CN1093879C - Thick series liquid detergent composition - Google Patents
Thick series liquid detergent composition Download PDFInfo
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- CN1093879C CN1093879C CN97118670A CN97118670A CN1093879C CN 1093879 C CN1093879 C CN 1093879C CN 97118670 A CN97118670 A CN 97118670A CN 97118670 A CN97118670 A CN 97118670A CN 1093879 C CN1093879 C CN 1093879C
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Abstract
The invention provides a kind of thick liquid detergent composition having excellent deterging force without impairing preserving stability and containing a surfactant in a high concentration by compounding a specific polymer compound. With specific radio, it comprises respectively (A) surfactant in which ratio of a nonionic surfactant is weight >=80% by wight, (B) polymer compound obtained by subjecting a trunk chain of a polyether compound to graft polymerization with a monoethylenic unsaturated monomer consisting mainly of an acrylic acid and/or methacrylic acid, the water content less than 60% by wight is thick liquid detergent composition.
Description
The invention relates to and contain concentrated surfactant, stable, and show the good thick series liquid detergent composition of washing clean performance.
The advantage of liquid cleaning agent, molten water-based is generally better than powder cleaning agent, can directly be coated on contaminated position, compare with the powder cleaning agent, be in manufacturing process, not need complicated apparatus such as drying plant with regard to the advantage that has.Yet the powder cleaning agent exists in the what is called and is separated, precipitates or muddy equistability problem, with combinations-of surfactants the time, and kind that must the careful consideration alkaline agent, the water yield etc.Particularly much less water-insoluble substance such as zeolite with the cooperation of the synergistic matter headed by the dispersion agents such as other metal ion encapsulant and polymkeric substance, becomes the reason of overslaugh stability, so must be noted that when cooperating synergistic agent.Usually in order to improve stability, propose to cooperate hydrotropic solvent and ethylene glycol, propylene glycol or ethanol equal solvents such as tosic acid.But and the powder lotion relatively, is difficult to cooperate the synergistic agent of q.s.
On the other hand, current liquid cleaning agent is attempting increasing surfactant concentration, and the amount of moisture in the minimizing system reduces to reach densification the standard usage quantity.Yet this thick series liquid detergent considered the cooperation of liquid cleaning agent itself more carefully than the past, moreover it also is very difficult cooperating synergistic agent in a large number.
Open in the flat 7-53993 communique the spy and to have put down in writing a kind of synergistic agent, the solid particulate that can stably cooperate in liquid cleaning agent has good soil removability and anti-tack again.The synergistic agent of above-mentioned communique record since with polyoxyethylene glycol as main chain, be that methacrylic acid and single ethylene unsaturated monomer are carried out the grafted macromolecular compound, but, to the synergistic agent performance of the nonionogenic tenside of high density with wash clean property, for example, nonionogenic tenside accounts for the synergistic agent of tensio-active agent gross weight more than 80%, not putting down in writing nonionogenic tenside fully, that greasy dirt is washed clean property is good, and and anion surfactant relatively, because micelle-forming concentration is very low, so help densification (コ Application パ Network ト, compact).Yet the influence that cooperated by synergy is so wish to develop more stable synergistic agent.
Therefore, the purpose of this invention is to provide a kind of liquid cleaning agent composition, in the thick series liquid detergent that with nonionogenic tenside is main tensio-active agent cooperation, neither infringement stability has detergency ability again and prevents adhesion property again.
Present inventors found that in the surfactant system that contains the high density nonionogenic tenside that through various researchs by cooperating specific macromolecular compound, neither infringement stability has the good clean ability of washing again.Thereby finished the present invention to making.
Promptly, the present invention is to provide the thick series liquid detergent composition that amount of moisture is lower than 60 (weight) %, this thick series liquid detergent composition contains, at the tensio-active agent of (A) 20-80 (weight) %, wherein, nonionogenic tenside accounts for 80 (weight) more than the %; (B) macromolecular compound of 0.1-15 (weight) %, it is on the main chain of polyether compound, graft polymerization contains the macromolecular compound of vinylformic acid and/or methylacrylic acid (methacrylic acid) being made single ethylene unsaturated monomer of main body.The amount of composition is benchmark with the composition.All the other are water.
Below describe thick series liquid detergent composition of the present invention in detail.
