CN1064701A - Peroxyacid bleach precursor compositions - Google Patents
Peroxyacid bleach precursor compositions Download PDFInfo
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- CN1064701A CN1064701A CN92101630A CN92101630A CN1064701A CN 1064701 A CN1064701 A CN 1064701A CN 92101630 A CN92101630 A CN 92101630A CN 92101630 A CN92101630 A CN 92101630A CN 1064701 A CN1064701 A CN 1064701A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
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Abstract
Solid peroxygen acid blanching precursor compositions is provided, wherein uses the outside surface of 2-20% (weight) solid organic acid compound treatment particle peroxy acid parent material.Described organic acid MPT＞30 ℃, and solubleness restrains water at 20 ℃ of at least 5 gram/100 in water.When processing like this, the bleach precursor material in 20 ℃ in a standard test after 3 minutes all-hydrolytic produce the degree of at least 90% untreated under the same conditions bleach precursor material hydrolysis.Preferred organic acid compound is monomeric aliphatic hydroxyl carboxylic acid and poly carboxylic acid, for example citric acid, lactic acid and oxyacetic acid.The peroxyacid bleach precursor particulate detergent composition that contains processing also has been disclosed.
Description
The present invention relates to solid peroxygen acid blanching precursor compositions, particularly inorganic perhydrate SYNTHETIC OPTICAL WHITNER and the granular detergent composition that contains peroxycarboxylic acid bleach precursor (so-called bleach activator) blending of N-or O-acyl group.In recent years, said composition is used widely in automatic washing machine especially as heavy duty type clean fabric product.The reaction of propagation fabric washing temperature that bleach activator uses descends, and is being accompanied by the ratio increase of yarn dyed fabric.
Have a problem to become more important, that is exactly by the fabric color that generation causes of the high local concentrations of albic material and the tendency of damage of materials.Owing to multiple reason may produce high bleaching concentration around the granular bleach material.Albic material itself may have the low solubleness of inherent, its solubleness may be subjected to other material for example the whipped state in the surrounding medium of the existence of viscous surface promoting agent material or albic material can not be high enough to the obstruction of the SYNTHETIC OPTICAL WHITNER of dispersing and dissolving.There, thus albic material forms a kind of component of composition produces potential problems.Except that the perhydroxyl radical ion potential ability of the high local concentrations that produces by the dissolving of the inorganic perhydrate in the detergent composition that is generally comprised within washing, the all-hydrolytic of bleach activator and form the peroxycarboxyl groups negatively charged ion and can produce very big local percarboxylate and bleach concentration.
The formation of so-called concentrated product and the diverting device in being installed in the machinery tube transmit with the fabric load can only increase the weight of these problems.Therefore, need a kind of detergent composition, wherein sneak into bleach activator it is dissolved in washings and the all-hydrolytic process in the color of fabric and the damage of material reduce to minimum degree, preferably can remove this damage.
Prior art comprises the example of many coatings or agglomerant bleach activator, so that increase the solution behavior that is stored in the solubleness in the detergent composition and/or influences it.
EP-A-0070474 disclose by spraying drying contain N-acyl group or O-acyl compounds and at least a water-soluble cellulose ether, starch or starch derivative (weight ratio of its promoting agent and coating is 98: 2 to 90: 10) but the extractive dispersion liquid of moisture pump prepare granular bleach activators.
GB-A-1507312 discloses with a kind of alkali-metal C
8-C
22The bleach activator of soap and corresponding lipid acid blended mixture coating.It especially is C that GB-A-1381121 uses a kind of
14-C
18The melt coating layer of fatty acid mixt is protected the solid bleach promoting agent.GB-A-1441416 discloses a kind of similar approach, wherein uses C
12-C
14Lipid acid and C
10-C
20The mixture of Fatty Alcohol(C12-C14 and C12-C18).The bleach activator extrudate that the EP-A-0375241 narration is stable, in extrudate, C
5-C
18Alkyl peroxycarboxylic acid parent mixes with the mixture that is selected from negatively charged ion and nonionic surface active agent, film-forming polymer lipid acid binding material or this binding material.
EP-A-0356700 discloses the C that comprises bleach activator, water-soluble, film-forming polymers and 2-15%
3-C
6The composition of polycarboxylic acid or hydroxycarboxylic acid is so that improve stability and be easy to dispersed/dissolved.Carboxylic acid (preferred example is a citric acid) is at first done with bleach activator and is mixed, then with the film-forming polymer granulation.The sure raising bleach activator of citric acid particulate dissolution rate.
EP-A-0382464 relates to the coating of the solids that contain bleaching compounds and bleach activator and the method for encapsulate, its melt is the coating material formation that particle forms disperse phase therein, the melt instability, make it be broken into particulate matter then, in the dispersed phase particles embedding continuous (coating) mutually.Disclose various coating materials in this patent, and informed that some material is useful as polyacrylic acid and cellulose acetate O-phthalic acid cellulose, the pH value is depended in the release of application substance.
Emphasize comprehensively in the prior art that the protection of bleach activator and the environment of lay up period are conflicting, and the dissolution characteristics of coating in use or agglomeration material gives seldom to note.Wherein coating and/or agglomeration have been proposed with low molten material such as lipid acid, if this has just caused the all-hydrolytic speed ratio of bleach activator so not protect slower.Use any quicker dissolved substance such as citric acid to interrelate as the quicker dissolving of agglomeration component and bleach activator.In two examples, because all-hydrolytic takes place at once, Betengent product begins dissolving and forms alkaline hydrogen peroxide solution, and the local spissated problem of peroxy acid bleach that keeps is still unresolved.
A kind of terms of settlement of relevant this problem is to postpone all-hydrolytic, the fabric color damage problem that interrelates with the solubility behavior of avoiding with other Betengent product component.But importantly the dispersion when the all-hydrolytic of bleach precursor and percarboxylate SYNTHETIC OPTICAL WHITNER subsequently is fast as far as possible at the very start, and this is to die because of the washing time of the weak point of modern automatic washing machine.
Satisfy this simultaneously two problems that purpose produced are imputed in the prior art and can not occur.
The all-hydrolytic speed of having known the percarboxylic acids bleach precursor in oxidizing aqueous medium is along with the reduction of medium pH value is lowered gradually, particularly drops under the PKa of parent acid of leavings group parent especially like this as PH.Yet lipid acid is otiose as applying agent as the method for low ph environment is provided in water lotion in the prior art, because it is insoluble.And, found to lower when lipid acid is used as the coating of peroxyacid bleach precursor and/or agglomerant the all-hydrolytic speed of parent to have lowered the validity of resultant peroxycarboxylic acid bleaching thus.
The applicant now is surprised to find that, acid mass-energy with some special property is used for surface treatment particle peroxyacid bleach precursor, so that under the pressure agitation condition of the laundry machine barrel of loading, in the dissolution process of product, delay fully hydrolyzed beginning and all-hydrolytic hinder to take place on the contrary.
According to the present invention; the solid peroxygen acid blanching that comprises a kind of particle peroxyacid bleach precursor material precursor compositions is provided; described parent contains one or more N-or O-acyl group and Mpt＞30 ℃; the outside surface of described particle peroxyacid bleach precursor material is handled with organic acid compound so that described compound is sticked on the described outside surface; the amount of described compound is processed particulate 2～20%(weight); solubleness is at least 5 grams/100 gram water at 20 ℃ in the water of described organic acid compound; its Mpt＞30 ℃, the granular bleach parent material of wherein said processing produce at least 90% the peroxy acid that is produced by described untreated granular bleach parent material under the same conditions after 3 minutes in 20 ℃ of Beaker all-hydrolytics tests.
Organic acid compound is monomeric or the carboxylate salt of oligopolymer preferably, and solubleness is at least 20 grams/100 gram water in 20 ℃ of its water, and most preferred is the monomeric aliphatic carboxylic acid with high-dissolvability very and Mpt＞40 ℃.
The outside surface of peroxyacid bleach precursor particle (no matter be with single particle or agglomerate form) is handled so that organic acid compound is adhered to thereon, vital to the objective of the invention is.Processing can make compound with the coating of continuous or discontinuous form or be dispersed on the particle surface or with each particle random dispersion from the teeth outwards with a large amount of acidic cpds.What need is that the surface treatment material is can get at once, and in being exposed to hydrolyte, dissolving is rapid, and makes bleach precursor particulate exterior circumferential environment be acid ph value.Because this reason, sneak into organic acid compound and be dispersed in the peroxyacid bleach precursor particle as agglomerant and be unprofitable to the present invention.This is because under the dissolution conditions of concentrated granular cleaning product, particularly is transported in the washing machine agglomeration but do not have surface-treated peroxyacid bleach precursor all-hydrolytic to largely and produce high bleaching concentration and produce local fabric damage by diverting device.
Solid peroxygen acid blanching precursor compositions of the present invention is sneaked into the parent that contains one or more N-or O-acyl group, and described parent can be selected from various types of materials.Suitable type comprises the acylated derivatives of acid anhydride, ester, imide and imidazoles and oxime, and the example of useful matter is disclosed among the GB-A-1586789 in these types.Most preferred type is an ester, and is disclosed in 864798,1147871 and 2143231 as GB-A-836988, and imide, as disclosed in GB-A-855735 and 1246338.
Specific O-acidylate parent compound comprises 2,3,3-trimethyl acetyl hydroxy benzene sulfonate, benzyl hydroxy benzene sulfonate and penta-acetyl glucose.
Particularly preferred parent compound is N-, N, and N ' N ' tetrem acylated compounds, its formula is
Wherein X may be 0 or the integer of 1-6.Some examples comprise tetra-acetylated methylene diamine (TAMD) (wherein X=1), tetra acetyl ethylene diamine (TAED) (wherein X=2) and tetra-acetylated hexamethylenediamine (TAHD) (wherein X=6).These compounds and similar compound are narrated in GB-A-907356.Most preferred peroxyacid bleach precursor is TAED.
Mpt＞30 of the solid peroxygen acid blanching parent that the present invention is useful ℃ are preferably＞40 ℃.Described parent is generally fine powder or crystallized form, wherein 90%(weight at least) size of particles＞150 micron of powder.
