CN103459579A - Liquid detergent - Google Patents

Liquid detergent Download PDF

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Publication number
CN103459579A
CN103459579A CN2012800167564A CN201280016756A CN103459579A CN 103459579 A CN103459579 A CN 103459579A CN 2012800167564 A CN2012800167564 A CN 2012800167564A CN 201280016756 A CN201280016756 A CN 201280016756A CN 103459579 A CN103459579 A CN 103459579A
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liquid washing
quality
composition
washing agent
carbonatoms
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CN2012800167564A
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CN103459579B (en
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神藤宏明
黑川贵行
小仓弘嗣
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Lion Corp
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Lion Corp
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/08—Liquid soap, e.g. for dispensers; capsuled
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • C11D3/323—Amides; Substituted amides urea or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

A liquid detergent which contains 40% by mass or more of (A) a surfactant, 150 ppm or less (on a mass basis) of (B) a dye, and 0.5-12% by mass of (C) urea or a derivative thereof.

Description

Liquid washing agent
Technical field
The present invention relates to a kind of liquid washing agent that contains urea.
The application be take No. 2011-081768, the patent application Patent that proposes in Japan on April 1st, 2011 for basis opinion right of priority, at this, quotes its content.
Background technology
Recently, the washing composition used as home washings, liquid washing agent due to have the speciality different from washing powder (such as: residual without dissolving, the happy fragrance etc. of enjoying), price is reasonable grounds also, and its demand is just at expanding day.
About liquid washing agent, exist the unsatisfied places of human consumer such as " the hand-held container that liquid washing agent is housed is very heavy ", " from shop, bringing back the inconvenience of returning home ", " having used up soon ".
On the other hand, at detergent applications, surging due to carrying capacity of environment consciousness, seeking to reduce washing composition each washing usage quantity, hold the miniaturization of container dimensional of washing composition to reduce the discarded amount of resin etc.
For so dissatisfied, requirement, as the composition of liquid washing agent, having developed a kind of tensio-active agent that contains high density, each washing can be with half the composition of what is called " concentrated type " of former usage quantity.
The increase along with the time containing proportional high liquid washing agent of tensio-active agent, especially on fluid surface, the easy gelation of aforesaid liquid washing composition self, produce the problem of usability variation thus.Once the liquid washing agent gelation, liquid washing agent is difficult to be measured (that is, metering) with bottle cap, and the pouring out property of while from bottle cap to the washing machine input port be variation also.Thus, about the concentrated type liquid washing agent, except requiring high cleaning force, also require increase in time that gelation etc. does not occur and keep mobility, liquid is good.
To this, a kind of concentrated type liquid washing agent (refer to Patent Document 1,2) of specific polyoxyethylene fatty acid methyl esters as tensio-active agent that use disclosed.
In addition, when measuring liquid washing agent with bottle cap, when outward appearance is water white liquid, owing to being difficult to contrast with the scale of bottle cap, so the amount of liquid that measures of bottle cap during easily than specified amount and too much or the time and very few.Especially the situation of concentrated type liquid washing agent, from considering more in the past than the aspect that usage quantity reduced, therefore correctly measure very important with bottle cap.
For such problem, done to make an effort: coordinate pigment to make liquid washing agent painted, further bottle cap is made transparently, the amount that makes thus liquid washing agent measure with bottle cap is easily differentiated, and is easy to metering.
The prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2008-7706 communique
Patent documentation 2: Japanese Patent Laid-Open 2008-7707 communique
Summary of the invention
But, about the concentrated type liquid washing agent that contains pigment, there are the following problems: the washing object (washing clothes) that has been coated with the aforesaid liquid washing composition is through a placement round the clock or rinsing when insufficient, and washing clothes is easily by pigment dyeing.
The present invention In view of the foregoing completes, and its problem is: in the concentrated type liquid washing agent that contains pigment, provide a kind of when having high cleaning force, also can suppress the liquid washing agent to the washing clothes pigment dyeing.
The inventor, through constantly making great efforts the result of research, provides following means to solve above-mentioned problem.That is, the first form of the present invention is the liquid washing agent of the urea or derivatives thereof (C) that contains the following pigment (B) of the above tensio-active agent (A) of 40 quality %, quality criteria 150ppm, 0.5～12 quality %.
The second form of the present invention is in the liquid washing agent of above-mentioned the first form, the liquid washing agent that above-mentioned tensio-active agent (A) contains at least one tensio-active agent in the nonionogenic tenside that is selected from following general formula (a1)～(a3) expression.
[changing 1]
R 1CO-(OR 2)s-OR 3···(a1)
R 4-O-(R 5O)t-H···(a2)
R 6-O-[(EO)p/(PO)q]-(EO)r-H···(a3)
[in formula (a1), R 1for the straight chain shape of carbonatoms 5～21 or alkyl or the thiazolinyl of a chain, R 2for the alkylidene group of carbonatoms 2～4, R 3for the alkyl of carbonatoms 1～4, s means OR 2average number of repeat unit, be 5～30 integer; In formula (a2), R 4for the alkyl of carbonatoms 10～22, R 5for the alkylidene group of carbonatoms 2～4, t means R 5the average number of repeat unit of O is 5～20 integer; In formula (a3), R 6alkyl or thiazolinyl for carbonatoms 10～16, p means the average number of repeat unit of EO, q means the average number of repeat unit of PO, r means the average number of repeat unit of EO, p, q, r are for meeting the integer of p>1, r>=0,0<q≤3 and p+r=10～30, EO means oxyethylene group, and PO means oxypropylene group, and (EO) EO and the PO in p/ (PO) q also can mix arrangement.]
In addition, the 3rd form of the present invention be above-mentioned first or the liquid washing agent of the second form in, further contain the liquid washing agent of the organic solvent (D) that following general formula (d1) means.
[changing 2]
R 7-[(EO)n/(PO)m]-H···(d1)
[in formula, R 7alkyl for hydrogen atom, hydroxyl or carbonatoms 1～4; M means the average number of repeat unit of PO, and n means the average number of repeat unit of EO, the integer that m is 0～2, the integer that n is 0～3, and 1≤m+n≤5; EO means oxyethylene group, and PO means oxypropylene group, and EO and PO also can mix arrangement.]
According to the present invention, in the concentrated type liquid washing agent that contains pigment, can be provided in when thering is high cleaning force, can suppress the liquid washing agent to the washing clothes pigment dyeing.
Embodiment
Liquid washing agent of the present invention, contain the above tensio-active agent (A) of 40 quality %, the pigment (B) below quality criteria 150ppm, the urea or derivatives thereof (C) of 0.5～12 quality %.
Below, these three kinds of compositions are called respectively (A) composition, (B) composition, (C) composition sometimes.
[tensio-active agent (A)]
As tensio-active agent (A), can mix nonionogenic tenside, anion surfactant, cats product, amphoterics etc. and be generally used for the tensio-active agent that clothing washes agent by liquid.
(nonionogenic tenside)
As nonionogenic tenside, can enumerate tensio-active agent and polyoxyalkylene alkyl that following general formula (a1)～(a3) means.
[changing 3]
R 1CO-(OR 2)s-OR 3···(a1)
[in formula (a1), R 1for the straight chain shape of carbonatoms 5～21 or alkyl or the thiazolinyl of a chain, R 2for the alkylidene group of carbonatoms 2～4, R 3for the alkyl of carbonatoms 1～4, s means OR 2average number of repeat unit, be 5～30 integer.]
In above-mentioned formula (a1), R 1for the straight chain shape of carbonatoms 5～21 or the alkyl of a chain, or the thiazolinyl of the straight chain shape of carbonatoms 5～21 or a chain.