The nonionogenic tenside of (A) of the present invention composition preferably uses the nonionogenic tenside of polyoxyethylene and/or polyoxytrimethylene type, especially uses ideal of selecting from following (1)-(3) more than a kind or 2 kinds.
(1) on 1 yuan of alcohol of 8-16 carbon atom average addition the Voranol EP 2001 of 5-15 mole ethylene oxide
(2) on 2 yuan of alcohol of 8-16 carbon atom average addition the Voranol EP 2001 of 5-15 mole ethylene oxide (EO)
(3) polyoxyethylene polyoxy-propylene of average addition 5-15 mole ethylene oxide and 1-5 mole propylene oxide on 1 yuan of alcohol of 8-16 carbon atom or 2 yuan of alcohol.The addition of ethylene oxide and propylene oxide does not have particular restriction in proper order, can be block polymerization, can be random polymerization yet.No matter use which kind of material, can select according to purposes, purpose and the stability of cleaning agent.
As other nonionogenic tenside, polyxyethylated phenylate class is for example arranged, sucrose-fatty lipid, fatty mono glyceride class, higher fatty acid alkylolamide class, polyoxyethylene higher fatty acid alkylolamide class, oxidation amine and alkyl glycoside class etc.As alkyl glycoside, preferably by the alkyl glycoside class of descending general formula (a) expression.
R
1-(OR
2)xGy (a)
In the formula, R
1Be the straight or branched alkyl of 8-18 carbon atom, alkenyl or alkane phenyl, R
2Be the alkylene worker of 2-4 carbon atom, G is the residue from the reducing sugar of 5 or 6 carbon atoms, and x is the number of average 0-6, and Y is the number of average 1-10.
By cooperating 1-10 (weight) % in composition, the best this alkyl glycoside of 1-5 (weight) % can further improve the stability of liquid cleaning agent composition.
Among the present invention, nonionogenic tenside accounts for 80 (weight) of tensio-active agent total amount more than the %, not only cleaning ability and good stability, and also densification might as well.Thick series liquid detergent composition of the present invention, because the surfactant concentration height, so viscosity also uprises easily.At this moment, be to reduce the viscosity of liquid cleaning agent, the nonionogenic tenside of above-mentioned (1)-(3), preferably share from 1 yuan of alcohol and from 2 yuan of alcohol.
Thick series liquid detergent composition of the present invention in tensio-active agent, except cooperating nonionogenic tenside, can cooperate 15 (weight) below the %, is preferably the anion surfactant of 1-10 (weight) %.As anion surfactant, can use the tensio-active agent that in common cleaning agent, cooperates, the anion surfactant of fits best sulfonate type, sulfate type and/or carboxylic acid type.Specifically, preferably use shown in following (4)-(7).
(4) on average has the alkylbenzene sulfonate of 10-20 carbon atom alkyl.
(5) have from 1 yuan of alcohol of straight chain of 10-20 carbon atom or 2 yuan of alcohol of straight chain or from the alkyl of branched-chain alcoho, at the sulfated alkyl ether of 1 intramolecularly addition 0.5-6 mole ethylene oxide.
(6) on average have the alkyl or the alkenyl sulfate of 10-20 carbon atom alkyl or alkenyl.
(7) soap of average 8-18 carbon atom.
Counter ion as these anion surfactants can be selected from following: i.e. positively charged ion and their mixtures such as sodium, potassium, calcium and thanomin.When cooperating above-mentioned anion surfactant, with cooperating of acid type, also can use other approach, add the method for alkali (thanomin etc.).
As other tensio-active agent, can limit the quantity of in cleaning agent cooperates known anion surfactant, amphoterics, can not hinder stability.
In the thick series liquid detergent composition of the present invention, the tensio-active agent total concn is 20-80%, preferably the high density of 30-60 (weight) %.
(B) macromolecular compound of composition is on the main chain of polyether compound, graft polymerization based on the macromolecular compound of single ethylene unsaturated monomer of vinylformic acid and/or methacrylic acid, as the preferably following general formula of polyether compound (1) expression,
Y-O(CH
2CH
2O)nH (1)
In the formula, Y is hydrogen, methyl, phenyl or benzyl, methyl or phenyl preferably, and n is average addition mole number, is the number of 2-200.Good especially is with polyoxyethylene glycol as skeleton, and an end has alkyl, or the aromatic base of phenyl and benzyl etc.Thick series liquid detergent composition of the present invention though have methyl, phenyl on dried chain, can the most stably cooperate.
