CN1159824A - Handwash laundry detergent compositions - Google Patents

Handwash laundry detergent compositions Download PDF

Info

Publication number
CN1159824A
CN1159824A CN95195446A CN95195446A CN1159824A CN 1159824 A CN1159824 A CN 1159824A CN 95195446 A CN95195446 A CN 95195446A CN 95195446 A CN95195446 A CN 95195446A CN 1159824 A CN1159824 A CN 1159824A
Authority
CN
China
Prior art keywords
alkyl
composition
acid
laundry detergent
preferred
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN95195446A
Other languages
Chinese (zh)
Inventor
A·D·M·布鲁克
S·包威尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of CN1159824A publication Critical patent/CN1159824A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • 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
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • 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
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Abstract

The present invention relates to a handwash laundry detergent composition comprising a surfactant system comprising anionic, cationic and nonionic surfactants in specific ratios. Said system provides improved overall cleaning and skin mildness benefits.

Description

Handwash laundry detergent compositions
Invention field
The present invention relates to Handwash laundry detergent compositions.This laundry detergent composition comprises a kind ofly can be provided improved cleaning and high foaming power and surfactant system to the gentle benefit of skin is provided, and this system comprises negatively charged ion, nonionic and cats product.
Background of invention
Use the detergent composition of synthetic detergent particle, liquid and stick form to wash the dirt clothing in global many areas.In the also not general area of washing machine, washing dirt clothing and fabric generally need be washed by hand washing methods.
The detergent composition that preparation is used to hand-wash fabric need provide the multiple performance benefit relevant with the human consumer, especially about cleaning, to the mildness and the foaming power of skin, it need be applicable to the wash conditions and the custom of wide region.
In order to satisfy the human consumer for cleaning and performance requriements, current Handwash laundry detergent compositions usually comprises high-load tensio-active agent.The prescription teacher who generally is applicable to the detergent composition of hand washing operation can mix high-load anion surfactant, especially linear alkylbenzene sulfonate and alkyl sulfate surfactant.Linear alkyl sulfonate surfactant has the ability of fabulous cleaning grease and oil-dirt owing to them and generally is used.Alkyl sulfate surfactant is desirable, because they have the performance of fabulous removal particulate fouling.In addition, this two classes tensio-active agent all is effective under the washing water condition of hot and cold.
Yet many anion surfactants, when particularly existing with high density, they can make pachylosis.The hand washing method comprises that user's hand and arm are exposed in the wash water solution that contains detergent composition.Be exposed to repeatedly in the washing soln in hand washing operation and can cause the skin irriate, this can finally cause skin injury or other skin lesion.The prescription teacher of Handwash laundry detergent has done many trials and has hand-washed the detrimental action of operating the user who uses this class Betengent product that hand and arm were produced to alleviate.Therefore a kind of laundry detergent composition that is applicable to the hand washing operation need be provided, and its reply user's skin has mildness to keep simultaneously or improves cleaning performance.
In addition, in certain areas, washing soln usually is recycled and reused for multiple washing operation.This causes the detergent active thing content to reduce and has increased dirt amount contained in the wash water solution.In addition, in order to remove dirt and spot well, detergent composition should provide the character of fabulous soil suspension to washings, and this also is important.This is even more important for washing heavy dirt fabric effectively.
In addition, the human consumer will to hand-wash the performance of detergent formulations general with their formation with keep the ability of high foam level to equate.Therefore this detergent for washing clothes that just need be used to hand-wash operation has foaming or foaming power highly.
Therefore, an object of the present invention is to provide a kind of Handwash laundry detergent compositions, it has at the improved cleaning performance of wide temperature range with to user's hand and arm and has the gentle benefit of skin.In addition, another object of the present invention provides a kind of detergent composition that keeps fabulous foaming or foaming feature.
Have now found that these purposes can be mixed accomplished by negatively charged ion, positively charged ion and nonionogenic tenside being pressed specified proportion.
The detergent composition that comprises negatively charged ion, nonionic and cats product that is used for automatic washing machine is described in prior art.Referring to for example EP-O000225, US4347168, US4321165, US4302364, EP-O051986 and US4259217.
U. S. application 08/078494 discloses the detergent composition that comprises with a certain proportion of polyhydroxy fatty acid amide and anion surfactant.United States Patent (USP) 2,982,737; 3,312,627 and 5,254,281 disclose cloth-washing detergent or the perfumed soap that comprises various tensio-active agents.
Summary of the invention
The present invention is a kind of Handwash laundry detergent compositions of the 15%-35% of comprising surfactant system, wherein surfactant system comprises negatively charged ion, nonionic and cats product, it is characterized in that said ionic surfactant pack draws together polyhydroxy fatty acid amide, with the ratio of said anion surfactant and said cats product be 3: 1 to 15: 1, the ratio of said cats product and said nonionogenic tenside is 2: 1 to 1: 10.
The invention still further relates to the method for washing dirt fabric, wherein said fabric carries out manual the contact with the laundry detergent composition according to the present invention of significant quantity in the aqueous solution.
Except as otherwise noted, all percentage ratios, amount and ratio are that weight by composition provides.
Detailed Description Of The Invention
The present invention is a kind of Handwash laundry detergent compositions, and it comprises 15%-35%, preferred 18%-30%, more preferably 18%-25% surfactant system.Said system comprises negatively charged ion, nonionic and cats product.
According to the present invention, the ratio of said anion surfactant and said cats product is 3: 1 to 15: 1, preferred 5: 1 to 15: 1, and most preferably 7: 1 to 15: 1.The ratio of said cats product and said nonionogenic tenside is 2: 1 to 1: 10, preferred 2: 1 to 1: 7, and more preferably 2: 1 to 1: 5.Found that said system has provided improved cleaning performance for the hand washing detergent composition.
Anion surfactant
According to the present invention, this detergent composition is included as the anion surfactant of essential feature.This anion surfactant can be any anion surfactant basically, comprises anion sulfate, sulfonate or carboxylate surface active agent.
According to the present invention, this detergent composition can comprise 8%-25%, preferred 10%-20%, the more preferably said anion surfactant of 12%-20%.
The anion sulfate acid salt surfactant
The anion sulfate acid salt surfactant can be any organic sulfate tensio-active agent.It is preferably selected from every mol of alcohol by about 0.5 C to about 20 moles of ethylene oxide ethoxylations 10-C 16Alkyl-sulphate, C 9-C 17Acyl group-N-(C 1-C 4Alkyl) glucosamine sulfate, C 9-C 17-N-(C 2-C 4Hydroxyalkyl) glucosamine sulfate and its mixture, wherein as at United States Patent (USP) 2,717, described in 894, C 9-C 17Acyl group is obtained by Oleum Cocois palm-kernel oil.More preferably, the anion sulfate acid salt surfactant is every mol of alcohol by about 0.5 to about 20, preferred about 0.5 C to about 12 moles of ethylene oxide ethoxylations 10-C 16Alkyl-sulphate.
Alkyl ethoxy sulfate surfactant comprises by C 10-C 16Alcohol and average about 0.5 to about 20, the preferred about 0.5 primary alkyl ethoxy sulfate that obtains to the condensation product of about 12 moles of ethylene oxide groups.C 10-C 16Alcohol itself is commercial buying.Every mol of alcohol is by about 3 C to about 10 moles of ethylene oxide ethoxylations 12-C 14Alkyl-sulphate is preferred.
The preparation average degree of ethoxylation is that the ethoxylation process of 12 conventional base catalysis has produced the distribution that every mol of alcohol has each ethoxylate of 1 to 15 mole of oxyethyl group, and therefore available several different methods obtains required average degree of ethoxylation.Mixture can be made of following material, promptly by adopting specific ethoxylation technology and procedure of processing thereafter, as the material with different ethoxylation degrees and/or the distribution of different ethoxylate of distillation generation.
The counterion of anion sulfate surface active agent composition is preferably selected from calcium, sodium, potassium, magnesium, ammonium or alkanol ammonium and its mixture, and calcium and magnesium are respectively preferred to cleaning and foaming.
The anion sulfoacid salt surfactant
Be applicable to that anionic sulphonate tensio-active agent of the present invention comprises, for example C 9-C 20The salt of linear alkyl benzene sulphonic acid, C 8-C 22Uncle or secondary paraffin sulfonate, C 8-C 24Alkene sulfonate, sulfonated poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil thiazolinyl glycerol sulfonate, paraffin sulfonate (for example an alkali metal salt) and its any mixture.
The negatively charged ion alkyl ethoxy carboxylate surfactant
Be applicable to that alkyl ethoxy carboxylate of the present invention comprises having formula: RO (CH 2CH 2O) xCH 2COO -M +Those materials, wherein R is C 12To C 16Alkyl, x scope are 0 to 10, and the distribution of ethoxylate is such, and by weight, wherein x is that 0 amount of substance is lower than 20%, preferably is lower than 15%, most preferably is lower than 10%; Wherein x is lower than 25% greater than 7 amount of substance, preferably is lower than 15%, most preferably is lower than 10%, when mean value R is C 13Or when lower, mean value x is about 2 to 4, when mean value R greater than C 13The time, mean value x is 3 to 6, and M is a positively charged ion, and it is preferably selected from basic metal, alkaline-earth metal, ammonium,, two and triethanol ammonium, most preferably is selected from the mixture of sodium, potassium, ammonium and itself and magnesium ion.Preferred alkyl ethoxy carboxylate is that those R wherein are C 12To C 14The alkyl ethoxy carboxylate of alkyl.
Negatively charged ion alkyl polyethoxye polycarboxylate tensio-active agent
Be applicable to that alkyl polyethoxye polycarboxylate tensio-active agent of the present invention comprises those materials with following formula:
Figure A9519544600061
Wherein R is C 6To C 18Alkyl, x are 1 to 25, R 1And R 2Be selected from hydrogen, methyl acid group, amber acidic group, hydroxy succinic acid base and its mixture, wherein at least one R 1Or R 2Be amber acidic group or hydroxy succinic acid base, R 3Be selected from hydrogen, have 1 to 8 carbon atom replacement or unsubstituted hydrocarbon and its mixture.
The secondary soap surfactant of negatively charged ion
The useful secondary soap surfactant (aka " alkyl carboxyl tensio-active agent ") of the present invention is to contain unitary those the secondary soap surfactants of the carboxyl that is connected on the secondary carbon(atom).People it will be appreciated that secondary carbon can be on the ring structure among the present invention, for example the secondary carbon on the cyclohexane carboxylic acid salt that the secondary carbon on the octyl group phenylformic acid or alkyl are replaced.This, soap surfactant should not contain ehter bond, ester bond and hydroxyl second month in a season.On end group (amphiphilic moieties), should not have nitrogen-atoms.Secondary soap surfactant contains 11-15 carbon atom altogether usually, but slightly a plurality of (for example as many as is 16) carbon atom also can be accepted, for example to the octyl group phenylformic acid.
Below generalized structure further illustrate useful some the secondary soap surfactants (or their precursor acids) of the present invention.
A. the useful secondary soap of a class very preferably of the present invention comprises formula: R 3CH (R 4) the secondary carboxyl material of COOM, wherein R 3Be CH 3(CH 2) x, R 4Be CH 3(CH 2) y, wherein y can be 0 or 1 to 4 integer, x is 4 to 10 integer, (x+y) and be 6-14, preferred 7-13 most preferably is 12.
B. the useful another kind of secondary soap of the present invention comprises carboxyl substituent those carboxylic compounds on the cyclic hydrocarbon group unit wherein, i.e. formula: R 5-R 6The secondary soap of-COOM, wherein R 5Be C 7-C 10, preferred C 8-C 9Alkyl or alkenyl, R 6Be ring texture, as benzene, pentamethylene and hexanaphthene.(note: R 5With respect to the carboxyl on the ring can be adjacent, or contraposition).
C. also have another kind of secondary soap to comprise formula: CH 3(CHR) k-(CH 2) m-(CHR) n-CH (COOM) (CHR) o-(CH 2) p-(CHR) q-CH 3Secondary carboxylic compound, wherein each R is C 1-C 4Alkyl, wherein k, n, o, q are the integer of 0-8, condition is that the sum of carbon atom (comprising carboxylate salt) is in 10 to 18 scopes.
In above each formula A, B and C, material M can be an any suitable, especially the counterion of water lyotropy, for example H, basic metal, alkaline-earth metal, ammonium, alkanol ammonium, two and three alkanol ammonium and C 1-C 5The ammonium that alkyl replaces.Sodium is easily, and the di-alcohol ammonium also is easily.
The preferred secondary soap surfactant that the present invention uses is water miscible, is selected from the water-soluble salt of following acid: 2-methyl isophthalic acid-undecanoic acid, 2-ethyl-1-capric acid, 2-propyl group-1-n-nonanoic acid, 2-butyl-1-are sad, 2-amyl group-1-enanthic acid and different pentadecylic acid.
Other also can be included in the present composition the useful anion surfactant of washing purpose.These salt that can comprise following material (comprise; for example the ammonium salt of sodium, potassium, ammonium and replacement as one, two and triethanolamine salt): the fatty acid amide of soap, fatty oil thiazolinyl glycerine vitriol, alkyl phenol epoxy ethane ether salt, alkylphosphonic, isethionate such as acyl isethinate, N-acyl taurine salt, N-methyltaurine, alkyl succinate, N-acyl sarcosinate, the primary alkyl sulphates of side chain, alkyl polyethoxye carboxylate salt, suc as formula RO (CH 2CH 2O) kCH 2COO -M +Those alkyl polyethoxye carboxylate salts, wherein R is C 8-C 22Alkyl, k are 0 to 10 integer, and M is the salt-forming cation of solubility and with the isethionic acid esterification and with sodium hydroxide neutral lipid acid.Resinous acid and hydrogenated resin acid also suit, as rosin, staybelite and the resinous acid and the hydrogenated resin acid that are present in the oil slick or are obtained by oil slick.Other example provides in " tensio-active agent and washing composition (Surface Active Agentand Detergents) " (Schwartz, Perry and Berch work, I and II volume).This a large amount of class tensio-active agents also is disclosed in United States Patent (USP) 3,929,678,23 hurdles 58 that licensed to people such as Laughlin on December 30th, 1975 prevailingly and walks in 29 hurdles, 23 row.
