CN105793410B

CN105793410B - Liquid detergent

Info

Publication number: CN105793410B
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: 2019-05-10
Anticipated expiration: 2034-12-04
Also published as: TW201529836A; KR20160093613A; HK1226436A1; SG11201604459SA; JP6504710B2; TWI663252B; JPWO2015083800A1; WO2015083800A1; MY176485A; KR102305050B1; CN105793410A

Abstract

A kind of liquid detergent, it contains the surfactant as (A) ingredient, as (B) ingredient is carbohydrate degradation enzyme preparation and hydroxycarboxylic acid or its salt as (C) ingredient, and mass ratio represented by (B) ingredient/(C) ingredient is 1 or less.

Description

Liquid detergent

Technical field

The present invention relates to liquid detergents.

The application is basic CLAIM OF PRIORITY at Patent 2013-253646 of Japanese publication on December 6th, 2013, and Its content is incorporated herein.

Background technique

Due to the raising required cleaning, for the liquid detergent of dress material, dress material etc. is attached in addition to requiring to remove Other than the spot (washing effect) of (substrate), also requires to remove the undesirable smell generated by substrate and prevent from being washed Object generates undesirable smell.

Substrate generates undesirable smell mainly due to being attached to fiber in the drying of substrate or keeping Caused by microbial growth.

In this regard, proposing the washing for being mixed with the cationic surfactant with bactericidal effect or antibacterial effect in the past Agent.It is disclosed in patent document 1 containing cationic surfactant, nonionic surfactant and benzoic acid and/or its salt Liquid detergent.

Existing technical literature

Patent document

Patent document 1: Japanese Patent Laid-Open 2006-316130 bulletin

Summary of the invention

Problems to be solved by the invention

However, carrying out night washing with the variation of recent life style and drying the substrate after washing indoors Such a family for drying operation within doors is increasing.For drying within doors, due to divulging information, poor, substrate is difficult to drying, because And the microorganism for being attached to fiber is easy proliferation.

Therefore, it is desirable to detergent below: even if dried within doors, can also inhibit from the unhappy of substrate Smell (hereinafter, otherwise referred to as dry within doors taste) generation.The inhibition for the liquid detergent recorded in above patent document 1 The effect for drying taste generation within doors is insufficient.In addition, only increasing has the cationic surface of bactericidal effect or antibacterial effect living Property agent content when, washing effect is deteriorated, and consequently also becomes difficult to be inhibited and dries the effect of taste generation within doors.

As the method for inhibiting to dry the effect that taste generates within doors is improved, the present inventor, which is newly conceived to, will be attached to substrate Or the aspect of the especially biofilm breakup of inside of sink, removing, and it is studied.As a result, it has been found that passing through effectively benefit With the carbohydrate degradations enzyme such as mannase, can effectively inhibit to dry taste within doors.

However, there is the storage stability for being difficult to ensure liquid detergent (for example, transparent equal when mixing carbohydrate degrading enzyme One property and mobility) the problem of.

The present invention has been made in view of the above-described circumstances, and project is to provide a kind of effect for inhibiting to dry taste generation within doors Fruit is good and the good liquid detergent of storage stability.

The means solved the problems, such as

By further studying, the inventors discovered that by the way that the carbohydrates such as mannase are dropped in surfactant solution Solution enzyme preparation simultaneously be used in combination with hydroxycarboxylic acid or its salt, wherein the dosage of hydroxycarboxylic acid or its salt be and carbohydrate degradation enzyme preparation Equivalent or its more than, to solve the above problems, complete the present invention.That is, liquid detergent of the invention is related to liquid below Detergent: the liquid detergent contains the surfactant as (A) ingredient, as the carbohydrate degradation enzyme preparation of (B) ingredient With the hydroxycarboxylic acid or its salt as (C) ingredient, and with mass ratio represented by (B) ingredient/(C) ingredient be 1 or less.

In liquid detergent of the invention, preferably above-mentioned (A) ingredient contains cationic surfactant.

That is, the present invention relates to the following contents.

[1] a kind of liquid detergent, contains:

(A) ingredient: surfactant；

(B) ingredient: carbohydrate degradation enzyme preparation；And

(C) ingredient: hydroxycarboxylic acid or its salt；

And with mass ratio represented by (B) ingredient/(C) ingredient for 1 or less.

[2] such as the liquid detergent of [1] record, wherein (A) ingredient contains cationic surfactant.

The effect of invention

Liquid detergent according to the present invention inhibits the effect for drying taste generation within doors good and storage stability is good.

Specific embodiment

Liquid detergent of the invention contains the surfactant as (A) ingredient, as the carbohydrate degradation enzyme of (B) ingredient Preparation and hydroxycarboxylic acid or its salt as (C) ingredient.

Liquid detergent of the invention can be used for it is home-use, commercially use, industrial purposes, wherein be suitable for family With the particularly suitable liquid detergent as dress material.

The type for washing object (substrate) can be enumerated and the washing object phase in home washings as washing object Same washing object, for example, fibres such as clothes, rag, towel class, sheet, curtain etc. can be enumerated.

<(A) ingredient: surfactant>

Liquid detergent of the invention is by having washing performance containing (A) ingredient.

As (A) ingredient, commonly used surfactant in the liquid detergents such as dress material use can be used, can enumerate Nonionic surfactant, anionic surfactant, cationic surfactant and amphoteric surfactant etc..

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

((A-1) ingredient: nonionic surfactant)

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

(1) polyoxyalkylene alkyl (or alkenyl) ether.

(2) polyxyethylated (or alkenyl) phenyl ether.

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

(4) polyoxyethylene sorbitan fatty acid ester.

(5) polyoxyethylene sorbitol aliphatic ester.

(6) polyoxyethylene fatty acid ester.

(7) Crodaret.

(8) fatty acid glyceride.

(9) alkylamine alkoxylates obtained by addition alkylene oxide on chain alkyl (or alkenyl) amine.

(A-1) in ingredient, preferably above-mentioned (1), (3) and (9).Wherein, from further increase storage stability and inhibit liquid Face is formed from the point of view of epithelium effect, further preferred above-mentioned (3).In addition, when using aftermentioned (A-2) ingredient as main wash ingredient, , it is preferable to use above-mentioned (1) from the point of view of being easier to obtain effect of the present invention.

As the preferred object of above-mentioned (3), poly (oxyalkylene) fundamental mode non-ionic surface shown in the following general formula (a-1-1) can be enumerated Activating agent (hereinafter also referred to " (a-1-1) ingredient ").

In addition, the preferred object as above-mentioned (1), can enumerate poly (oxyalkylene) fundamental mode shown in the following general formula (a-1-2) it is non-from Poly (oxyalkylene) fundamental mode nonionic table shown in sub- surfactant (hereinafter also referred to " (a-1-2) ingredient ") and general formula (a-1-3) Face activating agent (hereinafter also referred to " (a-1-3) ingredient ").

In addition, the preferred object as above-mentioned (9), can enumerate amines shown in the following general formula (a-1-4) Type nonionic surfactant (hereinafter also referred to " (a-1-4) ingredient ").

About (a-1-1) ingredient

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

R¹-CO-[(EO’)s/(PO’)t]-R² (a-1-1)

[in formula, R¹It is the alkyl of carbon atom number 7~18 or the alkenyl of carbon atom number 7~18；R²It is carbon atom number 1~3 Alkyl；S indicates the averaged repeating numbers of EO ', and the number for being 6~20；T indicates the averaged repeating numbers of PO ', and the number for being 0~6；EO' Indicate that oxyethylene group, PO ' indicate oxypropylene group；[(EO ') s/ (PO ') t] means EO ' and PO ' it can be mixed.]

In above-mentioned formula (a-1-1), from the viewpoint of washing performance, R¹It is preferred that the alkyl or carbon atom of carbon atom number 9~18 The alkenyl of number 9~18 for straight-chain or can contain branched.

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

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

In above-mentioned formula (a-1-1), s is 6~20 number, preferably 6~18 number, more preferable 11~18 number, particularly preferably 14~16 number.In addition, s can be integer, decimal can also be contained.

When s is more than 20, HLB value becomes excessively high, has washing performance downward trend.On the other hand, when s is less than 6, have (a-1-1) trend of the variable difference of the raw material smell of ingredient itself.

T is 0~6 number, preferably 0~3 number.In addition, t can be integer, decimal can also be contained.

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

In addition, " averaged repeating numbers " in this specification and claims mean relative to 1 mol of alcohol used The molal quantity of the ethylene oxide or propylene oxide that are reacted.

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

(a-1-1) in ingredient, the repeat number distribution of EO ' or PO ' are not particularly limited, and are easy according to manufacture (a-1-1) Reaction method when ingredient is changed.For example, for EO ' or PO ' repeat number distribution, use common sodium hydroxide, hydrogen The base catalysts such as potassium oxide and enable ethylene oxide or propylene oxide addition in hydrophobic based raw material (that is, the higher alcohol of level-one or second level, Higher fatty acids, higher fatty acid amides etc.) when, having becomes more eurytopic trend.In addition, Japanese Patent Laid-fair 6- The use recorded in No. 15038 bulletins is added with Al³⁺、Ga³⁺、In³⁺、Tl³⁺、Co³⁺、Sc³⁺、La³⁺And Mn²⁺Equal metal ions The specific alkoxylating catalyst such as magnesia and enable ethylene oxide or propylene oxide addition when above-mentioned hydrophobic based raw material, EO ' or The repeat number distribution of PO ' has the trend become compared with narrow ditribution.

As the preference of (a-1-1) ingredient, such as can enumerate relative to carbon atom number 10~18 (preferably 12~14) Fatty acid methyl ester, addition are equivalent to poly (oxyalkylene) fundamental mode non-ionic surface obtained by the ethylene oxide of 11~18 (preferably 15) mole Activating agent etc..

