CN103666805A - Liquid detergent - Google Patents
Liquid detergent Download PDFInfo
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- CN103666805A CN103666805A CN201310379886.0A CN201310379886A CN103666805A CN 103666805 A CN103666805 A CN 103666805A CN 201310379886 A CN201310379886 A CN 201310379886A CN 103666805 A CN103666805 A CN 103666805A
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Abstract
The invention provides a liquid detergent seeking for increasing viscosity and having excellent storage stability at a low temperature by using an inorganic salt. The liquid detergent comprises a component (A): polyoxyethylene alkyl ether sulfate, a component (B): a compound having the following general formula (b1), a component (C): a compound having the following general formula (c1) and a component (D): a water-soluble inorganic salt. In the formula (b1), R<1> is a straight-chain hydrocarbyl with a carbon number of 8-18; AO is an oxyalkylene group with a carbon number of 2-4; and x is an average repeat unit number of the oxyalkylene group and is a number between 5 and 30. In the formula (c1), R<2> is a branched chain hydrocarbyl with a carbon number of 8-18; and y is an average repeat unit number of the oxyalkylene group and is a number larger than 0 but smaller than 7. [Chemical formula 1]: R<1>-O-(AO)[x]-H+++ (b1); R<2>-O-(CH2CH2O)[y]-H+++ (c1).
Description
Technical field
The present invention relates to liquid washing agent.
Background technology
For various liquid washing agents, from the viewpoint of usability etc., by adding tackifier, give its viscosity.
Usually, in order to improve the viscosity of liquid washing agent, allocate the tackifier such as polymkeric substance into.For example in patent documentation 1, propose a kind ofly to contain nonionogenic tenside, as the cross-linking type carboxyvinyl polymer of tackifier and the liquid washing agent of monovalent cation tensio-active agent.
Yet, while using polymkeric substance as tackifier, according to the difference of maintaining requirement, have following problem: the viscosity of liquid washing agent can greatly increase or reduce or liquid color changes etc. along with the time, was difficult to guarantee storage stability.Moreover, use polymkeric substance that cost is improved.
In addition, as the tackifier of liquid washing agent, except polymkeric substance, also can use inorganic salt.Inorganic salt and polymer phase ratio, have cost low, the advantage of aspect such as obtains easily.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2007-297510 communique
Summary of the invention
Yet, while using inorganic salt as the tackifier of liquid washing agent, have and under cold condition, preserve the problem of particularly easily separating out due to the temperature change in winter.
The present invention is In view of the foregoing and the invention done that its problem is: use inorganic salt can seek to increase viscosity and the liquid washing agent of excellent storage stability under cold condition.
The result that the inventor conscientiously studies, in order to solve above-mentioned problem, provides following means.
; liquid washing agent of the present invention, is characterized in that containing (A) composition: polyoxyethylene alkyl ether sulfate salt, (B) composition: the compound shown in following general formula (b1), (C) composition: the compound shown in following general formula (c1) and (D) composition: water-soluble inorganic salt.
[Chemical formula 1]
R
1-O-(AO)
x-H+++(b1)
R
2-O-(CH
2CH
2O)
y-H+++(c1)
[in formula (b1), R
1be that carbonatoms is 8～18 straight chain shape alkyl, A0 is that carbonatoms is 2～4 oxyalkylene group, and x represents the average number of repeat unit of oxyalkylene group, is 5～30 numeral; In formula (c1), R
2be that carbonatoms is a chain alkyl of 8～18, y represents the average number of repeat unit of oxyethylene group, is to be greater than 0 numeral that is less than 7.]
In liquid washing agent of the present invention, preferably (B) composition/(C) the represented mass ratio of composition is 1～10.
And, in liquid washing agent of the present invention, further preferably contain (E) composition: alpha-sulfo fatty acid ester salt.
In addition, in liquid washing agent of the present invention, preferably containing above-mentioned (A) composition is that 3～20 quality %, above-mentioned (B) composition are that 1～15 quality %, above-mentioned (C) are that 0.1～10 quality %, above-mentioned (D) composition are 0.1～10 quality %.
While further containing above-mentioned (E) composition, the amount that is somebody's turn to do (E) composition is preferably 0.01～8 quality % with respect to liquid washing agent total mass.
In addition, liquid washing agent of the present invention preferably in the time of 30 ℃ viscosity be 100～1000mPas.
According to liquid washing agent of the present invention, use inorganic salt can seek to increase viscosity and excellent storage stability under cold condition.
Embodiment
Liquid washing agent of the present invention contains (A) composition: polyoxyethylene alkyl ether sulfate salt, (B) composition: the compound shown in following general formula (b1), (C) composition: the compound shown in following general formula (c1) and (D) composition: water-soluble inorganic salt.
That liquid washing agent of the present invention can be used as is home-use,, industrial purposes for business, wherein suitable to home-use purposes, is suitable for especially the liquid washing agent that clothing is used.