Nonionogenic tenside
According to the present invention, this detergent composition is included as the 1%-10% of essential feature, preferred 2%-8%, and more preferably 3%-7.5% nonionogenic tenside, it comprises polyhydroxy fatty acid amide.
The nonionic polyhydroxy fatty acid amide surfactant
The fatty acid amide surfactant that is fit to the present invention's use is those polyhydroxy fatty acid amides with following chemical formula:
Figure A9519544600081
R in the formula 1Be H or C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, and R 2Be C 5-C 31Alkyl, Z are to have at least 3 polyhydroxy alkyls that directly are connected in the hydroxyl on the straight-chain alkyl chain, or its alkoxy derivative.Preferred R 1Be methyl, R 2It is straight chain C 11-C 15Alkyl or alkenyl, as coconut alkyl or its mixture, Z is obtained as glucose, fructose, maltose, lactose by reducing sugar in the reductive amination reaction.
Other is applicable to that polyhydroxy fatty acid amide of the present invention is the two polyhydroxy fatty acid amides with following chemical formula: Wherein X has the about 2 abutment groups to about 200 atoms; Z and Z ' be identical or different have two or more hydroxyls contain alcohol moiety (glycerine and for example, the part that obtains as glucose, maltose etc.) by reducing sugar, perhaps among Z or the Z ' (but not being both) is a hydrogen; R and R ' are identical or different about 1 alkyl to about 21 carbon atoms that has, their can be saturated, side chain or unsaturated (for example oleoyl) and its mixtures.
Preferred X group is selected to have about 2 and replaces or unsubstituted, branched-chain or straight-chain alkyl, ether alkyl, aminoalkyl group or amidoalkyl part to about 15 carbon atoms.Preferred moieties is the unsubstituted formula-(CH that has 2) n-the straight chained alkyl part, wherein n is 2 to about 15 integer, preferred 2 to about 10, most preferably 2 to about 6 integer; Can also be to have 3 to about 15 carbon atoms, preferred 3 to about 10 carbon atoms, most preferably the 3 unsubstituted branched-chain alkyls to about 6 carbon atoms.Ethylidene and propylidene (side chain or straight chain) moieties most preferably.Also preferably has formula-R 2-(O-R 2) m-unsubstituted side chain or linear moieties, each R wherein 2Be independently selected from C 2-C 8Branched-chain or straight-chain alkyl and/or aryl moiety (preferred ethyl, propyl group or its combination), m is 1 to about 5 integer.X has formula-R 2-(N (R 3)-R 2) m-unsubstituted side chain or straight chain amino and/or amidoalkyl part, wherein each R 2Be independently selected from C 2-C 8Branched-chain or straight-chain alkyl and/or aryl (preferred ethyl, propyl group or its combination), m is 1 to about 5 integer, R 3Be selected from hydrogen, C 1-C 5Alkyl and-C (O) R 4, R wherein 4Be C 1-C 21Alkyl comprises-C (O) R.The X part can be by the commercial amine compound of buying, for example Jeffamines R(supplying with) by Texaco, as JED600, JEDR148, JEDR192, JED230, JED2000, J-D200 and J-D400 obtain.
Therefore preferred X partly comprises :-(CH 2) 2-,-(CH 2) 3-,-(CH 2) 4-,-(CH 2) 5-,-(CH 2) 6-,-CH 2CH (CH 3) (CH 2) 3-,-(CH 2) 2-O-(CH 2) 2-,-(CH 2) 3-O-(CH 2) 3-,-(CH 2) 2-O-(CH 2) 3-,-(CH 2) 2-O-(CH 2) 2-O-(CH 2) 2-,-(CH 2) 3-O-(CH 2) 2-O-(CH 2) 3-,-(CH 2) 2-O-(CH 2) 3-O-(CH 2) 2-,-(CH 2) 2-NH-(CH 2) 2-,-(CH 2) 3-NH-(CH 2) 3-,-(CH 2) 2-NH-(CH 2) 3-,-(CH 2) 2-N (C (O) R)-(CH 2) 2-,-(CH 2) 3-N (C (O) R)-(CH 2) 3-,-(CH 2) 2-N (C (O) R)-(CH 2) 3-,-(CH 2) 2-NH (C 6H 4) NH-(CH 2) 2-,-(CH 2) 3-NH (C 6H 4) NH-(CH 2) 3-,-(CH 2) 2-NHCH 2(C 6H 4) CH 2NH-(CH 2) 2-,-(CH 2) 3-NHCH 2(C 6H 4) CH 2NH-(CH 2) 3-, etc.
Preferred Z and Z ' group are independently selected from least two hydroxyls (when being glycerine) or at least 3 hydroxyls (when being other sugar) directly are connected in the polyhydroxy alkyl on the straight-chain alkyl chain, or its alkoxy derivative (preferred ethoxylation or propoxylation).Z and Z ' are preferably obtained by reducing sugar, and more preferably Z and/or Z ' are glycosyls.Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar, and Glycerose.The same high glucose maize treacle, high-fructose corn syrup and the high malt sugar maize treacle that can use with above listed monose to raw material form.These maize treacle can produce the sugar component mixture of Z and Z '.Be understood that this does not mean that other suitable raw material of eliminating.Z and/or Z ' are preferably selected from-CH 2-(CHOH) p-CH 2OH ,-CH (CH 2OH)-(CHOH) P-1CH 2OH ,-CH 2-(CHOH) 2(CHOR ') (CHOH)-CH 2OH, wherein p is 1 to 5 integer, comprises 1 and 5, R ' is H or ring-type single or many saccharidess and its oxyalkylated derivative.Most preferably wherein p is 4 glycosyl, particularly-and CH 2-(CHOH) 4-CH 2OH.
Preferred R and R ' group are independently selected from C 3-C 21Alkyl, preferred straight or branched C 3-C 13Alkyl or alkenyl, more preferably straight chain C 5-C 11Alkyl or alkenyl, most preferably straight chain C 5-C 9Alkyl or alkenyl, or its mixture.R-CO-N＜and/or R '-CO-N＜can be, for example coconut monoethanolamide, stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitic amide, butter acid amides etc.
Therefore the example of this compounds includes, but are not limited to: CH 3(CH 2) 6C (O) N[CH 2(CHOH) 4CH 2OH]-(CH 2) 2-[CH 2(CHOH) 4CH 2OH] NC (O) (CH 2) 6CH 3CH 3(CH 2) 8C (O) N[CH 2(CHOH) 4CH 2OH]-(CH 2) 2-[CH 2(CHOH) 4CH 2OH] NC (O) (CH 2) 8CH 3CH 3(CH 2) 10C (O) N[CH 2(CHOH) 4CH 2OH]-(CH 2) 2-[CH 2(CHOH) 4CH 2OH] NC (O) (CH 2) 10CH 3CH 3(CH 2) 8C (O) N[CH 2(CHOH) 4CH 2OH]-(CH 2) 2-O-(CH 2) 2-O-(CH 2) 2-[CH 2(CHOH) 4CH 2OH] NC (O) (CH 2) 8CH 3CH 3(CH 2) 8C (O) N[CH 2(CHOH) 4CH 2OH]-CH 2CH (CH 3) (CH 2) 3-[CH 2(CHOH) 4CH 2OH] NC (O) (CH 2) 8CH 3CH 3(CH 2) 8C (O) N[CH 2(CHOH) 4CH 2OH]-(CH 2) 3-O-(CH 2) 2-O-(CH 2) 3-[CH 2(CHOH) 4CH 2OH] NC (O) (CH 2) 8CH 3CH 3(CH 2) 3CH (CH 2CH 3) C (O) N[CH 2(CHOH) 4CH 2OH]-(CH 2) 2-[CH 2(CHOH) 4CH 2OH] NC (O) CH (CH 2CH 3) (CH 2) 3CH 3CH 3(CH 2) 6C (O) N[CH 2(CHOH) 4CH 2OH]-(CH 2) 3-O-(CH 2) 2-O-(CH 2) 3-[CH 2(CHOH) 4CH 2OH] NC (O) (CH 2) 6CH 3CH 3(CH 2) 4C (O) N[CH 2(CHOH) 4CH 2OH]-(CH 2) 3-O-(CH 2) X-O-(CHX) 3-[CH 2(CHOH) 4CH 2OH] NC (O) (CH 2) 8CH 3C 6H 5C (O) N[CH 2(CHOH) 4CH 2OH]-(CH 2) 3-O-(CH 2) 2-O-(CH 2) 3-[CH 2(CHOH) 4CH 2OH] NC (O) C 6H 5CH 3(CH 2) 4C (O) N[CH 2(CHOH) 4CH 2OH]-(CH 2) 2-[CH 2(CHOH) 4CH 2OH] NC (O) (CH 2) 8CH 3
These compounds can be easily synthetic by following disaccharides diamines:
HN[CH 2(CHOH) 4CH 2OH]-(CH 2) 2-[CH 2(CHOH) 4CH 2OH]NH；
HN[CH 2(CHOH) 4CH 2OH]-CH 2CH(CH 3)(CH 2) 3-[CH 2(CHOH) 4CH 2OH]NH；
HN[CH 2(CHOH) 4CH 2OH]-(CH 2) 2-O-(CH 2) 2-O-(CH 2) 2-[CH 2(CHOH) 4CH 2OH]NH；
HN[CH 2(CHOH) 4CH 2OH]-(CH 2) 3-O-(CH 2) 2-O-(CH 2) 3-[CH 2(CHOH) 4CH 2OH] NH; With
HN[CH 2(CHOH) 4CH 2OH]-(CH 2) 3-[CH 2(CHOH) 4CH 2OH]NH。
According to the present invention, nonionogenic tenside also can comprise other nonionogenic tenside except polyhydroxy fatty acid amide, especially oxyalkylated nonionogenic tenside.
The alkylphenol condensation of nonionic
The polyethylene oxide of alkylphenol, poly(propylene oxide) and polybutylene oxide condenses be applicable to of the present invention.Generally, polyethylene oxide condensation compound is preferred.These compounds comprise having and contain about 6 to the alkylphenol of about 12 carbon atoms alkyl that is the straight or branched configuration and the condensation product of alkylene oxide.
The ethoxylated alcohol surfactant of nonionic
Fatty alcohol and about 1 alkyl ethoxylated condensation product to about 25 moles of ethylene oxide be applicable to of the present invention.The alkyl chain of fatty alcohol can be straight or branched, uncle or secondary, contain 6 to 22 carbon atoms usually.Particularly preferably be every mol of alcohol and have alcohol and about 2 the condensation products that contain 8 to 20 carbon atom alkyls to about 10 moles of ethylene oxide.Most preferably every mole has alcohol and about 3 condensation products to about 9 moles of ethylene oxide that contain 8 to 14 carbon atom alkyls.The example of commercial this type nonionogenic tenside of buying comprises Tergitol TM15-S-9 (C 11-C 15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Tergitol TM24-L-6NMW (C 12-C 14The condensation product of primary alconol and 6 moles of ethylene oxide has narrow molecular weight distribution), the both sells by Union Carbide Corporation; Neodol TM45-9 (C 14-C 15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Neodol TM23-6.5 (C 12-C 13The condensation product of straight chain alcohol and 6.54 moles of ethylene oxide), Neodol TM45-7 (C 14-C 15The condensation product of straight chain alcohol and 7 moles of ethylene oxide), Neodol TM45-4 (C 14-C 15The condensation product of straight chain alcohol and 4 moles of ethylene oxide), Neodol TM23-3 (C 12-C 13The condensation product of straight chain alcohol and 3 moles of ethylene oxide), Dobanol TMC 12-C 15E5 (C 12-C 15The condensation product of straight chain alcohol and 5 moles of ethylene oxide), all sell by ShellChemical Company, and Kyro TMEOBN (C 13-C 15The condensation product of alcohol and 9 moles of ethylene oxide), by The Procter ﹠amp; Gamble Company sells, and Dobanol91 and Dobanol 25 are sold by Shell Chemical Company, and Lial111 is sold by Enichem.
EO/PO condenses nonionic and propylene glycol
The hydrophobic group thing that forms by propylene oxide and propylene glycol condensation and the condensation product of oxyethane be applicable to of the present invention.The example of this type compound comprises some commercial Pluronic that buy TMTensio-active agent is sold by BASF.
Nonionic and EO condensation product propylene oxide/quadrol affixture
The product that obtains by propylene oxide and reacting ethylenediamine and the condensation product of oxyethane be applicable to of the present invention.The example of such nonionogenic tenside comprises some commercial Tetronic that buy TMCompound is sold by BASF.
The nonionic alkyl polysaccharide surfactant
Be applicable to that alkyl polysaccharide of the present invention is disclosed in the United States Patent (USP) 4 of the Llenado that authorized on January 21st, 1986,565, in 647, it has and contains about 6 to about 30 carbon atoms, preferred about 10 hydrophobic group and polysaccharide to about 16 carbon atoms, for example many glycosides, its hydrophilic group contain has an appointment 1.3 to about 10, preferred about 1.3 to about 3, most preferably from about 1.3 to 2.7 saccharides unit.Can use any reducing sugar that contains 5 or 6 carbon atoms, for example glucose, semi-lactosi and galactosyl part can replace glucosyl group part (hydrophobic group randomly is connected in positions such as 2-, 3-, 4-, has provided glucose or semi-lactosi corresponding to glucoside or galactoside like this).Key can be between 2-, 3-, 4-and/or 6-position on additional unitary a kind of position of saccharides and the previous saccharides unit between sugar.Preferred alkyl polysaccharide has following formula:
R 2O (C nH 2nO) t(glycosyl) x
R in the formula 2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and its mixture, alkyl wherein contains 10 to 18, preferred 12 to 14 carbon atoms; N is 2 or 3, and x is 0 to 10, and preferred about 1.3 to about 3, and most preferably from about 1.3 to about 2.7, and t is 0 to 10.Glycosyl preferably comes from glucose.
Cats product
According to the present invention, another neccessary composition of the present composition is a cats product.Detergent composition of the present invention comprises 0.1% to 10%, preferred 0.5%-5%, most preferably 0.5%-3% cats product.
Be applicable to those that cats product of the present invention is a following formula:
R m 1R x 2Y LZ is each R wherein 1Be the organic group that contains straight or branched alkyl or alkenyl, said alkyl or alkenyl are optional to be replaced by 3 phenyl of as many as or hydroxyl, and randomly is inserted into 4 structures that are selected from following group and composition thereof of as many as:
Figure A9519544600131
-O-,
Figure A9519544600132
And R 1Contain 8 to 22 carbon atoms of having an appointment.R 1Group can contain 12 ethoxy groups of as many as in addition.M is 1 to 3 numerical value.When m is 2, a no more than R in molecule 1Group can have 16 or more a plurality of carbon atom, or when m is 3, a no more than R 1Group can have no more than 12 carbon atoms.Each R 2Group is alkyl or the hydroxyalkyl that contains 1 to 4 carbon atom, or benzyl, a no more than R in molecule 2Group is a benzyl, and x is 0 to 11 number, preferred 0 to 6.Any carbon atom position that stays on Y group replaces with hydrogen.Y is selected from: , wherein p is 1 to 12
Figure A9519544600135
, wherein p is 1 to 12
Figure A9519544600141
And composition thereof.L is 1 or 2, and when L was 2, Y group is selected from had 1 to 22 carbon atom and two single bonded and R of free carbon 1And R 2Similarly group (preferred alkylidene group or alkenylene) separately.Z is for example halogenide, vitriol, Methylsulfate, oxyhydroxide or a nitrate anions of water soluble anion, preferred especially chlorine, bromine, iodine, vitriol or methylsulfuric acid salt anionic, and its quantity is to make this cationic components reach electric neutrality.
The example of this cationoid tensio-active agent comprises the ammonium salt tensio-active agent, has the tensio-active agent of following formula such as alkyl dimethyl ammonium halide and those:
[R 2(OR 3) y] [R 4(OR 3) y] 2R 5N +X -R wherein 2Be one and in its alkyl chain, contain about 8 alkyl or alkyl benzyls to about 18 carbon atoms; Each R 3Be to be selected from-CH 2CH 2-,-CH 2CH (CH 3)-,-CH 2CH (CH 2OH)-,-CH 2-CH 2-CH 2-these groups or their mixture; When the y value is not zero, each R 4Be to be selected from C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, by connecting two R 4The benzyl ring texture that group forms ,-CH 2-CHOH-CHOH-COR 6CHOHCH 2OH, R wherein 6Be any molecular weight less than group and hydrogen such as about 1,000 hexose or hexose polymkeric substance; R 5Be and R 4Identical group, or alkyl chain, wherein a R 2And R 5The total number of carbon atoms be no more than about 18; Each y value can be from about 0 to about 10, and the y value and be 0 to about 15; X is any suitable negatively charged ion.
The preferred cationic surfactants that is used for the present composition is the soluble quaternary ammonium compound with following formula:
R 1R 2R 3R 4N +X -(i) R wherein 1Be C 8-C 16Alkyl, each R 2, R 3And R 4Can be C independently of one another 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, benzyl and-(C 2H 4O) xH, x value wherein can from 1 to 5, and X is a negatively charged ion.R 2, R 3Or R 4In can not to have more than one be benzyl.
Preferred R 1The chain length of alkyl is C 12-C 15, particularly wherein alkyl is a mixture by cocounut oil or palm-kernel fat deutero-alkyl chain length, or by the synthetic and deutero-alkyl of alkene or OXO alcohol.Preferred R 2, R 3And R 4Group is methyl and hydroxyethyl, and negatively charged ion X can be selected from halogenide, methylsulfate, acetate moiety and phosphate anion.
The example of the suitable quarternary ammonium salt compound that the present invention uses has:
Cocounut oil alkyl trimethyl ammonium muriate or bromide;
Cocounut oil alkyl methyl dihydroxy ethyl ammonium muriate or bromide;
The decyl trimethyl ammonium chloride;
Decyl dimethyl hydroxyethyl ammonium muriate or bromide;
C 12-15Dimethyl hydroxyethyl ammonium muriate or bromide;
Cocounut oil alkyl dimethyl hydroxyethyl ammonium muriate or bromide;