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

(a-1-2) ingredient is poly (oxyalkylene) fundamental mode nonionic surfactant, (a-1- shown in the following general formula (a-1-2) 3) ingredient is poly (oxyalkylene) fundamental mode nonionic surfactant shown in the following general 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 indicate the alkyl of carbon atom number 8~18 or the alkenyl of carbon atom number 8~18；u Indicate the averaged repeating numbers of EO ', and the number for being 5~20；P indicates that the averaged repeating numbers of EO ', q indicate the averaged repeating numbers of PO ', r Indicate that the averaged repeating numbers of EO ', p, q, r are the number for meeting 17>p>1,17>r>1,0<q≤3 and p+r=10~20；EO ' table Show that oxyethylene group, PO ' indicate oxypropylene group；[(EO')_p/(PO’)_q] mean 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^3bIt is separately excellent The alkyl of carbon atom number 10~18 or the alkenyl of carbon atom number 10~18 are selected, for straight-chain or branched can be contained.

In above-mentioned formula (a-1-2), u is 5~20 number, preferably 8~18 number, more preferable 10~16 number, particularly preferably 14~16 number.When u is more than 20, HLB value becomes excessively high, has washing performance downward trend.On the other hand, when u is less than 5, tool Have the tendency that the raw material smell of (a-1-2) ingredient itself is easy to be deteriorated.

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

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

(a-1-2) ingredient and (a-1-3) ingredient can be manufactured by known method respectively.(a-1-2) ingredient, example It such as, can be by the way that there is R what is obtained by natural oil derivative^3aAlcohol on addition ethylene oxide and manufacture.(a-1-3) ingredient, example It such as, can be by the way that there is R what is obtained by natural oil derivative^3bAlcohol on, successively carry out ethylene oxide and propylene oxide addition Carried out after mixing addition (random addition) after reaction or with ethylene oxide and propylene oxide, again addition ethylene oxide and make It makes.

When using (a-1-2) ingredient or (a-1-3) ingredient, liquid detergent becomes easy to obtain viscosity appropriate, also becomes It must be easy to inhibit gelation.In addition, foaming characteristic improves, biological degradability also becomes more good.

As (a-1-2) ingredient and the preference of (a-1-3) ingredient, for example, can enumerate for Mitsubishi Chemical's strain formula meeting Neodol (the commodity that the Diadol (product name, the alcohol (C13) of carbon atom number 13) of society's manufacture, shell (Shell) company manufacture Title, the mixture of alcohol (C12) and C13 of carbon atom number 12), the Safol23 of husky rope (Sasol) company manufacture (product name, The mixture of C12 and C13) etc. non-ionic surface active obtained by the ethylene oxide of 12 molar equivalent of alcohol addition or 15 molar equivalents Agent；To the CO-1214 (product name) or CO-1270 of the manufacture of (プロ Network ターア Application De ギャ Application Block Le) company, P&G Nonionic surfactant obtained by the ethylene oxide of 12 molar equivalent of the natural alcohols such as (product name) addition or 15 molar equivalents； The oxidation second of 7 molar equivalent of C13 alcohol addition arrived for the resulting C12 alkene of butylene trimerizing is supplied in oxo synthesis Alkene and obtain nonionic surfactant (for example, product name: Lutensol TO7, BASF AG manufacture)；For by penta Alcohol is supplied in nonionic table obtained by the ethylene oxide for 9 molar equivalent of C10 alcohol addition that Guerbet (Guerbet) reaction obtains Face activating agent (for example, product name: Lutensol XP90, BASF AG's manufacture)；It is anti-for amylalcohol is supplied in Guerbet Nonionic surfactant obtained by the ethylene oxide for 7 molar equivalent of C10 alcohol addition that should be obtained (for example, product name: Lutensol XL70, BASF AG's manufacture)；For amylalcohol is supplied in 6 moles of the C10 alcohol addition that Guerbet reaction obtains Nonionic surfactant obtained by the ethylene oxide of equivalent is (for example, product name: Lutensol XA60, BASF AG's system It makes)；9 molar equivalent of secondary alcohol addition to carbon atom number 12~14 or non-ionic surface obtained by the ethylene oxide of 15 molar equivalents Activating agent (for example, product name: Softanol90, Softanol150, Nippon Catalyst K. K.'s manufacture)；To natural alcohol (alcohol of carbon atom number 12 and the mixture of the alcohol of carbon atom number 14 etc.) successively the ethylene oxide of 8 molar equivalent of addition, 2 moles work as Nonionic surfactant etc. after the propylene oxide of amount, again obtained by the ethylene oxide of 8 molar equivalent of addition.

About (a-1-4) ingredient

(a-1-4) ingredient is the amines type nonionic surfactant that the following general formula (a-1-4) is indicated.

[changing 1]

[in formula, R⁰It is the alkyl of carbon atom number 10~20 or the alkenyl of carbon atom number 10~20；A¹O and A²O difference is only On the spot indicate the oxyalkylene of carbon atom number 2~3；I indicates A¹The averaged repeating numbers of O；J indicates A²The averaged repeating numbers of O；I > 0, j > 0, and i+j is 10~50 number.]

In above-mentioned formula (a-1-4), R⁰Carbon atom number be 10~20, from the viewpoint of washing performance, preferred carbon atom number 10~18 alkyl or the alkenyl of carbon atom number 10~18 for straight-chain or can contain branched.

R⁰Carbon atom number be 10 or more when, good washing performance can be obtained；R⁰Carbon atom number be 20 or less when, energy Access good dissolubility.

In above-mentioned formula (a-1-4), (A¹O)_iAnd (A²O)_jIndicate the repetitive structure of the oxyalkylene of carbon atom number 2~3, Its repetitive structure that can be merely oxyethylene group (EO ') respectively, is also possible to the repetitive structure of only oxypropylene group (PO '), Structure obtained by arrangement can be also mixed for EO ' and PO '.In the case where the two is mixed arrangement, EO ' and PO ' can add It is in block-wise as random shape or addition.Wherein, in terms of 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 the numbers that 40 > i > 0,40 > j > 0 and i+j are 10~50.I+j preferably 10~40, more It is preferred that 10~30.When i+j is more than the lower limit value of above range, scourability becomes more good, and i+j is in the upper of above range When below limit value, the storage stability of liquid detergent is further increased.

As the preference of (a-1-4) ingredient, for example, alkylamine addition 20 for carbon atom number 16 can be enumerated (that is, i+ J=20) amines type nonionic surfactant etc. obtained by the ethylene oxide of molar equivalent.

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

(A-1) in ingredient, preferably above-mentioned (1), (3) and (9), more preferable above-mentioned (1) and (3), wherein from washing Property, liquid detergent low-temperature stability it is better from the aspect of, further preferred (a-1-1) ingredient, (a-1-2) ingredient and (a-1-3) ingredient, particularly preferred (a-1-1) ingredient.(a-1-1) in ingredient, when t=0 in more preferable above-mentioned formula (a-1-1) Fatty acid ester type nonionic surfactant.

Entirely ratio shared by (A-1) ingredient is not particularly limited in (A) ingredient, relative to the gross mass of (A) ingredient, Its preferably 10~96 mass %, more preferable 30~90 mass %, further preferred 50~90 mass %, particularly preferred 70~ 90%.If the ratio of (A-1) ingredient in above-mentioned preferred scope, further increases washing for the spot for being attached to substrate Washing property.

((A-2) ingredient: anionic surfactant)

As (A-2) ingredient, for example, the anionic surfactant of (11) as shown below~(22) can be enumerated.

(11) with carbon atom number 8~18 alkyl straight-chain or containing branched alkylbenzene sulfonate (LAS or ABS)。

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

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

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

(15) it (rubs by any of the epoxyalkane of carbon atom number 2~4 or by ethylene oxide (EO) and propylene oxide (PO) You are than EO/PO=0.1/9.9~9.9/0.1) obtained by addition 0.5~10 mole average (that is, averaged repeating numbers are 0.5~10) Straight-chain with atomicity 10~20 or the alkyl containing branched (or alkenyl) alkyl (or alkenyl) ether sulfate (AES, AEPS)。

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

(17) it (rubs by any of the epoxyalkane of carbon atom number 2~4 or by ethylene oxide (EO) and propylene oxide (PO) You are than EO/PO=0.1/9.9~9.9/0.1) have obtained by addition is 0.5~10 mole (that is, averaged repeating numbers 0.5~10) average There is alkyl (or alkenyl) ether carboxylate of the straight-chain of carbon atom number 10~20 or the alkyl (or alkenyl) containing branched.

(18) the alkyl polyols ether sulfate such as alkyl glyceryl ether sulfonate of carbon atom 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 atom number 14~18.

(22) fatty acid salt (soap) of carbon atom number 10~22.

(A-2) in ingredient, alkali earth metal salts, monoethanolamine and the diethanols such as the alkali metal salts such as sodium and potassium, magnesium can be used The alkanolamines such as amine, ammonium salt etc..

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

(A-2) in ingredient, preferably above-mentioned (11), (15), (21) and (22), particularly preferred above-mentioned (11).

Entirely ratio shared by (A-2) ingredient is not particularly limited in (A) ingredient, relative to the gross mass of (A) ingredient, Its preferably 1~30 mass %, more preferable 2~20 mass %, further preferred 3~15 mass %.If the ratio of (A-2) ingredient exists In above-mentioned preferred scope, then the washing performance for the spot being attached on substrate is further increased.

((A-3) ingredient: cationic surfactant)

As (A-3) ingredient, such as the cationic surfactant of (31) as shown below~(33) can be enumerated.

Two short-chain alkyl type quaternary ammonium salt of (31) two chain alkyl.

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

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

" chain alkyl " in these (31)~(33) indicates the alkyl of carbon atom number 10~26.The above-mentioned alkane of chain alkyl The carbon atom number of base preferably 10~18.Specifically, C12 alkyl trimethyl ammonium chloride, dimercaptodimethyl ammonium chloride etc. can be enumerated As cationic surface active agent appropriate.