This powder may be that directly handle on the surface, but before surface treatment, more generally is the agglomerated form particulate matter, and wherein at least 85% size of particles is between 400 and 1700 microns.Suitable agglomerant comprises C
12-C
18Lipid acid, C
12-C
18Fatty alcohol and every mol of alcohol are 10～80 moles oxirane condensation product, and derivatived cellulose such as methyl, carboxymethyl and Natvosol, MWt are the polyoxyethylene glycol of 4000-10000 and as the polymer materials of Polyvinylpyrolidone (PVP) and so on.
Agglomerant particle parent material itself can not be of value to the present invention, but preferred parent form is to make surface-treated with organic acid compound.
Organic acid compound must satisfy several criterions, at first, must be solid when room temperature, so fusing point must at least 30 ℃, and preferably at least 40 ℃.The fusing point of preferred organic acid compound is above 50 ℃.Secondly organic acid compound must be soluble in water when room temperature, for purpose regulation Yi Rongwei of the present invention dissolves at least 5 grams in 20 ℃ of 100 gram distilled water.The solubleness of more suitable organic acid compound is at 20 ℃ of at least 20 gram/100 gram water, and most preferred organic acid compound equals the weight of water 20 ℃ of dissolvings.The 3rd organic acid compound does not have under the compulsory condition the influence of the all-hydrolytic speed of peroxyacid bleach precursor very little in fine stirring, preferred essentially no influence.For purpose regulation of the present invention does not have compulsory fine agitation condition for being described in detail in the condition in the test of Beaker all-hydrolytic hereinafter.For purpose predetermined processing material of the present invention allowed to produce at least 90% the peroxy acid that is produced by the bleach precursor material that is untreated under the same conditions to the influence of parent all-hydrolytic speed is very little after 3 minutes in 20 ℃ of Beaker all-hydrolytic tests.Preferably the all-hydrolytic speed with untreated material of Chu Liing is basic identical.
The organic acid compound that is suitable as treatment agent for purpose of the present invention comprises the carboxylate salt of aliphatic series or aromatic monomer or oligopolymer.Preferably comprise monomeric aliphatic carboxylic acid.The example of described aliphatic acid compound is L-glutamic acid, oxyacetic acid, citraconic acid, Succinic Acid, L-lactic acid and citric acid.The amount of using acid is for handling particulate 2-20%(weight), more preferably 2-15% is preferably 3-10%(weight).Be to handle the about 5%(weight of particle) oxyacetic acid be particularly preferred surface treatment agent.
Can handle by several method with organic acid compound surface treatment bleach precursor particle.Method itself is not strict for purposes of the invention.
Organic acid compound can a kind of melt substance or above the solution in solvents/carriers liquid or dispersion liquid be sprayed at, liquid was removed by evaporation subsequently.Organic acid compound also can be as powder coating as being employed by electrostatic technique, although this method is not preferred, because adhering powder shape application substance is more to be difficult to realize, and may be more expensive.
Fusion coating is a kind of preferred technology to the organic acid compound of Mpt＜80 ℃ such as oxyacetic acid and L-lactic acid, but high-melting-point acid (promptly＞100 ℃) is difficult to be fit to as citric acid.For the organic acid compound of Mpt＞80 ℃, preferably thereon with solution or dispersion liquid spraying.Can use as ethanol and Virahol and so on organic solvent and form solution or dispersion liquid, it is economical that this method is used, but the use of organic solvent also produces safety problem as flammable and operator's safety, so the aqueous solution or dispersion liquid are preferred.
The part advantage of the aqueous solution is that organic acid compound has high water solubility (as citric acid) and solution to have enough low viscosity to make to be treated as possibility.Carry out after drying/evaporation in order to reduce surface treatment, preferably use the concentration of organic acid compound in solvent to be at least 25%(weight).Treatment unit can be for this purpose normally used those, for example rotary pot of Qing Xieing, rotating cylinder and fluidized-bed.
Solid peroxygen acid blanching precursor compositions of the present invention can adopt various physical form, and therefore surface-treated peroxyacid bleach precursor particle itself also can be sneaked into other solid ingredient, as tablet, extrudate and agglomerate.Particle also can be suspended in the on-aqueous liquid component, and organic acid surface treatment material is insoluble to wherein and is inertia.But advantageous applications solid peroxygen bleach precursor compositions of the present invention is the grain fraction as granular detergent composition, especially is added to so-called spissated detergent composition in the washing machine by putting charging device in having the machinery drum of dirty fabric load.The concentrated granular detergent composition that is dispersed in the washings through charging device adds more easy-clear problem of composition than the dispersing chamber through washing machine, because stir near the environment of product and be subjected to obstruction in the presence of the fabric load in initial period wash(ing)cycle, this may constitute to benefit and allow to produce the washing assistant of high instantaneous concentration and the damage (annotating as the front) that tensio-active agent, the instantaneous peroxy acid enriched material of generation height can cause fabric and color.When the peroxyacid bleach precursor particle of coating of the present invention also is transported in the washings through diverting device in sneaking into spissated washing composition product, also can alleviate even can not eliminate this problem.
Be mixed with surface-treated peroxyacid bleach precursor particulate detergent composition and contain 0.5～10% parent usually, 1-8% more preferably is preferably 2-6%(based on composition weight).
Certainly, described detergent composition contains the alkaline hydrogen peroxide source need form the peroxy acid bleach material in washing soln, preferably also contain other common component in detergent composition.Therefore, preferred detergent composition will mix one or more tensio-active agents, organic and inorganic builders, soil-suspending agent and anti redeposition agent, froth suppressor, enzyme, white dyes, photolytic activity SYNTHETIC OPTICAL WHITNER, spices and tinting material.
The detergent composition that is mixed with surface treatment particle peroxy acid parent of the present invention comprises the source of a kind of inorganic perhydrate SYNTHETIC OPTICAL WHITNER (usually with sodium-salt form) as washings neutral and alkali hydrogen peroxide.The common mixed volume of this perhydrate is the 3-22%(weight of composition), be more preferably 5-20%(weight), most preferably be 8-18%(weight).
Perhydrate can be any inorganic salt, as perborate, percarbonate, superphosphate and persilicate, but generally is alkali-metal perborate or percarbonate.When the fabric color damage that is produced by composition according to the present invention is low, no matter whether use perborate or percarbonate, compare with the precursor granule of uncoated, more noticeable with its improvement of percarbonate bleach, because when the bleach precursor of no any coating exists, can cause bigger fabric color damage.
SPC-D is preferred perhydrate, and it is a kind of addition compound, and corresponding molecular formula is 2Na
2CO
33H
2O
2, and can buy on market with crystalline solid.Most of commerce can get material and comprise low-level heavy metal chelate such as EDTA, 1-hydroxy ethylene 1, and 1-di 2 ethylhexyl phosphonic acid (HEDP) or amino phosphonates do, it is sneaked in manufacturing processed.For detergent composition of the present invention, the percarbonate that can sneak in the detergent composition does not have supplementary protection, but the preferred said composition that realizes is used the form of application of material.Although various coating can use, most economical is water glass, wherein SiO
2: Na
2The ratio of O is 1.6: 1～3.4: 1, is preferably 2.8: 1, and with aqueous solution application is the common 3-5% of 2-10%(of percarbonate) (weight) water glass solid, Magnesium Silicate q-agent also can be included in the coating.
The size of particles scope of crystallization percarbonate is 350～450 microns, average about 400 microns.After coating, the crystallite size scope is the 400-600 micron.
Heavy metal in existing in the yellow soda ash that is used for making percarbonate can be by reaction mixture in the inclusion of sequestrant when controlling, percarbonate still needs to make heavy metal to avoid existing in other component of product as impurity.Therefore, use in the detergent composition of percarbonate as perhydrate salt, the total amount of iron, copper and mn ion is no more than 25ppm in the product, is preferably less than 20ppm, and this is for fear of percarbonate stability is produced unacceptable bad influence.Apply for pendent GB Patent Application No. 9021761.3(Attorney ' s Docket No.CM343 the applicant) in the detergent composition that improves the alkali metal percarbonate bleach stability is disclosed.
Available wide scale surface-active agent in detergent composition.1975,12,30 are issued to the tensio-active agent of having listed typical anionic, non-ionic type, both sexes and zwitter-ion type among the USP3929678 of Laughlin and Heuring, and the kind of these tensio-active agents.1981,3,31 are issued among the USP4259217 of Murphy and have listed a series of suitable cats products.
The mixture of anion surfactant is applicable to the present invention, particularly the blend of vitriol, sulfonate and/or carboxylation tensio-active agent.Usually the weight ratio of sulfonate and vitriol is 5: 1 to 1: 2 in the mixture of sulfonate of using and sulfate surfactant, is preferably 3: 1 to 2: 3, more preferably 3: 1 to 1: 1.Preferred sulfonate comprises alkylbenzene sulfonate (wherein the carbon atom of alkyl is 9-15, particularly 11-13) and α-sulfonated fatty acid methyl ester, and wherein lipid acid is from C
12-C
18Fat source, be preferably C
16-C
18Fat source.In each example, positively charged ion is a basic metal, is preferably sodium.In described sulfonate sulfate mixture, preferred sulfate surfactant is an alkyl-sulphate, and wherein alkyl is 12-22, is preferably 16-18 carbon atom.Other useful surfactant system comprises the mixture of two kinds of alkyl-sulphate materials, and each refers to different chain length mutually respectively.One of described system comprises C
14-C
15Alkyl-sulphate and C
16-C
18The mixture of alkyl-sulphate, wherein C
14-C
15: C
16-C
18Weight ratio be 3: 1 to 1: 1.Alkyl-sulphate can be 10-20 with the alkyl carbon atoms number also, is preferably 10-16, and average degree of ethoxylation is that 1 to 6 alkyl ethoxy sulfate combines use.Positively charged ion in each example is a basic metal, preferably sodium.
Other anion surfactant that is suitable for the object of the invention is the basic metal sarcosinate, and molecular formula is R-CON(R
1) CH
2COOM wherein R is C
9-C
17Straight or branched alkyl or alkenyl, R
1Be C
1-C
4Alkyl, M are alkalimetal ions, and preferred example is lauroyl, the coconut acyl group (C with sodium-salt form
12-C
14) (cocoyl), tetradecanoyl and oleoyl methyl sarcosinate.