The kind of washing object (washing clothes) can be enumerated the identical items with conduct washing object in home laundry, such as giving an example: the fibre products such as clothing, rag, towel class, sheet, curtain etc.
< (A) composition: polyoxyethylene alkyl ether sulfate salt >
(A) composition, for washing main component, is mainly brought into play washing effect by allocating (A) composition into.
As (A) composition, can use well-known polyoxyethylene alkyl ether sulfate salt, can be set forth in the polyoxyethylene alkyl ether sulfate salt easily obtaining on market.Preferably there is carbonatoms and is 10～20 alkyl, the polyoxyethylene alkyl ether sulfate salt that the average addition mole number of oxyethane is 1～10.This alkyl can be straight chain shape, can be also side chain shape.As the polyoxyethylene alkyl ether sulfate salt (being designated as below " straight chain shape AES ") with straight chain-like alkyl, can enumerate the polyoxyethylene alkyl ether sulfate salt of the white natural matter in source (plant etc.)., allocating under the situation of inorganic salt in the past, and when using straight chain shape AES as washing main component, under cold condition, preserving and easily separate out inorganic salt.But, in the present invention, even while using straight chain shape AES as washing main component, preserve and be also not easy to separate out inorganic salt under cold condition.Therefore, the present invention is particularly useful when using straight chain shape AES as cleaning main component.
The carbonatoms of this alkyl more preferably 10～14, in addition, the average addition mole number of oxyethane more preferably 1～4.
As the form of salt, can enumerate: an alkali metal salts such as sodium salt, sylvite; The alkanol amine salt such as monoethanolamine salt, diethanolamine salt etc.Wherein preferred as alkali salt, particularly preferably sodium salt.
As (A) composition, specifically can enumerate the suitable commercially available prod such as EMAL270N, Shinorine, SPE1350 (being trade(brand)name) that have.
(A) composition can a kind be used separately, also can two or more and use.
In liquid washing agent, with respect to the total mass of this liquid washing agent, (A) preferably 3～20 quality %, more preferably 5～15 quality % of composition amount.
(A) when composition amount surpasses preferred higher limit, the easy variation of solvability when the mobility of preparation and use.On the other hand, during not enough preferred lower value, be difficult to obtain sufficient cleaning performance.
< (B) composition: the compound > that general formula (b1) represents
(B) composition is the straight chain shape alcohol alkoxide that following general formula (b1) represents.
[Chemical formula 2]
R
1-O-(AO)
x-H+++(b1)
[in formula, R
1be that carbonatoms is 8～18 straight chain shape alkyl, AO is that carbonatoms is 2～4 oxyalkylene group, and x represents the average number of repeat unit of oxyalkylene group, is 5～30 numeral.]
In above-mentioned formula (b1), R
1alkyl can enumerate the alkyl of straight chain shape or the thiazolinyl of straight chain shape.R
1the carbonatoms of alkyl be 8～18, from the viewpoint of improving clearing power, carbonatoms preferably 10～16, more preferably 10～14.If R
1carbonatoms more than 8, just can give full play to the function as tensio-active agent, give the clearing power of liquid washing agent excellence.On the other hand, carbonatoms is 18 when following, and (B) composition easily keeps liquid state, has therefore more improved the liquid stabilising of liquid washing agent.
In above-mentioned formula (b1), AO can be any one in oxyethylene group, oxypropylene group or oxybutylene base, can be also that in these, two or more mixing exist.Preferential oxidation vinyl and/or oxypropylene group, more preferably oxyethylene group in AO.When two or more of oxyethylene group, oxypropylene group or oxybutylene base mixed, can be that random shape mixes existence, can be also that block-wise is mixed existence.
In above-mentioned formula (b1), the numeral that x is 5～30, from the viewpoint of improving clearing power, x is 10～20 numeral preferably, more preferably 12～18 numeral.
In addition, x represents oxyethylene group " on average " number of repeat unit.Namely, (B) composition is the different molecular aggregate of number of repeat unit of oxyethylene group.In addition, can be also R
1different molecular aggregates.
(B) composition can a kind be used separately, also can two or more and use.
In liquid washing agent, with respect to the total mass of this liquid washing agent, (B) preferred 1～15 quality % of composition amount, more preferably 1～10 quality %, further preferred 1～5 quality %.
(B), when composition amount surpasses preferred higher limit, the storage stability under cold condition may variation.And, due to the increase of viscosity, the easy variation of solvability when the mobility of preparation and use.On the other hand, during not enough preferred lower value, be difficult to obtain improve fully clearing power effect.
< (C) composition: the compound > that general formula (c1) represents
(C) composition is the chain alcohol ethoxylate that following general formula (c1) represents.
[chemical formula 3]
R
2-O-(CH
2CH
2O)
y-H+++(c1)
[in formula, R
2be that carbonatoms is a chain alkyl of 8～18, y represents the average number of repeat unit of oxyethylene group, is to be greater than 0 numeral that is less than 7.]