" short-chain alkyl " indicates the alkyl that can have the carbon atom number 1~4 of substituent group.The carbon of the abovementioned alkyl of short-chain alkyl Atomicity preferably 1 or 2.The substituent group that abovementioned alkyl as short-chain alkyl can have can enumerate phenyl, benzyl, hydroxyl, hydroxyl alkane Base, polyoxy alkylidene etc..The carbon atom number of hydroxyalkyl preferably 2~4, more preferable 2 or 3.Oxyalkylene in polyoxy alkylidene Carbon atom number preferably 2~4, more preferable 2 or 3.

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

(A-3) in ingredient, above-mentioned (32) particularly preferably are used.

Entirely ratio shared by (A-3) ingredient is not particularly limited in (A) ingredient, relative to the gross mass of (A) ingredient, Its preferably 0.01~30 mass %, more preferable 0.1~20 mass %, particularly preferred 0.5~10 mass %.(if A-3) ingredient Ratio is in above-mentioned preferred scope, then when being dried within doors, can further suppress the undesirable gas from substrate The generation of taste (drying taste within doors).

As amphoteric surfactant, for example, imidazoline system amphoteric surfactant, the both sexes of amide betaine system can be enumerated Surfactant, alkyl dimethyl amine oxide, alkyl amidopropyldimethyl amine oxide etc..Specifically, 2- alkyl-N- can be enumerated Carboxymethyl-N- hydroxyethyl imidazole quinoline glycine betaine, lauric amide propyl betaine, the C12 oxidation in alkyl dimethyl amine oxide Amine and C14 amine oxide etc. are used as amphoteric surfactant appropriate.

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

Entirely ratio shared by amphoteric surfactant is not particularly limited in (A) ingredient, relative to the total of (A) ingredient Quality, preferably 0~60 mass %, more preferable 0~30 mass %.If the ratio of amphoteric surfactant is in above-mentioned preferred model In enclosing, then further increased for the washing performance for the spot for being attached to substrate.

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

As (A) ingredient, (A-1) ingredient and (A-2) ingredient is preferably used in combination.(A-1) when ingredient and (A-2) ingredient coexist, It is further increased for the washing performance of the various spots such as the sebum spot, protein contaminants, carbohydrate spot for being attached to substrate, because This, is easy to significantly show effect of the invention.

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

If mass ratio (A-1)/(A-2) more than preferred lower limit value, especially for sebum spot washing performance into One step improves；On the other hand, if mass ratio (A-1)/(A-2) in preferred upper limit value hereinafter, if especially for protein dirt The washing performance of stain further increases.

In the present invention, " mass ratio that (A-1) ingredient/(A-2) ingredient indicates " mean (A-1) in liquid detergent at Divide mass ratio of the content relative to (A-2) component content.

In addition, the mass ratio that (A-1) ingredient/(A-2) ingredient indicates can be 5~20.

In addition, preferably (A) ingredient contains (A-3) ingredient in liquid detergent of the invention.By containing (A-3) ingredient, When being dried within doors, the effect for inhibiting to dry taste generation within doors can be further improved.

In addition, drying taste production within doors from improving the washing performance for various spots and being easily obtained inhibition as (A) ingredient From the point of view of raw effect, (A-1) ingredient, (A-2) ingredient and (A-3) ingredient is preferably used in combination.

The mass ratio that [(A-1) ingredient+(A-2) ingredient]/(A-3) ingredient indicates (also is indicated as " mass ratio [(A-1)+(A- 2)]/(A-3) ") preferably 1~50, more preferable 5~30, further preferred 18~46.

If mass ratio [(A-1)+(A-2)]/(A-3) further increases storage stability more than preferred lower limit value (transparent homogeneity and mobility)；On the other hand, if mass ratio [(A-1)+(A-2)]/(A-3) preferred upper limit value with Under, then further increase the effect for inhibiting to dry taste generation within doors.

In the present invention, " mass ratio that [(A-1) ingredient+(A-2) ingredient]/(A-3) ingredient indicates " means liquid scrubbing Mass ratio of the total content of (A-1) ingredient and (A-2) ingredient in agent relative to (A-3) component content.

Relative to the gross mass of aforesaid liquid detergent, the content preferably 20 mass % of (A) ingredient in liquid detergent More than, more preferable 30 mass % or more, particularly preferred 40 mass % or more.The content of (if A) ingredient preferred lower limit value with On, then it becoming prone to obtain for the good washing effect for the spot for being attached to substrate, the content of (A) ingredient becomes higher, It is more easy to obtain effect caused by the present invention significantly.

On the other hand, the upper limit value of the content of (A) ingredient preferably in 80 mass % hereinafter, more preferable 70 mass % hereinafter, Further preferred 60 mass % or less.If (A) ingredient content in preferred upper limit value hereinafter, if can more easily ensure it is outer The transparent homogeneity and mobility seen.

That is, the gross mass relative to liquid detergent, the content of (A) ingredient preferably 20 mass % or more, 80 mass % with Under, more preferable 30 mass % or more, 70 mass % are hereinafter, further preferred 40 mass % or more, 60 mass % or less.

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

<(B) ingredient: carbohydrate degradation enzyme preparation>

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

In liquid detergent of the invention, by containing (B) ingredient, the effect that taste generation is dried in main inhibition within doors is obtained To performance.

As carbohydrate degradation enzyme, cellulase, amylase, mannonase pectase, zytase, saccharification can be enumerated Enzyme, glucuroide, dextranase, dextranase, chitinase, sialidase, mannosidase, invertase, fucose Glycosides enzyme, algin catenase and pectin lyase etc..In these, the effect that taste generates is dried within doors from inhibition is more readily available From the aspect of, preferred cellulose enzyme, amylase and mannase, particularly preferred amylase and mannase.

For the commercially available product that can specifically obtain of (B) ingredient, as the enzyme preparation containing cellulase, can enumerate can be from promise Endolase 5000L, the Celluzyme 0.4L, Carezyme Premium 4500L that dimension letter (Novozymes) company obtains (more than, product name) etc..As the enzyme preparation containing amylase, can enumerate can be from Novozymes Company's acquisition Termamyl300L、Termamyl Ultra 300L、Duramyl 300L、Stainzyme 12L、Stainzyme Plus 12L (above, product name)；Can from (Genencor) company, Jie Neng section obtain product name Maxamyl, can be from amano enzyme system Product name pullulanase amano of product Co., Ltd. acquisition, the trade name that can be obtained from Seikagaku Kogyo Co. Ltd. Claim DB-250 etc..As the enzyme preparation containing mannase, the product name that can be obtained from Novozymes Company can be enumerated Mannaway 4L etc..

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

From further increasing washing effect and inhibiting from the aspect of drying the effect that taste generates within doors, relative to aforesaid liquid The gross mass of detergent, (B) component content preferably 0.01 mass % or more, more preferable 0.03 mass % in liquid detergent with On, further preferred 0.05 mass % or more.

On the other hand, from the saturation of the mixed effect for ensuring (inhibition enzyme precipitation etc.) and (B) ingredient of storage stability From the aspect of, relative to the gross mass of aforesaid liquid detergent, the upper content limit value of (B) ingredient preferably 2 mass % are hereinafter, more excellent 1.5 mass % are selected hereinafter, further preferred 1 mass % or less.That is, the gross mass relative to liquid detergent, (B) ingredient contains Preferably 0.01 mass % or more, 2 mass % are measured hereinafter, more preferable 0.03 mass % or more, 1.5 mass % are hereinafter, further excellent Select 0.05 mass % or more, 1 mass % or less.

In addition, the gross mass relative to liquid detergent, particularly preferred 0.1~0.5 mass % of the content of (B) ingredient.

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

(C) ingredient is hydroxycarboxylic acid or its salt, that is, it is in the group being made of hydroxycarboxylic acid and hydroxycarboxylate At least one kind of compound.

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

In liquid detergent of the invention, by containing (C) ingredient, mainly the appearance of liquid detergent can be remained saturating It is bright uniform, furthermore it is possible to ensure the mobility of liquid detergent, make excellent storage stability.

As hydroxycarboxylate, the alkali metal salts such as sodium salt and the sylvite of above-mentioned hydroxycarboxylic acid can be enumerated；Calcium salt and magnesium salts etc. Alkali earth metal salt；Alkanolamines such as ammonium salt and ethanolamine salt etc..

As the preference of (C) ingredient, the following general formula (c-1) compound represented can be enumerated.

[changing 2]

[in formula, R⁴And R⁵It separately indicates hydrogen atom, can have the alkyl of the carbon atom 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 base Group；R⁶And R⁷Separately indicate the alkyl of hydrogen atom or carbon atom number 1~5；V is 0~4 integer；M⁺It is counter ion.]

In above-mentioned formula (c-1), R⁴And R⁵In alkyl carbon atom number be 1~10, preferably carbon atom number be 1~5, In, more preferable methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, amyl, isopentyl and neopentyl；Into The preferred methyl of one step, ethyl, propyl and isopropyl；Particularly preferred methyl and ethyl；Most preferable.R⁴And R⁵In Aryl, preferably carbon atom number are 6~15, and more preferable carbon atom number is 6~10, wherein further preferred phenyl and naphthalene.

As R⁴And R⁵In ester group, for example,-COOR can be enumerated suitably⁸.As R⁴And R⁵In ether, for example, - R can suitably be enumerated⁴-O-R⁵。

R⁴And R⁵In, " alkyl with substituent group, the aryl with substituent group, the amino with substituent group " means The hydrogen atom for constituting alkyl, the hydrogen atom for constituting aryl, the respective at least one hydrogen atom constituted in the hydrogen atom of amino are substituted Alkyl replaced base, aryl and amino.

The substituent group that alkyl as carbon atom number 1~10 can have, for example, aryl, nitro, nitro-derivative can be enumerated Group, hydroxyl (- OH), hydroxyl derivative groups, ester group, ether, amino, amine derivative group, amide groups, amide derivatives base Group and halogen atom etc..

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

As the substituent group that amino can have, for example, can enumerate 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..

As alkyl, aryl and the ester group in above-mentioned substituent group, can enumerate and above-mentioned R⁴And R⁵In alkyl, aryl and The identical group of ester group.

