CN1225114A - Detergent composition - Google Patents
Detergent composition Download PDFInfo
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- CN1225114A CN1225114A CN97196401A CN97196401A CN1225114A CN 1225114 A CN1225114 A CN 1225114A CN 97196401 A CN97196401 A CN 97196401A CN 97196401 A CN97196401 A CN 97196401A CN 1225114 A CN1225114 A CN 1225114A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/005—Compositions containing perfumes; Compositions containing deodorants
-
- 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
- C11D1/38—Cationic compounds
- C11D1/645—Mixtures of compounds all of which are cationic
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0052—Gas evolving or heat producing compositions
-
- 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
- C11D3/042—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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D3/2086—Hydroxy carboxylic 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
- C11D1/12—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
- C11D1/22—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
- C11D1/29—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
- C11D1/40—Monoamines or polyamines; 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
- C11D1/38—Cationic compounds
- C11D1/42—Amino alcohols or amino ethers
- C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Organic Chemistry (AREA)
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- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
This invention relates to a detergent composition comprising an anionic surfactant and a cationic surfactant, an acid source and an alkali source capable of reacting together in the presence of water to produce a gas.
Description
Technical field
The present invention relates to a kind of washing composition that comprises negatively charged ion and cats product and acid source and alkali source, this washing composition is applicable to washing clothes and tableware.
Background of the present invention
The commercial at present all kinds of granulated detergents of being sold have the higher trend of content of the active ingredient (as various tensio-active agents) of tap density increase and this granular detergent composition.This class washing composition can provide bigger facility for the human consumer.The human consumer impels the quantity of weighting material in the washing composition to reduce to the demand of this type of concentrated product, and the wrapping material of washing composition are finally abandoned.
The human consumer also has a kind of demand to washing composition, wishes promptly that it can have to clean dirt-removing functions more efficiently.Therefore, washing composition is among the update always in recent years, has developed at present and has contained high density, eurypalynous tensio-active agent in the washing composition, as negatively charged ion, nonionic and cats product.
Poorly soluble problem can appear in the high density detergent that contains concentrated surfactant, this is because the dissolution rate of this type of washing composition is low or generate due to the gel, the result causes the bad dispersion of this product, or this is because the dispersion box of washing machine, or because due to the built-in metering device of washing machine.This bad dispersion usually is by due to the surfactant granules chance water generates gelation with high density.This gel stops the part detergent powder soluble in water, thereby has reduced the washing effect of this powder.When low hydraulic pressure and/or low wash temperature, this is a distinctive problem.
WO 94/28098 has set forth a kind of non-spray-dried detergent powder, and it is the C by ethoxylation
8-18Primary alconol, composite alkali aluminum silicon washing assistant and 5～40% water-soluble citrates are formed.
EP-A-0639637 discloses with a kind of alkali metal percarbonate and has replaced perborate bleach, to improve the dispersion and the dissolution rate thereof of washing composition.The mixture of Citrate trianion or Citrate trianion and vitriol or carbonate can be used for the percarbonate bleach dressing.EP-A-0639637 also has similar introduction to this.
The dispersiveness of improving particulate matter with effervesce is widely used in the pharmaceutical preparation.Wherein the most frequently used effervescent system is citric acid and supercarbonate and uses.As GB-A-2, described in 184,946, this effervescent system also is used to improve the dispersiveness of sterilant composition to control aquatic insect.
EP-A-0534525 has narrated the use of granular citric acid, and its specified particle diameter scope is 350～1500 μ m.
US-A-5,114,647 disclose a kind of sanitizing agent composition, and it comprises alkaline carbonate and two kinds of particles of aliphatic carboxylic acid, and its particle size range is 150～2000 μ m.
EP-A-0 333 223 discloses a kind of preparation of bath shampoo, and this bath shampoo contains the fumaric acid that average particle size range is 50～500 μ m.
The adding of citric acid causes alkalescence to descend.But alkaline pH is necessary for various washing composition compositions as some tensio-active agent performance optimum performance.The alkaline pH of total system helps cleaning, decontamination and dirt to suspend.Therefore it is unfavorable adding acid in detergent composition.US-A-4 for example, 414,130 have narrated and have contained the organic acid washing composition, and wherein some compound such as cats product just should be abandoned.
The application has had now found that the specific question relevant with the dispensing of detergent composition, this detergent composition contains negatively charged ion and cats product, the dispersion of this detergent composition can be improved by comprising a kind of acid or alkali, and the property retention of while negatively charged ion and cats product is constant.This just solves or has reduced the detergent solids particle residue in washing machine and the problem on the washing clothes.
In addition, because tensio-active agent more effectively is dispersed in the bath water, makes its overall efficiency better, thereby improved cleaning, decontamination and dirt suspension effect on the whole.
In addition, disperse the washing composition residue in box or the diverting device to reduce.
Here its relevant portion of whole data of enumerating is incorporated this paper into as a reference.
Brief summary of the invention
The invention provides a kind of detergent composition, said composition comprise anion surfactant (0.5%～60%, by weight), cats product (0.01～30%, by weight), a kind of acid source and alkali source, wherein said acid source and alkali source can be at mutually reactives in the presence of the water.
Detailed description of the present invention
Detergent composition of the present invention contains four kinds of essential compositions: anion surfactant, cats product, a kind of acid source and a kind of alkali source.These compositions and optional composition, and the method for preparing described washing composition will describe in detail below.Detergent surfactant
As described below, detergent composition of the present invention can contain one or more anion surfactants and one or more cats products.
Other tensio-active agent can also be arranged, and they are optional certainly with next group: negatively charged ion and cats product, nonionic, zwitterionic compound, zwitter-ion and amphoterics.
The weight percent that the total amount of tensio-active agent accounts for detergent composition is tending towards best by following putting in order: 1～90%, 3～70%, 5～40%, 10～30%, 12～25%.
Granular detergent composition to the effect that of the present invention.Contain one or more tensio-active agents in its basic composition, also contain a kind of washing assistant simultaneously.This basic composition can be by spraying drying and the preparation of dry type mixing/nodulizing.This basic composition also can contain some or all alkaline matters.On the other hand, acid and/or alkali can be used as independent component, join in the basic composition of washing composition with granular form.Anion surfactant
Detergent composition of the present invention contains one or more anion surfactants.Any anion surfactant that is used to wash purpose all can.Example has anion sulfate, sulfonate, carboxylate salt and sarcosinate surfactivity.Wherein select headed by the anion sulfate acid salt surfactant.Above-mentioned salt comprises the ammonium salt of sodium, potassium, ammonium and replacement, as single, double and triethanolamine salt.
Other anion surfactant has isethionate, as the acidylate oxyacetate, and the fatty acid amide of N-acidylate taurate, N-methyltaurine, alkyl succinic acid ester salt and esters of sulfosuccinic acids salt, sulfo-monomester succinate (especially saturated and undersaturated C
12-C
18Monoesters), sulfo-succsinic acid dibasic acid esters (especially saturated and undersaturated C
6-C
14Dibasic acid esters), N-acidylate sarcosinate.Resinous acid and hydrogenated resin acid also are suitable for, and as rosin, hydrogenated rosins, resinous acid and hydrogenated resin acid, they all are present in or come from the tallow oil.
Anion surfactant accounts for the weight percent of detergent composition, is tending towards best by following putting in order: 0.5～60%, 3～50%, 5～35%, 65～20%.
The proportioning of anion surfactant and cats product is tending towards best by following putting in order: 25: 1～1: 3,15: 1～1: 1,10: 1～1: 1.The anion sulfate acid salt surfactant
The anion sulfate tensio-active agent that is fit to use comprises brothers alkyl-sulphate, alkyl ethoxy sulfate, fatty oleoyl glycerine vitriol, alkylphenol oxyethane ether sulfate, the C of straight chain and side chain
5-C
17Acyl group-N-(C
1-C
4Alkyl) and-N-(C
1-C
2Hydroxyalkyl) glucosamine sulfate, and alkyl polysaccharide class vitriol are as the vitriol of alkyl poly glucoside (what introduce is the compound of nonionic non-sulfuric acidization) herein.
Alkyl-sulphate preferably from straight chain shape and side chain uncle C
9-C
22Alkyl-sulphate preferably is selected from C
11-C
15The alkyl-sulphate of side chain and C
12-C
14The alkyl-sulphate of straight chain.
Alkyl ethoxy sulfate surfactant preferably contains C
10-C
18Alkyl-sulphate, this compound are to carry out ethoxylation by every mole of molecule with 0.5 to 20 mole oxyethane.The carbonatoms of further selectable alkyl ethoxy sulfate surfactant is C
11-C
18, best carbonatoms is C
11-C
15, its ethoxylation be by every mole of molecule with 0.5 to 7, preferred 1 to 5 mole oxyethane carries out ethoxylation.
The content of particularly important of the present invention is to adopt preferred alkyl-sulphate and alkyl ethoxy sulfate surfactant mixture.This mixture is introduced in PCT number of patent application WO 93/18124.The anion sulfoacid salt surfactant
The anionic sulphonate tensio-active agent that is suitable for comprises C
5-C
20Linear alkylbenzene sulfonate, alkyl ester sulfonate, C
6-C
22Uncle or secondary paraffin sulfonate, C
6-C
24Alkene sulfonate, sulfonation poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oleoyl glycerol sulfonate and their any mixture.The anionic carboxylic acid salt surfactant
Suitable anionic carboxylate tensio-active agent comprises alkyl ethoxy carboxylate, alkyl polyethoxye multi-carboxylate's tensio-active agent and soap (alkyl caboxyls), the secondary soap of especially described herein some.
Suitable alkyl ethoxy carboxylate comprises having formula R O (CH
2CH
2O)
xCH
2COO
-M
+Salt, wherein R is C
6-C
18Alkyl, x are 0～10, and the distribution of ethoxylate is such, and with regard to weight, x is 0 o'clock, and its shared weight is less than 20%, and M is a positively charged ion.Suitable alkyl polyethoxye multi-carboxylate tensio-active agent comprises having formula R O-(CHR
1-CHR
2-O)
x-R
3Salt, wherein R is C
6-C
8Alkyl, x are 1～25, R
1And R
2Can be selected from hydrogen, formate (methylacid radical), amber acid radical (succinicacid radical), hydroxy succinic acid root and their mixture, R
3Can be selected from hydrogen, replacement or unsubstituted C
1-C
8The mixture of hydrocarbon and composition thereof.
Suitable soap surfactants comprises secondary soap surfactants, and it contains a carboxyl unit that is connected on the secondary carbon.Here the secondary soap surfactants of advantageous applications is water miscible, it be selected from 2-methyl isophthalic acid-undecanoic acid, 2-ethyl-1 capric acid, 2-propyl group-1-n-nonanoic acid, 2-butyl-1 is sad and the salt of the water dissolvable of 2-amyl group-1-enanthic acid.Some soap also comprises suds suppressor.The basic metal sarcosinate surfactant
Other suitable anion surfactant has the basic metal sarcosinate, and its general formula is R-CON (R
1) CH
2COOM, wherein R is C
5-C
17Straight or branched alkyl or alkenyl, R
1Be C
1-C
4Alkyl, M are alkalimetal ion.Preferred examples is tetradecyl and oleoyl methyl sodium sarcosinate.Cats product
Another necessary composition is an anion surfactant in the detergent composition of the present invention, and it accounts for 0.1～30% of described detergent composition weight.The weight percent that this cats product accounts for described detergent composition is tending towards best by following putting in order: 0.1～20%, 0.4～7%, 0.5～3%.
The ratio of anion surfactant and cats product is tending towards best by following putting in order: 25: 1～1: 3,15: 1～1: 1,10: 1～1: 1.
Cats product preferably is selected from cationic ester tensio-active agent, cation mono alkoxylate amine tensio-active agent, positively charged ion bis-alkoxy amine tensio-active agent and their mixture.The cationic ester tensio-active agent
Cats product can comprise the cationic ester tensio-active agent.
If the cationic ester tensio-active agent is arranged in detergent composition of the present invention, its weight percent of accounting for described detergent composition is tending towards best with following putting in order so: 0.1～20%, 0.4～7%, 0.5～3%.
The cationic ester tensio-active agent preferably has the character of tensio-active agent, contains an ester (COO-) dispersible compound in the water of key and at least one cationic charge group at least.
Suitable cationic ester tensio-active agent has for example cholinesterase tensio-active agent, and they are open in US patent 4228042,4239660 and 4260529.