A classification that is used for anion surfactant of the present invention comprises the condenses of oxyethane and hydrophobic part, the tensio-active agent that obtains has, and on average hydrophobic-lipophile balance value (HLB) is in 8 to 17 scopes, being preferably 9.5～13.5, is better especially with 10-12.5.Hydrophobic (lipophilic) part may be in nature aliphatic series or aromatics, and and the length of the polyoxyethylene groups of any specific hydrophobic grouping condensation can easily regulate the water-soluble cpds (between hydrophobic and hydrophilic unit, having required balanced degree) of generation.Particularly preferred nonionic surface active agent is the C that every mol of alcohol contains the 3-8 moles of ethylene oxide in this type
9-C
15Primary alcohol ethoxylate, particularly every mol of alcohol contains the C of 6-8 moles of ethylene oxide
14-C
15Primary alconol and every mol of alcohol contain the C of 3-5 moles of ethylene oxide
12-C
14Primary alconol is advisable.
The nonionic surface active agent of other type comprises that general formula is RO(CnH
2NO) the alkyl polyglucoside compound of tZx, wherein Z is a glucose deutero-part, R is saturated hydrophobic alkyl, contains 12 to 18 carbon atoms; T is 0 to 10, and n is 2 or 3; X is 1.3 to 4, and this compound comprises less than 10% unreacted Fatty Alcohol(C12-C14 and C12-C18) with less than 50% short-chain alkyl polyglucoside.This compounds and the application in detergent composition thereof be at EP-B-0070074, and be open in 0070077,0075996 and 0094118.
Another kind of tensio-active agent is semi-polarity tensio-active agent, for example amine oxide.The amine oxide that is fit to is to be selected from single C
8-C
20, be preferably C
10-C
14N-alkyl or alkenyl amine oxide and propylene 1,3-diamines dioxide wherein remains the N position and is replaced by methyl, hydroxyethyl or hydroxypropyl.
Cats product also can be used in the detergent composition of the present invention, and suitable quaternary ammonium surfactant is selected from single C
8-C
16, be preferably C
10-C
14N-alkyl or alkenyl ammonium surfactant wherein remain the N position and are replaced by methyl, hydroxyethyl or hydroxypropyl.
Detergent composition comprises 5～20% tensio-active agent, but more generally comprises 7-20%, more preferably 10-15%(weight) tensio-active agent (is benchmark with the composition).
The bonded surfactant types is more suitable, more especially negatively charged ion-nonionic and negatively charged ion-nonionic-cationic blend.Particularly preferred combination is narrated in GB-A-2040987 and EP-A-0087914.Though tensio-active agent can mix in the composition by mixture, every kind of amount of surfactant that preferably control adds reaches for the rerum natura that obtains best composition and avoids processing problems.Preferable methods and tensio-active agent add order and will narrate hereinafter.
The another kind of utmost point preferred ingredient of detergent composition of sneaking into the peroxy acid precursor granule of the present invention coating is the detergent builders system that has comprised one or more non-phosphate detergent washing assistants.These components can include, but are not limited to alkaline carbonate, supercarbonate, silicate, aluminosilicate, monomeric polycarboxylate, all or the poly carboxylic acid of copolymerization or its salt, wherein poly carboxylic acid comprises at least two carboxyls, they are not more than two carbon atoms each other and separate the mixture of Organophosphonate and amino alkenyl poly-(alkenyl phosphonic acid ester) and aforementioned any component.The builder system amount is 25～60%(weight of composition), be more preferably 30-60%(weight).
Preferred builder system is that organic substance no boron compound and any polymkeric substance is best biodegradable.
Suitable silicate is to have SiO
2: Na
2O is than the silicate that is 1.6 to 3.4, SiO
2: Na
2The ratio of O is that 2.0 to 2.8 so-called amorphous silicate is preferred.These materials can add by each point in manufacturing processed, for example in the slurry of exsiccant component of waiting to spray or in aqueous solution form, add, or wherein silicate itself is added in other grain fraction of composition with particle form such as solid as the agglomerant of other solid ingredient.But for composition speech, the percentage ratio of spray-dried component is low, promptly 30%, preferably include the amorphous silicate in spray-dried component.
In the silicate types, fabulous material is a crystalline layered sodium silicate, its general formula
Wherein M is sodium or hydrogen, and x is 1.9 and 4 a number, and y is 0 to 20 number.Such crystalline layered sodium silicate has been disclosed among the EP-A-0164514, and its manufacture method is disclosed among DE-A-3417649 and the DE-A-3742043.For purpose of the present invention, X is 2,3 or 4 in the above-mentioned general formula, preferably 2, and preferred M is a sodium, and y is 0, and the preferred example of this molecular formula comprises the Na of γ and δ form
2Si
2O
5These materials obtain from Hoechst AG FRG with NaSKS-11 and NaSKS-6 respectively.Most preferred material is-Na
2Si
2O
5, (NaSKS-6).Crystalline layered silicate promptly can be used as dried blended solid, and the solid ingredient that can be used as agglomerate again is with other component blending.
One eka-aluminum silicate ion exchange material can be used, and preferred sodium aluminium silicate zeolite has the unit cell molecular formula and is
Wherein Z and y are at least 6; The mol ratio of Z and y is 1.0 to 0.5, and x is at least 5, is preferably 7.5 to 276, more preferably 10 to 264.The aluminosilicate material is a hydrate forms, and preferably crystallisate contains 10-28%, the water of 18-22% combining form more preferably.
Another of above-mentioned aluminosilicate ion exchange material is characterised in that the size of particles diameter is 0.1 to 10 micron, preferably 0.2 to 4 micron.Term " size of particles diameter " representative as for example use the measurement microscope of scanning electronic microscope or by the average particle size diameter of a kind of given ion exchange material of laser particle size instrumentation amount by the general analysis technology.Another feature of aluminosilicate ion exchange material is its calcium ion-exchanged capacity, is 200mg equivalent CaCO at least
3The water hardness/gram aluminosilicate (be with anhydrous basic calculation) generally is a 300mg equivalent/restrain to 352mg equivalent/gram.The aluminosilicate ion exchange material also has another feature to be that calcium ion exchange rate is the normal CaCO of 130mg at least
3/ liter/minute/(grams per liter) (2 grains (grains) Ca
++/ gpm/(gram/gallon)) aluminosilicate (anhydrous is benchmark) generally is in 130mg equivalent CaCO
3/ liter/minute/(grams per liter) (2 grains/gpm/(gram/gallon)) be to 390mg equivalent CaCO
3/ liter/minute/(grams per liter) (6 grains/gpm/(gram/gallon)) (is benchmark with calcium ion hardness) scope in.
The aluminosilicate of best washing assistant purpose presents calcium ion exchange rate 260mg equivalent CaCO at least
3/ liter/minute/(grams per liter) (4 grains/gpm/(gram/gallon)).
Being used in aluminosilicate ion exchange material of the invention process is that market can get, and may be the material that nature exists, but preferably synthetic obtaining.Produce the method for aluminosilicate ion exchange material and discuss in US3985669, the useful preferred synthesising crystal aluminium silicate ion exchange material of the present invention is available trade mark zeolite A, zeolite B, X zeolite, zeolite HS and composition thereof.In certain preferred embodiment, the crystalline aluminosilicate ion exchange material is zeolite A, and its molecular formula is
Wherein x is 20-30, and especially 27 for well, and molecular formula is
Na
86((AlO
2)
86(SiO
2)
106) 276H
2The X zeolite of O also is fit to, and molecular formula is Na
6((AlO
2)
6(SiO
2)
6) 7.5H
2O) zeolite HS is suitable equally.
Suitable carboxylate salt washing assistant water-soluble monomer or oligopolymer can be selected from large-scale compound, but described compound preferably has first carboxyl logarithm acidity/constant (pK
1) less than 9, preferably between 2 and 8.5, more preferably 4 to 7.5.
The logarithm acidity constant is by following relationship balanced type defined
Wherein A is the carboxylate anion of complete Ionized builder salt.Therefore the equilibrium constant is:
K
1= ((H
＋A))/((H
＋)(A))
And pK
1=log
10K
For this specification sheets purpose, acidity constant is defined within and obtains under 25 ℃ and zero ionic strength.The literature value that may get in the literary composition is (referring to the stability constant of metal-ionic complex, Special Publication No.25, The Chemical Society, London), produce query at this, they record by using the titration of glass electrode electrode potential.
Preferred also available its calcium ion stability constant of carboxylate salt (pKca
++) define, be similar to pK
1, define by following equation
pKca
++＝log
10Kca
++
Kca wherein
++=((Ca
++A))/((Ca
++) (A))
Multi-carboxylate's pKca preferably
++For about 2 to about 7, especially with about 3 to about 6 for well.May get the literature value of stability constant again at this.Stability constant is defined in 25 ℃ and zero ionic strength and utilizes the glass electrode measuring method and decide described in the Complexation among the Analytical Chemistry that (as by Anders Ringbom(1963) show).
Carboxylate salt or multi-carboxy acid salt washing agent can be monomeric or oligomer types, obviously consider that from price and performance monomeric multi-carboxylate is generally better.
That monomeric and washing assistant oligopolymer may be selected from is acyclic, alicyclic ring, heterocyclic and aromatic carboxylic acid salt, and its general formula is
R wherein
1Represent H, C
1-30Alkyl or alkenyl (replaced by hydroxyl, carboxyl, sulfonic group, phosphono arbitrarily or be connected with the polyethyleneoxy part that contains up to 20 vinyloxy grouies); R
2Represent H, C
1-4Alkyl, alkenyl or hydroxyalkyl, or alkaryl, sulfonic group or phosphono; X represents singly-bound; O; S; SO; SO
2; Or NR
1; Y represents H; Carboxyl; Hydroxyl; The carboxyl methoxyl group; Or arbitrarily by the C of hydroxyl or carboxyl substituted
1-30Alkyl or alkenyl; Z represents H or carboxyl; M is 1 to 10 integer; N is 3 to 6 integer; P, q are 0 to 6 integers; P+q is 1 to 6; Wherein each of X, Y and Z has identical or different representative in the given molecular formula of multiple, and at least one Y or Z contain carboxyl in molecule.