Except vinylformic acid and/or methacrylic acid,, toxilic acid, fumaric acid, methylene-succinic acid and maleic anhydride etc. are arranged as spendable unsaturated carboxylic acid.Macromolecular water-soluble polymkeric substance of the present invention is with vinylformic acid, the methacrylic acid composition as necessity, adds other unsaturated carboxylic acid, carries out graft polymerization on polyether compound, and obtain.As polymerization starter, can use known free-radical initiator.Macromolecular compound preferably obtains by following reaction, for the main chain polyether compound, contains vinylformic acid, and the weight ratio of single ethylene unsaturated monomer of methacrylic olefin(e) acid is at least more than 1/4.Concrete grammar as the preparation macromolecular compound is, under nitrogen gas stream, more than 90 ℃, be preferably between 100-200 ℃, polyether compound is stirred on the limit, and the limit slowly drips single ethylene unsaturated monomer and initiator respectively, can obtain acid type macromolecular compound of the present invention.When being made into alkalescence, after the cooling,, can be easy to obtain by neutralizing with alkaline agents such as sodium hydroxide.Identical with anion surfactant, with cooperating of acid type, can in liquid cleaning agent, neutralize.Macromolecular compound cooperates 0.1-15 (weight) %, preferably 0.5-10 (weight) %.
Macromolecular compound of the present invention for the main chain polyether compound, contains single ethylene unsaturated monomer of vinylformic acid and methacrylic acid, with the ratio of weight ratio more than at least 1/4, makes by reaction.
The rest part of the present composition is a water, and the amount of moisture of thick series liquid detergent of the present invention below the %, particularly when % is following, can obtain stable liquid cleaning agent in 40 (weight) in 60 (weight).
For thick series liquid detergent composition of the present invention, as any composition, can limit the principal component that cooperated the past in cleaning agent, to cooperate, do not damage stability and washability.For example, polymkeric substance such as polyoxyethylene glycol, carboxymethyl dimension element are arranged; The anti-toner that moves such as polyvinylpyrrolidone; Citric acid, two grape acid, phosphoric acid or its metal trapping agent such as salt; Alkaline agents (also can be used as the pH regulator agent) such as basic carbonate, alkalimetal silicate or alkanolamine; Enzymes such as proteolytic enzyme, cellulase, lipase; Enzyme stabilizers such as calcium chloride, formic acid, boric acid; Defoamers such as silicone; Lower alcohols such as ethanol; Low alkyl group benzene sulfonates such as benzene sulfonate, P-toluenesulphonic acids; Glycolss such as propylene glycol, ethylene glycol, polypropylene glycol, polyoxyethylene glycol; Benzoate, solubility agent such as urea; Oxidation inhibitors such as butylhydroxy toluene, toluylene cresols, S-WAT, sodium bisulfite; Tinopal CbsX CBS fluorescent dyes such as (チ バ ガ イ ギ-society's system), upward blue agent; In liquid cleaning agent, the general common stabilizing perfume of knowing, antibiotic antiseptic etc.In these any compositions, propylene glycol or ethylene glycol can demonstrate the character of further raising thick series liquid detergent stability, but use level is also meaningless too much, because unfavorable to densification, so be controlled at 20 (weight) below the % when cooperating, best 15 (weight) are below the %.
Below with embodiment the present invention is described, but the present invention is not limited in these embodiment.
Synthesizing of synthesis example 1＜macromolecular compound (1) 〉
In the glass reactor that has thermometer, stirrer, nitrogen ingress pipe, reflux cooler, the 100 weight part molecular-weight average of packing into are 1500 phenoxy group polyoxyethylene glycol, 5 weight part toxilic acids, and heating for dissolving under nitrogen gas stream is warmed up to 150 ℃ under stirring.Then, the limit remains on 150-151 ℃ with temperature, and the limit dripped 30 parts by weight of acrylic acid, 4.5 weight parts, two-tert-butyl peroxide respectively continuously in 1 hour, afterwards, continue to stir 40 minutes.After the cooling, add 135 parts by weight of purified water, sub-compound (1) secures satisfactory grades.