The content that should note is in the molecule of this type of tensio-active agent, ester bond and cationic charge group will be separated from each other, its interval group is made up of at least three atoms (i.e. three atom chain lengths), also can be three to eight atoms or three to five atoms, is preferably three atoms.The atom that forms the spacer groups chain can be selected from: the mixed group of carbon, nitrogen and Sauerstoffatom and composition thereof, subsidiary restrictive condition are that nitrogen or the Sauerstoffatom in the described chain only links to each other with carbon atom.Therefore for example contain-O-O-(being peroxide bridge) ,-N-N-,-spacer groups of N-O-should get rid of, and for example should contain-CH
2-O-CH
2-and-CH
2-NH-CH
2-spacer groups.The content of a practical application is that the spacer groups chain only contains carbon atom, and preferably this spacer groups chain is a hydrocarbyl chain.The cationic ester tensio-active agent that preferably has following formula:
R wherein
1Be C
5-C
31The alkyl of straight or branched, alkenyl or alkaryl or M
-N
+(R
6R
7R
8) (CH
2)
sX and Y independently are selected from following group: COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO, and wherein at least one is COO, OCO, OCOO, OCONH or NHCOO group among X or the Y; R
2, R
3, R
4, R
6, R
7And R
8Can be independently selected from alkyl, alkenyl, C
1-C
4Hydroxyalkyl and hydroxyl alkenyl, and alkaryl; R
5Can be independently selected from H or a C
1-C
3Alkyl; M, n, s, t selected value scope independently are 0～8, and b value scope is 0～20; A, u, v selected value independently are 0 or 1, condition be u or v one of them be necessary for 1; M is an anti-charge anions.
It is better that M is selected from halogen, methylsulfate, sulfate radical and nitrate radical, preferably is selected from methylsulfate, chlorine, bromine or iodine ion.
Preferably select cationic ester tensio-active agent for use with following formula,
R wherein
1Be C
5-C
31Straight or branched alkyl, alkenyl or alkaryl chain; X system is selected from COO, OCO, OCOO, OCONH and NHCOO; R
2, R
3And R
4Can be independently selected from alkyl and hydroxyalkyl, its carbon containing is C
1-C
4R
5Can be H or C independently
1-C
3Alkyl; The n value is 0～8, and the b value is 0～20, and a value is 0 or 1, and the m value is 3～8.
Best R
2, R
3And R
4Be independently selected from C
1-C
4Alkyl and C
1-C
4Hydroxyalkyl.R in the application
2, R
3, R
4In at least or have only one to be hydroxyalkyl.Hydroxyalkyl has C
1-C
4Better, C is arranged
2-C
3Better, be preferably two carbon atoms.R in the application
2, R
3And R
4In at least one is C
2-C
3Alkyl is preferably two C
2-C
3Alkyl.
R in the application
2, R
3And R
4In two and cationic charge group nitrogen form ring texture.It is better that this ring structure contains another nitrogen-atoms, or it is better to contain another Sauerstoffatom, or the mixture of being made up of them.It is better that ring structure contains 5～8 atoms, preferably contains 6 atoms.
R in the practical application
2, R
3And R
4In two and cationic charge group nitrogen form morpholino or replace the morpholino structure better.Most preferred this type of cationic ester surfactant structure formula is:
R wherein
1Be C
5-C
31The alkyl of straight or branched, alkenyl or alkaryl chain; X is selected from group COO, OCO, OCOO, OCONH and NHCOO; R
9Be selected from group C
1-C
4Alkyl, alkenyl, hydroxyalkyl and hydroxyl-alkenyl, and alkaryl; R
5Be independently selected from H or C
1-C
3Alkyl; N value 0～8, b value 0～20, a value are 0 or 1, m value 3～8.
Best R
2, R
3And R
4Be independently selected from C
1-C
4Alkyl and C
1-C
4Hydroxyalkyl.R in the application
2, R
3And R
4In have only one at least or preferably for hydroxyalkyl.This hydroxyalkyl contains C
1-C
4Better, contain C
2-C
3Two carbon atoms better, are preferably arranged.R
2, R
3And R
4In at least one is C
2-C
3Alkyl is better, and wherein two is C
2-C
3Alkyl is better.
The cationic ester surfactant structure formula of water-dispersion is preferably:
Wherein m is 1～4, is 2～3 better, R
1Be C
11-C
19The alkyl chain of straight or branched.
The particularly preferred cholinesterase class of this type of tensio-active agent has: stearyl cholinesterase halogenation methyl quaternary ammonium (R
1Be C
17Alkyl), palmityl cholinesterase halogenation methyl quaternary ammonium (R
1Be C
15Alkyl), mnyristoyl cholinesterase halogenation methyl quaternary ammonium (R
1Be C
13Alkyl), lauroyl cholinesterase halogenation methyl quaternary ammonium (R
1Be C
11Alkyl), cocoyl phatidylcholine ester halogenation methyl quaternary ammonium (R
1Be C
11-C
13Alkyl), tallow phatidylcholine ester halogenation methyl quaternary ammonium (R
1Be C
15-C
17Alkyl), the mixture of forming and thus.
Other suitable cationic ester surfactant structure is:
Wherein d is 0～20.The cationic ester tensio-active agent is preferably hydrolyzable under the condition of laundry washing methods.
Above-mentioned particularly preferred cholinesterase class can be under acid catalysis, by the lipid acid and the dimethylamino-ethanol direct esterification preparation of suitable chain length.Reaction product is quaternized with methyl halogenide, and reaction is preferably in solvent such as ethanol, water, propylene glycol or is preferably in fatty alcohol ethoxylate, as C
10-C
18Under existing, fatty alcohol ethoxylate (degree of its ethoxylation is: forming used cationic substance needs with 3～50 moles of ethoxy groups for a mole) carries out.The preparation of this type of tensio-active agent also can be under acid catalysis, by the longer chain fatty acid and the direct esterification of 2-halogen ethanol of suitable chain length.Reaction product can be quaternized with Trimethylamine 99, obtains the target cationic substance.Cation mono alkoxylate amine tensio-active agent
Cats product of the present invention comprises cation mono alkoxylated amines tensio-active agent, and its general structure is:
R wherein
1Be alkyl or alkenyl, it contains carbon number is C
6-C
18, or C
6-C
16Better, be preferably C
6-C
11R
2And R
3Be alkyl independently separately, it contains carbon number is C
1-C
3, often select methyl for use; R
4It is better that system is selected from hydrogen, is methyl and ethyl secondly.X
-Be negatively charged ion, as chlorine, bromine, methylsulfate, sulfate radical or the like, its effect provides electric neutrality; A is selected from C
1-C
4Alkoxyl group, especially oxyethyl group (promptly-CH
2CH
2O-), propoxy-, butoxy and their mixed group; P value 1～30,1～15 is better, and value 1～8 is best.
Cation mono alkoxylate amine surfactant structure formula commonly used is:
R wherein
1Be C
6-C
18Alkyl and mixture thereof are often selected C for use
6-C
14Alkyl, especially C
6-C
11Alkyl is preferably C
8-C
10Alkyl.X be any negatively charged ion that is easy to get so that charge balance to be provided, often select chlorine or bromine for use.
As mentioned above, the compound of the above-mentioned type comprises following compound, wherein ethoxy group (CH
2CH
2O) unit (EO) is by butoxy, isopropoxy [CH (CH
3) CH
2O] and [CH
2CH (CH
3) O] unit (i-Pr) or positive propoxy unit (Pr), and EO and/or Pr and/or the replacement of i-Pr unit.
When cation mono alkoxylate amine tensio-active agent is used for the granular detergent composition, hydrocarbyl substituent R wherein
1Be C
6-C
11Preferred especially C
10, reason is to compare with longer chain, they can improve washing particulate dissolution rate in cold water.
The weight percentage ranges of positively charged ion monoalkoxy amine surfactant comprise detergent composition is 0.1～20% among the present invention, and 0.4～7% is better, and 0.5～3.0% is better.Positively charged ion bis-alkoxy amine tensio-active agent
Cats product of the present invention can be a positively charged ion bis-alkoxy amine tensio-active agent, and its general formula is:
R wherein
1Be alkyl or alkenyl, containing carbon number is C
6-C
18, C
6-C
16Better, C
6C
11Better, be preferably C
8-C
10R
2Be C
1-C
3Alkyl is often selected methyl for use; R
3And R
4But independent variation often is selected from hydrogen (best), methyl and ethyl; X
-Be negatively charged ion, as chlorine, bromine, methylsulfate, sulfate radical or the like, its effect is that electric neutrality can be provided.But A and A ' independent variation are selected from C separately
1-C
4Alkoxyl group, especially oxyethyl group (promptly-CH
2CH
2O-), propoxy-, butoxy reach the mixture of forming thus; The p value is 1～30,1～4 better, q value 1-30, and 1-4 is better, and preferably p and q are 1.
Most preferred positively charged ion bis-alkoxy amine surfactant structure formula is:
R wherein
1Be C
6-C
18Alkyl and composition thereof is especially selected C for use
6, C
8, C
10, C
12, C
14Alkyl and composition thereof.X be a kind of negatively charged ion that is easy to get with balancing charge, often select muriate for use.With reference to above-mentioned general positively charged ion bis-alkoxy amine structure, R in used compound
1From C
12-C
14Alkyl fatty acid, R
2Be methyl and ApR
3And A ' qR
4Be respectively monosubstituted ethoxy.
The structural formula of the bis-alkoxy amine cats product that other is suitable for is:
R wherein
1Be C
6-C
18Alkyl is often selected C for use
6-C
14Alkyl, independent value p are 1～3, and q is 1～3; R
2Be C
1-C
3Alkyl is often selected methyl for use; X is negatively charged ion, especially chlorine or bromine.
Other compound of the above-mentioned type comprises following situation: oxyethyl group (CH wherein
2CH
2O) unit (EO) can be by group such as butoxy (Bu), isopropoxy [CH (CH
3) CH
2O] and [CH
2CH (CH
3) O] and (i-Pr) or positive propoxy (Pr) replace, and the mixed group of EO and/or Pr and/or i-Pr replaces.
According to the present invention, when positively charged ion bis-alkoxy amine tensio-active agent is used for granular detergent composition, hydrocarbyl substituent R wherein
1Be C
6-C
11, preferred C
8Or C
10, reason is to compare them can improve laundry particulate dissolution rate with longer chain under the cold water condition.
The weight percentage ranges that is used for the positively charged ion bis-alkoxy amine surfactant comprise detergent composition of detergent composition of the present invention is 0.1～20%, and 0,4～7% is better, preferred 0.5～3.0% alkali source
According to the present invention, the alkali source of detergent composition can with the acid source generated reactive gas in the water.Usually this gas is carbonic acid gas, so this alkali is a kind of carbonate or a kind of suitable carbonate derivative.
The weight percentage ranges of alkali source is 2～75% in the detergent composition of the present invention, and 5～60% is better, is preferably 10～30%.When alkali source was present in the detergent particles of agglomerationization, this agglomerate often contained 10～60% alkali source.
Alkali source is a carbonate described in concrete the application.The example of preferred carbonate is basic metal and alkaline earth metal carbonate, and as yellow soda ash, supercarbonate and sesquicarbonate, and the mixture that forms with calcium carbonate superfine powder, this is at German Patent 2,321, the middle explanation of 001 (announcements on November 15th, 1973).Alkali metal percarbonate also is the carbonate that is suitable for, and describes in detail in the application's " inorganic perhydrate salt " part.
Alkali source also can contain other composition, as silicate.The silicate that is suitable for comprises water-soluble metasilicate, wherein SiO
2With Na
2The O proportioning is 1.0～2.8, and it is 1.6～2.0 better selecting ratio for use, and it is 2.0 that the best is selected ratio for use.Silicate can be anhydrous salt or moisture salt form.Has SiO
2: Na
2O is that 2.0 silicate is best silicate.The basic metal persilicate also is the silicate that is suitable for.
The professional who is familiar with the present technique field knows the source that other is suitable for.Acid source
According to the present invention, acid source is present in the detergent composition, it can with alkali source generated reactive gas in the water.
The weight percent of acid source in detergent composition is tending towards best by following putting in order: 0.1～50%, 0.5～25%, 1～12%, 1～7%, 2～5%.Acid source generally accounts for 1～3% of composition weight in the concrete application of the present invention, uses 3% usually.
The particle size range of selecting the acid source more than 80% or 80% for use is 150 μ m～710 μ m, and wherein the particle diameter of at least 37% (weight) acid source is at 350 μ m or better below the 350 μ m.The particle diameter of selecting 100% acid source for use is at 710 μ m or be unnecessary below the 710 μ m, as long as aforesaid standards can reach.The another kind of selection is greater than 38.0%, and the particle diameter of commonly used 38.7% granular acid source is at 350 μ m or below the 350 μ m.
The acid source size can be come out by the acid source sample calculation of sieving on the Taylor series screen size.For example, to be equivalent to pore size be 150 μ m to Tyler mesh 100.Therefore can be according to the screen size pore size corresponding to the weight fraction mapping that obtains.
Acid source can be appropriate organic, mineral acid or mineral acid, or derivatives thereof or its mixture.Acid source can be single, double or three protonic acids.The derivative of selecting for use comprises the salt or the ester of acid.Acid source is preferably non-hygroscopic, and this can improve stability in storage.But a hydration acid source is operable.Organic acid and derivative thereof are also selected.The preferential selection of acid is water miscible.The acid that is suitable for comprises citric acid, pentanedioic acid, tartrate, succsinic acid or hexanodioic acid, SODIUM PHOSPHATE, MONOBASIC, sodium pyrosulfate, boric acid, and salt or ester.Citric acid is selected for use especially.Other washing composition composition
Detergent composition of the present invention also contains other washing composition composition.The characteristic of these other compositions and the amount that is added depend on the physical aspect of described composition and select the character of washing operation for use.