The carboxylate salt that is fit to that contains a carboxyl comprises lactic acid, oxyacetic acid and ether derivant thereof, described in belgian patent numbers 831368,821369 and 821370.The multi-carboxylate of containing two carboxyls comprises the water-soluble salt of Succinic Acid, propanedioic acid, (ethylenedioxy) two acetic acid, toxilic acid, diethyl alkyd, tartrate, tartronic acid and fumaric acid, and ether carboxylate, these German Patent 2446686 and 2446687 and the US patent No. 3935257 in narration, the sulfinyl carboxylate salt is narrated in belgian patent numbers 840623.The multi-carboxylate of containing three carboxyls comprises particularly water-soluble citrate, aconitate (aconitrates) and citraconate, and butanedioic acid derivative such as carboxyl methoxy succinate, narration in British Patent No. 1379241, the narration in British Patent No. 1389732 of breast oxygen base succinate, amino-succinic acid salt is narration in Holland's application 7205873, and oxo multi-carboxylate material such as 2-oxo-1,1, the narration in British Patent No. 1387447 of 3-tricarballylic acid salt.
The multi-carboxylate of containing four carboxyls comprises oxo two succinates (open in British Patent No. 1261829), 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 comprise sulfosuccinate derivant, British Patent No. 1398421 and 1398422 and U.S. Patent number 3936448 in open, sulfonation pyrolysis Citrate trianion, narration in British Patent No. 1439000.
Alicyclic ring and heterocycle multi-carboxylate comprise that pentamethylene is suitable, suitable, suitable-the tetracarboxylic acid hydrochlorate, cyclopentadiene metallide (cyclopentadienids) pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF)-tetracarboxylic acid hydrochlorate, 1,2,3,4,5, the carboxyl methyl-derivatives of 6-hexane-hexacarboxylic acid salt and polyvalent alcohol such as Sorbitol Powder, mannitol and Xylitol.Aromatic multi-carboxy acid's salt comprises benzene hexacarboxylic acid, pyromellitic acid, phthalic acid derivative, has been disclosed in the British Patent No. 1425343.
Above-mentioned preferred multi-carboxylate is that per molecule contains the hydroxycarboxylate up to three carboxyls, is more particularly Citrate trianion.
The mixture of the parent acid of monomer or oligomeric multi-carboxylate's sequestrant or itself and their salt, for example citric acid or Citrate trianion/citric acid mixture also can be considered as the component of the builder system of detergent composition of the present invention.
Other suitable water-soluble organic salt is poly carboxylic acid or its salt of homopolymerization or multipolymer, and wherein poly carboxylic acid contains by being not more than two carbon atom two carboxyls spaced apart from each other at least.The polymkeric substance of latter's type is disclosed among the GB-A-1596756.The example of described salt be MWt be 2000-5000 polyacrylic ester and with the multipolymer of maleic anhydride, the molecular weight of this multipolymer is 20000～70000, is in particular about 40000.The common usage quantity of these materials is 0.5～10%(weight of composition), more preferably 0.75～8%, be preferably 1-6%(weight).
Organic phosphonate and amino alkene many (alkene phosphonates) comprise basic metal ethane 1-hydroxyl diphosphonate, nitrilo trimethylene phosphonic salt, 1,2-ethylenediamine tetramethylene phosphonic acid salt and diethylenetriamine pentamethylenophosphonic acid(DTPP) salt, although these materials seldom preferably use, wish that phosphine compound is a minimum degree in composition.
For the purpose of surface treatment bleach precursor particulate detergent composition of the present invention, the nonphosphate builders auxiliary agent is the 25-60%(weight of composition), 30-60%(weight more preferably).In composition preferably, sodium aluminium silicate such as zeolite A comprise 20-60%(weight) (based on the washing assistant total amount), carboxylate salt monomeric or oligopolymer comprises 10-30%(weight) (based on the washing assistant total amount) and crystalline layered silicate comprise 10-65%(weight) (based on the washing assistant total amount).In described composition, the washing assistant auxiliary agent is preferably also sneaked into the auxiliary inorganic and organic washing-assisting detergent of compound, for example yellow soda ash and maleic anhydride/acrylic copolymer, its amount is up to the 35%(weight of total washing assistant).
Be suitable for antiredeposition of the present invention and soil-suspending agent and comprise derivatived cellulose, for example the poly carboxylic acid of methylcellulose gum, carboxymethyl cellulose and Natvosol and homopolymerization or multipolymer or its salt.The polymkeric substance of this type comprises the multipolymer of maleic anhydride and ethene, methylvinylether or methacrylic acid, at least 20 moles of % of maleic anhydride in the multipolymer.These materials common consumption in composition is the 0.5-10%(weight of composition), more preferably 0.75-8% most preferably is 1-6%(weight).
Other useful polymer material is a polyoxyethylene glycol, and particularly molecular weight is 1000-10000, more preferably 2000-8000 and most preferably be these polyoxyethylene glycol of about 4000.These polymer loadings are 0.20～5%, more preferably 0.25～2.5%(weight).The polycarboxylate salt pair of these polymkeric substance and aforementioned homopolymerization or multipolymer improves to be kept whiteness, fabric ash fractional precipitation and is valuable at the clean-up performance on carclazyte, protein and oxidable dirt in the presence of the transition metal impurity.
Preferred white dyes is an anion characteristic, its example is a disodium 4,4 '-two-(2-diethanolamino-4-anilino-S-triazine-6-base is amino) stilbene-2: 2 ' stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, disodium 4,4 '-two-(2-morpholino-4-anilino-2-triazine-6-base is amino) stilbene-2: 2 ' stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, disodium 4,4 '-two-(2,4-hexichol amido-S-triazine-6-base is amino) stilbene-2: 2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, single sodium 4 ', 4 " and two-(2; 4-hexichol amido-S-triazine-6-base is amino) stilbene-2-sulfonate; disodium 4; 4 '-two-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-2-triazine-6-base is amino) stilbene-2,2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, disodium 4; 4 '-two-(4-phenyl-2; 1,3-triazole-2-yl) stilbene-2,2 ' stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, disodium 4,4 ' two (2-anilino-4-(1-methyl-2-hydroxyethylamino)-S-triazines-6-base is amino) stilbene-2,2 ' stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate and sodium 2(stilbene radicals 4 " (naphtho--1 ', 2 ': 4,5)-1; 2,3-triazole-2 " sulfonate.
The soil releasing agent that is used for composition of the present invention is the traditional multipolymer or the terpolymer of terephthalic acid and ethylene glycol and/or propylene glycol, and wherein the unit is by various multi-form arrangements.The example of described polymkeric substance U.S. Patent number 4116885 and 4711730 and European publication application number 0272033 in open.According to EP-A-0272033, the molecular formula of particularly preferred polymkeric substance is
(CH
3(PEG)
43)
0.75(POH)
0.25(T-PO)
2.8(T-PEG)
0.4) T(PO-H)
0.25((PEG)
43CH
3)
0.75Wherein PEG is-(OC
2H
4) O-, PO is (OC
3H
6O) and T be (pCOC
6H
4CO), some polymer material such as Polyvinylpyrolidone (PVP) (typical molecular weight be 5000-20000, be preferably 10000-15000) prevent from also to form useful reagent in the transfer of unstable dyestuff between fabric in washing process.
Other available detergent composition auxiliary agent is a kind of froth suppressor, by polysiloxane and silicon-dioxide one polysiloxane mixture as the proof example.Polysiloxane is representative by alkylation polysiloxane material generally, and silicon-dioxide is usually with finely divided form, is example by various types of aerosils and xerogel and water drain silica.These materials can particulate forms be sneaked into, and sneak into a kind of water-soluble or water dispersible, on-surface-active detergent one impervious carrier helps the release of froth suppressor basically.In addition, froth suppressor solubilized or be dispersed in the liquid vehicle is employed by being sprayed on one or more other components.
As mentioned above, useful polysiloxane Foam Control can comprise the mixture of alkylation polysiloxane and solid silica, and the former is the type that relates to previously.Described mixture is by preparing on the surface of polysiloxane being added to solid silica.Preferred polysiloxane Foam Control represents that by the silicon-dioxide of (being preferred trimethylammonium-silanization) of hydrophobic silanization its silicon dioxide granule magnitude range is the 10-20 millimicron, and specific surface is 50 meters
2/ restrain, and evenly sneak into (molecular weight of its dimethyl polysiloxane is about 500-about 200000) with dimethyl polysiloxane liquid, the weight ratio of the silicon-dioxide of polysiloxane and silanization is about 1: 1 to about 1: 2.
Preferred polysiloxane Foam Control is open in the United States Patent (USP) 3933672 of Bartollota etc.Other useful especially froth suppressor is a self-emulsifying polysiloxane froth suppressor, is published in 1977.4.28 at German patent application DTOS2646126() in the narration.An example of described compound is that DCO544(is from commercial the getting of Dow Corning company), it is a kind of siloxanes/diol copolymer.
Above-mentioned froth suppressor application quantity is generally the 0.001-0.5%(weight of composition), be preferably 0.01-0.1%(weight).
The preferred method of sneaking into comprises and the liquid form of froth suppressor can be sprayed on one or more main ingredients of composition, or froth suppressor is formed divided particles, mixes with other solid ingredient of composition then.Foam properties-correcting agent is sneaked into discrete particles and is also allowed to comprise other Foam Control, for example C
20-C
24The oxyethane of lipid acid, crystallite paraffin wax and high MWt and the multipolymer of propylene oxide, otherwise the dispersiveness of matrix is had otherwise impact.The technology that generates the foam modified particles is open in the U.S. Patent number 3933672 of above-mentioned Bartolotta etc.
But other used additives used in this invention is one or more enzymes.
Usually be impregnated in the detergent composition preferred enzyme material and comprise the amylase that market can get.Neutrality and Sumizyme MP, lipase, esterase and cellulase.Suitable enzyme was discussed in United States Patent (USP) 3519570 and 3533139.