In above-mentioned formula (c1), R
2alkyl can enumerate the alkyl of chain or the thiazolinyl of a chain.R
2the carbonatoms of alkyl be 8～18, from the viewpoint of improving clearing power, carbonatoms preferably 10～16.If R
2carbonatoms more than 8, just can give full play to the function as tensio-active agent, give the clearing power of liquid washing agent excellence.On the other hand, carbonatoms is 18 when following, and (C) composition easily keeps liquid state, has therefore more improved the liquid stabilising of liquid washing agent.
In above-mentioned formula (c1), y is greater than 0 numeral that is less than 7, improves the aspect of storage stability and consider from cold condition, and y is 1～7 numeral preferably, more preferably 1～5 numeral, further preferred 3～5 numeral.
In addition, y represents oxyethylene group " on average " number of repeat unit.Namely, (C) composition is the different molecular aggregate of number of repeat unit of oxyethylene group.And, can be also R
2different molecular aggregates.
As (C) composition, for example, with inferior, can suitablely use: (i) by the product obtaining after addition of ethylene oxide on the alcohol of positive alkene oxo; (ii) by the product obtaining after addition of ethylene oxide on the alcohol of alpha-olefin oxo; (iii) under the existence of an acidic catalyst, the product obtaining after addition of ethylene oxide on the product after normal alkane is oxidized; (iv) by the product obtaining after addition of ethylene oxide on the alcohol of three polybutene oxos; (v) by the product obtaining after addition of ethylene oxide on the alcohol of tetrapropylene oxo; (vi) product obtaining after addition of ethylene oxide on the alcohol of the mixed olefins oligopolymer oxo of the alkene that is 4 at the alkene that is 3 by carbonatoms and carbonatoms etc.
Wherein, preferably (v) by the product obtaining after addition of ethylene oxide on the alcohol of tetrapropylene oxo.As object lesson, the commercial goods such as Lutensol TO3, Lutensol TO5 (being trade(brand)name) that can have for example BASF AG to manufacture.
As (C) composition, particularly, the compound shown in following general formula (c1-1) particularly preferably.
[chemical formula 4]
[in formula, R
3that carbonatoms is 1～14 chain alkyl.R
4hydrogen atom, methyl, ethyl, propyl group, butyl or hydroxyl.R
5that carbonatoms is a chain alkylidene group of 2～16.Y is less than 7 numeral, identical with the y in above-mentioned formula (c1).]
In above-mentioned formula (c1-1), R
3on chain alkyl can be that alkyl can be also thiazolinyl, from the viewpoint of improving clearing power, preferred carbonatoms is 1～12.
In above-mentioned formula (c1-1), R
4preferred hydrogen atom, methyl, ethyl, more preferably methyl, ethyl.
In above-mentioned formula (c1-1), R
5the carbonatoms of alkylidene group be 2～16, preferably carbonatoms is 2～12, more preferably carbonatoms is 2～9.R
5object lesson be exemplified below.
[chemical formula 5]
(C) composition can a kind be used separately, also can two or more and use.
In liquid washing agent, with respect to the total mass of this liquid washing agent, (C) preferred 0.1～10 quality % of composition amount, more preferably 0.1～5 quality %, further preferred 0.5～2 quality %.
(C), when composition amount surpasses preferred higher limit, be difficult to seek the viscosity increase of liquid washing agent.On the other hand, during not enough preferred lower value, the storage stability under cold condition may variation.
" mass ratio that (B) composition/(C) composition represents " in the present invention represents, with respect to (C) composition amount containing in liquid washing agent, (B) ratio of composition amount (quality criteria).
In liquid washing agent of the present invention, (B) the represented mass ratio of the composition of composition/(C) preferably 1～10, and more preferably 2～6, further preferably 3～4.
(B), when composition/(C) composition surpasses preferred higher limit, the storage stability under cold condition may variation.On the other hand, during not enough preferred lower value, be difficult to seek the viscosity increase of liquid washing agent.Moreover, the easy variation of mobility during low temperature.
< (D) composition: water-soluble inorganic salt >
(D) composition is water-soluble inorganic salt.
" water-soluble inorganic salt " in the present invention refers to, belongs to the inorganic salt that " a little easily dissolving " arrives " very easily dissolving " scope in Japanese Pharmacopoeia.At 20 ℃, dissolve the required water yield of 1g and can be called water-soluble inorganic salt less than 30mL.
As (D) composition, be not particularly limited, can enumerate sodium sulfate, sodium-chlor, Repone K, sodium carbonate, calcium chloride, calcium sulfate etc.Wherein, from the viewpoint of liquid washing agent Efficient Adhesive Promotion, sodium sulfate preferably used.In addition the also situation of preferably sulfuric acid sodium and other water-soluble inorganic salts use.
(D) composition can a kind be used separately, also can two or more and use.
In liquid washing agent, with respect to the total mass of this liquid washing agent, (D) preferably 0.1～10 quality %, more preferably 0.1～5 quality % of composition amount.