Detergent composition of the present invention preferably contains one or more other compositions, and they are tensio-active agent, SYNTHETIC OPTICAL WHITNER, washing assistant, organic polymer, enzyme, froth suppressor, lime soap dispersion agent, dirt suspension and anti-sludging agent and the corrosion inhibitor that is selected from other.Alkoxy-based non-ionic surface active agent
Any alkoxy-based non-ionic surface active agent all is suitable in fact.Here preferred oxyethyl group and propoxylation nonionogenic tenside.
Used alkoxy-based surface-active agent system is selected from a few class nonionic condensess, as the condensation product of alkylphenol, nonionic ethoxylated alcohol, nonionic oxyethyl group/propoxylated fatty alcohol, nonionic oxyethyl group/propoxylated glycerine and propylene glycol, the condensation product of nonionic ethoxylate and propylene oxide/quadrol affixture.Nonionic alcohol alcoxylates tensio-active agent
The condensation product of fatty alcohol and 1～25 mole of epoxide, particularly oxyethane and/or propylene oxide is suitable for.The alkyl chain of fatty alcohol can be the uncle or the secondary alkyl of straight or branched, generally contains C
6-C
22Especially preferably by C
8-C
20The condensation product of the oxyethane of the alcohol of alkyl and 2～10 times of moles.The nonionic polyhydroxy fatty acid amide surfactant
The structural formula of the polyhydroxy fatty acid amide that is suitable for is: R
2CONR
1Z, wherein R
1Be H, C
1-C
4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, oxyethyl group, propoxy-and composition thereof are generally selected C
1-C
4Alkyl is selected C
1Or C
2Alkyl is better, optimal selection C
1Alkyl (being methyl); R
2Be C
5-C
31Alkyl is generally selected C
5-C
19Straight chained alkyl or alkenyl are selected straight chain C
9-C
17Alkyl or alkenyl are better, the optimal selection straight chain C
11-C
17Alkyl or alkenyl, or the mixture of forming thus; Z is the poly-hydroxy hydrocarbon, directly links to each other with three hydroxyls at least on its straight chain hydrocarbon chain, or is its alkoxy derivative (oxyethyl group commonly used or propoxylated derivative).Z often is selected from the reducing sugar in the reductive amination process, and Z is preferably glycosyl (glycityl).The nonionic fatty acid amide surfactant
The structural formula of suitable fatty acids acidamide surfactant is: R
6CON (R
7)
2, R wherein
6Be C
7-C
21Alkyl, C commonly used
9-C
17Alkyl; R
7Can be selected from hydrogen, C respectively
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, and-(C
2H
4O)
xH, wherein the x value 1～3.Nonionic alkane polysaccharide tensio-active agent
The alkane polysaccharide that is suitable for is explanation in U.S. patent 4,565,647 (Llenado, on January 21st, 1986 issued).This compounds contains C
6-C
30Hydrophobic grouping and a polysaccharide as a kind of polysaccharide glycosides, contain the hydrophilic radical of 1.3 to 10 sugared units.
The structural formula of preferred APG is:
R
2O (C
nH
2nO) t (giycosyl)
xR wherein
2Be selected from alkyl, alkane phenyl, hydroxyalkyl, hydroxyl alkane phenyl and composition thereof, wherein alkyl contains C
10-C
18N value 2 or 3; T value 0～10, x value 1.3～8.The glycosyl base is preferably from glucose.Amphoterics
The amphoterics that is suitable for comprises amine oxide tensio-active agent and alkyl both sexes carboxylic acid.
The amine oxide structural formula that is suitable for is: R
3(OR
4)
xN
0(R
5)
2, R wherein
3Be selected from alkyl, hydroxyalkyl, amido propyl group and alkane phenyl and composition thereof, they all contain C
8-C
26R
4For containing C
2-C
3Alkenyl or hydroxyl alkenyl, and the mixture that forms thus; X value 0～5 often gets 0～3; R
5Respectively do for oneself and contain C
1-C
3Alkyl or hydroxyalkyl, and the polyethylene oxide that contains 1～3 ethylene oxide group.Preferred C
10-C
18Alkyl-dimethyl amine oxide and C
10-C
18Amidoalkyl dimethylin oxide compound.
The example of the alkyl both sexes carboxylic acid that is suitable for is Miranol (TM) C2M Conc., and (Dayton NJ.) produces by Miranol company.Zwitterionics
According to the present invention, zwitterionics can be added in detergent composition or its component.These tensio-active agent wide material sources can be secondary and tertiary amines derived thing, the heterocycle second month in a season and tertiary amines derived thing, quaternary ammonium derivative, quaternary phosphine or uncle's sulfonium compound.Trimethyl-glycine and sultaine tensio-active agent are the zwitterionicss of typically used.
The betaines structural formula of compound that is suitable for is: R (R ')
2N
+R
2COO
-, wherein R is C
6-C
18Alkyl, the R ' typical C of respectively doing for oneself
1-C
3Alkyl, R
2Be C
1-C
5Alkyl.The trimethyl-glycine of selecting for use is C
12-C
18Dimethyl-caproic acid ammonium and C
10-18Acyl group amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.The compound beet alkali surface activator also is suitable for.The water soluble detergency promoter compound
Detergent composition of the present invention preferably contains the water soluble detergency promoter compound, and its weight percent that accounts for described composition is 1～80% better, accounts for 10～70% better, and the best accounts for 20～60%.
The water soluble detergency promoter compound that is suitable for comprises the water-soluble monomer multi-carboxylate, or its sour form, homotype or interpolymer poly carboxylic acid or its salt, and wherein poly carboxylic acid contains at least two carboxyls that are no more than two carbon atoms apart.This compounds also has the mixture that borate, phosphoric acid salt and above-mentioned substance are formed in addition.
Although because price and the common preferred monomers multi-carboxylate of performance reason be as washing assistant, carboxylate salt or multi-carboxy acid salt washing agent can be monomer or oligomer.
The carboxylate salt that contains a carboxyl that is suitable for comprises water-soluble lactic acid salt, glycol hydrochlorate and ether derivant thereof.The multi-carboxylate of containing two carboxyls comprises water-soluble succinate, malonate, (ethylidene dioxy base) diacetin, maleate, glycol ether alcohol hydrochlorate, tartrate, tartronate, fumarate, and ether carboxylate and sulfinyl carboxylate salt.The multi-carboxylate spy of containing three carboxyls comprises water-soluble citrate, aconitate, citraconate in addition, and the succinate derivative, as in English Patent 1,379, the carboxy methoxy-succinic acid salt of explanation in 241 is in English Patent 1,389, the newborn oxydisuccinic acid salt of explanation in 732, the aminosuccinic acid salt of explanation in Netherlands patent applications 7205873, and in English Patent 1,387, the oxo multi-carboxylate of explanation in 447 is as 2-oxa--1.1.3-tricarballylic acid salt.
The multi-carboxylate of containing four carboxyls is included in English Patent 1,261, disclosed oxo disuccinate in 829,1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group and be included in English Patent 1,398,421,1,398,422 and United States Patent (USP) 3,936,448 in disclosed sulfo-succinic acid salt derivative, and in English Patent 1,439, the sulfonation pyrolytic Citrate trianion of explanation in 000.Preferred multi-carboxylate is for containing hydroxycarboxylate, the especially Citrate trianion up to three carboxyls in every mole of molecule.
The borate washing assistant and washing composition store or wash conditions under can produce the boratory washing assistant that contains borate formation thing, be suitable water soluble detergency promoter.
The example of the water-soluble phosphate washing assistant that is suitable for has the tripolyphosphate an alkali metal salt, the sodium salt of tetra-sodium, sylvite and ammonium salt, and the sodium salt of former phosphoric acid and sylvite, and many metals of phosphoric acid sodium salt (polymerization degree scope is 6～21) also have phytate.Solvable or the insolubility washing-aid compound of part
Detergent composition of the present invention can contain the solvable or insolubility washing-aid compound of part, and the weight percent that it accounts for described composition is 1～80% better, accounts for 10～70% better, and the best accounts for 20～60%.
The example of main water insolubility washing assistant comprises sodium silicoaluminate.
The modular of aluminosilicate zeolite that is suitable for is: Na
z[(AlO
2)
z(SiO
2) y] xH
2O, wherein z and y are at least 6; The molar ratio scope of z and y is 1.0～0.5; X is at least 5, is 7.5～276 better, is 10～264 better.Silico-aluminate is hydrate forms, generally contains bonding water 10～28%, and preferred 18～22%.
Aluminosilicate zeolite can be a crude substance, but preferred synthesis of derivatives.The crystalline aluminosilicate ion exchange material of synthetic is with zeolite A, zeolite B, zeolite P, X zeolite, zeolite HS, and the title of their mixtures can have been bought.Zeolite A has following formula, Na
12[AlO
2)
12(SiO
2)
12] xH
2O is x value 20～30 wherein, gets 27 especially.X zeolite has following formula, [(AlO
2)
86(SiO
2)
106] 276H
2The crystalline layered silicate of O advantageous applications has following general formula, NaMSi
xO
2x-1YH
2O wherein M is sodium or hydrogen, x value 1.9～4, y value 0～20.Such is crystalline, and the layering water glass illustrates in patent EP-A-0164514, and its preparation method is open in patent DE-A-3417649 and DE-A-3742043.At this, the x value often is 2,3 or 4, preferred 2 in the formula.Best material is δ-Na
2Si
2O
5, it can be buied by the NaSKS-6 title from Hoechst AG.The organic peroxide acid bleaching system
The feature that detergent composition of the present invention had is the organic peroxide acid bleaching system.This bleaching system contains hydrogen peroxide and organic peroxide acid bleach precursor compound in concrete the application.The preparation of organic peroxide acid can be undertaken by described precursor and hydroperoxidation.Used hydrogen peroxide comprises inorganic perhydrate SYNTHETIC OPTICAL WHITNER.Another object lesson is that the ready-formed organic peroxide acid directly is added in the described composition.The composition that contains hydrogen peroxide, organic peroxy acid precursor and ready-formed organic peroxide acid mixture also is subject to people's attention.Inorganic perhydrate SYNTHETIC OPTICAL WHITNER
Inorganic perhydrate salt is the source of hydrogen peroxide.These salt add with alkali metal form usually, and its weight percent that accounts for composition is generally 1～40%, account for 2～30% better, preferably account for 5～25%.
The example of inorganic perhydrate salt comprises perborate, percarbonate, superphosphate, persulphate and persilicate.Described inorganic perhydrate salt is generally an alkali metal salt.Described inorganic perhydrate salt comprises the crystalline solid that does not add protection.But to some perhydrate salt, the preferred embodiment of this granular composition is a form of taking dressing, and this can provide better stability in storage to such granulated salt product.The coating material that is suitable for comprises inorganic salt, as alkalimetal silicate, carbonate, borate and composition thereof, or organism, as wax, oil or fatty soap.
Sodium peroxoborate is preferred perhydrate salt, and the standard type of its monohydrate is NaBO
2H
2O
2, the standard type of tetrahydrate is NaBO
2H
2O
23H
2O.
Alkali metal percarbonate, particularly SPC-D are preferred perhydrate salt.SPC-D is to have formula 2Na
2CO
33H
2O
2Addition compound, commercially available is crystalline solid.
The conduct of peroxide Potassium peroxysulfate is the another kind of inorganic perhydrate salt that is used for detergent composition.Peroxyacid bleach precursor
Peroxyacid bleach precursor is to carry out the all-hydrolytic reaction to prepare a compounds of peroxy acid with hydrogen peroxide.The peroxyacid bleach precursor compound is general available to be represented with following formula: O X-C-L wherein L is a leavings group, X is essential arbitrary functional group, through the all-hydrolytic reaction, the structure of the peroxy acid of generation is
O
X-C-OOH
It is better that the peroxyacid bleach precursor compound accounts for the weight percent 0.5～20% of detergent composition, accounts for 1～15% better, preferably accounts for 1.5～10%.
The peroxyacid bleach precursor compound that is suitable for contains one or more N-or O-acyl group usually, and this makes the wide material sources of precursor.The kind that is suitable for has the acylated derivatives of acid anhydrides, ester, imide, lactan, imidazoles and oxime.Useful examples for compounds is open in patent GB-A-1586789 in such.The ester class that is suitable for is at patent GB-A-836988,864798,1147871,2143231 and EP-A-0170386 in open.Leavings group
Leavings group (following represent with the L group) must have enough activity, takes place so that all-hydrolytic is reflected in the Best Times scope (i.e. washing operation).If but L is too active, this activator is used for whitener composition and just is difficult to stablize so.
Preferred L group is to be selected from next group and composition thereof.
With
R wherein
1Contain C
1-C
14Alkyl, aryl or alkaryl, R
3For containing C
1-C
8Alkyl chain, R
4Be H or R
3, Y is H or a solubilizing group.R
1, R
3And R
4In any can be replaced by arbitrary functional group (as alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical, acid amides and ammonium or alkyl ammonium group) in fact.