As the amide groups in above-mentioned substituent group, for example,-C (=O) NH-R can be enumerated suitably⁹。

As the halogen atom in above-mentioned substituent group, for example, fluorine atom, chlorine atom, bromine atom and iodine atom can be enumerated, it is excellent Select fluorine atom.

Among the above, R⁴And R⁵Respectively preferred hydrogen atom, can have substituent group carbon atom number 1~10 alkyl, can have The aryl of substituent group.

In addition, the preferred R of difference⁴And R⁵Both of which is hydrogen atom, R⁴And R⁵A side be hydrogen atom and another party is Can have alkyl, the R of the carbon atom number 1~10 of substituent group⁴And R⁵A side be hydrogen atom and another party is can have substituent group Aryl.

In above-mentioned formula (c-1), R⁶And R⁷In alkyl separately indicate the alkyl of carbon atom number 1~5, wherein it is excellent Select methyl, ethyl, propyl or isopropyl, more preferable methyl or ethyl, further preferred methyl.

In addition, the preferred R of difference⁶And R⁷Both of which is hydrogen atom, R⁶And R⁷A side be hydrogen atom and another party is Methyl.

V is 0~4 integer, preferably 0,1 or 2, more preferable 0 or 1, particularly preferred 0.

M⁺It is counter ion, as long as can be with-COO^-It is formed together 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 can be enumerated Deng.In addition, M⁺When being proton, general formula (c-1) compound represented indicates hydroxycarboxylic 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 that can obtain above-mentioned counter ion can be any one of primary amine, secondary amine, tertiary amine, and preferably total carbon atom number is 1 ~6.Above-mentioned amine can have hydroxyl, as such amine, can enumerate alkanolamine, and the carbon atom number of preferably above-mentioned silane alcohol base is 1~ 3.As the specific example of alkanolamine, monoethanolamine, diethanol amine and triethanolamine etc. can be enumerated.

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

As M⁺, from the difficulty of acquisition and from the aspect of further increasing dissolubility, preferred as alkali ion, preferably sodium Ion and potassium ion, particularly preferred sodium ion.

As the preference of (C) ingredient, specifically, glycolic, lactic acid (α-hydracrylate and beta-hydroxy third can be enumerated Acid), hydroxybutyric acid (2- hydroxybutyric acid, 3-hydroxybutyrate and gamma-hydroxybutyric acid), hydroxy-iso-butyric acid (2- hydroxy-iso-butyric acid with And 3-HIB), mandelic acid and their optical isomer or their salt etc..

Among the above, as (C) ingredient, from the aspect of especially becoming good from storage stability, preferably alpha-hydroxy carboxylic acid compounds or Its salt, more preferable Alpha-hydroxy-monocarboxylic acid or its salt, the compound that particularly preferred the following general formula (c-1-1) indicates.

[changing 3]

[in formula, R⁴' and R⁵' separately indicate hydrogen atom, can have substituent group carbon atom number 1~10 alkane Base, the aryl that can have 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)⁺It is identical.]

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

It is preferred that R⁴' and R⁵' both of which is hydrogen atom, R⁴' and R⁵' a side be hydrogen atom and another party is that can have The alkyl or R of the carbon atom number 1~10 of substituted base⁴' and R⁵' a side be hydrogen atom and another party is that can have substitution The aryl of base；More preferable R⁴' and R⁵' a side be hydrogen atom and another party is the carbon atom number 1~10 that can have substituent group Alkyl or R⁴' and R⁵' a side be hydrogen atom and another party is the aryl that can have substituent group；Particularly preferred R⁴' and R⁵' a side be hydrogen atom and another party is the alkyl that can have the carbon atom number 1~10 of substituent group.

As the preference of compound shown in above-mentioned formula (c-1-1), glycolic, α-hydracrylate, 2- hydroxyl fourth can be enumerated Acid, 2- hydroxy-iso-butyric acid, mandelic acid and their optical isomer or their salt etc.；It is preferred that α-hydracrylate, almond Acid or their salt；More preferable α-hydracrylate, mandelic acid or their salt；Particularly preferred α-hydracrylate or its salt.

(C) ingredient 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 matter of (C) ingredient in liquid detergent Measure %, more preferable 0.5~4 mass %, further preferred 1~3 mass %, particularly preferred 1~2 mass %.

If the content of (C) ingredient, in above-mentioned preferred range, the stability of (B) ingredient in liquid detergent mentions It is high.Additionally it is possible to which the liquid level that is more easily inhibited forms the effect of epithelium.

If the content of (C) ingredient is more than preferred lower limit value, the appearance transparent for further increasing liquid detergent is equal One property and mobility.On the other hand, if the content of (C) ingredient in preferred upper limit value hereinafter, if when liquid detergent is made It is more difficult to generate precipitating etc..

In the present invention, " mass ratio that (B) ingredient/(C) ingredient indicates " means (B) component content in liquid detergent Mass ratio relative to (C) component content.

(B) mass ratio (also being indicated as " mass ratio (B)/(C) ") that ingredient/(C) is indicated is 1 hereinafter, it is preferred that 0.001~1, More preferable 0.01~0.75, further preferred 0.1~0.25.

If mass ratio (B)/(C) in above-mentioned upper limit value hereinafter, if liquid detergent appearance transparent homogeneity and flowing Property is ensured and excellent storage stability.In addition, being also easily available the effect for inhibiting liquid level to form epithelium.Mass ratio (B)/ (C) more than above-mentioned upper limit value when, the situations such as precipitating may be generated when liquid detergent is made.

On the other hand, if more than preferred lower limit value, washing performance improves and inhibits the effect for drying taste generation within doors Also it improves.

<(D) ingredient>

(D) ingredient in the present invention is selected from by isopropyl methyl phenol (IPMP), the iodo- 2- propynyl ester of butylamino formic acid 3- (IPBC), at least one kind of in the group that probenazole (TBZ), polylysine, poly hexamethylene biguanide and their hydrochlorate are constituted. It, mainly being capable of endowing antibacterial by containing (D) ingredient.

" polylysine and its hydrochlorate "

As polylysine, the poly- D-Lys of α-poly-L-Lysine, epsilon-poly-L-lysine, α-can be used and ε-is poly- Any one of D-Lys.In these, from the aspect of safety, preferably α-poly-L-Lysine and the poly- L- of ε-rely ammonia Acid, more preferable epsilon-poly-L-lysine.Wherein, from the aspect of safety, ε-shown in particularly preferred the following general formula (d1) is poly- L-lysine.

[changing 4]

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

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

Epsilon-poly-L-lysine can be obtained by the microorganism that culture streptomycete (Streptomyces) belongs to, and be logical It crosses polypeptide obtained from the condensation of the lysine as human body institute essential amino acid.When the polylysine is hydrolyzed by intracorporal enzyme etc. It can be changed to the L-lysine of script constituent, therefore, safety is very high.

As polylysine, the poly- of the polylysine of free shape and the hydrochlorate form of inorganic acid or organic acid can be used Any one of lysine.

In the case where hydrochlorate form, preferably hydrochloride, gluconate and acetate, more preferable hydrochloride.

In addition, it is easy in order to operate, the polylysine after excipient or filler processing can be used.

" poly hexamethylene biguanide or its hydrochlorate "

As poly hexamethylene biguanide or its hydrochlorate, for example, can enumerate the following general formula (d2) compound represented (hereinafter, Referred to as " (d2) ingredient ".).

[changing 5]

[in formula, m is 2~14 integer；HR⁴Indicate organic acid or inorganic acid；N means HR⁴Number, and be 0~5m Integer.]

In above-mentioned formula (d2), m is 2~14 integer, preferably 10~14 integer, more preferable 11~13 integer, especially It is preferred that 12.

In above-mentioned formula (d2), HR⁴Indicate organic acid or inorganic acid, preferably hydrochloric acid, gluconic acid and acetic acid, more preferable salt Acid.

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

When n is 0, (d2) ingredient is poly hexamethylene biguanide.When n is not 0, (d2) ingredient is the portion of poly hexamethylene biguanide Divide hydrochlorate or whole hydrochlorates.The n preferably integer of 1~5m, the integer of more preferable 2~3m, the integer of further preferred m~2m are special Not preferred m.

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

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

As (D) ingredient, from the aspect of it more easily can ensure appearance stability, preferably IPMP, IPBC and The combination of IPMP and IPBC, more preferable IPMP.

Relative to the gross mass of aforesaid liquid detergent, content preferably 0.01~2 matter of (D) ingredient in liquid detergent Measure %, more preferable 0.1~1 mass %.If (D) ingredient more than preferred lower limit value, can obtain more good inhibition The effect of taste is dried within doors；If below the upper limit, the storage stability of liquid detergent becomes more good.

In the present invention, " mass ratio that (B) ingredient/(D) ingredient indicates " means (B) component content in liquid detergent Mass ratio relative to (D) component content.

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

If mass ratio (B)/(D) is more than above-mentioned lower limit, the appearance transparent homogeneity of liquid detergent and flowing Property is ensured and excellent storage stability.In addition, being also easily available the effect for inhibiting liquid level to form epithelium.If mass ratio (B)/ (D) in above-mentioned upper limit value hereinafter, then washing performance improves and the effect for drying taste generation within doors is inhibited also to improve.

Liquid detergent of the invention, the viewpoints such as dissolubility consider from water when difficulty, the use of preparation, preferably contain There are the water as solvent, further preferably ion exchange water.

Relative to the gross mass of aforesaid liquid detergent, the content preferably 70 mass % of the water in liquid detergent hereinafter, More preferable 60 mass % is hereinafter, further preferred 50 mass % or less.The content of water becomes fewer, more easy to obtain this significantly Effect caused by inventing.In addition, being also easy to prepare concentrated cleaning.

On the other hand, the lower limit value of the content of water preferably 30 mass % or more.If the content of water preferred lower limit value with On, then the storage stability for the liquid detergent passed at any time becomes more good.

That is, when containing the water as solvent, content preferably 30 mass % or more, the 70 mass % of the water in liquid detergent Hereinafter, more preferable 30 mass % or more, 60 mass % are hereinafter, further preferred 30 mass % or more, 50 mass % or less.

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

In liquid detergent of the invention, within the scope of the effect of the invention, as needed, can also it contain above-mentioned (A)~(C) ingredient (other ingredients) other than ingredient.

It as other ingredients, is not particularly limited, can be mixed into commonly used in the liquid detergent of dress material use etc. Ingredient can enumerate enzyme preparation (hereinafter, the case where there is also referred to as any enzyme preparations) other than (B) ingredient, enzyme stabilizers, anti-corrosion Agent, alkaline agent, antioxidant, miscible organic solvents, fragrance, viscosity reductant or solubilizer, colorant, washing performance builder, Defoaming agent, pH adjusting agent, silicone, fluorescent whitening agent, dye transfer inhibitor, recontamination inhibitor, pearling agent, detergent, control Infusion, chelating agent, opacifiers and extraction species etc..

For the enzyme preparation (any enzyme preparation) other than (B) ingredient, the liquid system that enzyme component is scattered in liquid can be used The powder formulation etc. of agent, the stabilizer that enzyme is fixed on to powder etc..As enzyme component, as long as the liquid of previous dress material can be used for The enzyme component of body detergent.As any enzyme preparation, for example, protease preparation and lipase preparation etc. can be enumerated.

As protease preparation, Savinase 16L, the Savinase Ultra that can be obtained from Novozymes Company can be enumerated 16L、Savinase Ultra 16XL、Everlase 16L TypeEX、Everlase Ultra 16L、Esperase 8L、 Alcalase 2.5L、Alcalase Ultra 2.5L、Liquanase 2.5L、Liquanase Ultra 2.5L、 Liquanase Ultra 2.5XL and Coronase48L (more than, product name)；It can be obtained from Genencor Company Purafect L, Purafect OX, Properase L (more than, product name) etc..

As lipase preparation, can enumerate can from Novozymes Company obtain Lipex 100L and Lipolase 100L (with On, product name) etc..

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

By the way that at least one kind of and (B) ingredient in any enzyme preparation to be used in combination, it can be further improved inhibition and dry taste production within doors Raw effect.

The mass ratio preferably 0.2~1, more preferable 0.5~1 that " (B) ingredient/any enzyme preparation " indicates.If the mass ratio exists In above-mentioned preferred range, then the effect for inhibiting to dry taste generation within doors is further increased.

In the present invention, " mass ratio that (B) ingredient/any enzyme preparation indicates " means (B) ingredient in liquid detergent Mass ratio of the content relative to the enzyme preparation content other than (B) ingredient.

In any enzyme preparation, optimization protein enzyme preparation, wherein more preferable Savinase16L, Savinase Ultra 16L、Savinase Ultra 16XL、Everlase 16L、Everlase Ultra 16L、Liquanase 2.5L、 Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL and Coronase 48L；Further preferred Everlase 16L, Savinase 16L and Coronase 48L.

In liquid detergent, relative to the gross mass of aforesaid liquid detergent, the content of any enzyme preparation preferably 0.01~2 Quality %, more preferable 0.01~1 mass %, further preferred 0.03~0.8 mass %.If the content of any enzyme preparation is preferred Lower limit value more than, then be easy play enzyme mixed effect；Even if if in preferred upper limit value hereinafter, if it is few in moisture content It is also difficult to that enzyme preparation is precipitated in composition.

As enzyme stabilizers, for example, boric acid, borax, formic acid or their salt can be enumerated；And calcium chloride and calcium sulfate etc. Calcium salt.Relative to the gross mass of liquid detergent, the content of enzyme stabilizers preferably 0.001 mass % or more, 2 mass % or less.

As preservative, for example, the product name Kathon of ROHM AND HAAS (Rohm and Haas) corporation can be enumerated CG etc..Relative to the gross mass of liquid detergent, the content of preservative preferably 0.001~1 mass %.

In addition, in order to improve storage stability, also containing with as the benzoic acid of preservative effectiveness or its salt.Relatively In the gross mass of liquid detergent, the content of benzoic acid or its salt preferably 0.1~5 mass %, more preferable 0.15~2 mass %.

As alkaline agent, monoethanolamine, diethanol amine and triethanolamine etc. can be enumerated.Total matter relative to liquid detergent Amount, the content of alkaline agent preferably 0.5~5 mass %.

It as antioxidant, is not particularly limited, but from can more be well maintained washing performance and liquid stability From the aspect of, preferred phenolic antioxidant, wherein the more preferable single phenols such as dibutyl hydroxy toluene and butylated hydroxyanisole (BHA) system is anti- Double phenolic antioxidants such as oxidant, 2,2' methylene bis (4- methyl-6-tert-butylphenol) and dl- alpha-tocopherol are contour Molecule-type phenolic antioxidant, further preferably list phenolic antioxidant and polymer electrolyte phenolic antioxidant.Relative to liquid The gross mass of body detergent, the content of antioxidant preferably 0.01~2 mass %.

Miscible organic solvents refer to the organic solvent that 50g or more is dissolved in 25 DEG C of ion exchange water 1L.As Miscible organic solvents, as long as the solvent of uniform solution can be formed when mixing with water, for example, ethyl alcohol, 1- can be enumerated The alcohols such as propyl alcohol, 2- propyl alcohol and n-butyl alcohol；The glycols such as propylene glycol, butanediol and hexylene glycol；Diethylene glycol, triethylene glycol, four Polyethylene glycol that polyethylene glycol that ethylene glycol, average molecular weight are about 200, average molecular weight are about 400, average molecular weight are about The polyethylene glycols such as 1000 polyethylene glycol, dipropylene glycol；Alkyl ethers 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 solubilizer, for example, toluenesulfonic acid, xylene monosulfonic acid, isopropyl sulfonic acid, substitution or not can be enumerated Substituted naphthalene sulfonic acids, toluene fulfonate, xylenesulfonate, cumene sulfonate, substituted or unsubstituted naphthalene sulfonate.As The salt of aromatic sulphonic acid can enumerate sodium salt, sylvite, calcium salt, magnesium salts, ammonium salt, alkanolamine etc..

Viscosity reductant or solubilizer can be used alone or two or more kinds may be used.Relative to the total of liquid detergent The content of quality, viscosity reductant or solubilizer preferably 0.01~15 mass %.The content of viscosity reductant or solubilizer is in the preferred model When enclosing interior, the shape for inhibiting to be formed by epithelium in liquid detergent liquid level by aforesaid liquid detergent gels is further increased At effect.

As washing performance builder, any one of inorganic builders or organic washing-assisting detergent can be used.Relative to liquid The gross mass of detergent, the content of washing performance builder preferably 0.01~20 mass %.

In addition, liquid detergent of the invention can also contain short chain fatty acids, wherein wash relative to liquid in order to defoam The gross mass for washing agent preferably comprises 0~5 mass % short chain fatty acids.

PH at preferably 25 DEG C of liquid detergent of the invention is 4~9, more preferable pH6~9.PH within the above range when, The storage stability of liquid detergent can be more well maintained.

The pH of liquid detergent can be adjusted by addition pH adjusting agent.As pH adjusting agent, hydrochloric acid, sulphur can be enumerated Acid, sodium hydroxide, potassium hydroxide and alkanolamine etc..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 indicate by liquid detergent adjust to 25 DEG C and by pH meter (name of product: HM-30G, DKK Toa Corp.'s manufacture) etc. the numerical value that is measured.Even in addition, other than range specified in this specification PH value, as long as being the pH value of range specified in this specification when pH value when being modified to 25 DEG C, then it includes Yu Benfa In bright range.

Liquid detergent of the invention considers from viewpoints such as the discharges of container, viscosity at preferably 25 DEG C is 10~ 1000mPas or so, more preferable 80~500mPas or so.

In the present invention, the viscosity of liquid detergent indicates to adjust liquid detergent to 25 DEG C and by Brookfield viscometer institute The numerical value of measurement.In addition, even if value other than range as defined in this specification, as long as value when being modified to 25 DEG C is in this theory The viscosity number of bright book prescribed limit, then it includes within the scope of the invention.

Liquid detergent of the invention passes through mixed solvent (preferably water), (A) ingredient, (B) ingredient and (C) ingredient and root It is prepared according to other ingredients of needs.

For example, further then mixing (B) ingredient and (C) ingredient add pH wherein after mixed solvent and (A) ingredient Regulator adjusts pH, in the case where solvent has remaining situation, adds its remainder, mixes, to obtain as object Liquid detergent.

That is, a mode of the preparation method of liquid detergent of the invention includes by the one or all of solvent and (A) Ingredient mixing；Further addition (B) ingredient is mixed with (C) ingredient in above-mentioned mixed solution.It further, can be with It is included in above-mentioned mixed solution and adds other ingredients and mixed, and when solvent has remainder, it may include above-mentioned mixed Addition solvent remainder in solution is closed to be mixed.

The application method of liquid detergent of the invention can be identical as the application method of liquids in general detergent.For example, can Enumerate the method put into liquid detergent of the invention together with washings in washing in water, by liquid scrubbing of the invention The method and liquid detergent of the invention is dissolved in the water and is impregnated in advance that agent is directly coated in the spot of washings The method etc. of clothing.Furthermore it is preferred that the following method: it is appropriate to place after liquid detergent of the invention is coated on washings, Then, common washing is carried out using usual cleaning solution.At this point, the usage amount of liquid detergent of the invention is 10g/30L.

As described above, in liquid detergent of the invention, by the solution containing (A) ingredient with specific mass ratio (mass ratio that (B) ingredient/(C) ingredient indicates is below 1) (B) ingredient and (C) ingredient are used in combination, and can obtain following effect: It improves the effect for inhibiting to dry taste generation within doors and storage stability is good.

That is, by the mixing of (B) ingredient, it can will be helpful to be attached to especially on the inside of it of substrate or sink The carbohydrate breakdown that biofilm structure body is formed removes, so that the substrate bacterial number after being attached to washing is reduced, therefore, even if When being dried within doors, it can also inhibit the generation of the undesirable smell (drying taste within doors) from substrate.

In addition, by combining (B) ingredient and (C) ingredient with specific mass ratio, make (C) ingredient be sufficiently adsorbed in (B) at The dissolubility of (B) ingredient in liquid detergent is improved, thus storage stability (transparent homogeneity, mobility) in the surface divided Become good.

In addition, liquid detergent according to the present invention, due to having the effect of decomposing, removing biomembrane, by anti- After backwashing is washed, it is difficult to form biomembrane in substrate or sink.

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

As the other way of liquid detergent of the invention, liquid detergent below can be enumerated:

The liquid detergent contains: (A) ingredient: surfactant；(B) ingredient: carbohydrate degradation enzyme preparation；(C) ingredient: At least one kind of compound in the group being made of hydroxycarboxylic acid and its salt；Solvent (preferably water, more preferable ion exchange water)； And other compositions as needed；

Relative to the gross mass of the liquid detergent, the content of (A) ingredient be 20 mass % or more, 80 mass % with Under, preferably 27~48 mass %；(B) content of ingredient is 0.01 mass % or more, 2 mass % hereinafter, it is preferred that 0.1~0.5 matter Measure %；(C) content of ingredient is 0.1~5 mass %, preferably 1~2 mass %；The content of solvent is 30 mass % or more, 70 matter % is measured hereinafter, it is preferred that 48~70 mass %；And the total of the content of above-mentioned total ingredient is no more than 100 mass %；

(B) mass ratio that ingredient/(C) ingredient indicates is 0.001~1, preferably 0.1~0.25.

The liquid detergent contains: (A) ingredient: selected from by (A-1) nonionic surfactant, (A-2) anion table At least one kind of surfactant in group that face activating agent, (A-3) cationic surfactant are constituted；(B) ingredient: selected from by fibre Tie up at least one kind of carbohydrate degradation enzyme preparation in the group that plain enzyme, amylase and mannase are constituted；(C) ingredient: following formula (c-1) compound indicated；Solvent (preferably water, more preferable ion exchange water)；And other ingredients as needed；

Relative to the gross mass of the liquid detergent, the content of (A) ingredient be 20 mass % or more, 80 mass % with Under, preferably 27~48 mass %；(B) content of ingredient is 0.01 mass % or more, 2 mass % hereinafter, it is preferred that 0.1~0.5 matter Measure %；(C) content of ingredient is 0.1~5 mass %, preferably 1~2 mass %；The content of solvent is 30 mass % or more, 70 matter % is measured hereinafter, it is preferred that 48~70 mass %；And the content of above-mentioned total ingredient is total no more than 100 mass %；

(B) mass ratio that ingredient/(C) ingredient indicates is 0.001~1, preferably 0.1~0.25 (zero evaluation of ← embodiment Range)；

When containing (A-1) ingredient with (A-2) ingredient, the mass ratio that (A-1) ingredient/(A-2) ingredient indicates is 0.1~20, It is preferred that 5~20；

When containing (A-1) ingredient and (A-2) ingredient with (A-3) ingredient, [(A-1) ingredient+(A-2) ingredient]/(A-3) ingredient The mass ratio of expression is 1~50, preferably 18~46.

[changing 6]

[in formula, R⁴And R⁵It separately indicates hydrogen atom, can have the alkyl of the carbon atom 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 base Group；R⁶And R⁷It is each independently the alkyl of hydrogen atom or carbon atom number 1~5；V is 0~4 integer；M⁺It is counter ion.]

As liquid detergent other way of the invention, liquid detergent below can be enumerated:

The liquid detergent contains: (A) ingredient: selected from by (A-1) nonionic surfactant, (A-2) anion table At least one kind of surfactant in group that face activating agent and (A-3) cationic surfactant are constituted；(B) ingredient: selected from by forming sediment At least one kind of carbohydrate degradation enzyme preparation in group that powder enzyme and mannase are constituted；(C) ingredient: following formula (c-1-1) indicates Compound；Solvent (preferably water, more preferable ion exchange water)；And other ingredients as needed；

Above-mentioned (A-1) ingredient be selected from the poly (oxyalkylene) fundamental mode nonionic surfactant indicated by following formula (a-1-1), under State the poly (oxyalkylene) fundamental mode nonionic surfactant of general formula (a-1-2) expression, the poly (oxyalkylene) that the following general formula (a-1-3) indicates The amines type nonionic surfactant that fundamental mode nonionic surfactant and the following general formula (a-1-4) indicate It is at least one kind of in the group of composition；

Above-mentioned (A-2) ingredient is selected from the straight-chain by the alkyl with carbon atom number 8~18 or the alkylbenzene containing branched Sulfonate, carbon atom number 2~4 any one of epoxyalkane or by ethylene oxide (EO) and propylene oxide (PO) (mole Than EO/PO=0.1/9.9~9.9/0.1) straight chain obtained by average 0.5~10 mole of addition with carbon atom number 10~20 or The α-sulfofattyacidmethylestersalt of alkyl (or alkenyl) ether sulfate of the alkyl (or alkenyl) containing branch, carbon atom number 14~18 And it is at least one kind of in the group of the Zhi Fang Suan salt composition of carbon atom number 10~22；

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

When containing (A-1) ingredient and (A-2) ingredient with (A-3) ingredient, [(A-1) ingredient+(A-2) ingredient]/(A-3) ingredient The mass ratio of expression is 1~50, preferably 18~46；

R¹-CO-[(EO’)s/(PO’)t]-R² (a-1-1)

[in formula, R¹It is the alkyl of carbon atom number 7~18 or the alkenyl of carbon atom number 7~18；R²It is carbon atom number 1~3 Alkyl；S indicates the averaged repeating numbers of EO ', and the number for being 6~20；T indicates the averaged repeating numbers of PO ', and the number for being 0~6；EO' Indicate that oxyethylene group, PO ' indicate oxypropylene group；[(EO ') s/ (PO ') t] means EO ' and PO ' it 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 atom number 8~18 or the alkenyl of carbon atom number 8~18；U table Show the averaged repeating numbers of EO ', and the number for being 5~20；P indicates that the averaged repeating numbers of EO ', q indicate the averaged repeating numbers of PO ', r table Show that the averaged repeating numbers of EO ', p, q, r are the numbers for meeting p>1, r>1,0<q≤3 and p+r=10~20；EO ' indicates ethylene oxide Base, PO ' indicate oxypropylene group；[(EO ') p/ (PO ') q] means EO ' and PO ' it can be mixed.]；

[changing 7]

[in formula, R⁰It is the alkyl of carbon atom number 10~20 or the alkenyl of carbon atom number 10~20；A¹O and A²O difference is only On the spot indicate the oxyalkylene of carbon atom number 2~3；I indicates A¹The averaged repeating numbers of O；J indicates A²The averaged repeating numbers of O；i>0,j > 0 and i+j is 10~50 number.]；

[changing 8]

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

The liquid detergent contains: (A) ingredient: surfactant；(B) ingredient: carbohydrate degradation enzyme preparation；(C) ingredient: At least one kind of compound in the group being made of hydroxycarboxylic acid and its salt；(D) ingredient: selected from by isopropyl methyl phenol (IPMP), the iodo- 2- propynyl ester (IPBC) of butylamino formic acid 3-, probenazole (TBZ), polylysine, poly hexamethylene biguanide with And it is at least one kind of in the group of their hydrochlorate composition；Solvent (preferably water, more preferable ion exchange water)；And as needed Other ingredients；

Relative to the gross mass of the liquid detergent, the content of (A) ingredient be 20 mass % or more, 80 mass % with Under, preferably 27~48 mass %；(B) content of ingredient is 0.01 mass % or more, 2 mass % hereinafter, it is preferred that 0.1~0.5 matter Measure %；(C) content of ingredient is 0.1~5 mass %, preferably 1~2 mass %；(D) content of ingredient is 0.1~2 mass %； The content of solvent is 30 mass % or more, 70 mass % hereinafter, it is preferred that 48~70 mass %；And the content of above-mentioned total ingredient is total No more than 100 mass %；

The liquid detergent contains: (A) ingredient: selected from by (A-1) nonionic surfactant, (A-2) anion table At least one kind of surfactant in group that face activating agent and (A-3) cationic surfactant are constituted；(B) ingredient: selected from by fibre Tie up at least one kind of carbohydrate degradation enzyme preparation in the group that plain enzyme, amylase and mannase are constituted；(C) ingredient: following formula (c-1) compound indicated；Solvent (preferably water, more preferable ion exchange water)；(D) ingredient: selected from by the following general formula (d1) table It is at least one kind of in the group that the compound that the compound and the following general formula (d2) shown indicates is constituted；And as needed other at Point；

[changing 9]

[in formula, R⁴And R⁵It separately indicates hydrogen atom, can have the alkyl of the carbon atom 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 base Group；R⁶And R⁷It is each independently the alkyl of hydrogen atom or carbon atom number 1~5；V is 0~4 integer；M⁺It is counter ion.]；

[changing 10]

[in formula, r is 5~100 integer.]；

[changing 11]

[in formula, m is 2~14 integer；HR⁴Indicate organic acid or inorganic acid；N means HR⁴Number, and be 0~5m Integer.].