(D) when composition amount surpasses preferred higher limit, because viscosity increases, the easy variation of solvability when the mobility of preparation and use.On the other hand, during not enough preferred lower value, be difficult to fully obtain the Efficient Adhesive Promotion to liquid washing agent.
" mass ratio that (A) composition/[(C) composition+(D) composition] represents " in the present invention represents, with respect to (C) composition containing in liquid washing agent, become the amount of subtotaling, (A) ratio of composition amount (quality criteria) with (D).
In liquid washing agent of the present invention, with mass ratio that (A) composition/[(C) composition+(D)] composition represents preferably 1～15, more preferably 1～5.
(A), when composition/[(C) composition+(D) composition] surpasses preferred higher limit, the viscosity that is difficult to seek liquid washing agent increases or is difficult to obtain suitable viscosity.On the other hand, during not enough preferred lower value, viscosity may increase excessively or stability of solution variation.
" mass ratio that [(B) composition+(C) composition]/(D) composition represents " in the present invention represents, with respect to (D) composition amount containing in liquid washing agent, (B) composition becomes the ratio (quality criteria) of the amount of subtotaling with (C).
In liquid washing agent of the present invention, [(B) composition+(C)] mass ratio that composition/(D) composition represents preferably 0.2～10, more preferably 0.4～5, further preferably 0.5～2.5.
When [(B) composition+(C)] composition/(D) composition surpasses preferred higher limit, the viscosity that is difficult to seek liquid washing agent increases.On the other hand, during not enough preferred lower value, the storage stability under cold condition may variation.
< solvent >
The aspect considerations such as solvability during from preparation accessibility, use water, liquid washing agent of the present invention preferably contains water as solvent.
In liquid washing agent, with respect to the total mass of this liquid washing agent, the amount of water is preferably more than 45 quality %, more preferably 60～90 quality %.
The amount of water when preferred lower value is above, liquid washing agent through time liquid stabilising can become better, on the other hand, when preferred higher limit is following, liquid viscosity can appropriate step-down, from the viewpoint of usability well.
As solvent, except water, also can use water miscibility organic solvent.
" water miscibility organic solvent " refers in the ion exchanged water 1L of 25 ℃ can dissolve the above organic solvent of 50g.As water miscibility organic solvent, and water forms uniform solution while mixing, and wherein can enumerate carbonatoms and be 2～4 monohydroxy-alcohol, the polyvalent alcohol that carbonatoms is 2～4, glycol ether etc.
The monohydroxy-alcohol that is 2～4 as carbonatoms, can enumerate ethanol, 1-propyl alcohol, 2 propyl alcohol, n-butyl alcohol etc.
The polyvalent alcohol that is 2～4 as carbonatoms, can enumerate ethylene glycol, propylene glycol, butyleneglycol, glycerine etc.
As glycol ether, can enumerate ethylene glycol monobutyl ether, ethylene glycol ether, ethyleneglycol monophenylether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether etc.
Other compositions of < >
In the scope of harmless effect of the present invention, can be as required, in liquid washing agent of the present invention, allocate other the composition in addition of mentioned component (A)～(D) into.
As other compositions, be not particularly limited, normally used composition in the liquid washing agent that clothing uses etc. can be allocated into, anion surfactant beyond (A) composition, (B) composition and (C) nonionogenic tenside, alkaline agent, cationic compound, sanitas, white dyes, secondary pollution preventing agent, Foam Control, sequestrant, viscosity-depression agent or the solubilizing agent beyond composition, enzyme, sweetener, tinting material, emulsifying agent, extract class, pH adjusting agent etc. can be allocated particularly into.< < (E) composition: α monosulfonic acid fatty acid ester salt > >
In liquid washing agent of the present invention, can further contain (E) composition: alpha-sulfo fatty acid ester salt.By allocating (E) composition into, can improve especially the clearing power to sebum spot.In addition, even if use (E) composition, also easy preparation.
(E) composition can be used by known manufacture method, such as obtained this composition by following methods: use with the tank reactor of stirrer according to regulation etc., by feedstock fat acid esters and sulphuric anhydride etc. being contacted to sulfonation, be modulated into alpha-sulfo fatty acid ester (α-SF acid), then by this α-SF neutralization such as sodium hydroxide for acid.In addition, before and after neutralization, also can bleach with hydrogen peroxide etc.
As (E) composition, the compound can the following general formula of suitable use (e1) representing.
[chemical formula 6]
[in formula, R
6that carbonatoms is 8～18 alkyl, R
7time the carbonatoms alkyl that is 1～6, M is gegenion.]
In above-mentioned formula (e1), R
6alkyl can be that straight chain shape can be also chain, can also contain ring texture.Wherein, R
6alkyl preferred aliphat alkyl, the more preferably thiazolinyl of the alkyl of straight chain shape or chain or straight chain shape or a chain, further preferably the alkyl of straight chain shape, the thiazolinyl of straight chain shape.