Preferred solubilizing group has-SO
3 -M
+,-CO
2 -M
+,-SO
4 -M
+,-N
+(R
3)
4X
-And O＜-N (R
3)
3, best is-SO
2 -M
+And CO
2 -M
+, R wherein
3For containing C
1-C
4Alkyl chain, M can increase the deliquescent positively charged ion of bleach activator, X can increase the deliquescent negatively charged ion of bleach activator.M is that the ammonium cation of basic metal, ammonium or replacement is better, and sodium and potassium are best; X is halogenide, oxyhydroxide, Methylsulfate or acetate negatively charged ion.Alkyl percarboxylic acids bleach precursor.
Alkyl percarboxylic acids bleach precursor produces percarboxylic acids through all-hydrolytic.Such preferably precursor can produce peracetic acid through all-hydrolytic.
Preferred acid imide alkyl peroxycarboxylic acid precursors compound comprises N, N, and N', N' tetrem acidylate Alkylenediamine, wherein alkylidene group contains C
1-C
6, particularly wherein alkylidene group contains the compound of 1,2 and 6 carbon atom.Tetraacetyl ethylene diamine (TAED) is particularly preferred.
Other preferred alkyl peroxycarboxylic acid precursors has: 3,5, and 5-trimethyl acetyl oxygen Phenylsulfonic acid sodium salt (iso-NOBS), nonanoyl oxygen benzene sulfonic acid sodium salt (NOBS), acetyl oxygen benzene sulfonic acid sodium salt (ABS) and five acetyl glucose.The alkyl peroxy acids precursor that acid amides replaces
The alkyl peroxy acids precursor compound that acid amides replaces is suitable for, and it comprises the compound with following general formula,
Or
R wherein
1Be C
1-C
14Alkyl, R
2Be C
1-C
14Alkylidene group, R
5Be H or C
1-C
10Alkyl, L are essentially arbitrary leavings group.The bleach activating immunomodulator compounds that such acid amides replaces illustrates in patent EP-A-0170386.Peroxybenzoic acid precursors
The peroxybenzoic acid precursors compound produces peroxybenzoic acid through all-hydrolytic.Oxygen-acidylate peroxybenzoic acid precursors the compound that is suitable for comprises and replacing and unsubstituted benzoyl oxygen benzene sulfonate; the benzoylation product that sorbyl alcohol, glucose and all carbohydrates and benzozlating agent reaction obtain; and acid imide; N-benzoyl succinimide is wherein arranged, the urea that four benzoyl quadrols and N-benzoyl replace.The imidazoles peroxybenzoic acid precursors that is suitable for has N-benzoyl imidazoles and N-benzoyl benzoglyoxaline.The peroxybenzoic acid precursors that contains the N-acyl group that other is useful comprises N-benzoyl pyrrole alkane ketone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.The negatively charged ion peroxyacid precursor
Positively charged ion peroxyacid precursor compound generates the positively charged ion peroxy acid through all-hydrolytic.Preparation positively charged ion peroxyacid precursor, general available positive charge functional group replaces the peroxy acid part of suitable peroxyacid precursor compound, and this positive charge functional group has for example ammonium or alkane ammonium group, preferred ethyl or ammonium methyl.The positively charged ion peroxyacid precursor is present in the solid phase detergent composition with the form of suitable negatively charged ion (as halide ions) with salt usually.
The peroxyacid precursor compound that replaces with positively charged ion can be peroxybenzoic acid and substitutive derivative thereof, in addition the precursor compound of introducing above.In addition, the peroxyacid precursor compound can be the alkyl peroxy acids precursor that alkyl peroxycarboxylic acid precursors compound or the acid amides introduced above replace.
The positively charged ion peroxyacid precursor all has introduction in many patents, as U.S.4, and 904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K.1,382,594; EP 475,512; 458,396; 284,292 and JP 87-318,332.
Introduce in the example of the preferred cation peroxyacid precursor patent below, as U.K. patent application 9407944.9 and U.S. patent application 08/298903,08/298650,08/298904 and 08/298906.
The positively charged ion peroxyacid precursor that is suitable for comprises alkyl or benzoyl oxygen benzene sulfonate, N-acidylate hexanolactam and the single benzoyl tetrem acyl glucose benzoyl peroxide that ammonium or alkylammonium replace.The positively charged ion peroxyacid precursor of preferred N-acidylate hexanolactam class has trialkyl ammonium methylene radical benzoyl caprolactam and trialkyl ammonium methylene radical alkyl hexanolactam.Benzo oxazinyl organic peroxy acid precursor
The benzo oxazinyl precursor compound (this compounds that especially has following formula) that is suitable for is at patent EP-A-332, introduces in 294 and EP-A-482,807,
R wherein
1Be H, alkyl, alkaryl, aryl or aralkyl.The ready-formed organic peroxide acid
Except organic peroxide acid bleach precursor compound, or as another selection, organic peroxide acid SYNTHETIC OPTICAL WHITNER system can contain a kind of ready-formed organic peroxide acid, and it accounts for 1～15% of detergent composition weight usually, accounts for 1～10% better.
Preferred organic peroxy acid compounds is the acid amides substitution compound with following general formula:
Or
R wherein
1Be C
1-C
14Alkyl, aryl or alkaryl, R
2Be C
1-C
14Alkylidene group, arylidene and alkyl arylene, R
5Be H or C
1-C
10Alkyl, aryl or alkaryl.The organic peracid compounds that such acid amides replaces is existing explanation in patent EP-A-0170386.
Other organic peroxide acid comprises diacyl and four acyl peroxides, especially diperoxy dodecanedioic acid, diperoxy tetradecane diacid and diperoxy Thapsic acid.Single and two nonane diacid, list and two undecane dicarboxylic acid and N-O-phthalic amido peroxide caproic acid crossed also is suitable for.Bleaching catalyst
In the present composition bleaching catalyst that contains transition metal can be arranged at random.Suitable catalysis system of this catalyzer contains determines the active heavy metal cation of bleach catalyst, as copper, iron or manganese positively charged ion, also has the almost assistant metal positively charged ion of catalytically inactive, as zinc or aluminium cations, also has the sequestrant that catalysis and assistant metal positively charged ion are had definite stability constant in addition, as ethylenediamine tetraacetic acid (EDTA).
The bleaching catalyst of other type has the manganese mixture, and it is at patent U.S.5, introduces in 246,621 and U.S.5,244,594.The preferred embodiment of described catalyzer has: Mn
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)
2, Mn
IIIMn
IV 4(u-O)
1(u-OAc)
2-(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2-(ClO
4)
3, and the mixture that forms thus.Other catalyzer is referring to European patent application publication No. 549,272.Other ligand that is suitable for has: 1,5, and 9-trimethylammonium-1,5,9-triazododecane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane, and their mixture.
The example of the bleaching catalyst that is suitable for is referring to patent U.S.4, and 246,612 and U.S.5,227,084.The patent of introducing monokaryon manganese (IV) mixture has U.S.5, and 194,416, mixture wherein is Mn (1,4,7 trimethylammoniums-1,4,7-7-triazacyclononane) (OCH
3)
3-(PF
6).The bleaching catalyst of another type is the water-soluble compound of manganese (III) and/or (IV) and ligand formation, and ligand wherein is non-carboxylic acid poly hydroxyl compound, and it contains at least three successive C-OH groups, the visible patent U.S.5 of detailed content, 114,606.Other example has double-core manganese and four-N-dentate and two-N-dentate, as N
4Mn
III(u-O)
2Mn
IVN
4)
+[Bipy
2Mn
III(u-O)
2Mn
IVBipy
2]-(ClO
4)
3The mixture that generates.
Other bleaching catalysts that are suitable for all have introduction in some patents, as EP number of patent application 408,131 (cobalt complex catalyst), EP number of patent application 384,503 and 306,089 (catalysis of metalloporphyrin agent), U.S.4,728,455 (manganese/polygamy position is catalyst based), U.S.4,711,748 and EP number of patent application 224,952 (the absorption Mn catalysts on the silico-aluminate), U.S.4,601,845 (have manganese, the aluminosilicate carrier of zinc and magnesium salts), U.S.4,626,373 (manganese ligand catalyzer), U.S.4,119,557 (positive iron complexes catalyzer), German Patent 2,054,019 (cobalt sequestrant catalyzer), Canadian Patent 866,191 (salt that contains transition metal), U.S.4,430,243 (with the sequestrant of manganese positively charged ion and on-catalytic metallic cation), U.S.4,728,455 (managanese gluconate catalyzer).Heavy metal ion chelating agent
Detergent composition of the present invention preferably contains heavy metal ion chelating agent as a composition.Heavy metal ion chelating agent is meant the composition of chelating heavy metal ion.Described composition also has sequestering action to calcium and magnesium, but their para-linkage heavy metal ion such as iron, manganese and copper have selectivity.
The weight percent that heavy metal ion chelating agent accounts for described composition usually is 0.005%～20%, accounts for 0.1～10% better, preferably accounts for 0.5～5%.
The heavy metal ion chelating agent that is suitable for comprises organophosphate, as amino alkylidenyl poly-(alkylidene group phosphoric acid salt), basic metal ethane 1-hydroxyl diphosphate and inferior amino trimethylene methyl phosphate.
Diethylenetriamine five (methylene radical phosphoric acid salt) is preferably arranged, quadrol three (methylene radical phosphoric acid salt), hexamethylene-diamine four (methylene radical phosphoric acid salt) and hydroxy ethylene 1,1-diphosphate in the mentioned kind.
Other heavy metal ion chelating agent that is suitable for has: inferior nitrilotriacetic acid and polyaminocarboxylic acid, and as ethylenediamine tetraacetic acid (EDTA), ethylidene pentaacetic acid, ethylenediamine disuccinic acid, the two pentanedioic acids of quadrol, the two succsinic acids of 2-hydroxy propylidene diamines and salt thereof.Particularly preferably be quadrol-N, the ammonium salt of N '-two succsinic acids (EDDS) or its basic metal, alkaline-earth metal, ammonium or replacement, and their mixture.
Other heavy metal ion chelating agent that is suitable for has iminodiacetic acid derivatives, as 2-hydroxyethyl oxalic acid or glycerine iminodiethanoic acid, sees patent EP-A-317 for details, and 542 and EP-A-399,133.Iminodiethanoic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrant also are suitable for, and see patent EP-A-516 for details, 102.Beta-alanine-N, N '-oxalic acid, aspartic acid-N, single acetate of N '-oxalic acid, aspartic acid-N-and imino-diacetic succsinic acid sequestrant also are suitable for, and see patent EP-A-509 for details, 382.
Patent EP-A-476,257 have introduced the suitable sequestrant based on amino.Patent EP-A-510,331 have introduced by collagen protein, Keratin sulfate and casein derived suitable sequestrant, patent EP-A-528,859 have introduced suitable alkyl imino oxalic acid sequestrant.Two pyridine carboxylic acids and 2-phosphinylidyne butane-1,2, the 4-tricarboxylic acid also is suitable for.G-NH2-N, N '-disuccinic acid (GADS), quadrol-N, N '-two pentanedioic acids (EDDG) and 2-hydroxyl trimethylene diamine-N, N '-disuccinic acid (HPDDS) also is suitable for.Enzyme
Another that is used for detergent composition composition preferably is one or more enzymes that add.
Preferred additional enzyme has on the market can available lipase, at, amylase, neutrality and Sumizyme MP, esterase, cellulase, polygalacturonase, Sumylact L and peroxidase, and these enzymes can join in the detergent composition easily.The enzyme that is suitable for is at patent U.S.3, detailed description arranged in 519,570 and 3,533,139.
Preferred commercially available proteolytic enzyme comprises the proteolytic enzyme of selling with following trade name: Alcalse, Savinase, Primase, Durazvm and Esperase (being produced Denmark by Novo Industries A/S); Maxatase, Maxacal and Maxapem (selling) by Gist-Brocades; And the proteolytic enzyme of selling by Genencor International; Opticlean and Optimase (selling) by Solvay Enzymes.Proteolytic enzyme can be added in the present composition, organized enzyme accounts for 0.0001～4% of composition weight.
Preferred amylase comprises for example α-Dian Fenmei, and it is that special bacterial strain from the Type B licheniformin obtains, and sees patent GB-1 for details, 269,839.Preferred commercially available amylase comprises the amylase of selling with following trade name: Rapidase (being sold by Gist-Brocades), Termamyl and BAN (being sold by Novo Industries A/S).Amylase can be added in the present composition, organized enzyme accounts for 0.0001%～2% of composition.
Lipolytic enzyme may reside in the composition, and its active lipolytic enzyme accounts for 0.0001～2% of composition weight, accounts for 0.001～1% better, preferably accounts for 0.0001%～0.5%.
Lipase can derive from fungi or bacterium, and the bacterial strain that for example produces lipase has Humicola, Thermomvces to belong to or Rhodopseudomonas, and the latter comprises pseudomonas pseudoalcaligenes or Pseudomonas fluorescens.The lipase that comes from the mutant of these bacterial strain chemistry or genetic modification also is suitable for.Preferred a kind of lipase is from pseudomonas pseudoalcaligenes, and this has explanation in patent EP-B-0218272.