Consider R from the aspect that improves cleaning force and storage stability 1the carbonatoms of middle alkyl and thiazolinyl respectively preferably 9～13, more respectively preferably 11～13.
As abovementioned alkyl, C specifically can give an example 11h 23, C 13h 27deng.
As above-mentioned thiazolinyl, C specifically can give an example 11h 21, C 13h 25deng.
R 2for the alkylidene group of carbonatoms 2～4, the alkylidene group of preferred carbonatoms 2～3, more preferably vinyl.In addition, (OR 2) s can be a kind of repeating unit structure of independent oxyalkylene group, also can mix the oxyalkylene group more than two kinds.While mixing the oxyalkylene group more than two kinds, oxyalkylene group can the block-wise addition, also can random shape addition.
R 3for the alkyl of carbonatoms 1～4, preferable methyl.
In above-mentioned formula (a1), s means OR 2average number of repeat unit, be 5～30 integer.From the aspect of the liquid stabilising that improves cleaning force and liquid washing agent (particularly low temperature ageing stability etc.), consider, s preferably 12～18.
In the composition that above-mentioned formula (a1) means, for meaning OR 2the stenosis rate of the compound distribution proportion that number of repeat unit is different (narrow rate) is preferably more than 20 quality %.The higher limit of stenosis rate is preferably in fact below 80 quality %.That is, this stenosis rate is 20～80 quality % preferably, more preferably 20～60 quality %, further preferred 30～45 quality %.Above-mentioned stenosis rate is higher, more can obtain good cleaning force, but too high, and likely the low temperature ageing stability descends.
" stenosis rate " in this specification sheets refers to, the represented numerical value of following mathematical formula (S).
[several 1]
Figure BDA0000390693550000041
In above-mentioned formula (S), S maxmean that composition that above-mentioned formula (a1) means exists maximum alkylene oxides to add the alkylene oxide addition mole number of adult in all.
I means the addition mole number of alkylene oxide.Yi means that the composition alkylene oxide that all the middle alkylene oxide addition mole number existed is i meaned in above-mentioned formula (a1) adds the ratio (quality %) of adult.
The manufacture method of the composition that above-mentioned stenosis rate can mean by above-mentioned (a1) etc. is controlled.
The manufacture method of the composition that above-mentioned formula (a1) is meaned is not particularly limited, as an example, by using the O composite metallic oxide catalyst of surface modification, according to the method (with reference to Japanese Patent Laid-Open 2000-144179 communique) of addition polymerization alkylene oxide on fatty acid alkyl ester, can easily manufacture.
Suitable example as the multiple containing metal oxide catalyzer of this surface modification specifically has: with metal hydroxides etc. carry out surface modification, added metal ion (Al 3+, Ga 3+, In 3+, Tl 3+, Co 3+, Sc 3+, La 3+, Mn 2+deng) the O composite metallic oxide catalysts such as magnesium oxide; Perhaps with the calcined material catalyzer etc. that is selected from the compound of at least one in metal hydroxides and metal alkoxide etc. and carries out the hydrotalcite of surface modification.In addition, in the surface modification of above-mentioned O composite metallic oxide catalyst, complex metal oxides with the blending ratio that is selected from the compound of at least one in metal hydroxides and metal alkoxide is: with respect to complex metal oxides 100 mass parts, the ratio that is selected from the compound of at least one in metal hydroxides and metal alkoxide preferably sets in 0.5～10 mass parts, more preferably is set in 1～5 mass parts.
[changing 4]
R 4-O-(R 5O)t-H···(a2)
[in formula (a2), R 4for the alkyl of carbonatoms 10～22, R 5for the alkylidene group of carbonatoms 2～4, t means R 5the average number of repeat unit of O is 5～20 integer.]
In above-mentioned formula (a2), R 4carbonatoms be 10～22, preferably 10～20, more preferably 10～18.R 4in alkyl can be that the straight chain shape can be also chain, unsaturated link(age) can also be arranged.As R 4in alkyl, specifically there are C 10h 21, C 12h 25, C 14h 29, C 16h 33, C 18h 37, C 20h 41deng.
The composition that the composition that above-mentioned formula (a2) means can be comprised of single chain length can be also the mixture with multiple chain long component.Raw material during as the composition that means for the synthesis of above-mentioned formula (a2), can use natural fats and oils such as being derived from Oleum Cocois, plam oil, butter alcohol, be derived from the synthol of oil etc.
In above-mentioned formula (a2), R 5for the alkylidene group of carbonatoms 2～4, the alkylidene group of preferred carbonatoms 2～3, more preferably vinyl.In addition, (R 5o) t can be a kind of repeating unit structure of independent oxyalkylene group, also can the oxyalkylene group more than two kinds mixes and exists.Oxyalkylene group more than two kinds mixes while existing, and oxyalkylene group can be with the block-wise addition, also can be with random shape addition.
In above-mentioned formula (a2), t means R 5the average number of repeat unit of O, be 5～20 integer, preferably 8～18 integer, more preferably 10～16 integer.If t surpasses 20, because HLB becomes too high, it is unfavorable that sebum is cleaned, thereby cleansing power easily descends.If t, more than 5, easily prevents the deteriorated of foul smell.Particularly, t, when 10～16 scope, demonstrates high cleaning force to the sebum spot.
R 5reaction method when the addition mole number of O distributes the composition meaned along with the above-mentioned formula of preparation (a2) and changing, be not particularly limited.For example, use the alkaline catalystss such as general sodium hydroxide or potassium hydroxide, while adding on the hydrophobic group raw material by alkylene oxide, R 5the addition mole number of O distributes and has more eurytopic tendency.In addition, the interpolation of putting down in writing in using Japanese Patent JP 6-15038 communique Al 3+, Ga 3+, In 3+, Tl 3+, Co 3+, Sc 3+, La 3+, Mn 2+deng the specific alkane oxidation catalysts such as magnesium oxide of metal ion, while adding on the hydrophobic group raw material by alkylene oxide, R 5the addition mole number of O distributes and has the tendency of narrower distribution.
The object lesson of the composition meaned as above-mentioned formula (a2) has for example: the commodity Neodol that Shell Co. Ltd is produced (mixture of the alcohol of the alcohol of carbonatoms 12 and carbonatoms 13: the following C12/C13 of being sometimes referred to as), the pure addition of the Safol23 (C12/C13) that produces of Sa Suoer company etc. be equivalent to 12 or 15 moles of ethylene oxide and must composition; To P& The natural alcohol additions such as the trade(brand)name CO-1214 that G company produces and CO-1270 be equivalent to 9,12 or 15 moles oxyethane and composition; To the secondary alcohol addition of carbonatoms 12～14 be equivalent to 9,12 or 15 moles oxyethane and composition (SOFTANOL90,120 or 150 that Nippon Shokubai Co., Ltd produces) etc.
[changing 5]
R 6-O-[(EO)p/(PO)q]-(EO)r-H···(a3)
[in formula (a3), R 6alkyl or thiazolinyl for carbonatoms 10～16, p means the average number of repeat unit of EO, q means the average number of repeat unit of PO, r means the average number of repeat unit of EO, p, q, r are for meeting the integer of p>1, r>=0,0<q≤3 and p+r=10～30, EO means oxyethylene group, PO representative ring oxypropylene group, and (EO) EO and the PO in p/ (PO) q also can mix arrangement.]
In above-mentioned formula (a3), R 6in alkyl, the carbonatoms of thiazolinyl be 10～16, preferably 10～14.R 6in alkyl and thiazolinyl can be the straight chain shape, can be also chain.
As the alkyl of above-mentioned straight chain shape or a chain, concrete example has: C 10h 21, C 12h 25, C 14h 29deng.