Synthesizing of synthesis example 2＜macromolecular compound (2) 〉
In the glass reactor that has thermometer, stirrer, nitrogen ingress pipe, reflux cooler, the 100 weight part molecular-weight average of packing into are 2000 phenoxy group polyoxyethylene glycol, 10 weight part toxilic acids, under nitrogen gas stream, heating for dissolving is warmed up to 145 ℃ under stirring.Then, the limit remains on 145-147 ℃ with temperature, and the limit is continuous Dropwise 50 parts by weight of acrylic acid of difference, 2.5 weight parts, two-tert-butyl peroxide in 1 hour, afterwards, continue to stir 80 minutes, after the cooling, add 150 parts by weight of purified water, obtain macromolecular compound (2).
Synthesizing of synthesis example 3＜macromolecular compound (3) 〉
In the glass reactor that has thermometer, stirrer, nitrogen ingress pipe, return channel water cooler, the 100 weight part molecular-weight average of packing into are 1500 mono methoxy polyethylene glycol, 10 weight part toxilic acids, under the nitrogen gas stream, be warmed up to 145 ℃ under heating for dissolving, the stirring.Then, the limit remains 145-147 ℃ with temperature, and the limit dripped 15 parts by weight of acrylic acid, 1.0 weight parts, two-tert-butyl peroxide respectively continuously in 1 hour, afterwards, continue to stir 100 minutes.After the cooling, add 125 parts by weight of purified water, obtain macromolecular compound (3).
Synthesizing of synthesis example 4＜macromolecular compound (4) 〉
In the glass reactor that has thermometer, stirrer, nitrogen ingress pipe, reflux cooler, the 100 weight part molecular-weight average of packing into are 2000 mono methoxy polyethylene glycol, 10 weight part toxilic acids, under nitrogen gas stream, heating for dissolving is warmed up to 145 ℃ under stirring.Then, the limit keeps 145-147 ℃ with temperature, and the limit was dripped 50 parts by weight of acrylic acid, 2.5 weight parts, two-tert-butyl peroxide respectively continuously in 1 hour, afterwards, continue to stir 60 minutes.After the cooling, add 150 parts by weight of purified water, obtain macromolecular compound (4).
Example 1
With composition shown in the macromolecular compound that obtains in the above-mentioned synthesis example (1)-(4) and the table 1-2, modulate various cleaning agent compositions, measure storage stability and prevent mud adhesion property again with following method.The results are shown in table 1-2.
1) storage stability test
Each composition is packed in the 100ml vial, seal up with plug.With the keeping 10 days in the thermostatic bath of 50 ℃ and 5 ℃ of this sample.Preserve the sample after finishing, with the naked eye with the naked eye judge by following standard.
Zero: do not have separation, precipitation or gonorrhoea
△: gonorrhoea is arranged slightly
*: produce separation, precipitation or gonorrhoea
2) prevent mud adhesion property test method(s) again
The continuous calico of wood (golden towel 2003 cloth) is cut into 10cm * 10cm, one group 5.At 1 liter of evaluation adding gardening deer natural pond laterite in the cleaning agent aqueous solution, in Ta Gete (-go ト) survey meter, test by following condition.
＜experiment condition 〉
Wash 10 minutes clean time
Cleaning agent concentration 0.08%
4 ° of water hardness
20 ℃ of water temps
Wash and carry out flowing water washing in 5 minutes in 20 ℃ of tap water
Anti-recontaminate ability is washed clean preceding former cloth (calico) and test after stain cloth with writing down color meter (Shimadzu Seisakusho Ltd.'s system) mensuration automatically, and the reflectivity under 460nm is obtained anti-recontaminate rate by following formula.