Fabric softener also can be sneaked in the detergent composition of the present invention.These reagent may be inorganic or organic types, and inorganic tenderizer example is disclosed green Shi Baishi in GB-A-1400898.The organic fabric tenderizer comprises water-insoluble tertiary amine, as disclosed among GB-A-1514276 and the EP-B-0011340.They and single C
12-C
14The complex form of quaternary ammonium salt has been disclosed in EP-B-0026527 and 0026528.Other useful organic fabric tenderizer is the two long-chain acid amides that are disclosed among the EP-B-0242919.The other organic additive of fabric-softening system comprises the high molecular weight polyethylene oxide material, as disclosed in EP-A-0299575 and 0313146.
The usage quantity of green Shi Baishi is generally 5-15%, is preferably 8-12%(weight) in the scope, it is added in other component of batching with the dry mixed component.Organic fabric tenderizer such as water-insoluble tertiary amine or two long-chain acid amides material amount of being impregnated in are 0.5～5%(weight), be generally 1-3%(weight), and high molecular weight polyethylene oxide material and the water-soluble cationic material amount of being added into are 0.1-2%, are generally 0.15-1.5%(weight).At this composition partly is spraying drying, these materials can add in the spray-drying tower with the aqueous slurry charging, although in some instances, it can add them so that the dry blending particle is more convenient, or with melt liquid they is sprayed on other solid ingredient of composition.
Surface-treated peroxyacid bleach precursor particle of the present invention is particularly useful in concentrating granular detergent composition, it is characterized in that comparing with the cleaning composition of general washing having quite high density.The bulk density of described high-density composition is at least 650 grams per liters, is more typically at least 700 grams per liters, more preferably surpasses 800 grams per liters.
Bulk density is measured with simple funnel and cup device, this device is connected by the conical hopper mold pressing at the end, low side at funnel is equipped with a clack valve, allow the funnel content to enter to be arranged in the garden that the axially aligns shape cup below the funnel, the upper end of funnel and bottom are respectively 130mm and 40mm, and it is installed into so that low side 140mm above the upper surface at the end, the whole height of cup is 90mm, interior height is 87mm, and interior diameter is 84mm, and its nominal volume is 500ml.
In order to measure, fill funnel by hand with powder, open clack valve, allow powder go in the whole cup.The cup that fills up powder is removed from shelf,,, from cup, removed excess powder as the top of cutter crosscut cup by a horizontal trimming instrument.The cup of filling of weighing then also gets the value (grams per liter) that the powder weight value is folded in half into bulk density, carries out replicate measurement as needs.
Concentrated cleaning compositions is also sneaked at least a multiple adjuvant component usually, and promptly they do not comprise only by doing the composition that mixes each component formation.It generally is pulverous adopting and doing the composition that mixes each component; Dissolve very slowly, also tendency caking produces the particle flow characteristic of difference in storage.
Be subjected to the restriction of above-mentioned bulk density and component concentration, composition of the present invention can comprise through the whole bag of tricks do to mix, spraying drying, agglomeration and prilling process make, preferable methods comprises the combination of these technology.The preferred method of making composition comprises spraying drying, agglomeration (in super mixer) and does the combination that mixes.
The preferred detergent composition of the present invention comprises at least two kinds of multiple adjuvant components of particle.First kind of component comprises at least 15% of composition, is generally 25-50%, but more preferably no more than 35%(weight), second kind of component is the 1-50% of composition, more preferably 10-40%(weight).
First kind of component comprises the particle that is mixed with anion surfactant, and its consumption is 0.75～40%(weight of powder) and one or more inorganic and/or organic salts, its consumption is 99.25～60%(weight of powder).Particle can adopt any suitable form, for example particle, thin slice, bead, Marumes or noodles shape, but particle preferably.Particle itself can form agglomerates by pot or drum agglomeration or by a series of mixing tanks, but the aqueous slurry production spray dried particle traditionally by the atomizing auxiliary agent of in hot blast, (removing most of water).The further densification of spray-dried granules then, for example by high speed cutting tool mixing tank and/or compacting grinding machine to increase the density before the reagglomeration.For illustrative purposes, first kind of component narrating hereinafter is as spray-dried powders.
Be found for the suitable anion surfactant of first kind of component purpose and be dissolved in very slowly in straight chained alkyl sulfuric acid and the straight-chain alkyl carboxylic acid's ester salt, the alkyl average carbon atom number is 16-22 in the straight chained alkyl sulfuric acid, and the average carbon atom number of the alkyl in straight-chain alkyl carboxylic acid's ester salt is 16-24.The alkyl of two types tensio-active agent preferably for example derive and get by natural source by Tallow, beef and hydrocoles oil.
The consumption of anion surfactant is a 0.75-40%(weight in the spray-dried powders that forms first kind of component), more, preferably use 3-20% through 2.5-25% commonly used, most preferably be 5-15%(weight).Can comprise or alternative water soluble surfactant active for example linear alkylbenzene sulfonate or C
14-C
15Alkylsulfonate is applied to subsequently on spraying spray-dried powders thereon.
The main auxiliary agent of other of spray-dried powders is that one or more inorganic or organic salts are to give particulate crystalline texture.Inorganic and/or organic salt can be water miscible, and is also non-water-soluble, and the part or the major portion of water-insoluble washing assistant contain the latter, and form the part of washing assistant auxiliary agent.The water-soluble inorganic salt that is suitable for comprises alkaline carbonate or hydrocarbon hydrochlorate.Alkali-metal silicate rather than crystalline layered silicate also can exist in the spray-dried granules, as long as aluminosilicate does not form the part of spray-dried component.
But, in concentrated cleaning compositions, best water soluble sulfate, special sodium sulfate amount can not be greater than the 2.5%(weight of composition).Preferably do not add sodium sulfate as sepa-ration aid and as byproduct as reducing to minimum degree with mixing of sulfonated surfactants.
Aluminosilicate zeolites forms the washing assistant auxiliary agent or forms the part of washing assistant auxiliary agent, is preferably in dried the mixing directly not to be added in other component.But sneak in the multiple adjuvant component.Sneaking in spray-dried granules of zeolite carried out, and the silicate of any existence does not form the part of spray-dried granules.Can adopt several method to realize sneaking into of these environment mesosilicic acid salt, for example by producing the isolating silicate spray-dried granules that contains, realize by method in the agglomerate of silicate being sneaked into other, perhaps better silicate is added as a kind of dried mixed solid additive.
First kind of component also can comprise up to 15%(weight) other auxiliary agent, for example brightening agent, anti-redeposition agent, photoactivation SYNTHETIC OPTICAL WHITNER (as four sulfonated zinc phthalocyanines) and heavy metal chelant.First kind of component is a kind of spray-dried powders, and it is dried to the 7-11%(weight that moisture content is a spray-dried powders usually), 8-10%(weight more preferably).The moisture content of the powder of being produced by other method such as agglomeration method may be lower, is 1-10%(weight) in the scope.
The size of particles of first kind of component generally and preferably is no more than 5%(weight) should more than 1.4mm, be not more than 10%(weight simultaneously) should be less than the overall dimension of 0.15mm.Preferably at least 60%, 80%(weight at least most preferably) powder (size) is between 0.7mm and the 0.25mm.For spray-dried powders, the bulk density of the particle from spray-drying tower is generally in 540-600 grams per liter scope, then by further procedure of processing, for example size reduces in high speed cutting instrument/mixing tank, compacting subsequently further improves, and therefore available method except that spraying drying directly forms high density granular.
Second kind of component of preferred composition of the present invention is other the multiple builder granule that contains a kind of water soluble surfactant active.
This can be any mixture of negatively charged ion, nonionic, positively charged ion or semi-polarity type or these types.Suitable tensio-active agent is listed at preamble, but preferred surfactants is C
14-C
15Alkyl-sulphate, straight chain C
11-C
15Alkylbenzene sulfonate and fatty C
14-C
18Methyl ester sulfonate.
Second kind of component can have any proper physical form, can think thin slice, bead, ball (marumes), noodles, ribbon or particle form, and they may be spraying drying or non-spraying drying agglomerate.Though second kind of component can comprise water soluble surfactant active thereon in theory, in fact at least a organic or inorganic salt is comprised in interior so that processing, this just provides a kind of crystallization degree, increasing the acceptable flow characteristics of particle, also can be any one or more organic or inorganic salt that exists in first kind of component.
The size of particles scope of second kind of component should reach the separate particles of avoiding with first kind of component when blend.Therefore, in out to out, be not more than 5%(weight) should be on 1.4mm, and be not more than 10% should be less than 0.15mm.
The bulk density of second kind of component is the function of its preparation method.But, the preferred method of second kind of component is a kind of agglomerate of mechanically mixing, agglomerate can be added in pot cyclone agglomerator (Z blade mixing tank) with dried auxiliary agent or with agglomerant, perhaps better be added in the serial mixing tank and make (for example by Schugi(Holland) BV, 29 Chroomstraat 8211AS, Lelystad, Holland and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, these that Postfach 2050F.R.G. makes).The bulk density scope that can obtain second kind of component by this method is 650 grams per liter to 1190 grams per liters, more preferably 750-850 grams per liter.
Preferred compositions comprises that the amount of second kind of alkaline carbonate in the component is equivalent to the 3-15%(weight of amount of composition), 5-12%(weight more preferably).This is a 20-40%(weight with regard to the amount that carbonate in second kind of component is provided).
The auxiliary agent of extremely preferred second kind of component also is a kind of aluminosilicate ion exchange material of water-insoluble synthetic zeolite type of hydration, and amount is the 10-35%(weight of second kind of component).The 1-10%(weight that the water-insoluble aluminosilicate amount of substance of sneaking into by this method is a composition).2-8%(weight more preferably).
In a kind of method of second kind of component of preparation, surfactant salt forms in serial mixing tank on the spot.The tensio-active agent of liquid acid form is added at a continuous high speed mixing tank, in the mixture as the sodium aluminum silicate of particle anhydrous sodium carbonate in the Lodige KM mixing tank and hydration, and neutralization forms surfactant salt, keeps the particle characteristics of mixture simultaneously.The agglomeration mixture that generates forms second kind of component, is added to then in other component of product.In the changing method of this method, surfactant salt is to give first neutral and be added to as a kind of viscous pastes in the mixture of other auxiliary agent, and in changing method, mixing tank only forms second kind of component as the agglomeration auxiliary agent.