Another preferred lipase is the gene through clone Humicola lanuginosa, and this gene of expression obtains in host Aspergillus oryza, this has introduction in patent application EP-A0258068.This enzyme is by Denmark Novo Industri A/S, and Bagsvaerd sells, and commodity are called Lipolase.This lipase has explanation also at patent U.S.4 in 810,414 (HugeJensen etc., the promulgations on March 7th, 1989).Organic poly-compounds
Organic poly-compounds is the composition that adds of preferred detergent composition of the present invention, preferably exist with granular form, and they can work with other granular component bonding.Organic poly-compounds is meant the arbitrary polymeric organic compound that is used as dispersion agent, anti-sludging agent and soil-suspending agent in detergent composition usually in fact, comprises the organic poly-compounds of arbitrary high molecular that can be used as the clay flocculating agent.
Organic poly-compounds accounts for 0.1～30% of composition weight in detergent composition of the present invention, accounts for 0.5%～15% better, preferably accounts for 1%-10%.
The example of organic poly-compounds comprises water-soluble organic homotype or copolymerization poly carboxylic acid and salt thereof, and wherein poly carboxylic acid contains at least two carboxyls, and they are separated by separately and are no more than two carbon atoms.The polymer of back one type is at patent GB-A-1, and is open in 596,756.The example of this class salt have molecular weight 2000～5000 polyacrylate and with the interpolymer of maleic anhydride, the molecular weight of this interpolymer is 20,000 to 100,000, especially is 40,000 to 80,000.
Polyamino compounds is useful, and they can be obtained by aspartic acid, specifically referring to patent EP-A-305282, EP-A-305283 and EP-A-351629.
Contain the terpolymer that is selected from monomer toxilic acid, vinylformic acid, poly aspartic acid and vinyl alcohol, especially molecular-weight average is that 5,000 to 10,000 terpolymer also is suitable for.
Other organic poly-compounds that are fit to the adding detergent composition have derivatived cellulose, as methylcellulose gum, carboxymethyl cellulose, Vltra tears and Natvosol.
Other organic poly-compounds that are suitable for have polyoxyethylene glycol, and generally selecting its molecular weight is 100010000, often chooses 2000 to 8000, and the most normal selecting for use is about 4000.
Another organism (they are preferred clay suspending agent/anti-sludging agents) is ethoxylation positively charged ion monoamine and the diamines with following formula,
Wherein X is a non-ionic group, is selected from H, C
1-C
4Alkyl or hydroxy alkyl ester or ether group, and their mixture, a value 0～20, normal value 0～4 (being ethylidene, propylidene, hexylidene), b value 1 or 0; For positively charged ion monoamine (b gets 0), n is at least 16, and general range is 20～35; For positively charged ion monoamine (b=1), n is at least 12, and general range is 12～42.
Here other dispersion agent/anti-sludging agent of Ying Yonging can be referring to patent EP-B-011965 and U.S.4, and 659,802, U.S.4,664,848.Foam inhibition system
When being used for machine-washing, the foam inhibition system that detergent composition of the present invention contained accounts for the 0.01～15% better of composition weight, accounts for 0.05～10% better, preferably accounts for 0.1～5%.
The foam inhibition system that is suitable for contains arbitrary known anti-foamed compound basically, for example anti-foamed compound of type siloxane and the anti-foamed compound of 2-alkyl alcohols.
Anti-foamed compound is meant here and can be used for suppressing the foam that solution produced of detergent composition or the mixture of arbitrary compound lathery or compound, especially is suppressed at the foam that easily produces when detergent solution stirs.
Particularly preferred anti-foamed compound is the anti-foamed compound of type siloxane, comprises that silicone component is defined as anti-foamed compound here.The anti-foamed compound of described type siloxane contains the silicon composition.Terminology used here " siloxanes " comprises the polymer of the various relative higher molecular weights that contain siloxane unit and dissimilar alkyl in whole industry member.The preferred anti-foamed compound of siloxanes is a siloxanes, especially has the unitary polydimethylsiloxane of trimethyl silicane end closure.
Other anti-foamed compound that is suitable for has mono carboxylic lipid acid and soluble salt thereof, sees patent U.S.2 for details, 954,347 (Wayne St.John, promulgations on September 27 nineteen sixty).These compounds generally contain C as froth suppressor
10-C
24Hydrocarbyl chain is generally C
12-C
18The salt that is suitable for comprises an alkali metal salt, as sodium, potassium and lithium salts, and ammonium and alkanol ammonium salts.
Other anti-foamed compound that is suitable for comprises for example fatty acid ester of high molecular fatty ester (being fatty acid triglycercide), monovalent alcohol, C
18-C
40Ketone (as stearone) N-alkylamino triazine, to tetraalkyl diammonium chloride triazine, it is the C that contains of cyanuryl chloride and two or three moles as three to six alkyl melamines or two
1-C
24The product that uncle or secondary amine propylene oxide, two stearic amide and single stearyl two basic metal (being Na, K, Li) phosphoric acid salt and phosphoric acid ester form.
Preferred foam inhibition system comprises (a) anti-foamed compound, often select the anti-foamed compound of siloxanes for use, preferably contain the anti-foamed compound of siloxanes of following composition, (ⅰ) polydimethylsiloxane, it accounts for 50～99% of the anti-foamed compound of siloxanes weight
Usually selecting scope for use is 75～95%; (ⅱ) silicon-dioxide, it accounts for 1～50% of the anti-foamed compound of siloxanes/silicon-dioxide weight,
Usually select 5～25% for use.
With the anti-foamed compound of described siloxanes/silicon-dioxide by weight 5～50%, often select for use 10～40% to add.(b) compound dispersing agent, preferably contain siloxanes glycol rake interpolymer, polyoxy alkylidene content is 72-78% in this interpolymer, and the ratio of oxyethane and propylene oxide is 1: 0.9～1: 1.1, its content is 0.5～10%, is generally 1-10% (by weight); These the most frequently used interpolymer commodity are called DCO 544, are to be sold by DOW Corning company.(c) inert carrier fluid compound preferably contains C
16-C
18Ethoxyquin ethanol, wherein the degree of ethoxyquin is 5～50, is generally 8～15, and its content is 5～80%, and usual range was 10～70% (by weight).
Introduced granular foam commonly used among the patent EP-A-0210731 and suppressed system, this system contains anti-foamed compound of siloxanes and organic support material, and its melting range is 50～85 ℃, and this organic support material contains by glycerine and C
12-C
20The monoesters that lipid acid is formed.Patent EP-A-0210721 has introduced other preferred granular foam and has suppressed system, and wherein organic support material is for containing C
12-C
20Lipid acid or alcohols, or be their mixture, the fusing point of this organic support material is 45 ℃～85 ℃.The clay softening system
Detergent composition can contain the clay softening system, and this system comprises clay mineral compound and any clay flocculating agent composition.
The preferred a kind of smectic clays compound of clay mineral compound.This smectic clays is at U.S.3, and 862,058, U.S.3,948,790, U.S.3 introduces in 954,632 and U.S.4,062,647.EP A-299,575 and EP-A-313, the clay flocculating agent of the organic poly that is suitable for has been introduced by 146 (Procter and Gamble companies).The dye transfer inhibitor of poly
Detergent composition can also contain the dye transfer inhibitor of poly, and its weight percent is generally 0.01～10%, and usual range is 0.05～0.5%.
The dye transfer inhibitor of poly often is selected from interpolymer, the polyvinylpyrrolidone polymer of polyamine N-oxide polymer, N-V-Pyrol RC and N-ethene imidazoles, and their mixture.
A) polyamine N-oxide polymer
The polyamine N-oxide polymer that is suitable for contains the unit that following structural formula is represented,
P(1)????Ax
R wherein P is one and can gathers the unit; With
O O OA be NC, CO, C ,-O-,-S-,-N-; X value 0 or 1; R is aliphatic group, ethoxyquin aliphatic group, aromatic group, heterocyclic group or alicyclic group or their mixture, and the N in the N-O base can be connected on these groups, or becomes the part of these groups.
The N-O group can following general structure be represented:
Or
R wherein
1, R
2And R
3Be aliphatic group, aromatic group, heterocyclic group or alicyclic group or their mixture, x or/and y or/and z value 0 or 1, the N in the N-O base can be connected on these groups or become the part of these groups.The N-O group can be the part that can gather unit (P), or is connected on the main chain of poly, or takes this dual mode simultaneously.
The polyamine oxynitride that is suitable for (wherein the N-O base is as gathering a unitary part) contains polyamine oxynitride (wherein R is selected from aliphatic group, aromatic group, alicyclic group or heterocyclic group).The described polyamine N-oxide of one class contains polyamine N oxide groups (wherein the N in the N-O base is the part as the R group).Preferred N-oxide compound is as follows, and wherein R is a heterocyclic group, as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and their derivative.
Other polyamine N oxide compound that is suitable for has the polyamine oxide compound, and wherein the N-O base can be connected and can gather on the unit.The described polyamine N-oxide of a preferred class is the polyamine N-oxide that comprises general formula I, and wherein R is aromatic group, heterocyclic group or alicyclic group, and the nitrogen of described N-O functional group is the part of described R group.The example of described type is the polyamine oxide compound, and wherein R is a heterogeneous ring compound, as pyridine, pyrroles, imidazoles and derivative thereof.
Polyamine N-oxide can obtain by degree polymerization arbitrarily almost.As long as material has desired water-soluble and dye suspension ability, the polymerization degree is unimportant.The average molecular weight range of this compounds normally, 000.
B) interpolymer of N-V-Pyrol RC and N-ethene imidazoles
N-V-Pyrol RC and N-ethene imidazoles interpolymer are suitable for, and its average molecular weight range is 5,000-50,000.The mol ratio of N-ethene imidazoles and N-V-Pyrol RC is 1: 0.2 in the interpolymer of selecting for use.
C) polyvinylpyrrolidone
It is 2 that detergent composition also can adopt average molecular weight range, 500-400,000 polyvinylpyrrolidone (" PVP ").The polyvinylpyrrolidone commerical prod that is suitable for is sold by New York ISP company and Canadian NY and Montreal company, its commodity are called PVPK-15, and (viscosity-average molecular weight is 10,000), PVP K-30 (molecular-weight average 40,000), PVPK-60 (molecular-weight average 160,000) and PVP K-90 (molecular-weight average 360,000).PVP K-15 is also sold by ISP company.Other polyvinylpyrrolidone that is suitable for has SokalanHP 165 and Sokalan HP 12, and they are to be sold by BASF AG.
D) Ju Yi Xi oxazolidone
Detergent composition also can adopt the dye transfer inhibitor of Ju Yi Xi oxazolidone as poly.The average molecular weight range of described Ju Yi Xi oxazolidone is 2,500～400,000.
E) polyethylene imidazole
Detergent composition also can adopt the dye transfer inhibitor of polyvinyl imidazole as poly.The preferred average molecular weight range of described polyvinyl imidazole is 2,500～400,000.White dyes
Detergent composition also can contain the wetting ability white dyes of some types, and its consumption was 0.005～5% (by weight).
The suitable hydrophilic white dyes comprises the compound with following structural formula:
R wherein
1Be selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R
2Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chlorine and amino; M is the salifiable positively charged ion of shape, as sodium or potassium.
R in said structure
1Be anilino, R
2For N-2-two-hydroxyethyl, when M is positively charged ion (as sodium), whitening agent is 4,4 '-two [(4 anilinos-6-(N-2-two-hydroxyethyl)-s-triazine-2 base) amino] 2,2 '-the Stilbene disulfonic acid disodium salt.This special whitening agent is can be available, is produced by Ciba-Geigy company, and commodity are called Tinopal-UNPA-GX.Tinopal UNPA-GX is for being used for detergent composition wetting ability white dyes preferably.
R in the said structure formula
1Be anilino, R
2Be N-2-hydroxyethyl-N-2-methylamino, when M was positively charged ion (as sodium), whitening agent was 4,4 '-two [(4-anilino-6 (N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl) amino] 2,2 '-the Stilbene disulfonic acid disodium salt.This whitening agent is can be available, is produced by Ciba-Geigy company, and commodity are called Tinopal 5BM-GX.
In the said structure formula, R
1Be anilino, R
2Be morpholino, when M was positively charged ion (as sodium), whitening agent was 4,4 '-two [(4-anilino-6-morpholino-s-triazine 2-yl) amino] 2,2 '-the Stilbene disulfonic acid sodium salt.This kind whitening agent is can be available, is produced by Ciba-Geigy company, and commodity are called AMS-GX.Cationic fabric softener
Cationic fabric softener can also be added in the detergent composition of the present invention.The cationic fabric softener that is suitable for comprises water-insoluble tertiary amine or two long-chain acid amides materials, sees patent GB-A-1514 276 and EP-B-0 011 340 for details.
The general amount that adds of cationic fabric softener is 0.5～15%, 1～5% (by weight) commonly used.Other optional composition
Be applicable to that other the optional composition that is included in the detergent composition of the present invention has spices, pigment and filling salt, sodium sulfate is preferred filling salt.The pH of composition
The pH of the present composition measures with 1% distilled water solution, and pH should be 10.0 at least, often selects 10.0～12.5, is preferably 10.5-12.0.The shape of composition
Detergent composition of the present invention can pass through prepared in various methods, comprises the dry mixed and the agglomeration of various compositions in the composition.Acid substance among the present invention is selected dried addition for use.
The present composition can be made into various physical forms, comprises granular, sheet, bar-shaped and flow morphology.The present composition especially can be made so-called concentrated granular detergent composition, and it is applicable to that the diverting device by placing the machine bucket that dirty fabric load is housed is added to washing machine.
The median size of granular composition basal component is 0.1～5.0mm among the present invention, but should be to have to be no more than 5% particle diameter greater than 1.7mm, and has and be no more than 5% particle diameter less than 0.15mm.
Defined mean particle size can calculate, and method is composition sample to be sieved into several grades (being generally Pyatyi) on a series of Tyler meshs.Therefore the weight grade that obtains can be mapped with screen size.Mean particle size can be regarded the screen-aperture size that 50% (by weight) sample can pass through as.
The tap density of granular detergent composition of the present invention is at least 600 grams per liters usually, and the normal scope of selecting is 650 grams per liters～1200 grams per liters.Tap density can be measured by a kind of simple funnel and beaker device, this device comprises a molded conical hopper composition that is fixed on the pedestal, be provided with a plate washer valve at this device lowest part, can make under the funnel inclusion priming funnel in the axial aligned round shape beaker.The high 130mm of funnel, internal diameter 130mm, its top and bottom respectively are 40mm.Fixed funnel makes its above 140mm of end distance base-plates surface place down.The total height of beaker is 90mm, inner height 87mm, and internal diameter 84mm, its standard volume are 500ml.
For measuring, funnel will be with hand injection method filling powder, opens the plate washer valve and makes the powder beaker that overfills.The beaker of filling shifts out from shelf, and excessive powder is removed from beaker, and method is to be passed the upper limb of cup by straight flange instrument (as knife).The beaker that has installed is weighed, and can get tap density after gained powder weight value doubles, and its unit is a grams per liter.As required, can carry out replication.The surfactant agglomerates particle
The surfactant system that is present in the particulate composition is preferably surfactant agglomerates particulate form, and agglomerate can be for thin slice, bead, marume, strip, band shape but be commonly used granular.Processing the most frequently used method of this particle is to make powder (for example aluminosilicate, carbonate) carry out agglomeration with the high active surfactant slurry, and the particle diameter of the agglomerate of control generation is in restricted portion.This working method relates to makes the high active surfactant slurry mix with the powder of significant quantity in one or more cyclone agglomerators, described cyclone agglomerator has cooking-pot type cyclone agglomerator, Z-blade mixing machine, commonly used is in line mixing machine, as by Dutch Schugi BV company (29 Chroomstraat8211 AS, Lelystad) and German Gebruder Lodige Maschinenbau GmbH (the D-4790 Paderborn 1 of company.Elsenerstrase 7-9, Postfach 2050) mixing machine produced.The most frequently used is a kind of high shear mixing machine, and its commodity are called Lodige CB.
Usually use the weight that contains tensio-active agent and generally account for 50～90%, preferably account for 70～85% high active surfactant slurry.Slurry can pump in the cyclone agglomerator, and this requires temperature enough high, keeping the viscosity that available pump is taken out, but also requires temperature suitably low, to avoid the degraded of used anion surfactant.The service temperature of slurry is generally 50～80 ℃.
In the particularly preferred example of the present invention, the density of detergent composition is greater than 600 grams per liters, and is Powdered or granular, wherein contains the alkali greater than 5% (by weight), carbonate (supercarbonate) commonly used or percarbonate.Carbonate can adopt dry method to add or supply with by agglomerate.Acid citric acid (up to 10%) commonly used, sour available dry method adds or joins in the product by independent particle.Clothes washing method
The laundry washer method generally includes with the dirty clothing of washings processing that has dissolved or disperseed certain significant quantity detergent composition of the present invention in the washing machine among the present invention.The significant quantity of this detergent composition is meant in 5～65 premium on currency washing lotions dissolving or has disperseed 40～300 gram products that this is to be applied to the product volume commonly used in the general laundry washer method and the volume of water lotion.
In application facet preferably, in washing methods, adopted decollator.Before washing operation began, the decollator that Betengent product is housed was introduced Betengent product in the cylinder of washing machine.Its volume should be able to hold the Betengent product of using always of q.s in washing methods.
In case washing machine is configured in the laundry, the decollator that Betengent product is housed just is placed in the cylinder of washing machine.When beginning the washing operation of washing machine, water is just introduced in the cylinder, and cylinder is with regard to periodic rotation.The design requirements of decollator is both to have allowed to load dried Betengent product, can the stirring with the cylinder rotation discharge Betengent product when washing operation again, and the result makes product contact with washing water.
Can discharge Betengent product when washing for making, decollator can have several openings that product is passed through.Perhaps decollator can be made by a kind of material, this material liquid permeable, but impermeable solid phase prod, and this can make lysed product discharge.Usually, when washing operation began, Betengent product promptly discharged, thereby obtained the Betengent product of moment high local concentrations in washing operation stage washing machine drum.
Preferred decollator is reusable, and its design can make the integrity that all keeps container in anhydrous state and the washing operation.The particularly preferred decollator that is used for detergent composition of the present invention illustrates in following patent: GB-B-2,157,717, GB-B-2,157,718, EP-A-0201376, EP-A-0288345 and EP-A-0288346.Also introduced particularly preferred decollator by the paper that is published on " Manufacturing Chemist " (in November, 1989, p 41-46) that J.Bland writes, this decollator uses granulated product, promptly is commonly referred to " granular solid " type.Another decollator of preferably using detergent composition of the present invention has explanation in patent application WO 94/11562.
The patent of introducing preferred especially decollator has EP application 0343069 and 0343070.The latter applies for that the decollator of introducing comprises an active sheath, and this sheath is a pocket, and it extends from the supporting ring of fixing a tubule, and this tubule can make pocket load onto the Betengent product of washing operation q.s.The part of washing medium flows into the pocket from tubule, the dissolving cleaning product, and solution passes tubule and outwards enters washing medium.Supporting ring provides safety guard, to stop wetting not molten product excessive, this device generally comprises the wall of circumferentially extending, and this wall extends out from the central boss of a width of cloth wheel construction, or is that a spiral-shaped similar structures extends out from its intermediate interlayer.
In addition, decollator can be the container of a flexibility, as a pocket or capsule.Pocket can be made of fiber, scribbles impermeable protective material on it, to keep inclusion, sees European publication application number 0018678 for details.In addition, the insoluble synthetic polymer material preparation of decollator used water, its edge sealing and sealing, purpose is to form breach in aqueous medium, sees the number of patent application 0011500,0011501,0011502 and 0011968 of European publication for details.The easily loose closing form of a kind of water easily comprise that the water soluble adhesive is handled and airtight capsule on one side, this airtight be to finish with impermeable polymer film, this film can be polyethylene or polypropylene.The packing of composition
The finished product of business-like whitener composition can be packed with arbitrary suitable containers, and these containers can be made with paper, fiber board, plastics and any suitable veneer sheet.Preferred packing effect sees European Patent Application No. 9492150.7 for details.
The initialism that uses in the following examples
The symbol of abbreviation part has following connotation in the detergent composition.LAS: the C of straight chain
12Alkyl group benzene sulfonic acid sodium salt TAS: tallow alkyl sodium sulfate C45AS: the C of straight chain
14-C
15Alkyl group sodium sulfate CxyEzS:C
1x-C
1yThe sodium alkyl sulfate of side chain and zmol ethylene oxide condensation C45E7:C
14-15The ethylene oxide condensation C25E3:C of the primary alconol of main straight chain and average 7mol
12-15The primary alconol of side chain and average 3mol ethylene oxide condensation C25E5:C
12-15The primary alconol of side chain and average 5mol ethylene oxide condensation CEQ:R
1COOCH
2CH
2N
+(CH
3)
3, R wherein
1=C
11-C
13QASI:R
2N
+(CH
3)
2(C
2H
4OH), R wherein
2=C
12-C
14QASII:R
2N
+(CH
3) (C
2H
4OH)
2, R wherein
2=C
10-C
14Soap: the straight-chain alkyl carboxylic acid's sodium TFAA:C that from 80/20 tallow and cocounut oil mixture, obtains
16-C
18Alkyl N methyl glucose amide TPKFA:C
12-C
14The full cut lipid acid of cat head STPP: anhydrous sodium tripolyphosphate zeolite A: general formula Na
12(AlO
2SiO
2)
12The hydrated aluminum silicate of 27HO, its main grain
The footpath size is 0.1～10 μ mNaSKS-6: general formula δ-Na
2Si
2O
5The crystalline layered silicate citric acid: Citric Acid, usp, Anhydrous Powder carbonate: anhydrous sodium carbonate, its size scope is 200 μ m and 900 μ m supercarbonates: anhydrous sodium bicarbonate, its particle size distribution scope are 400 μ m to 1200 μ m silicate: amorphous sodium silicate (SiO
2With Na
2The O ratio is 2: 1) sodium sulfate: the anhydrous slufuric acid na citrate: citrate trisodium dihydrate, activity 86.4%, the particle size distribution scope is
425 μ m to 850 μ mMA/AA:1: 4 toxilic acids/acrylic acid interpolymer, molecular-weight average is about 70, and 000CMC: Xylo-Mucine proteolytic enzyme: protease, activity are 4KNPU/g, are sold by NOVO Industries A/S
Sell, commodity are called SavinaseAlcalase: protease, and activity 3A U/g, sell cellulase by NOVO Industries A/S: the Mierocrystalline cellulose Dispase, activity 1000 CEVU/g are by NOVO Industries A/S
Sell, commodity are called Carezyme amylase: amylolytic enzyme, and activity 60KNU/g is sold by NONO Industries A/S,
Trade(brand)name Termamyl 60T lipase: lipolytic enzyme, activity 100KLU/g is sold by NOVO Industries A/S, the merchant
Trade(brand)name LipolaseEndolase: endoglucanase (endoglunase), activity 3000CEVU/g is by NONO
Industries A/S sells PB4: standard type is NaBO
23H
2OH
2O
2Four hydrated sodium perborate PB1: standard type is NaBO
2H
2O
2Anhydrous sodium perborate monohydrate SYNTHETIC OPTICAL WHITNER percarbonate: the general standard formula is 2Na
2CO
33H
2O
2SPC-D NOBS: nonanoyl oxygen benzene sulfonic acid sodium salt TAED: tetra acetyl ethylene diamine DTPMP: diethylenetriamine five (phosphonic acids methylene radical ester).By name by Monsanto with commodity
Dequest 2060 sells optical active matter: sulfonic acid zinc phthalocyanine, be encapsulated in whitening agent 1:4 in the SYNTHETIC OPTICAL WHITNER dextrin solubility polymer, 4 '-two (2-sulfo group styryl) biphenyl disodium whitening agent 2:4,4 '-two (4 anilinos-6-morpholino-1,3,5-triazines-
2 bases) Stilbene-2 amino); 2 '-disulfonic acid disodium HEDP:1; 1 hydroxyl ethane bisphosphate PVNO: polyvinylpyridine N-oxide compound PVPVI: the interpolymer SRP1 of polyvinylpyrrolidone and ethene imidazoles: the ester SRP2 of the sulfo group benzoyl end closure of aerobic ethylidene oxygen and terephthaloyl skeleton: diethoxyization poly-(1; 2 propylidene terephthalates) lack block polymer silicone antifoam agent: the polydimethylsiloxane Foam Control, with siloxanes-oxyalkylene copolymerization
Body is as dispersion agent, the ratio of Foam Control and dispersion agent be 10: 1 to
100: 1 alkalescence: be equivalent to the weight percent of NaOH, measure with alkaline release test method
All content are all represented with the weight percent that accounts for composition among the following embodiment.Embodiment 1
Prepare following granular laundry agent composition A and B according to the present invention, its tap density is 750 grams per liters:
Embodiment 2
| ?????A | ????B | ????C | ????D | |
| ?LAS | ????5.61 | ????4.76 | ????5.5 | ????6.5 |
| ?TAS | ????1.86 | ????1.57 | ????2.1 | ????1.5 |
| ?C45AS | ????2.24 | ????3.89 | ????2.4 | ????3.2 |
| ?C25AE3S | ????0.76 | ????1.18 | ????0.8 | ????1.3 |
| ?C45E7 | ????- | ????5.0 | ????- | ????2.5 |
| ?C25E3 | ????5.5 | ????- | ????2.5 | ????- |
| ?CEQ | ????2.0 | ????1.0 | ????- | ????- |
| ?QAS | ????- | ????1.0 | ????2.0 | ????1.5 |
| Zeolite A | ????19.5 | ????19.5 | ????16.5 | ????16.5 |
| NaSKS-6/ citric acid (79: 21) | ????10.6 | ????10.6 | ????10.6 | ????6.9 |
| Carbonate | ????21.4 | ????21.4 | ????16.5 | ????19.3 |
| Supercarbonate | ????2.0 | ????2.0 | ????2.0 | ?????- |
| Silicate | ????2.0 | ????- | ????- | ????2.0 |
| Sodium sulfate | ????14.3 | ????- | ????- | |
| Percarbonate | ????12.7 | ????- | ????12.0 | ????- |
| ?TAED | ????3.1 | ????- | ????4.5 | ????- |
| ?DETPMP | ????0.2 | ????0.2 | ????0.2 | ????0.2 |
| ?HEDP | ????0.3 | ????0.3 | ????0.3 | ????0.3 |
| Proteolytic enzyme | ????0.85 | ????0.85 | ????0.85 | ????0.85 |
| Lipase | ????0.15 | ????0.15 | ????0.15 | ????0.15 |
| Cellulase | ????0.28 | ????0.28 | ????0.28 | ????0.18 |
| Amylase | ????0.1 | ????0.1 | ????0.1 | ????0.1 |
| ?MA/AA | ????1.6 | ????1.6 | ????1.0 | ????2.2 |
| ?CMC | ????0.4 | ????0.4 | ????0.7 | ????0.7 |
| Photolytic activity SYNTHETIC OPTICAL WHITNER (ppm) | ????27?ppm | ????27?ppm | ????27?ppm | ????27?ppm |
| Whitening agent 1 | ????0.19 | ????0.19 | ????0.19 | ????0.19 |
| Whitening agent 2 | ????0.04 | ????0.04 | ????0.04 | ????0.04 |
| Spices | ????0.3 | ????0.3 | ????0.3 | ????0.3 |
| The siloxanes foam reducing composition | ????2.4 | ????2.4 | ????2.4 | ????2.4 |
| Citric acid | ????1.5 | ????2.0 | ????4.5 | ????5.5 |
| Other adds to 100% |
According to the present invention, the detergent composition that preparation is following.
Embodiment 3
| ????E | ????F | ????G | |
| Sparklet | |||
| ????????????????STPP | ????14.0 | ????- | ????14.0 |
| Zeolite A | ????- | ????20.0 | ????- |
| ???????????????C45AS | ????9.0 | ????6.0 | ????8.0 |
| ???????????????MA/AA | ????2.0 | ????4.0 | ????2.0 |
| ?????????????????LAS | ????6.0 | ????8.0 | ????9.0 |
| ?????????????????TAS | ????2.0 | ????- | ????- |
| ???????????????QASⅡ | ????1.5 | ????3.0 | ????3.5 |
| Silicate | ????7.0 | ????8.0 | ????8.0 |
| ?????????????????CMC | ????1.0 | ????1.0 | ????0.5 |
| Whitening agent 2 | ????0.2 | ????0.2 | ????0.2 |
| Soap | ????1.0 | ????1.0 | ????1.0 |
| ???????????????DTPMP | ????0.4 | ????0.4 | ????0.2 |
| Sprays | |||
| ???????????????C45E7 | ????2.5 | ????2.5 | ????2.0 |
| ???????????????C25E3 | ????2.5 | ????2.5 | ????2.0 |
| The siloxanes foam reducing composition | ????0.3 | ????0.3 | ????0.3 |
| Spices | ????0.3 | ????0.3 | ????0.3 |
| The additive of doing | ????- | ||
| Carbonate | ????26.0 | ????23.0 | ????25.0 |
| Percarbonate | ????18.0 | ????18.0 | ????10 |
| ?????????????????PB1 | ????- | ????- | ????2.0 |
| ????????????????TAED | ????3.0 | ????3.0 | ????1.0 |
| The photolytic activity SYNTHETIC OPTICAL WHITNER | ????0.02 | ????0.02 | ????0.02 |
| Proteolytic enzyme | ????1.0 | ????1.0 | ????1.0 |
| Lipase | ????0.4 | ????0.4 | ????0.4 |
| Amylase | ????0.25 | ????0.30 | ????0.15 |
| Dry mixed sodium sulfate | ????3.0 | ????3.0 | ????5.0 |
| Citric acid | ????2.5 | ????2.0 | ????5.0 |
| Equal amount (moisture and other) | ????100.0 | ????100.0 | ????100.0 |
| Density (grams per liter) | ????630 | ????670 | ????670 |
According to the present invention, be used for the granular detergent composition that does not contain SYNTHETIC OPTICAL WHITNER of washing colored clothing below the preparation:
Embodiment 4
| ????H | ????I | |
| Foaming powder | ||
| Zeolite A | ????15.0 | ????- |
| Sodium sulfate | ????- | ????- |
| ?????????LAS | ????3.0 | ????- |
| ????????QASI | ????- | ????1.5 |
| ?????????CEQ | ????2.0 | ????1.3 |
| ???????DTPMP | ????0.4 | ????- |
| ?????????CMC | ????0.4 | ????- |
| ???????MA/AA | ????4.0 | ????- |
| Agglomerate | ||
| ???????C45AS | ????- | ????11.0 |
| ?????????LAS | ????6.0 | ????- |
| ?????????TAS | ????3.0 | ????- |
| Silicate | ????4.0 | ????- |
| Zeolite A | ????10.0 | ????13.0 |
| ?????????CMC | ????- | ????0.5 |
| ???????MA/AA | ????- | ????2.0 |
| Carbonate | ????9.0 | ????7.0 |
| Sprays | ||
| Spices | ????0.3 | ????0.5 |
| ???????C45E7 | ????4.0 | ????4.0 |
| ???????????????????C25E3 | ????2.0 | ????2.0 |
| The additive of doing | ||
| ???????????????????MA/AA | ????- | ????3.0 |
| ?????????????????NaSKS-6 | ????- | ????12.0 |
| Citric acid | ????4.0 | ????3.0 |
| Citrate trianion | ????10.0 | ????8.0 |
| Supercarbonate | ????7.0 | ????5.0 |
| Carbonate | ????8.0 | ????7.0 |
| ??????????????PVPVI/PVNO | ????0.5 | ????0.5 |
| The alkalescence enzyme | ????0.5 | ????0.9 |
| Lipase | ????0.4 | ????0.4 |
| Amylase | ????0.6 | ????0.6 |
| Cellulase | ????0.6 | ????0.6 |
| The siloxanes foam reducing composition | ????5.0 | ????5.0 |
| The additive of doing | ||
| Sodium sulfate | ????0.0 | ????0.0 |
| Equal amount (moisture and other) | ????100.0 | ????100.0 |
| Density (grams per liter) | ????700 | ????700 |
According to the present invention, the detergent composition that preparation is following:
Embodiment 5
| ?????J | ????K | ????L | ????M | |
| LAS | ????12.0 | ????12.0 | ????12.0 | ????10.0 |
| QAS | ????0.7 | ????1.0 | ????- | ????0.7 |
| TFAA | ????- | ????1.0 | ????- | ????- |
| C25E5/C45E7 | ????- | ????2.0 | ????- | ????0.5 |
| C45E3S | ????- | ????2.5 | ????- | ????- |
| QASⅡ | ????2.0 | ????1.5 | ????1.0 | ????1.0 |
| STPP | ????30.0 | ????18.0 | ????15.0 | ????- |
| Silicate | ????9.0 | ????7.0 | ????10.0 | ????- |
| Carbonate | ????15.0 | ????10.5 | ????15.0 | ????25.0 |
| Supercarbonate | ????- | ????10.5 | ????- | ????- |
| DTPMP | ????0.7 | ????1.0 | ????- | ????- |
| SRP1 | ????0.3 | ????0.2 | ????- | ????0.1 |
| MA/AA | ????2.0 | ????1.5 | ????2.0 | ????1.0 |
| CMC | ????0.8 | ????0.4 | ????0.4 | ????0.2 |
| Proteolytic enzyme | ????0.8 | ????1.0 | ????0.5 | ????0.5 |
| Amylase | ????0.8 | ????0.4 | ????- | ????0.25 |
| Lipase | ????0.2 | ????0.1 | ????0.2 | ????0.1 |
| Cellulase | ????0.15 | ????0.05 | ????- | ????- |
| Photolytic activity SYNTHETIC OPTICAL WHITNER (ppm) | ????70ppm | ????45ppm | ????- | ????10ppm |
| Whitening agent 1 | ????0.2 | ????0.2 | ????0.08 | ????0.2 |
| Percarbonate | ????6.0 | ????2.0 | ????- | ????- |
| NOBS | ????2.0 | ????1.0 | ????- | ????- |
| Citric acid | ????3.5 | ????5.0 | ????3.0 | ????2.0 |
| Equal amount (moisture and other) | ????100 | ????100 | ????100 | ????100 |
According to the present invention, the detergent composition that preparation is following:
Embodiment 6
| ????N | ????O | ????P | |
| Sparklet | |||
| Zeolite A | ????10.0 | ????15.0 | ????6.0 |
| Sodium sulfate | ????19.0 | ????5.0 | ????7.0 |
| ???????????????????MA/AA | ????3.0 | ????3.0 | ????6.0 |
| ?????????????????????LAS | ????10.0 | ????8.0 | ????10.0 |
| ???????????????????C45AS | ????4.0 | ????5.0 | ????7.0 |
| ????????????????????QASI | ????2.0 | ????4.0 | ????1.0 |
| Siloxanes | ????- | ????1.0 | ????7.0 |
| Soap | ????- | ????- | ????2.0 |
| Whitening agent 1 | ????0.2 | ????0.2 | ????0.2 |
| Carbonate | ????28.0 | ????26.0 | ????20.0 |
| ???????????????????DTPMP | ????- | ????0.4 | ????0.4 |
| Sprays | ?????? | ||
| ???????????????????C45E7 | ????1.0 | ????1.0 | ????1.0 |
| The additive of doing | |||
| ??????????????PVPVI/PVNO | ????0.5 | ????0.5 | ????0.5 |
| Proteolytic enzyme | ????1.0 | ????1.0 | ????1.0 |
| Lipase | ????0.4 | ????0.4 | ????0.4 |
| Amylase | ????0.1 | ????0.1 | ????0.1 |
| Cellulase | ????0.1 | ????0.1 | ????0.1 |
| ????????????????????NOBS | ????- | ????6.1 | ????4.5 |
| Percarbonate | ????1.0 | ????5.0 | ????6.0 |
| Sodium sulfate | ????- | ????6.0 | ????- |
| Citric acid | ????2.5 | ????2.5 | ????2.0 |
| Equal amount (moisture and other) | ????100 | ????100 | ????100 |
According to the present invention, the high-density below the preparation also contains the detergent composition of SYNTHETIC OPTICAL WHITNER:
Embodiment 7
| ????Q | ????R | |
| Sparklet | ||
| Zeolite A | ????15.0 | ????15.0 |
| Sodium sulfate | ????0.0 | ????0.0 |
| ???????????????????????????????LAS | ????8.0 | ????3.0 |
| ???????????????????????????????QAS | ????1.5 | |
| ???????????????????????????????CEQ | ????2.0 | ????- |
| ?????????????????????????????DTPMP | ????0.4 | ????0.4 |
| ???????????????????????????????CMC | ????0.4 | ????0.4 |
| ?????????????????????????????MA/AA | ????4.0 | ????2.0 |
| Agglomerate | ||
| ???????????????????????????????LAS | ????4.0 | ????4.0 |
| ???????????????????????????????TAS | ????2.0 | ????1.0 |
| Silicate | ????3.0 | ????4.0 |
| Zeolite A | ????8.0 | ????8.0 |
| Carbonate | ????8.0 | ????6.0 |
| Sprays | ||
| Spices | ????0.3 | ????0.3 |
| ?????????????????????????????C45E7 | ????2.0 | ????2.0 |
| ?????????????????????????????C25E3 | ????2.0 | ????- |
| The additive of doing | ||
| Citric acid | ????2.0 | ????3.0 |
| Citrate trianion | ????5.0 | ????2.0 |
| Supercarbonate | ????- | ????- |
| Carbonate | ????8.0 | ????10.0 |
| ??????????????????????????????TAED | ????6.0 | ????5.0 |
| Percarbonate | ????14.0 | ????10.0 |
| Polyethylene oxide (molecular weight 5,000,000) | ????- | ????0.2 |
| Wilkinite | ????- | ????10.0 |
| Proteolytic enzyme | ????1.0 | ????1.0 |
| Lipase | ????0.4 | ????0.4 |
| Amylase | ????0.6 | ????0.6 |
| Cellulase | ????0.6 | ????0.6 |
| The siloxanes foam reducing composition | ????5.0 | ????5.0 |
| The additive of doing | ||
| Sodium sulfate | ????2.0 | ????0.0 |
| Equal amount (moisture and other) | ????100.0 | ????100.0 |
| Density (grams per liter) | ????850 | ????850 |
According to the present invention, the high density detergent composition that preparation is following:
| ????S | ????T | |
| Agglomerate | ||
| ???????C45AS | ????11.0 | ????14.0 |
| ????????QASI | ????1.0 | ????2.0 |
| ?????????CEQ | ????3.0 | ????- |
| Zeolite A | ????15.0 | ????6.0 |
| Carbonate | ????4.0 | ????8.0 |
| ???????MA/AA | ????4.0 | ????2.0 |
| ?????????CMC | ????0.5 | ????0.5 |
| ???????DTPMP | ????0.4 | ????0.4 |
| Sprays | ||
| ???????C25E5 | ????5.0 | ????5.0 |
| Spices | ????0.5 | ????0.5 |
| The additive of doing | ||
| Citric acid | ????1.5 | ????2.0 |
| ????????HEDP | ????0.5 | ????0.3 |
| ????????????????????SKS6 | ????13.0 | ????10.0 |
| Citrate trianion | ????3.0 | ????1.0 |
| ????????????????????TAED | ????5.0 | ????7.0 |
| Percarbonate | ????20.0 | ????20.0 |
| ????????????????????SRP1 | ????0.3 | ????0.3 |
| Proteolytic enzyme | ????1.4 | ????1.4 |
| Lipase | ????0.4 | ????0.4 |
| Cellulase | ????0.6 | ????0.6 |
| Amylase | ????0.6 | ????0.6 |
| The siloxanes foam reducing composition | ????5.0 | ????5.0 |
| Whitening agent 1 | ????0.2 | ????0.2 |
| Whitening agent 2 | ????0.2 | ????- |
| Equal amount (moisture and other) | ????100 | ????100 |
| Density (grams per liter) | ????850 | ????850 |
Claims (21)
1. the detergent composition that contains anion surfactant, cats product, acid source and alkali source, wherein anion surfactant accounts for 0.5～60% weight, cats product accounts for 0.01～30% weight, and used acid source and alkali source can be in interreactions in the presence of the water.
2. the described detergent composition of claim 1, wherein cats product system is selected from cationic ester tensio-active agent, cation mono alkoxylated amines tensio-active agent, positively charged ion bis-alkoxy amine tensio-active agent, and their mixture.
3. claim 1 or 2 described detergent composition, wherein said anion surfactant accounts for 3%～50% of composition weight.
4. any one described detergent composition during aforesaid right requires, wherein said anion surfactant accounts for 6%～20% of composition weight.
5. any one described detergent composition during aforesaid right requires, wherein said cats product accounts for 0.1%～20% of composition weight.
6. any one described detergent composition during aforesaid right requires, wherein said cats product accounts for 0.5%～3% of composition weight.
7. any one described detergent composition during aforesaid right requires, wherein said cationic ester tensio-active agent are to be selected from the cholinesterase with following formula,
Wherein the m value 1 to 4, R
1Be C
11-C
19The alkyl chain of straight or branched.
8. aforesaid right requires any one described detergent composition in 1 to 5, and wherein said cationic ester tensio-active agent contains a positively charged amine groups, and this group is by one or two methyl and one or two hydroxyethyl or hydroxypropyl replacement.
9. any one described detergent composition during aforesaid right requires, wherein said cation mono alkoxylated amines tensio-active agent contains a positively charged amine groups, and this group is by one or two methyl, one or two C
6-C
18Alkyl and (a gathering) ethoxy group replace, and wherein the number of ethoxylation is 1 to 4.
10. the described detergent composition of claim 9, wherein said positively charged amido is by one or two C
6-C
11Alkyl replaces.
Any one described detergent composition or its composition during 11. aforesaid right requires, wherein said positively charged ion is two-and the ethoxylated amine tensio-active agent contains a positively charged amido, and this amido is by a methyl, a C
6-C
18Alkyl and two (gathering) oxyethyl groups replace, its separately independently the ethoxyquin number be 1 to 4.
12. the described detergent composition of claim 11, wherein said positively charged amido is by a C
6-C
11Alkyl replaces.
Any one described detergent composition or its composition during 13. aforesaid right requires, wherein the ratio of anion surfactant and cats product is 25: 1～1: 3.
Any one described detergent composition during 14. aforesaid right requires, wherein alkali source comprises basic salt, and this basic salt system is selected from carbonate, supercarbonate, the sesquicarbonate of basic metal or alkaline-earth metal, or alkali metal percarbonate.
Any one described detergent composition during 15. aforesaid right requires, wherein said acid source comprises organic acid, mineral acid or mineral acid.
16. the described detergent composition of claim 15, wherein said acid source are pentanedioic acid, succsinic acid, tartrate, hexanodioic acid, SODIUM PHOSPHATE, MONOBASIC, sodium pyrosulfate or boric acid.
17. the described detergent composition of claim 15, wherein said acid source is a citric acid.
Any one described detergent composition during 18. aforesaid right requires, wherein said alkali source accounts for about 2%～75% of composition weight.
Any one described detergent composition during 19. aforesaid right requires, wherein said acid source accounts for 0.5%～25% of composition weight.
Any one described detergent composition during 20. aforesaid right requires, wherein the particle diameter of 100% acid source is no more than 710 μ m.
21. the clothes washing method of domestic washing machine, this method is included in the decollator of placing in the washing machine drum, or in the dispersion box of washing machine, any one described detergent composition in the claim 1 to 20 of introducing significant quantity.
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1788496P | 1996-05-17 | 1996-05-17 | |
| US1788696P | 1996-05-17 | 1996-05-17 | |
| US1788396P | 1996-05-17 | 1996-05-17 | |
| US60/017,886 | 1996-05-17 | ||
| US60/017,884 | 1996-05-17 | ||
| US60/017,883 | 1996-05-17 | ||
| GB9616076.6 | 1996-07-31 | ||
| GB9616076A GB2315761A (en) | 1996-07-31 | 1996-07-31 | Detergent composition comprising a particulate acid source and an alkaline source |
| GB9705824A GB2323380A (en) | 1997-03-20 | 1997-03-20 | A detergent composition |
| GB9705824.2 | 1997-03-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1225114A true CN1225114A (en) | 1999-08-04 |
| CN1104489C CN1104489C (en) | 2003-04-02 |
Family
ID=27517364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97196401A Expired - Fee Related CN1104489C (en) | 1996-05-17 | 1997-05-16 | Detergent composition |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0906385A4 (en) |
| CN (1) | CN1104489C (en) |
| BR (1) | BR9710680A (en) |
| CA (1) | CA2255594C (en) |
| CZ (1) | CZ371898A3 (en) |
| HU (1) | HUP9902766A3 (en) |
| MX (1) | MX210136B (en) |
| WO (1) | WO1997043366A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107530742A (en) * | 2015-03-05 | 2018-01-02 | 克罗斯福德国际有限责任公司 | System and method for the cleaning of tablet pipe |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0872544A1 (en) | 1997-04-14 | 1998-10-21 | The Procter & Gamble Company | Dry effervescent granules and granular compositions comprising the same |
| US6063390A (en) | 1998-08-07 | 2000-05-16 | Chesebrough-Pond's Usa Co., A Division Of Conopco, Inc. | Cosmetic effervescent cleansing pillow |
| DE19847281A1 (en) * | 1998-10-14 | 2000-04-20 | Henkel Kgaa | Detergent tablets, especially for use in domestic washing machines, contain rapidly dissolving coarse oligocarboxylic acid particles |
| DE19926376A1 (en) * | 1999-06-10 | 2000-12-14 | Henkel Kgaa | Storage stable effervescent tablets |
| US6451331B1 (en) | 2000-01-31 | 2002-09-17 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Pleated cosmetic effervescent cleansing pillow |
| US6506713B1 (en) | 2000-01-31 | 2003-01-14 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Cosmetic effervescent cleansing compositions |
| GB0006037D0 (en) | 2000-03-13 | 2000-05-03 | Unilever Plc | Detergent composition |
| ES2264926T3 (en) * | 2000-06-19 | 2007-02-01 | THE PROCTER & GAMBLE COMPANY | PROCEDURE TO TREAT A TISSUE GENERATING HEAT. |
| GB0031827D0 (en) * | 2000-12-29 | 2001-02-14 | Unilever Plc | Detergent compositions |
| GB0031823D0 (en) | 2000-12-29 | 2001-02-14 | Unilever Plc | Detergent compositions |
| GB0109763D0 (en) | 2001-04-20 | 2001-06-13 | Reckitt Benckiser Inc | Improvements in and relating to organic compositions |
| GB0115552D0 (en) | 2001-05-16 | 2001-08-15 | Unilever Plc | Particulate laundry detergent composition containing zeolite |
| US20050042262A1 (en) | 2003-08-21 | 2005-02-24 | The Procter & Gamble Company | Effervescent cleansing article |
| US7018968B2 (en) | 2003-09-17 | 2006-03-28 | Unilever Home & Personal Care Usa | Liquid laundry detergent with polyanionic ammonium surfactant |
| US7037883B2 (en) | 2003-09-17 | 2006-05-02 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Process of making a liquid laundry detergent with polyanionic ammonium surfactant |
| US6969700B2 (en) | 2004-02-12 | 2005-11-29 | Unilever Home & Personal Care, Usa Division Of Conopco, Inc | Liquid detergent with polyanionic ammonium surfactant and a high pKa solid inorganic base |
| US20050187131A1 (en) * | 2004-02-23 | 2005-08-25 | The Procter & Gamble Company | Granular laundry detergent composition comprising a ternary detersive surfactant system and low levels of, or no, zeolite builders and phosphate builders |
| US20050197275A1 (en) * | 2004-03-03 | 2005-09-08 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Solid laundry detergents with polyanionic ammonium surfactant |
| US7179772B2 (en) | 2004-06-24 | 2007-02-20 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Extended lathering pillow article for personal care |
| ATE485361T1 (en) | 2005-08-19 | 2010-11-15 | Procter & Gamble | SOLID DETERGENT COMPOSITION CONTAINING ALKYLBENZENESULPHONATE, CARBONATE SALT AND CARBOXYLATE POLYMER |
| EP1754780B1 (en) | 2005-08-19 | 2010-04-21 | The Procter and Gamble Company | A solid laundry detergent composition comprising alkyl benzene sulphonate and a hydratable material |
| PL1754781T3 (en) | 2005-08-19 | 2013-09-30 | Procter & Gamble | A solid laundry detergent composition comprising anionic detersive surfactant and a calcium-augmented technology |
| EP1754779B1 (en) | 2005-08-19 | 2012-10-17 | The Procter and Gamble Company | A solid laundry detergent composition comprising anionic detersive surfactant and a highly porous carrier material |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4228044A (en) * | 1978-06-26 | 1980-10-14 | The Procter & Gamble Company | Laundry detergent compositions having enhanced particulate soil removal and antiredeposition performance |
| CH646727A5 (en) * | 1977-06-29 | 1984-12-14 | Procter & Gamble | LAUNDRY ADDITIVE PRODUCT. |
| DE2857161A1 (en) * | 1977-06-29 | 1980-03-06 | Procter & Gamble | DETERGENT AND CLEANING AGENT |
| US4259217A (en) * | 1978-03-07 | 1981-03-31 | The Procter & Gamble Company | Laundry detergent compositions having enhanced greasy and oily soil removal performance |
| CA1104451A (en) * | 1978-02-28 | 1981-07-07 | Manuel Juan De Luque | Detergent bleach composition and process |
| EP0028432B1 (en) * | 1979-11-03 | 1984-01-18 | THE PROCTER & GAMBLE COMPANY | Granular laundry compositions |
| US4597898A (en) * | 1982-12-23 | 1986-07-01 | The Proctor & Gamble Company | Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties |
| ATE219136T1 (en) * | 1991-01-16 | 2002-06-15 | Procter & Gamble | COMPACT DETERGENT COMPOSITIONS WITH HIGHLY ACTIVE CELLULASES |
| EP0581857B1 (en) * | 1991-04-19 | 1996-01-03 | The Procter & Gamble Company | Granular laundry detergent compositions having improved solubility |
| GB9120657D0 (en) * | 1991-09-27 | 1991-11-06 | Unilever Plc | Detergent powders and process for preparing them |
-
1997
- 1997-05-16 WO PCT/US1997/008544 patent/WO1997043366A1/en not_active Application Discontinuation
- 1997-05-16 BR BR9710680A patent/BR9710680A/en not_active Application Discontinuation
- 1997-05-16 CA CA002255594A patent/CA2255594C/en not_active Expired - Fee Related
- 1997-05-16 CZ CZ983718A patent/CZ371898A3/en unknown
- 1997-05-16 HU HU9902766A patent/HUP9902766A3/en unknown
- 1997-05-16 CN CN97196401A patent/CN1104489C/en not_active Expired - Fee Related
- 1997-05-16 EP EP97926620A patent/EP0906385A4/en not_active Ceased
-
1998
- 1998-11-17 MX MX9809626A patent/MX210136B/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107530742A (en) * | 2015-03-05 | 2018-01-02 | 克罗斯福德国际有限责任公司 | System and method for the cleaning of tablet pipe |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0906385A1 (en) | 1999-04-07 |
| HUP9902766A3 (en) | 2001-10-29 |
| CA2255594A1 (en) | 1997-11-20 |
| BR9710680A (en) | 1999-08-17 |
| WO1997043366A1 (en) | 1997-11-20 |
| MX9809626A (en) | 1999-03-31 |
| CA2255594C (en) | 2002-07-23 |
| MX210136B (en) | 2002-09-04 |
| HUP9902766A2 (en) | 2000-01-28 |
| EP0906385A4 (en) | 1999-06-09 |
| CN1104489C (en) | 2003-04-02 |
| CZ371898A3 (en) | 1999-03-17 |
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