Myristyl trimethyl ammonium Methylsulfate;
Lauryl dimethyl hexadecyldimethyl benzyl ammonium muriate or bromide;
Lauryl dimethyl (oxyethyl group) 4 ammonium muriates or bromination and cholinesterase.The useful cats product of other the present invention also is described in United States Patent (USP) 4,228, in 044.
The surfactant system of detergent composition of the present invention also can contain 0.1%-10% except comprising negatively charged ion, nonionic and cats product, preferred 0.5%-3% both sexes or zwitterionics and its mixture.
Both sexes (amphoteric) tensio-active agent
Be applicable to that amphoterics of the present invention comprises the alkyl both sexes carboxylic acid of following formula:
Figure A9519544600151
R is C in the formula 8-C 18Alkyl, Ri has general formula:
Figure A9519544600152
Or
Figure A9519544600153
R in the formula 1Be (CH 2) xCOOM or CH 2CH 2OH, x are 1 or 2, and M is preferably selected from basic metal, alkaline-earth metal, ammonium,, two and trolamine, most preferably are selected from the mixture of sodium, potassium, ammonium and itself and magnesium ion.Preferred R alkyl chain length is C 10-C 14Alkyl chain.Preferred both sexes carboxylic acid is served as reasons, and fatty tetrahydroglyoxaline makes, and wherein the dicarboxylic acid functional group of both sexes dicarboxylic acid is oxalic acid and/or dipropionic acid.The suitable example of the alkyl both sexes dicarboxylic acid that the present invention uses is by Miranol, Inc., Dayton, amphoterics Miranol (TM) the C2M Conc that NJ produces.
Zwitterionics
In the preferred embodiment of the invention, this detergent composition also comprises zwitterionics for example trimethyl-glycine and sultaine.
Beet alkali surface activator
The trimethyl-glycine that is suitable for is to have formula: R (R ') 2N +R 2COO -Those compounds, R is C in the formula 6-C 18Alkyl, preferred C 10-C 16Alkyl or C 10-C 16The acyl group amidoalkyl, each R 1Generally be C 1-C 3Alkyl, preferable methyl; R 2Be C 1-C 5Alkyl, preferred C 1-C 3Alkylidene group, more preferably C 1-C 2Alkylidene group.The example of suitable trimethyl-glycine comprises coconut acyl group amido propyl-dimethyl trimethyl-glycine; The hexadecyldimethyl benzyl ammonium trimethyl-glycine; C 12-14The acyl group amido propyl betaine; C 8-14Acyl group amido hexyl diethyl betaines; 4[C 14-16Acyl group methyl amido diethyl ammonium (ammonio)]-1-carboxyl butane; C 16-18Acyl group amido dimethyl betaine; C 12-16Acyl group amido pentane diethyl betaines; [C 12-16Acyl group methyl amido dimethyl betaine.Preferred trimethyl-glycine is C 12-18Dimethyl Ammonium hexanoate and C 10-C18Acyl group amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.
The coordination trimethyl-glycine that the present invention uses has following formula:
Figure A9519544600161
R is the alkyl with 7 to 22 carbon atoms in the formula, and A is (C (O)) group, and n is 0 or 1, R 1Be hydrogen or low alkyl group, x is 2 or 3, and y is 0 to 4 integer, and Q is-R 2COOM group, wherein R 2For having the alkylidene group of 1 to 6 carbon atom, M is hydrogen or the ion that is selected from the ammonium of basic metal, alkaline-earth metal, ammonium and replacement, and B is hydrogen or Q group as defined above.
Sultaine
Useful sultaine is to have formula R (R among the present invention 1) 2N +R 2SO 3 -Those compounds, wherein R is C 6-C 18Alkyl, preferred C 10-C 16Alkyl, more preferably C 12-C 13Alkyl, each R 1Be generally C 1-C 3Alkyl, preferable methyl; R 2Be C 1-C 6Alkyl, preferred C 1-C 3Alkylidene group or preferred hydroxy alkylidene.The example of suitable sultaine comprises C 12-C 14Dimethyl Ammonium (ammonio)-2-hydroxypropyl sulfonate, C 12-14Amido propyl ammonium-2-hydroxypropyl sultaine, C 12-14Dihydroxy ethyl ammonium propane sulfonate and C 16-18Dimethyl Ammonium hexane sulfonate, C 12-14Amido propyl ammonium-2-hydroxypropyl sultaine is preferred.
Amine oxide surfactant
Composition of the present invention also can comprise the amine oxide as optional member.The useful amine oxide of the present invention comprises those compounds with following formula:
Figure A9519544600171
R in the formula 3Be selected from and contain 8 to 26 carbon atoms, the alkyl of preferred 8 to 16 carbon atoms, hydroxyalkyl, acyl group amido propionyl and alkyl phenyl, or its mixture; R 4For containing 2 to 3 carbon atoms, the alkylidene group of preferred 2 carbon atoms or hydroxyl alkylidene group, or its mixture, x is 0 to 3, is preferably 0; Each R 5Be and contain 1 to 3, the alkyl or the hydroxyalkyl of preferred 1 to 2 carbon atom, or, be preferably the polyethylene oxide group of 1 ethylene oxide group for containing 1 to 3.R 5Group can be connected to each other, and for example forms ring texture by oxygen or nitrogen-atoms.
These amine oxide surfactants especially comprise C 10-C 18Alkyl dimethyl amine oxide and C 8-C 12Alkoxyethyl dihydroxy ethyl amine oxide.These examples of substances comprise dimethyloctylamine oxide, diethyl decyl amine oxide, two-(2-hydroxyethyl) dodecyl amine oxide, dimethyl dodecyl amine oxide, dipropyl tetradecyl amine oxide, methylethyl hexadecyl amine oxide, dodecyl amido propyl-dimethyl amine oxide and dimethyl-2-hydroxyl octadecyl amine oxide.Preferred C 10-C 18Alkyl dimethyl amine oxide and C 10-C 18Acyl group amidoalkyl dimethyl oxidation amine.
Composition of the present invention can be included as the detergent additives of optional member, and it is selected from SYNTHETIC OPTICAL WHITNER, bleach-activating agent, enzyme, polymeric anti redeposition agent, polymeric dispersant, polymerization dirt release agent, sequestrant, washing assistant, dye transfer inhibitor and its mixture.
Enzyme-for the purpose of multiple laundering of textile fabrics, comprise and for example remove spot protein-based, carbohydrate-based or the triglycerin ester group, and the dye migration that comes off for inhibitor and for the recovery of fabric can comprise enzyme in preparation of the present invention.The enzyme that can mix comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase, with and composition thereof.The enzyme that also can comprise other type.They can be from any suitable source, as plant, animal, bacterium, mould and yeast source.Yet their selection determines by Several Factors, as pH-activity and/or optimal stability point, thermostability, to stability of activated detergent and washing assistant etc.Aspect this, bacterial enzyme or fungous enzyme are preferred, as bacterial amylase and proteolytic enzyme, and the mould cellulase.
Enzyme is impregnated in enough amounts usually so that as many as about 5 milligrams (weight) in every gram composition to be provided, and is generally about 0.01 to about 3 milligrams organized enzyme.Explanation is in addition, and composition herein generally comprises about 0.001% to about 5%, preferred 0.01% to 1% (weight) commercial enzyme goods.The proteolytic enzyme amount in this article of commerce usually is enough to guarantee that every gram composition has 0.005 activity to 0.1Anson unit (AU).
Suitable examples of proteases is a subtilisin, and it is that special bacterial strain by Bacillus subtillis and bacillus licheniformis obtains.Another kind of suitable proteolytic enzyme is obtained by bacillus strain, wherein has maximum activity in the pH8-12 scope, and by Novo Industries A/S exploitation and sale, the trade name of registration is ESPERASE.The preparation of this kind of enzyme and similar enzyme is described in the british patent specification 1243784 of Novo.The commercial commercially available suitable proteolytic ferment of removing protein-based spot comprises to be sold by Novo Industries A/S (Denmark), commodity ALCALASE by name and SAVINASE, with by International Bio-Synthetics, the MAXATASE that Inc. (Holland) sells.Other proteolytic enzyme comprises that protease A is (referring to european patent application 130756,1985.01.09 open) and proteolytic enzyme B (referring to european patent application series number 87303761.8,1987.04.28 people's such as application and Bott the disclosed european patent application 130756 of 1985.01.09).
Amylase comprises α-Dian Fenmei, the International Bio-Synthetics that for example describes in british patent specification 1296839 (Novo), the TERMAMYL that RAPIDASE that Inc. sells and Novo Industries sell.
The cellulase that can be used among the present invention comprises bacterium and mould cellulase.Preferably they have best pH scope 5-9.5.Suitable cellulase is disclosed in the United States Patent (USP) 4435307 of authorizing in 6 days March in 1984 of people such as Barbesgoard, it discloses the cellulase that extracts by in Humicola insolens and rotten cellulase 212 of planting mould cellulase that trichoderma strain DSM1800 produces or being produced by the mould that belongs to Aeromonas and the hepatopancreas by extra large mollush (Dolabella A ù riculaSolander).Suitable cellulase also is disclosed in GB-A-2075028; Among GB-A-2095275 and the DE-OS-2247832.CAREZYME (Novo) is a particularly suitable.
The spendable suitable lipase of washing composition comprises by the microorganism in the Rhodopseudomonas family, as those lipase of Situ Ci Shi (stutzeri) aeruginosa atcc 19.154 generations, as is disclosed in the English Patent 1372034.Also referring to the lipase in the Japanese patent application 53-20487 of open special permission on February 24th, 1978.This lipase can be by Amano PharmaceuticalCo.Ltd., Nagoya, and Japan has bought, and commodity are called lipase P " Amano ", hereinafter are referred to as " Amano-P ".Other commercial lipase comprises Amano-CES, from the lipase of Chromobacter viscosum, for example, Chromobacter viscosum var.lipolyticum NRRLB3673, commercial can be by Toyo Jozo Co., Tagata, Japan has bought; With other pigment bacillus viscosum lipase, by U.S.Biochemical Corp., USA and Disoynth Co., Holland has bought and from the lipase of gladiolus pseudomonas (Pseudomonasgladioli).Plant that Pseudomonas fetal hair bacterium (Humicola lanuginosa) obtains and be the preferred fat enzyme that is used for herein by corruption at the commercial LIPOLASE enzyme that can buy by Novo (equally referring to EPO34197).
Peroxidase is and oxygen source that for example percarbonate, perborate, persulphate, hydrogen peroxide etc. are used in combination.They are used for " liquid lime chloride ", promptly are suppressed on the dyestuff that comes off from basic thing in the washing process or pigment migration other basic thing to the washing soln.Peroxidase is being known in the art, comprises for example horseradish peroxidase, lignoenzyme and halo peroxidase, as chloro and bromoperoxidase.The detergent composition that contains peroxidase is disclosed in, and for example in the PCT International Application No. WO 89/099813, on October 19th, 1989 is open, transfers Novo Industries A/S by O.Kirk.
Various enzyme materials and the method that they are mixed in the synthetic detergent particle also are disclosed in the United States Patent (USP) 3553139 that licensed to people such as McCarty on January 5th, 1971.Some enzymes also be disclosed in the people's such as Place that authorized on July 18th, 1978 United States Patent (USP) 4101457 and the people's such as Hughes that authorized on March 26th, 1985 United States Patent (USP) 4507219 in.Be used for the enzyme material of liquid detergent preparation and they and be incorporated into method in these preparations and be disclosed in and authorized on April 14th, 1981, in people's such as Hora the United States Patent (USP) 4261868.The enzyme that is used for washing composition can make its stabilization with various technology.The enzyme stabilization technology is open and illustrate United States Patent (USP) 3600319 and the European patent application publication No. 0199405 that licenses to people such as Gedge on August 17th, 1971, and application number is open on October 29th, 86200586.5,1986, Venegas.The enzyme stabilization system for example also is described in the United States Patent (USP) 3519570.
Enzyme stabilizers-enzyme used herein can be by being stabilized in the presence of the water dissolvable calcium in the composition finished product and/or magnesium ion thing source (it provides this ion to enzyme).(if calcium ion generally slightly is effective in magnesium ion and only uses one type positively charged ion, and calcium ion is that the present invention is preferred).Stability in addition can obtain under especially borate family exists by at the disclosed stablizer of various other prior aries.U.S.4537706 referring to Severson.General washing composition, especially liquid comprises by every liter of composition finished product about 1 to about 30, preferred about 2 to about 20, and more preferably from about 5 to about 15, most preferably from about 8 calcium ions to about 12 mmoles.It can slightly change according to the amount of the enzyme that exists and the enzyme responsive to calcium ion or magnesium ion.Should select the amount of calcium or magnesium ion like this, make its with composition in complexing such as washing assistant, lipid acid after, for enzyme, always have available minimum.Any water-soluble calcium or magnesium salts all can be used as calcium or magnesium ion thing source, and it comprises that but non-limiting in this, calcium chloride, calcium sulfate, calcium malate, calcium maleate, sodium hydroxide, calcium formiate and lime acetate reach corresponding magnesium salts.Because enzyme slurries and prescription contain calcium ion in the water, make this small amount of calcium ion, general about 0.05 to about 0.4 mmole/liter, also often be present in the composition.In solid detergent composition, the water-soluble calcium ion thing source that can comprise q.s in the preparation is to be provided at required amount in the laundry aqueous solution.On the other hand, natural water hardness may be enough.
The amount that it should be understood that above-mentioned calcium and/or magnesium ion is enough to guarantee enzyme stability.The supplementary means to provide realization that grease is removed in the composition can be provided for more calcium and/or magnesium ion.Therefore, composition of the present invention generally comprise into the said composition conventional amount used about 0.05% to about 2% (weight) water-soluble calcium or magnesium ion thing source, or the two.Certainly this amount can change with the amount and the type of employed enzyme in the composition.
The present composition also can be randomly, but preferably contain various other stablizers, especially borate family stablizer.Generally, the consumption of this stablizer in composition is calculated as about 0.25% to about 10% by the boric acid in the composition or other borate compound (calculating based on boric acid) that can form boric acid, preferred about 0.5% to about 5%, and more preferably from about 0.75% to about 3% (weight).Though other compound is to suit as boron oxide, borax and other alkali metal borate (for example ortho-boric acid sodium, sodium metaborate and sodium pyroborate and penta borate), preferred boric acid.The boric acid that replaces (for example, phenyl-boron dihydroxide, butane boric acid and to bromophenyl boric acid) also can replace boric acid to use.
Bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach-activating agent
Detergent composition of the present invention can randomly contain SYNTHETIC OPTICAL WHITNER or contain SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or more bleach-activating agents.When containing SYNTHETIC OPTICAL WHITNER, the amount of SYNTHETIC OPTICAL WHITNER be generally detergent composition about 1% to about 30%, more preferably from about 5% to about 20%.If contain bleach-activating agent, its content is generally about 0.1% to about 60%, more preferably about 0.5% to about 40% of the bleaching composition that contains SYNTHETIC OPTICAL WHITNER and bleach-activating agent.