Be mixed with in the special preferred method of peroxyacid bleach precursor particulate detergent composition of the present invention coating in manufacturing, the part that will comprise the spray dried prod of first kind of granular component is shifting before the blend with its excess again and is spraying thereon with low amount nonionic surface active agent.Use above-mentioned preferred method to make second kind of granular component.Then the bleach precursor particle of first kind and second kind of component and coating and cross hydration SYNTHETIC OPTICAL WHITNER, other mixed aid of doing as any carboxy acid salt chelator, discharge contaminated polymers, or the silicate of crystalline multilayer type and the enzyme travelling belt of packing into, by travelling belt they are transferred in the revolving horizontal drum, on its product of in drum, spices and polysiloxane froth suppressor being sprayed.In utmost point preferred compositions, in another drum of application mix step, introduce low amount (approximately 2%(weight)) thin isolating crystalline material to increase density and to improve particle flow characteristics.
In sneaking into the preferred concentrated cleaning product of alkali metal percarbonate, several aspects of control product need have been found, for example its heavy metal ion content and its equilibrium relative humidity as perhydrate salt.Contain this type of composition of SPC-D, and improved its stability and applied for October 6 at GB Patent Application No. 9021761.3(1990, Attorney ' s Docket No CM343) in disclose.
Also can be benefited from transfer system according to composition of the present invention, this system provides instantaneous high local concentrations product in the tube of automatic washing machine when begin wash(ing)cycle, has therefore also avoided the problem relevant with product loss in the pipework of machinery or storage tank.
By composition is put into bag or container be transferred to tube may the easiest reaching, with the beginning of the wash(ing)cycle of stirring beginning, the temperature rising or the submergence of tube washed water, composition discharges soon.In addition, washing machine itself can adapt to permission composition directly is added in the tube, for example by the distribution device at the entrance door place.
Comprise that the product that is enclosed in the detergent composition in the bag or in the container is designed to keep at the state of doing the integrity of container usually, to prevent excessive (the doing) of content, but product should adapt to and is exposed in the wash environment, is immersed in usually in the aqueous solution, and the content of container discharges.
Container is softish normally, for example bag or box.Bag can be that the fibrous texture that applied with fluid-tight protecting materials is so that the maintenance content is for example open in EP-A-0018678.Container can be designed to that the water-insoluble synthetic polymer material of in water medium edge sealing or sealing equipment makes in addition, and is at EP-A-0011500, open in 0011501,0011502 and 0011968.The water closed one side that makes things convenient for the box that water-soluble adhesive substance that form comprises independent arrangement and sealing form by fluid-tight polymeric film such as polyethylene or polypropylene of can breaking.In various bag or vessel form, can use laminates, in this product, the center soft layer is with composition dipping and/or coating, then with one or more skins to produce seemingly fibrous aesthetic effect.Multilayer can be enclosed in together so that in use keep combining, or can separate when contacting with water and promote to apply or the release of impregnation of matters.
Another laminates form comprises that one deck embossing or distortion is to provide a series of like box container, detergent composition is deposited on each like in the box container by measured quantity, with the topped the first layer of the second layer, and seal like these areas between box container, wherein two-layer the contact.Component can be with particle, pasty state or fusion form deposition, and the laminates layer should prevent before it is added in the water overflowing like the content of box container.These layers can separate when contacting with water and maybe can keep combining, as long as need this structure to allow like fast fast being released in the solution of the content of box container.Like the number of box container multiple choices are arranged on the substrate of per unit area, but change between every square metre 500 and 25000/ usually.
The suitable material that can be used for this flexible laminated gas producing formation on the one hand of the present invention comprises foam materials, paper and textiles and nonwoven webs with other.
But the preferred method of realizing the inventive method is that the re-use distribution device of composition through wall is arranged entered in the tube in the fabric outer liquid this wall liquid permeable, but impermeable solids composition.Such device is disclosed in EP-A-0343069 and 0343070.Disclose a kind of device among the EP-A-0343070, it comprises that the pliable and tough adventitia of a bag extends from a hole of fixed support ring, but described hole to adapt in wash(ing)cycle one wash(ing)cycle bag container adequate prod is arranged.Part washing is separated matter circulation via hole and is entered bag, dissolved product, and solution upwards enters in the washing medium by the hole then.Support ring is equipped with a screening hurdle device and prevents that the not dissolved product that wets is excessive, and this device typical case comprises that the center hub of radiation wall extension from the spoke wheel structure extends, or similar structures, is spiral form at this structure mesospore.
The present invention illustrates that with following unrestricted embodiment in example, all percentage ratio all is benchmark except as otherwise noted with weight.
In detergent composition, abbreviation component symbol has following meanings
C
12LAS: straight chain C
12Sodium alkyl benzene sulfonate
TAS: lipidol sodium sulfate
C
14/15AS:C
14-C
15Sodium alkyl sulfate
TAEn: every mol of alcohol lipidol of n moles of ethylene oxide ethoxylation.
45E7: with the C of average 7 moles ethylene oxide condensation
14-15It is main straight-chain monohydric alcohol
CnAE
E65: with the C of 6.5 moles ethylene oxide condensation
12-C
13Primary alconol.
PEG: polyoxyethylene glycol (MWt generally is connected in the back)
TAED: tetraacetyl ethylene diamine
Silicate: amorphous sodium silicate (SiO
2: Na
2O is than generally being connected in the back)
NaSKS-6: molecular formula is Na
2Si
2O
5Crystalline layered silicate
Yellow soda ash: anhydrous sodium carbonate
CMC: Xylo-Mucine
Zeolite A: molecular formula is Na
12(AlO
2SiO
2)
1227H
2The hydrated aluminum silicate of O, main size of particles scope is the 1-10 micron
Polyacrylic ester: MWt is acrylic acid homopolymer of 4000
Citrate trianion: citrate trisodium dihydrate
Photoactivation SYNTHETIC OPTICAL WHITNER: four sulfonated zinc phthalein cyanines
MA/AA:1: 4 toxilic acids/acrylic acid multipolymer, molecular-weight average are about 80000.
MVEMA: maleic anhydride/vinyl methyl ether multipolymer, think that molecular-weight average is 240000, this material carried out giving hydrolysis with NaOH before adding
Perborate: sodium perborate tetrahydrate, the demarcation molecular formula is NaBO
23H
2OH
2O
2
Perborate: anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER
Monohydrate empirical formula NaBO
2H
2O
2
Percarbonate: SPC-D, demarcate molecular formula 2Na
2CO
33H
2O
2
Enzyme: blended proteolytic enzyme and amylase (AS sells by NOVO industry)
Brightening agent: disodium 4,4 '-two (2-morpholino-4-anilino-S-triazine-6-base is amino) stilbene-2,2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate
DETPMP: diethylenetriamine five (methylene phosphonic acid) is Dequest 2060 supply the markets with the trade mark by Monsanto
Mix-froth inhibitor 25% paraffin wax, 50 ℃ of fusing points, 17% water drain silica, 58% Valelinum Liquidum
For the purposes of the present invention, do not have and force dissolution conditions to be defined in the existing Beaker all-hydrolytic test, (by the supply of Sotax AG CH-4008B ASEL Switzerland) these conditions of using Sotex solubility test instrument Model AT6 to carry out.This instrument comprises the polycarbonate beaker of arrangement, and each can hold 1 premium on currency, is supported in the thermostatic control water-bath, and each beaker is equipped with the paddle agitator, its stirring velocity may command.
In crossing the hydrolysis program, use two beakers among the Sotax Tester, use following method:
1. set water-bath in required temperature (20 ℃).
2. 1 liter of distilled water is added in each Sotax beaker, and allows to equilibrate to temperature required
3. accurately be sampled to the sample of 2 * 10 gram washing composition and parent
4. by adding 25ml3: 2 Glacial acetic acid distilled water solutions and 2 ice cubes prepare some titration beakers
5. the stir speed (S.S.) of setting Sotax is to 150rpm
6. first sample is added to the Sotax beaker No. 1 and starts clock (t=0 branch).The 5ml liquor kalii iodide is added in the first titration beaker
7. from No. 1, Sotax beaker, take out the 10ml aliquots containig, and in the first titration beaker is packed in the t=1 timesharing into
8. second sample is added in No. 2, the Sotax beaker (t=1 branch) and the 5ml potassiumiodide is added in second titration beaker
With 0.005M sodium thiosulfate solution titrated first aliquots containig up to solution fade for the first time (color is because solution heating and regeneration very slowly, and perhydrate and iodide react).
10. (t=2 branch) gets the 10ml aliquots containig from No. 2, Sotax beaker, and in second the titration beaker of packing into, repeating step 9.
11., get aliquots containig (t=branch) again by the following time
Beaker No.1 beaker No.2
（t）??（t）
3??4
5??6
10??11
15??16
20??21
Constituted replicate(determination) at 1 minute from the aliquots containig of No. 1, beaker with 2 minutes aliquots containigs from No. 2, beaker, on average its result obtains numeral, and calculates with the % all-hydrolytic.
Embodiment 1
The TAED(size of particles 90%(weight of fine powder form)＜150 microns) carry out the 85%(weight that agglomeration obtains particle with TAE25) be between the 400-1700 micron.This material is divided into 5 parts, is defined as A-F, and part A is untreated, and all the other each minutes are all carried out following processing.
The surface treatment material
B 5% is sad
C 5% polyacrylic acid (MWt2000)
D 5% oxyacetic acid
E 5% citric acid
Handle and all adopt hand spraying to go in the little coating tube.Melt during 60 ℃ of sad employings, other adopts the aqueous solution down in room temperature (20 ℃).Citric acid solution is a 50%(weight), glycollic acid solution is a 66%(weight), polyacrylic acid solution is a 50%(weight).
Take from the material of each part and sneak in the model detergent prescription, component is a weight fraction
C
12LAS 9.0
TAS??2.8
Dobanol??45E7??3.8
Zeolite A 23.5
Citrate trianion 7.5
MA/AA??3.75
Carbonate 17.0
Silicate (SiO
2: Na
2O=2: 1) 4.2
DETPMP??0.4
CMC??0.5
Percarbonate 18.7
TAED??5.85
Other are 3.00 years old
5 batchings are carried out aforesaid Beaker all-hydrolytic test then, and gained peroxy acid productive rate is illustrated in the table 1.The corresponding elapsed time of gained result is 1,3,5,10,15 and 20 minutes, represents with the theoretical weight percentage that can get peracid.