The liquid detergent contains: (A) ingredient: selected from by (A-1) nonionic surfactant, (A-2) anion table At least one kind of surfactant in group that face activating agent and (A-3) cationic surfactant are constituted；(B) ingredient: selected from by forming sediment At least one kind of carbohydrate degradation enzyme preparation in group that powder enzyme and mannase are constituted；(C) ingredient: following formula (c-1-1) indicates Compound；(D) ingredient: selected from by isopropyl methyl phenol (IPMP), the iodo- 2- propynyl ester (IPBC) of butylamino formic acid 3-, The polyhexamethylene pair of polylysine or its hydrochlorate, above-mentioned formula (d2) expression that probenazole (TBZ) and above-mentioned formula (d1) indicate The group that the combination for the poly hexamethylene biguanide that the polylysine and above-mentioned formula (d2) that guanidine and above-mentioned formula (d1) indicate indicate is constituted In it is at least one kind of；Solvent (preferably water, more preferable ion exchange water)；And other ingredients as needed；

Above-mentioned (A-2) ingredient is selected from the straight-chain by the alkyl with carbon atom number 8~18 or the alkylbenzene containing branched Any one of sulfonate and the epoxyalkane of carbon atom number 2~4 (rub ethylene oxide (EO) and propylene oxide (PO) You are than EO/PO=0.1/9.9~9.9/0.1) straight chain with carbon atom number 10~20 obtained by addition is 0.5~10 mole average The alpha-sulfo-fatty acid of alkyl (or alkenyl) ether sulfate of shape or the alkyl (or alkenyl) containing branched, carbon atom number 14~18 It is at least one kind of in the group that the fatty acid salt of methyl esters salt and carbon atom number 10~22 is constituted；

When containing (A-1) ingredient and (A-2) ingredient with (A-3) ingredient, [(A-1) ingredient+(A-2) ingredient]/(A-3) ingredient When the mass ratio of expression is 1~50, preferably 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 indicate hydrogen atom, there can be the alkane of the carbon atom number 1~10 of substituent group Base can have the aryl of substituent group, nitro (- NO₂), ether can have amino the base (- NH of substituent group₂) or amine derivative base Group；M⁺It is counter ion.]

[embodiment]

Hereinafter, illustrating the present invention in further detail using embodiment, but the present invention is not limited to these embodiments.This reality It applies in example, " % " unless defined otherwise, is indicated " quality % ".

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

Raw material used in the present embodiment is as follows.

<(A) ingredient: surfactant>

(A-1) ingredient: nonionic surfactant

A-1-1: for coconut oil fatty acid methyl ester (by quality ratio, methyl laurate/methyl myristate=8/2 Mixture), using alkoxylating catalyst, the ethylene oxide of 15 molar equivalent of addition and obtain (MEE).Above-mentioned general formula (a-1- 1) in, R¹The alkyl of=carbon atom number 11 and the alkyl of carbon atom number 13, R²=methyl, s=15, t=0.Pass through following synthesis Method synthesizes to obtain.

[synthetic method of MEE]

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

Group is divided into 2.5MgOAl₂O₃·wH₂The aluminum magnesium hydroxide (キョーワー De 300 (product name) of O, association Manufactured with chemical industry Co., Ltd.) it is burnt into 1 hour under 600 DEG C, nitrogen atmosphere, it obtains firing aluminum magnesium hydroxide and (does not change Property) catalyst.It will firing aluminum magnesium hydroxide (unmodified) catalyst 2.2g and 0.5N potassium hydroxide-ethanol solution 2.9mL, the moon Acid methylester 280g, methyl myristate 70g are fed in 4L autoclave, and the modification of catalyst is carried out in autoclave.Then, After being replaced in autoclave with nitrogen, by temperature maintains 180 DEG C, pressure maintains 0.3MPa, and import ethylene oxide 1052g makes its reaction while stirring.

Obtained reaction solution is cooled to 80 DEG C, adds water 159g, atlapulgite and diatomite as filtration adjuvant After each 5g mixing, catalyst filtration is separated, MEE is obtained.

A-1-2: substance obtained by the ethylene oxide to 15 molar equivalent of natural alcohol addition (LMAO).Above-mentioned general formula (a-1- 2) in, R^3aThe alkyl of=carbon atom number 12 and the alkyl of carbon atom number 14, u=15.It synthesizes to obtain by following synthetic methods.

[synthetic method of LMAO]

By Procter & Gamble manufacture CO-1214 (product name) 861.2g and 30 mass %NaOH aqueous solution 2.0g feed in In pressure resistant type reaction vessel, nitrogen displacement will be carried out in above-mentioned reaction vessel.Then, in 100 DEG C of temperature, pressure 2.0kPa or less Under conditions of by behind reaction fluid dewatering 30 minutes in above-mentioned reactor, the temperature in above-mentioned reactor is warming up to 160 DEG C.It connects , while stirring above-mentioned reaction solution, ethylene oxide (gaseous state) 760.6g is slowly made an addition in above-mentioned reaction solution.At this point, While adjusting adding speed makes the reaction temperature of above-mentioned reaction solution be no more than 180 DEG C, ethylene oxide is added with pipe is blown into.

It is after ethylene oxide addition, above-mentioned reaction solution is old under the conditions of 180 DEG C of temperature, pressure 0.3MPa are below After changing 30 minutes, unreacted oxygen is distilled off in liquid from the reactions above under the conditions of 180 DEG C of temperature, pressure 6.0kPa are below Change ethylene, lasts 10 minutes.

Then, after the temperature of above-mentioned reaction solution being cooled to 100 DEG C or less, the p-methyl benzenesulfonic acid of 70 mass % of addition is carried out It neutralizes, making the pH of 1 mass % aqueous solution of reactant is about 7, obtains LMAO.

A-1-3: to natural alcohol (by quality ratio, alcohol=7/3 of alcohol/carbon atom number 14 of carbon atom number 12) successively block Nonionic surfactant obtained by the ethylene oxide that 8 mole of addition, 2 moles of propylene oxide, 8 moles of ethylene oxide.On It states in general formula (a-1-3), R^3bThe alkyl of=carbon atom number 12 and the alkyl of carbon atom number 14, p=8, q=2, r=8.

[synthetic method for the nonionic surfactant that formula (a-1-3) indicates]

Put into Procter & Gamble manufacture CO-1214 (product name) 194.5g and potassium hydroxide 1.1g, 110 DEG C, After carrying out dehydration under conditions of 1.3kPa 30 minutes, nitrogen displacement is carried out.After nitrogen displacement, 140 DEG C are warming up to, imports oxidation second Alkene 352g carries out addition reaction and burnin operation.Then, 120 DEG C are cooled to, propylene oxide 116g is imported, carries out addition reaction And burnin operation.Then, it is warming up to 140 DEG C again, imports ethylene oxide 352g, carries out addition reaction and burnin operation.Reaction After, after being cooled to 80 DEG C, acetic acid 1.2g is added in autoclave and is extracted, is obtained after stirring 30 minutes at 80 DEG C (a-1-3)。

A-1-4: the substance (Ethomeen) synthesized by following synthetic methods.In above-mentioned general formula (a-1-4), R⁰= The alkyl of carbon atom number 16, A¹O=oxyethylene group, A²O=oxyethylene group, i+j=20.

[synthetic method of Ethomeen]

By fatty acid amine (Tokyo Chemical Industry Co., Ltd's manufacture, hexadecane amine) charging in autoclave (pressure-resistant nitre Industrial Co., Ltd's manufacture) in, after being replaced in system with nitrogen, 150 DEG C are heated to, gradually addition ethylene oxide (EO) on a small quantity Until reaching specified amount, the tertiary amine (first stage) that the average addition molal quantity (that is, averaged repeating numbers) of EO is 2 moles is synthesized.

Then, by obtained tertiary amine and base catalyst (NaOH；Relative to above-mentioned 100 mass parts of tertiary amine, 0.8 mass is used The 40 mass %NaOH aqueous solutions of part) it feeds in autoclave, it will be replaced in system with nitrogen, be dehydrated using heating decompression Afterwards, 150 DEG C are heated to, gradually addition EO obtains the average addition molal quantity (that is, averaged repeating numbers) of EO up to specified amount on a small quantity For 20 moles of products (second stage).

After the addition reaction of EO, above-mentioned product is neutralized by acetic acid, obtains Ethomeen.Pass through amine Value measurement, calculates molecular weight, result 1121.

(A-2) ingredient: anionic surfactant

A-2-1:LAS, straight chained alkyl (carbon atom number 10~14) benzene sulfonic acid [manufacture of lion king (ライオ Application) Co., Ltd., Product name ライ Port Application LH-200 (LAS-H, purity=96 mass %)] sodium salt, average molecular weight 322 (prepares liquid to wash When washing agent, LAS-H is neutralized and referred to as sodium salt).

A-2-2:MES, α-sulfofattyacidmethylestersalt, lion king chemistry in ecology (ライオ Application エ U ケミカ Le ズ) strain formula Commercial firm's manufacture, product name " MIZULAN FL-80 ".

A-2-3:AES, polyoxyethylene lauryl ether sulfuric acid, New Japan Chem Co., Ltd's manufacture, product name " シノリンSPE-1350”。

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

A-2-5: fatty acid distribution of coconut oil sodium, in sodium and obtained by fatty acid distribution of coconut oil (product name, Japan Oil Co's manufacture) Substance.

(A-3) ingredient: cationic surfactant

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

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

A-3-3: chlorination alkyl (carbon atom number 16~18) trimethyl ammonium, the manufacture of Shi Wang special chemical Co., Ltd., commodity Title " アーカー De T-800 ".

A-3-4: didecyldimethylammonium chloride, the manufacture of Shi Wang special chemical Co., Ltd., product name " アーカー De 210”。

<(B) ingredient: carbohydrate degradation enzyme preparation>

B-1: mannase preparation, Novi believe the manufacture of (ノボザイ system ズ) company, product name " Mannaway 4L”。

B-2: diastase, Novozymes Company's manufacture, product name " Termamyl 300L ".

<(B ') ingredient: protein breakdown enzyme preparation, the comparison ingredient of (B) ingredient>

B ' -1: protease preparation, Novozymes Company's manufacture, product name " Coronase 48L ".

B ' -2: protease preparation, Novozymes Company's manufacture, product name " Everlase 16L ".

<(C) ingredient: at least one kind of compound in the group being made of Alpha-hydroxy-monocarboxylic acid and its salt>

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

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

< (D) ingredient: selected from by isopropyl methyl phenol (IPMP), the iodo- 2- propynyl ester (IPBC) of butylamino formic acid 3-, Probenazole (TBZ), polylysine, poly hexamethylene biguanide and they hydrochlorate constitute group in it is at least one kind of >

D-1: polylysine, product name " 25% aqueous solution of polylysine ", the manufacture of Chisso (チッソ) Co., Ltd..