SYNTHETIC OPTICAL WHITNER used herein can be to detergent composition at fabric cleaning, hard surface cleaning or other known now or with known cleaning use in useful any SYNTHETIC OPTICAL WHITNER.It comprises oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.Preferred oxygen bleaching agent is a perhydrate, for example percarbonate and perborate, for example Sodium peroxoborate of list or tetrahydrate form.
Unrestricted operable another kind of SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The example that is fit to of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium, 4-nonyl amino-4-oxo Perbutyric Acid magnesium and diperoxy dodecanedioic acid magnesium.These SYNTHETIC OPTICAL WHITNER are disclosed in the United States Patent (USP) 4483781 of the Hartman that authorized on November 20th, 1984, in the people's such as Chung that U.S. Patent application 20, people's such as disclosed Banks in 740446,1985 on February of the people such as Burns of application on June 3rd, 1985 european patent application 0133354 and November 1 nineteen eighty-three authorize the United States Patent (USP) 4412934.SYNTHETIC OPTICAL WHITNER very preferably also comprises 6-amino in the ninth of the ten Heavenly Stems-6-oxo-mistake oxy hexanoic acid of describing as in the United States Patent (USP) 4634551 that licenses to people such as Burns on January 6th, 1987.
Also can use peroxygen bleach.The peroxy bleaching compound that is fit to comprises carbonate peroxyhydrate and its equivalent " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.Also can use persulphate SYNTHETIC OPTICAL WHITNER (for example, OXONE is by the DuPont commercial production).
A kind of preferred percarbonate bleach comprise mean particle size be about 500 microns to about 1000 microns dried particles, less than no more than about 10% (weight) of about 200 microns described particle, greater than no more than about 10% (weight) of about 1,250 micron described particle.Percarbonate can randomly use silicate, borate or water soluble surfactant active to coat.Percarbonate can be obtained by various commercial things source, for example FMC, Solvay and Tokai Denka.
Also can use the mixture of SYNTHETIC OPTICAL WHITNER.Peroxygen bleach, perborate, percarbonate etc. preferably are used in combination with bleach-activating agent, and this causes producing on the spot the peroxy acid corresponding to bleach-activating agent in the aqueous solution (promptly at washing process).The various non-limiting examples of activator are disclosed in the United States Patent (USP) 4915854 and United States Patent (USP) 4412934 that licenses to people such as Mao April 10 nineteen ninety.Nonanoly acyloxy benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) activator are used always, also can use its mixture.Typical SYNTHETIC OPTICAL WHITNER of useful herein other and activator are in addition referring to United States Patent (USP) 4634551.
Acid amides deutero-bleach-activating agent very preferably is to have those of following formula:
R 1N (R 5) C (O) R 2C (O) L or R 1C (O) N (R 5) R 2R in C (O) the L formula 1Be to contain 6 the alkyl of having an appointment, R to about 12 carbon atoms 2Be to contain 1 alkylidene group, R to about 6 carbon atoms 5Be H or contain have an appointment 1 alkyl, aryl or alkaryl that L is the leavings group of any suitable to about 10 carbon atoms.Leavings group be by owing to cross hydrolysis negatively charged ion nucleophilic attack bleach-activating agent from the bleach-activating agent substituted any group.Preferred leavings group is a phenylbenzimidazole sulfonic acid salt.
The example of preferred bleach-activating agent comprises (6-decoyl amino-caproyl) oxygen benzene sulfonate, (the amino caproyl of 6-nonanoyl) oxygen benzene sulfonate, (6-caprinoyl amino-caproyl) oxygen benzene sulfonate and its mixture in the following formula; they are described in United States Patent (USP) 4; 634; in 551, the document is quoted for referencial use at this paper.
Another kind of bleach-activating agent comprises the disclosed benzoxazine type activator in the United States Patent (USP) 4,966,723 of authorizing October 30 nineteen ninety by people such as Hodge, and the document is quoted as a reference in this article.Benzoxazine type activator very preferably is:
Also have another kind of preferred bleach-activating agent to comprise the acyl lactam activator, especially the acyl caprolactam of following formula and acyl group Valerolactim: R in the formula 6For H or contain 1 alkyl, aryl, alkoxy aromatic yl or alkaryl to about 12 carbon atoms.Lactan activator very preferably comprises benzoyl caprolactam; the capryloyl hexanolactam; 3; 5; 5-trimethyl acetyl base hexanolactam; the nonanoyl hexanolactam; the decanoyl hexanolactam; the undecylene acyl caprolactam; the benzoyl Valerolactim; the capryloyl Valerolactim; the decanoyl Valerolactim; undecylene acyl group Valerolactim; the nonanoyl Valerolactim; 3; 5; 5-trimethyl acetyl base Valerolactim and its mixture; also license to the United States Patent (USP) 4 of Sanderson referring on October 8th, 1985; 545; 784; it discloses acyl caprolactam; comprise benzoyl caprolactam, it is adsorbed in the Sodium peroxoborate.
Those SYNTHETIC OPTICAL WHITNER except oxygen bleaching agent also are well known in the art, and can be with in the present invention.The non-oxygen bleaching agent that one class is good especially comprises photoactivation SYNTHETIC OPTICAL WHITNER such as sulfonated Phthalocyanine Zinc and/or aluminium.License to people's such as Holcombe United States Patent (USP) 4033718 referring on July 5th, 1977.If necessary, detergent composition generally contains this SYNTHETIC OPTICAL WHITNER of about 1.25% (weight) of the 0.025%-that has an appointment, especially sulfonated Phthalocyanine Zinc.
If necessary, bleaching compounds can be used manganic compound catalysis.These compounds are known in the art technology, comprise for example being disclosed in United States Patent (USP) 5,246,621; United States Patent (USP) 5,244,594; United States Patent (USP) 5,194,416; United States Patent (USP) 5,114,606; With European patent application publication No. 549,271A1,549,272A1,544,440A2 and 544, the manganese-based catalyst among the 490A1.Preferred example comprises Mn in these catalyzer IV 2(u-O) 3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(PF 6) 2, Mn III 2(u-O) 1(u-OAc) 2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(ClO 4) 2, Mn IV 4(u-O) 6(1,4, the 7-7-triazacyclononane) 4(ClO 4) 4, Mn IIIMn IV 4(u-O) 1(u-OAc) 2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(ClO 4) 3, Mn IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH 3) 3(PF 6) and its mixture.The bleaching catalyst of other metal matrix comprises and is disclosed in United States Patent (USP) 4,430,243 and United States Patent (USP) 5,114,611 in those.Manganese and the various application that can strengthen the title complex ligand of bleaching also are reported in the following United States Patent (USP): 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084;
Washing assistant
Detergent builders can randomly be included in the composition of the present invention to help to control hardness of minerals.Can use inorganic and organic washing-assisting detergent.Washing assistant generally is used for fabric cleaning composition to help to remove dirt particles.
The content of washing assistant can change in wide region according to end-use and its required physical form of composition.When using washing assistant, generally contain washing assistant in the composition at least about 1%.It is about 50% that liquid preparation generally comprises about 5%-, more preferably from about 5%-about 30% (weight) detergent builders.Granular preparation generally comprises about 10% to about 80%, more typically comprises about 15% detergent builders to about 50% (weight).
Inorganic or phosphorus-containing detergent washing assistant comprises, but be not limited to this, basic metal, ammonium and the alkanol ammonium salts of poly-phosphate (for example tri-polyphosphate, pyrophosphate salt and glassy polymeric metaphosphate), phosphoric acid salt, phytinic acid, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate.Yet need nonphosphate builders in some place.Importantly the present composition in addition have so-called " weak " washing assistant (with phosphate ratio) have unexpected effect in as Citrate trianion or so-called " owing composite (underbuilt) " environment of being produced with zeolite or layered silicate washing assistant.
The example of silicate-like builder is an alkalimetal silicate, particularly has SiO 2With Na 2The silicate of the ratio of O in 1.6: 1 to 3.2: 1 scopes, and layered silicate are as the lamina sodium silicate of describing in the United States Patent (USP) 4664839 that licenses to H.P.Rieck on May 12nd, 1987.NaSKS-6 is the trade mark (being abbreviated as " SKS-6 " in this article usually) by the crystalline layered silicate of Hoechst sale.Do not resemble zeolite builders, the NaSKS-6 silicate-like builder does not contain aluminium.NaSKS-6 has δ-Na 2SiO 5The layered silicate of morphology configuration.It can be by the method preparation as describing in DE-A-3417649 and DE-A-3742043.SKS-6 is a layered silicate very preferably used herein, but can use other layered silicate, as has general formula NaMSi xO 2x+1YH 2O, wherein M is sodium or hydrogen, and x is 1.9 to 4 numerical value, is preferably 2, and y is 0 to 20 numerical value, is preferably 0 layered silicate.Various other layered silicates of buying from Hoechst comprise NaSKS-5, NaSKS-7 and NaSKS-11, are α, β and γ form.As mentioned above, δ-Na 2SiO 5(NaSKS-6 form) most preferably used herein.Other silicate also is useful, Magnesium Silicate q-agent for example, and it can be used as in the granular preparation crisp dose, the stablizer of oxygen bleaching agent and the component of control foam system.
The example of carbonate builders is alkaline-earth metal and the alkaline carbonate on November 15th, 1973 disclosed German patent application 2321001.
The silico-aluminate washing assistant is useful among the present invention.The silico-aluminate washing assistant is most important in most popular commercially available heavy dirty granular detergent composition, also is effective builder component in the liquid detergent preparation.The silico-aluminate washing assistant comprises the washing assistant with following empirical formula:
M z(zAlO 2) y] xH 2Wherein z and y are for being 6 integer at least for O, and the mol ratio of z and y is 1.0 to about 0.5 scope, and x is about 15 to about 264 integer.
Useful aluminosilicate ion exchange material is commercial the purchase.These silico-aluminates can be crystallization or amorphous structure, and can naturally occurring silico-aluminate or synthetic obtaining.A kind of method for preparing aluminosilicate ion exchange material is disclosed in the people's such as Krummel that authorized on October 12nd, 1976 the United States Patent (USP) 3985669.The preferred synthetic crystallization aluminosilicate ion exchange material that is used for this paper is bought by being registered as zeolite A, zeolite P (B), zeolite MAP and X zeolite.In particularly preferred embodiments, the crystal aluminosilicate ion-exchange material has following formula:
Na 12[(AlO 2) 12(SiO 2) 12] xH 2O wherein x is about 20 to about 30, especially is about 27.This material is called zeolite A.Dehydration zeolite (x=0-10) also can be used for the present invention.Preferred silico-aluminate has the granularity that diameter is about the 0.1-10 micron.
The organic washing-assisting detergent that is fit to purposes of the present invention includes, but are not limited to this, various polycarboxylic acid salt compounds." polycarboxylate " used herein refer to have a plurality of carboxylate groups, the compound of preferred at least 3 carboxylate groups.The polycarboxylate washing assistant can add in the composition with sour form usually, but also can add with the form of neutralized salt.When using with the form of salt, basic metal is preferred as sodium, potassium and lithium or alkanol ammonium salts.
In the polycarboxylate washing assistant, comprise polytype useful matter.An important class polycarboxylate washing assistant comprises the ether polycarboxylate, comprise the oxidation disuccinate, as those disclosed in the United States Patent (USP) 3128287 of the Berg that authorizes on April 7th, 1964 and the people's such as Lamberti that authorized on January 18th, 1972 the United States Patent (USP) 3635830.Also can license to " TMS/TDS " washing assistant in people's such as Bush the United States Patent (USP) 4663071 referring on May 5th, 1987.The ether polycarboxylate who is fit to also comprises ring compound, particularly alicyclic compound, as at United States Patent (USP) 3923679; 3835163; 4158635; Describe in 4120874 and 4102903.
Other useful detergency washing assistants comprise the ether hydroxy-polycarboxylate, the multipolymer of maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyl oxosuccinic acid, various poly-acetate, basic metal, ammonium and substituted ammonium salt as ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA), and polycarboxylate such as mellitic acid, succsinic acid, oxidation disuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxy methoxy-succinic acid and its water-soluble salt.
The Citrate trianion washing assistant, for example, citric acid and its water-soluble salt (particularly sodium salt) are the polycarboxylate washing assistants of particularly important in the heavy duty liquid laundry detergent preparation, reason is that they can be obtained and their biodegradability by renewable resource.Citrate trianion also can be used for particulate composition, especially can be used in combination with zeolite and/or layered silicate washing assistant.The oxidation disuccinate also is useful especially in these compositions and mixture.
Disclosed 3 in the United States Patent (USP) 4566984 that also has the people such as Bush that authorize on January 28th, 1986 that is adapted at using in the detergent composition of the present invention, 3-dicarboxyl-4-oxa--1, the compound that the 6-adipate is relevant with it.Useful succsinic acid washing assistant comprises C 5-C 20Alkyl and alkenyl succinic and its salt.Particularly preferred compound is the dodecenyl succinic succsinic acid in this type.The specific examples of succinate washing assistant comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates etc.The lauryl succinate is a preferred washing assistant in this group, and is described in the disclosed european patent application 86200690.5/0200263 on November 5th, 1986.
In the people's such as Diehl that other polycarboxylates that are fit to are disclosed in the people's such as Crutchfield that authorized on March 13rd, 1979 the United States Patent (USP) 4144226 and authorize on March 7th, 1967 the United States Patent (USP) 3308067.Also referring to the United States Patent (USP) 3723322 of Diehl.
Lipid acid, for example C 12-18Monocarboxylic acid also can mix in the composition separately, or mixes in the composition so that additional washing assistant activity to be provided with aforesaid washing assistant, especially Citrate trianion and/or the combination of succinate washing assistant.So use lipid acid generally can cause whipability to reduce, this prescription teacher should consider.
