion exchange water)；And other composition as required；

Relative to the gross mass of described liquid detergent, the content of (A) composition is more than 20 mass %, below 80 mass %, it is preferable that 27～48 mass %；(B) content of composition is more than 0.01 mass %, below 2 mass %, it is preferable that 0.1～0.5 mass %；(C) content of composition is 0.1～5 mass %, it is preferable that 1～2 mass %；(D) content of composition is 0.1～2 mass %；The content of solvent is more than 30 mass %, below 70 mass %, it is preferable that 48～70 mass %；And the content of above-mentioned total composition adds up to less than 100 mass %；

Described liquid detergent contains: (A) composition: at least one surfactant in the choosing group that freely (A-1) nonionic surfactant, (A-2) anion surfactant and (A-3) cationic surfactant are constituted；(B) composition: select at least one carbohydrate degradation enzyme preparation in the group of free cellulase, amylase and mannase composition；(C) composition: the compound that following formula (c-1) represents；Solvent (preferred water, more preferably ion exchange water)；(D) composition: at least one in the group that the choosing compound that freely following formula (d1) represents and the compound that following formula (d2) represents are constituted；And other compositions as required；

[changing 9]

[in formula, R⁴And R⁵Separately represent hydrogen atom, can have the alkyl of the carbon number 1～10 of substituent group, can have the aryl of substituent group, nitro (-NO₂), ester group, ether, can have the amino (-NH of substituent group₂) or amine derivative group；R⁶And R⁷It is each independently hydrogen atom or the alkyl of carbon number 1～5；V is the integer of 0～4；M⁺It it is counter ion.]；

[changing 10]

[in formula, r is the integer of 5～100.]；

[changing 11]

[in formula, m is the integer of 2～14；HR⁴Represent organic acid or mineral acid；N means HR⁴Number, and be the integer of 0～5m.].

Described liquid detergent contains: (A) composition: at least one surfactant in the choosing group that freely (A-1) nonionic surfactant, (A-2) anion surfactant and (A-3) cationic surfactant are constituted；(B) composition: select at least one carbohydrate degradation enzyme preparation in the group of free amylase and mannase composition；(C) composition: the compound that following formula (c-1-1) represents；(D) composition: select at least one in the group that the combination of poly hexamethylene biguanide that polylysine that free isopropyl methyl phenol (IPMP), butylamino formic acid 3-iodo-2-propynyl ester (IPBC), probenazole (TBZ) and above-mentioned formula (d1) represent or its hydrochlorate, above-mentioned formula (d2) represent and the poly hexamethylene biguanide that the polylysine that above-mentioned formula (d1) represents represents constitutes with above-mentioned formula (d2)；Solvent (preferred water, more preferably ion exchange water)；And other composition as required；

The choosing of above-mentioned (A-2) composition freely has any one in the straight-chain of alkyl of carbon number 8～18 or the epoxyalkane of the alkylbenzenesulfonate containing branched and carbon number 2～4 or by least one in the group of the soap composition of average to ethylene oxide (EO) and propylene oxide (PO) (mol ratio EO/PO=0.1/9.9～9.9/0.1) addition 0.5～10 mole and the straight-chain with carbon number 10～20 that obtains or alkyl (or thiazolinyl) ether sulfate of alkyl (or thiazolinyl) containing branched, the α-sulfofattyacidmethylestersalt of carbon number 14～18 and carbon number 10～22；

During containing (A-1) composition with (A-2) composition and (A-3) composition, when the mass ratio that [(A-1) composition+(A-2) composition]/(A-3) composition represents is 1～50, it is preferable that 18～46；

R¹-CO-[(EO’)s/(PO’)t]-R²(a-1-1)

R^3a-O-(EO’)u-H(a-1-2)

R^3b-O-[(EO’)p/(PO’)q]-(EO’)r-H(a-1-3)

[changing 12]

[changing 13]

[in formula, R⁴' and R⁵' separately represent hydrogen atom, can have the alkyl of the carbon number 1～10 of substituent group, it is possible to there is the aryl of substituent group, nitro (-NO₂), ether, can have the amino based (-NH of substituent group₂) or amine derivative group；M⁺It it is counter ion.]

[embodiment]

Hereinafter, use embodiment that the present invention is described in further detail, but the present invention is not limited to these embodiments.In the present embodiment, " % " unless defined otherwise, represents " quality % ".

The composition of the liquid detergent of each example is such as shown in table 1～3.

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

<(A) composition: surfactant>

(A-1) composition: nonionic surfactant

A-1-1: for coconut oil fatty acid methyl ester (by quality ratio, the mixture of methyl laurate/methyl myristate=8/2), uses alkoxylating catalyst, the ethylene oxide of addition 15 molar equivalent and obtain (MEE).In above-mentioned formula (a-1-1), R¹The alkyl of=carbon number 11 and the alkyl of carbon number 13, R²=methyl, s=15, t=0.It is synthetically derived by following synthetic method.

[synthetic method of MEE]

According to the synthetic method synthesis recorded in Japanese Patent Laid-Open 2000-144179 publication.

It is 2.5MgO Al by component₂O₃·wH₂The aluminum magnesium hydroxide of O (キョワ De 300 (trade name), Kyowa Chemical Industry Co., Ltd manufactures) 600 DEG C, burn till 1 hour under nitrogen atmosphere, obtain burning till aluminum magnesium hydroxide (unmodified) catalyst.Aluminum magnesium hydroxide (unmodified) catalyst 2.2g and 0.5N potassium hydroxide-ethanol solution 2.9mL, methyl laurate 280g, methyl myristate 70g charging will be burnt till in 4L autoclave, in autoclave, carry out the modified of catalyst.Then, by autoclave with nitrogen replace after, temperature is maintained 180 DEG C, pressure maintain 0.3MPa, and import ethylene oxide 1052g, make it react while stirring.

The reactant liquor obtained is cooled to 80 DEG C, adds water 159g, as after each 5g mixing of the active hargil of filtration adjuvant and kieselguhr, catalyst filtration is separated, obtains MEE.

A-1-2: the material (LMAO) that the ethylene oxide of natural alcohol addition 15 molar equivalent is obtained.In above-mentioned formula (a-1-2), R^3aThe alkyl of=carbon number 12 and the alkyl of carbon number 14, u=15.It is synthetically derived by following synthetic method.

[synthetic method of LMAO]

CO-1214 (trade name) 861.2g and 30 quality %NaOH aqueous solution 2.0g charging Procter & Gamble manufactured, in pressure resistant type reaction vessel, carries out nitrogen displacement by above-mentioned reaction vessel.Then, when temperature 100 DEG C, below pressure 2.0kPa by the reactant liquor dehydration in above-mentioned reactor 30 minutes after, by the temperature in above-mentioned reactor to 160 DEG C.Then, while stirring above-mentioned reactant liquor, ethylene oxide (gaseous state) 760.6g is slowly made an addition in above-mentioned reactant liquor.Now, adjustment interpolation speed adds ethylene oxide with being blown into pipe while making the reaction temperature of above-mentioned reactant liquor less than 180 DEG C.

After ethylene oxide interpolation terminates, by above-mentioned reactant liquor when temperature 180 DEG C, below pressure 0.3MPa after aging 30 minutes, unreacted ethylene oxide is distilled off in liquid from the reactions above when temperature 180 DEG C, below pressure 6.0kPa, lasts 10 minutes.

Then, the temperature of above-mentioned reactant liquor being cooled to after below 100 DEG C, the p-methyl benzenesulfonic acid adding 70 mass % is neutralized, and makes the pH of 1 mass % aqueous solution of reactant be approximately 7, obtains LMAO.

A-1-3: the nonionic surfactant that natural alcohol (by quality ratio, alcohol=7/3 of the alcohol/carbon number 14 of the carbon number 12) ethylene oxide of block addition 8 moles successively, the propylene oxide of 2 moles, the ethylene oxide of 8 moles are obtained.In above-mentioned formula (a-1-3), R^3bThe alkyl of=carbon number 12 and the alkyl of carbon number 14, p=8, q=2, r=8.

[synthetic method of the nonionic surfactant that formula (a-1-3) represents]

Put into Procter & Gamble manufacture CO-1214 (trade name) 194.5g and potassium hydroxide 1.1g, 110 DEG C, 1.3kPa when carry out dehydration 30 minutes after, carry out nitrogen displacement.After nitrogen displacement, it is warming up to 140 DEG C, imports ethylene oxide 352g, carry out additive reaction and burnin operation.Then, it is cooled to 120 DEG C, imports propylene oxide 116g, carry out additive reaction and burnin operation.Then, again it is warming up to 140 DEG C, imports ethylene oxide 352g, carry out additive reaction and burnin operation.After reaction terminates, after being cooled to 80 DEG C, in autoclave, add acetic acid 1.2g, after stirring 30 minutes at 80 DEG C, extract, obtain (a-1-3).

A-1-4: the material (Ethomeen) being synthetically derived by following synthetic method.In above-mentioned formula (a-1-4), R⁰The alkyl of=carbon number 16, A¹O=oxyethylene group, A²O=oxyethylene group, i+j=20.

[synthetic method of Ethomeen]

By fatty acid amine, (Tokyo HuaCheng Industry Co., Ltd manufactures, hexadecane amine) charging is in autoclave (manufacture of pressure Xiao Zi Industrial Co., Ltd), after replacing with nitrogen in system, heating is to 150 DEG C, gradually add ethylene oxide (EO) on a small quantity until reaching ormal weight, the tertiary amine (first stage) that average addition molal quantity (that is, averaged repeating numbers) is 2 moles of synthesis EO.

Then, by the tertiary amine obtained and base catalyst (NaOH；Relative to above-mentioned tertiary amine 100 mass parts, using 40 mass %NaOH aqueous solutions of 0.8 mass parts) charging is in autoclave, to replace with nitrogen in system, after utilizing heating decompression to carry out dehydration, heating is to 150 DEG C, gradually add EO on a small quantity until ormal weight, obtain the product (second stage) that average addition molal quantity (that is, averaged repeating numbers) is 20 moles of EO.

After the additive reaction of EO, by acetic acid, above-mentioned product is neutralized process, obtains Ethomeen.Being measured by amine number, calculate molecular weight, result is 1121.

(A-2) composition: anion surfactant

A-2-1:LAS, [lion king (ライオ Application) Co., Ltd. manufactures straight chained alkyl (carbon number 10～14) benzenesulfonic acid, trade name ライ Port Application LH-200 (LAS-H, purity=96 mass %)] sodium salt, mean molecule quantity 322 (when preparing liquid detergent, LAS-H is neutralized and is called sodium salt).

A-2-2:MES, α-sulfofattyacidmethylestersalt, lion king's chemistry in ecology (ライオ Application エ U ケミカ Le ズ) Co., Ltd. manufactures, trade name " MIZULANFL-80 ".

A-2-3:AES, polyoxyethylene lauryl ether sulfuric acid, New Japan Chem Co., Ltd manufactures, trade name " シノリ Application SPE-1350 ".

A-2-4:AEPS, (alkyl is the straight-chain alkyl of carbon number 10～14 to polyoxyalkylene alkyl ether sulfuric ester monoethanolamine salt, the average addition molal quantity of propylene oxide is (namely, averaged repeating numbers) it is 1, the average addition molal quantity (that is, averaged repeating numbers) of ethylene oxide is 3).

A-2-5: fatty acid distribution of coconut oil sodium, with in sodium and the material of fatty acid distribution of coconut oil (trade name, Japan Oil Co manufacture) gained.

(A-3) composition: cationic surfactant

A-3-1: chlorination alkyl (carbon number 12) trimethyl ammonium, lion king's special chemical (ライオ Application スペシャリティケミカ Le ズ) Co., Ltd. manufactures, trade name " アカ De 12-37W ".

A-3-2: chlorination alkyl (carbon number 14) trimethyl ammonium, Tokyo HuaCheng Industry Co., Ltd manufactures (reagent).

A-3-3: chlorination alkyl (carbon number 16～18) trimethyl ammonium, Shi Wang special chemical Co., Ltd. manufactures, trade name " アカ De T-800 ".

A-3-4: didecyldimethylammonium chloride, Shi Wang special chemical Co., Ltd. manufactures, trade name " アカ De 210 ".

<(B) composition: carbohydrate degradation enzyme preparation>

B-1: mannase preparation, letter (ノボザイ system ズ) company of Novi manufactures, trade name " Mannaway4L ".

B-2: diastase, Novozymes Company manufactures, trade name " Termamyl300L ".

<(B ') composition: albuminolysis enzyme preparation, the comparison composition of (B) composition>

B '-1: protease preparation, Novozymes Company manufactures, trade name " Coronase48L ".

B '-2: protease preparation, Novozymes Company manufactures, trade name " Everlase16L ".

<(C) composition: select at least one compound in the group of free Alpha-hydroxy-monocarboxylic acid and salt composition thereof>

C-1: sodium lactate, Northeast chemistry manufactures.In above-mentioned formula (c-1-1), R⁴=methyl, R⁵=hydrogen atom.

C-2: mandelic acid, Northeast chemistry manufactures.In above-mentioned formula (c-1-1), R⁴=phenyl, R⁵=hydrogen atom.

<(D) composition: select at least one in the group of the iodo-2-propynyl ester (IPBC) of free isopropyl methyl phenol (IPMP), butylamino formic acid 3-, probenazole (TBZ), polylysine, poly hexamethylene biguanide and their hydrochlorate composition>

D-1: polylysine, trade name " polylysine 25% aqueous solution ", Chisso (チッソ) Co., Ltd. manufactures.

D-2: poly hexamethylene biguanide, trade name " プロキセ Le IB ", (ロ Application ザジャパ Application) Co., Ltd. of the husky Japan of dragon manufactures.

D-3:2-isopropyl-5-methylphenol (IPMP), trade name " PVC オゾ Le ", Osaka Kasei Co., Ltd. manufactures

D-4: butylamino formic acid 3-iodo-2-propynyl ester (IPBC), trade name " GLYCACIL (グライカシ Le) ", Long Sha Amada Co., Ltd. manufactures

Common component:

Sodium benzoate: Toagosei Co., Ltd manufactures.

Monoethanolamine: Nippon Catalyst K. K. manufactures.

Dibenzylatiooluene: Sumitomo Chemical Co manufactures, trade name " SUMILZERBHT-R ".

Ethanol: Japan's alcohol is peddled Co., Ltd. and manufactured, trade name " specific 95 degree of synthesis of ア Le U Le ".

Fatty acid 2-Octyl Nitrite: Lion Corporation manufactures, trade name " パステ Le 2H-08 ".

Spice: the flavor compositions A recorded in the table 11～18 of Japanese Patent Laid-Open 2002-146399 publication.

P-methyl benzenesulfonic acid: Kyowa Hakkokogyo Co., Ltd manufactures, trade name " PTS ".

Pigment: be melted into Co., Ltd. the sixth of the twelve Earthly Branches in the last of the ten Heavenly stems and manufacture, trade name " green No. 3 ".

PH adjusting agent: sodium hydroxide (Tsurumi Soda Co., Ltd.'s manufacture), sulphuric acid (Dong Bang zinc Co., Ltd. manufacture).Ion exchange water.

(embodiment 1～35, comparative example 1～4)

Composition (blending constituent, content (quality %)) shown in table 1～3, prepares the liquid detergent of each example by following manufacture method.

In table, when blending constituent is empty hurdle, it does not have be mixed into this blending constituent.

In table, the content of blending constituent represents the amount after being scaled purity ingredients.

Represent that " in right amount " of pH adjusting agent content refers to regulate the pH (25 DEG C) of liquid detergent the total amount of the pH adjusting agent (sodium hydroxide, sulphuric acid) added to 7.0.

Represent that " balance " of ion exchange water content means the remainder added to make the total combined amount (quality %) of the total blending constituent contained by liquid detergent reach 100 mass %.

In table, (B) component content in " mass ratio (B)/(C) " meaning liquid detergent is relative to the mass ratio of (C) component content.For comparative example 2, it is meant that (the B ') component content in liquid detergent is relative to the mass ratio of (C) component content.

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

" mass ratio [(A-1)+(A-2)]/(A-3) " means the total content mass ratio relative to (A-3) component content of (A-1) composition in liquid detergent and (A-2) composition.

In table, common component composed as follows shown in.The content (quality %) of each blending constituent represents the ratio in liquid detergent.Relative to the gross mass of liquid detergent, the total content of common component is 11.5505 mass %.

Sodium benzoate 0.5 mass %, monoethanolamine 1 mass %, dibenzylatiooluene 0.05 mass %, ethanol 7 mass %, fatty acid 2-Octyl Nitrite 1.5 mass %, spice 0.5 mass %, p-methyl benzenesulfonic acid 1 mass %, pigment 0.0005 mass %.

[manufacture method of liquid detergent]

According to the composition shown in table 1～4, capacity 500mL beaker adds ethanol and (A) composition, is sufficiently stirred for magnetic stirring apparatus (MITAMURAKOGYOINC. manufacture).

Then, add the common component beyond ethanol and ion exchange water, stirring, meanwhile, add pH adjusting agent (sodium hydroxide or sulphuric acid) and make pH reach 7 (25 DEG C).Now, add ion exchange water, make the total amount in this moment reach 95 mass % compositions of final gained liquid detergent total amount.

It is after 7 by pH regulator, adds (B) composition or (B ') composition and (C) composition, stirring.Then, add pH adjusting agent (sodium hydroxide or sulphuric acid) further and make pH reach 7 (25 DEG C), add ion exchange water and make total amount reach 100 mass %, obtain liquid detergent.

The pH of liquid detergent can pass through to be regulated by sample to 25 DEG C and be measured with pH meter (name of product " HM-30G " that DKK Toa Corp. manufactures).

About the liquid detergent of each example, carry out the evaluation suppressing to dry the effect that the effect of taste generation, storage stability and suppression form epithelium at liquid level within doors respectively.

[suppressing to dry within doors the evaluation of the effect that taste produces]

Reusability in family and the wiping hands towel 10 pieces washing half a year are used about 2 days (not washing) respectively in generally life.Wipe hands towel to these 10 pieces and use the liquid detergent of each example, carry out carrying out washing treatment (injecting the tap water of about 20 DEG C of water temperature, about 3 DH of hardness, bath raio 20 times) by the usual program of washing machine (JW-Z23A type, company of Haier manufactures).Now, the liquid scrubbing dosage put into washing machine is 10mL/ tap water 30L, carries out carrying out washing treatment.

Additionally, as the dress material meeting bath raio, use and the shirt (BVD manufacture) of brand-new cotton 100% is carried out the dress material after 5 carrying out washing treatment (injecting the tap water of about 20 DEG C of water temperature, hardness about 3 DH) with the subscription procedure of automatic washing machine (Co., Ltd. of Panasonic manufactures, NA-F70SD1).Now, using commercially available synthetic detergent TOP (Lion Corporation's manufacture) as detergent, the detergent of every 1 carrying out washing treatment makes consumption be that 25g/ tap water 30L carries out carrying out washing treatment.

After the carrying out washing treatment of above-mentioned wiping hands towel terminates, by the indoor dry in the sun in room temperature (about 23 DEG C), relative humidity 90%RH of the above-mentioned wiping hands towel, to carry out 5 hours dry (drying within doors).

Then, the abnormal smells from the patient wiping hands towel after 10 pieces dry (drying within doors) 5 hours is carried out the sensory evaluation of so-called olfactory sensation by 6 specialized review persons respectively.

Above-mentioned sensory evaluation, can by carrying out based on following metewand scoring.Specifically, specialized review person hear 10 pieces dry within doors after wipe hands towel respective abnormal smells from the patient, show according to the odour intensity of 6 grades in following metewand and be evaluated.Then, calculate 10 pieces of average marks wiping hands towel, be equally divided into index with this, be evaluated suppressing the effect drying taste generation within doors.This average mark is such as shown in table 1～3.The conduct below 2.5 points of the described average mark is qualified.

The metewand (odour intensity shows) of sensory evaluation

0 point: entirely without abnormal flavour.

1 point: the abnormal flavour degree by inadequate perception can be experienced.

2 points: can feel faint abnormal flavour.

3 points: can feel slightly strong abnormal flavour.

4 points: can feel stronger abnormal flavour.

5 points: can feel strong abnormal flavour.

[evaluation of storage stability]

The liquid detergent 30mL of each example is filled in respectively cylindrical glass bottle, cover lid, seals.It is statically placed in the temperature chamber of 5 DEG C with this state, preserves 24 hours.

Then, from above-mentioned temperature chamber, take out the cylindrical glass bottle being filled with liquid detergent, observe transparent homogeneity and the mobility of the liquid detergent of 5 DEG C, and based on following metewand, the storage stability of the liquid detergent of each example is evaluated.Described evaluation result is that the liquid detergent of A, B is as qualified.

Metewand

A: transparent homogeneous, display mobility.

B: can confirm that a part of gelation, but there is mobility.

C: solidify, it does not have mobility, or confirm there is precipitation.

[suppressing liquid level to form the evaluation of epithelium effect]

Take the liquid detergent 5g of each example respectively in the container (Maruemu manufactures, MAJY ケス, model SS) of vertical 5.3cm × horizontal 3.3cm × high 1.5cm.

Above-mentioned vertical × horizontal face is not added a cover and when directly opening wide, the liquid level after standing 24 hours at observing 5 DEG C, based on following metewand, the effect that liquid level forms epithelium that suppresses of the liquid detergent of each example is evaluated.Described evaluation result is that the liquid detergent of A, B is as qualified.

Metewand

A: confirming the formation not having epithelium on liquid level, liquid detergent has mobility.

B: confirm the formation having epithelium on liquid level, but liquid detergent has mobility.

C: liquid detergent entirety gelation or solidification.

[table 1]

[table 2]

[table 3]

[table 4]

Can confirm that from the result shown in table 1～4, the effective of taste generation is dried in the suppression of the liquid detergent of application embodiments of the invention 1～35 within doors, and storage stability is good.

Additionally, also know that the liquid detergent of embodiment 1～35 is also good in suppressing liquid level to form the effect of epithelium.

[utilizing probability in industry]

Effective and the storage stability that taste generation is dried in the suppression of the liquid detergent of the present invention within doors is good, therefore, is industrially highly useful.

Claims

1. a liquid detergent, it is characterised in that described liquid detergent contains:

(A) composition: surfactant；

(B) composition: carbohydrate degradation enzyme preparation；And

(C) composition: hydroxy carboxylic acid or its salt；

2., such as the liquid detergent that claim 1 is recorded, wherein, described (A) composition contains cationic surfactant.

3., such as the liquid detergent that claim 1 or 2 is recorded, wherein, described liquid detergent is possibly together with (D) composition；At least one in the group that described (D) composition choosing iodo-2-propynyl ester IPBC of free isopropyl methyl phenol IPMP, butylamino formic acid 3-, probenazole TBZ, polylysine, poly hexamethylene biguanide and their hydrochlorate are constituted.