R
6carbonatoms be 8～18, preferably carbonatoms is 10～18, more preferably carbonatoms is 10～16, further preferably carbonatoms is 14～16.R
6carbonatoms be 8 when above, clearing power improves.On the other hand, R
6carbonatoms be 18 when following, liquid stabilising improves, separating out in the time of particularly suppressing gelation or cryopreservation.
In above-mentioned formula (e1), R
7alkyl can be that straight chain shape can be also chain, also can contain ring texture.Wherein, R
7alkyl preferred aliphat alkyl, the more preferably thiazolinyl of the alkyl of straight chain shape or chain or straight chain shape or a chain, the further preferred alkyl of straight chain shape, the thiazolinyl of straight chain shape.
R
7carbonatoms be 1～6, preferably 1～3.
As R
7alkyl, there are particularly methyl, ethyl, n-propyl, sec.-propyl etc., from the viewpoint of more improving clearing power, preferable methyl, ethyl, n-propyl, particularly preferably methyl.
In above-mentioned formula (e1), M is gegenion, as long as energy and R
6cH (COOR
7) SO
3 -together generate the just passable of water-soluble salt.As this gegenion, there are alkalimetal ion, protonated amines, ammonium etc.
As the alkali metal atom that can form this gegenion, there are for example sodium, potassium etc.As the amine that can form this gegenion, any one of one-level to three grade can, preferably total carbon atom number is 1～6.This amine also can have hydroxyl, and the aspect that the water-soluble of liquid washing agent is high from cold condition is considered, preferably had hydroxyl.Such amine for example has alkanolamine, the carbonatoms of this chain triacontanol base preferably 1～3.Object lesson as alkanolamine has monoethanolamine, diethanolamine, trolamine etc.Wherein as M, preferred as alkali ion.
(E) composition can a kind be used separately, also can two or more and use.
In liquid washing agent, with respect to the total mass of this liquid washing agent, (E) preferred 0.01～8 quality % of composition amount, more preferably 0.1～6 quality %, further preferred 1～3 quality %.
(E), when composition amount surpasses preferred higher limit, the storage stability under cold condition may variation.On the other hand, during not enough preferred lower value, be difficult to obtain the effect of allocating into of (E) composition.
In liquid washing agent of the present invention, also can be used together (A) composition and (E) anion surfactant beyond composition, such as linear alkylbenzene sulfonate (LAS) etc. and use.Thus, improve the comprehensive clearing power to multiple spot.
While using LAS in liquid washing agent, with respect to the total mass of anion surfactant, the amount of LAS is 20～70 quality % left and right preferably, more preferably 20～65 quality % left and right.LAS amount, when preferred lower value is above, can improve the clearing power to multiple spot more, when preferred higher limit is following, can improve the storage stability under cold condition.
In addition, in liquid washing agent, LAS is composition use preferably and (A), and the mass ratio that (A) composition/LAS represents is preferably 0.4～4, more preferably in 0.5～3 scope.(A) mass ratio of composition/LAS, when preferred lower value is above, can improve the storage stability under cold condition, on the other hand, when preferred higher limit is following, can more improve the clearing power to multiple spot.
In addition, liquid washing agent of the present invention also can be with (B) composition and (C) nonionogenic tenside beyond composition using.As such nonionogenic tenside, be not particularly limited, such as having: polyoxyethylene phenyl ether, in (between carbonyl and Sauerstoffatom) addition between the ester bond of long-chain fat acid alkyl ester the fatty acid alkyl ester alkoxide of alkylene oxide, polyoxyethylene sorbitan fatty acid ester, Polyoxyethylene Sorbitol Fatty Acid Esters, polyoxyethylene fatty acid ester, polyoxyethylene hydrogenated castor oil etc.
As alkaline agent, there are for example the alkanolamines such as monoethanolamine, diethanolamine, trolamine.
As sanitas, Kathon CG CG (trade(brand)name), the Proxel etc. that have for example M-nitro benzoic acid or its salt, Rhom and Hass to manufacture.
As enzyme, there are for example proteolytic enzyme, amylase, lipase, cellulase, mannase etc.For example, proteolytic enzyme can be used Ai Wei proteolytic enzyme (Everlase) 16L TypeEX, Savinase (Savinase) 16L TypeEX, liquid protease Ultra (Liquanase Ultra) 2.5XL (being trade(brand)name) that Novozymes Company manufactures.
As sweetener, as representative example, there is the flavor compositions of record in table 11～18 of saying this patent JP 2002-146399 communique etc.
In liquid washing agent of the present invention, in order to obtain the pH value of expectation, can allocate pH value conditioning agent into.But, when the pH value of liquid washing agent is exactly desired value when only allocating above-mentioned each composition into, just might not allocate pH adjusting agent into.
As pH adjusting agent, there is for example the acidic cpd of sulfuric acid, hydrochloric acid, citric acid etc., the alkanolamine of monoethanolamine, diethanolamine, trolamine etc., the basic cpd of sodium hydroxide, potassium hydroxide etc.These pH adjusting agents can be used separately a kind, also can two or more also use.
The pH of liquid washing agent of the present invention at 25 ℃ is preferably 7～11, and more preferably pH is 7～9.The pH of liquid washing agent is in above-mentioned preferable range time, and liquid stabilising improves more.And, while adding enzyme, can seek the stabilization of enzymic activity, easily keep good clearing power.
In the present invention, the pH of liquid washing agent represents liquid washing agent to be adjusted to 25 ℃, the value obtaining by mensuration such as pH meters (ProductName: HM-30G, DKK Toa Corp. manufactures).
In addition, from the viewpoint of to the coating of washing clothes with from the discharge of liquid detergent container, the viscosity that liquid washing agent of the present invention is 30 ℃ is 100～1000mPas, more preferably 200～500mPas preferably.
In the present invention, the viscosity of liquid washing agent represents liquid washing agent to be adjusted to 30 ℃, measures the value obtaining by Brookfield viscometer.
As mentioned above, liquid washing agent of the present invention, owing to containing (A)～(D) composition, is used inorganic salt can seek to increase viscosity and excellent storage stability under cold condition.
Liquid washing agent of the present invention, can be by allocating (D) constituent adjustment viscosity into by using (A) composition as washing main component.In addition, liquid washing agent of the present invention passes through and uses (B) composition and (C) composition, in adjusting viscosity, can seek the preservation stabilization under cold condition, particularly for winter temperature change, is also difficult for producing separating out.
Embodiment
By following examples, the present invention is described in further detail, but the present invention is not limited to these embodiment.In the present embodiment, " % " represents " quality % " during without special stipulation.
The composition of the liquid washing agent that each is routine is as shown in table 1～5.In table, the unit of each formulated component amount is " quality % ", all represents purity conversion amount.In table, when formulated component is empty hurdle, this formulated component is not allocated into.
In addition, raw material BC-3, the BC-4 using respectively in embodiment 8,9 and 11 and BC-6 are the mixtures of a chain molecule and straight chain molecule.In table, " BC origin " represents the straight chain molecule in this mixture.The amount of BC origin (this straight chain molecule) represents in bracket.The epimere of " BC-3 (side chain) " represents raw material BC-3, and the bracket of hypomere represents the chain molecule in this mixture.The epimere of BC-3 (side chain) represents the amount of raw material BC-3, and the bracket of hypomere represents the amount of this chain molecule." BC-4 (side chain) ", " BC-6 (side chain) " are too.
In addition, in table, " (B)/(C) " refers to the amount with respect to (C) composition in liquid washing agent (chain molecule), (B) ratio (mass ratio) of the amount of composition (straight chain molecule).
" [(B)+(C)]/(D) " refer to respect to (D) composition amount in liquid washing agent (B) composition (straight chain molecule) and (C) ratio (mass ratio) of the total amount of composition (chain molecule).
The raw material using in the present embodiment is as follows.
< (A) composition >
A-1: polyoxyethylene alkyl ether sulfate salt (molecule and the mixture of molecule with the straight chain-like alkyl of carbonatoms 14 with the straight chain-like alkyl of carbonatoms 12; The average addition mole number of oxyethane is 2) AES (2), trade(brand)name " EMAL270N ", Kao Corp manufactures.
A-2: polyoxyethylene alkyl ether sulfate salt (molecule and the mixture of molecule with the straight chain-like alkyl of carbonatoms 14 with the straight chain-like alkyl of carbonatoms 12; The average addition mole number of oxyethane is 3) AES (3), trade(brand)name " Shinorine SPE-1350 ", New Japan Chem Co., Ltd manufactures.
< (B) composition >
B-1: the Voranol EP 2001 (R in above-mentioned formula (b1)
1the straight chain-like alkyl of=carbonatoms 12,14, x=15), trade(brand)name " Ecolat24-15/85 ", Ecogreen company manufactures.In addition, " R
1the straight chain-like alkyl of=carbonatoms 12,14 " refer to, B-1 is the molecule and the mixture of molecule with the straight chain-like alkyl of carbonatoms 14 with the straight chain-like alkyl of carbonatoms 12.
BC origin: the straight chain shape Voranol EP 2001 comprising respectively in BC-3 described later, BC-4 or BC-6.
< (C) composition >
The C-1:C13-cladodification oxo alcohol (R in above-mentioned formula (c1)
2the branched-chain alkyl of=carbonatoms 12,13, y=3) only by a chain molecular composition, trade(brand)name " Lutensol TO3 ", BASF AG manufactures.In addition, " branched-chain alkyl of R2=carbonatoms 12,13 " refers to, C-1 is the molecule and the mixture (lower with) of molecule with the branched-chain alkyl of carbonatoms 13 with the branched-chain alkyl of carbonatoms 12.
The C-2:C13-cladodification oxo alcohol (R in above-mentioned formula (c1)
2the branched-chain alkyl of=carbonatoms 12,13, y=5) only by a chain molecular composition, trade(brand)name " Lutensol TO5 ", BASF AG manufactures.
BC-3: Voranol EP 2001 (molecule and the mixture of molecule with the straight chain-like alkyl of carbonatoms 12,13 with the branched-chain alkyl of carbonatoms 12,13, y=4.9) prop up the mixture (mass ratio: straight chain/side chain=5/5) of chain molecule and straight chain molecule, trade(brand)name " Safol4.9EO ", Sha Suo company manufactures.
BC-4: Voranol EP 2001 (molecule and the mixture of molecule with the straight chain-like alkyl of carbonatoms 12,13 with the branched-chain alkyl of carbonatoms 12,13, y=5) prop up the mixture (mass ratio: straight chain/side chain=8/2) of chain molecule and straight chain molecule, trade(brand)name " Dobanol5EO ", Mitsubishi chemical Co., Ltd.
C-5: the Voranol EP 2001 (R in above-mentioned formula (c1)
2the branched-chain alkyl of=carbonatoms 12,13, y=6) only by a chain molecular composition, trade(brand)name " Exxonl6EO ", exxon chemical company manufactures.
BC-6: the Voranol EP 2001 (R in above-mentioned formula (c1)
2=there is the molecule and the mixture of molecule with the straight chain-like alkyl of carbonatoms 12,13 of the branched-chain alkyl of carbonatoms 12,13, y=5) prop up the mixture (mass ratio: straight chain/side chain=8/2) of chain molecule and straight chain molecule, trade(brand)name " Neodol5EO ", shell KCC manufactures.
C-7: the Voranol EP 2001 (R in above-mentioned formula (c1)
2the branched-chain alkyl of=carbonatoms 12,13, y=3) only by a chain molecular composition, trade(brand)name " Softanol ", Nippon Shokubai Co., Ltd manufactures.
< (C ') composition: (C) the comparison composition > of composition
C '-1:C13-cladodification oxo alcohol (R in above-mentioned formula (c1)
2the branched-chain alkyl of=carbonatoms 12,13, y=10), trade(brand)name " Lutensol T010 ", BASF AG manufactures.
< (D) composition >
D-1:Na
2sO
4(saltcake), trade(brand)name " sodium sulfate ", Kanto Kagaku K. K. manufactures.
D-2:NaCl, trade(brand)name " sodium-chlor ", Tokyo HuaCheng Industry Co., Ltd manufactures.
D-3:KCl, trade(brand)name " Repone K ", Kanto Kagaku K. K. manufactures.
D-4:Na
2cO
3, trade(brand)name " sodium carbonate ", Kanto Kagaku K. K. manufactures.
D-5:CaCl
2, trade(brand)name " calcium chloride ", Kanto Kagaku K. K. manufactures.
< (E) composition >
E-1: α-sulfofattyacidmethylestersalt, trade(brand)name " MIZULAN FL-80 ", Lion Eco Chemicals Co., Ltd. manufactures.
Other compositions of < >
LAS: linear alkylbenzene sulphonic acid, trade(brand)name " LIPON LS-250 ", Lion Corporation's system.
MEA: monoethanolamine, Nippon Shokubai Co., Ltd manufactures.
Citric acid: citric acid, Fukawa Chemical Industries Co., Ltd. manufactures.
Sodium Benzoate: sodium benzoate, Fu Jian Pharmaceutical Co., Ltd manufactures.
Enzyme: trade(brand)name " Ai Wei proteolytic enzyme (Everlase) ", Novozymes Company manufactures.
Perfume: the flavor compositions A recording in Japanese Patent Laid-Open 2002-146399 communique table 11～18.
H
2sO
4: sulfuric acid, Kanto Kagaku K. K. manufactures.
Purified water.
The composition of common component:
Ratio in the amount of each formulated component (quality %) express liquid washing composition.
MEA0.5 quality %, Citric acid0.2 quality %, Sodium Benzoate0.5 quality %, Enzyme0.3 quality %, Perfume0.4 quality %, H
2sO
40.25 quality %, adds up to 2.15 quality %.
[preparation of liquid washing agent]
(embodiment 1～38,, comparative example 1～6)
According to the composition shown in table 1～5 (formulated component, amount), by following sequential system for each routine liquid washing agent.
In 500mL beaker, put into purified water, (A) composition and stirrer, with agitator (day is stretched physics and chemistry manufacture by magnetic stirring apparatus SW-RS077 Co., Ltd.), be stirred to evenly.Then, respectively by (B) composition, (C) composition or (C ') composition and (D) composition limit confirm uniform dissolution, limit adds.Then, add common component, be stirred to evenly.In addition, while allocating (E) composition or LAS into, add together with (A) composition.
The preparation of such liquid washing agent need not be controlled temperature especially, at room temperature carries out.About stirring velocity, suitably set rotating speed so that stirrer can rotate well.
[evaluation of liquid washing agent]
Respectively storage stability under the viscosimetric analysis of each routine liquid washing agent and cold condition is evaluated.