Under the situation that can use phosphorus base washing assistant, especially, can use various alkali metal phosphates, as is well known tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate at the stick preparation that is used for hand-washing operation.Phosphate builders such as ethane-1-hydroxyl-1,1-diphosphate and other known phosphate (referring to, US3159581 for example; 3213030; 3422021; 3400148 and 3422137) also can use.
The polymerization dirt release agent
Well known to a person skilled in the art that any polymerization dirt release agent can randomly be used for the compositions and methods of the invention.The polymerization dirt release agent is characterised in that it contains hydrophilic segment and hydrophobic part simultaneously, and wherein hydrophilic segment makes hydrophobic fiber, as the surface hydrophilic of polyester and nylon; Hydrophobic part attached to the surface of hydrophobic fiber and in whole washing, rinse cycle all the time attached to fiber surface on, therefore hydrophilic segment is played fixed action.This feasible spot easier cleaning in washing process thereafter that after dirt release agent is handled, produces.
The polymerization dirt release agent that the present invention uses especially comprises the polymerization dirt release agent with following composition: (a) basically by (i) or (ii) or one or more nonionic hydrophilic components of (iii) forming, wherein (i) is that the polymerization degree is at least 2 polyoxyethylene part, it (ii) is the polyoxypropylene part that the propylene oxide or the polymerization degree are at least 2-10, wherein said hydrophilic segment does not comprise any propylene oxide unit, unless this unit is attached at the two ends of adjacent part by ehter bond, the mixture that (iii) contains the oxidative chain olefin unit of about 30 propylene oxide units of ethylene oxide and 1-, wherein said mixture contains abundant ethylene oxide unit, thereby the wetting ability that makes hydrophilic component is big to the wetting ability that can increase normal polyester synthon surface, dirt release agent is promptly attached on this surface, described hydrophilic segment preferably contains the ethylene oxide unit at least about 25%, contains 20-30 the propylene oxide unit and be particularly preferred at least about the composition of 50% ethylene oxide unit of having an appointment; Or (b) comprise (i), (ii), (iii) or one or more hydrophobic ingredients (iv), wherein (i) is C3 oxyalkylene terephthaldehyde base acid esters part, if wherein described hydrophobic ingredient also comprises the ethylene oxide terephthalate, then ethylene oxide terephthalate and C 3The unitary ratio of oxyalkylene terephthaldehyde base acid esters is about 2: 1 or is lower, (ii) is C 4-C 6Alkene or oxidation C 4-C 6Alkene part, or their mixture (iii) are poly-(vinyl ester) parts, and preferred degree of polymerization is at least 2 poly-(vinyl-acetic ester), (iv) is C 1-4Alkyl oxide or C 4Hydroxyalkyl ether substituting group, or their mixture, described substituting group wherein is with C 1-4Alkyl oxide or C 4Hydroxyalkyl ether derivatived cellulose or its form of mixtures exist, and this derivatived cellulose is an amphipathic, therefore make them have enough C 1-4Alkyl oxide and/or C 4The hydroxyalkyl ether unit is with attached on the polyethylene terephthalate surface of routine and keep the hydroxyl of q.s, in case be adsorbed on these conventional synthon when surperficial when it, wetting ability that can the increased fiber surface; Or combination (a) and (b).
Generally speaking, be that 2-is about 200 in the polymerization degree of (a) polyoxyethylene part in (i), although also can use the higher polymerization degree, preferred 3-about 150; More preferably 6-about 100.The oxidation C that is fit to 4-6The alkene hydrophobic part includes, but are not limited to this, as MO 3S (CH 2) nOCH 2CH 2The polymerization dirt release agent end-blocking part of O-, M is a sodium in the formula, n is the integer of 4-6, license to as on January 26th, 1988 in the United States Patent (USP) 4721580 of Gosselink disclosed those.
The polymerization dirt release agent that uses among the present invention also comprises derivatived cellulose, for example segmented copolymer of hydroxy ethers cellulose polymer compound, glycol terephthalate or propylene glycol terephthalate and polyoxyethylene terephthalate or polyoxypropylene terephthalate etc.These reagent all have commercially available, comprising the Mierocrystalline cellulose hydroxy ethers as METHOCEL (Dow).The Mierocrystalline cellulose dirt release agent that the present invention uses also comprises C 1-4Alkyl and C 4Hydroxy alkyl cellulose; License to people's such as Nicol United States Patent (USP) 4000093 referring on December 28th, 1976.
The dirt release agent that is characterised in that poly-(vinyl ester) hydrophobic part comprises that poly-(vinyl ester) is as, C 1-6The graft copolymer of vinyl ester preferably connects poly-(vinyl-acetic ester) of branch on polyoxygenated alkene skeleton such as polyoxyethylene skeleton.European patent application 0219048 referring to people such as disclosed Kud on the 22nd April in 1987.This commercially available class dirt release agent comprises SOKALAN type material, and for example SOKALAN HP-22 is produced by BASF (West Germany).
A preferred class dirt release agent is to have glycol terephthalate and polyoxyethylene (PEO) terephthalate statistic copolymer.The molecular weight of this polymerization dirt release agent is about 25000-about 55000.United States Patent (USP) 3893929 referring to the United States Patent (USP) 3959230 of the Hays that authorized on May 25th, 1976 and the Basadur that authorized on July 8th, 1975.
Another kind of preferred polymerization dirt release agent is the polyester that has the glycol terephthalate repeating unit, wherein contain the glycol terephthalate unit of 10%-15% (weight) and the polyoxyethylene terephthalate unit of 90%-80% (weight), it is that the polyoxygenated ethylidene glycol of 300-5000 obtains from molecular-weight average.The example of this polymkeric substance comprises commercially available ZELCON5126 (Dupont production) and MILEASET (ICI production).License to the United States Patent (USP) 4702857 of Gosselink referring on October 27th, 1987.
Also having a kind of preferred polymerization dirt release agent is the sulfonated products that is essentially the linear ester oligopolymer, and this oligopolymer contains terephthaloyl and the multiple unit of oxyalkylene oxygen basic weight oligomer ester skeleton, and the terminal portions that links to each other with this skeleton covalency.License to November 6 nineteen ninety in the United States Patent (USP) 4968451 of J.J.Scheibel and E.P.Gosselink these dirt release agents are had complete description.Other polymerization dirt release agents that are suitable for comprise the terephthalate polyester in the United States Patent (USP) 4711730 that licensed to people such as Gosselink on December 8th, 1987, license to the end capped oligomer ester of negatively charged ion in the United States Patent (USP) 4721580 of Gosselink on January 26th, 1988 and license to block polyester oligopolymer in the United States Patent (USP) 4702857 of Gosselink on October 27th, 1987.
Preferred polymerization dirt release agent also comprises the dirt release agent in the United States Patent (USP) 4877896 that licensed to people such as Maldonado on October 31st, 1989, this patent disclosure negatively charged ion, the particularly end capped terephthalate of sulfo group aroyl.
If the use dirt release agent, then its consumption is about 10.0% for about 0.01%-of detergent composition weight of the present invention, and it is about 5% to be generally about 0.1%-, preferably about 0.2%-about 3.0%.
Preferred in addition dirt release agent is the oligopolymer with following repeating unit: terephthaloyl unit, sulfo group isophthaloyl unit, oxygen ethylidene oxygen and oxygen-propylene unit.These repeating units have constituted the skeleton and the preferred isethionate end-blocking with modification of oligopolymer.Particularly preferred this type of dirt release agent comprises an about sulfo group isophthaloyl unit, 5 terephthaloyl unit, ratio is about 1.7 to about 1.8 the oxygen ethylidene oxygen and the end-blocking unit of oxygen-propylene oxygen unit and two 2-(2-hydroxy ethoxy) ethane sulfonic acid sodium.Said dirt release agent also comprises the reduction crystalline stablizer by the about 0.5%-of oligopolymer weight about 20%, and this stablizer is preferably selected from xylenesulfonate, cumene sulfonate, tosylate and its mixture.
In fact, the present composition and method are unrestricted and be adjustable to be provided in the aqueous cleaning medium approximately 1/10,000,000 active bleaching catalyst material, preferably in wash water solution, provide about 0.1ppm to about 700ppm, more preferably about 1ppm about 500ppm catalyst substance extremely.
Sequestrant
Cleaning composition of the present invention can also randomly contain the sequestrant of one or more iron and/or manganese.This class sequestrant can be selected from fragrant chelating agent of aminocarboxylate, amino phosphonates do, multifunctional replacement and composition thereof, and all sequestrants are as definition hereinafter.Do not accept the restriction of opinion, it is believed that the advantage of these materials is that partly they have by forming the soluble chelating agent removes demanganize and iron from washing soln superperformance.
The aminocarboxylate that can be used as optional sequestrant comprises edetate, N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their an alkali metal salt, ammonium salt and substituted ammonium salt and their mixture.
When allowing at least to have low total phosphorous in detergent composition of the present invention, amino phosphonates do also is suitable as sequestrant of the present invention, comprising: ethylenediamine tetraacetic (methylene phosphonic acid salt), DEQUEST.These amino phosphonates do preferably do not contain alkyl or the alkenyl that surpasses about six carbon atom.
In the present composition, can also use the aromatic chelating agent of multifunctional replacement.License to people's such as Connor United States Patent (USP) 3812044 referring on May 21st, 1974.The compound of preferred this class acid form is the dihydroxyl disulfobenzene, for example: 1,2-dihydroxyl-3,5-disulfobenzene.
The preferred in the present invention biodegradable cheating agent of using was ethylenediamine disuccinate (" EDDS "), and its [S, S] isomer especially licenses to the United States Patent (USP) 4704233 of Hartman and Perkins referring on November 3rd, 1987.
If the use sequestrant, then its consumption is about 0.1%-about 10% of detergent composition weight of the present invention.Preferred amount of chelant is about 0.1%-about 3.0% of said composition weight.
Clay soil removal/anti is deposition agent again
Composition of the present invention can also contain the water-soluble ethoxylated amine with clay soil removal and antiredeposition performance.The granular detergent composition that contains these compounds generally contains the water-soluble ethoxylated amine of about 10.0% (wt) of the 0.01%-that has an appointment.Liquid detergent composition generally contains the 0.01%-that has an appointment about 5%.
Most preferred dirt is removed and anti redeposition agent is the ethoxylation tetren.The example of ethoxylated amine has description in the United States Patent (USP) 4597898 of the VanderMeer of mandate on July 1st, 1986.Another kind of preferred clay soil removal/anti again deposition agent be on June 27th, 1984 disclosed Oh and the european patent application 111965 of Gosselink in the cation compound of report.Other clay soil removal/anti that can use in the present invention deposition agent again comprise the ethoxylated amine polymer of reporting in the european patent application 111984 of disclosed Gosselink on the 27th June in 1984; July in 1984 disclosed Gosselink on the 4th european patent application 112592 in the report amphiphilic polymers; With the amine oxide in the United States Patent (USP) 4548744 of the Connor that authorized on October 22nd, 1985.Other clay soil removal/anti as known in the art deposition agent more also can be used in the composition of the present invention.Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC) material.These materials are well known in the art.
Polymeric dispersant
Content can be advantageously used in the present composition for the polymeric dispersant of about 0.1%-about 7% (wt), especially when zeolite and/or layered silicate washing assistant exist.The polymeric dispersant that is fit to comprises polymeric polycarboxylate and polyoxyethylene glycol, and other known polymeric dispersants of this area also can use.Do not limited by theoretical although do not wish, but can be sure of when polymeric dispersant with other washing assistants (comprising low-molecular-weight polycarboxylate) when using, by the crystal growth restraining effect, especially free the peptization and the anti-redeposition of dirt, can improve the performance of all detergent builder compounds.
By making suitable unsaturated monomer, preferably the polymerization of the unsaturated monomer of its sour form or copolymerization can prepare the polymer poly-carboxylate.Can comprise vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid through the suitable polymer poly-carboxylate's of polymerization preparation unsaturated monomer acid.In polymer poly-carboxylate of the present invention, contain the monomer segment that does not have carboxylate groups such as vinyl methyl ether, vinylbenzene, ethene etc. and be fit to, as long as it is no more than about 40% (weight).
Especially the polymer poly-carboxylate of Shi Heing can obtain from vinylformic acid.Such that uses among the present invention is the water-soluble salt of polymeric acrylic acid with vinylformic acid as the polymkeric substance of matrix.The molecular-weight average of this base polymer that exists with sour form is preferably about 2000-10000, and more preferably about 4000-7000 most preferably is about 4000-5000.The example of the water-soluble salt of such acrylate copolymer comprises for example an alkali metal salt, ammonium salt and substituted ammonium salt.Such polymer soluble is known.The application of such polyacrylate in detergent composition disclosed in the United States Patent (USP) 3308067 of the Diehl that on March 7th, 1967 authorized.
With vinylformic acid/toxilic acid is that the multipolymer of matrix also can be as the preferred ingredient of dispersion/anti redeposition agent.This class material comprises the water-soluble salt of vinylformic acid and maleic acid.The molecular-weight average of this analog copolymer that exists with sour form is preferably about 2000-100000, and more preferably about 5000-75000 most preferably is about 7000-65000.The ratio of acrylate moiety and toxilic acid part was generally more preferably from about 10: 1 to 2: 1 about 30: 1 to about 1: 1 in this analog copolymer.The water-soluble salt of this class vinylformic acid/maleic acid can comprise, for example an alkali metal salt, ammonium salt and substituted ammonium salt.The water-soluble salt of this class vinylformic acid/maleic acid is a disclosed european patent application 66915 and at disclosed EP193 on September 3rd, 1986 on December 15 nineteen eighty-two, the known substance of describing in 360, the latter has also described this base polymer that comprises the hydroxypropyl acrylate.Also have other useful dispersion agent to comprise toxilic acid/vinylformic acid/vinyl alcohol terpolymer.This class material also is disclosed in EP193, in 360, comprises for example vinylformic acid/toxilic acid of 45/45/10/vinyl alcohol terpolymer.