D-2: poly hexamethylene biguanide, product name " プロキセ Le IB ", imperial Sha Ben (ロ Application ザジャパ Application) strain The manufacture of formula commercial firm.

D-3:2- isopropyl -5- methylphenol (IPMP), product name " ビオゾー Le ", Osaka Kasei Co., Ltd.'s system It makes

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

Common component:

Sodium benzoate: Toagosei Co., Ltd's manufacture.

Monoethanolamine: Nippon Catalyst K. K.'s manufacture.

Dibutyl hydroxy toluene: Sumitomo Chemical Co's manufacture, product name " SUMILZER BHT-R ".

Ethyl alcohol: Japanese alcohol peddles Co., Ltd.'s manufacture, product name " 95 degree of Le of specific ア Le U ー synthesis ".

Fatty acid 2- ethylhexyl: Lion Corporation's manufacture, product name " パステ Le 2H-08 ".

Fragrance: the spice composition A recorded in the table 11~18 of Japanese Patent Laid-Open 2002-146399 bulletin.

P-methyl benzenesulfonic acid: Kyowa Hakkokogyo Co., Ltd's manufacture, product name " PTS ".

Pigment: the sixth of the twelve Earthly Branches in the last of the ten Heavenly stems is melted into Co., Ltd.'s manufacture, product name " green 3 ".

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

(Examples 1 to 35, comparative example 1~4)

(blending constituent, content (quality %)) is formed according to shown in table 1~3, prepares each example by following manufacturing methods Liquid detergent.

In table, when blending constituent is empty column, it is not mixed into the blending constituent.

In table, the content expression of blending constituent is scaled the amount after purity ingredients.

It indicates that " appropriate " of pH adjusting agent content refers to add in order to which the pH of liquid detergent (25 DEG C) is adjusted to 7.0 PH adjusting agent (sodium hydroxide, sulfuric acid) total amount.

Indicate that " balance " of ion exchange water content means the conjunction in order to make total blending constituent contained by liquid detergent Count the remainder that combined amount (quality %) reaches 100 mass % and add.

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

" mass ratio (A-1)/(A-2) " means that (A-1) component content in liquid detergent contains relative to (A-2) ingredient The mass ratio of amount.

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

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

0.5 mass % of sodium benzoate, 1 mass % of monoethanolamine, 0.05 mass % of dibutyl hydroxy toluene, 7 matter of ethyl alcohol Measure %, 1.5 mass % of fatty acid 2- ethylhexyl, 0.5 mass % of fragrance, 1 mass % of p-methyl benzenesulfonic acid, 0.0005 matter of pigment Measure %.

[manufacturing method of liquid detergent]

It is formed according to shown in table 1~4, ethyl alcohol and (A) ingredient is added in capacity 500mL beaker, uses magnetic stirring apparatus (MITAMURA KOGYO INC. manufacture) is sufficiently stirred.

Then, the common component and ion exchange water other than ethyl alcohol are added, is stirred, meanwhile, add pH adjusting agent (hydroxide Sodium or sulfuric acid) so that pH is reached 7 (25 DEG C).At this point, addition ion exchange water, makes the total amount at the moment reach final gained liquid and washes Wash 95 mass % ingredients of agent total amount.

After pH is adjusted to 7, (B) ingredient or (B ') ingredient and (C) ingredient, stirring are added.Then, pH is further added Regulator (sodium hydroxide or sulfuric acid) makes pH reach 7 (25 DEG C), and addition ion exchange water makes total amount reach 100 mass %, obtains Liquid detergent.

The pH of liquid detergent can be by being adjusted to 25 DEG C for sample and with the pH meter (production that DKK Toa Corp. manufactures The name of an article claims " HM-30G ") it is measured.

About the liquid detergent of each example, inhibited to dry within doors respectively the effect of taste generation, storage stability and Inhibit to form the evaluation of the effect of epithelium in liquid level.

[inhibiting the evaluation for drying the effect of taste generation within doors]

Reusability in family and 10 pieces of the wiping hand towel of washing half a year (were not washed in usual life using about 2 days respectively It washs).The liquid detergent that hand towel uses each example is wiped to this 10 pieces, with leading to for washing machine (JW-Z23A type, the manufacture of company, Haier) Chang Chengxu carries out carrying out washing treatment (tap water of about 20 DEG C of water temperature of injection, about 3 ゜ DH of hardness, 20 times of bath raio).At this point, to washing The liquid scrubbing dosage of clothing machine investment is 10mL/ tap water 30L, carries out carrying out washing treatment.

In addition, as the dress material for meeting bath raio, using by the shirt (BVD manufacture) of completely new cotton 100% with automatic washing It is (about 20 DEG C of water temperature of injection, hard that the subscription procedure of clothing machine (Co., Ltd., Panasonic manufacture, NA-F70SD1) carries out 5 carrying out washing treatment Spend about 3 ゜ DH tap water) after dress material.At this point, using commercially available synthetic detergent TOP (Lion Corporation's manufacture) as washing Agent is washed, the detergent usage amount of every 1 carrying out washing treatment is that 25g/ tap water 30L carries out carrying out washing treatment.

After the carrying out washing treatment of above-mentioned wiping hand towel, by above-mentioned wiping hand towel in room temperature (about 23 DEG C), relatively wet The indoor sunning of 90%RH is spent, to carry out drying (drying within doors) in 5 hours.

Then, 6 specialized review persons respectively carry out the smell of the wiping hand towel after 10 pieces of dryings (drying within doors) 5 hours The sensory evaluation of so-called smell.

Above-mentioned sensory evaluation can be carried out and being scored based on following evaluation criteria.Specifically, specialized review person hears 10 Block dry within doors after wiping hand towel respective smell, according to the odour intensity of 6 grades in following evaluation criteria show into Row evaluation.Then, the average mark for calculating 10 pieces of wiping hand towels, is equally divided into index with this, dries taste generation within doors to inhibition Effect is evaluated.The average mark is as shown in table 1~3.The average mark is below as qualified at 2.5 points.

The evaluation criteria of sensory evaluation (odour intensity is shown)

0 point: absolutely not peculiar smell.

1 point: the degree that peculiar smell is perceived reluctantly can be experienced.

2 points: can feel faint peculiar smell.

3 points: can feel slightly strong peculiar smell.

4 points: can feel stronger peculiar smell.

5 points: can feel strong peculiar smell.

[evaluation of storage stability]

The liquid detergent 30mL of each example is filled in cylindrical glass bottle respectively, is closed the lid, is sealed.It is quiet with the state It is placed in 5 DEG C of thermostat, saves 24 hours.

Then, the cylindrical glass bottle for being filled with liquid detergent is taken out from above-mentioned thermostat, the liquid of 5 DEG C of observation is washed Wash the transparent homogeneity and mobility of agent, and based on the following evaluation criteria, to the storage stability of the liquid detergent of each example into Row evaluation.The evaluation result is the liquid detergent of A, B as qualified.

Evaluation criteria

A: transparent uniform, display mobility.

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

C: solidification has precipitation without mobility, or confirmation.

[liquid level is inhibited to form the evaluation of epithelium effect]

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

It does not cover and in the state of direct open wide, is observed after standing 24 hours at 5 DEG C on above-mentioned vertical × horizontal face Liquid level, based on following evaluation criteria, the effect for forming epithelium to the inhibition liquid level of the liquid detergent of each example is evaluated.Institute It states the liquid detergent that evaluation result is A, B and is used as qualification.

Evaluation criteria

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

B: there is the formation of epithelium on confirmation liquid level, but liquid detergent has mobility.

C: the gelation of liquid detergent entirety or solidification.

[table 1]

[table 2]

[table 3]

[table 4]

The result shown in the table 1~4 can confirm, using the inhibition room of the liquid detergent of the embodiment of the present invention 1~35 The effect for inside drying taste generation is good, and storage stability is good.

In addition, also knowing that the liquid detergent of Examples 1 to 35 is also good in terms of the effect for inhibiting liquid level to form epithelium.

[the utilization possibility in industry]

The effect that taste generation is dried in the inhibition of liquid detergent of the invention within doors is good and storage stability is good, therefore, It is industrially highly useful.

Claims

1. a kind of liquid detergent, which is characterized in that the liquid detergent contains:

(A) ingredient: surfactant；

(B) ingredient: carbohydrate degradation enzyme preparation；And

(C) ingredient: hydroxycarboxylic acid or its salt；

And with mass ratio represented by (B) ingredient/(C) ingredient be 1 hereinafter,

Relative to the gross mass of liquid detergent, the content of (A) ingredient is 20~80 mass %,

Relative to the gross mass of liquid detergent, the content of (B) ingredient is 0.01~2 mass %,

Relative to the gross mass of liquid detergent, the content of (C) ingredient is 0.1~5 mass %,

(A) ingredient contains the nonionic surfactant as (A-1) ingredient,

(A-1) ingredient is selected from the ester of polyoxyalkylene alkyl ether or polyoxy alkylidene alkene ether, long-chain fat acid alkyl ester Addition ring on fatty acid alkyl esters alcoxylates and chain alkyl amine obtained by addition alkylene oxide or long alkenyl amine between key At least one of alkylamine alkoxylates obtained by oxygen alkane,

Ratio shared by (A-1) ingredient is 50~90 mass % in all (A) ingredients,

(B) ingredient is selected from least one of amylase and mannase,

(C) ingredient is selected from glycolic, α-hydracrylate, 2- hydroxybutyric acid, 2- hydroxy-iso-butyric acid, mandelic acid, their light Learn at least one of the salt of isomers and they.

2. the liquid detergent recorded such as claim 1, wherein (A) ingredient contains cationic surfactant.

3. the liquid detergent recorded such as claims 1 or 2, wherein the liquid detergent also contains (D) ingredient；(D) Ingredient is selected from by the iodo- 2- propynyl ester IPBC of isopropyl methyl phenol IPMP, butylamino formic acid 3-, probenazole TBZ, poly- bad ammonia It is at least one kind of in the group that acid, poly hexamethylene biguanide and their hydrochlorate are constituted.