(viscosimetric analysis)
Filling liquid washing composition 50g in the bottle of capacity 50mL (SV-50A says electric physics and chemistry Xiao Zi Co., Ltd. and manufactures), in being set as the thermostatic bath (manufactures of T22LA thomas company) of 30 ℃, preservation is 2 hours.Then, with Brookfield viscometer (viscometer TV-20, Tokyo Keiki Inc. manufactures), measure the viscosity of liquid washing agent.
Condition determination is set as rotating speed 30rpm, rotor No.2, rotational time 30 seconds, 30 ℃ of temperature, the viscosity of measuring is 100～1000mPas, and (this considers to obtain from the following aspects: the preparation of the not enough 100mPas of viscosity for qualified, because viscosity is low, so to the easy variation such as the coating of washing clothes, anelasticity, and be difficult to obtain sufficient clearing power; Viscosity surpasses the preparation of 1000mPas, because viscosity is too high, so the easy variation of discharge from container).(storage stability under cold condition)
Filling liquid washing composition 50g in the bottle (SV-50A, a day physics and chemistry Xiao Zi Co., Ltd. manufactures) of capacity 50mL preserves 1 angel's liquid washing agent fully charge under the environment of-5 ℃.Then, under the environment of 5 ℃, preserve 1 day, naturally thaw.
Repeating such operation (preserves under the environment of 5 ℃ after 1 day, preserves 1 day :-5 ℃ under the environment of 5 ℃
5 ℃) after 5 times and after 10 times, the outward appearance of observing liquid washing agent under the environment of 5 ℃.Then, according to following metewand, the storage stability under cold condition is evaluated.
In addition, be somebody's turn to do-5 ℃
the repetitive operation of 5 ℃ is the appreciation condition of supposing especially the change of the temperature on daytime in winter.
The conduct of < < metewand > > Crystal is defective.
Clear: can not see separating out of muddiness or crystallization completely.
Cloudy: can see muddiness.
Sedimentation: can see separation.
Crystal: can see separating out of crystal.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
From the result shown in table 1～5, can know, the liquid washing agent of applicable embodiments of the invention is used inorganic salt can seek to increase the excellent storage stability under viscosity and cold condition.
Claims (3)
1. a liquid washing agent, it contains (A) composition: polyoxyethylene alkyl ether sulfate salt, (B) composition: the compound shown in following general formula (b1), (C) composition: the compound shown in following general formula (c1) and (D) composition: water-soluble inorganic salt
R
1-O-(AO)
x-H+++(b1)
R
2-O-(CH
2CH
2O)
y-H+++(c1)
In formula (b1), R
1be that carbonatoms is 8～18 straight chain shape alkyl, AO is that carbonatoms is 2～4 oxyalkylene group, and x represents the average number of repeat unit of oxyalkylene group, is 5～30 numeral; In formula (c1), R
2be that carbonatoms is a chain alkyl of 8～18, y represents the average number of repeat unit of oxyethylene group, is to be greater than 0 numeral that is less than 7.
2. liquid washing agent as claimed in claim 1, is 1～10 with the mass ratio that (B) composition/(C) composition represents.
3. liquid washing agent as claimed in claim 1 or 2, it further contains (E) composition: alpha-sulfo fatty acid ester salt.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
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| JP2012-189300 | 2012-08-29 | ||
| JP2012189300 | 2012-08-29 | ||
| JP2013-161863 | 2013-08-02 | ||
| JP2013161863A JP6155133B2 (en) | 2012-08-29 | 2013-08-02 | Liquid cleaning agent |
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| CN103666805B CN103666805B (en) | 2018-06-05 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107709529A (en) * | 2015-06-18 | 2018-02-16 | 狮王株式会社 | The liquid of the sulfo fatty acid ester salt containing α |
| CN111819273A (en) * | 2018-04-04 | 2020-10-23 | 陶氏环球技术有限责任公司 | Aqueous light duty liquid detergent formulations |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1827759A (en) * | 2005-02-28 | 2006-09-06 | 花王株式会社 | Surfactant composition |
| CN101186863A (en) * | 2007-12-10 | 2008-05-28 | 北京绿伞化学有限公司 | Low concentration water-saving type clothes washing agent and preparation method thereof |
| US20120083437A1 (en) * | 2010-09-30 | 2012-04-05 | Ecolab Usa Inc. | Solid cleaning composition |
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| CN1827759A (en) * | 2005-02-28 | 2006-09-06 | 花王株式会社 | Surfactant composition |
| CN101186863A (en) * | 2007-12-10 | 2008-05-28 | 北京绿伞化学有限公司 | Low concentration water-saving type clothes washing agent and preparation method thereof |
| US20120083437A1 (en) * | 2010-09-30 | 2012-04-05 | Ecolab Usa Inc. | Solid cleaning composition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107709529A (en) * | 2015-06-18 | 2018-02-16 | 狮王株式会社 | The liquid of the sulfo fatty acid ester salt containing α |
| CN111819273A (en) * | 2018-04-04 | 2020-10-23 | 陶氏环球技术有限责任公司 | Aqueous light duty liquid detergent formulations |
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