The another kind of polymkeric substance that can be comprised is polyoxyethylene glycol (a PEG multipolymer).The PEG multipolymer also has the performance of dispersion agent the deposition agent again except can be used as clay soil removal/anti.It is about 100000 to be generally about 500-as the molecular-weight average of the polyoxyethylene glycol of this purposes, and it is about 50000 to be preferably about 1000-, more preferably about 1500-about 10000.
Also can use polyaspartic acid salts and polyglutamate, especially be used in combination with zeolite builders.For example the preferred molecular weight of the dispersion agent of polyaspartic acid salts (on average) is about 10,000.
Dye transfer inhibitor
The present composition also can comprise and effectively is suppressed at dyestuff in the washing process is transferred to another kind of fabric from a kind of fabric one or more materials.General this dye transfer inhibitor comprises multipolymer, manganese phthalocyanine, peroxidase and its mixture of polyvinyl pyrrolidone polymers, polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.If use, it is about 10% that these reagent are generally about 0.01%-of present composition weight, and preferably about 0.01%-is about 5%, and more preferably from about 0.05%-about 2%.
More particularly, be preferred for the unit that polyamine N-oxide pllymers of the present invention contains following structural formula: R-A x-P, wherein P connects the polymerisable unit of N-O group or polymerizable unit that the N-O group constitutes its part or N-O group can be connected on polymerizable unit on these two kinds of unit; A is one of following structure :-NC (O) ,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; R is that the nitrogen or the N-O group that can connect in the N-O group are aliphatic series, ethoxylation aliphatic series, aromatics, heterocycle or alicyclic group or its arbitrary combination of its part.Preferred polyamine N-oxide compound be those wherein R be heterocycle such as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines and its derivative.
The N-O group can be represented by following general structural formula:
Figure A9519544600321
R wherein 1, R 2, R 3Be aliphatic series, aromatics, heterocycle or alicyclic group or its combination; X, y and z are 0 or 1; Nitrogen-atoms in the N-O group can be linked on any aforementioned group or the N-O group is the component part of aforementioned group.The unitary pKa of the amine oxide of polyamine N-oxide＜10, preferred pKa＜7, more preferably pKa＜6.
As long as the amine oxide polymers that forms is water miscible and has the character that suppresses dye transfer that polymer backbone all can be used arbitrarily.The example of suitable polymeric skeleton is polyvinyl, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylate and its mixture.These polymkeric substance comprise random or segmented copolymer, and the monomer of one type is that amine n-oxide and other type monomers are the N-oxide compounds.The ratio that the amine n-oxide polymkeric substance generally has amine and amine n-oxide is 10: 1 to 1: 1000,000.Yet the number of the amine oxide group that exists in the polyoxygenated amine polymer can change according to suitable co-polymerization or suitable N-degree of oxidation.Almost can obtain the polyoxygenated amine of any polymerization degree.Generally, its molecular-weight average is 500 to 1,000, in 000 scope, and more preferably 1,000 to 500,000, most preferably 5,000 to 100,000.The preferred material of this class is called as " PVNO ".
Useful most preferred polyamine N-oxide is poly-(4-vinylpridine-N-oxide compound) in detergent composition of the present invention, and its molecular-weight average is about 50,000, and the ratio of amine and amine n-oxide is about 1: 4.
The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance (being called " PVPVI " this class) also is that the present invention preferably uses.The average molecular weight range of preferred PVPVI is 5000 to 1,000,000, more preferably 5000 to 200,000, most preferably 10,000 to 20,000.(this average molecular weight range is to measure by the light scattering technique described in the following document, and the document is people's such as Barth a chemical analysis (Chemical Analysis), the 113rd volume." modernism of polymer characterization (Modern Methods of Polymer Characterization) ", its disclosure is at this paper as a reference).The mol ratio that the PVPVI multipolymer generally has N-vinyl imidazole and N-vinyl pyrrolidone is 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, and most preferably 0.6: 1 to 0.4: 1.These multipolymers can be straight chain or side chain.
The present composition also can use molecular-weight average for about 5,000 to about 400,000, and preferred about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000 polyvinylpyrrolidone (" PVP ").The PVP class is that the technician of detergent applications is known, referring to, EP-A-262 for example, and 897 and EP-A-256,696, it is quoted as a reference at this paper.It is about 500 to about 100,000 that the composition that contains PVP also can contain molecular-weight average, preferred about 1000 to about 10,000 polyoxyethylene glycol (" PEG ").What preferably provide in washing soln is about 2: 1 to about 50: 1 in the PEG of ppm calculating and the ratio of PVP, more preferably from about 3: 1 to about 10: 1.
Detergent composition of the present invention also can randomly contain to have an appointment 0.005% also provides the hydrophilic white dyes of some type that suppresses the dye transfer effect to about 5% (weight).If adopt, the present composition will preferably include this white dyes of about 0.01%-1% (weight).
Useful in the present invention hydrophilic white dyes is to have those of following structural formula: R wherein 1Be selected from anilino, N-2-double hydroxyethyl and NH-2-hydroxyethyl; R 2Be selected from N-2-double hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine and amino; M is a salt-forming cation, as sodium or potassium.
When in following formula, R 1Be anilino, R 2Be N-2-double hydroxyethyl and M when being positively charged ion such as sodium, this whitening agent is 4,4 '-two [(4-anilino-6-(N-2-double hydroxyethyl)-S-triazine-2-yl) amino]-2,2 '-Stilbene disulfonic acid and its disodium salt.This concrete whitening agent is sold by Ciba-Geigy Corporation commercial, and trade mark is Tinopal-UNPA-GX.Tinopal-UNPA-GX is a preferred wetting ability white dyes useful in the detergent composition of the present invention.
When in following formula, R 1Be anilino, R 2Be N-2-hydroxyethyl-N-2-methylamino-and M when being positively charged ion such as sodium, this whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-S-triazine-2-yl) amino] 2,2 '-Stilbene disulfonic acid disodium salt.This concrete whitening agent is sold by Ciba-Geigy Corporation commercial, and trade mark is Tinopal 5BM-GX.
When in following formula, R 1Be anilino, R 2Be morpholino and M when being positively charged ion such as sodium, this whitening agent is 4,4 '-two [(4-anilino-6-morpholino-S-triazine-2-yl) amino] 2,2 '-Stilbene disulfonic acid and sodium salt thereof.This concrete whitening agent is sold by Ciba-Geigy Corporation commercial, and trade mark is Tinopal AMS-GX.
Be selected for these specific white dyess of the present invention when the performance benefit that especially effectively suppresses dye transfer is provided when selecteed polymeric dye transfer inhibitor mentioned above is used in combination.The combination of this selecteed polymkeric substance (for example PVNO and/or PVPVI) and this selecteed white dyes (for example Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) all provides the significantly good inhibition to dye transfer in wash water solution than any of this two kinds of detergent composition components of independent use.Do not accept opinion and keep within bounds, believe that the mode of action of this whitening agent is:, therefore be deposited on relatively apace on these fabrics because they have high affinity to the fabric in the washing soln.Whitening agent is deposited on the degree on the fabric in the washing soln and is defined with the parameter that is called " consumption coefficient ".This consumption coefficient refers generally to a) be deposited on whitening agent material and the b on the fabric) ratio of initial whitening agent concentration in wash water solution.Whitening agent with relative high flow rate coefficient is suitable for suppressing dye transfer most in this class technology contents of the present invention.
Certainly, can be appreciated that also other types of conventional white dyes of these compounds can randomly be used for the present composition and " brighten " benefit so that conventional fabric to be provided, but in fact do not suppress the effect of dye transfer.This application is conventional and is known in the washing composition preparation.
Other composition
Detergent composition of the present invention can be any form, comprises particle, particle, liquid, gel and stick.In the present composition, can also include other useful in various detergent composition compositions, comprising other activeconstituentss, as carrier, hydrotropic agent, processing aid, dyestuff or pigment, be used for the solvent of liquid preparation and be used for the solid packing of strip block composition.Can in said composition, mix as C 10-16The suds booster of alkanolamide, its content is generally 1-10%.C 10-14Monoethanolamine and diglycollic amide are the representative instances of such suds booster.If necessary, also can add as MgCl 2, MgSO 4Deng the solubility magnesium salts obtaining more foam and to strengthen the degrease performance, the consumption of this magnesium salts is generally 0.1%-2%.
The various decontamination compositions that use in the present composition can also be by being adsorbed on these components on the porous hydrophobic matrix, and then with hydrophobicity apply agent with this matrix coated with further making its stabilization.Preferably before adsorbing, this dirty component is mixed with tensio-active agent with porous matrix.In use, this decontamination component is discharged into the wash water solution from matrix, and finishes the washing functions of its expection in this washing soln.
In order to illustrate in greater detail this technology, with porous hydrophobic silicon-dioxide (trade mark SIPERNATD10, DeGussa) with contain 3%-5%C 13-15The proteolysis enzyme solution of the nonionogenic tenside of ethoxylated alcohol (EO7) mixes.The amount of this enzyme/surfactant soln generally is 2.5 times of silica weight.The gained powder (can use the various polysiloxane oils of viscosity as 500-12500) through dispersed with stirring in polysiloxane oil.Add in the final washing composition matrix with the polysiloxane oil dispersion thing emulsification of gained or with it.By this method; with each composition as the aforementioned enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, light activating agent, dyestuff, white dyes, fabric conditioner and hydrolyzable tensio-active agent can be used for washing composition with " protected form ", comprise in the liquid laundry detergent compositions.
Liquid detergent composition can contain water and other solvent as carrier.Low-molecular-weight uncle or secondary alcohol, for example methyl alcohol, ethanol, propyl alcohol and Virahol suit.Monohydroxy-alcohol is preferred solubilizing surfactant, also can use to about 6 carbon atoms and 2 those polyvalent alcohols to about 6 hydroxyls (for example 1, ammediol, ethylene glycol, glycerine and 1,2-propylene glycol) but contain 2.Said composition can contain 5%-90%, is generally this carrier of 10%-50%.
The preferred detergent composition of being prepared of the present invention is manipulated in the process at aqueous cleaning, and the pH of washing water is about 8.5 to 11, and is preferred 9 to 11, most preferably pH9 to 10.The technology of control pH in the suggestion use range comprises uses buffer reagent, alkali, acid etc., and these are well known to a person skilled in the art.
Washing methods
Detergent composition according to the present invention can be used for any hand washing clothing method.The term used herein hand washing comprises any washing methods of incomplete automatization, and is included in high foaming washing machine, as the use in " twin-tub " formula washing machine.Preferred this detergent composition is used to comprise in the manual clothes washing method that stirs.
Hand washing clothing method
According to hand washing method of the present invention, the dirt fabric is contacted with the present composition of significant quantity.The actual amount of this detergent composition will and depend on multiple factor according to user's judgement, the method for using as degree, foam number and the human consumer of the quantity of the concentration of the specific product prescription of composition, composition, the clothing that will clean, clothing dirt.
The method that dirt is contacted with the present composition of significant quantity can be usually known any hand washing method basically, comprises method and the direct application process of diluting soln in container.
The method of solution in container
In the general method of diluting soln in container, with detergent composition and the 1000ml to 15000ml in container or groove, more preferably the water of 3000ml to 10000ml mixes.Can use room temperature water or add hot water.The clothing of dirt is immersed in the container that contains detergent composition and water, there by with hand agitate water and clothing cleaning clothes 1 to 5 minute-20 to 30 minute preset time, but the real time will change according to each application and user.In addition, before stirring with hand, clothing can be stayed in the washing soln through the removal to help dirt in 30 minutes to 12 hours.Water consumption substitution washing soln then, there, rinsing clothes is to remove detergent composition.This can repeat repeatedly.
The method of directly using
It is that a certain amount of detergent composition is mixed with enough water to form slurry that the method for directly using generally comprises first step.The clothing certain hour of scrubbing this dirt with this slurry is until consumer satisfaction then, and promptly dirt is removed from clothing.Then in water this clothing of rinsing to remove detergent composition.
According to the present invention, the relevant gentle effect to human consumer's hand of this detergent composition can be estimated by the control test that dermatologist is identified.
Embodiment
The component of the specified amount that all are listed is mixed and is prepared following granular detergent composition of the present invention.
123 4LAS, 15 12 15 12C12/14 dimethyl hydroxyethyl ammonium chlorides, 3 1.5 3 1.5C16-18N-methylglucosamines, 1 2.0 1 2.0C25E5,4 2.0 4 2.0C25E 3S-4.0-4.0-1.5-1.5STPP 25 25 15 15 3 3 3 3 1.6 1.6 1.6 1.6 0.4 0.4 0.4 0.4 1.0 1.0 1.0 1.0 0.15 0.15 0.15 0.15 0.12 0.12-- 0.4 0.4 0.4 0.4 7.0 7.0 7.0 7.0 0.3 0.3 0.3 0.3PB1--3.9 3.9NOBS--3.2 3.2 5 6LAS 12 12C12-14 1.5 1.5C12-C14 1.5 1.5C16-18N- 1.7 1.7C25E5 2.5 2.5C25E3S 4.0 4.0STPP 15 25 3 3 0.3 0.3 0.4 0.4 2.0 2.0 3.0 3.0 5.0 5.0 1.0 1.0 0.4 0.4-0.12 0.15 0.15NOBS 3.2-PB1 3.9- 1.6 1.6 0.15 0.15 50 50MgSO42.2 2.2

Claims (11)

1. Handwash laundry detergent compositions, it comprises the 15%-35% surfactant system, this system comprises negatively charged ion, nonionic and cats product, it is characterized in that said ionic surfactant pack draws together polyhydroxy fatty acid amide, the ratio of said anion surfactant and said cats product is 3: 1 to 15: 1, and the ratio of said cats product and said nonionogenic tenside is 2: 1 to 1: 10.
2. Handwash laundry detergent compositions according to claim 1, wherein said nonionogenic tenside also comprises oxyalkylated nonionogenic tenside.
3. Handwash laundry detergent compositions that requires according to arbitrary aforesaid right, wherein said cats product has formula R 1R 2R 3R 4N +X -, R wherein 1Be C 8-C 16Alkyl, R 2, R 3And R 4Be C independently 1-C 4Alkyl or hydroxyalkyl, benzyl and (C 2H 4O) xH, wherein x is 1 to 5, X is a negatively charged ion.
4. Handwash laundry detergent compositions according to claim 1 or 2, wherein said tensio-active agent also comprises the tensio-active agent that 0.5%-3% is selected from zwitter-ion, amphoteric tensio-active agent and composition thereof.
5. Handwash laundry detergent compositions according to claim 4, wherein said tensio-active agent is a trimethyl-glycine.
6. Handwash laundry detergent compositions that requires according to arbitrary aforesaid right, the ratio of wherein said anion surfactant and cats product is 5: 1 to 15: 1, and the ratio of said cats product and nonionogenic tenside is 2: 1 to 1: 7.
7. Handwash laundry detergent compositions that requires according to arbitrary aforesaid right, it also comprises detergent additives, and it is selected from SYNTHETIC OPTICAL WHITNER, bleach-activating agent, enzyme, polymerization anti redeposition agent, polymeric dispersant, polymerization dirt release agent, sequestrant, washing assistant, dye transfer inhibitor and its mixture.
8. Handwash laundry detergent compositions that requires according to arbitrary aforesaid right, wherein said composition is granular.
9. Handwash laundry detergent compositions that requires according to arbitrary aforesaid right, wherein said composition is liquid.
10. Handwash laundry detergent compositions that requires according to arbitrary aforesaid right, wherein said composition is that laundry bars is blocky.
11. a method of washing the dirt fabric is carried out manual the contact with said fabric with the laundry detergent composition according to claim 1 of significant quantity in the aqueous solution.
CN95195446A 1994-08-11 1995-07-28 Handwash laundry detergent compositions Pending CN1159824A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9416224.5 1994-08-11
GB9416224A GB2292155A (en) 1994-08-11 1994-08-11 Handwash laundry detergent composition comprising three surfactants

Publications (1)

Publication Number Publication Date
CN1159824A true CN1159824A (en) 1997-09-17

Family

ID=10759727

Family Applications (1)

Application Number Title Priority Date Filing Date
CN95195446A Pending CN1159824A (en) 1994-08-11 1995-07-28 Handwash laundry detergent compositions

Country Status (13)

Country Link
EP (1) EP0775190A4 (en)
JP (1) JPH10504056A (en)
CN (1) CN1159824A (en)
BR (1) BR9508535A (en)
EG (1) EG20780A (en)
GB (2) GB2292155A (en)
IL (1) IL114824A (en)
MA (1) MA23645A1 (en)
MX (1) MX9701081A (en)
PE (1) PE13696A1 (en)
TR (1) TR199500995A2 (en)
WO (1) WO1996005280A1 (en)
ZA (1) ZA956663B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8098468B2 (en) 2006-04-13 2012-01-17 Emerson Network Power, Energy Systems, North America, Inc. Hardware overvoltage disconnecting circuit
CN104629943A (en) * 2013-11-14 2015-05-20 青岛锦涟鑫商贸有限公司 Improved concentrated detergent

Families Citing this family (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2317390A (en) * 1996-05-17 1998-03-25 Procter & Gamble Detergent compositions
EP0968266A1 (en) * 1996-05-31 2000-01-05 The Procter & Gamble Company Detergent composition
WO1998001521A1 (en) * 1996-07-08 1998-01-15 The Procter & Gamble Company Hand wash laundry detergent compositions containing a combination of surfactants
GB2315765A (en) * 1996-08-01 1998-02-11 Procter & Gamble Detergent compositions for laundering clothes with low levels of sulphate and silicates
GB2319038A (en) * 1996-11-06 1998-05-13 Procter & Gamble Detergent particle
GB2317391A (en) * 1996-09-24 1998-03-25 Procter & Gamble Detergent compositions
GB2317392A (en) * 1996-09-24 1998-03-25 Procter & Gamble Detergent compositions
EP0929625A4 (en) * 1996-09-24 2000-01-05 Procter & Gamble Detergent compositions
GB2318799A (en) * 1996-10-31 1998-05-06 Procter & Gamble Detergent compositions
DE69715463T2 (en) * 1996-10-18 2003-08-07 Procter & Gamble DETERGENTS CONTAINING A MIXTURE OF A QUATERIAL AMMONIUM TENSIDE AND AN ALKYL SULFATE
DE19715836C1 (en) * 1997-04-16 1998-07-23 Henkel Kgaa Liquid detergent for fine laundry
BR9810933A (en) * 1997-06-23 2000-09-26 Procter & Gamble Granular detergent composition containing an optimal surfactant system for washing clothes at cold temperature
WO1999025796A2 (en) * 1997-11-18 1999-05-27 Unilever Plc Detergent powder compositions with glucamide-like bleach enhancers
CN1222606C (en) * 1998-08-07 2005-10-12 荷兰联合利华有限公司 Mild particulate laundry detergent compositions for washing textile fabrics by hand
DE19948670A1 (en) * 1999-10-08 2001-04-19 Cognis Deutschland Gmbh laundry detergent
GB0002752D0 (en) * 2000-02-07 2000-03-29 Unilever Plc Detergent compositions
GB0002749D0 (en) 2000-02-07 2000-03-29 Unilever Plc Detergent compositions
AU2000232314A1 (en) * 2000-02-14 2001-08-27 The Procter And Gamble Company Methods for making laundry detergent compositions with an emulsified compositioncontaining a skin conditioning oil and a polyamine emulsifier
US7015180B2 (en) 2000-02-29 2006-03-21 Clariant S.A. Hair treatment compositions comprising an anionic surfactant and a C8-C22 alkyl dimethyl hydroxyethyl ammonium chloride
DE60025561T2 (en) * 2000-09-21 2006-08-10 Clariant S.A. Use of cosmetic preparations containing anionic and cationic hair-treatment surfactants
GB2364961B (en) 2001-08-10 2002-06-26 Tecan Components Ltd Stencil for use with stencil mounting frame
EP1465584B1 (en) * 2001-12-21 2008-01-23 Rhodia Inc. Combined stable cationic and anionic surfactant compositions
MXPA04006002A (en) 2001-12-21 2004-09-27 Rhodia Stable surfactant compositions for suspending components.
EP1418226B1 (en) * 2002-11-07 2006-10-04 Unilever N.V. Detergent composition
CA2681998A1 (en) 2007-03-23 2008-10-02 Rhodia Inc. Structured surfactant compositions
US20110166370A1 (en) 2010-01-12 2011-07-07 Charles Winston Saunders Scattered Branched-Chain Fatty Acids And Biological Production Thereof
CN103380107B (en) 2011-02-17 2015-06-10 宝洁公司 Bio-based linear alkylphenyl sulfonates
CA2827627C (en) 2011-02-17 2016-10-11 The Procter & Gamble Company Compositions comprising mixtures of c10-c13 alkylphenyl sulfonates
HUE028912T2 (en) 2012-03-26 2017-01-30 Procter & Gamble Cleaning compositions comprising ph-switchable amine surfactants
CN105026539A (en) 2013-03-05 2015-11-04 宝洁公司 Mixed sugar compositions
EP3109305B1 (en) * 2015-06-26 2019-05-29 Clariant International Ltd Automatic dishwashing detergent compositions comprising n-acylglucamine
WO2018035191A1 (en) * 2016-08-17 2018-02-22 The Procter & Gamble Company Cleaning composition
EP3530723B1 (en) 2018-02-21 2023-03-29 The Procter & Gamble Company Automatic dishwashing composition
WO2022162062A1 (en) * 2021-02-01 2022-08-04 Unilever Ip Holdings B.V. Detergent composition
US20220380701A1 (en) * 2021-05-27 2022-12-01 The Procter & Gamble Company Cleaning compositions comprising renewable components

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8724899D0 (en) * 1987-10-23 1987-11-25 Unilever Plc Detergent bleach compositions
DK0551410T3 (en) * 1990-09-28 1996-02-05 Procter & Gamble Detergent compositions containing anionic surfactants, polyhydroxy fatty acid amides and magnesium
ES2079680T3 (en) * 1990-09-28 1996-01-16 Procter & Gamble POLYHYDROXY-AMIDES OF FATTY ACIDS IN DETERGENT COMPOSITIONS CONTAINING AN AGENT FOR RELEASE OF DIRT.
IN184497B (en) * 1990-10-12 2000-08-26 Procter & Gamble
US5254281A (en) * 1991-01-29 1993-10-19 The Procter & Gamble Company Soap bars with polyhydroxy fatty acid amides
GB9116852D0 (en) * 1991-08-05 1991-09-18 Unilever Plc Detergent composition
DE69229503T2 (en) * 1991-09-06 2000-01-27 Procter & Gamble DETERGENT COMPOSITIONS CONTAINING CALCIUM AND POLYHYDROXY FATTY ACID
US5283009A (en) * 1992-03-10 1994-02-01 The Procter & Gamble Co. Process for preparing polyhydroxy fatty acid amide compositions
US5223179A (en) * 1992-03-26 1993-06-29 The Procter & Gamble Company Cleaning compositions with glycerol amides
GB9216410D0 (en) * 1992-08-01 1992-09-16 Procter & Gamble Detergent compositions
US5298636A (en) * 1992-09-23 1994-03-29 The Procter & Gamble Company Process for reducing the levels of unreacted amino polyol contaminants in polyhydroxy fatty acid amide surfactants
US5318728A (en) * 1992-11-30 1994-06-07 The Procter & Gamble Company Low sudsing polyhydroxy fatty acid amide detergents
US5415801A (en) * 1993-08-27 1995-05-16 The Procter & Gamble Company Concentrated light duty liquid or gel dishwashing detergent compositions containing sugar
WO1995033038A1 (en) * 1994-06-01 1995-12-07 The Procter & Gamble Company Sarcosinate with clay softeners in laundry compositions
MX9606567A (en) * 1994-06-17 1997-03-29 Procter & Gamble Hand wash laundry compositions.

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8098468B2 (en) 2006-04-13 2012-01-17 Emerson Network Power, Energy Systems, North America, Inc. Hardware overvoltage disconnecting circuit
US8547674B2 (en) 2006-04-13 2013-10-01 Emerson Network Power, Energy Systems, North America Hardware overvoltage disconnecting circuit
CN104629943A (en) * 2013-11-14 2015-05-20 青岛锦涟鑫商贸有限公司 Improved concentrated detergent

Also Published As

Publication number Publication date
JPH10504056A (en) 1998-04-14
MX9701081A (en) 1997-05-31
EP0775190A1 (en) 1997-05-28
WO1996005280A1 (en) 1996-02-22
GB9511601D0 (en) 1995-08-02
ZA956663B (en) 1996-03-22
GB2292564A (en) 1996-02-28
PE13696A1 (en) 1996-05-07
GB2292155A (en) 1996-02-14
EP0775190A4 (en) 1999-06-30
BR9508535A (en) 1997-10-28
MA23645A1 (en) 1996-04-01
TR199500995A2 (en) 1996-06-21
GB9416224D0 (en) 1994-10-05
IL114824A0 (en) 1995-12-08
EG20780A (en) 2000-02-29
IL114824A (en) 1999-10-28

Similar Documents

Publication Publication Date Title
CN1159824A (en) Handwash laundry detergent compositions
CN1086732C (en) Compositions comprising ethoxylated/propoxylated polyalkyleneamine polymers as soil dispersing agents
CN1094517C (en) Detergent composition containing efficient enduring perfume
CN1105174C (en) Color-safe bleach boosters, compositions and laundry methods employing same
CN1101464C (en) Detergent compositions comprising multiperacid-foaming bleach activators
CN1117611C (en) Method for preparing fatty acid amide surfactants
CN1083005C (en) Quarternary substituted bleach activators
CN1161451C (en) Aqueous gel laundry detergent composition
CN1211474C (en) Deteragent composition containing mixtures of crystallinity-disrupted surfactants
CN1085247C (en) Secondary alkyl sulfate surfactant with improved solubility by compacting/coating process
CN1151753A (en) Handwash laundry detergent composition having improved mildness and cleaning performance
CN1292062C (en) Bleaching detergent compositions
CN1270621A (en) Improved alkylbenzenesulfonate surfactants
CN87101761A (en) Detergent builder compound containing ether carboxylate and polycarbexylate
CN1090887A (en) The high-sudsers composition that contains specially selected soap
CN1270622A (en) Improved alkylbenzenesulfonate surfactants
CN1202197A (en) High efficiency delivery system comprising zeolites
CN1247561A (en) Color-safe bleach boosters, compsns. and laundry methods employing same
CN1133612A (en) Bar composition with N-alkoxy or N-aryloxy polyhydroxy fatty acid amide surfactant
CN1090886A (en) Calcium ions and polyhydroxy fatty acid amide nonionic/selected anionic/soap surfactant mixture detergent composition
CN1059930A (en) Detergent composition
CN1151158A (en) Cationic bleach activators
CN1233274A (en) Hand wash laundry detergent compositions containing a combination of surfactants
CN1294627A (en) Liquid laundry detergent compsns, comprising HEDP and polyamines
CN1218500A (en) Agglomerated high density detergent composition containing secondary alkyl sulfate surfactant and processes for making same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C01 Deemed withdrawal of patent application (patent law 1993)
WD01 Invention patent application deemed withdrawn after publication