The table I
The beginning all-hydrolytic time
Product 135 10 15 20 with the TAED part
A??37.3??74.2??86.0??93.9??97.8??97.2
B??23.2??60.1??75.9??90.8??97.4??96.5
C??29.0??67.2??77.2??88.2??90.8??90.0
D??37.6??73.7??85.1??94.9??97.5??98.6
E??36.8??74.5??87.2??92.5??96.8??97.6
The batching that therefrom contains part D and E as can be seen shows that as containing the essentially identical peracid of part A (all being 3 minutes and whole all-hydrolytic reaction back) all-hydrolytic is not having the influence that is not subject to processing basically under the pressure dissolution conditions.The low peroxy acid output of allocation sheet publicly price-reduction that contains part B and C on the contrary is especially at the all-hydrolytic baseline.
Embodiment 2
Contain the TAED part A of example 1 and the batching of D, use Miele automatic washing machine (Model W754) to set about short-term wash(ing)cycle, carry out washing machine test in kind at 40 ℃.4 cotton bed coverlets (3.3Kg) of every machine loading and 100g batching are through Arielator(RTM) distribution device is added in the fabric in the machine barrel of doing washing.150ppm hardness (by CaCO
3Expression) 12 premium on currency of (Ca: the Mg ratio is 3: 1) are packed in every washing machine.
Two washing machines (during running period, in order to take a sample, allowing to open load door) are used to realize as used same program in the test of Beaker all-hydrolytic.The result is illustrated in the II, and as shows the I same procedure and represent.
The table II
From time opening wash(ing)cycle minute
Product 135 10 15 20 with the TAED part
A??31.5??56.1??82.1??92.1??89.4??89.4
D??9.1??50.6??68.0??99.5??98.5??96.7
This shows that under the pressure dissolution conditions of load washing machine, in initial period wash(ing)cycle, product (the oxyacetic acid surface-treated TAED) all-hydrolytic that contains part D is slower than the product that contains part A (untreated material).This just shows that oxyacetic acid surface-treated TAED has suppressed all-hydrolytic during the local high product concentration of the beginning of wash(ing)cycle, thinks that at this highly water-soluble of acid hangs down the pH value environment in the foundation on every side of TAED particle.Yet, to get well by the untreated material of rate ratio of the peroxy acid of the TAED generation of handling in the later stage of wash(ing)cycle, this release that delays that just shows TAED causes more effective peroxy acid that is transformed into.
Embodiment 3
Relatively contain part B, the C of surface-treated parent of example 1 and three kinds of prescriptions of D, carry out washing machine test in kind, described three samples branch is added to respectively in the improved form of example 1 detergent formulation, and wherein the SPC-D monohydrate with identical weight replaces SPC-D.
Except that 20 ℃ of wash temperatures, washing machine contrast is adopted as used constructed in the example 2.This temperature be European's wash(ing)cycle initial cold water fill with the representative temperature in stage.The result is illustrated in the following table III
The table III
Begin the time branch of wash(ing)cycle
The prescription 135 10 15 20 that contains part
B??4.6??33.6??54.7??74.8??78.0??80.3
C??4.6??32.6??54.3??80.7??84.8??88.0
D??3.65??54.8??70.8??83.0??88.5??85.0
This just shows and does not carry out the surface treatment parent by the present invention and compare that carrying out the surface-treated peroxyacid bleach precursor by the present invention can provide more peroxy acid output under the Actual laundering condition.
The embodiment IV
The washing machine control formula is similar to and is carried out in the routine III, and sneaks into parent fraction A, B, C and E, comprises testing bleaching responsive painted fabric sample in fabric load.Textile (by the Borval Fabrics, Albert Street, Huddersfield, West Yorkshire, Britain supplies) of the 100% lamb's wool braiding that these samples dye with purple 48 dyestuffs (design No.W3970).Every kind of processing is carried out 24 times and is repeated, and by Sub-Committee of Experts, uses following hierarchy system, according to the fabric color degree of injury, and these samples of visual classification.
Three painted samples of the color of showed different damage are established four characteristic scales as standard, and wherein 1 actual not damaged of representative and 4 representative damages are very serious.Three kinds of standards are used to specified color and damage various inter-step mid points, promptly
1 actual not damaged
2 slight damages
3 damages
4 major injuries
Adopt two Sub-Committees of Experts, and get their average result.
Utilize this technology relatively to use the damage of the color that prescription causes that contains parent fraction A.B.C and E, the gained result is as follows
% with sample of grade
Prescription 1234 integrated levels that contain parent fraction
A??50??29.2??8.33??12.5??1.83
B??52.2??26.1??21.7??0??1.70
C??47.8??30.4??17.4??4.4??1.78
E??66.6??16.6??10.5??6.2??1.56
Therefrom as can be seen, the recipe ratio of sneaking into part E according to the present invention does not have the surface-treated parent or produces obviously few fabric color damage not according to surface-treated parent of the present invention.
The embodiment V
Use contains the prescription that contains TAED part A and D of example 1, and comprises part A and 10%(weight) the further agglomerant additional TAED part F of oxyacetic acid (is benchmark with total agglomerate weight), repeat the washing machine contrast of routine IV.Prescription carries out the painted sample degraded test described in routine IV, and the gained result is as follows
% with sample of grade
1234 integrated levels
A??16??20??25??38??2.83
D??29??38??29??4??2.08
F??9??35??35??22??2.70
This shows that the part D that sneaks into by 5% oxyacetic acid surface-treated precursor granule of the present invention has significantly low comprehensive damage rank than the part A that does not have to handle.On the contrary, being doubled amount with 10%() oxyacetic acid produces as agglomerant and seldom reduces impairment scale (for the material that not have processing).This just confirms, the importance that the bleach precursor particle surface is handled in obtaining the benefit that the present invention reduces fabric damage.
Claims (22)
1; a kind of solid peroxygen acid blanching precursor compositions; it is characterized in that comprising particle peroxyacid bleach precursor material; described parent MPt＞30 ℃ also is selected from and contains at least one N-acylated compound and contain at least one O-acyl compounds; the outside surface of described granular bleach parent material is handled so that described compound is bonded on the described outside surface with organic acid compound; particulate about 2%-about 20% (weight) of described acid compound amount for handling; in the water of described organic acid compound solubleness 20 ℃ at least about 5 grams/100 gram water and MPt greater than about 30 ℃, the granular bleach parent material of wherein said processing is at 20 ℃ of peroxy acids that produced by the described granular bleach parent material of the form of being untreated under the same conditions that produce after 3 minutes in the test of Beaker all-hydrolytic at least about 90%.
2, according to the solid peroxygen acid blanching precursor compositions of claim 1, wherein solubleness restrains water at 20 ℃ at least about 20 grams/100 in the water of organic acid compound.
3, according to the solid peroxygen acid blanching precursor compositions of claim 1, wherein organic acid compound is selected from the carboxylate salt of monomeric or oligopolymer.
4, according to the solid peroxygen acid blanching precursor compositions of claim 3, wherein organic acidifying compound is monomeric aliphatic carboxylic acid, and its Mpt is greater than about 40 ℃.
5, according to the solid peroxygen acid blanching precursor compositions of claim 4, wherein organic acid compound is selected from oxyacetic acid, 1-lactic acid and citric acid and composition thereof.
6, according to the solid bleach peroxy acid precursor compositions of claim 4, wherein the amount of treated substance is about 2-15%(weight of composition).
7, according to the solid peroxygen acid blanching precursor compositions of claim 6, wherein the amount of treated substance is about 3-10%(weight of composition).
8, according to the solid peroxygen acid blanching precursor compositions of claim 7, wherein particle peroxyacid bleach precursor material is handled so that the coating of the outside surface that is coated on the granular bleach parent material to be provided with the fusion organic acid compound that is selected from oxyacetic acid and 1-lactic acid.
9, according to the solid peroxygen acid blanching precursor compositions of claim 7, wherein the outside surface of particle peroxyacid bleach precursor material is handled with the solution or the dispersion liquid of citric acid.
10, according to Claim 8 with any solid peroxygen acid blanching precursor compositions of 9, wherein organic acid compound is with a kind of finely divided spray applications.
11, according to the solid peroxygen acid blanching precursor compositions of claim 1, wherein parent is selected from ester and inferior acid amides.
12; a kind of solid peroxygen acid blanching precursor compositions that comprises a kind of particle peroxyacid bleach precursor material; described parent Mpt＞30 ℃ also is selected from and contains at least one N-acylated compound and contain at least one O-acylated compound; the outside surface of described granular bleach parent material is with being selected from oxyacetic acid; the organic acid compound of 1-lactic acid and citric acid and composition thereof is handled so that described compound sticks to described outside surface; described acid compound amount is the processed about 2-20%(weight of particulate), wherein said processing granular bleach parent material 20 ℃ of peroxy acids that in Beaker all-hydrolytic test, produce after 3 minutes with produce basic identical amount by the granular bleach parent material of the form of being untreated under the same conditions.
13, according to the solid peroxygen acid blanching precursor compositions of claim 12, wherein peroxyacid bleach precursor contains at least one N-diacyl part.
14, according to the solid peroxygen acid blanching precursor compositions of claim 13, wherein peroxyacid bleach precursor is a tetrem acidylate Alkylenediamine.
15, according to the solid peroxygen acid blanching precursor compositions of claim 14, wherein peroxyacid bleach precursor is a tetrem acidylate ethylene diamine.
16, according to the solid peroxygen acid blanching precursor compositions of claim 15, wherein the particle parent material comprises agglomerant parent particle, and this agglomerative particle is handled with organic acid compound.
17, according to the solid peroxygen acid blanching precursor compositions of claim 16, wherein agglomerant is selected from ethoxylized fatty alcohol, polyoxyethylene glycol, derivatived cellulose and composition thereof.