Anti-recontaminate rate (%)=(reflectivity of the reflectivity after the test/former cloth) * 100
Table 1
| Gradation composition (weight %) | The present invention's product | |||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | ||||
| (A) | (a) composition | Nonionic surfactant (1) | 50.0 | 40.0 | 40.0 | 40.0 | ||||
| Nonionic surfactant (2) | 50.0 | |||||||||
| Nonionic surfactant (3) | 60.0 | |||||||||
| Nonionic surfactant (4) | 60.0 | |||||||||
| Alkyl glycoside | 5.0 | |||||||||
| (b) composition | LAS-Na | 6.0 | 6.0 | 8.0 | 8.0 | 5.0 | 5.0 | |||
| ES-Na | 5.0 | |||||||||
| Lipid acid | 1.0 | |||||||||
| (B) | Macromolecular compound (1) | 3.0 | 3.0 | 3.0 | 3.0 | |||||
| Macromolecular compound (2) | 3.0 | |||||||||
| Macromolecular compound (3) | 2.0 | |||||||||
| Macromolecular compound (4) | 1.0 | |||||||||
| Polyacrylic acid Na (molecular-weight average 5,000) | ||||||||||
| Monoethanolamine | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | |||
| Ethanol | 3.0 | 3.0 | 3.0 | 3.0 | 5.0 | 5.0 | 5.0 | |||
| Propylene glycol | 3.0 | 3.0 | 3.0 | 8.0 | 8.0 | |||||
| デユラザイム16.0L | 0.5 | |||||||||
| リポラ-ゼ | 0.5 | |||||||||
| Tinopal CbsX CBS | 0.2 | 0.2 | ||||||||
| S-WAT | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | |||
| Spices | Trace | Trace | Trace | Trace | Trace | Trace | Trace | |||
| Water | Balance | Balance | Balance | Balance | Balance | Balance | Balance | |||
| Preserve stability | 50℃ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ||
| 5℃ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |||
| Preventing property of mud recontaminate | 91 | 92 | 91 | 92 | 92 | 89 | 89 | |||
Table 2
| Gradation composition (weight %) | The present invention's product | Product relatively | ||||||||
| 8 | 9 | 10 | 11 | 12 | 13 | 14 | ||||
| (A) | (a) composition | Nonionic surfactant (1) | 25.0 | 25.0 | 50.0 | 40.0 | 40.0 | |||
| Nonionic surfactant (2) | 10.0 | 20.0 | ||||||||
| Nonionic surfactant (3) | ||||||||||
| Nonionic surfactant (4) | ||||||||||
| Alkyl glycoside | 5.0 | |||||||||
| (b) composition | LAS-Na | 3.5 | 5.0 | 6.0 | 5.0 | |||||
| ES-Na | 10.0 | 20.0 | ||||||||
| Lipid acid | 1.0 | 1.0 | 1.0 | |||||||
| (B) | Macromolecular compound (1) | 5.0 | ||||||||
| Macromolecular compound (2) | ||||||||||
| Macromolecular compound (3) | ||||||||||
| Macromolecular compound (4) | 1.0 | |||||||||
| Polyacrylic acid Na (molecular-weight average 5,000) | 2.0 | 0.5 | 0.5 | 0.5 | ||||||
| Monoethanolamine | 4.0 | 5.0 | 4.0 | 4.0 | 4.0 | 5.0 | 5.0 | |||
| Ethanol | 2.0 | 2.0 | 3.0 | 5.0 | 2.0 | 2.0 | 2.0 | |||
| Propylene glycol | 10.0 | 1.0 | 3.0 | 3.0 | 3.0 | 3.0 | ||||
| デユラザイム16.0L | 0.2 | |||||||||
| リポラ-ゼ | 0.2 | |||||||||
| Tinopal CbsX CBS | 0.2 | |||||||||
| S-WAT | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | |||
| Spices | Trace | Trace | Trace | Trace | Trace | Trace | Trace | |||
| Water | Balance | Balance | Balance | Balance | Balance | Balance | Balance | |||
| Preserve stability | 50℃ | ○ | ○ | ○ | × | ○ | × | × | ||
| 5℃ | ○ | ○ | ○ | × | ○ | × | × | |||
| Preventing property of mud recontaminate | 90 | 89 | 74 | 92 | 82 | 86 | 80 | |||
● nonionogenic tenside (1): farm chemical emulgent 120 (trade(brand)name of Kao Corp, lauryl alcohol EO11.7 mole annexation)
● nonionogenic tenside (2): ソ Off ノ-Le 70 (trade(brand)name of Nippon Catalyst K. K., Sec-C12, C13 alcohol EO7.0 mole annexation)
● nonionogenic tenside (3): ノ ニ テ Star ト R-9 (commodity of シ エ Le ジ ヤ パ Application Co., Ltd., De バ ノ-Le 25 (C
12-C
15Alcohol, C
12=21.7%, C
13=28.2%, C
14=32.7%.C
15=17.4%) EO9.0 mole affixture)
● nonionogenic tenside (4): 12 carbon atoms, average EO addition mole number 8, the polyoxyethylene polyoxy-propylene of mean P O addition mole number 2
● alkyl glycoside: in general expression (a), R
5The alkyl of=8-16 carbon atom, X=0, Y=1.3, G=glucosyl residue
● the linear alkylbenzene sodium sulfate of LAS-Na:10-14 carbon atom
● ES-Na: Voranol EP 2001 sodium sulfate (alkyl of 10-12 carbon atom, average EO addition mole number 2.5)
● lipid acid: Le Na Star Network L-55 (merchant's name of Kao Corp, mixed fatty acid, its composition C
10=1%, C
12=57%.C
14=22%, C
16=10%, C
18=3%, C
18: 1=6%, C
18: 2=1%) (C
18: n) n represent the number of unsaturated link(age))
● デ ユ ラ ザ イ system 16.0L: proteolytic enzyme (trade(brand)name of ノ ボ ノ Le デ イ ス Network バ イ オ イ Application ダ ス ト リ-Co., Ltd.)
● リ Port デ-ゼ 100L: lipase (trade(brand)name of ノ ボ ノ Le デ イ ス Network バ イ オ イ Application ダ ス ト リ-Co., Ltd.)
● チ ノ パ-Le CBS-X: the trade(brand)name of Japanese チ バ ガ イ ギ-Co., Ltd., fluorescent dye
● balance: for will totally being taken as 100 the water yield.
Claims (7)
1. thick series liquid detergent composition, it is that amount of moisture dense thick below 60 weight % is cleaning agent composition, said composition contains the tensio-active agent of (A) 20-80 weight %, and nonionogenic tenside accounts for more than the 80 weight % in this tensio-active agent; (B) macromolecular compound of 0.1-15 weight %, it is on the main chain of polyether compound, graft polymerization a kind of macromolecular compound that contains based on single ethylene unsaturated monomer of vinylformic acid and/or methacrylic acid.
2. according to the composition of claim 1 record, wherein, nonionogenic tenside is the Voranol EP 2001 of average 5-15 mole ethylene oxide that has been selected from 1 yuan of 8-16 carbon atom or 2 yuan of alcohol addition, perhaps, on 1 yuan of alcohol of 8-16 carbon atom or 2 yuan of alcohol addition more than one in the polyoxyethylene polyoxy-propylene of average 5-15 mole ethylene oxide and average 1-5 mole propylene oxide.
3. according to the compositions of claim 1 or 2 records, wherein, the content of anion surfactant is in 15 (weight) below the %.
4. according to the composition of claim 1 record, wherein, (B) the main chain polyether compound of the macromolecular compound of composition is the compound by formula (1) expression
Y-O(CH
2CH
2O)
nH (1)
In the formula, Y is hydrogen, methyl, phenyl or benzyl, and n is average addition mole number, is 2-200.
5. according to the composition of claim 1 record, wherein, (B) macromolecular compound of composition is with respect to the main chain polyether compound, makes the single ethylene unsaturated monomer that contains aforesaid propylene acid and methacrylic acid, and the ratio more than at least 1/4 reacts and obtains by weight.
6. according to the composition of claim 1 record, wherein, (A) be (a) nonionogenic tenside and (b) mixture of anion surfactant.
7. according to the composition of claim 1 record, wherein, rest part is a water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22252896A JP3264837B2 (en) | 1996-08-23 | 1996-08-23 | Concentrated liquid detergent composition |
| JP222528/96 | 1996-08-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1178828A CN1178828A (en) | 1998-04-15 |
| CN1093879C true CN1093879C (en) | 2002-11-06 |
Family
ID=16783851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97118670A Expired - Fee Related CN1093879C (en) | 1996-08-23 | 1997-08-23 | Thick series liquid detergent composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3264837B2 (en) |
| CN (1) | CN1093879C (en) |
| TW (1) | TW460576B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3983398B2 (en) * | 1998-12-09 | 2007-09-26 | 花王株式会社 | Detergency improver |
| JP5014819B2 (en) * | 2007-02-02 | 2012-08-29 | 花王株式会社 | Liquid bleach detergent composition |
| JP5331412B2 (en) * | 2007-12-28 | 2013-10-30 | ライオン株式会社 | Liquid detergent composition |
| US8283303B2 (en) | 2008-09-10 | 2012-10-09 | Lion Corporation | Liquid detergent composition |
| JP5495640B2 (en) * | 2008-11-21 | 2014-05-21 | 花王株式会社 | Liquid detergent in containers |
| JP2010168429A (en) * | 2009-01-20 | 2010-08-05 | Kao Corp | Liquid detergent composition for hard surface |
| JP5571349B2 (en) * | 2009-03-02 | 2014-08-13 | 花王株式会社 | Liquid detergent composition |
| JP5548390B2 (en) | 2009-05-29 | 2014-07-16 | 花王株式会社 | Liquid detergent composition |
| EP2302026A1 (en) * | 2009-09-15 | 2011-03-30 | The Procter & Gamble Company | Detergent composition comprising surfactant boosting polymers |
| US20120157656A1 (en) * | 2010-12-17 | 2012-06-21 | Nippon Shokubai Co, Ltd | Polyalkylene glycol-based polymer and process for producing the same |
| JP6067409B2 (en) | 2012-04-10 | 2017-01-25 | 花王株式会社 | Method for improving solubility of alkaline protease |
| CN111615559B (en) | 2018-01-16 | 2024-01-16 | 花王株式会社 | Keratin dirt cleaning agent and method for evaluating Keratin dirt decomposing ability |
| JP7245676B2 (en) | 2019-03-11 | 2023-03-24 | 花王株式会社 | mutant protease |
| WO2021085563A1 (en) | 2019-10-30 | 2021-05-06 | 花王株式会社 | Leather improving agent |
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| JPS5925896A (en) * | 1982-05-10 | 1984-02-09 | ザ・プロクタ−・エンド・ギヤンブル・カンパニ− | Low phosphate laundry detergent composition |
| EP0639592A1 (en) * | 1993-08-18 | 1995-02-22 | Nippon Shokubai Co., Ltd. | Water-soluble graft polymers and production process thereof |
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| DE3711298A1 (en) * | 1987-04-03 | 1988-10-13 | Basf Ag | USE OF GASKET POLYMERISATS BASED ON POLYALKYLENE OXIDES AS GRAY INHIBITORS IN THE WASHING AND TREATMENT OF TEXTILE MATERIAL CONTAINING SYNTHESIS FIBERS |
| GB8821034D0 (en) * | 1988-09-07 | 1988-10-05 | Unilever Plc | Detergent compositions |
| CA2029631A1 (en) * | 1989-11-22 | 1991-05-23 | Kathleen A. Hughes | Graft polymers as biodegradable detergent additives |
| JPH0753993A (en) * | 1993-08-18 | 1995-02-28 | Nippon Shokubai Co Ltd | Builder and detergent composition |
| EP0770122B1 (en) * | 1994-07-14 | 1998-12-09 | Basf Corporation | Stable, aqueous concentrated liquid detergent compositions containing hydrophilic copolymers |
| JP2918798B2 (en) * | 1995-02-03 | 1999-07-12 | 株式会社日本触媒 | Water-soluble graft polymer, its production method and use |
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1996
- 1996-08-23 JP JP22252896A patent/JP3264837B2/en not_active Expired - Fee Related
-
1997
- 1997-08-08 TW TW86111386A patent/TW460576B/en not_active IP Right Cessation
- 1997-08-23 CN CN97118670A patent/CN1093879C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5925896A (en) * | 1982-05-10 | 1984-02-09 | ザ・プロクタ−・エンド・ギヤンブル・カンパニ− | Low phosphate laundry detergent composition |
| EP0639592A1 (en) * | 1993-08-18 | 1995-02-22 | Nippon Shokubai Co., Ltd. | Water-soluble graft polymers and production process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1060496A (en) | 1998-03-03 |
| TW460576B (en) | 2001-10-21 |
| JP3264837B2 (en) | 2002-03-11 |
| CN1178828A (en) | 1998-04-15 |
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