As the thiazolinyl of above-mentioned straight chain shape or a chain, concrete example has: C 10h 19, C 12h 23, C 14h 27deng.In above-mentioned formula (a3), r is r >=0, preferably r >=1.P+r=10～30, preferably p+r=14～20.
In above-mentioned formula (a3), the ratio of EO and PO, the ratio meaned with q/ (p+r) preferably 0.1～0.5, more preferably 0.1～0.3.The ratio meaned with q/ (p+r), can excess foam formation when lower value is above, can obtain appropriate foaming.The ratio meaned with q/ (p+r), when higher limit is following, is easy to obtain appropriate viscosity, is easy to suppress gelation.In addition, as q, 3 when following, biodegradability improves.
(EO) EO and the PO in p/ (PO) q, can only have one of them existence arbitrarily, also can mix arrangement.(EO) EO in p/ (PO) q and PO can random shape additions, also can the block-wise addition.
The composition that above-mentioned formula (a3) means can be synthetic according to known method.As an example, carry out addition reaction with oxyethane and propylene oxide successively on the alcohol derivative by natural fats and oils after or after mixing addition of ethylene oxide and propylene oxide (random addition), addition of ethylene oxide, can synthesize the composition that above-mentioned formula (a3) means thus again.
As polyoxyalkylene alkyl, there are: carbonatoms 6～22, preferably on the fatty alcohol of carbonatoms 8～18 with average 3～30 moles, preferably the oxyalkylene of 5～20 moles of addition carbonatomss 2～4 generates polyoxyalkylene alkyl, or polyoxyalkylene alkene ether (pure alkoxide).Wherein, preferred Voranol EP 2001, polyoxyethylene alkene ether, polyoxyethylene polyoxy-propylene and polyoxyethylene polyoxypropylene alkene ether.
As fatty alcohol as used herein, have for example: primary alconol or secondary alcohol.The alkyl of fatty alcohol can have side chain.As the preferred primary alconol of fatty alcohol.
(anion surfactant)
As anion surfactant, have for example: alkylbenzene sulfonate, alkyl-sulphate, secondary alkyl sulfonate, polyoxyethylene alkyl ether sulfate salt, α olefin sulfonate, alpha-sulfo fatty acid ester salt, Voranol EP 2001 carboxylate salt etc.
As anion surfactant, specifically there can be exemplified: the linear alkylbenzene sulfonate (LAS) with carbonatoms 8～16 (preferably carbonatoms 10～14) alkyl; Alkyl-sulphate (AS) with carbonatoms 10～20 alkyl; Polyoxyethylene alkyl ether sulfate salt (AES) with average addition mole number 1～10 (preferably average addition mole number 1～4) of carbonatoms 10～20 (preferably carbonatoms 10～14) alkyl and oxyethane; α olefin sulfonate (AOS) with carbonatoms 10～20 alkyl; Secondary alkyl sulfonate (SAS) with carbonatoms 10～20 (preferably carbonatoms 10～14) alkyl; α-sulfofattyacidmethylestersalt (α-SF) with carbonatoms 10～20 alkyl; Voranol EP 2001 carboxylate salt etc. with average addition mole number 1～10 of carbonatoms 10～20 alkyl and oxyethane.
Salt as these compounds has for example: an alkali metal salts such as sodium salt, sylvite; The alkanol amine salt such as monoethanolamine salt, diethanolamine salt etc., preferred as alkali salt.
As polyoxyethylene alkyl ether sulfate salt; the polyoxyethylene alkyl ether sulfate salt be preferably as follows: in the time will in all ethyleneoxide addition bodies that form polyoxyethylene alkyl ether sulfate salt, in quality criteria, existing the ethyleneoxide addition mole number of maximum ethyleneoxide addition bodies to count " nlmax ", the summation that the ethyleneoxide addition mole number is (nlmax-1), nlmax and ethyleneoxide addition body (nlmax+1) accounts for the polyoxyalkylene alkyl vitriol of ratio more than 55 quality % of all ethyleneoxide addition bodies; More preferably at the polyoxyethylene alkyl ether sulfate salt of 55～80 quality % scopes.If in above-mentioned scope, the mobility of polyoxyethylene alkyl ether sulfate salt improves, and manufacturing improves.
Wherein, as anion surfactant, the good angle from the secondary pollution preventive, preferred alkyl benzene sulfonate, polyoxyethylene alkyl ether sulfate salt and secondary alkyl sulfonate; More preferably alkylbenzene sulfonate and polyoxyethylene alkyl ether sulfate salt; Alkylbenzene sulfonate particularly preferably.
As cats product, have for example: alkylamine salt, alkyl quaternary ammonium salts etc.
As amphoterics, have for example: carboxylic acid type amphoterics (amino acid pattern and betaine type), sulfuric acid ester type amphoterics, sulfonic acid type amphoterics, phosphate type amphoterics etc.
In addition, as other tensio-active agents, also can have for example: the tensio-active agent of the derivative of natural surface active agent, protolysate, polymeric surface active agent, titaniferous/silicon, fluorocarbons are tensio-active agent etc.
(A) composition can independent a kind of use, also can be two or more and use.
Wherein, as (A) composition, preferably use nonionogenic tenside and anion surfactant.
Particularly, (A) in composition, preferably contain nonionogenic tenside more than 50 quality % with respect to (A) composition, more preferably nonionogenic tenside is more than 80 quality %, further preferred nonionic surfactants is more than 90 quality %, and nonionogenic tenside can be also 100 quality %.By using nonionogenic tenside, even the tensio-active agent that contains high density gelation etc. can not occur yet, easily obtain demonstrating the concentrated type liquid washing agent of good storage stability.And, owing to being the concentrated type liquid washing agent, while to the washing clothes coating, using liquid washing agent, can obtain excellent coating cleaning force.
As nonionogenic tenside, the high angle from cleaning force, preferably contain at least one nonionogenic tenside be selected from the nonionogenic tenside that above-mentioned general formula (a1)～(a3) means.
In addition, as (A) composition, from preventing spot, again be attached to the high angle of secondary pollution preventive on washing clothes washings, preferred nonionic surfactants and anion surfactant are together also used.
In liquid washing agent, the amount of (A) composition is more than 40 quality % with respect to the liquid washing agent total mass, preferably 40～70 quality %, more preferably 45～65 quality %.
(A), if the amount of composition is more than 40 quality % with respect to the liquid washing agent total mass, effect of the present invention is performance significantly.In addition, also can obtain good cleaning force.And, due to the tensio-active agent that contains high density, as validity (commodity value) raising of concentrated type liquid washing agent.
(A) amount of composition is with respect to the liquid washing agent total mass preferably below 70 quality %, more preferably 65 quality % when following, and along with the time increases and the difficult generations such as liquid washing agent gelation that produce at fluid surface, the fluid surface epithelium is difficult for forming.
Together and the used time, the amount of anion surfactant is preferably 1～10 quality % with respect to the liquid washing agent total mass for nonionogenic tenside and anion surfactant, more preferably 1～5 quality %, further preferred 2～5 quality %.
If the amount of anion surfactant is below 10 quality % with respect to the liquid washing agent total mass,, at the fluid surface of liquid washing agent, the aforesaid liquid washing composition self is difficult to gelation, and epithelium is difficult to form.In addition, the coating cleaning force improves preferably.If the amount of anion surfactant is that more than 1 quality %, secondary pollution preventive further improves with respect to the liquid washing agent total mass.
[pigment (B)]
Pigment (B) is not particularly limited, and has for example: matching stain, basic dyestuff, cationic dyestuff, medium (oil soluble) dyestuff, vat dyes, naphthol dye (azoic dyestuff), reactive dye (chemically-reactive dyes), dispersed dye, oxidation dye etc.The structure of each dyestuff is documented in " in legal pigment handbook (Japanese cosmetic industry contact can be compiled).
Wherein, as (B) composition, be easy to the significantly angle of performance from effect of the present invention, the pigment of maximum absorption wavelength is preferably arranged at 400～700m, the pigment of maximum absorption wavelength is more preferably arranged at 500～700nm, the pigment of the blueness of maximum absorption wavelength～green is arranged particularly preferably in 590～650nm.
As pigment (B), particularly, can enumerate blue series dyestuff shown below, green based dye.
Blue series dyestuff: C.I. acid blue 5, C.I. acid blue 9, C.I. Acid Blue 74, C.I. solvent blue 19 1, C.I. solvent blue 19 2, C.I. solvent blue 36, C.I. solvent blue 63, C.I. EX-SF DISPERSE BLUE EX-SF 300 1, C.I. EX-SF DISPERSE BLUE EX-SF 300 3, C.I. EX-SF DISPERSE BLUE EX-SF 300 5, C.I. EX-SF DISPERSE BLUE EX-SF 300 6, C.I. EX-SF DISPERSE BLUE EX-SF 300 7, C.I. EX-SF DISPERSE BLUE EX-SF 300 26, C.I. EX-SF DISPERSE BLUE EX-SF 300 27, C.I. EX-SF DISPERSE BLUE EX-SF 300 54, C.I. EX-SF DISPERSE BLUE EX-SF 300 55, C.I. Disperse Blue-56, C.I. Disperse Blue-60, C.I. EX-SF DISPERSE BLUE EX-SF 300 61, C.I. EX-SF DISPERSE BLUE EX-SF 300 62, C.I. EX-SF DISPERSE BLUE EX-SF 300 64, C.I. EX-SF DISPERSE BLUE EX-SF 300 72, C.I. EX-SF DISPERSE BLUE EX-SF 300 73, C.I. EX-SF DISPERSE BLUE EX-SF 300 81, C.I. EX-SF DISPERSE BLUE EX-SF 300 87, C.I. EX-SF DISPERSE BLUE EX-SF 300 90, C.I. EX-SF DISPERSE BLUE EX-SF 300 91, C.I. EX-SF DISPERSE BLUE EX-SF 300 97, C.I. EX-SF DISPERSE BLUE EX-SF 300 98, C.I. EX-SF DISPERSE BLUE EX-SF 300 99, C.I. EX-SF DISPERSE BLUE EX-SF 300 103, C.I. EX-SF DISPERSE BLUE EX-SF 300 104, C.I. EX-SF DISPERSE BLUE EX-SF 300 105, C.I. Blue 7, C.I. vat blue 1, C.I. reductive blue 6, C.I. pigment indigo plant 15 etc.
In addition, for solvent system (oil soluble) pigment wherein, can be also to carry out chemically modified to increase water miscible pigment in the end of chromophoric group structure with water-soluble polymers such as polyoxyethylene glycol or polypropylene glycols.Concrete example has: the commodity of the trade(brand)names such as Liquitint Blue HP, Liquitint Blue BL that Mei Liken Co., Ltd. produces.
Green based dye: C.I. acid green 1, C.I. acid green 3, C.I. acid green 5, C.I. ACID GREEN 25, C.I. food indigo plant 2, C.I. Food Green 3, C.I. solvent green 3, C.I. Food Green 3, C.I. solvent are green 7, the C.I. solvent is green etc.
(B) composition can independent a kind of use, also can be two or more and use.
Angle from the dyeability for washing clothes and mixed liquid color degree, in liquid washing agent, the amount of (B) composition is that 1ppm (quality criteria) is above, 150ppm (quality criteria) following (0.015 quality % is following) with respect to the liquid washing agent total mass, preferably 1～100ppm (quality criteria) (0.0001～0.01 quality %), more preferably 3～50ppm (quality criteria) (0.0003～0.005 quality %).
(B), if the amount of composition does not arrive lower value, the liquid of liquid washing agent likely can not be fully painted.On the other hand, if (B) amount of composition surpasses higher limit, likely can not suppress the pigment dyeing to washing clothes fully.
[urea or derivatives thereof (C)]
As urea or derivatives thereof (C), have for example: urea [CO (NH 2) 2], urea double salt, and beyond urea derivative.
As urea double salt, can use HNO 3cO (NH 2) 2, H 3pO 4cO (NH 2) 2, H 2c 2o 42CO (NH 2) 2, Ca (NO 3) 24CO (NH 2) 2, CaSO 44CO (NH 2) 2, Mg (NO 3) 2cO (NH 2) 22H 2o, CaSO 4(5～6) 4CO (NH 2) 22H 2o etc.
" derivative of urea " in the present invention comprises the compound with structure shown in following general formula (c1).In urea derivative, can enumerate the compound that general formula (c1-1) means.
[changing 6]
Figure BDA0000390693550000101
In above-mentioned formula (c1-1), R ahydroxyalkyl for methyl, ethyl or carbonatoms 1～2.R b, R cand R dbe hydrogen atom, methyl or ethyl independently of one another.
The compound meaned as above-mentioned formula (c1-1), have: 1,3-dimethyl urea, N-(2-hydroxyethyl) urea etc. for example.
(C) composition can independent a kind of use, also can be two or more and use.
In liquid washing agent, the amount of (C) composition is with respect to preferred 0.5～12 quality % of liquid washing agent total mass, more preferably 1～10 quality %, further preferred 1～8 quality %.
(C), if the amount of composition does not arrive lower value, likely can not fully suppress the pigment dyeing to washing clothes.On the other hand, when (C) amount of composition surpasses higher limit, easily produce resolvent ammonia after preserving, as detergent product sometimes smell can become problem.In addition, because the affinity of spot is easily reduced, so the coating cleaning force likely reduces.
In liquid washing agent of the present invention, (A) composition and (C) blending ratio of composition, the mass ratio meaned in (A)/(C) is preferably below 30, and more preferably 6～15, further preferably 9～11.
If the mass ratio (A)/(C) meaned, below higher limit, easily suppresses the pigment dyeing to washing clothes.On the other hand, when the mass ratio (A)/(C) meaned does not arrive lower value, the coating cleaning force likely reduces.
In the present invention, " mass ratio (A)/(C) meaned " means the amount with respect to (C) composition in liquid washing agent, (A) ratio of the amount of composition (mass ratio).
[solvent: water]
The viewpoint such as solvability water from easy modulating liquid body washing composition, while using, liquid washing agent of the present invention preferably contains water as solvent.
In liquid washing agent, the amount of water is preferably 15～45 quality % with respect to the liquid washing agent total mass, more preferably 25～40 quality %.
If the amount of water more than lower value, liquid washing agent through the time liquid stabilising become better; If below higher limit, the appropriate step-down of liquid viscosity, from the viewpoint of usability, better.
[organic solvent (D)]
In liquid washing agent of the present invention, the organic solvent (D) (following also referred to as " (D) composition ") preferably further meaned containing useful following general formula (d1).By containing (D) composition, the coating cleaning force cleaning force of greasy dirt or marker pen spot (particularly for) improves, and, especially at low temperatures (supposition winter) inhibition of the pigment dyeing of washing clothes is more prone to.In addition, (D) composition is also effective as viscosity modifier and the gelation inhibitor of aforesaid liquid washing composition.
[changing 7]
R 7-[(EO)n/(PO)m]-H···(d1)
[in formula, R 7alkyl for hydrogen atom, hydroxyl or carbonatoms 1～4; M means the average number of repeat unit of PO; N means the average number of repeat unit of EO; The integer that m is 0～2, the integer that n is 0～3, and 1≤m+n≤5; EO means oxyethylene group, and PO means oxypropylene group, and EO and PO also can mix arrangement.]
In above-mentioned formula (d1), R 7for hydrogen atom, hydroxyl or the carbonatoms alkyl that is 1～4.R 7in alkyl can be that the straight chain shape can be also chain.
As above-mentioned straight chain shape and branched-chain alkyl, concrete example has: CH 3, C 2h 5, C 3h 7, C 4h 9deng.(EO) EO in n/ (PO) m and PO can only have one of them existence arbitrarily, also can mix arrangement.(EO) EO in n/ (PO) m and PO can random shape additions, also can the block-wise addition.
As (D) composition, have for example: the alkanols (D1) such as ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol; The aklylene glycol classes (D2) such as the multipolymer of ethylene glycol, propylene glycol, ethylene glycol and propylene glycol, Diethylene Glycol, triethylene glycol, dipropylene glycol; (gathering) aklylene glycol that (gathering) aklylene glycol that the aklylene glycol that the carbonatomss such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, TC, diethylene glycol diethyl ether, DPGME, dihydroxypropane single-ethyl ether, diethylene glycol monobutyl ether are 2～3 is unit and the alkanol of carbonatoms 1～4 form (list or two) alkyl oxide (D3) etc.
(D) composition can independent a kind of use, also can be two or more and use.
Wherein, as (D) composition, preferably use and be selected from least one organic solvent in above-mentioned (D1)～(D3), more preferably be used in combination the two or more organic solvents that are selected from above-mentioned.By being used in combination two or more organic solvents, easily obtain the viscosity adjustment of liquid washing agent and the inhibition of gelation.
In liquid washing agent, the amount of (D) composition is with respect to preferred 5～20 quality % of liquid washing agent total mass, more preferably 5～18 quality %, further preferred 5～15 quality %.
(D) amount of composition does not arrive lower value, is difficult to obtain suitable viscosity, and during the coating washing clothes, liquid washing agent easily solidifies.On the other hand, if (D) amount of composition surpasses higher limit, likely produce the foul smell that is derived from (D) composition, and consider also not preferred from the angle of cost.
[other compositions]
In the scope that does not affect effect of the present invention, also can mix as required mentioned component other compositions in addition in liquid washing agent of the present invention.
As other compositions, there is no particular limitation, can mix normally used composition in liquid detergent composition for clothes, concrete example composition shown below.
In order to improve appearance stability, in liquid washing agent of the present invention, also can mix alkanolamine.
Particularly, the mixed anion tensio-active agent is during as tensio-active agent (A), and alkanolamine is the composition that possible become the anion surfactant gegenion, by the mixed anion tensio-active agent, can suppress to be easy to the white casse that produces etc., performance improves the effect of appearance stability.Therefore, in liquid washing agent of the present invention, above-mentioned tensio-active agent (A), when containing anion surfactant, also preferably further contains alkanolamine.
As alkanolamine, the alkanolamine preferably worked as the gegenion of anion surfactant; The alkanolamine that preferably there is carbonatoms 1～3 alkyl; The alkanolamine that more preferably there is carbonatoms 1～2 alkyl; Further preferred monoethanolamine, diethanolamine and trolamine.
Alkanolamine can independent a kind of use, also can be two or more and use.
In liquid washing agent, the amount of alkanolamine is with respect to preferred 0.1～3 quality % of liquid washing agent total mass, more preferably 0.5～3 quality %, further preferred 0.5～2 quality %.
If the amount of alkanolamine, is easy to get to and improves the effect of this composition appearance stability with respect to the liquid washing agent total mass more than 0.1 quality %.In addition, if the amount of alkanolamine with respect to the liquid washing agent total mass below 3 quality %, be easy to suppress absorb due to alkanolamine the generation of the recessed phenomenon of container that oxygen causes.
For improve cleaning force can and mixed stability etc., in liquid washing agent of the present invention, can mix: organic solvent, thickening material (longer chain fatty acid alkylamide etc.), feel rising agent, pH adjusting agent, sanitas, fluorescent agent in addition of enzyme (proteolytic enzyme, lipase, cellulase etc.), (D) composition, move and dye preventing agent, pearling agent, antioxidant, stain remover etc.
From the aspect of liquid stabilising, consider, as pH adjusting agent, preferably sulfuric acid, sodium hydroxide, potassium hydroxide etc.
Further, in order to improve the value added of commodity, liquid washing agent of the present invention can also mix fragrant agent, emulsifying agent etc.
As fragrant agent, can use flavor compositions A, B, C, the D etc. of record in the table 11 of No. 2002-146399, Japanese Patent Laid-Open～18.The amount of fragrant agent is with respect to preferred 0.1～1 quality % of liquid washing agent total mass.
As emulsifying agent, can have for example: polystyrene emulsion, polyvinyl acetate emulsion etc., the emulsion of common suitable use solids component 30～50 quality %.As object lesson, have for example: polystyrene emulsion (Saiden chemical company produces, " Saivinol RPX-196PE-3 ", solids component 40 quality %) etc.The amount of emulsifying agent is with respect to preferred 0.01～0.5 quality % of liquid washing agent total mass.
Liquid washing agent of the present invention is preferably 5～10 at the pH of 25 ℃, and more preferably 5～9.5, further preferably 5～9, particularly preferably 6～9.
If the pH of liquid washing agent, more than lower value, when long-time preservation liquid washing agent, is easy to the cleaning force that keeps good.If above-mentioned pH does not arrive higher limit, will more be easy to suppress the pigment dyeing to washing clothes.Also be easy to keep well liquid stabilising.
In this explanation, the pH value representation of liquid washing agent (temperature adjustment to 25 ℃) is according to the value of the mensuration such as pH meter (ProductName: HM-30G, DKK Toa Corp. manufactures).
Liquid washing agent of the present invention is a kind of in the concentrated type liquid washing agent that contains pigment, when having high cleaning force, has suppressed the liquid washing agent to the washing clothes pigment dyeing.
In the concentrated type liquid washing agent that contains pigment, following problem easily occurs: the washing object (washing clothes) that has been coated with the aforesaid liquid washing composition temporarily be placed or while with roller washing machine etc., carrying out once washing (, when rinsing is insufficient) etc., easily washing clothes is carried out to pigment dyeing.
The easy generation of this pigment dyeing on washing clothes changes according to the impact of kind, temperature and the water temperature of the composition of liquid washing agent, clothing (fiber).Such as cold condition or according to the kind of organic solvent hydrophobic fibre (trevira etc.), pigment dyeing more easily occurs.
As washing clothes being carried out to the reason of pigment dyeing, be considered to: if the tensio-active agent of high density and washing clothes Long contact time, perhaps because rinsing is insufficient, make tensio-active agent partly remain on washing clothes, tensio-active agent will too be penetrated in clothing (fiber), pigment will be adsorbed onto the deep layer of clothes class (fiber) thereupon, and pigment is easily dyeed to washing clothes thus.
In addition, according to temperature condition and storage period, the moisture in liquid washing agent and solvent evaporation, composition gels, in the time of can making to wash, liquid washing agent can not fully dissolve in water.Therefore can think, due to tensio-active agent and the state of washing clothes in Long contact time of high density, therefore pigment is easy to washing clothes is dyeed.
In liquid washing agent of the present invention, with respect to the liquid washing agent total mass, contain tensio-active agent, the pigment more than 40 quality %, also contain urea or derivatives thereof (C) simultaneously.(C) composition is the strongly hydrophilic material, and concern itself and the tensio-active agent because of himself structural performance has strong interaction on the other hand, therefore think (C) composition in preparation, easily be present in surfactant molecule around.When coating is washed thus, due to the existence of (C) composition, can suppress absorption or the infiltration of tensio-active agent to clothing, also can suppress the interaction of hydrophobic fibre and tensio-active agent.According to its result, supposition can obtain effect of the present invention.
According to liquid washing agent of the present invention, even be coated with, the washing clothes of liquid washing agent temporarily is placed or rinsing is insufficient, also can suppress the pigment dyeing to washing clothes.
In addition, according to liquid washing agent of the present invention, by containing (C) composition, especially, the liquid xanthochromia that also can suppress when and easily produce during with the alkanolamine that can become above-mentioned anion surfactant gegenion with the anion surfactant that suppresses secondary pollution, keep appearance stability well.
Liquid washing agent of the present invention, just can bring into play high washing effect with a small amount of washing composition usage quantity.
Liquid washing agent of the present invention, be particularly suitable as the dress material washing composition, is a kind of when containing pigment, also has the liquid washing agent that the high surface agent concentration forms (the concentrated composition).
A kind of form as liquid washing agent of the present invention is listed below liquid washing agent:
The liquid washing agent that contains tensio-active agent (A), pigment (B), urea or derivatives thereof (C), organic solvent (D), with respect to the total mass of aforesaid liquid washing composition,
Above-mentioned (A) composition is 40～70 quality %,
Above-mentioned (B) composition is 1～150ppm (quality criteria),
Above-mentioned (C) composition is 0.5～12 quality %,
Above-mentioned (D) composition is 5～20 quality %,
And the total amount of above-mentioned each composition is no more than 100 quality %.
Other forms as liquid washing agent of the present invention are listed below liquid washing agent:
The liquid washing agent that contains tensio-active agent (A), pigment (B), urea or derivatives thereof (C), water, with respect to the total mass of aforesaid liquid washing composition,
Above-mentioned (A) composition is 40～70 quality %,
Above-mentioned (B) composition is 1～150ppm (quality criteria),
Above-mentioned (C) composition is 0.5～12 quality %,
Above-mentioned water is 15～45 quality %,
And the total amount of above-mentioned each composition is no more than 100 quality %.
Other forms as liquid washing agent of the present invention are listed below liquid washing agent:
The liquid washing agent that contains tensio-active agent (A), pigment (B), urea or derivatives thereof (C), organic solvent (D), water, with respect to the total mass of aforesaid liquid washing composition,
Above-mentioned (A) composition is 40～70 quality %,
Above-mentioned (B) composition is 1～150ppm (quality criteria),
Above-mentioned (C) composition is 0.5～12 quality %,
Above-mentioned (D) composition is 5～20 quality %,
Above-mentioned water is 15～45 quality %,
And the total amount of above-mentioned each composition is no more than 100 quality %.
Embodiment
Below with embodiment, further describe the present invention, but the present invention is not limited in these embodiment.In addition, " % " do not having under the condition of specified otherwise all to mean " quality % ".
The composition of each routine liquid washing agent is as shown in table 1～3.
The raw material used in the present embodiment is as follows.
[tensio-active agent (A)]
A-1:C 11h 23cO-(OC 2h 4) 15-OCH 3, stenosis rate 33 quality %; Synthetics.A-1 produces according to the method for putting down in writing in Japanese Patent Laid-Open 2002-144179 communique.That is by chemical constitution, be, 2.5MgOAl 2o 3nH 2the aluminum magnesium hydroxide of O (trade(brand)name: Kyoward300, Kyowa Chemical Industry Co., Ltd produces) calcining obtains in 1 hour in 600 ℃ of lower nitrogen environments calcinations of aluminum hydroxide Mg catalyst (unmodified) 2.2g, as potassium hydroxide-ethanol solution 2.9mL, the Laurate methyl 350g of 0.5 regulation of the surface-modifying agent 4L autoclave of packing into, carry out catalyst modification in above-mentioned autoclave.Then, carry out in autoclave heating after nitrogen replacement, when keeping 180 ℃ of temperature, pressure 3 * 105Pa, import 1079g oxyethane, make while stirring its reaction.
Subsequently, reaction solution is cooled to 80 ℃, after adding 159g water, atlapulgite and each 5g of diatomite as filtration adjuvant, filtering catalyst obtains target compound A-1.
A-2:C 11h 23cO-(OC 2h 4) 15-OCH 3with C 13h 27cO-(OC 2h 4) 15-OCH 3mass ratio be 8/2 mixture, stenosis rate 33 quality %; Synthetics.
But A-2 is in above-mentioned A-1 synthetic, except Laurate methyl 350g being replaced with to the mixture of Laurate methyl 280g and nutmeg acid 70g, imports beyond oxyethane 1052g, with same synthetic method manufacture.
A-3: be the nonionogenic tenside that the oxyethane of average 9 moles of block addition, the propylene oxide of average 2 moles, the oxyethane of average 9 moles form successively on the primary alconol of carbonatoms 10～14.R in general formula (a3) 6the straight chain shape alkyl of=carbonatoms 10～14, p=9, q=2, r=9.
A-4: be the nonionogenic tenside that the oxyethane of average 9 moles of addition forms on the secondary alcohol of carbonatoms 12～14, trade(brand)name: SOFTANOL90, Nippon Shokubai Co., Ltd produces.R in general formula (a2) 4the branched-chain alkyl of=carbonatoms 12～14, t=9.
A-5: polyxyethylated (C12-13) ether.In raw alcohol SAFOL23 (trade(brand)name, the production of Sa Suoer company; The mixture that the mass ratio of the alcohol of the alcohol of carbonatoms 12 and carbonatoms 13 is C12/C13=55%/45% is 50 quality % with respect to the ratio of the straight chain carbochain of all carbochains) product that forms of upper average 15 moles of ethylene oxide of addition.
A-6: straight chained alkyl (carbonatoms 10～14) Phenylsulfonic acid [Lion Corporation produces, trade(brand)name: LIPON LH-200 (LAS-H purity 96 quality %)].
A-7:AES-Na, carbonatoms 12～13 Voranol EP 2001 sodium sulfate (the average addition mole number of oxyethane is 2), synthetics (raw alcohol trade(brand)name: Neodol23, Shell Co. Ltd produces).
A-8: be at natural alcohol (P& G company produces, trade(brand)name: CO-1214) upper addition is equivalent to the product [LMAO (C12/14-15EO)] that 12 moles of ethylene oxide form, synthetics.Synthesized as follows.
Get P& Trade(brand)name " CO-1214 " 861.2g, 30 quality %NaOH aqueous solution 2.0g that G company produces, put into the pressure resistant type reaction vessel, uses nitrogen replacement in container.Then, after 30 minutes, be warming up to 160 ℃ in 100 ℃ of temperature, dehydration below pressure 2.0kPa.Then limit stirring reaction liquid, oxyethane (gas shape) 760.6g is slowly added in limit in reaction solution.Now, use and to be blown into pipe, limit is regulated interpolation speed and is made temperature of reaction be no more than 180 ℃ of limits to be added.After oxyethane adds end, in 180 ℃ of temperature, the following slaking of pressure 0.3MPa, after 30 minutes, in 180 ℃ of temperature, distillation below pressure 6.0kPa 10 minutes, remove unreacted oxyethane.Then, after being cooled to below 100 ℃ by temperature, add 70 quality % tosic acid to be neutralized, make the pH of the reactant 1 quality % aqueous solution be about 7, obtain LMAO (C12/14-15EO).
[pigment (B)]
B-1:C.I. Food Green 3, and green No. 3, occasion change into Co., Ltd. and produce the sixth of the twelve Earthly Branches; Maximum absorption wavelength 610nm.
B-2:Liquitint Blue HP, Mei Liken Co., Ltd. produces; Maximum absorption wavelength 595nm, 645nm.
B-3:C.I. solvent blue 63, and blue No. 403, occasion change into Co., Ltd. and produce the sixth of the twelve Earthly Branches; Maximum absorption wavelength 600nm, 645nm.
[pigment (C)]
C-1: urea, reagent, Junsei Chemical Co., Ltd. produces.
C-2:1,3-dimethyl urea, reagent, Tokyo HuaCheng Industry Co., Ltd produces.
[organic solvent (D) that general formula (d1) means]
D-1:1,2-propylene glycol (trade(brand)name Propylene glycol, Showa Denko K. K produces) purity 100 quality %.R in general formula (d1) 7=hydroxyl, m=1, n=0.
D-2: Diethylene Glycol butyl ether (trade(brand)name Butyl diglycol, Japanese emulsifying agent Co., Ltd. produces) purity 100 quality %.R in general formula (d1) 7=ethyl, m=0, n=3.
D-3: ethanol (the specific alcohol 95 degree synthetic alcohols of trade(brand)name, Japan's alcohol is sold Co., Ltd. and produced).R in general formula (d1) 7=hydrogen atom, m=0, n=1.
[other compositions]
MEA: monoethanolamine (Nippon Shokubai Co., Ltd's production) purity 100 quality %.
DEA: diethanolamine (Nippon Shokubai Co., Ltd's production) purity 100 quality %.
Polyoxyethylene glycol: lion king KCC produces, trade(brand)name " PEG#1000-L60 ", the polymerization degree 20.
Enzyme: proteolytic enzyme, trade(brand)name " Everlase 16L Type EX ", Novozymes Company produces.
Citric acid: Fukawa Chemical Industries Co., Ltd. produces, purity 100 quality %.
PH adjusting agent: KOH (Asahi Glass Co., Ltd's production) and sulfuric acid (Toho Zinc Co., Ltd.'s production).
Ion exchanged water.
The Production Example of<liquid washing agent >
According to the mixing element, the amount (quality %) that form shown in table 1～3, manufacture respectively each routine liquid washing agent according to following manufacture method and (in table, if any mixing element, be space, do not mix this mixing element.)
In table, the amount of mixing element shows with purity conversion scale.In addition, only have the amount of (B) composition to mean with " ppm " (quality criteria).
The combined amount of the total amount of liquid washing agent that " balance " that means the water amount means to adjust final preparation during to 100 quality %.
" in right amount " that means the pH adjusting agent amount means the combined amount when adjusting liquid washing agent pH (25 ℃) pH that arrives that it is as shown in the table.
" mass ratio: (A)/(C) " means the amount with respect to (C) composition in liquid washing agent, (A) ratio of composition amount (mass ratio).
(embodiment 1～19, comparative example 1～3, reference example 1)
Respectively according to the amount (quality %) shown in table, (D) composition, polyoxyethylene glycol, MEA or DEA, A-6 or A-7 are added in the 500mL beaker and stirred (in addition, be space if any mixing element in table, do not mix this mixing element).Then, add and (C) composition and citric acid are dissolved in to (C) composition aqueous solution (concentration 50 quality %) and the aqueous citric acid solution (concentration 50 quality %) that form in water are separately stirred.
Then, by pH adjusting agent, the pH of solution (25 ℃) is adjusted to the value shown in table.
Then, add remaining (A) composition to be stirred.Add afterwards enzyme to be stirred, then interpolation is dissolved in by (B) composition the pigment aqueous solution (pigment concentration 1000ppm) formed in water and arrives determine concentration, stirs.Thereafter, the total amount that adds ion exchanged water to make final preparation, to 100 quality %, obtains respectively each routine liquid washing agent thus.
The pH of solution (25 ℃) measures as follows: use pH meter (ProductName: HM-30G, DKK Toa Corp. produces), in the solution of temperature adjustment to 25 ℃, put into the electrode of above-mentioned pH meter, read the value of measuring after 2 minutes.
The evaluation of<liquid washing agent >
According to evaluation method shown below, to each, routine liquid washing agent carries out respectively the evaluation that " coating cleaning force ", " to the pigment dyeing of clothing " reach " appearance stability ".It the results are shown in table 1～3.
[coating cleaning force]
Pollute the preparation of cloth
By oiliness marker pen (marker pen printing ink/superfine M700-T1) inking back and forth equably on cotton fabrics (5cm * 5cm), blacking Cheng Yuanzhuan (diameter 2cm), every example is made 5, as the pollution cloth of coating cleaning force evaluation use.
(wash conditions)
Use with respect to the liquid washing agent of water 30L standard usage quantity (concentrated type 10g/ water 30L, usually type 20g/ water 30mL) to above-mentioned 5 pollute cloth every 1 be coated with after, at 20 ℃ of temperature, place 5 minutes.Particularly, every 1 glue spread of polluting the liquid washing agent of cloth is respectively 0.3g in embodiment 1～19, comparative example 1～3 (concentrated type), in reference example 1, is 0.6g.
Thereafter, in Terg-o-tometer (production of United States Testing company), put into 3 ° of DH hard water 900ml, 5 of above-mentioned pollution cloth and cotton underwear (the LL size of 15 ℃ with 20 times of bath raioes, DVD commercial firm produces) fritter (3cm * 3cm left and right) that is cut into, under 120rpm, the condition of 15 ℃, washing is 10 minutes.
(rinsing condition)
After above-mentioned washing, dewater 1 minute, subsequently, in 3 ° of DH hard water 900ml of 15 ℃, under 120rpm, the condition of 15 ℃, rinsing is 3 minutes.This dehydration and rinsing are carried out 2 times repeatedly.
(drying conditions)
After the 2nd rinsing, dewater 1 minute, subsequently, every pollution cloth after washing all is clipped in filter paper and carries out drying with electric iron.
The evaluation of coating cleaning force is by before washing and after washing, with albedometer (beam splitting type colour-difference meter SE2000, Japanese electric look Industrial Co., Ltd manufactures), measures reflectivity (Z value), calculates according to following formula that cleaning rate (%) carries out.
Cleaning rate (%)=(the Z value of the pollution cloth before the Z value of the pollution cloth after washing-washing)/(the Z value of the pollution cloth before the Z value of former cloth-washing) * 100
In formula, " former cloth " refers to the cotton knitwear that in the preparation of above-mentioned pollution cloth, the enforcement pollution is processed.
Calculate respectively 5 cleaning rates (%) that pollute cloth of each example, obtain its mean value, according to following metewand evaluation coating cleaning force.◎, zero, △ are qualified.
Metewand
◎: the mean value of cleaning rate (%) is more than 15%.
Zero: the mean value of cleaning rate (%) is more than 10%, less than 15%.
△: the mean value of cleaning rate (%) is more than 5%, less than 10%.
*: the mean value less than 5% of cleaning rate (%).
[to the evaluation of the pigment dyeing of clothing]
Only white is wiped to the end (thickening place, sewing part) of hand cotton towel (29cm * 72cm) long side direction and cut, as estimating with trial target (cotton) (quality 5g part)
Subsequently, the liquid washing agent of 5g in the liquid washing agent standard usage quantity (15g) of relative washes 4kg is coated on and estimates with trial target (cotton) above, place 12 hours.
Thereafter, using be coated with the 5g lotion above-mentioned for evaluation trial target (cotton) and as the cotton underwear that loads cloth altogether 4kg put into washing machine, add remaining liquid washing agent to be washed.
Wash conditions is now set as follows.Washing machine uses Toshiba's drum-type washing machine (ProductName: TW-4000VFL).Washing procedure is: washing time 10 minutes, rinsing is specified 1 time, dewaters 8 minutes.
Above operation (during cotton towel) respectively the supposition summer and the supposition winter condition under carry out.
While supposing summer, the trial target for evaluation (cotton) that has been coated with the 5g liquid washing agent is placed 12 hours 25 ℃ of temperature, used the water of temperature adjustment to 25 ℃ during washing.
While supposing winter, the trial target for evaluation (cotton) that has been coated with the 5g liquid washing agent is placed 12 hours 5 ℃ of temperature, used the water of temperature adjustment to 5 ℃ during washing.
In addition, polyester (PE) sweat shirt (valley head shop) is cut to 5cm * 5cm, as estimating with trial target (PE) (quality 0.2g part).
Subsequently, the liquid washing agent of 2g in the liquid washing agent standard usage quantity (15g) of relative washes 4kg is coated on and estimates with trial target (PE) above, place 12 hours.
Thereafter, using be coated with the 5g lotion above-mentioned for evaluation trial target (PE) and as the cotton underwear that loads cloth altogether 4kg put into washing machine, add remaining liquid washing agent, with the condition identical with above-mentioned wash conditions, washed.
Above operation (during PE) only with the above-mentioned supposition similarity condition in summer under carry out.
Then, evaluation for the trial target (cotton) of visual judgement after washing, estimate with on trial target (PE), whether confirming pigment dyeing, estimated according to following metewand.◎, zero, △ are qualified.
Metewand
◎: the evaluation after washing with full confirmation on trial target less than pigment dyeing.
Zero: the evaluation after washing is with only confirming considerably less pigment dyeing on trial target.
△: the evaluation after washing is with confirming a small amount of pigment dyeing on trial target.
*: the evaluation after washing is with confirming obvious pigment dyeing on trial target.
[appearance stability]
After manufacture, by each, routine liquid washing agent 100g puts into cylinder vial (PS100) immediately, closes lid sealing, preserves 30 under 50 ℃.
Then, the outward appearance (liquid color) of the liquid washing agent after visual judgement is preserved changes, and according to following metewand, is estimated.◎, zero is qualified.
In addition, while because of preservation, causing the liquid washing agent xanthochromia, before keeping, (initial stage) was the blue green that becomes originally, and the initial stage was the green yellow-green colour that becomes originally.
Metewand
◎: and preliminary phase is relatively, full confirmation changes less than outward appearance (liquid color).
Zero: slightly confirm respectively following variation: the initial stage was the blue green that becomes originally, and the initial stage was the green yellow-green colour that becomes originally.
*: obviously confirm respectively following variation: the initial stage was the blue green that becomes originally, and the initial stage was the green yellow-green colour that becomes originally.
Figure BDA0000390693550000211
Table 2
Figure BDA0000390693550000221
Table 3
Result by table 1～3 can confirm, and the liquid washing agent of embodiment 1～19, when having high cleaning force, has also suppressed the pigment dyeing to washing clothes.
The industrial possibility of utilizing
The present invention, in the concentrated type liquid washing agent that contains pigment, can provide a kind of when having high cleaning force, has also suppressed the liquid washing agent to the pigment dyeing of washing clothes, thereby industrial very useful.

Claims (3)

1. a liquid washing agent, contain: the tensio-active agent (A) more than 40 quality %, the pigment (B) below quality criteria 150ppm, the urea or derivatives thereof (C) of 0.5～12 quality %.
2. liquid washing agent according to claim 1, described tensio-active agent (A) contains at least one tensio-active agent be selected from the nonionogenic tenside that following general formula (a1)～(a3) means,
R 1CO-(OR 2)s-OR 3···(a1)
R 4-O-(R 5O)t-H···(a2)
R 6-O-[(EO)p/(PO)q]-(EO)r-H···(a3)
In formula (a1), R 1for the straight chain shape of carbonatoms 5～21 or alkyl or the thiazolinyl of a chain, R 2for the alkylidene group of carbonatoms 2～4, R 3for the alkyl of carbonatoms 1～4, s means OR 2average number of repeat unit, be 5～30 numeral; In formula (a2), R 4for the alkyl of carbonatoms 10～22, R 5for the alkylidene group of carbonatoms 2～4, t means R 5the average number of repeat unit of O is 5～20 numeral; In formula (a3), R 6alkyl or thiazolinyl for carbonatoms 10～16, p means the average number of repeat unit of EO, q means the average number of repeat unit of PO, r means the average number of repeat unit of EO, p, q, r are for meeting the integer of p>1, r>=0,0<q≤3 and p+r=10～30, EO means oxyethylene group, and PO means oxypropylene group, and (EO) EO and the PO in p/ (PO) q also can mix arrangement.
3. liquid washing agent according to claim 1 and 2, it further contains the organic solvent (D) that following general formula (d1) means,
R 7-[(EO)n/(PO)m]-H···(d1)
In formula, R 7alkyl for hydrogen atom, hydroxyl or carbonatoms 1～4; M means the average number of repeat unit of PO, and n means the average number of repeat unit of EO, the integer that m is 0～2, and the integer that n is 0～3, and 1≤m+n≤5, EO means oxyethylene group, and PO means oxypropylene group, and EO and PO also can mix arrangement.
CN201280016756.4A 2011-04-01 2012-03-28 Liquid washing agent Expired - Fee Related CN103459579B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107922903A (en) * 2015-09-03 2018-04-17 狮王株式会社 Dress material washes agent by liquid

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* Cited by examiner, † Cited by third party
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JP6468738B2 (en) * 2014-06-26 2019-02-13 ライオン株式会社 Liquid cleaning agent
JP6598360B2 (en) * 2015-09-03 2019-10-30 ライオン株式会社 Liquid detergent for clothing
JP2017066394A (en) * 2015-09-28 2017-04-06 三洋化成工業株式会社 Detergent for clothing
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JP6979831B2 (en) * 2017-05-09 2021-12-15 ライオン株式会社 How to wash textiles and liquid cleaners
JP6500148B1 (en) * 2018-05-21 2019-04-10 第一工業製薬株式会社 Surfactant and liquid detergent
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4556509A (en) * 1984-10-09 1985-12-03 Colgate-Palmolive Company Light duty detergents containing an organic diamine diacid salt
US4734221A (en) * 1984-05-11 1988-03-29 Lever Brothers Company Detergent compositions
JP2000144179A (en) * 1998-11-10 2000-05-26 Lion Corp Detergent composition
JP2011021138A (en) * 2009-07-17 2011-02-03 Kao Corp Cleaning agent composition

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE14142T1 (en) * 1981-04-03 1985-07-15 Procter & Gamble LIQUID DETERGENT COMPOSITIONS.
GB8412048D0 (en) * 1984-05-11 1984-06-20 Unilever Plc Detergent compositions
JPH05310542A (en) * 1992-05-14 1993-11-22 Kao Corp Detergent composition
JPH0711288A (en) * 1993-06-25 1995-01-13 Ajinomoto Co Inc Liquid detergent composition
JP2002284670A (en) * 2001-03-28 2002-10-03 Shiseido Co Ltd Remover of dyeing material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4734221A (en) * 1984-05-11 1988-03-29 Lever Brothers Company Detergent compositions
US4556509A (en) * 1984-10-09 1985-12-03 Colgate-Palmolive Company Light duty detergents containing an organic diamine diacid salt
JP2000144179A (en) * 1998-11-10 2000-05-26 Lion Corp Detergent composition
JP2011021138A (en) * 2009-07-17 2011-02-03 Kao Corp Cleaning agent composition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107922903A (en) * 2015-09-03 2018-04-17 狮王株式会社 Dress material washes agent by liquid
CN107922903B (en) * 2015-09-03 2021-12-10 狮王株式会社 Liquid detergent for clothing

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