18, a kind of bleaching composition of sneaking into solid peroxygen acid blanching precursor compositions comprises:
A) particle peroxyacid bleach precursor material, the Mpt of described parent＞30 ℃ also are selected from and contain at least one N-acylated compound and contain at least one O-acylated compound, the outside surface of described granular bleach parent material is handled so that described compound is sticked on the described outside surface with organic acid compound, described acid compound amount is the about 20%(weight of the about 2-of processed particulate), described organic acid compound solubleness in water is at least about 5 grams/100 gram water and Mpt greater than about 30 ℃ in the time of 20 ℃, wherein said processing granular bleach parent material produces about 90% peroxy acid that is produced by the described granular bleach parent material of the form of being untreated under the same conditions at 20 ℃ after 3 minutes in the test of Beaker all-hydrolytic; With
B) a particulate inorganic perhydrate salt SYNTHETIC OPTICAL WHITNER.
19, according to the granular bleach composition of claim 18, wherein the perhydrate SYNTHETIC OPTICAL WHITNER is Sodium peroxoborate or SPC-D, and exist with drying adding particulate matter.
20, according to the granular bleach detergent composition of claim 19, also sneak into the organic surface active agent that is selected from negatively charged ion, nonionic, positively charged ion and amphoterics and composition thereof.
21, according to the granular bleach detergent composition of claim 20, wherein said tensio-active agent exists with the component that is separated with described solid peroxygen acid blanching precursor compositions and described inorganic perhydrate, described component comprise be not more than about 5%(weight) size of particles less than about 250 microns particle.
22, according to the granulated detergent bleaching composition of claim 21, wherein the bulk density of said composition is at least 650 grams per liters.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB919102507A GB9102507D0 (en) | 1991-02-06 | 1991-02-06 | Peroxyacid bleach precursor compositions |
| GB9102507.2 | 1991-02-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1064701A true CN1064701A (en) | 1992-09-23 |
Family
ID=10689607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92101630A Pending CN1064701A (en) | 1991-02-06 | 1992-02-07 | Peroxyacid bleach precursor compositions |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0571524A1 (en) |
| JP (1) | JP2657114B2 (en) |
| CN (1) | CN1064701A (en) |
| AR (1) | AR244798A1 (en) |
| AU (1) | AU661681B2 (en) |
| CA (1) | CA2101448A1 (en) |
| CZ (1) | CZ159393A3 (en) |
| GB (1) | GB9102507D0 (en) |
| HU (1) | HU9302289D0 (en) |
| IE (1) | IE920384A1 (en) |
| MX (1) | MX9200518A (en) |
| MY (1) | MY107914A (en) |
| NZ (1) | NZ241533A (en) |
| PT (1) | PT100101A (en) |
| SK (1) | SK83693A3 (en) |
| WO (1) | WO1992013798A1 (en) |
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| EP0700427B2 (en) † | 1993-05-26 | 2005-08-10 | Unilever Plc | Detergent compositions |
| US5780410A (en) * | 1993-07-14 | 1998-07-14 | The Procter & Gamble Company | Detergent compositions containing percarbonate and making processes thereof |
| US5534196A (en) * | 1993-12-23 | 1996-07-09 | The Procter & Gamble Co. | Process for making lactam bleach activator containing particles |
| US5534195A (en) * | 1993-12-23 | 1996-07-09 | The Procter & Gamble Co. | Process for making particles comprising lactam bleach activators |
| EP0659876A3 (en) * | 1993-12-24 | 1996-12-04 | Procter & Gamble | Detergent additive composition. |
| WO1995033038A1 (en) * | 1994-06-01 | 1995-12-07 | The Procter & Gamble Company | Sarcosinate with clay softeners in laundry compositions |
| CA2191439A1 (en) * | 1994-06-01 | 1995-12-07 | Suzanne Powell | Bleach compositions comprising oleoyl sarcosinate surfactants |
| JPH10501278A (en) * | 1994-06-01 | 1998-02-03 | ザ、プロクター、エンド、ギャンブル、カンパニー | Dye transfer inhibiting composition containing oleoyl sarcosinate |
| DE4424005A1 (en) * | 1994-07-07 | 1996-01-11 | Henkel Kgaa | Powdery bleach and detergent |
| DE4439039A1 (en) | 1994-11-02 | 1996-05-09 | Hoechst Ag | Granulated bleach activators and their manufacture |
| GB9423374D0 (en) * | 1994-11-19 | 1995-01-11 | Procter & Gamble | Peroxyacid bleach precursor compositions |
| FR2728171B1 (en) | 1994-12-14 | 1997-01-24 | Chemoxal Sa | PRODUCTION OF BIOCIDAL DISINFECTANT FORMULATIONS BASED ON PERACETIC IONS |
| US5925609A (en) * | 1995-03-11 | 1999-07-20 | Procter & Gamble Company | Detergent composition comprising source of hydrogen peroxide and protease enzyme |
| ATE300603T1 (en) * | 1995-03-11 | 2005-08-15 | Procter & Gamble | DETERGENT AND CLEANING PRODUCT CONTAINING HYDROGEN PEROXIDE SOURCE AND PROTEASE |
| BR9710077A (en) * | 1996-06-28 | 1999-08-10 | Procter & Gamble | Liquid non-aqueous cleaning compositions containing coated particles |
| DE19641708A1 (en) * | 1996-10-10 | 1998-04-16 | Clariant Gmbh | Process for the preparation of a coated bleach activator granulate |
| DE19740671A1 (en) * | 1997-09-16 | 1999-03-18 | Clariant Gmbh | Bleach activator granulate containing ammonium nitrile and layered silicate |
| DE19740668A1 (en) | 1997-09-16 | 1999-03-18 | Clariant Gmbh | Storage-stable bleach activator granulate obtained using acid-modified layered silicate as binder |
| DE19740669A1 (en) * | 1997-09-16 | 1999-03-18 | Clariant Gmbh | Coated ammonium nitrile bleach activator granules used in e.g. detergents |
| US6017867A (en) * | 1998-06-05 | 2000-01-25 | The Procter & Gamble Company | Detergent compositions containing percarbonate and making processes thereof |
| EP3662046B1 (en) * | 2017-07-31 | 2024-08-14 | Dow Global Technologies LLC | Detergent additive |
| US20190297881A1 (en) * | 2018-03-29 | 2019-10-03 | Randall Andrew PILON | Antimicrobial compositions containing alkyl sarcosine and/or salt thereof |
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| IE51848B1 (en) * | 1980-11-06 | 1987-04-15 | Procter & Gamble | Bleach activator compositions,preparation thereof and use in granular detergent compositions |
| FI67092C (en) * | 1980-12-09 | 1985-01-10 | Unilever Nv | BLEKNINGSAKTIVATOR-KORN AVSEDDA FOER TVAETT- OCH / ELLER BLEKNINGSBLANDNINGAR |
| US4486327A (en) * | 1983-12-22 | 1984-12-04 | The Procter & Gamble Company | Bodies containing stabilized bleach activators |
| DE3504628A1 (en) * | 1985-02-11 | 1986-08-14 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING GRANULATE GRANULATE |
| US4678594A (en) * | 1985-07-19 | 1987-07-07 | Colgate-Palmolive Company | Method of encapsulating a bleach and activator therefor in a binder |
| US4657784A (en) * | 1986-03-10 | 1987-04-14 | Ecolab Inc. | Process for encapsulating particles with at least two coating layers having different melting points |
| DE3639115A1 (en) * | 1986-11-15 | 1988-05-19 | Henkel Kgaa | STORAGE BLENDER MIXTURE WITH IMPROVED SOLUTION |
| FI881255A (en) * | 1987-03-17 | 1988-09-18 | Procter & Gamble | BLEKNINGSKOMPOSITIONER. |
| DE3812693A1 (en) * | 1988-03-19 | 1989-09-28 | Reckitt Gmbh | CLEANING TABLET FOR DENTAL PROSTHESIS |
-
1991
- 1991-02-06 GB GB919102507A patent/GB9102507D0/en active Pending
-
1992
- 1992-01-28 WO PCT/US1992/000664 patent/WO1992013798A1/en not_active Application Discontinuation
- 1992-01-28 SK SK836-93A patent/SK83693A3/en unknown
- 1992-01-28 CZ CS931593A patent/CZ159393A3/en unknown
- 1992-01-28 CA CA002101448A patent/CA2101448A1/en not_active Abandoned
- 1992-01-28 EP EP19920906781 patent/EP0571524A1/en not_active Ceased
- 1992-01-28 HU HU9302289A patent/HU9302289D0/en unknown
- 1992-01-28 AU AU14199/92A patent/AU661681B2/en not_active Ceased
- 1992-02-05 IE IE038492A patent/IE920384A1/en unknown
- 1992-02-05 NZ NZ241533A patent/NZ241533A/en unknown
- 1992-02-06 MX MX9200518A patent/MX9200518A/en not_active IP Right Cessation
- 1992-02-06 AR AR92321749A patent/AR244798A1/en active
- 1992-02-06 PT PT100101A patent/PT100101A/en not_active Application Discontinuation
- 1992-02-06 MY MYPI92000178A patent/MY107914A/en unknown
- 1992-02-07 CN CN92101630A patent/CN1064701A/en active Pending
- 1992-10-01 JP JP5506608A patent/JP2657114B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0571524A1 (en) | 1993-12-01 |
| EP0571524A4 (en) | 1993-09-23 |
| CZ159393A3 (en) | 1994-03-16 |
| AR244798A1 (en) | 1993-11-30 |
| SK83693A3 (en) | 1994-04-06 |
| JP2657114B2 (en) | 1997-09-24 |
| HU9302289D0 (en) | 1993-11-29 |
| AU1419992A (en) | 1992-09-07 |
| AU661681B2 (en) | 1995-08-03 |
| CA2101448A1 (en) | 1992-08-07 |
| MX9200518A (en) | 1992-12-01 |
| WO1992013798A1 (en) | 1992-08-20 |
| JPH06505691A (en) | 1994-06-30 |
| NZ241533A (en) | 1995-01-27 |
| PT100101A (en) | 1993-03-31 |
| IE920384A1 (en) | 1992-08-12 |
| MY107914A (en) | 1996-06-29 |
| GB9102507D0 (en) | 1991-03-27 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |